WO2023243967A1 - Black polyimide film and manufacturing method thereof - Google Patents

Black polyimide film and manufacturing method thereof Download PDF

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Publication number
WO2023243967A1
WO2023243967A1 PCT/KR2023/008058 KR2023008058W WO2023243967A1 WO 2023243967 A1 WO2023243967 A1 WO 2023243967A1 KR 2023008058 W KR2023008058 W KR 2023008058W WO 2023243967 A1 WO2023243967 A1 WO 2023243967A1
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bis
aminophenoxy
dianhydride
mol
phenyl
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PCT/KR2023/008058
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French (fr)
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Moon Jin Yeo
Jin Seok Jeon
Dong Young Won
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Pi Advanced Materials Co., Ltd.
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Publication of WO2023243967A1 publication Critical patent/WO2023243967A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Provided is a black polyimide film formed by imidizing a polyamic acid obtained from a dianhydride monomer and a diamine monomer, comprising: a black pigment containing bituminous coal and lactam black.

Description

BLACK POLYIMIDE FILM AND MANUFACTURING METHOD THEREOF
The present invention relates to a black polyimide film and a manufacturing method thereof, and more particularly, to a low dielectric (low-k) black polyimide film comprising black pigment and a manufacturing method thereof.
Polyimide is a general term for polymers having an imide structure, and in general, is prepared by condensation reaction of aromatic acid anhydride and aromatic diamine, and has excellent characteristics such as high heat resistance to withstand from extremely low temperatures to high temperatures of over 400℃, electrical insulation, radiation resistance, chemical resistance, and the like, and thus it is used in a wide range of fields as high-tech materials and insulating coatings, for example, in the fields of electrical and electronics, semiconductors, displays, automobiles, aerospace, and space materials.
However, the use of polyimide has been limited due to the "insoluble or infusible" property that it is not soluble in solvents and it is not molded by heating. Accordingly, most polyimides are manufactured by processing polyamic acid, which is a precursor, followed by high temperature heat treatment and a curing imidization process, and a representative product manufactured in this way is a polyimide film.
Recently, it is widely used as a coverlay for portable electronic devices and communication devices. Coverlay is designed for protecting electronic components such as printed wiring boards and lead frames of semiconductor integrated circuits, and the like, and requires physical properties such as thin filming and slimming, and the like, and in recent years, also requires optical properties as well as security, portability, visual effects, and concealability of electronic or mounted components.
Generally, both matting agents and color additives (for example, pigments or dyes) are used in manufacture of polyimide films. In conventional manufacturing processes, color additives (such as carbon black) may be usually contained to reduce the transparency of the polyimide film, while matting agents such as SiO2 may be added to reduce the gloss of the polyimide film. However, neither the color additive nor the matting agent alone is capable of achieving matting property and reducing transparency. Thus, the conventional manufacturing processes require the use of large amounts of color additives and matting agents in order to impart desired properties to polyimide films, which may cause problems such as not only difficulty in handling and poor dispersion of additives but also high dielectric constant and dielectric loss factor, which has a difficult problem in internalizing 5G electronic devices.
Therefore, there is a need to develop a black polyimide film for high-speed transmission containing an optimal black pigment capable of satisfying all of low dielectric constant and dielectric loss factor, and low gloss and transmittance without adding a matting agent.
An object of the present invention is to provide a low dielectric (low-k) black polyimide film comprising a black pigment having a controlled particle diameter in polyimide, having excellent optical properties such as gloss, transmittance, and the like, and achieving a low dielectric constant and a low dielectric loss factor.
In addition, another object of the present invention is to provide a manufacturing method of the black polyimide film.
Further, still another object of the present invention is to provide a coverlay comprising the black polyimide film.
In addition, still another object of the present invention is to provide an electronic device for high-speed transmission comprising the coverlay.
Hereinafter, exemplary embodiments of the present invention will be described in more detail in the order of "black polyimide film" and "manufacturing method of black polyimide film" according to the present invention.
Since the present invention may make various modifications and have various exemplary embodiments, specific exemplary embodiments are described in detail. However, these are not intended to limit the present invention to specific exemplary embodiments, and should be understood to comprise all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.
Terms used in the present application are only used to describe specific exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise", "have", and the like, are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and it should be understood that these terms do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.
When an amount, concentration, or other value or parameter in the present specification is provided as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed.
Where a range of numerical values is recited herein, unless otherwise stated, it is not intended that the range be limited to the endpoints and the scope of the invention be limited to the specific values recited when defining a range.
As used herein, term "dianhydride" is intended to include precursors or derivatives thereof, also referred to as "dianhydride acid", "dianhydride" or "acid dianhydride". This may not technically be dianhydride, but nevertheless, it will react with diamine to form polyamic acid, which may be converted back to polyimide.
"Diamine" herein is intended to include precursors or derivatives thereof, which may technically not be diamine, but may nonetheless react with dianhydride acid to form a polyamic acid, which may be converted back to polyimide.
Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiments belong. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in this application, it is not to be construed in an idealized or overly formal sense. Specific details for the implementation of the invention will be described below.
Black polyimide film
The present invention provides a black polyimide film comprising a black pigment containing bituminous coal and lactam black, wherein the black polyimide film is formed by imidizing a polyamic acid obtained from a dianhydride monomer and a diamine monomer.
Bituminous coal, also called soft coal, is black or dark black coal with a glass luster or resin luster, and has a high content of volatile substances. In the present invention, bituminous coal may contain up to 20% of volatile matter and about 75% of fixed carbon. In addition, bituminous coal may contain up to 1% of moisture, up to 0.9% of SO2, and about 7.5% of ash. By containing bituminous coal in the polyimide film of the present invention, gloss may be lowered.
