JP2017119869A - Composition for producing polyimide film, production method of the composition, and production method of polyimide film using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide precursor and a production method of the polyimide precursor, and a production method of a polyimide film using the precursor.SOLUTION: The production method of a polyimide precursor relating to the present invention includes: a step of adding an anhydride monomer to a polymerization solvent containing a diamine monomer to react; a step of adding a terminal-capping formulation to the reaction solution to react to synthesize a polyamic acid; and a step of adding and mixing a crosslinking agent with the polyamide acid.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composition for producing a polyimide film containing a polyimide precursor, a method for producing the same, and a method for producing a polyimide film using the composition.

  The polyimide material is excellent in heat resistance characteristics and chemical resistance, and is a material with high applicability for a flexible display substrate.

  In general, a polyimide substrate material is coated with polyamic acid (PAA) on a carrier glass using an applicator or a slit coater, and then heated by a high-temperature thermal imide reaction. Produced by type. However, the amount of production that can be performed in a convention oven in a batch type process (ie, thermal imidization process), which is not a continuous process, is limited, and a high temperature process of 400 ° C. or higher. Therefore, a long process time is required.

  Production CAPA (capacity), which depends on the curing process in convention ovens, is due to the high process speed, thermal imidization with the substrate coated at a high temperature above 120 ° C where the oven is not completely cooled To advance. At this time, the leveling characteristic of the film surface decreases due to the rapid volatilization of the solvent. For this reason, many studies have been conducted to improve such problems using a crosslinking agent (Patent Document 1 below).

Korean Registered Patent No. 10-0889910

  The present invention was made to solve the above-mentioned problems caused by the prior art, and by using a polyimide precursor containing a specific content of a cross-linking agent, by improving the properties of the polyimide film surface even at imidization at a high temperature. The present invention has been completed.

  One aspect of the present invention is a step of adding an hydride monomer to a polymerization solvent containing a diamine monomer and reacting; adding a terminal-capping preparation to the reaction solution, and then reacting the polyamic acid. And a step of adding and mixing a crosslinking agent to the polyamic acid.

  Another aspect of the present invention is a step of adding an hydride monomer to a polymerization solvent containing a diamine monomer and reacting the resultant; adding a terminal-capping preparation to the reaction solution, and then reacting to synthesize a polyamic acid. Adding a crosslinking agent to the polyamic acid and mixing; coating a composition comprising the polyamic acid to which the crosslinking agent has been added on the support; and on the support at a temperature of 100 ° C. or higher. Thermally imidizing a coated polyimide precursor. A method for producing a polyimide film is provided.

  The polyimide precursor according to the present invention is formed by adding a specific content of a crosslinking agent to polyamic acid, and can improve the surface characteristics of the polyimide film even at high temperature imidization. In particular, the leveling characteristics of the surface of the polyimide film can be improved and the loss of transmittance can be reduced.

1 is an image of a polyimide film according to an embodiment of the present invention. 1 is an image of a polyimide film according to an embodiment of the present invention. 1 is an image of a polyimide film according to an embodiment of the present invention. It is an image of the polyimide film by the comparative example of this invention. It is an image of the polyimide film by the comparative example of this invention. It is an image of the polyimide film by the comparative example of this invention. It is an image of the polyimide film by the comparative example of this invention.

  Hereinafter, embodiments and embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains can easily implement the present invention.

  However, the present invention may be embodied in various different forms and is not limited to the embodiments and examples described herein. In the drawings, in order to clearly describe the present invention, parts not related to the description are omitted, and like parts are denoted by like reference numerals throughout the specification.

  One aspect of the present invention is a step of adding an hydride monomer to a polymerization solvent containing a diamine monomer and reacting it; adding an end-capping agent to the reaction solution, and then reacting the polyamic A method for producing a polyimide precursor, comprising: synthesizing an acid; and adding and mixing a crosslinking agent to the polyamic acid.

