TW201536835A - Polyimide polymer and polyimide film including the same - Google Patents

Abstract

A polyimide polymer of Formula (I) is:. Wherein, A is a fluoroaryl group, A' is a polycyclic aliphatic group and B is an aryl group. The ratio of n/m is between 19:1 and 1:1. The polyimide film includes a film layer, and the film layer includes the above polyimide polymer. The film layer optionally includes a pigment and a nano inorganic particle. Therefore, the thermal resistance and the transparency of the polyimide film are improved and polyimide films having high thermal resistances with different colors are available.

Description

Polyimine polymer and polyimine film using polyimine polymer

The invention relates to a polyimine polymer and a polyimine film using a polyimine polymer, in particular to a polyimide film with excellent transparency and high heat resistance, and the use of the poly The quinone imine polymer is made into a highly heat-resistant polyimide film of various colors.

In a general display and a touch sensor, it is necessary to use a transparent conductive substrate because it is required to satisfy both light transmission and electrical conductivity. The transparent conductive substrate refers to a substrate having a light transmittance of 80% or more in the wavelength range of visible light (380-760 nm) and high conductivity (resistivity less than 1×10 ^-3 Ω·cm). .

Generally, the transparent conductive substrate comprises a transparent substrate and a conductive layer on the transparent substrate. In the case of a display, a glass substrate is a relatively common transparent substrate. However, because glass is thicker, heavier and brittle, the search for alternative substrates for glass and technology development is the focus of display development.

Because the plastic substrate has the advantages of light weight, flexibility, impact resistance and easy cutting, it is a better alternative to the glass substrate, and how to form a conductive layer with high transparency, low resistance and high flatness on the plastic substrate. It has also become an important research topic.

On the other hand, in the process of preparing a transparent substrate and a touch panel into a display, since a thin film transistor (TFT) process is required, the conductive layer on the transparent substrate needs to withstand the high temperature in the process ( >200 ° C), chemical attack in cleaning and development procedures. Therefore, how to design a conductive layer with a heat-resistant and chemically resistant display becomes a problem that researchers need to solve.

In view of the above problems, the present invention relates to a polyimine polymer and a polyimide film using a polyimide pigment polymer, thereby providing a substrate having a heat-resistant and chemically resistant display capable of withstanding a display The high temperature and chemical process are used to form a transparent conductive substrate.

The polyimine polymer disclosed in one embodiment of the present invention has the structure of the chemical formula (I): Among them, A is a fluorine-containing aromatic, A' is a polycyclic aliphatic, B is aromatic, and the ratio of n/m is between 19:1 and 1:1.

The polyimide film disclosed in one embodiment of the present invention has a film layer. The film layer has a polyimine polymer. The polyimide film can be prepared as a transparent conductive substrate for display, which can replace glass and has the advantages of light weight, flexibility, impact resistance and easy cutting.

According to the polyimine polymer disclosed in the above embodiments of the present invention and the polyimine film using the polyimine polymer, the polyimine polymer has the structure of the formula (I), and the fluorine is contained therein. The aromatic and polycyclic aliphatic groups have a specific ratio, and thus the polyiminoimine polymer of the embodiment of the invention has colorlessness, high transparency, high heat resistance, good chemical resistance and flexibility, and thus can be applied. In the production of the display.

The above description of the present invention and the following description of the embodiments of the present invention are intended to illustrate and explain the principles of the invention.

The detailed features and advantages of the present invention are set forth in the detailed description of the embodiments of the present invention. The objects and advantages associated with the present invention can be readily understood by those skilled in the art. The following examples are intended to describe the present invention in further detail, but do not limit the scope of the invention in any way.

The polyimine polymer disclosed in one embodiment of the present invention has the structure of the chemical formula (I):

A is a fluorine-containing aromatic, such as: (TFMB[341-58-2]), (HFBAPP[69563-88-8]), BTFDPE [344-48-9], FAPQ [94525-05-0] or a combination of the above.

A' is a polycyclic aliphatic, for example: Or a combination of the above.

B is aromatic, for example: Or a combination of the above.

Among them, the ratio of n / m is between 19:1 and 1:1.