The bituminous coal, for example, may be Mineral Black 325 BA (Keystone Filley & Mfg.Co.), Austin Black 325 (Coal Fillers Inc.), or a combination thereof, and Examples of the present invention used Austin Black 325 manufactured by Coal Fillers Inc.
Lactam black pigment, which is an infrared ray transmitting pigment, is one of black organic pigments made of organic materials and absorbing light in a visible light wavelength range to show a black color, and contains a lactam structure in a molecule.
Examples of the lactam black may include BASF's Black 582 and Irgaphor (registered trademark) Black S0100CF, and SKC High-Tech & Marketing's SBPI-1. In an embodiment of the present invention, SBPI-1 manufactured by SKC Hi-Tech & Marketing Co., Ltd., was used.
In the present invention, the film may contain 5 to 30% by weight of the black pigment based on the total weight of the film. Preferably, the lower limit amount of the black pigment may be 5% by weight or more, 6% by weight or more, 7% by weight or more, 8% by weight or more, 9% by weight or more, 10% by weight or more, 11% by weight or more, 12% by weight or more, 13% by weight or more or 14% by weight or more, and the upper limit amount thereof may be 30% by weight or less, 29% by weight or less, 28% by weight or less, 27% by weight or less, 26% by weight or less, 25% by weight or less, 24% by weight or less, 23% by weight or less, 22% by weight or less, 21% by weight or less, 20% by weight or less, 19% by weight or less, 18% by weight or less, or 17% by weight or less. When the amount of the black pigment in the film is less than 5% by weight, the light transmittance may increase, and when the amount is more than 30% by weight, the dispersibility and physical properties of the film may be poor.
In the present invention, the film may contain 3 to 15% by weight of bituminous coal and 2 to 15% by weight of lactam black based on the total weight of the film. Preferably, the film may contain 5 to 10% by weight of the bituminous coal and 4 to 10% by weight of the lactam black based on the total weight of the film. For example, the lower limit amount of the bituminous coal may be 3% by weight or more, 3.5% by weight or more, 4% by weight or more, 4.5% by weight or more, 5% by weight or more, 5.5% by weight or more, 6% by weight or more, or 6.5% by weight or more, and the upper limit amount thereof may be 10% by weight or less, 9% by weight or less, 8% by weight or less, or 7% by weight or less. When bituminous coal is used in excess of 15% by weight, it is not effective in lowering the transmittance.
Further, as an example, the lower limit amount of lactam black may be 2% by weight or more, 2.5% by weight or more, 3% by weight or more, 3.5% by weight or more, 4% by weight or more, 4.5% by weight or more, 5% by weight or more, 5.5% by weight or more, 6% by weight or more, 6.5% by weight or more, 7% by weight or more or 7.5% by weight or more, and the upper limit amount thereof may be 10% by weight or less, 9.5% by weight or less, 9% by weight or less, 8.5% by weight or less, or 8% by weight or less.
In the present invention, it is possible to keep gloss, transmittance, dielectric constant, and dielectric loss factor lower by comprising the black pigment containing bituminous coal and lactam black.
In the present invention, the bituminous coal may have an average particle diameter (D50) of 0.5 to 10 μm, preferably 1 to 8 μm, and more preferably 2 to 5 μm. In addition, the bituminous coal may have an average particle diameter (D10) of 0.5 to 2 μm and an average particle diameter (D90) of 3 to 7 μm. The average particle diameter of bituminous coal may indicate an average particle diameter after milling. When the average particle diameter (D50) exceeds 10 μm, surface properties of the film may be damaged, dispersibility may be lowered, or mechanical properties of the film may be deteriorated.
In the present invention, the lactam black may have an average particle diameter (D50) of 30 nm to 1000 nm, specifically 40 nm to 900 nm, more specifically 50 nm to 500 nm, still more specifically 100 nm to 300 nm, and even more specifically, 100 nm to 200 nm. In addition, the lactam black may have an average particle diameter (D10) of 100 to 200 nm, and an average particle diameter (D90) of 100 to 300 nm. The average particle diameter of lactam black may indicate an average particle diameter after milling. When the average particle diameter (D50) exceeds 1000 nm, surface properties of the film may be damaged, dispersibility may be lowered, or mechanical properties of the film may be deteriorated.
The present invention may implement a black polyimide film having low gloss, transparency, dielectric constant and dielectric loss factor by adjusting the particle diameter of the black pigment to an appropriate particle diameter through milling.
In the present invention, the dianhydride monomer may be at least one selected from the group consisting of pyromellitic dianhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), diphenylsulfone-3,4,3',4'-tetracarboxylic dianhydride (DSDA), bis(3,4-dicarboxyphenyl)sulfide dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, p-phenylenebis(trimellitic monoester acid anhydride), p-biphenylenebis(trimellitic monoester acid anhydride), m-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 4,4'-(2,2-hexafluoroisopropylidene)diphthalic acid dianhydride, and specifically, may be at least one selected from the group consisting of pyromellitic dianhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), and 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), and more specifically, may be at least one selected from the group consisting of pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), and 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA).
