Matte Polyimide Film and its Manufacturing Method

Abstract

This invention relates to a matte polyimide film and a method for manufacturing the same. The method includes the following steps: providing an aromatic dianhydride and an aromatic diamine, adding a solvent and polymerizing to form a first polyamide solution, wherein the intrinsic viscosity of the first polyamide solution is less than 1.2 dL / g; providing a dianhydride and a diamine, adding a solvent and polymerizing to form a second polyamide solution; mixing the first polyamide solution and the second polyamide solution to form a polyamide mixed solution; forming a polyimide coating liquid by chemical cyclization of the polyamide mixed solution; and coating the polyimide coating liquid onto a carrier, and heating to 300-450°C to form a matte polyimide film having a first polyimide and a second polyimide with a gloss level of less than 60 GU at 60 degrees.

Description

Technical Field

[0001] The present invention relates to a matt polyimide film and a method for manufacturing the same, and in particular to a polyimide film having matt properties without adding a matt agent, which is relatively simple to manufacture and has a low cost. Prior Art

[0002] Polyimide films are commonly used as cover layers for flexible printed circuits (FPCs). Matte polyimide films, due to their unique optical properties, can reduce visual discomfort caused by reflective film. They also provide protection for electronic components, preventing unnecessary visual inspection and damage. Therefore, they are often used in specialized FPC applications.

[0003] However, conventional methods for manufacturing matte polyimide films primarily rely on adding matte particles to alter the film's surface roughness. Because surface roughness varies with the size and proportion of the matte particles, it alters the angle at which ambient light reflects off the film, thereby achieving a matte effect.

[0004] Conventional matte particles can be broadly categorized as organic and inorganic. Regardless of their composition, production requires a thorough dispersibility assessment. This not only increases manufacturing costs, but poor dispersion can also negatively impact the optical properties of the finished product.

[0005] In recent years, with the trend toward thinner, lighter, and smaller electronic products, there is still a demand for ultra-thin matte polyimide films. Therefore, conventional methods for manufacturing ultra-thin films are limited by the particle size of the matte particles themselves. To maintain the original matte properties, the amount of small-sized matte particles must be increased, which also affects the appearance quality of the finished product.

[0006] To improve the above-mentioned problem, the present invention provides a matte polyimide film and a method for manufacturing the same, which can achieve a matte effect without adding a matte agent. Summary of the Invention

[0007] The present invention relates to a matte polyimide film and a method for manufacturing the same. The method comprises the following steps: providing an aromatic dianhydride and an aromatic diamine, adding a solvent and polymerizing to form a first polyimide solution, wherein the first polyimide solution has an intrinsic viscosity of less than 1.2 dL / g; providing a dianhydride and a diamine, adding a solvent and polymerizing to form a second polyimide solution; mixing the first polyimide solution and the second polyimide solution to form a polyimide mixed solution; and chemically cyclizing the polyimide mixed solution to form a coating solution, coating the coating on a carrier, and heating to form a matte polyimide film having a 60-degree gloss of less than 60 GU.

[0008] Simple diagram description

[0009] FIG1 is a flow chart of the method for manufacturing a matte polyimide film according to the present invention. Implementation Method

[0010] The matte polyimide film of the present invention and its manufacturing method include the following steps:

[0011] A first polyamide solution (S1) is provided, which is formed by polymerizing aromatic dianhydride and aromatic diamine.

[0012] The aromatic dianhydride may be pyromellitic dianhydride (PMDA) or 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA).

[0013] The aromatic diamine may be p-phenylenediamine (PDA) or 4,4'-diaminodiphenyl ether (ODA).

[0014] A second polyamide solution (S2) is provided, which is formed by polymerization of a dianhydride and a diamine, wherein the dianhydride can be any one of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), hexafluorodianhydride (6FDA), bisphenol A diether dianhydride (BPADA), cyclobutanetetracarboxylic dianhydride (CBDA) or a combination of more than one thereof, and the diamine can be 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 3,4'-diaminodiphenyl ether (3,4ODA), 4,4'-bis(3-aminophenoxy)diphenylsulfone (m-BAPS), 2,2-bis[4-(4 -aminophenoxy)phenyl]propane (BAPP), 3,5-diaminobenzoic acid (3,5DABA), 3,3'-diaminodiphenylsulfone (3,3DDS), 4,4'-diaminodiphenylsulfone (4,4DDS), 4,4'-[1,3-phenylenebis(1-methylethylidene)]dianiline (Bisaniline-M), 4,4'-[1,4-phenylenebis(1-methylethylidene)]dianiline (Bisaniline-P), or a combination of any one or more thereof.

[0015] The first polyamine solution and the second polyamine solution are mixed to form a polyamine mixed solution (S3).

[0016] The polyamide mixed solution is chemically cyclized to form a polyimide coating solution (S4).

[0017] The polyimide coating liquid is coated on a carrier and heated to 350 degrees to form a matte polyimide film (S5) with a 60-degree glossiness less than 60GU.

[0018] [Preparation of the first polyamine solution]

[0019] The first polyamine solution is composed of aromatic dianhydride and aromatic diamine. The aromatic dianhydride component and the aromatic diamine component are polymerized in an organic solvent to form the first polyamine solution.

