TWI573815B - Polyimide resin and film thereof - Google Patents

Description

Polyimine resin and film thereof

The present invention relates to a polyimine resin and a film thereof, and more particularly to a polyimide resin which is excellent in optical properties, thermal stability and mechanical properties and which can be used for a substrate for a display element, and the like. Amine film.

Polyimide (PI) film is generally prepared by thinning a polyimide resin, and polyimine resin is a solution polymerization of an aromatic dianhydride with an aromatic diamine or an aromatic diisocyanate. After obtaining a polyproline derivative, the mixture is subjected to ring closure dehydration at a high temperature to carry out hydrazine imidation to obtain a high heat resistant resin. In order to prepare a polyimine resin, pyromellitic dianhydride (PMDA) or biphenyl tetracarboxylic dianhydride (BPDA) may be used as the aromatic dianhydride component, and diphenylamine (ODA) may be used as the aromatic diamine component. ), p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), methylene bisaniline (MDA), diaminophenyl hexafluoropropane (HFDA), and the like.

The polyimine resin is an insoluble and infusible ultra-high heat-resistant resin, and has excellent properties such as heat resistance oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance, and thus is widely used in automotive materials. Heat-resistant materials such as aerospace materials and spacecraft materials, and electronic materials such as insulating coating agents, insulating films, semiconductors, and electrode protective films for liquid crystal displays (TFT-LCDs) have recently been used for display materials such as optical fibers or liquid crystal alignment films. And a conductive screening test in the film or a surface coating for the transparent electrode film.

However, the polyimide resin exhibits a brown color and a yellow color due to a high aromatic ring density, a low light transmittance in a visible light region, a light transmittance due to a yellow color, and a high birefringence. Not suitable for use as an optical component.

In order to solve the above problems, a method of refining and purifying a monomer and a solvent with high purity has been proposed, but the improvement in light transmittance is not large.

U.S. Patent No. 5,053, 480 discloses a method of using an alicyclic dianhydride in place of an aromatic dianhydride, which is improved in transparency and color upon liquid or film formation, but improved in light transmittance. It is still limited and cannot meet the demand for high light transmittance. In addition, it also results in lowering thermal and mechanical properties.

In addition, U.S. Patent Nos. 4,595,548, 4,601,061, 4,460,824, 4,895,972, 5,158,083, 5,093,453, 5,218,077, 5,367,046, 5,338,826, 5, 968, 036, 6,232, 024, and Korean patents In the publication No. 2003-0009437, a monomer having a bent structure in which a linking group such as -O-, SO ₂ -, or CH ₂ - is bonded to a non-para-position (p) but a meta-position (m) is described, or has - The aromatic dianhydride and the aromatic diamine monomer having a substituent such as CF ₃ have a novel structure of transparent polyimine which can improve light transmittance and color transparency without significantly reducing thermal properties.

However, such a transparent polyimide film has limitations in application in the field of cutting materials such as displays or semiconductors requiring high preparation temperatures due to insufficient heat resistance or mechanical properties, and it occurs during display preparation. The tearing phenomenon also has a problem of causing a decrease in product yield.

SUMMARY OF THE INVENTION A primary object of the present invention is to provide a polyimide pigment which can greatly improve heat resistance and mechanical properties while forming a film while maintaining optical properties.

Another object of the present invention is to provide a polyimide film and a substrate for a display element which are formed of the above polyimine resin.

In order to achieve the above object, an embodiment of the present invention provides a quinone imine compound comprising a polyaminic acid copolymerized by a polymerization component of a diamine monomer and a dianhydride monomer, the diamine monomer and At least one of the dianhydride monomers is one or more monomers comprising a group selected from the group consisting of an oxy group, a sulfo group, and a fluorine group, the diamine monomer comprising a group selected from the group consisting of 1,3-bis(4-amino) Phenyloxy)benzene (1,3-bis(4-aminophenoxy)benzene) and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane A polyimine resin characterized by one or more of the group consisting of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane).

According to a preferred embodiment of the present invention, the diamine monomer comprises at least one monomer containing at least one selected from the group consisting of an oxy group, a sulfo group and a fluorine group, the dianhydride monomer comprising at least one kind It contains one or more monomers selected from the group consisting of an oxy group, a sulfo group, and a fluorine group.