Further, the diamine monomer may be at least one selected from the group consisting of paraphenylenediamine (PPD), metaphenylenediamine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzoic acid (DABA), 4,4'-oxydianiline (ODA), 4,4'-diamino diphenylether, 3,4'-diaminodiphenylether, 4,4'-diaminodiphenylmethane (4,4'-Methylenedianiline), 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis(4-aminophenyl)sulfide, 4,4'-diaminobenzanilide, 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenylether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfoxide, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,4-bis(3-aminophenoxy)benzene (TPE-Q), 1,3-bis(3-aminophenoxy)-4-trifluoromethylbenzene, 3,3'-diamino-4-(4-phenylphenoxy)benzophenone, 3,3'-diamino-4,4'-di(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenylsulfide)benzene, 1,3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenylsulfide)benzene, 1,3-bis(3-aminophenylsulfone)benzene, 1,3-bis(4-aminophenylsulfone)benzene, 1,4-bis(4-aminophenylsulfone)benzene, 1,3-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4-aminophenyl)isopropyl]benzene, 3,3'-bis(3-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[3-(3-aminophenoxy)phenyl]ketone, bis[3-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone, bis[3-(3-aminophenoxy)phenyl]sulfide, bis[3-(4-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[3-(3-aminophenoxy)phenyl]sulfone, bis[3-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]methane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, and the like, and specifically, may be at least one selected from the group consisting of paraphenylenediamine (PPD), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), 4,4'-oxydianiline (ODA) and 1,3-bis(4-aminophenoxy)benzene (TPE-R), and more specifically, may be para-phenylenediamine (PPD) and 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine).
In an embodiment, the polyamic acid contains, as polymerized units, a mixture of dianhydride monomers including pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), and 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), and diamine monomers including paraphenylenediamine (PPD) and 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine).
Here, among the total dianhydride monomer components, pyromellitic dianhydride (PMDA) may be included in an amount of 20 mol% or more to 80 mol% or less, preferably 22 mol% or more, 24 mol% or more, 26 mol% or more, 28 mol% or more, 30 mol% or more, 31 mol% or more, 32 mol% or more, 33 mol% or more, 34 mol% or more, 35 mol% or more, 36 mol% or more, 37 mol% or more, 38 mol% or more, 39 mol% or more, or 40 mol% or more, wherein the upper limit thereof may be 80 mol% or less, 75 mol% or less, 70 mol% or less, 65 mol% or less, 60 mol% or less, 55 mol% or less, 50 mol% or less, 48 mol% or less, 46 mol% or less, 44 mol% or less, 42 mol% or less, 40 mol% or less, 39 mol% or less, 38 mol% or less, 37 mol% or less, 36 mol% or less, 35 mol% or less, 34 mol% or less, 33 mol% or less, 32 mol% or less, 31 mol% or less, or 30 mol% or less.
In addition, among the total dianhydride monomer components, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) may be included in an amount of 10 mol% or more to 50 mol% or less, preferably 10 mol% or more, 15 mol% or more, 20 mol% or more, 22 mol% or more, 24 mol% or more, 26 mol% or more, 28 mol% or more, 30 mol% or more, 31 mol% or more, 32 mol% or more, 33 mol% or more, 34 mol% or more, 35 mol% or more, 36 mol% or more, 37 mol% or more, 38 mol% or more, 39 mol% or more, or 40 mol% or more, wherein the upper limit thereof may be 50 mol% or less, 48 mol% or less, 46 mol% or less, 44 mol% or less, 42 mol% or less, 40 mol% or less, 39 mol% or less, 38 mol% or less, 37 mol% or less, 36 mol% or less, 35 mol% or less, 34 mol% or less, 33 mol% or less, 32 mol% or less, 31 mol% or less, or 30 mol% or less.
Further, among the total dianhydride monomer components, 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) and/or 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA) may be included in an amount of 10 mol% or more to 50 mol% or less, preferably 10 mol% or more, 15 mol% or more, 20 mol% or more, 22 mol% or more, 24 mol% or more, 26 mol% or more, 28 mol% or more, 30 mol% or more, 31 mol% or more, 32 mol% or more, 33 mol% or more, 34 mol% or more, 35 mol% or more, 36 mol% or more, 37 mol% or more, 38 mol% or more, 39 mol% or more, or 40 mol% or more, wherein the upper limit thereof may be 50 mol% or less, 48 mol% or less, 46 mol% or less, 44 mol% or less, 42 mol% or less, 40 mol% or less, 39 mol% or less, 38 mol% or less, 37 mol% or less, 36 mol% or less, 35 mol% or less, 34 mol% or less, 33 mol% or less, 32 mol% or less, 31 mol% or less, or 30 mol% or less.
In the present invention, in the polyamic acid, amounts of respective dianhydride monomer components, including pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) and 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), may be appropriately adjusted within the range in which the total amount of the dianhydride monomer components is 100 mol%.
In an embodiment, the dianhydride monomer may include 20 to 80 mol% of pyromellitic dianhydride (PMDA); 10 to 50 mol% of 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA) and/or 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA); and 10 to 50 mol% of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA).
In addition, among the total diamine monomer components, paraphenylenediamine (PPD) may be included in an amount of 10 mol% or more to 80 mol% or less, and preferably 10 mol% or more, 15 mol% or more, 20 mol% or more, 25 mol% or more, 30 mol% or more, 35 mol% or more, 40 mol% or more, 42 mol% or more, 44 mol% or more, 46 mol% or more % or more, 48 mol% or more, 50 mol% or more, 52 mol% or more, 54 mol% or more, 56 mol% or more, 58 mol% or more, 60 mol% or more, 62 mol% or more, 64 mol% or more, 66 mol% or more, 68 mol% or more, 70 mol% or more, 72 mol% or more, 74 mol% or more, or 76 mol% or more, wherein the upper limit thereof may be 80 mol% or less, 78 mol% or less, 76 mol% or less, 74 mol% or less, 72 mol% or less, 70 mol% or less, 68 mol% or less, 66 mol% or less, 64 mol% or less, 62 mol% or less, 60 mol% or less, 55 mol% or less, 50 mol% or less or 45 mol% or less.