The present invention relates to a polyimide film having excellent transparency and high heat resistance. The polyimide film has a film layer having the above-mentioned polyimine polymer. The polyimide film can be prepared as a transparent substrate for display, which can replace glass and has the advantages of light weight, flexibility, impact resistance and easy cutting.

In some embodiments of the invention, a colorant may also be blended into the film layer. The coloring material is, for example, titanium white powder, aluminum oxide, calcium carbonate, calcium sulfate, cerium oxide, boron nitride, carbon black, ultramarine blue or indigo blue, or a combination thereof, but is not limited thereto. Since the polyimide film of the present invention is nearly colorless and transparent, the film layer can be dyed according to the needs of the user, and various color requirements can be easily achieved. For example, the addition of titanium dioxide can be applied to the Cover Bar of the LED Bar to increase the reflectivity, and a small amount of blue pigment can be added to adjust the appropriate chromaticity coordinates.

In some embodiments of the invention, one nanometer of inorganic particles may also be blended into the film layer. The nano inorganic particles are, for example, cerium oxide, talc, mica, clay or titanium dioxide, or a combination thereof, but are not limited thereto. Thereby, the heat resistance and light transmittance of the formed film layer are improved.

In the above embodiment of the present invention, the polyimine polymer is formed by condensation polymerization (i.e., polycondensation) of a diamine and a dianhydride.

In the above embodiment, the dianhydride is selected from the group consisting of: 1,2,4,5 benzene tetracarboxylic dianhydride, 2,32',3'-biphenyl tetracarboxylic dianhydride , 3,4,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride (2,3,3',4 '-biphenyl tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,4'-oxydiphthalic anhydride, benzophenone IV Benzenephenonetetracarboxylic dianhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)]propane dianhydride (2,2-bis[4-(3,4dicarboxyphenoxy)phenyl) ]propane dianhydride), 2,2-bis(3,4-anhydrodicarboxyphenyl)hexafluoropropane 4,4'-(hexafluoroisopropene) diacetic anhydride, diphenyl maple tetracarboxylic dianhydride (3,3',4, 4'-diphenyl sulfonetetracarboxylic dianhydride), 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, Cas.No.135876-30-1,9,9-bis[4-(3,4-dicarboxyphenoxt)phenyl] Fluorene dianhydride, Cas.No.59507-08-3, naphthyltetracarboxylic dianhydride (1,2,5,6-naphthalene Tetracarboxylic dianhydride, naphthalenetetracaboxylic dianhydride, bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride, 1,3-double (3,4) -Dicarboxyphenyl)-1,1,3,3-tetracarboxylic dimethoxy hydride (1,3-bis (4'-phthalic anhydride)-tetramethyldisiloxane) or a combination thereof.

The preparation method of the polyimine polymer is as follows.

In a preparation method, first, the diamine is dissolved in a polar aprotic solvent such as dimethylformamide (DMF) or N-methylethylpyrrolidone (NMP). , N,N-dimethylacetamide N,N-Dimethyl acetamid (DMAC), m-cresol Cresol, gamma- Butyrolactone (γ-butyrolactone or GBL) or a combination thereof, followed by the addition of dianhydride to make two The amine reacts with the dianhydride to form polyamic acid (PAA). Then, the coating film is dried to form a film of poly-proline, and then imidization is carried out to bring the poly-proline to a dehydration and ring closure effect. In this step, the polyglycine may be dehydrated, closed by high temperature (250 ° C - 400 ° C), or a dehydrating agent (for example, an acid anhydride) may be added to dehydrate the polyamic acid, and the ring is closed (ie, chemical cyclization). ). Thereby, a polyimide film can be obtained.

In some embodiments, in order to prepare a film layer of the blended colorant and/or nano-inorganic particles, the diamine used is also blended with colorants and/or nano-inorganic particles. The preparation method is as follows. First, the coloring material and/or the nano inorganic particles are added to the solvent, and the mixture is rapidly stirred and dispersed at a frequency of 20 to 100 Hz or dispersed by grinding. Next, the suspension solution containing the colorant and/or the nano inorganic particles is added to the diamine to dissolve. Next, a dianhydride is added to polymerize the diamine and the dianhydride to prepare a polyamido acid mixture. Alternatively, the suspension of the coloring material and/or the nano inorganic particles may be directly added to the polylysine (PAA) which has been previously reacted, and the obtained polyamido acid mixture (PAA) has a viscosity of 10 poise (poise, Ps) to 3000 poise (ie between 1,000 cps and 30,000 cps). Next, the polyaminic acid mixture is dried at a temperature of from 120 ° C to 200 ° C to form a polyphthalic acid mixture film. Finally, the polyamiginic acid mixture film is heated at a temperature of 250 ° C to 400 ° C to carry out a mercaptomination reaction to form a polyimine polymer.