[0020] The aforementioned organic solvents may include dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and N,N-dimethylformamide (DMF). In the present invention, dimethylacetamide is used as the solvent.

[0021] The first polyamine solution has an intrinsic viscosity of less than 1.2 dL / g.

[0022] The lower limit of the aforementioned intrinsic viscosity is not particularly limited and can be selected according to the application, etc., and can be 0.4 dL / g, 0.5 dL / g, 0.6 dL / g, 0.7 dL / g, etc.

[0023] The aforementioned aromatic dianhydride may be any one of pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-diphenyl ether dianhydride (ODPA), p-phenylene trimellitic dianhydride (TAHQ), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), or a combination of more than one thereof.

[0024] The aforementioned aromatic dianhydride is preferably pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-diphenyl ether dianhydride (ODPA), or a combination of one or more thereof.

[0025] When the aforementioned aromatic dianhydride includes pyromellitic dianhydride (PMDA), the ratio of pyromellitic dianhydride (PMDA) can be 1-50 mol% of the aromatic dianhydride.

[0026] When the aforementioned aromatic dianhydride includes 4,4'-diphenyl ether dianhydride (ODPA), the ratio of 4,4'-diphenyl ether dianhydride (ODPA) can be 1-15 mol% of the aromatic dianhydride.

[0027] The aforementioned aromatic diamine may be p-phenylenediamine (PDA), 4,4'-diaminodiphenyl ether (ODA), 1,4-bis(4-aminophenoxy)benzene (TPEQ), 1,3-bis(4-aminophenoxy)benzene (TPER), 1,3-bis(3-aminophenoxy)benzene (APB-N), 4-aminophenyl-4-aminobenzoate (APAB), 4,4'-bis(4-aminophenoxy)biphenyl (BAPB), 9,9-bis(4-aminophenyl)fluorene (BAFL), 4,4'-diamino-2,2'-dimethylbiphenyl (m-TB), or a combination of more than one thereof.

[0028] The aforementioned aromatic diamine is preferably p-phenylenediamine (PDA) and 4,4'-diaminodiphenyl ether (ODA), or a combination of one or more thereof.

[0029] When the aforementioned aromatic diamine comprises p-phenylenediamine (PDA) and 4,4'-diaminodiphenyl ether (ODA), the ratio of p-phenylenediamine (PDA) can be 0-35 mol% of the aromatic diamine; the ratio of 4,4'-diaminodiphenyl ether (ODA) can be 100-65 mol% of the aromatic diamine.

[0030] [Preparation of the second polyamine solution]

[0031] The second polyamine solution is composed of dianhydride and diamine. The dianhydride component and the diamine component are polymerized in an organic solvent to form the second polyamine solution.

[0032] The aforementioned organic solvents may include dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and N,N-dimethylformamide (DMF). In the present invention, dimethylacetamide is used as the solvent.

[0033] The dianhydride is selected from any one of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), hexafluorodianhydride (6FDA), bisphenol A diether dianhydride (BPADA), and cyclobutanetetracarboxylic dianhydride (CBDA), or a combination of more than one thereof.

[0034] The aforementioned dianhydride is preferably any one of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), hexafluorodianhydride (6FDA), and bisphenol A diether dianhydride (BPADA), or a combination of more than one thereof.

[0035] When the aforementioned dianhydride includes 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), the ratio of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) can be 5-20 mol% of the aromatic dianhydride.

[0036] When the aforementioned dianhydride includes cyclobutanetetracarboxylic dianhydride (CBDA), the ratio of cyclobutanetetracarboxylic dianhydride (CBDA) can be 50-80 mol% of the dianhydride.

[0037] The diamine is selected from 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 3,4'-diaminodiphenyl ether (3,4ODA), 4,4'-bis(3-aminophenoxy)diphenylsulfone (m-BAPS), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 3,5-diaminobenzoic acid (3,5DABA), 3,3'-diaminodiphenylsulfone (3,3DDS), 4,4'-diaminodiphenylsulfone (4,4DDS), 4,4'-[1,3-phenylenebis(1-methylethylidene)]dianiline (Bisaniline-M), 4,4'-[1,4-phenylenebis(1-methylethylidene)]dianiline (Bisaniline-P), 1,4-bis(4-aminophenoxy)benzene (TPEQ), or a combination of more than one thereof.

[0038] The aforementioned diamine is preferably 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4'-[1,3-phenylenebis(1-methylethylidene)]dianiline (Bisaniline-M), 4,4'-[1,4-phenylenebis(1-methylethylidene)]dianiline (Bisaniline-P), or 1,4-bis(4-aminophenoxy)benzene (TPEQ), or a combination of one or more thereof.

[0039] [Production of matte polyimide film]

[0040] The first polyamide solution and the second polyamide solution are mixed to form a polyamide mixed solution. A catalyst and a dehydrating agent are added to the polyamide mixed solution for chemical cyclization to obtain a polyimide coating solution. The polyimide coating solution is coated on a glass substrate and then baked to obtain a matte polyimide film.

[0041] In the aforementioned film forming process, the substrate may be a glass substrate or a metal substrate.

[0042] The first polyamine solution is converted into a first polyimide through chemical cyclization.