In addition, among the total diamine monomer components, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine) may be included in an amount of 20 mol% or more to 90 mol% or less, preferably 22 mol% or more, 24 mol% or more, 26 mol% or more, 28 mol% or more, 30 mol% or more, 31 mol% or more, 32 mol% or more, 33 mol% or more, 34 mol% or more, 35 mol% or more, 36 mol% or more, 37 mol% or more, 38 mol% or more, 39 mol% or more, or 40 mol% or more, wherein the upper limit thereof may be 90 mol% or less, 88 mol% or less, 86 mol% or less, 84 mol% or less, 82 mol% or less, 80 mol% or less, 78 mol% or less, 76 mol% or less, 74 mol% or less, 72 mol% or less, 70 mol% or less, 68 mol% or less, 66 mol% or less, 64 mol% or less, 62 mol% or less, 60 mol% or less, 58 mol% or less, 56 mol% or less, 54 mol% or less, 52 mol% or less, 50 mol% or less, 48 mol% or less, 46 mol% or less, 44 mol% or less, 42 mol% or less, 40 mol% or less, 39 mol% or less, 38 mol% or less, 37 mol% or less, 36 mol% or less, or 35 mol% or less.
In the present invention, in the polyamic acid, amounts of respective diamine monomer components including paraphenylenediamine (PPD) and 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine) may be appropriately adjusted within the range in which the total amount of the diamine monomer components is 100 mol%.
In an embodiment, the diamine monomer includes 10 to 80 mol% of paraphenylenediamine (PPD); and 20 to 90 mol% of 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine).
In the present invention, a molar ratio of the diamine monomer to the dianhydride monomer may be 0.5 to 2 equivalents. The molar ratio may be specifically 0.8 to 1.5 equivalents. When the molar ratio is less than 0.5 equivalent or more than 2 equivalents, the finally formed polyimide has a very small molecular weight, and accordingly, there is a problem in that physical and chemical properties of polyimide are very poor.
The black polyimide film according to the present invention may have a thickness of 3 to 100 μm, specifically 4 to 90 μm, more specifically 5 to 80 μm, and still more specifically, 5.5 to 75 μm. The thickness of the film is not particularly limited as long as it is capable of being flexibly applied, and the thickness may be adjusted in consideration of mechanical strength, handling, productivity, and the like.
The black polyimide film of the present invention has a transmittance in the visible light region of 0.2% or less, a gloss (60°) of 50 or less, a dielectric constant (Dk) of 4.0 or less, and a dielectric loss factor (Df) of 0.01 or less.
Further, the black polyimide film of the present invention may satisfy all conditions in which a transmittance in the visible light region is 0.2% or less, a gloss (60°) is 50 or less, a dielectric constant (Dk) is 4.0 or less, and a dielectric loss factor (Df) is 0.01 or less.
As an example, the black polyimide film according to the present invention may have a dielectric constant of 4.0 or less at 10 GHz, preferably 3.9 or less, wherein the lower limit thereof may be at least 3.0. It may be appreciated that the polyimide film exhibits an ideal dielectric constant as an insulator, considering that the engineering properties of the polyimide film are at the highest level.
Further, the black polyimide film according to the present invention may have a dielectric loss factor of 0.01 or less at 10 GHz, preferably 0.0099 or less, wherein the lower limit thereof may be at least 0.005 or more. "Dielectric loss factor" means the force dissipated by a dielectric (or insulator) when molecular friction hinders molecular motion caused by an alternating electric field, and the value of the dielectric loss factor is commonly used as an index indicating the ease of dissipation of electric charges (dielectric loss), wherein as the dielectric loss factor is higher, it becomes easier for charges to dissipate, and on the contrary, as the dielectric loss factor is lower, it may be difficult to dissipate charges. In other words, since the dielectric loss factor is a measure of power loss, the lower the dielectric loss factor, the faster the communication speed may be maintained while reducing the delay in signal transmission caused by the power loss.
Therefore, the polyimide film of the present invention has an advantage in that it is easy to maintain insulation even in electronic devices for high-speed transmission operating at a frequency of GIGA units, for example, 10 GHz or higher.
In addition, the black polyimide film according to the present invention may have a transmittance of, for example, 0.2% or less, preferably 0.18% or less, wherein the lower limit thereof may be at least 0.01%. It may be understood that the polyimide film has properties suitable for use as a coverlay.
Further, the black polyimide film according to the present invention may have a gloss (60°) of, for example, 50 or less, preferably 48 or less, wherein the lower limit thereof may be at least 1. When the gloss exceeds 50, there may be problems in that the visual aesthetics are lowered and the cover function is poor.
Therefore, when a polyimide film satisfies all of dielectric constant, dielectric loss factor, gloss, and transmittance, the polyimide film may be utilized as an insulating film for coverlay, and even if the manufactured coverlay is used for an electrical signal transmission circuit that transmits signals at a high frequency of 10 GHz or higher, it is possible to secure insulation stability thereof and minimize the delay in signal transmission.
The black polyimide film of the present invention having all of the conditions described above is a novel black polyimide film that has not been known until now.