According to a preferred embodiment of the invention, the one selected from the group consisting of 1,3-bis(4-aminophenoxy)benzene and 2,2-bis[4-(4) -Aminophenoxy)phenyl]hexafluoropropane (1,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane), a group of more than one diamine monomer relative to a diamine The total molar number of the body is 10 mol% or less, preferably 2 to 10 mol%.

According to a preferred embodiment of the present invention, the monomer containing one or more selected from the group consisting of an oxy group, a sulfo group and a fluorine group is selected from the group consisting of 3,3,4,4-diphenylphosphonium tetracarboxylic acid dianhydride (SO) ₂ DPA), 4,4'-oxo phthalic anhydride (ODPA) and more than one dianhydride monomer in 4,4'-(hexafluoroisopropene) diacetic anhydride (6FDA); bis(4-amino) Phenyl) hexafluoropropane (33-6F, 44-6F), diaminodiphenyl hydrazine (4DDS, 3DDS), bis(trifluormethyl)-1,1'-biphenyl -4,4'-diamine, TFDB), one of bis(aminohydroxyphenyl)hexafluoropropane (DBOH), oxydianiline (ODA) and bis(aminophenoxy)diphenylhydrazine (DBSDA) a group consisting of the above diamine monomers; and a mixture of the foregoing.

According to a preferred embodiment of the present invention, the polyimine resin is a quinone imine compound of polylysine which is obtained by copolymerization of a polymerization component containing a monomer having a polyfunctional group.

According to a preferred embodiment of the present invention, the total number of moles of the polyfunctional group-containing monomer relative to the dianhydride monomer is 2 mol% or less.

According to a preferred embodiment of the invention, the polyfunctional group-containing monomer is selected from the group consisting of Hexamethyl Benzenehexacarboxylate and diethyl azobenzene-4,4'-dicarboxylate (Diethyl 4). , 4'-Azodibenzoate), trimethyl benzene-1,3,5-tricarboxylate and trimethyl benzene-trimethyl benzene- 1,2,4-tricarboxylate) One or more of the group consisting of.

In another embodiment of the present invention, a polyimide film comprising the above polyimine resin is provided.

According to a preferred embodiment of the present invention, the polyimide film has a light transmittance of 550 nm or more and a thermal expansion coefficient at 50 to 250 ° C using a UV spectrophotometer with a thickness of 50 to 100 μm. (CTE) is 45 ppm/°C or less.

According to a preferred embodiment of the present invention, the polyimide film has a yellowness of 5 or less based on a thickness of 50 to 100 μm.

According to a preferred embodiment of the present invention, the polyimide film has a tensile strength of 150 MPa as measured based on ASTM D882 (film thickness 50 to 100 μm).

According to another preferred embodiment of the present invention, a substrate for a display element comprising the polyimide film is provided.

According to the present invention, it is possible to provide a polyimide film having improved heat resistance and mechanical properties, and preferably provide a colorless and transparent polyimide film, and thus can be applied to a semiconductor insulating film, a liquid crystal display (TFT-LCD) insulation. Various fields such as a film, a passivation layer, a liquid crystal alignment film, a material for optical communication, a protective film for a solar cell, and a flexible display substrate.

Unless otherwise defined, all technical and scientific terms used in the specification have the same meaning meaning The nomenclature used in this specification is generally used in the art.

In the entire specification, when a certain component "includes" a certain component, if it is not described to the contrary, the other components are not excluded, and other components may be included.

One aspect of the present invention relates to a unit structure comprising a monomer structure derived from a diamine monomer and a monomer derived from a dianhydride monomer, wherein at least one of the diamine monomer and the dianhydride monomer comprises a component selected One or more monomers selected from the group consisting of an oxy group, a sulfo group, and a fluoro group, the diamine monomer comprising a 1,3-bis(4-aminophenoxy)benzene (1,3-) Bis(4-aminophenoxy)benzene) and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane One or more of the group consisting of polyimine resins.

According to another aspect of the present invention, a polyimide film comprising the polyimide film and a substrate for a display element comprising the polyimide film.

The invention will be described in detail below.

In order to maintain the transparency of the transparent polyimide, it is often the case that the heat resistance peculiar to the polyimine and the mechanical properties are lowered. In order to improve the heat resistance and mechanical properties of the transparent polyimide resin, diamine monomers such as p-phenylene diamine (p-PDA) and 4,4-diphenylamine (4,4-ODA) may be used or It is a dianhydride monomer such as biphenyltetracarboxylic dianhydride (BPDA) or pyromellitic dianhydride (PMDA), but the degree of improvement is minimal.