Hereinafter, the polyimine polymers disclosed in the present proposal will be described by way of several examples and comparative examples, and experimental tests are conducted to compare the difference in properties.

Embodiment 1.

First, 28.82 g of TFMB (2,2'-Bis(trifluoromethyl)benzidine; CAS number: 341-58-2) and 1.54 g of NBDA (Bis (aminomethyl) norbornane; CAS number: 56602-77-8) were mixed. In DMAC solvent. After the TFMB and NBDA are completely dissolved, add 21.81 grams of PMDA (1,2,4,5-Benzenetetracarboxylic anhydride; CAS number: 89-32-7) (TFMB: NBDA: PMDA molar ratio is 0.9:0.1:1), stirring is continued for at least 1 hour until PMDA is completely reacted to form poly-plycine PAA solution, wherein the solid content is 20%. Then, the film was dried at 120 ° C for 10 minutes to form a film of poly-proline, and then imidization was carried out at 300 ° C for 10 minutes to effect the dehydration and ring closure of the poly-proline. A polyimide film can be obtained.

Example 2.

First, 22.42 grams of TFMB and 4.63 grams of NBDA were mixed in a DMAC solvent. After TFMB and NBDA are completely dissolved, add 21.81 g of PMDA (TFMB: NBDA: PMDA molar ratio of 0.7:0.3:1), and continue stirring for at least 1 hour until PMDA is completely reacted to form polylysine. A PAA solution in which the solid content is 20%. Then, the film was dried at 120 ° C for 10 minutes to form a film of poly-proline, and then imidization was carried out at 300 ° C for 10 minutes to effect the dehydration and ring closure of the poly-proline. A polyimide film can be obtained.

Example 3.

First, 16.01 grams of TFMB and 7.71 grams of NBDA were mixed in a DMAC solvent. After TFMB and NBDA are completely dissolved, add 21.81 g of PMDA (TFMB: NBDA: PMDA molar ratio of 0.5:0.5:1), and continue stirring for at least 1 hour until PMDA is completely reacted to form polylysine. A PAA solution in which the solid content is 20%. Then, the film was dried at 120 ° C for 10 minutes to form a film of poly-proline, and then imidization was carried out at 300 ° C for 10 minutes to effect the dehydration and ring closure of the poly-proline. A polyimide film can be obtained.

Example four.

First, 28.82 grams of TFMB and 1.54 grams of NBDA were mixed in a DMAC solvent. After the TFMB and NBDA are completely dissolved, add 29.42 grams of BPDA. (3,3',4,4'-Biphenyltetracarboxylic dianhydride;CAS number: 2420-87-3) (TFMB: NBDA: BPDA molar ratio of 0.9:0.1:1), stirring for at least 1 hour until BPDA Completely reacted to form a polyaminic acid PAA solution having a solids content of 20%. Then, the film was dried at 120 ° C for 10 minutes to form a film of polylysine, and then imidization was carried out at 280 ° C for 10 minutes to effect the dehydration and ring closure of the polylysine. A polyimide film can be obtained.

Example 5.

First, 13.37 grams of TFMB and 1.85 grams of NBDA were mixed in a DMAC solvent. After the TFMB and NBDA were completely dissolved, add 29.42 g of BPADA (3,3',4,4'-Biphenyltetracarboxylic dianhydride; CAS number: 2420-87-3) (TFMB: NBDA: BPADA has a molar ratio of 0.8). : 0.2:1), stirring was continued for at least 1 hour until the BPDA was completely reacted to form a poly-proline PAA solution in which the solid content was 20%. Then, the film was dried at 120 ° C for 10 minutes to form a film of polylysine, and then imidization was carried out at 280 ° C for 10 minutes to effect the dehydration and ring closure of the polylysine. A polyimide film can be obtained.