Manufacturing method of black polyimide film of present invention
Further, still another embodiment of the present invention is directed to providing a manufacturing method of a black polyimide film, comprising:
(1) polymerizing a polyamic acid solution from at least one dianhydride monomer and at least one diamine monomer;
(2) preparing a polyimide precursor composition by mixing the polyamic acid solution with a black pigment containing bituminous coal and lactam black; and
(3) film-forming the polyimide precursor composition on a support, followed by heat treatment and imidization.
In the manufacturing method of a black polyimide film, the "dianhydride monomer" and the "diamine monomer" are the same as described above, and the manufacturing method of a black polyimide film of the present invention may generally be a method for forming a polyimide film.
In an embodiment, in step (1), the polyamic acid solution is obtained by reacting the dianhydride and diamine using an organic solvent. Here, the solvent is not particularly limited as long as the polyamic acid is capable of being dissolved, but the solvent may be, for example, an aprotic polar solvent. As the solvent, N-methyl-pyrrolidone (NMP), N,N'-dimethylformamide (DMF), N,N'-diethylformamide (DEF), N,N'-dimethylacetamide (DMAc), dimethylpropanamide (DMPA), N,N-diethylacetamide (685-91-6, DEAc), 3-methoxy-N,N-dimethylpropanamide (53185-52-7, KJCMPA), and the like, may be preferably used alone or in combination, but most preferably N-methyl-pyrrolidone (NMP).
In the present invention, the weight average molecular weight of the polyamic acid solution of the present invention may be 100,000 g/mol to 300,000 g/mol. The lower limit of the weight average molecular weight may be 100,000 g/mol, 120,000 g/mol, 150,000 g/mol, or 200,000 g/mol or more, and the upper limit of the weight average molecular weight may be 300,000 g/mol, 280,000 g/mol, 270,000 g/mol , 260,000 g/mol, or 250,000 g/mol or less.
In the present invention, the weight of the monomers added in the total polyamic acid solution in a state in which diamine and dianhydride are added in substantially equimolar amounts is referred to as a solid content, wherein the polyamic acid solution may have a solid content of 5 to 30% by weight. The lower limit of the weight percent of the solid content may be 5% by weight, 8% by weight, 9% by weight, 10% by weight, 15% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, or 29% by weight or more, and the upper limit of the weight percent of the solid content may be 29% by weight, 27% by weight, 25% by weight, 23% by weight, 21% by weight, 20% by weight, 19% by weight, or 18% by weight or less. By adjusting the solid content of the polyamic acid solution, it is possible to control the increase in viscosity and shorten the process time in a curing process.
In the present invention, the polyamic acid solution may have a viscosity in the range of 20,000 to 400,000 cP, the viscosity being measured under conditions of a temperature of 23℃ and a shear rate of 1s-1. For example, the upper limit of the viscosity may be 400,000 cP, 350,000 cP, 300,000 cP or 250,000 cP or less. The lower limit of the viscosity is not particularly limited, but may be 20,000 cP, 30,000 cP, 40,000 cP, 50,000 cP, 60,000 cP or 80,000 cP or more. The viscosity may be measured under conditions of a shear rate of 1/s, a temperature of 23℃, and a plate gap of 1 mm, using, for example, Haake's Rheostress 600. The present invention may provide a precursor composition having excellent processability by adjusting the viscosity range.
In Step (2), the bituminous coal and lactam black contained in the polyimide precursor composition may be milled through a milling process to adjust the particle diameter, thereby increasing the degree of dispersion to uniformly mix when mixed with the polyamic acid solution, while simultaneously lowering gloss, transmittance, dielectric constant, and dielectric loss factor.
Regarding this, before Step (2), the manufacturing method may further comprise a step of milling with a milling machine to manufacture bituminous coal having an average particle diameter (D50) of 0.5 to 10 μm and lactam black having an average particle diameter (D50) of 30 to 1000 nm, respectively.
In an embodiment, the milling process may be performed to manufacture bituminous coal and/or lactam black having a particle diameter in the range described above using a bead mill employing beads having a particle diameter of 1.0 to 2.0 mm, wherein the milling process may be performed on bituminous coal and lactam black alone, respectively, or in combination with bituminous coal and lactam black. At the time of the milling process, the stirring speed and milling time may be appropriately adjusted depending on the desired particle diameter, and thus these conditions are not particularly limited. In addition, bituminous coal and/or lactam black having a particle diameter in the range described above may be manufactured by milling using a bead mill employing beads having a particle diameter of 0.8 to 1.5 mm.
In addition, in Step (2), the black pigment includes bituminous coal and lactam black dispersed in an organic solvent, wherein the organic solvent may be at least one selected from the group consisting of N-methylformamide, N,N'-dimethylformamide (DMF), N-methylformanilide, N,N'-dimethylacetamide (DMAC), N-methyl-pyrrolidone (NMP), propylene glycol methyl ether acetate (PGMEA), ethyleneglycolacetate, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, and acetylacetone, and preferably, may be at least one selected from the group consisting of N,N'-dimethylformamide (DMF), N,N'-dimethylacetamide (DMAC), N-methyl-pyrrolidone (NMP), and propylene glycol methyl ether acetate (PGMEA).
In the present invention, Step (3) includes forming a gel film by casting the polyimide precursor composition prepared in Step (2) on a support and drying, followed by imidization on the gel film to form a black polyimide film.
In the process of forming a gel film, the polyimide precursor composition may be subjected to casting the polyimide precursor composition on a support such as an aluminum foil, an endless stainless belt, or a stainless drum, to be in the form of a film, followed by drying the precursor composition on the support at a variable temperature ranging from 50℃ to 200℃, specifically, 80℃ to 150℃.