Further, as a method for improving the heat resistance and mechanical properties of the transparent polyimide, there is also a method of reacting a functional group with a crosslinking agent by introducing a crosslinking agent, a method of using a metal or an organic-inorganic mixed catalyst such as a Grubb catalyst, A method of treating a terminal by a UV crosslinking method or a monomer such as an alkoxy group or a decyl group, but these methods are also difficult to control crosslinking, and in the case of crosslinking using a monomer having an unsaturated group, In order to replace the terminal of the main chain and adjust the equivalent ratio of the diamine and the dianhydride to 1:1, this also fails to improve the physical properties of the polyimide film.

In order to solve the above problems, the inventors of the present invention have found that the diamine monomer and/or dianhydride monomer including one or more monomers selected from the group consisting of an oxy group, a sulfo group, and a fluorine group is used. The body, here adjusted in a specific ratio, comprises 1,3-bis(4-aminophenoxy)benzene (134APB) and 2,2-bis[4- (1,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane) (4BDAF), more than one diamine monomer, can be obtained as colorless and transparent The polyimide film having excellent mechanical properties and thermal stability, thereby completing the present invention.

In this case, the one or more monomers containing a group selected from the group consisting of an oxy group, a sulfo group and a fluorine group may be selected from the group consisting of 3,3,4,4-diphenylphosphonium tetracarboxylic acid dianhydride (SO _{2 ).} DPA), 4,4'-oxo phthalic anhydride (ODPA) and more than one dianhydride monomer in 4,4'-(hexafluoroisopropene) diacetic anhydride (6FDA); bis(4-aminobenzene) Hexafluoropropane (33-6F, 44-6F), diaminodiphenyl hydrazine (4DDS, 3DDS), bis(trifluormethyl)-1,1'-biphenyl- 4,4'-diamine, TFDB), bis(aminohydroxyphenyl)hexafluoropropane (DBOH), oxydianiline (ODA), and bis(aminophenoxy)diphenylhydrazine (DBSDA) a diamine monomer; and a mixture of the foregoing.

Further, in order to improve the mechanical properties such as tensile strength and elongation of the polyimide film of the present invention, the diamine monomer must contain a compound selected from 1,3-bis(4-aminophenoxy)benzene ( One or more of 134APB) and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (4BDAF). The content thereof is 10 mol% or less, preferably 2 to 10 mol%, based on the total number of moles of the diamine monomer.

The second one selected from the group consisting of 1,3-bis(4-aminophenoxy)benzene (134APB) and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (4BDAF) When the amine monomer exceeds 10 mol% with respect to the total number of moles, the alignment of the polymer chains is broken, and thus optical characteristics and thermal characteristics are greatly lowered.

Further, the polyimine resin according to the present invention further contains a monomer having a polyfunctional group, so that heat resistance and mechanical properties can be further improved. In this case, the total number of moles of the monomer having a polyfunctional group relative to the dianhydride monomer is 2 mol% or less. When the content is in the above range, the tensile strength can be improved by crosslinking in the polymer chain. Mechanical strength such as elongation.

The polyfunctional group-containing monomer may be selected from the group consisting of hexamethyl hexacarboxylate (HB), diethyl azobenzene-4,4'-dicarboxylate, trimethyl-1,3,5- One or two or more of the group consisting of trimellitic acid and trimethyl-1,2,4-benzenetricarboxylic acid are not limited thereto.

The polyimine resin of the present invention is obtained by dissolving the dianhydride monomer and/or the monomer having a polyfunctional group and a diamine monomer in an organic solvent to prepare a polyaminic acid solution, and then preparing the polyaminic acid solution. Made by hydrazine imidization.

The polymerization reaction conditions are not particularly limited, but a preferred reaction temperature is -20 to 80 ° C, preferably a reaction time of 2 to 48 hours, and further preferably an inert ring of argon or nitrogen during the reaction. Conducted in the environment.

In this case, in the present invention, a solvent may be used in order to carry out a solution polymerization reaction of each monomer, and the solvent is not particularly limited as long as it can dissolve the polyamic acid. Preferably, a solvent selected from the group consisting of m-cresol and N- can be used. Methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl hydrazine (DMSO), acetone, diethylacetate, etc. More than one polar solvent. Further, a low-boiling solvent such as tetrahydrofuran (THF) or chloroform or a low-absorbent solvent such as γ-butyrolactone may be used.