[0043] The second polyamine solution is converted into a second polyimide through chemical cyclization.

[0044] The matte polyimide film comprises a first polyimide and a second polyimide.

[0045] The aforementioned second polyimide accounts for 5-40 wt% of the matte polyimide film.

[0046] The matte polyimide film may have a thickness of 5 to 100 μm.

[0047] The perception of matte effect varies from person to person. The generally acceptable 60-degree glossiness is 30-80 GU. The matte effect defined in the present invention is less than 60 GU at 60-degree glossiness. In this case, the matte polyimide film has a matte effect.

[0048] The matte polyimide film may be added with fillers selected from at least one of carbon black, silicon dioxide, titanium dioxide, boron nitride, aluminum oxide, and polyimide powder, or a combination thereof.

[0049] The aforementioned catalyst can be pyridine, 3-methylpyridine, 2-methylpyridine, 4-methylpyridine, isoquinoline, quinoline, or triethylamine, with pyridine, 3-methylpyridine, 2-methylpyridine, and 4-methylpyridine being preferred. In the present invention, 3-methylpyridine is selected as the catalyst.

[0050] The aforementioned dehydrating agent can be acetic anhydride or benzoic anhydride. In the present invention, acetic anhydride is selected as the dehydrating agent.

[0051] The present invention is described in detail based on the following examples, but the present invention is not limited thereto. Furthermore, the abbreviations and full names of the components of the present invention are as follows:

[0052] Dianhydride: PMDA:Pyromellitic Dianhydride BPDA:3,3',4,4'-biphenyltetracarboxylic dianhydride 6FDA: Hexafluorodianhydride BPADA: Bisphenol A diether dianhydride CBDA: Cyclobutanetetracarboxylic dianhydride 6FODA: Bis-(4-amino-2-methylthio-thiazol-5-yl)-one

[0053] Diamine: PDA: p-phenylenediamine ODA:4,4'-diaminodiphenyl ether 3,4ODA: 3,4'-diaminodiphenyl ether TFMB:2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl m-BAPS:4,4'-bis(3-aminophenoxy)diphenylsulfone BAPP:2,2-bis[4-(4-aminophenoxy)phenyl]propane Bisaniline-M:4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline Bisaniline-P:4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline

[0054] Solvent: DMAc: dimethylacetamide AA: Acetic anhydride AP:3-Picoline

[0055] <Detection method>

[0056] Intrinsic viscosity measurement

[0057] The first polyamine solution in the embodiment was prepared into a test solution with a concentration of 0.5 wt %, 18 g.

[0058] Place 13 ml of DMAc solvent in an Oswald viscometer. Place the Oswald viscometer in a 25°C constant-temperature water bath. After temperature equilibration, measure the time using a kinematic viscometer (SI Analytics, model AVS470). Record the time as T0.

[0059] After cleaning and drying the Oswald viscometer, place the solution to be tested in the Oswald viscometer in a 25°C constant-temperature water bath. After the temperature equilibrates, use a dynamic viscometer (SI Analytics, model: AVS470) to measure the time. Record the time as T1.

[0060] Substitute the concentration of the test solution, T0, and T1 into the following formula to calculate the inherent viscosity of the first polyamine solution.

[0061] Intrinsic viscosity = (ln(T1 / T0)) / C

[0062] Gloss measurement

[0063] Gloss: A BYK micro-TRI-gloss gloss meter was used to measure gloss at 60 degrees. [[Example 1]]

[0064] Preparation of the first polyamine solution

[0065] 52.649 g of ODA was added to 440 g of DMAc and stirred. After the ODA was dissolved, 57.351 g of PMDA was added. The temperature was controlled at 25°C. After stirring for 2 hours, a small amount of PMDA was used to adjust the viscosity. The resulting first polyamine solution had a solids content of 20% and a viscosity of 147,000 cps.

[0066] Preparation of the second polyamine solution

[0067] 59.957 g of TFMB was added to 412.5 g of DMAc and stirred. After TFMB was dissolved, 11.016 g of BPDA was added. After stirring for 30 minutes, 66.533 g of 6FDA was added. The temperature was controlled at 25°C to obtain a second polyamine solution with a solid content of 25%.

[0068] Preparation of matte polyimide film

[0069] After uniformly mixing 22 grams of the first polyamide solution, 18 grams of DMAc solvent, and 0.9263 grams of the second polyamide solution, AA and DMAc were diluted in a weight ratio of 5:1, and AP and DMAc were diluted in a weight ratio of 1:1. 3.87 milliliters of the AA dilution and 2.35 milliliters of the AP dilution were added to the mixture. After uniform mixing, the mixture was degassed using a centrifugal degasser. The degassed solution was poured onto a glass substrate and coated using a doctor blade with a 300μm gap. The coated sample was baked in an 80°C oven for 20 minutes, then heated at a rate of 1.8°C / min to 170°C for 20 minutes, and then heated at a rate of 2.0°C / min to 350°C for 20 minutes to form a matte polyimide film.