The imidization may be performed through heat treatment, wherein the heat treatment may be performed at a variable temperature in the range of 50℃ to 500℃, specifically 150℃ to 500℃ to remove remaining water, residual solvent, and the like, and imidize almost all remaining amic acid groups, thereby manufacturing the black polyimide film of the present invention. In some cases, the polyimide film obtained as described above may be further cured by heat-finishing the polyimide film at a temperature of 400℃ to 650℃ for 5 seconds to 400 seconds, and in order to relieve internal stress that may remain in the obtained polyimide film, the polyimidefilm may be cured under a predetermined tension.
The present invention provides a coverlay comprising the black polyimide film as described above and an electronic device for high-speed transmission comprising the coverlay as described above.
The black polyimide film of the present invention contains a black pigment containing a combination of bituminous coal and black lactam, thereby having low gloss and transmittance, resulting in excellent optical properties, and having low dielectric constant and dielectric loss factor, resulting in excellent low dielectric properties.
The following Examples are presented to facilitate the understanding of the present invention. These Examples are only provided to more easily understand the present invention, but the content of the present invention is not limited by the following Examples.
<Example>
Example 1: Preparation of polyimide precursor composition
Example 1-1
For a polyamic acid solution polymerization process, 408.62 g of dimethylformamide (DMF) was added as a solvent to a 500 mL reactor under a nitrogen atmosphere. After setting the temperature to 25℃, PPD (66 mol%) and m-tolidine (34 mol%) were added as diamine monomers and stirred for 30 minutes to confirm that the monomers were dissolved. Then, PMDA (35 mol%), BTDA (33 mol%) and BPDA (32 mol%) were added as dianhydride monomers and stirred to react until there was no change in viscosity, thereby obtaining a polyamic acid solution.
A polyimide precursor composition was prepared by mixing the polyamic acid solution prepared above with a black pigment containing bituminous coal (6.6% by weight) and lactam black (4.5% by weight) dispersed in an organic solvent. The black pigment was contained in a total of 11.1% by weight in the polyimide precursor composition.
Example 1-2
A polyimide precursor composition was prepared in the same manner as in Example 1-1 above, except that a black pigment containing bituminous coal (6.6% by weight) and lactam black (5.5% by weight) was used instead of using the black pigment containing bituminous coal (6.6% by weight) and lactam black (4.5% by weight) in Example 1-1. The black pigment was contained in a total of 12.1% by weight in the polyimide precursor composition.
Example 1-3
A polyimide precursor composition was prepared in the same manner as in Example 1-1 above, except that a black pigment containing bituminous coal (6.6% by weight) and lactam black (6.5% by weight) was used instead of using the black pigment containing bituminous coal (6.6% by weight) and lactam black (4.5% by weight) in Example 1-1. The black pigment was contained in a total of 13.1% by weight in the polyimide precursor composition.
Example 1-4
A polyimide precursor composition was prepared in the same manner as in Example 1-1 above, except that a black pigment containing bituminous coal (6.6% by weight) and lactam black (7.5% by weight) was used instead of using the black pigment containing bituminous coal (6.6% by weight) and lactam black (4.5% by weight) in Example 1-1. The black pigment was contained in a total of 14.1% by weight in the polyimide precursor composition.
The components and contents of the polyimide precursor compositions prepared according to Examples 1-1 to 1-4 are summarized in Table 1 below (wherein the percent (%) by weight of the black pigment indicates the content in the polyimide precursor composition).
Polyimide precursor composition Polyamic acid solution Black pigment
Dianhydride (mol%) Diamine (mol%) Bituminous coal
(% by weight)		 Lactam black
(% by weight)		 Total weight % of black pigment
PMDA BTDA BPDA PPD m-tolidine
Example 1-1 35 33 32 66 34 6.6 4.5 11.1
Example 1-2 35 33 32 66 34 6.6 5.5 12.1
Example 1-3 35 33 32 66 34 6.6 6.5 13.1
Example 1-4 35 33 32 66 34 6.6 7.5 14.1
Comparative Example 1: Preparation of polyimide precursor composition
Comparative Example 1-1 (not comprising black pigment)
For a polyamic acid solution polymerization process, 408.62 g of dimethylformamide (DMF) was added as a solvent to a 500 mL reactor under a nitrogen atmosphere. After setting the temperature to 25℃, PPD (66 mol%) and m-tolidine (34 mol%) were added as diamine monomers and stirred for 30 minutes to confirm that the monomers were dissolved. Then, PMDA (35 mol%), BTDA (33 mol%) and BPDA (32 mol%) were added as dianhydride monomers and stirred to react until there was no change in viscosity, thereby obtaining a polyimide precursor composition.
Comparative Example 1-2 (containing only soft coal as black pigment)
A polyimide precursor composition was prepared in the same manner as in Example 1-1 above, except that a black pigment containing only bituminous coal (6.6% by weight) was used instead of using the black pigment containing bituminous coal (6.6% by weight) and lactam black (4.5% by weight) in Example 1-1. The black pigment was contained in a total of 6.6% by weight in the polyimide precursor composition.
Comparative Example 1-3 (containing soft coal and carbon black as black pigment)
A polyimide precursor composition was prepared in the same manner as in Example 1-1 above, except that a black pigment containing bituminous coal (6.6% by weight) and carbon black (2.5% by weight) was used instead of using the black pigment containing bituminous coal (6.6% by weight) and lactam black (4.5% by weight) in Example 1-1. The black pigment was contained in a total of 9.1% by weight in the polyimide precursor composition.