The content of the solvent is not particularly limited, and the solvent is contained in an amount of 50 to 95% by weight, preferably 70 to 90% by weight based on the total polyaminic acid solution, in order to obtain a suitable molecular weight and viscosity of the polyaminic acid solution.

The polyamic acid solution obtained above was subjected to hydrazine imidization to prepare a polyimide resin. In this case, the ruthenium imidation method which can be used can be appropriately selected by using a known ruthenium imidation method, for example, a thermal hydrazylation method, a chemical hydrazylation method or a combination of a hydrazine imidization method and a chemical hydrazine method. Amination method.

The polyimine resin thus prepared has a glass transition temperature of 200 to 400 ° C in consideration of thermal stability.

At the same time, when preparing a polyimide film by using a polyaminic acid solution, a filler may be added to the polyaminic acid solution in order to improve various properties such as slidability, thermal conductivity, electrical conductivity, and corona resistance of the polyimide. . The filler is not particularly limited, but as a preferred example, ceria, titania, layered ceria, carbon nanotubes, alumina, tantalum nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, Mica and so on.

The particle diameter of the above-mentioned filler may be changed depending on the characteristics of the film to be modified and the type of the filler to be added, and is not particularly limited. Usually, the average particle diameter may be 0.001 to 50 μm, preferably 0.005 to 25 μm, more preferably 0.01~10μm. At this time, the modification effect of the polyimide film is easy to appear, and the polyimide film can obtain good surface properties, electrical conductivity, and mechanical properties.

Further, the amount of the filler to be added may be changed depending on the characteristics of the film to be modified or the particle diameter of the filler, and the like, and is not particularly limited. In order not to hinder the combination of polymer resins In the case of the structure, the characteristics of the modification are exhibited, and the content of the filler may be usually 0.001 to 20 parts by weight, preferably 0.002 to 10 parts by weight, per 100 parts by weight of the polyamic acid solution.

The method of adding the filler is not particularly limited, and for example, a method of adding to the polyaminic acid solution before or after the polymerization may be used; after the polymerization of the polyamic acid, a triaxial roll, a high-speed mixer, a rotary mixer, or the like may be used. A method of kneading a filler; a method of mixing a dispersion containing a filler in a polyphthalic acid solution, and the like.

The polyimine film of the present invention can be prepared from the polyamic acid solution obtained above by a known method. For example, a polyaminic acid solution can be formed on a support and then imidized to obtain a film.

The ruthenium imidation method which is suitable at this time may be a combination of a hydrazine imidization method, a chemical hydrazine imidation method or a thermal hydrazylation method and a chemical hydrazylation method. The chemical hydrazine imidation method is a method in which a dehydrating agent and a ruthenium iodide photocatalyst are added to a polyamic acid solution, and a representative example of the dehydrating agent may be an acid anhydride such as acetic anhydride, and a representative example of the imidization catalyst may be an iso quinine. Triamines such as porphyrin, β-picoline, and pyridine. In the case of the thermal imidization method or the combination of the thermal imidization method and the chemical imidization method, the heating conditions of the polyaminic acid solution may be according to the type of the polyaminic acid solution, and the prepared polyamic acid film. The thickness and other adjustments change.

The preparation examples of the polyimine film in combination with the thermal imidization method and the chemical imidization method are specifically described as follows. A dehydrating agent and a ruthenium amide catalyst are added to the polyamid acid solution to form a support. After being heated, it is heated to 80-200 ° C, preferably 100-180 ° C, to activate the dehydrating agent and the ruthenium iodide catalyst. After partial curing and drying, the gel-like poly-proline film is peeled off from the support. The gel-like film was fixed to a support table and heated at 200 to 400 ° C for 5 to 400 seconds to obtain a polyimide film. The gelatinous film can be fixed using a pin frame or a clip frame. As the support, a peeling plate, an aluminum film, a circulating stainless steel belt, a stainless steel drum or the like can be used.

Further, the present invention can produce a polyamidoximine film by the following method from the polylysine solution obtained as described above. That is, after the obtained polyamic acid solution is imidized, the ruthenium solution is added to the second solvent for precipitation, filtration, and drying to obtain a solid component of the polyimide resin, and then The solid component of the obtained polyimine resin was dissolved in a first solvent to obtain a polyamidoximine solution, which was obtained by a film forming procedure.