[0070] The glass substrate was immersed in water, and the matte polyimide film was peeled off from the glass substrate. The film had a thickness of 15 μm. [Example 2]

[0071] The preparation of the first polyamine solution is the same as in Example 1

[0072] The preparation of the second polyamine solution is the same as in Example 1

[0073] Production of matte polyimide film

[0074] After thoroughly mixing 22 grams of the first polyamide solution, 18 grams of DMAc solvent, and 3.1059 grams of the second polyamide solution, AA and DMAc were diluted in a weight ratio of 5:1, and AP and DMAc were diluted in a weight ratio of 1:1. 3.87 milliliters of the AA dilution and 2.35 milliliters of the AP dilution were then added. After thorough mixing, the mixture was degassed using a centrifugal degasser. The degassed solution was poured onto a glass substrate and coated using a doctor blade with a 300μm gap. The coated sample was baked in an 80°C oven for 20 minutes, then heated at a rate of 1.8°C / min to 170°C for 20 minutes, and then heated at a rate of 2.0°C / min to 350°C for 20 minutes to form a matte polyimide film.

[0075] The glass substrate was immersed in water, and the matte polyimide film was peeled off from the glass substrate. The film had a thickness of 15 μm. [Example 3]

[0076] The preparation of the first polyamine solution is the same as in Example 1

[0077] The preparation of the second polyamine solution is the same as in Example 1

[0078] Preparation of matte polyimide film

[0079] After mixing 22 grams of the first polyamide solution, 18 grams of DMAc solvent, and 5.8667 grams of the second polyamide solution, AA and DMAc were diluted in a weight ratio of 5:1, and AP and DMAc were diluted in a weight ratio of 1:1. 3.87 milliliters of the AA dilution and 2.35 milliliters of the AP dilution were added to the mixture. After uniform mixing, the mixture was degassed using a centrifugal degasser. The degassed solution was poured onto a glass substrate and coated using a doctor blade with a 300μm gap. The coated sample was baked in an 80°C oven for 20 minutes, then heated at a rate of 1.8°C / min to 170°C for 20 minutes, and then heated at a rate of 2.0°C / min to 350°C for 20 minutes to form a matte polyimide film.

[0080] The glass substrate was immersed in water, and the matte polyimide film was peeled off from the glass substrate. The film had a thickness of 15 μm. [[Example 4]]

[0081] The preparation of the first polyamine solution is the same as in Example 1

[0082] The preparation of the second polyamine solution is the same as in Example 1

[0083] Preparation of matte polyimide film

[0084] After uniformly mixing 22 grams of the first polyamide solution, 18 grams of DMAc solvent, and 7.5429 grams of the second polyamide solution, AA and DMAc were diluted in a weight ratio of 5:1, and AP and DMAc were diluted in a weight ratio of 1:1. 3.87 milliliters of the AA dilution and 2.35 milliliters of the AP dilution were added, respectively. After uniform mixing, the mixture was degassed using a centrifugal degasser. The degassed solution was poured onto a glass substrate and coated using a doctor blade with a 300μm gap. The coated sample was baked in an 80°C oven for 20 minutes, then heated at a rate of 1.8°C / min to 170°C for 20 minutes, and then heated at a rate of 2.0°C / min to 350°C for 20 minutes to form a matte polyimide film.

[0085] The glass substrate was immersed in water, and the matte polyimide film was peeled off from the glass substrate. The film had a thickness of 15 μm. [Example 5]

[0086] Preparation of the first polyamine solution

[0087] 46.280 g of ODA and 4.411 g of PDA were added to 440 g of DMAc and stirred. After the ODA and PDA were dissolved, 58.123 g of PMDA was added. The temperature was controlled at 25°C. After stirring for 2 hours, a small amount of PMDA was used to adjust the viscosity. The resulting first polyamine solution had a solids content of 20% and a viscosity of 141,000 cps.

[0088] The preparation of the second polyamine solution is the same as in Example 1

[0089] Production of matte polyimide film

[0090] After mixing 22 grams of the first polyamide solution, 18 grams of DMAc solvent, and 3.1059 grams of the second polyamide solution, AA and DMAc were diluted in a weight ratio of 5:1, and AP and DMAc were diluted in a weight ratio of 1:1. 4.00 milliliters of the AA dilution and 2.43 milliliters of the AP dilution were added to the mixture. After uniform mixing, the mixture was degassed using a centrifugal degasser. The degassed solution was poured onto a glass substrate and coated using a doctor blade with a 300μm gap. The coated sample was baked in an 80°C oven for 20 minutes, then heated at a rate of 1.8°C / min to 170°C for 20 minutes, and then heated at a rate of 2.0°C / min to 350°C for 20 minutes to form a matte polyimide film.

[0091] The glass substrate was immersed in water, and the matte polyimide film was peeled off from the glass substrate. The film had a thickness of 15 μm. [Example 6]

[0092] Preparation of the first polyamine solution

[0093] 36.152 g of ODA and 10.513 g of PDA were added to 442.8 g of DMAc and stirred. After the ODA and PDA were dissolved, 59.373 g of PMDA was added. The temperature was controlled at 25°C. After stirring for 2 hours, a small amount of PMDA was used to adjust the viscosity. The resulting first polyamine solution had a solids content of 19.5% and a viscosity of 79,920 cps.

