TWI670329B - Composition for forming polyimide, polyimide and polyimide film - Google Patents

Abstract

A composition for forming a polyimine, comprising a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent. The diamine monomer component comprises from 20 moles to 65 mole parts of 4,4'-diaminodiphenyl ether (ODA; 4,4'-diaminodiphenyl ether), from 30 moles to 70 moles. From the compound of formula (I) and from 1 mole to 10 moles of melamine: Wherein the sum of x and z is from 1 to 20 and y is from 4 to 50.

Description

Composition for forming polyimine, polyimine, and polyimide film

The present invention relates to a composition, and more particularly to a composition for forming a polyimine, a polyimine prepared from the composition, and a polyimine prepared from the polyimide. Polyimine film.

In general, polyimide (PI) is a polymer material obtained by a polycondensation reaction of a diamine monomer and a dianhydride monomer. At present, polyimine has been widely used in various industries due to its chemical stability, electrical properties and thermal stability, such as semiconductor industry, optoelectronic industry, aviation materials, biomedical materials, textile industry, and construction. In the automotive industry, communications materials, machinery industry or film industry, it has become an indispensable material in life. In order to further enhance the applicability of polyimine, the research of novel polyimines by those skilled in the art continues to be developing.

The present invention provides a composition for forming a polyimine which can produce a polyimide or polyimide film having heat resistance and elasticity.

The composition for forming a polyimine of the present invention includes a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent. The diamine monomer component comprises from 20 moles to 65 mole parts of 4,4'-diaminodiphenyl ether (ODA; 4,4'-diaminodiphenyl ether), from 30 moles to 70 moles. From the compound of formula (I) and from 1 mole to 10 moles of melamine: Formula (I) wherein the sum of x and z is from 1 to 20 and y is from 4 to 50.

In one embodiment of the present invention, the above tetracarboxylic dianhydride monomer component includes an aromatic tetracarboxylic dianhydride.

In one embodiment of the invention, the diamine monomer component comprises from 25 moles to 65 mole parts of 4,4'-diaminodiphenyl ether, from 30 moles to 70 moles. From the compound of formula (I), and from 1 mole to 10 moles of melamine.

In one embodiment of the present invention, the tetracarboxylic dianhydride monomer component is 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride (ODPA; 3, 4, 3', 4' -oxydiphthalic anhydride).

In one embodiment of the invention, the diamine monomer component comprises from 20 moles to 45 mole parts of 4,4'-diaminodiphenyl ether, from 50 moles to 70 moles. From the compound of formula (I), and from 5 moles to 10 moles of melamine.

In one embodiment of the invention, the tetracarboxylic dianhydride monomer component is pyromellitic dianhydride (PMDA; pyromellitic dianhydride).

In one embodiment of the invention, the diamine monomer component comprises from 25 moles to 45 mole parts of 4,4'-diaminodiphenyl ether, from 50 moles to 70 moles. From the compound of formula (I), and from 5 moles to 10 moles of melamine.

In one embodiment of the present invention, the above tetracarboxylic dianhydride monomer component is 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA; 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride).

In an embodiment of the invention, the diamine monomer component further comprises a decane diamine.

In an embodiment of the invention, the above-mentioned oxoxane diamine comprises a compound represented by the formula (II): Formula (II) wherein n is from 8 to 11.

In one embodiment of the invention, the diamine monomer component comprises from 35 moles to 45 mole parts of 4,4'-diaminodiphenyl ether, from 40 moles to 50 moles. From the compound of formula (I), from 5 moles to 10 moles of melamine, and from 5 moles to 10 moles of oxime diamine.

The polyimine of the present invention is produced from the composition for forming a polyimine as described above.

The polyimine membrane of the present invention is produced from the polyimine as described above.

Based on the above, the composition for forming a polythenimine of the present invention comprises a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent, wherein the diamine monomer component includes a content in a specific range. The 4,4'-diaminodiphenyl ether in the form, the compound represented by the formula (I), and melamine may have good film formability. As a result, a polyimide film having excellent material properties can be obtained by the composition for forming a polyimide of the present invention. Further, the composition for forming a polyimine according to the present invention includes a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent, wherein the diamine monomer component includes a content within a specific range. The 4,4'-diaminodiphenyl ether, the compound represented by the formula (I) and the melamine can thereby produce a polyimide or polyimide film having heat resistance and elasticity. In addition, the composition for forming a polyimine of the present invention is more permeable to a specific range of oxoxane diamine to have good film formability, thereby being made into heat resistance and elasticity. Polyimine film.