Example 6.

100 g of PAA of Example 5 was added to 30 g of SiO ₂ sol-gel (solid content: 20%), and stirring was continued for at least 1 hour to form a nanopolyphthalic acid PAA solution having a solid content of 20%. Then, the film was dried at 120 ° C for 10 minutes to form a film of polylysine, and then imidization was carried out at 280 ° C for 10 minutes to effect the dehydration and ring closure of the polylysine. A polyimide film can be obtained.

Comparative example one.

First, 32.02 grams of TFMB was dissolved in the DMAC solvent. After the TFMB is completely dissolved, add 21.81 g of PMDA (PMDA: TFMB molar ratio is 1:1). Stirring was continued for at least 1 hour until the PMDA was completely reacted to form a polyplysine PAA solution having a solids content of 20%. Then, the film is dried at 120 ° C for 10 minutes to form a film of poly-proline, and then imidization at 300 ° C to achieve the effect of dehydration and ring closure of poly-proline, thereby obtaining a poly Bismuth film.

Comparative example 2.

First, 26.03 g of ODA (Octadecylamine) was dissolved in a DMAC solvent. After the ODA is completely dissolved, add 28.36 g of PMDA (ODA: PMDA molar ratio is 1:1), and continue stirring for at least 1 hour until the PMDA is completely reacted to form a poly-proline PAA solution. The content is 20%. Then, the film is dried at 120 ° C for 10 minutes to form a film of poly-proline, and then imidization at 300 ° C to achieve the effect of dehydration and ring closure of poly-proline, thereby obtaining a poly Bismuth film.

Finally, the polyimine polymers of Examples 1 to 5 and Comparative Example 1 and Comparative Example 2 were tested, and the results are shown in the following table. Among them, the test for the chemical resistance was to soak the films of Examples 1 to 5 and Comparative Example 1 and Comparative Example 2 to N-methyl-2-pyrrolidone (NMP, N-Methyl-2-pyrrolidone), N, respectively. N-dimethylacetamide (DMAc, dimethylacetamide), oxalic acid, developer, and stripper were tested at 50 ° C for 1 hour. The film was evaluated for the resistance of the film by observing the solubility of the film in the above solvent.

According to the polyimine polymer disclosed in the above embodiments of the present invention and the polyimine film using the polyimine polymer, the polyimine polymer has the structure of the formula (I), and the fluorine is contained therein. The aromatic and polycyclic aliphatic groups have a specific ratio, and thus the polyiminoimine polymer of the embodiment of the invention has colorlessness, high transparency, high heat resistance, good chemical resistance and flexibility, and thus can be applied. In the production of the display.

Although the embodiments of the present invention are disclosed above, it is not intended to limit the present invention, and those skilled in the art, regardless of the spirit and scope of the present invention, the shapes, structures, and features described in the scope of the present application. And the spirit of the invention is subject to change. Therefore, the scope of patent protection of the present invention is subject to the scope of the patent application attached to the specification.

Claims (9)

A polyimine polymer having the structure of formula (I): Among them, A is a fluorine-containing aromatic, A' is a polycyclic aliphatic, B is aromatic, and the ratio of n/m is between 19:1 and 1:1. The polyimine polymer according to claim 1, wherein A is Or a combination of the above. The polyimine polymer according to claim 1, wherein A' is Or a combination of the above. The polyimine polymer according to claim 1, wherein B is Or a combination of the above. A polyimine film having a film layer having the polyimine polymer according to any one of claims 1 to 4. The polyimine film of claim 5, further comprising a colorant blended in the film layer. The polyimine film according to claim 6, wherein the colorant is selected from the group consisting of titanium dioxide, aluminum oxide, calcium carbonate, calcium sulfate, cerium oxide, boron nitride, carbon black, ultramarine blue or indigo blue. Or one or more combinations. The polyimine film according to claim 5, further comprising a nano inorganic particle, the nano inorganic particle being blended in the film layer. The polyimine film according to claim 8, wherein the nano inorganic particles are selected from the group consisting of ceria, talc, mica, clay or titanium dioxide, or a combination thereof.