  In one embodiment of the present invention, the diamine monomer may be PPDA (p-phenylenediamine), ODA (4,4′-oxydianiline), MDA (4,4′-methylenedianiline), m-tolidine. (2,2′-dimethyl-4,4′-diaminobiphenyl), TPE-R (1,3-bis (4′-aminophenoxy) benzene), TFMB (2,2′-bis (trifluoromethyl) benzidine ), HFBAPP (2,2′-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane), BIS-AP-AF (2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoro Propane), DRFB (1,3-diamino-2,4,5,6-tetrafluorobenzene), DDS (3,3′-diaminodiphenylsulfone), ASD 4,4′-diaminodiphenyl sulfide), BAPS (bis [4- (4-aminophenoxy) phenyl] sulfone), m-BAPS (2,2′-bis [4- (3-aminophenoxy) benzene] sulfone) And a group selected from the group consisting of these, and may preferably be PPDA. PPDA is an aromatic monomer and can provide high heat resistance.

  In one embodiment of the present invention, the anhydride monomer may be an aromatic dianhydride monomer, such as BTDA (3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride), PMDA (pyromellitic anhydride), BPDA (3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride), 6FDA (2,2-bis (3,4-anhydrodicarboxyphenyl) -hexafluoro Propane dianhydride), a-BPDA (2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride), ODPA (4,4′-oxydiphthalic anhydride), DSDA (3,3 ′, 4 , 4'-diphenylsulfonetetracarboxylic dianhydride), BPADA (5,5 '-[1-methyl-1,1-ethanediylbis (1,4-phenylene) bisoxy] bi (Isobenzofuran-1,3-dione), HQDA (hydroquinone diphthalic anhydride), and combinations thereof may include one aromatic dianhydride monomer. As described above, for example, at least two monomers can be used.

  In one embodiment of the present invention, the synthetic solvent can be used without limitation as long as it is a solvent used in this field. For example, amide solvents, ketone solvents, ether solvents, ester solvents, symmetric glycol diethers Those selected from the group consisting of solvents, ether solvents and combinations thereof can be included. The amide solvent may include dimethylformamide (DMF), dimethylacetamide (DMAC), n-methylpyrrolidone (NMP), and the ketone solvent may be acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK). ), Cyclopentanone, cyclohexanone, and the like. The ether solvent may include tetrahydrofuran (THF), 1,3-dioxolane, 1,4-dioxane, and the ester solvent may include methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, α- Acetolactone, β-propiolactone, δ-valerolactone and the like can be included. The symmetric glycol diether solvents are methyl monoglyme (1,2-dimethoxyethane), methyl diglyme (bis (2-methoxyethyl) ether), methyltriglyme (1,2-bis (2-methoxyethoxy) ethane) , Methyl tetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyl diglyme (bis (2-ethoxyethyl) ether), butyl diglyme (bis (2 -Butoxyethyl) ether) and the like, and the ether solvents include glycol diethers, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether. , Propi Glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n-propyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Ethylene glycol monoethyl ether, and the like. As the polymerization solvent, at least one solvent is preferably used. For example, NMP can be used.

  In one embodiment of the present invention, the end-capping preparation is used to control the polymerization reaction, and an unhydride monomer can be used. Examples of the monomer of the anhydride form include PA (phthalic anhydride), TSA (n-tetradecyl succinic anhydride), HAS (hexadecyl succinic anhydride), OSA (octadecyl succinic anhydride), and these. And may be selected from the group consisting of: PA, preferably PA. The end-capping formulation can adjust the molecular weight of the polymer in a mono-anhydride form, reduce the content of unreacted substances, and improve storage stability.

  In one embodiment of the present invention, the method may further include a step of adding a solvent for adjusting viscosity and a solid powder satisfying the standard of the product to be manufactured after synthesizing the polyamic acid. As the solvent, the same solvent as the synthesis solvent can be used, and a different type of solvent can be used for improving physical properties.