The above described features and advantages of the present invention will be more apparent from the following description.

In the present specification, the range represented by "a value to another value" is a schematic representation that avoids enumerating all the values in the range in the specification. Therefore, the recitation of a particular range of values is intended to include any value in the range of values and the range of values defined by any value in the range of values, as in the specification. The scope is the same.

One embodiment of the present invention provides a composition for forming a polyimine comprising a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent. In the present embodiment, the ratio of the total molar percentage of the diamine monomer component to the total molar percentage of the tetracarboxylic dianhydride monomer component is 1:0.95 to 1:1.05.

In the present embodiment, the diamine monomer component includes 4,4'-diaminodiphenyl ether (ODA; 4,4'-diaminodiphenyl ether), a compound represented by the formula (I), and melamine. : Formula (I) wherein the sum of x and z is from 1 to 20 and y is from 4 to 50. That is, in the present embodiment, the diamine monomer component includes three diamine monomers. Further, the compound represented by the formula (I) has an amine hydrogen equivalent weight of from 250 to 270 and a number average molecular weight of about 1,000.

In addition, in the present embodiment, the diamine monomer component comprises from 20 moles to 65 mole parts of 4,4'-diaminodiphenyl ether, from 30 moles to 70 moles of formula ( The compound shown in I), and 1 mole to 10 mole parts of melamine. If the molar component of 4,4'-diaminodiphenyl ether, at least one of the compound represented by the formula (I) and the melamine does not fall within the above range, the composition for forming the polyimine The material is not film-forming.

In the present embodiment, the tetracarboxylic dianhydride monomer component includes an aromatic tetracarboxylic dianhydride. Specifically, examples of the aromatic-containing tetracarboxylic dianhydride include, but are not limited to, 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride (ODPA; 3, 4, 3', 4'- Oxydiphthalic anhydride), pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA; 3,3',4,4'-biphenyltetracarboxylic dianhydride) , 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-di Benzophenone tetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylate Acid dianhydride (DSDA; 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA; 2 ,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane), bis(2,3-dicarboxyphenyl)ruthenic anhydride, bis(3,4-dicarboxyphenyl)ruthenium anhydride or Glycol trimellitic acid dianhydride (TMEG; ethylene glycol bis (4-tri Mellitate anhydride)), and preferably 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride, pyromellitic dianhydride Or 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA).

On the other hand, in the present embodiment, the tetracarboxylic dianhydride monomer component includes a tetracarboxylic dianhydride monomer. For example, in one embodiment, the tetracarboxylic dianhydride monomer component is 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride (ODPA), and at this point, the diamine monomer group The fraction comprises 25 moles to 65 mole parts of 4,4'-diaminodiphenyl ether, 30 moles to 70 moles of the compound of formula (I), and 1 mole to 10 moles of melamine, and the composition used to form the polyimine has good film forming properties. In another embodiment, in one embodiment, the tetracarboxylic dianhydride monomer component is pyromellitic dianhydride (PMDA), and at this point, the diamine monomer component comprises from 20 moles to 45 moles. 4,4'-diaminodiphenyl ether of the ear, 50 moles to 70 moles of the compound of formula (I), and 5 moles to 10 moles of melamine, and The composition for forming a polyimine has good film formability. In another embodiment, in one embodiment, the tetracarboxylic dianhydride monomer component is 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and at this time, the diamine single The body component comprises from 25 moles to 45 moles of 4,4'-diaminodiphenyl ether, from 50 moles to 70 moles of the compound of formula (I), and 5 moles The melamine is 10 parts by mole, and the composition for forming the polyimine has good film formability.