Comparative Example 1-4 (containing only lactam black as black pigment)
A polyimide precursor composition was prepared in the same manner as in Example 1-1 above, except that a black pigment containing only lactam black (6.5% by weight) was used instead of using the black pigment containing bituminous coal (6.6% by weight) and lactam black (4.5% by weight) in Example 1-1. The black pigment was contained in a total of 6.5% by weight in the polyimide precursor composition.
The components and contents of the polyimide precursor compositions prepared according to Comparative Examples 1-1 to 1-4 are summarized in Table 2 below.
Classification Polyamic acid solution Black pigment
Dianhydride (mol%) Diamine
(mol%)		 Bituminous coal
(% by weight)		 Lactam black
(% by weight)		 Carbon black
(% by weight)		 Total weight % of black pigment
PMDA BTDA BPDA PPD m-tolidine
Comparative Example 1-1 35 33 32 66 34 - - - 0
Comparative Example 1-2 35 33 32 66 34 6.6 - - 6.6
Comparative Example 1-3 35 33 32 66 34 6.6 - 2.5 9.1
Comparative Example 1-4 35 33 32 66 34 - 6.5 - 6.5
Example 2: Manufacture of black polyimide film
Example 2-1
The polyimide precursor composition prepared in Example 1-1 was subjected to casting on a SUS plate (100SA, Sandvik) to a thickness of 70 μm using a doctor blade, followed by drying at a temperature range of 100℃ to 200℃. Then, the film was peeled from the SUS plate, fixed to a pin frame, and transferred to a high-temperature tenter. The film was heated from 200℃ to 600℃ in a high-temperature tenter, cooled at 25℃, and separated from the pin frame, thereby manufacturing a black polyimide film having a thickness of 12.5 ± 0.5 μm containing 6.6% by weight of bituminous coal and 4.5% by weight of lactam black based on the total weight of the polyimide film.
Example 2-2
A black polyimide film containing 6.6% by weight of bituminous coal and 5.5% by weight of lactam black based on the total weight of the polyimide film was manufactured in the same manner as in Example 2-1 above, except that the polyimide precursor composition prepared in Example 1-2 above was used instead of using the polyimide precursor composition of Example 1-1 above.
Example 2-3
A black polyimide film containing 6.6% by weight of bituminous coal and 6.5% by weight of lactam black based on the total weight of the polyimide film was manufactured in the same manner as in Example 2-1 above, except that the polyimide precursor composition prepared in Example 1-3 above was used instead of using the polyimide precursor composition of Example 1-1 above.
Example 2-4
A black polyimide film containing 6.6% by weight of bituminous coal and 7.5% by weight of lactam black based on the total weight of the polyimide film was manufactured in the same manner as in Example 2-1 above, except that the polyimide precursor composition prepared in Example 1-4 above was used instead of using the polyimide precursor composition of Example 1-1 above.
Comparative Example 2: Manufacture of polyimide film
Comparative Example 2-1 (not containing black pigment)
A polyimide film was manufactured in the same manner as in Example 2-1 above, except that the polyimide precursor composition prepared in Comparative Example 1-1 above was used instead of using the polyimide precursor composition of Example 1-1 above. The polyimide film of Comparative Example 2-1 did not contain a black pigment.
Comparative Example 2-2 (containing only bituminous coal as black pigment)
A black polyimide film containing 6.6% by weight of bituminous coal based on the total weight of the polyimide film was manufactured in the same manner as in Example 2-1 above, except that the polyimide precursor composition prepared in Comparative Example 1-2 above was used instead of using the polyamide precursor composition of Example 1-1 above.
Comparative Example 2-3 (containing bituminous coal and carbon black as black pigment)
A black polyimide film containing 6.6% by weight of bituminous coal and 2.5% by weight of carbon black based on the total weight of the polyimide film was manufactured in the same manner as in Example 2-1 above, except that the polyimide precursor composition prepared in Comparative Example 1-3 above was used instead of using the polyimide precursor composition of Example 1-1 above.
Comparative Example 2-4 (containing only lactam black as black pigment)
A black polyimide film containing 6.5% by weight of lactam black based on the total weight of the polyimide film was manufactured in the same manner as in Example 2-1 above, except that the polyimide precursor composition prepared in Comparative Example 1-4 above was used instead of using the polyimide precursor composition of Example 1-1 above.
<Experimental Examples>
Experimental Example 1. Evaluation of gloss
The gloss was measured according to the ASTM D523 method at an angle of 60° using a gloss measuring device (PG-IIM manufactured by NIPPON DENSHOKU), and results thereof are shown in Table 3 below.
Experimental Example 2. Evaluation of transmittance
Transmittance was measured according to the ASTM D1003 method in the visible light region using a transmittance measuring device (ColorQuesetXE manufactured by HunterLab), and results thereof are shown in Table 3 below.
Experimental Example 3. Evaluation of dielectric constant (Dk)
The dielectric constant was measured at 10 GHz using split post dielectric resonator (SPDR) manufactured by Keysight Technologies, Inc., and results thereof are shown in Table 3 below.
Experimental Example 4. Dielectric loss factor (Df)
Roll-to-roll copper foil lamination was performed on both sides of the polyimide film to prepare a flexible metal clad laminate. Dielectric loss factor (Df) was measured by leaving the flexible metal clad laminate for 72 hours using an ohmmeter Agilent 4294A, and results thereof are shown in Table 3 below.