In one embodiment of the present invention, the bridging agent may include 4,4′-methylenebis (N, N-diglycidylaniline). The cross-linking agent may preferably be 4,4′-methylenebis (N, N-diglycidylaniline) having the following chemical formula:

  In one embodiment of the present invention, the crosslinking agent may be added in an amount of about 2000 to about 4000 ppm relative to the monomer. When the cross-linking agent is added in a content of less than 2000 ppm, the surface of the polyimide film may be in a poor state, and when it is added in a content of over 4000 ppm, the transparency of the polyimide film may be lowered.

  The other side surface of this invention provides the composition for polyimide film manufacture containing the polyimide precursor manufactured by the manufacturing method of the polyimide precursor by this application.

  In an exemplary embodiment of the present invention, the polyimide precursor may include a polyamic acid polymer form.

  In one embodiment of the present invention, the polyimide precursor is formed by adding a specific content of a crosslinking agent to polyamic acid, and can improve the surface characteristics of the polyimide film even at high temperature imidization. In particular, the leveling characteristics of the surface of the polyimide film can be improved and the transmission loss can be reduced.

  According to another aspect of the present invention, a step of adding an hydride monomer to a polymerization solvent containing a diamine monomer and reacting the mixture; adding a terminal-capping preparation to the reaction solution and reacting the resultant to synthesize a polyamic acid And a step of adding a crosslinking agent to the polyamic acid and mixing; coating a composition containing the polyamic acid to which the crosslinking agent has been added on a support; and the support at a temperature of 100 ° C. or higher. Thermally imidizing a polyimide precursor coated thereon; and a method for producing a polyimide film.

  In one embodiment of the present application, the thermal imidization may be performed at, for example, about 100 ° C to about 500 ° C, about 100 ° C to about 400 ° C, about 100 ° C to about 300 ° C, about 100 ° C to about 200 ° C, about 200 ° C. However, the present invention is not limited to this.

  Hereinafter, the present invention will be described in more detail through examples, but the scope of the present invention is not limited by these examples.

Example 1
After PPDA 21.62 g (0.2 mol) was completely dissolved in 529.2 g of NMP kept at room temperature, 52.96 g (0.18 mol) of BPDA and 4.36 g (0.02 mol) of PMDA were sequentially added. After 1 hour had been completely dissolved, 0.43 g (0.0029 mol) of PA was added and reacted for 16 hours to complete the PAA polymerization. Then, 2000 ppm of 4,4′-methylenebis (N, N-diglycidylaniline) (0.15874 g) having a monomer (PPDA, BPDA and PMDA) content was dissolved in NMP which is the same reaction solvent, Added to PAA and mixed.

Example 2
After PPDA 21.62 g (0.2 mol) was completely dissolved in 529.2 g of NMP kept at room temperature, 52.96 g (0.18 mol) of BPDA and 4.36 g (0.02 mol) of PMDA were sequentially added. After 1 hour had elapsed after complete dissolution, 0.43 g (0.0029 mol) of PA was added. After the reaction for 16 hours, monomer (PPDA, BPDA and PMDA) content of 3000 ppm of 4,4′-methylenebis (N, N-diglycidylaniline) (0.23811 g) was dissolved in the same reaction solvent NMP. Then, in addition to the PAA, further mixing was performed.

Example 3
After PPDA 21.62 g (0.2 mol) was completely dissolved in 529.2 g of NMP kept at room temperature, 52.96 g (0.18 mol) of BPDA and 4.36 g (0.02 mol) of PMDA were sequentially added. After 1 hour had elapsed after complete dissolution, 0.43 g (0.0029 mol) of PA was added. After the reaction for 16 hours, 4000 ppm of 4,4′-methylenebis (N, N-diglycidylaniline) (0.31748 g) having a monomer (PPDA, BPDA and PMDA) content was dissolved in the solvent, and the reaction was completed. Further mixing was performed in addition to PAA.