Further, from the viewpoint of enhancing the elasticity of the polyimide, the diamine monomer component may further include a decane diamine. Specifically, examples of the oxane diamine include, but are not limited to, a compound represented by the following formula (II), Formula (II) wherein n is from 8 to 11. In one embodiment, the diamine monomer component comprises from 35 moles to 45 mole parts of 4,4'-diaminodiphenyl ether, from 40 moles to 50 moles of formula (I) The compound shown, 5 moles to 10 mole parts of melamine, and 5 moles to 10 mole parts of oxane diamine.

In the present embodiment, the solvent is not particularly limited as long as it can dissolve the tetracarboxylic dianhydride monomer component and the diamine monomer component. Specifically, examples of the solvent include, but are not limited to, N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF). , N, N'-diethylacetamide, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, trimethylamine hexamethylphosphate, etc. a guanamine solvent; a urea solvent such as tetramethylurea or N,N-dimethylethylurea; an hydrazine or anthraquinone solvent such as dimethyl hydrazine, diphenyl hydrazine or tetramethyl hydrazine; chloroform; Halogenated alkyl solvent such as dichloromethane; aromatic hydrocarbon solvent such as benzene or toluene; phenolic solvent such as phenol or cresol; or tetrahydrofuran, 1,3-dioxolane, dimethyl ether, diethyl ether, and para An ether solvent such as phenol methyl ether. The above solvents may be used singly or in combination of two or more. In order to improve the solubility and reactivity of the tetracarboxylic dianhydride monomer component and the diamine monomer component, the solvent is preferably a guanamine solvent such as DMAc, DMF or NMP.

It should be noted that, as described above, in the present embodiment, the permeation includes a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent, wherein the diamine monomer component includes a content within a specific range. 4,4'-diaminodiphenyl ether, a compound represented by the formula (I), and melamine, whereby a composition for forming a polyimine can have good film formability.

Another embodiment of the present invention provides a polyimine which is produced from the composition for forming a polyimine in any of the foregoing embodiments. The related description of the diamine monomer component, the tetracarboxylic dianhydride monomer component and the solvent in the composition for forming the polyimine has been described in detail in the foregoing embodiments, and thus will not be described herein. .

In detail, in the present embodiment, the polyimine is prepared by subjecting a diamine monomer component and a tetracarboxylic dianhydride monomer component to a condensation polymerization reaction in a solvent. In one embodiment, the polyimine can be prepared using three diamine monomers and one tetracarboxylic dianhydride monomer. In another embodiment, the polyimine can be prepared using four diamine monomers and one tetracarboxylic dianhydride monomer. It should be noted that since the diamine monomer and the tetracarboxylic dianhydride monomer react to produce polyimine, the total mole number of the amino group in the diamine monomer and the anhydride in the tetracarboxylic dianhydride monomer The ratio of the total number of moles of the base is about 1:1. In more detail, the ratio may be between 1:0.95 and 1:1.05.

Further, in the present embodiment, the polyimine is prepared, for example, by a thermal cyclization method or a chemical cyclization method. The thermal cyclization method and the chemical cyclization method can each be carried out by any step known to those skilled in the art. For example, the preparation of polyimine by thermal cyclization includes the steps of: heating a poly-proline solution to form a hydrazine solution after polymerization is carried out using a composition that forms a polyimine to form a polyaminic acid solution. The imidization reaction (ie, the dehydration cyclization reaction) forms a polyimine. In detail, the preparation method for forming a polyimine is, for example, a diamine monomer component and a tetracarboxylic dianhydride monomer component in a temperature range of 5 ^o C to 40 ^o C Mix well in the solvent. The method of mixing is not particularly limited as long as the diamine monomer component and the tetracarboxylic dianhydride monomer component are uniformly mixed in a solvent. In one embodiment, the step of forming polyamide acid solution, the reaction temperature is between, for example, between 5 ^o C to 40 ^o C; the reaction time is, for example, between 3-12 hours. In one embodiment, the conditional acyl imidization reaction are, for example, 1-2 hours at ambient temperature 100 ^o C, 150 ^o C and 220 ^o C in.