[0094] The preparation of the second polyamine solution is the same as in Example 1

[0095] Preparation of matte polyimide film

[0096] After uniformly mixing 22.56 g of the first polyamide solution, 17.44 g of DMAc solvent, and 3.1059 g of the second polyamide solution, AA and DMAc were diluted in a weight ratio of 5:1, and AP and DMAc were diluted in a weight ratio of 1:1. 4.19 ml of the AA dilution and 2.55 ml of the AP dilution were then added. After uniform mixing, the mixture was degassed using a centrifugal degasser. The degassed solution was poured onto a glass substrate and coated using a doctor blade with a 300 μm gap. The coated sample was baked in an 80°C oven for 20 minutes, then heated at a rate of 1.8°C / min to 170°C for 20 minutes, and then heated at a rate of 2.0°C / min to 350°C for 20 minutes to form a matte polyimide film.

[0097] The glass substrate was immersed in water, and the matte polyimide film was peeled off from the glass substrate. The film had a thickness of 15 μm. [Example 7]

[0098] Preparation of the first polyamine solution

[0099] 36.010 g of ODA and 10.472 g of PDA were added to 442.8 g of DMAc and stirred. After the ODA and PDA were dissolved, 1.628 g of BPDA was added. After 10 minutes of reaction, 58.537 g of PMDA was added. The temperature was controlled at 25°C. After stirring for 2 hours, a small amount of PMDA was used to adjust the viscosity. The resulting first polyamine solution had a solids content of 19.5% and a viscosity of 76,200 cps.

[0100] The preparation of the second polyamine solution is the same as in Example 1

[0101] Preparation of matte polyimide film

[0102] After mixing 22.56 grams of the first polyamide solution, 17.44 grams of DMAc solvent, and 3.1059 grams of the second polyamide solution, AA and DMAc were diluted in a weight ratio of 5:1, and AP and DMAc were diluted in a weight ratio of 1:1. 4.17 milliliters of the AA dilution and 2.54 milliliters of the AP dilution were added to the mixture. After uniform mixing, the mixture was degassed using a centrifugal degasser. The degassed solution was poured onto a glass substrate and coated using a doctor blade with a 300μm gap. The coated sample was baked in an 80°C oven for 20 minutes, then heated at a rate of 1.8°C / min to 170°C for 20 minutes, and then heated at a rate of 2.0°C / min to 350°C for 20 minutes to form a matte polyimide film.

[0103] The glass substrate was immersed in water, and the matte polyimide film was peeled off from the glass substrate. The film had a thickness of 15 μm. [[Example 8]]

[0104] Preparation of the first polyamine solution

[0105] 5.974 g of ODA and 29.037 g of PDA were added to 431.8 g of DMAc and stirred. After the ODA and PDA were dissolved, 13.015 g of PMDA was added. After 10 minutes of reaction, 69.346 g of BPDA was added. The temperature was controlled at 25°C and the reaction was stirred for 12 hours. After that, a small amount of BPDA was used to adjust the viscosity. The resulting first polyamine solution had a solids content of 21.5% and a viscosity of 102,600 cps.

[0106] The preparation of the second polyamine solution is the same as in Example 1

[0107] After mixing 20.47 g of the first polyamide solution, 19.53 g of DMAc solvent, and 3.1059 g of the second polyamide solution, AA and DMAc were diluted in a weight ratio of 5:1, and AP and DMAc were diluted in a weight ratio of 1:1. 4.08 ml of the AA dilution and 2.48 ml of the AP dilution were added to the mixture. After uniform mixing, the mixture was degassed using a centrifugal degasser. The degassed solution was poured onto a glass substrate and coated using a 300 μm-gap doctor blade. The coated sample was baked in an 80°C oven for 20 minutes, then heated at a rate of 1.8°C / min to 170°C for 20 minutes, and then heated at a rate of 2.0°C / min to 350°C for 20 minutes to form a matte polyimide film.

[0108] The glass substrate was immersed in water, and the matte polyimide film was peeled off from the glass substrate. The film had a thickness of 15 μm. [Example 9]

[0109] Preparation of the first polyamine solution

[0110] 21.455 g of ODA and 22.747 g of m-TB were added to 442.8 g of DMAc and stirred. After complete dissolution, 62.418 g of BPDA was added. The temperature was controlled at 25°C. After stirring for 12 hours, a small amount of BPDA was used to adjust the viscosity. The resulting first polyamine solution had a solids content of 19.5% and a viscosity of 124,000 cps.

[0111] The preparation of the second polyamine solution is the same as in Example 1

[0112] Preparation of matte polyimide film

[0113] After uniformly mixing 22.56 g of the first polyamide solution, 17.44 g of DMAc solvent, and 3.1059 g of the second polyamide solution, AA and DMAc were diluted in a weight ratio of 5:1, and AP and DMAc were diluted in a weight ratio of 1:1. 3.56 ml of the AA dilution and 2.16 ml of the AP dilution were added to the mixture. After uniform mixing, the mixture was degassed using a centrifugal degasser. The degassed solution was poured onto a glass substrate and coated using a doctor blade with a 300 μm gap. The coated sample was baked in an 80°C oven for 20 minutes, then heated at a rate of 1.8°C / min to 170°C for 20 minutes, and then heated at a rate of 2.0°C / min to 350°C for 20 minutes to form a matte polyimide film.