When the polyamic acid solution is imidized, as described above, a thermal hydrazylation method, a chemical hydrazylation method, or a combination of a thermal hydrazylation method and a chemical hydrazylation method may be used. The above-mentioned examples of the ruthenium imidation method using the thermal hydrazylation method and the chemical hydrazylation method can add a dehydrating agent and a ruthenium amide catalyst to the obtained poly phthalic acid solution, and then at 20 to 180 ° C. The hydrazine imidization is carried out by heating for 1 to 12 hours.

The first solvent may be the same solvent as the organic solvent used in the polymerization of the polyaminic acid solution, and the second solvent may be a solvent having a lower polarity than the first solvent in order to obtain a solid component of the polyimide solvent. One or more selected from the group consisting of water, alcohols, ethers, and ketones can be used. At this time, the content of the second solvent is not particularly limited, and is preferably 5 to 20 times by weight relative to the weight of the polyaminic acid solution.

In view of the boiling point of the second solvent, the solid content of the thus obtained polyiminoimine resin is filtered and dried under the following conditions, preferably at a temperature of 50 to 120 ° C for a period of 30 minutes to 24 hours.

Thereafter, in the film forming process, the polyimine solution in which the solid component is dissolved is formed on the support, and gradually heated in the range of 40 to 400 ° C, and heated for 1 minute to 8 hours to obtain a polyimine. film.

In the embodiment of the present invention, the polyimine film obtained above is subjected to heat treatment again to eliminate thermal history and residual stress remaining in the film, thereby obtaining a film having stable thermal characteristics. At this time, the temperature of the additional heat treatment is preferably 100 to 500 ° C, the heat treatment time is 1 minute to 3 hours, and the residual volatile component after completion of the heat treatment is 5% or less, preferably 3% or less.

The thickness of the polyimide film thus obtained is not particularly limited, but is preferably from 10 to 250 μm, more preferably from 25 to 150 μm.

According to the polyimine film of the present invention, the light transmittance measured at 550 nm is 85% or more and the yellowness is 5 or less based on the film thickness of 50 to 100 μm; according to the thermomechanical analysis method (TMA-Method) at 50 The coefficient of thermal expansion (CTE) measured at ~250 ° C was 45 ppm / ° C.

Further, the polyimine film according to the present invention can satisfy a strip having a tensile strength of 150 MPa or more as measured based on ASTM D882 (film thickness: 50 to 100 μm). Pieces.

The polyimine film according to the present invention is transparent, colorless, and has excellent thermal stability and mechanical properties as described above, and can be effectively applied to a semiconductor insulating film, a TFT-LCD insulating film, a passivation layer, a liquid crystal alignment film, and an optical communication. Materials, solar cell protective films, flexible display substrates, and many other fields.

The invention will be further illustrated by the following examples, but the scope of the invention is not limited to the following examples.

[Example 1]

The reactor was purged with nitrogen using a 1 L reactor equipped with a stirrer, a nitrogen injection device, a titration funnel, a temperature regulator and a cooler. 556 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. After adding 62.12 g (0.194 mol) of TFDB and stirring for 1 hour to dissolve it, after adding 1.75 g (0.006 mol) of 134APB to dissolve it, the solution temperature was maintained at 25 °C. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyamic acid solution, and the mixture was stirred for 30 minutes, and then stirred at 80 ° C for 2 hours. After cooling to room temperature, a polyimine resin was obtained, which was slowly poured. Precipitation was carried out in a container containing 20 L of methanol, and the solid component of the precipitated polyimine resin was filtered and pulverized, and then vacuum dried at 80 ° C for 6 hours to obtain 120 g of a solid powder (glass transition temperature of 339 ° C). It was again dissolved in 680 g of N,N-dimethylacetamide (DMAc) to give a 20% by weight solution (viscosity 1800 poise).

The solution obtained above was applied to a stainless steel plate, molded at a thickness of 300 μm, dried by hot air at 80 ° C for 30 minutes, and heated again to 120 ° C for 30 minutes. The film was peeled off from the stainless steel plate and fixed to the frame with a needle. on. The frame of the fixed film was placed in a hot air oven and slowly heated from 120 ° C to 300 ° C for 2 hours at a rate of 3 ° C/min, and then slowly cooled, and the film was peeled off from the frame to obtain a polyimide film. . Then, a final heat treatment procedure was carried out, and the polyimine film prepared above was heat-treated at 300 ° C for 30 minutes.