In another example, the preparation of the polyimine by chemical cyclization includes the steps of: using a composition to form a polyimine to carry out a polymerization reaction to form a polyaminic acid solution, and then dehydrating the agent with the quinone The agent is added to the polyaminic acid solution to carry out the oxime imidization reaction (ie, dehydration cyclization reaction) to form a polyimine. In detail, the preparation method for forming a polyimine is, for example, a diamine monomer component and a tetracarboxylic dianhydride monomer component in a temperature range of 5 ^o C to 40 ^o C Mix well in the solvent. The method of mixing is not particularly limited as long as the diamine monomer component and the tetracarboxylic dianhydride monomer component are uniformly mixed in a solvent. In one embodiment, the step of forming polyamide acid solution, the reaction temperature is between, for example, between 5 ^o C to 40 ^o C; the reaction time is, for example, between 3-12 hours. In one embodiment, the conditional acyl imidization reaction at a temperature, for example, 120 ^o C environment for 2 hours to 5 hours, preferably 3 hours. In one embodiment, examples of the dehydrating agent include, but are not limited to, acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride or trifluoroacetic anhydride; examples of guanidine imidizing agents include, but are not limited to, pyridine, methyl Pyridine, quinoline or isoquinoline. In one embodiment, the amount of the dehydrating agent added is, for example, 0.5 to 10.0 times the molar equivalent of the guanamine group of the polyaminic acid, and the amount of the sulfiminating agent added is, for example, 0.5 to 5.0 times the molar amount. equivalent.

It is to be noted that, as described above, in the present embodiment, since the composition for forming the polyimine is permeated through the monomer component including the tetracarboxylic dianhydride, the content including 4, 4' in a specific range is respectively included. -diaminodiphenyl ether, a compound represented by the formula (I) and a diamine monomer component of melamine and a solvent, which have good film formability, and thus are composed of a composition for forming a polyimine The obtained polyimine can form a film having excellent material properties.

On the other hand, the composition for forming the polyimine comprises a tetracarboxylic dianhydride monomer component, and 4,4'-diaminodiphenyl ether having a content within a specific range, respectively, The compound shown and the diamine monomer component of the melamine and the solvent, whereby the polyimide also has excellent film formability, and the formed film is more resistant to heat and elasticity. As a result, the applicability and commercial value of the polyimine of the present invention in various industries are greatly improved.

Further, the polyimine may be blended with the additive as needed to further increase the applicability and commercial value of the polyimine in a range that does not impair the essential effects of the polyimine of the present invention. The additive includes, for example, a conductive material, a flame retardant, a colorant, a filler, or a combination thereof. For example, in order to impart conductivity to the polyimide, in order to meet the industrial requirements for conductivity, the polyimide may be blended with a conductive material, for example, including graphene, carbon nanotubes, nano silver, A nano silver wire or a conductive polymer; a method of blending, for example, comprising directly mixing a polyimide with a conductive material, or a composition for forming a polyimide, further comprising a conductive material.

Further, as described above, although the composition for forming a polyimide may have good film formability so that the polyimide produced therefrom can form a film, the polyimine of the present invention can also A form such as a powder or a solution exists.

Another embodiment of the present invention provides a polyimine film produced by the polyamidene of any of the foregoing embodiments. The related description of polyimine has been described in detail in the foregoing embodiments, and thus will not be described again. In the present embodiment, the thickness of the polyimide film varies depending on the application, and generally, the thickness is about 15 μm to 200 μm, preferably 15 μm to 100 μm.

Further, in the present embodiment, the polyimide film can be prepared by any method known to those skilled in the art. For example, in one embodiment, a polyimide film can be formed by solution casting a polyimine. As another example, in an embodiment, referring to the foregoing method for preparing a polyimine, the preparation method of the polyimide film may include: after forming the polyamic acid solution, the polyamine is passed through a coating process. The acid solution is applied to a substrate and then subjected to a hydrazine imidization reaction. In detail, the coating process can be carried out by any coating method known to those skilled in the art, such as blade coating, spin coating, pneumatic blade coating, and slit coating. , extrusion coating or roller coating; depending on the application, the substrate can be any suitable substrate, such as fabric, copper foil, glass, Teflon or plastic substrates.