[0114] The glass substrate was immersed in water, and the matte polyimide film was peeled off from the glass substrate. The film had a thickness of 15 μm. [Example 10]

[0115] Preparation of the first polyamine solution

[0116] 65.812 g of ODA was added to 412.5 g of DMAc and stirred. After the ODA was dissolved, 70.254 g of PMDA was added. The temperature was controlled at 25°C. After stirring for 2 hours, a small amount of PMDA was used to adjust the viscosity. The resulting first polyamine solution had a solids content of 25% and a viscosity of 153,000 cps.

[0117] Preparation of the second polyamine solution

[0118] 10.486 g of 34ODA was added to 101.3 g of DMAc and stirred. After the 34ODA was completely dissolved, 23.264 g of 6FDA was added and the temperature was controlled at 25°C to obtain a second polyamine solution with a solid content of 25%.

[0119] Preparation of matte polyimide film

[0120] After uniformly mixing 17.60 g of the first polyamide solution, 22.40 g of DMAc solvent, and 3.1059 g of the second polyamide solution, AA and DMAc were diluted in a weight ratio of 5:1, and AP and DMAc were diluted in a weight ratio of 1:1. 3.87 ml of the AA dilution and 2.35 ml of the AP dilution were then added. After uniform mixing, the mixture was degassed using a centrifugal degasser. The degassed solution was poured onto a glass substrate and coated using a doctor blade with a 300 μm gap. The coated sample was baked in an 80°C oven for 20 minutes, then heated at a rate of 1.8°C / min to 170°C for 20 minutes, and then heated at a rate of 2.0°C / min to 350°C for 20 minutes to form a matte polyimide film.

[0121] The glass substrate was immersed in water, and the matte polyimide film was peeled off from the glass substrate. The film had a thickness of 15 μm. [Example 11]

[0122] The preparation of the first polyamine solution is the same as in Example 10

[0123] Preparation of the second polyamine solution

[0124] 16.876 g of TFMB was added to 101.3 g of DMAc and stirred. After TFMB was dissolved, 5.168 g of CBDA was added and allowed to react for 30 minutes. Then, 11.706 g of 6FDA was added and the temperature was controlled at 25°C to obtain a second polyamine solution with a solid content of 25%.

[0125] 15.317 g of m-BAPS was added to 101.3 g of DMAc and stirred. After the m-BAPS was completely dissolved, 18.433 g of BPADA was added. The temperature was controlled at 25°C to obtain a second polyamine solution with a solid content of 25%.

[0126] The preparation of matte polyimide film is the same as Example 10 [Example 12]

[0127] The preparation of the first polyamine solution is the same as in Example 10

[0128] Preparation of the second polyamine solution

[0129] 15.317 g of m-BAPS was added to 101.3 g of DMAc and stirred. After the m-BAPS was completely dissolved, 18.433 g of BPADA was added. The temperature was controlled at 25°C to obtain a second polyamine solution with a solid content of 25%.

[0130] The preparation of matte polyimide film is the same as Example 10 [Example 13]

[0131] The preparation of the first polyamine solution is the same as in Example 10

[0132] Preparation of the second polyamine solution

[0133] 13.442 g of Bisaniline-M was added to 101.3 g of DMAc and stirred. After the Bisaniline-M was dissolved, 20.308 g of BPADA was added and the temperature was controlled at 25°C to obtain a second polyamine solution with a solid content of 25%.

[0134] 13.442 g of Bisaniline-P was added to 101.3 g of DMAc and stirred. After the Bisamiline-P was completely dissolved, 20.308 g of BPADA was added and the temperature was controlled at 25°C to obtain a second polyamine solution with a solid content of 25%.

[0135] The preparation of matte polyimide film is the same as Example 10 [Example 14]

[0136] The preparation of the first polyamine solution is the same as in Example 10

[0137] Preparation of the second polyamine solution

[0138] 13.442 g of Bisaniline-P was added to 101.3 g of DMAc and stirred. After the Bisaniline-P was dissolved, 20.308 g of BPADA was added and the temperature was controlled at 25°C to obtain a second polyamine solution with a solid content of 25%.

[0139] The preparation of matte polyimide film is the same as Example 10 [Example 15]

[0140] The preparation of the first polyamine solution is the same as in Example 10

[0141] Preparation of the second polyamine solution

[0142] 14.882 g of BAPP was added to 101.3 g of DMAc and stirred. After BAPP was dissolved, 18.868 g of BPADA was added and the temperature was controlled at 25°C to obtain a second polyamine solution with a solid content of 25%.

[0143] The preparation of matte polyimide film is the same as Example 10 [Comparative Example 1]

[0144] The preparation of the first polyamine solution is the same as in Example 1

[0145] The preparation of the second polyamine solution is the same as in Example 1

[0146] Preparation of matte polyimide film

[0147] After mixing 22 grams of the first polyamide solution, 18 grams of DMAc solvent, and 17.60 grams of the second polyamide solution, AA and DMAc were diluted in a weight ratio of 5:1, and AP and DMAc were diluted in a weight ratio of 1:1. 3.87 milliliters of the AA dilution and 2.35 milliliters of the AP dilution were added to the mixture. After uniform mixing, the mixture was degassed using a centrifugal degasser. The degassed solution was poured onto a glass substrate and coated using a doctor blade with a 300μm gap. The coated sample was baked in an 80°C oven for 20 minutes, then heated at a rate of 1.8°C / min to 170°C for 20 minutes, and then heated at a rate of 2.0°C / min to 350°C for 20 minutes to form a matte polyimide film.