[Embodiment 2]

The reactor was purged with nitrogen using a 1 L reactor equipped with a stirrer, a nitrogen sparging device, a titration funnel, a temperature regulator and a cooler. 551 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. 60.84 g (0.19 mol) of TFDB was added and dissolved by stirring for 1 hour, and after adding 2.92 g (0.01 mol) of 134APB to dissolve it, the solution temperature was maintained at 25 °C. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid content of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide resin (glass transition temperature of 330 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Example 3]

The reactor was purged with nitrogen using a 1 L reactor equipped with a stirrer, a nitrogen sparging device, a titration funnel, a temperature regulator and a cooler. 537 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. After adding 57.64 g (0.18 mol) of TFDB and stirring for 1 hour to dissolve, after adding 5.85 g (0.02 mol) of 134APB to dissolve it, the solution temperature was maintained at 25 °C. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide resin (glass transition temperature of 317 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Example 4]

The reactor was purged with nitrogen using a 1 L reactor equipped with a stirrer, a nitrogen sparging device, a titration funnel, a temperature regulator and a cooler. 537 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. After adding 54.44 g (0.17 mol) of TFDB and stirring for 1 hour to dissolve, after adding 8.78 g (0.03 mol) of 134APB to dissolve it, the solution temperature was maintained at 25 °C. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide resin (glass transition temperature of 310 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Example 5]

The reactor was purged with nitrogen using a 1 L reactor equipped with a stirrer, a nitrogen sparging device, a titration funnel, a temperature regulator and a cooler. 537 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. After 51.24 g (0.16 mol) of TFDB was added and stirred for 1 hour to dissolve, 11.7 g (0.04 mol) of 134APB was further added to dissolve it, and the solution temperature was maintained at 25 °C. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide resin (glass transition temperature of 307 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Embodiment 6]

The reactor was purged with nitrogen using a 1 L reactor equipped with a stirrer, a nitrogen sparging device, a titration funnel, a temperature regulator and a cooler. 537 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. After adding 44.83 g (0.14 mol) of TFDB and stirring for 1 hour to dissolve it, after adding 17.55 g (0.06 mol) of 134APB to dissolve it, the solution temperature was maintained at 25 °C. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

Adding 31.64 g of pyridine and 40.8 g of acetic anhydride to the above polyimine solution, Then, a solid powder of a polyimide resin (glass transition temperature of 302 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Embodiment 7]

The reactor was purged with nitrogen using a 1 L reactor equipped with a stirrer, a nitrogen injection device, a titration funnel, a temperature regulator and a cooler. 568 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. After adding 62.12 g (0.194 mol) of TFDB and stirring for 1 hour to dissolve it, after adding 3.11 g (0.006 mol) of 4BDAF to dissolve it, the solution temperature was maintained at 25 °C. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide pigment (glass transition temperature of 342 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Embodiment 8]

The reactor was purged with nitrogen using a 1 L reactor equipped with a stirrer, a nitrogen injection device, a titration funnel, a temperature regulator and a cooler. 571 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. After adding 60.84 g (0.19 mol) of TFDB and stirring for 1 hour to dissolve it, after adding 5.18 g (0.01 mol) of 4BDAF to dissolve it, the solution temperature was maintained at 25 °C. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide resin (glass transition temperature of 336 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Embodiment 9]

The reactor was operated using a 1 L reactor equipped with a stirrer, a nitrogen injection device, a titration funnel, a temperature regulator and a cooler, and nitrogen gas was added thereto, and 579 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. After adding 57.64 g (0.18 mol) of TFDB and stirring for 1 hour to dissolve it, after adding 10.37 g (0.02 mol) of 4BDAF to dissolve it, the solution temperature was maintained at 25 °C. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide resin (glass transition temperature of 329 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Embodiment 10]

The reactor was operated using a 1 L reactor equipped with a stirrer, a nitrogen injection device, a titration funnel, a temperature regulator and a cooler, and nitrogen gas was added thereto, and 579 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. After adding 54.44 g (0.17 mol) of TFDB and stirring for 1 hour to dissolve it, after adding 15.55 g (0.03 mol) of 4BDAF to dissolve it, the solution temperature was maintained at 25 °C. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide resin (glass transition temperature of 327 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Example 11]

The reactor was operated using a 1 L reactor equipped with a stirrer, a nitrogen injection device, a titration funnel, a temperature regulator and a cooler, and nitrogen gas was added thereto, and 579 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. After adding 51.24 g (0.16 mol) of TFDB and stirring for 1 hour to dissolve it, after adding 20.73 g (0.04 mol) of 4BDAF to dissolve it, the solution temperature was maintained at 25 °C. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide resin (glass transition temperature of 323 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Embodiment 12]