It should be noted that, as described above, in the present embodiment, the composition for forming the polyimine comprises a tetracarboxylic dianhydride monomer component, and the content of 4, 4' including the content within a specific range. - Diaminodiphenyl ether, a compound represented by the formula (I) and a diamine monomer component of melamine, and a solvent, whereby the polyimide film can have excellent heat resistance and elasticity. As a result, the applicability and commercial value of the polyimide film of the present invention in various industries are greatly improved.

Further, as described above, in order to meet the requirements of conductivity, the polyimine of the present invention may be blended with a conductive material, and formed thereby, without impairing the essential effects of the polyimine of the present invention. The polyimide film can have electrical conductivity. In one embodiment, the conductive polyimide film can be formed, for example, by mixing a polyimide and a conductive material, followed by a solution casting method. In another embodiment, the conductive polyimide film can be formed, for example, by adding a conductive material to the polyamic acid solution and uniformly mixing, and then applying the mixed solution to the coating process through a coating process. The substrate is then subjected to a hydrazine imidization reaction. It is worth mentioning that the conductive polyimide film can be applied to, for example, a smart fabric (for example, a heartbeat belt, a body smart glove), a stretch display device, or the like because of its excellent film quality, heat resistance and elasticity. Smart wearable components such as surface electronic patch systems or electronic skin.

Features of the present invention will be described more specifically below with reference to Examples 1-25. Although the following Examples 1-25 are described, the materials used, the amounts and ratios thereof, the processing details, the processing flow, and the like can be appropriately changed without departing from the scope of the present invention. Therefore, the invention should not be construed restrictively by the examples described below. In particular, since the diamine monomer and the tetracarboxylic dianhydride monomer will react to produce a polyimine, and the total mole number of the amino group in the diamine monomer component and the tetracarboxylic dianhydride monomer component The ratio of the total number of moles of the anhydride group is about 1:1, so it is known that the molar content of the tetracarboxylic dianhydride monomer should be the equilibrium of the total moles of the amino groups in the diamine monomer component. The latter result, and the ratio can be between 0.95:1 and 1.05:1.

Information on the main materials used in the preparation of the polyimide film of Examples 1 to 25 is as follows.

Diamine monomer component: 4,4'-diaminodiphenyl ether (hereinafter referred to as ODA): purchased from Sigma-Aldrich; compound represented by formula (I): product name RT-1000, purchased from Huntsman Ltd.; melamine: purchased from Sigma Oric; dioxane diamine: purchased from Scientific Polymer Products, Inc.

Tetracarboxylic dianhydride monomer component: 3,4,3',4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA): purchased from Sigma Oric Company; pyromellitic dianhydride (hereinafter referred to as PMDA): purchased from Sigma Oric; 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter referred to as BPDA): purchased from Sigma Oric.

Dehydrating agent: Acetic anhydride: purchased from Sigma Oric.

Anthraquinone: Pyridine: purchased from Sigma Oric.

Conductive material: Graphene: Obtained from the Institute of Textile Industry Research (TTRI). Example 1

First, high purity nitrogen was passed through a 150 mL three-necked flask to keep the bottle dry. Next, 49 moles of ODA, 50 moles of RT-1000, 1 mole of melamine, and 25 mL of DMAc (as a solvent) were added to the three-necked flask at room temperature, and mixed well. Thereafter, 100.5 parts of ODPA of ODPA was added to the above mixed solution at room temperature, and the reaction was continued under nitrogen for 12 hours to form a polyamine solution having a solid content of 35%. Subsequently, 20 mL of acetic anhydride and 10 mL of pyridine was added a solution of polyamide acid, and acyl imidization 3 hours at 120 ^o C. After the reaction was completed, the resulting mixed solution was cooled to room temperature. Next, the obtained mixed solution was slowly poured into a large amount of methanol which was stirred, and then filtered to obtain a solid portion. Thereafter, the obtained solid was washed with methanol and dried at 120 ° C for 2 hours to obtain the polyimine of Example 1. Next, the polyimine of Example 1 was dissolved in an appropriate amount of DMAc to form a polyimine solution. Thereafter, the polyimide solution was cast on a glass plate and baked for 3 hours at 80 ^o C, to obtain a polyimide film of Example Embodiment 1. Example 2-14