[0148] The glass substrate was immersed in water, and the matte polyimide film was peeled off from the glass substrate. The film had a thickness of 15 μm. [Comparative Example 2]

[0149] Preparation of the first polyamine solution

[0150] 47.384 g of ODA was added to 451 g of DMAc and stirred. After the ODA was dissolved, 50.583 g of PMDA was added. The temperature was controlled at 25°C. After stirring for 2 hours, a small amount of PMDA was used to adjust the viscosity. The resulting first polyamine solution had a solids content of 18% and a viscosity of 222,700 cps.

[0151] The preparation of the second polyamine solution is the same as in Example 1

[0152] Preparation of matte polyimide film

[0153] After uniformly mixing 24.44 g of the first polyamide solution, 15.56 g of DMAc solvent, and 3.1059 g of the second polyamide solution, AA and DMAc were diluted in a weight ratio of 5:1, and AP and DMAc were diluted in a weight ratio of 1:1. 3.87 ml of the AA dilution and 2.35 ml of the AP dilution were then added. After uniform mixing, the mixture was degassed using a centrifugal degasser. The degassed solution was poured onto a glass substrate and coated using a doctor blade with a 300 μm gap. The coated sample was baked in an 80°C oven for 20 minutes, then heated at a rate of 1.8°C / min to 170°C for 20 minutes, and then heated at a rate of 2.0°C / min to 350°C for 20 minutes to form a matte polyimide film.

[0154] The glass substrate was immersed in water, and the matte polyimide film was peeled off from the glass substrate. The film had a thickness of 15 μm. [Comparative Example 3]

[0155] Preparation of the first polyamine solution is the same as in Comparative Example 2

[0156] The preparation of the second polyamine solution is the same as in Example 1

[0157] Preparation of matte polyimide film

[0158] After uniformly mixing 24.44 g of the first polyamide solution, 15.56 g of DMAc solvent, and 5.8667 g of the second polyamide solution, AA and DMAc were diluted in a weight ratio of 5:1, and AP and DMAc were diluted in a weight ratio of 1:1. 3.87 ml of the AA dilution and 2.35 ml of the AP dilution were then added. After uniform mixing, the mixture was degassed using a centrifugal degasser. The degassed solution was poured onto a glass substrate and coated using a doctor blade with a 300 μm gap. The coated sample was baked in an 80°C oven for 20 minutes, then heated at a rate of 1.8°C / min to 170°C for 20 minutes, and then heated at a rate of 2.0°C / min to 350°C for 20 minutes to form a matte polyimide film.

[0159] The glass substrate was immersed in water, and the matte polyimide film was peeled off from the glass substrate. The film had a thickness of 15 μm. [Comparative Example 4]

[0160] Preparation of the first polyamine solution

[0161] 27.700 g of ODA and 8.055 g of PDA were added to 467.5 g of DMAc and stirred. After the ODA and PDA were dissolved, 1.252 g of BPDA was added. After 10 minutes of reaction, 45.028 g of PMDA was added. The temperature was controlled at 25°C. After stirring for 2 hours, a small amount of PMDA was used to adjust the viscosity. The resulting first polyamine solution had a solids content of 15% and a viscosity of 50,640 cps.

[0162] The preparation of the second polyamine solution is the same as in Example 1

[0163] The preparation of matte polyimide film is the same as Example 7 [Comparative Example 5]

[0164] The preparation of the first polyamine solution is the same as in Example 6

[0165] Preparation of the second polyamine solution

[0166] 21.985 g of ODA and 14.512 g of PDA were added to 451 g of DMAc and stirred. After the ODA and PDA were dissolved, 35.893 g of BPDA was added. After 10 minutes of reaction, 26.077 g of PMDA was added. The temperature was controlled at 25°C and the reaction was stirred for 2 hours. A small amount of PMDA was then used to adjust the viscosity. The resulting second polyamine solution had a solids content of 18% and a viscosity of 154,000 cps.

[0167] The preparation of matte polyimide film is the same as Example 6 [Comparative Example 6]

[0168] The preparation of the first polyamine solution is the same as in Example 10

[0169] Preparation of the second polyamine solution

[0170] 69.843 g of TFMB was added to 412.5 g of DMAc. After TFMB was completely dissolved, 66.304 g of ODPA was added. The temperature was controlled at 25° C. to obtain a second polyamine solution with a solid content of 25%.

[0171] The preparation of matte polyimide film is the same as Example 10 [Comparative Example 7]

[0172] The preparation of the first polyamine solution is the same as in Example 10

[0173] Preparation of the second polyamine solution

[0174] 73.331 g of 6FODA was added to 412.5 g of DMAc. After the 6FODA was completely dissolved, 62.885 g of BPDA was added. The temperature was controlled at 25° C. to obtain a second polyamine solution with a solid content of 25%.

[0175] The preparation of matte polyimide film is the same as Example 10

[0176] The results of the embodiments and comparative examples are summarized in Table 1.