The reactor was operated using a 1 L reactor equipped with a stirrer, a nitrogen injection device, a titration funnel, a temperature regulator and a cooler, and nitrogen gas was added thereto, and 579 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. After adding 44.83 g (0.14 mol) of TFDB and stirring for 1 hour to dissolve, 31.10 g (0.06 mol) of 4BDAF was added and dissolved, and the solution temperature was maintained at 25 °C. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide pigment (glass transition temperature of 315 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Example 13]

The reactor was purged with nitrogen using a 1 L reactor equipped with a stirrer, a nitrogen sparging device, a titration funnel, a temperature regulator and a cooler. 551 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. After adding 60.84 g (0.19 mol) of TFDB and stirring for 1 hour to dissolve it, after adding 2.92 g (0.01 mol) of 134APB to dissolve it, the solution temperature was maintained at 25 °C. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 51.53 g (0.116 mol) of 6FDA was added, and after completely stirring for 3 hours, 1.71 g (0.004 mol) of hexamethylbenzene hexacarboxylate (hereinafter referred to as HB) was added and stirred for 24 hours to obtain a solid concentration of 20% by weight of a polyaminic acid solution.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide resin (glass transition temperature of 330 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Embodiment 14]

The reactor was purged with nitrogen using a 1 L reactor equipped with a stirrer, a nitrogen injection device, a titration funnel, a temperature regulator and a cooler. 571 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. After adding 60.84 g (0.19 mol) of TFDB and stirring for 1 hour to dissolve it, after adding 5.18 g (0.01 mol) of 4BDAF to dissolve it, the solution temperature was maintained at 25 °C. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 51.53 g (0.116 mol) of 6FDA was added, and after completely stirring for 3 hours, 1.71 g (0.004 mol) of hexamethylbenzene hexacarboxylate (hereinafter referred to as HB) was added and stirred for 24 hours to obtain a solid concentration of 20% by weight of a polyaminic acid solution.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide resin (glass transition temperature of 335 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Comparative Example 1]

The reactor was purged with nitrogen using a 1 L reactor equipped with a stirrer, a nitrogen injection device, a titration funnel, a temperature regulator and a cooler. 563 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. 64.05 g (0.2 mol) of TFDB was added and stirred for 1 hour to dissolve. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide pigment (glass transition temperature of 340 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Comparative Example 2]

The reactor was purged with nitrogen using a 1 L reactor equipped with a stirrer, a nitrogen injection device, a titration funnel, a temperature regulator and a cooler. 541 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. 58.46 g (0.2 mol) of 134APB was added and stirred for 1 hour to dissolve. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide resin (glass transition temperature of 280 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Comparative Example 3]

The reactor was purged with nitrogen using a 1 L reactor equipped with a stirrer, a nitrogen injection device, a titration funnel, a temperature regulator and a cooler. 722 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. 103.69 g (0.2 mol) of 4BDAF was added and stirred for 1 hour to dissolve. Thereafter, 28.66g (0.08 mole) SO ₂ DPA, stirred for 3 hours to completely dissolve SO ₂ DPA. At this point the solution temperature was maintained at 25 °C. Then, 53.31 g (0.12 mol) of 6FDA was added, and the reaction was stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide pigment (glass transition temperature of 302 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

[Comparative Example 4]

The reactor was purged with nitrogen using a 1 L reactor equipped with a stirrer, a nitrogen injection device, a titration funnel, a temperature regulator and a cooler. 611 g of N,N-dimethylacetamide (DMAc) was added to adjust the reactor temperature. Maintain at 25 ° C. After adding 64.046 g (0.2 mol) of TFDB and stirring for 1 hour to dissolve it, 87.07 g (0.196 mol) of 6FDA was added, and the mixture was stirred for 3 hours to completely dissolve, and the solution temperature was maintained at 25 °C. Thereafter, 1.71 g (0.004 mol) of hexamethylbenzene hexacarboxylate was added and stirred for 24 hours to obtain a polyglycine solution having a solid concentration of 20% by weight.

31.64 g of pyridine and 40.8 g of acetic anhydride were added to the above polyimine solution, and then a solid powder of a polyimide resin (glass transition temperature of 350 ° C) and a polyimide film were prepared in the same manner as in the above Example 1.