The polyimine films of Examples 2-14 were prepared according to a preparation procedure similar to that of Example 1, and the ingredients shown in Table 1 and their moles. Example 15

The polyimine film of Example 15 was prepared according to a preparation procedure similar to that of Example 1, and the components shown in Table 1 and their addition ratios, but the difference was mainly in the following steps: In the preparation of Example 15, After the polyimide, the polyimine of Example 15 was dissolved in 15 mL of NMP together with 5 wt% of graphene, and then cast on a glass plate. Example 16-19

The polyimine films of Examples 16-19 were prepared according to a preparation procedure similar to that of Example 15, and the ingredients shown in Table 1 and their addition ratios. Example 20

The polyimine film of Example 20 was prepared according to a preparation procedure similar to that of Example 1, and the components shown in Table 1 and their addition ratios, but the difference mainly lies in the following steps: In Example 20, ODA, RT-1000, melamine, and decane diamine were added together in DMAc; while in Example 1, no decane diamine was used. Example 21-22

The polyimine films of Examples 21-22 were prepared according to a preparation procedure similar to that of Example 20, and the ingredients shown in Table 1 and their addition ratios. Example 23

The polyimide film of Example 23 was prepared according to a preparation procedure similar to that of Example 20, and the components shown in Table 1 and their addition ratios, but the difference was mainly in the following steps: In the preparation of Example 23 After the polyimide, the polyimine of Example 23 was dissolved in 15 mL of NMP together with 16.7 wt% of graphene, and then cast on a glass plate. Further, the polyimide film of Example 23 had a thickness of 100 μm. Example 24-25

The polyimide film of Examples 24-25 was prepared according to a preparation procedure similar to that of Example 23, and the components shown in Table 1 and their addition ratios, wherein the thickness of the polyimide film of Example 24 was The polyimide film of Example 25 had a thickness of 100 μm at 25 μm. Table 1 a: calculated by the molar transmission of the diamine monomer component used; b: 100% based on the total weight of the polyimine, Table 1 (continued) a: calculated by the molar transmission of the diamine monomer component used; b: 100% based on the total weight of the polyimine, Table 1 (continued) a: calculated by the molar transmission of the diamine monomer component used; b: 100% based on the total weight of the polyimine

Thereafter, the filming properties of the polyimine films of Examples 1 to 25 were evaluated, respectively, and the polyimine films of Examples 1-6, 9-14, 20, and 22 were subjected to a 5% heat loss temperature. (T _{d 5%} ), 10% thermogravimetric loss temperature (T _d10% ), the residual weight ratio of 800 ° C to the polyimine film of Examples 1-6, 9-14, respectively (R _w800 ) The measurements of the glass transition temperature (T _g ) of the polyimide films of Examples 3, 10, 12, and 20-22 were respectively measured for Examples 3, 10, 12, and 20, respectively. The tensile strength of the polyimide film of -21 was measured for tensile strength and elongation at break, and the storage modulus of the polyimide film of Examples 10 and 20 was respectively performed. The surface resistivity of the polyimide films of Examples 15-19 and 23-25 was measured and measured. The description of each of the above measurement items is as follows, and the evaluation or measurement results are shown in Table 2. <Evaluation of film formation property>

The polyimine films of Examples 1-25 were observed by optical observation and optical microscopy respectively, and were classified into three types according to the actual situation: intact, damaged and incapable of forming. < Measurement of T _d5% , T _d10% and R _w800 >

The T _d5% and T _{d10% of the} polyimine of Examples 1-6, 9-14, 20, and 22 were measured by thermogravimetric analysis (TGA), respectively, and were measured by thermogravimetric analysis (TGA). R _{w800 of the} polyimine of Examples 1-6, _9-14 . The thermogravimetric analysis conditions were as follows: under a nitrogen atmosphere (flow rate of 60 cm ³ /min), the sample was heated at a constant rate (heating rate of 10 ° C / min) and the weight change of the material was recorded, and the measuring instrument was thermogravimetric analysis. Instrument (Model Q50, manufactured by TA Instruments).