[0177] The examples show that by using a first polyamide solution having an intrinsic viscosity of less than 1.2 dL / g in combination with a specific second polyamide solution, a polyimide film with low gloss can be obtained after film formation by chemical cyclization.

[0178] As shown in Examples 1 to 4, the higher the addition ratio of soluble polyimide within a specific range, the lower the glossiness. Conversely, if the addition ratio exceeds the specific range, the glossiness increases.

[0179] Comparing Example 2 with Comparative Example 2, if a first polyamide solution with an inherent viscosity greater than 1.2 dL / g is selected, the gloss value is greatly increased.

[0180] Since the value of intrinsic viscosity is proportional to the molecular weight, when the molecular weight is too large, the phase separation effect will be restrained by the larger molecular weight, resulting in the extinction effect of the two polyimides due to phase separation being not strong enough, and thus the gloss value is larger.

[0181] Comparative Examples 5 and 6 show that if the second polyimide of the specific composition is not used, the matting effect is still poor even if the intrinsic viscosity of the first polyimide is less than 1.2 dL / g.

[0182] The above specific embodiments are provided to illustrate the present invention in detail. However, these embodiments are for illustrative purposes only and are not intended to limit the present invention. Those skilled in the art will appreciate that various changes and modifications to the present invention that do not depart from the scope of the appended claims are considered to be within the scope of the present invention. S1: Providing a first polyamine solution S2: Providing a second polyamine solution S3: Forming a polyamine mixed solution S4: Forming a polyimide coating solution S5: Forming a matte polyimide film

Claims

1. A method for manufacturing a matte polyimide film, comprising the following steps: providing an aromatic dianhydride and an aromatic diamine; adding a solvent and polymerizing to form a first polyamide solution, wherein the intrinsic viscosity of the first polyamide solution is less than 1.2 dL / g; wherein the aromatic dianhydride may be any one or a combination of more than one of pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), 4,4'-diphenyl ether dianhydride (ODPA), p-phenylene bis(phenyl)trimethoxylate dianhydride (TAHQ), and 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA); and the aromatic diamine may be p-phenylenediamine (P... The following are provided: DA), 4,4'-diaminodiphenyl ether (ODA), 1,4-bis(4-aminophenoxy)benzene (TPEQ), 1,3-bis(4-aminophenoxy)benzene (TPER), 1,3-bis(3-aminophenoxy)benzene (APB-N), 4-aminophenyl-4-aminobenzoate (APAB), 4,4'-bis(4-aminophenoxy)biphenyl (BAPB), 9,9-bis(4-aminophenyl)fluorene (BAFL), 4,4'-diamino-2,2'-dimethylbiphenyl (m-TB) or a combination thereof; a dianhydride and a diamine are provided, and a solvent is added for polymerization to form a second polyacrylic acid solution, wherein... The dianhydride can be any one or a combination of more than one of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), hexafluorodianhydride (6FDA), bisphenol A type diether dianhydride (BPADA), and cyclobutanetetracarboxylic acid dianhydride (CBDA), and the diamine can be 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 3,4'-diaminodiphenyl ether (3,4ODA), or 4,4'-bis(3-aminophenoxy)diphenyl 2,2-Bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 3,5-diaminobenzoic acid (3,5DABA), 3,3'-diamine diphenyl benzoate (3,3DDS), 4,4'-diaminodiphenyl benzoate (4,4DDS), 4,4'-[1,3-phenylenebis(1-methylethylene)]bisaniline (Bisaniline-M), 4,4'-[1,4-phenylenebis(1-methylethylene)]bisaniline [1-Methylethylidene] Bisaniline (P), 1,4-bis(4-aminophenoxy)benzene (TPEQ) or a combination thereof; a first polyamide solution and a second polyamide solution are mixed to form a polyamide mixed solution; the polyamide mixed solution is added to a catalyst and a dehydrating agent for chemical cyclization to obtain a polyimide coating liquid; wherein the catalyst may be pyridine, 3-methylpyridine, 2-methylpyridine, 4-methylpyridine, or 4-methylpyridine. The polyimide coating solution is composed of one or more of methylpyridine, isoquinoline, quinoline, and triethylamine, and the dehydrating agent may be one or more of acetic anhydride or benzoic anhydride; and the polyimide coating solution is coated onto a carrier and heated to 300-450°C to form a matte polyimide film having a first polyimide and a second polyimide with a gloss level of less than 60 GU at 60 degrees, wherein the second polyimide accounts for 5-40 wt% of the weight of the matte polyimide film.

2. A matte polyimide film manufactured by the method described in claim 1, comprising: a first polyimide; a second polyimide, the second polyimide accounting for 5-25 wt% of the film weight; and the matte polyimide film having a 60-degree gloss level of less than 60 GU.

3. The matte polyimide film as described in claim 2, wherein, The first polyimide may be pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), p-phenylenediamine (PDA), and 4,4'-diaminodiphenyl ether (ODA).

4. The matte polyimide film as described in claim 2, wherein, It may also include a carbon black, which accounts for 2 to 8 wt% of the film.

5. The matte polyimide film as described in claim 2, wherein, The thickness of the matte polyimide film is between 5 and 100 μm.

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