Physical property evaluation method

(1) Light transmittance

The light transmittance of the films prepared in the respective examples and comparative examples was measured at 550 nm using a UV spectrophotometer (Varian Co., Cary 100).

(2) Yellowness

The yellowness was measured using a UV spectrophotometer (Varian, Cary 100) in accordance with ASTM E313.

(3) Thermal expansion coefficient (CTE)

The coefficient of thermal expansion was measured at 50 to 250 ° C using TMA (Perkin Elmer, Diamond TMA) according to the TMA-Method three times of the first to third tests. When the deviation between the first and second test measurement values is within 5% in addition to the measured value of the first test, the average value of the two values is obtained. At this time, the coefficient of thermal expansion was measured to be 0.1 N, and it was measured at a temperature elevation rate of 10 ° C/min after being stabilized at 40 ° C. The polyimide film sample was measured in a size of 4 mm × 25 mm.

(4) Determination of tensile strength and elongation

Tensile strength (MPa) and elongation (%) were measured at a tensile speed of 50 mm/min according to the ASTM D882 standard.

As shown in Table 1, Examples 1 to 14 were superior in mechanical properties and thermal stability as compared with Comparative Examples 1 to 4, and in particular, when the content of 134APB or 4BDAF was within a certain range, it was confirmed that colorless transparency was obtained. The optical properties also have excellent results.

It is to be understood that a person skilled in the art can easily implement the invention insofar as it is within the scope of the invention.

Claims (8)

A polyimine resin comprising bis(trifluormethyl)-1,1'-biphenyl-4,4'-diamine, TFDB a quinone imine compound obtained by copolymerizing a diamine monomer and a polymerization component containing a dianhydride monomer of 4,4'-(hexafluoroisopropene) dinonanhydride (6FDA), the diamine monomer and At least one of the dianhydride monomers is one or more monomers comprising a group selected from the group consisting of an oxy group, a sulfo group, and a fluorine group, the diamine monomer comprising a group selected from the group consisting of 1,3-bis (4- Aminophenoxy)benzene (1,3-bis(4-aminophenoxy)benzene) and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (2,2-bis[4 -(4-aminophenoxy)phenyl]hexafluoropropane), one or more of the group consisting of 1,3-bis(4-aminophenoxy)benzene And one or more of the group consisting of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane The total number of moles of the diamine monomer relative to the diamine monomer is 2 to 5 mol%. The polyimine resin according to claim 1, wherein the diamine monomer comprises at least one monomer containing at least one selected from the group consisting of an oxy group, a sulfo group and a fluorine group. The dianhydride-based monomer contains at least one monomer containing at least one selected from the group consisting of an oxy group, a sulfo group, and a fluorine group. The polyimine resin according to claim 1, wherein the monomer containing one or more selected from the group consisting of an oxy group, a sulfo group and a fluorine group is selected from the group consisting of 3,3,4,4-diphenyl. More than one dianhydride in tetracarboxylic acid dianhydride (SO ₂ DPA), 4,4′-oxo phthalic anhydride (ODPA) and 4,4′-(hexafluoroisopropene) diphthalic anhydride (6FDA) Monomers; bis(4-aminophenyl)hexafluoropropane (33-6F, 44-6F), diaminodiphenylhydrazine (4DDS, 3DDS), bis(trifluoromethyl)diaminobiphenyl (bis) Trifluormethyl)-1,1'-biphenyl-4,4'-diamine,TFDB), bis(aminohydroxyphenyl)hexafluoropropane (DBOH), oxydianiline (ODA) and bis(aminophenoxy) More than one diamine monomer in diphenylguanidine (DBSDA); and a group consisting of a mixture of the two. A polyimine film comprising the polyimine resin as described in claim 1 of the patent application. The polyimine film according to claim 4, wherein the polyimide film is When the thickness is 50 to 100 μm, the light transmittance at 550 nm is 85% or more and the thermal expansion coefficient (CTE) at 50 to 250 ° C is 45 ppm/° C. or less by a UV spectrophotometer. The polyimine film according to claim 4, wherein the polyimide film has a yellowness of 5 or less based on a thickness of 50 to 100 μm. The polyimine film according to claim 4, wherein the polyimide film has a tensile strength of 150 MPa as measured based on ASTM D882 (film thickness: 50 to 100 μm). A substrate for a display element comprising the polyimide film according to item 4 of the patent application.