T _d 5% means a temperature at which the weight loss is 5% by weight, wherein a higher T _{d 5%} represents a better heat resistance of the sample. T _d10% means a temperature at which the weight loss is 10% by weight, wherein a higher T _d10% represents a better heat resistance of the sample. R _w800 refers to the ratio of the residual weight of the material at a heating temperature of 800 °C. < Measurement of T _g >

The T _{g of the} polyimine films of Examples 3, 10, 12, 20, and 22 were measured by differential scanning calorimetry (DSC), respectively, and the analysis conditions were isothermal heating (heating rate was 10 ° C / min). The sample was recorded and the enthalpy change of the material was recorded, wherein the measuring instrument was a differential scanning calorimeter (Model: Q10, manufactured by TA Instruments). <Measurement of tensile strength and elongation at break>

The tensile strength of the polyimide film of Examples 3, 10, 12, and 20-21 was measured using a universal material testing machine (Model: HT-8336-S, manufactured by HUNG TA Instruments). And elongation at break, wherein the sample was a dumbbell shaped test piece and the stretching rate was 3 mm/min. <Measurement of storage modulus>

The storage modulus of the polyimide membranes of Examples 10, 20 was measured using dynamic mechanical analysis (DMA). The storage modulus analysis conditions were based on constant temperature heating (heating rate of 5 ° C / min, frequency: 1 Hz) and recorded changes in the storage modulus of the material. The measuring instrument was a dynamic mechanical analyzer (Model: Q800, Made by TA Instruments). <Measurement of surface resistivity>

The surface resistivity of the polyimide film of Examples 15-19 and 23-25 was measured using a four-point probe method, and the measuring instrument was a four-point probe low-impedance meter (manufactured by MITSUBISHI CHEMICAL, model: LORESTA-GP MCP-T600). The standard of conductivity is evaluated using the grade standard specified by FTTS-FA-009; where, when the surface resistivity is greater than 1 × 10 ¹² Ω/cm ² , it represents an insulating material; when the surface resistivity is between 1 × 10 ⁵ Ω/cm ² and 1×10 ¹² Ω/cm ² represent a static dissipative material; when the surface resistivity is less than 1×10 ⁴ Ω/cm ² , it represents a conductive material, and the lower the surface resistivity, the higher the conductivity. Excellent. Table 2 Table 2 (continued) Table 2 (continued)

As is apparent from the above Table 2, the polyimide film of Example 1-14 exhibited good performance in evaluation of film formability. This means that the composition for forming a polyimine according to the present invention comprises a tetracarboxylic dianhydride monomer component, and 4,4'-diaminodiphenyl ether having a content within a specific range, respectively. a compound represented by (I) and a diamine monomer component of melamine and a solvent, whereby a composition for forming a polyimide may have good film formability, and a polymer having excellent material properties can be obtained therefrom醯 imine film.

Further, as is clear from the above Table 2, the polyimide films of Examples 20 to 22 exhibited good performance in evaluation of film formability. This means that the composition for forming a polyimine of the present invention comprises a tetracarboxylic dianhydride monomer component, including 4,4'-diaminodiphenyl ether in a specific range, respectively. The compound represented by the formula (I) and the diamine monomer component of the melamine and the solvent, even if the diamine monomer component further comprises a decylamine diamine, the composition for forming the polyimine can still have a good A film-forming property, from which a polyimide film having excellent material properties can be obtained.

Further, as is clear from the above Table 2, the polyimide film of Examples 15 to 19 exhibited not only excellent evaluation of film formability but also conductivity. This means that the composition for forming a polyimine of the present invention comprises a tetracarboxylic dianhydride monomer component, including 4,4'-diaminodiphenyl ether in a specific range, respectively. The compound represented by the formula (I) and the diamine monomer component of the melamine and the solvent can not only obtain a polyimide film excellent in material properties, but also can penetrate the polyfluorene without damaging the essential effect. The imine is blended with the additive to impart additional properties to the polyimide film, such as electrical conductivity, thereby increasing the applicability and commercial value of the polyimide film.