Comparative Example 1
After PPDA 21.62 g (0.2 mol) was completely dissolved in 529.2 g of NMP kept at room temperature, 52.96 g (0.18 mol) of BPDA and 4.36 g (0.02 mol) of PMDA were sequentially added. After 1 hour had been completely dissolved, 0.43 g (0.0029 mol) of PA was added and reacted for 16 hours to complete the PAA polymerization. Then, the same amount of solvent NMP as in Example 1 was added to the PAA after the reaction, and further mixing was performed.

Comparative Example 2
After PPDA 21.62 g (0.2 mol) was completely dissolved in 529.2 g of NMP kept at room temperature, 52.96 g (0.18 mol) of BPDA and 4.36 g (0.02 mol) of PMDA were sequentially added. After 1 hour had been completely dissolved, 0.43 g (0.0029 mol) of PA was added and reacted for 16 hours to complete the PAA polymerization. Then, 1000 ppm of 4,4′-methylenebis (N, N-diglycidylaniline) (0.07937 g) having a monomer (PPDA, BPDA, and PMDA) content was dissolved in NMP, which is the same reaction solvent, and dissolved in the PAA. Added and mixed.

Comparative Example 3
After PPDA 21.62 g (0.2 mol) was completely dissolved in 529.2 g of NMP kept at room temperature, 52.96 g (0.18 mol) of BPDA and 4.36 g (0.02 mol) of PMDA were sequentially added. After 1 hour had been completely dissolved, 0.43 g (0.0029 mol) of PA was added and reacted for 16 hours to complete the PAA polymerization. Then, 1500 ppm of 4,4′-methylenebis (N, N-diglycidylaniline) (0.119055 g) having a monomer (PPDA, BPDA, and PMDA) content was dissolved in NMP, which is the same reaction solvent, and dissolved in the PAA. Added and mixed.

Comparative Example 4
After PPDA 21.62 g (0.2 mol) was completely dissolved in 529.2 g of NMP kept at room temperature, 52.96 g (0.18 mol) of BPDA and 4.36 g (0.02 mol) of PMDA were sequentially added. After 1 hour had elapsed after complete dissolution, 0.43 g (0.0029 mol) of PA was added. After the reaction for 16 hours, 5000 ppm of 4,4′-methylenebis (N, N-diglycidylaniline) (0.39685 g) having a monomer (PPDA, BPDA and PMDA) content was dissolved in NMP as the same reaction solvent. After that, further mixing was performed in addition to the PAA after the reaction.

Experimental example 1
Using the applicator (Baker applicator, YBA-4), the thickness of the polyimide precursors of Examples 1 to 3 and Comparative Examples 1 to 4 was changed to LCD Glass SM TECH, new glass (200 * 200 * 0.63). After coating to 400 μm, it was placed in a convention oven heated to 120 ° C. to allow the thermal imide reaction to proceed. Then, the temperature was raised at 3 ° C. per minute, kept at a maximum of 450 ° C. for 1 hour, and then gradually cooled. After cooling, the film was collected and analyzed for the external form and optical characteristics of the film. The results are shown in FIGS.

  As can be seen in FIGS. 1 to 7, when the 4,4′-methylenebis (N, N-diglycidylaniline) having a content of 2000 ppm to 4000 ppm is added (FIGS. 1 to 3), the leveling state of the film surface is good. However, when 4,4′-methylenebis (N, N-diglycidylaniline) was not added (FIG. 4), and when it was added at a content of 1000 ppm or 5000 ppm (FIGS. 5-7), the leveling state of the film surface was It can be confirmed that it is defective.

  Moreover, as can be seen from Tables 1 and 2, it can be confirmed that when the content is less than 2000 ppm or 5000 ppm or more, the transmittance decreases rapidly.

  The above description of the present invention is given for illustrative purposes only, and those having ordinary knowledge in the technical field to which the present invention pertains can be used without changing the technical idea and essential features of the present invention. It will be understood that it can be easily transformed into various forms. Thus, it should be understood that the embodiments described above are illustrative in all aspects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described in a distributed manner may be implemented in a combined form.

  The scope of the present invention is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and the equivalent concept thereof are described in the present invention. It should be construed as included in the scope of the invention.

Claims (13)

A polyimide precursor composition comprising: a polyamic acid; and a cross-linking agent having a content of 2000 to 4000 ppm relative to the polyamic acid.   The polyimide precursor composition according to claim 1, wherein the cross-linking agent includes 4,4′-methylenebis (N, N-diglycidylaniline).   The polyimide precursor according to claim 1, comprising a solvent selected from the group consisting of an amide solvent, a ketone solvent, an ether solvent, an ester solvent, a symmetric glycol diether solvent, an ether solvent, and combinations thereof. Composition. Adding an hydride monomer to a polymerization solvent containing a diamine monomer and reacting;
A method for producing a polyimide precursor composition, comprising: adding a terminal-capping preparation to the reaction solution and then reacting to synthesize a polyamic acid; and adding a crosslinking agent to the polyamic acid and mixing.   The method for producing a polyimide precursor composition according to claim 4, wherein the anhydride monomer is an aromatic dianhydride monomer.   The aromatic dianhydride monomer includes BTDA (3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride), PMDA (pyromellitic anhydride), BPDA (3,3 ′, 4,4 ′). -Biphenyltetracarboxylic dianhydride), 6FDA (2,2-bis (3,4-anhydrodicarboxyphenyl) -hexafluoropropane dianhydride), a-BPDA (2,3,3 ', 4' -Biphenyltetracarboxylic dianhydride), ODPA (4,4'-oxydiphthalic anhydride), DSDA (3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride), BPADA (5,5 '-[1-Methyl-1,1-ethanediylbis (1,4-phenylene) bisoxy] bis (isobenzofuran-1,3-dione), HQDA (hydroquinonedi) Tal anhydride) and is intended to include those selected from the group consisting of, producing a polyimide precursor composition according to claim 4.   The diamine monomer is PPDA (p-phenylenediamine), ODA (4,4′-oxydianiline), MDA (4,4′-methylenedianiline), m-tolidine (2,2′-dimethyl-). 4,4′-diaminobiphenyl), TPE-R (1,3-bis (4′-aminophenoxy) benzene), TFMB (2,2′-bis (trifluoromethyl) benzidine), HFBAPP (2,2 ′ -Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane), BIS-AP-AF (2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane), DRFB (1,3 -Diamino-2,4,5,6-tetrafluorobenzene), DDS (3,3'-diaminodiphenylsulfone), ASD (4,4'-diaminodiphe) Sulfido), BAPS (bis [4- (4-aminophenoxy) phenyl] sulfone), m-BAPS (2,2′-bis [4- (3-aminophenoxy) benzene] sulfone) and combinations thereof The manufacturing method of the polyimide precursor composition of Claim 4 which is selected from these.   The method for producing a polyimide precursor composition according to claim 4, wherein at least two anhydride monomers are added.   The polymerization solvent includes one selected from the group consisting of an amide solvent, a ketone solvent, an ether solvent, an ester solvent, a symmetric glycol diether solvent, an ether solvent, and combinations thereof. The manufacturing method of the polyimide precursor composition of description.   The end-capping formulation comprises PA (phthalic anhydride), TSA (n-tetradecyl succinic anhydride), HAS (hexadecyl succinic anhydride), OSA (octadecyl succinic anhydride), and combinations thereof The manufacturing method of the polyimide precursor composition of Claim 4 which is selected from these.   The method for producing a polyimide precursor composition according to claim 4, wherein the crosslinking agent contains 4,4′-methylenebis (N, N-diglycidylaniline).   The said crosslinking agent is a manufacturing method of the polyimide precursor of Claim 4 added by the quantity of 2000 ppm-4000 ppm with respect to polyamic acid. A polyimide film comprising: coating a polyimide precursor composition of claim 1 on a support; and thermally imidizing the polyimide precursor coated on the support at a temperature of 100 ° C. or higher. Manufacturing method.