Further, as is clear from the above Table 2, the polyimide film of Examples 23 to 25 exhibited not only excellent evaluation of film formability but also conductivity. This means that the composition for forming a polyimine of the present invention comprises a tetracarboxylic dianhydride monomer component, including 4,4'-diaminodiphenyl ether in a specific range, respectively. The compound represented by the formula (I) and the diamine monomer component of the melamine and the solvent, even if the diamine monomer component further includes a decane diamine, can not only obtain a polyimide film excellent in material properties, It can also impart additional properties to the polyimide film by blending polyimine with additives without damaging the essential effects, such as conductivity, thereby increasing the applicability and commerciality of the polyimide film. value.

Further, from the results of the above Table 2 regarding T _d5% , T _d10% , R _w800 , T _g , tensile strength and elongation at break, it is understood that the composition for forming a polyimide by the present invention includes a tetracarboxylic dianhydride monomer component, a 4,4'-diaminodiphenyl ether having a content within a specific range, a compound represented by the formula (I), and a diamine monomer component of a melamine and a solvent Thereby, the polyimide film can have heat resistance and elasticity.

Further, as is apparent from the above Table 2, the polyimide film of Example 20-21 exhibited good tensile strength and elongation at break. This means that the composition for forming a polyimine according to the present invention comprises a tetracarboxylic dianhydride monomer component, and 4,4'-diaminodiphenyl ether having a content within a specific range, respectively. The compound (I), the melamine and the diamine monomer component of the siloxane diamine, and the solvent, whereby the polyimide film obtained can have ductility or elasticity.

The present invention has been disclosed in the above embodiments, but it is not intended to limit the invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

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Claims (13)

A composition for forming a polyimine comprising: a tetracarboxylic dianhydride monomer component; a diamine monomer component comprising from 20 moles to 65 moles of 4,4'-diaminodi Phenyl ether (ODA; 4,4'-diaminodiphenyl ether), 30 moles to 70 moles of the compound of formula (I) and 1 mole to 10 moles of melamine: Formula (I) wherein the sum of x and z is from 1 to 20, and y is from 4 to 50; and a solvent. The composition for forming a polyimine according to claim 1, wherein the tetracarboxylic dianhydride monomer component comprises an aromatic tetracarboxylic dianhydride. The composition for forming a polyimine according to claim 1, wherein the diamine monomer component comprises from 25 moles to 65 moles of 4,4'-diaminodiphenyl. a base ether, 30 moles to 70 mole parts of the compound of formula (I), and 1 mole to 10 mole parts of melamine. The composition for forming a polythenimine according to claim 3, wherein the tetracarboxylic dianhydride monomer component is 3,4,3',4'-diphenyl ether tetracarboxylic acid Anhydride (3,4,3',4'-oxydiphthalic anhydride; ODPA). The composition for forming a polyimine according to claim 1, wherein the diamine monomer component comprises from 20 moles to 45 moles of 4,4'-diaminodiphenyl. a base ether, 50 moles to 70 mole parts of the compound of formula (I), and 5 moles to 10 mole parts of melamine. The composition for forming a polybendimimine according to claim 5, wherein the tetracarboxylic dianhydride monomer component is pyromellitic dianhydride (PMDA). The composition for forming a polyimine according to claim 1, wherein the diamine monomer component comprises from 25 moles to 45 moles of 4,4'-diaminodiphenyl. a base ether, 50 moles to 70 mole parts of the compound of formula (I), and 5 moles to 10 mole parts of melamine. The composition for forming a polythenimine according to claim 7, wherein the tetracarboxylic dianhydride monomer component is 3,3',4,4'-biphenyltetracarboxylic acid Anhydride (3,3',4,4'-biphenyltetracarboxylic dianhydride; BPDA). The composition for forming a polythenimine as described in claim 1, wherein the diamine monomer component further comprises a decane diamine. The composition for forming a polythenimine according to claim 9, wherein the oxirane diamine comprises a compound represented by the formula (II): Where n is 8 to 11. The composition for forming a polyimine according to claim 9, wherein the diamine monomer component comprises from 35 moles to 45 moles of 4,4'-diaminodiphenyl. a base ether, 40 moles to 50 mole parts of the compound of formula (I), 5 moles to 10 moles of melamine, and 5 moles to 10 moles of decane 2 amine. A polyimine which is produced by the composition for forming a polyimine as described in any one of claims 1 to 11. A polyimine film produced by the polyimine according to claim 12 of the patent application.