Polyimide film Transmittance
(%)		 Gloss
(60°)		 Dielectric constant
(Dk)		 Dielectric loss factor
(Df)
Example 2-1 0.15 43 3.60 0.00636
Example 2-2 0.12 47 3.70 0.00793
Example 2-3 0.07 48 3.79 0.00850
Example 2-4 0.03 48 3.77 0.00951
Comparative Example 2-1 65.5 176 3.60 0.00395
Comparative Example 2-2 2.21 17 3.56 0.00444
Comparative Example 2-3 0.10 42 4.61 0.03082
Comparative Example 2-4 0.61 104 3.56 0.00677
Referring to Table 3, the black polyimide film of the present invention satisfied all conditions of transmittance of 0.2% or less, gloss of 50 or less, dielectric constant of 4.0 or less, and dielectric loss factor of 0.01 or less. However, it could be confirmed that Comparative Example 2-1 containing no black pigment and Comparative Example 2-4 containing only lactam black as the black pigment had very high transmittance and gloss, and Comparative Example 2-2 containing only bituminous coal as the black pigment had a transmittance far exceeding 0.2%. In addition, it could be confirmed that Comparative Example 2-3 containing bituminous coal and carbon black as the black pigment had high dielectric constant of 4.61 and high dielectric loss factor of 0.03082.
In the specification, the detailed description of the contents capable of being sufficiently recognized and inferred by those skilled in the art of the present disclosure are omitted, and many variations and modification can be made within a range that does not change the technical spirit or essential configuration of the present disclosure in addition to the specific exemplary embodiments described in the present specification. Therefore, the present disclosure may also be practiced in a manner different from that specifically described and illustrated herein, which can be understood by those skilled in the art.

Claims (17)

  1. A black polyimide film comprising a black pigment containing bituminous coal and lactam black,
    wherein the black polyimide film is formed by imidizing a polyamic acid obtained from a dianhydride monomer and a diamine monomer.
  2. The black polyimide film of claim 1, wherein the black polyimide film contains 3 to 15% by weight of the bituminous coal and 2 to 15% by weight of the lactam black based on the total weight of the black polyimide film.
  3. The black polyimide film of claim 1, wherein the black polyimide film contains 5 to 10% by weight of the bituminous coal and 4 to 10% by weight of the lactam black based on the total weight of the black polyimide film.
  4. The black polyimide film of claim 1, wherein the bituminous coal has an average particle diameter (D50) of 0.5 to 10 μm.
  5. The black polyimide film of claim 1, wherein the lactam black has an average particle diameter (D50) of 30 to 1000 nm.
  6. The black polyimide film of claim 1, wherein
    the dianhydride monomer is at least one selected from the group consisting of
    pyromellitic dianhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), diphenylsulfone-3,4,3',4'-tetracarboxylic dianhydride (DSDA), bis(3,4-dicarboxyphenyl)sulfide dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, p-phenylenebis(trimellitic monoester acid anhydride), p-biphenylenebis(trimellitic monoester acid anhydride), m-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[(3,4-dicarboxy phenoxy)phenyl]propane dianhydride (BPADA), 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, and 4,4′-(2,2-hexafluoroisopropylidene)diphthalic acid dianhydride.
  7. The black polyimide film of claim 1, wherein
    the diamine monomer is at least one selected from the group consisting of
    paraphenylenediamine (PPD), metaphenylenediamine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobenzoic acid (DABA), 4,4'-oxydianiline (ODA), 4,4'-diamino diphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane (4,4'-Methylenedianiline), 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis(4-aminophenyl)sulfide, 4,4'-diaminobenzanilide, 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diamino diphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diamino-4,4'-dichlorobenzophenone, 3,3'-diamino-4,4'-dimethoxybenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 3,3'-diaminodiphenylsulfoxide, 3,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfoxide, 1,3-bis(3-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(3-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,4-bis(3-aminophenoxy)benzene (TPE-Q), 1,3-bis(3-aminophenoxy)-4-trifluoromethylbenzene, 3,3'-diamino-4-(4-phenylphenoxy)benzophenone, 3,3'-diamino-4,4'-di(4-phenylphenoxy)benzophenone, 1,3-bis(3-aminophenylsulfide)benzene, 1,3-bis(4-aminophenylsulfide)benzene, 1,4-bis(4-aminophenylsulfide)benzene, 1,3-bis(3-aminophenylsulfone)benzene, 1,3-bis(4-aminophenylsulfone)benzene, 1,4-bis(4-aminophenylsulfone)benzene, 1,3-bis[2-(4-aminophenyl)isopropyl]benzene, 1,4-bis[2-(3-aminophenyl)isopropyl]benzene, 1,4-bis[2-(4-aminophenyl)isopropyl]benzene, 3,3'-bis(3-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[3-(3-aminophenoxy)phenyl]ether, bis[3-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, bis[3-(3-aminophenoxy)phenyl]ketone, bis[3-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone, bis[3-(3-aminophenoxy)phenyl] sulfide, bis[3-(4-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[3-(3-aminophenoxy)phenyl]sulfone, bis[3-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]methane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-amino)phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane.
  8. The black polyimide film of claim 1, wherein
    the dianhydride monomer is at least one selected from the group consisting of pyromellitic dianhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), and 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), and
    the diamine monomer is at least one selected from the group consisting of paraphenylenediamine (PPD), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), 4,4'-oxydianiline (ODA), and 1,3-bis(4-aminophenoxy)benzene (TPE-R).
  9. The black polyimide film of claim 1, wherein the dianhydride monomer contains 20 to 80 mol% of pyromellitic dianhydride (PMDA); 10 to 50 mol% of 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA) and/or 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA); and 10 to 50 mol% of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), and
    the diamine monomer contains 10 to 80 mol% of paraphenylenediamine (PPD); and 20 to 90 mol% of 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine).
  10. The black polyimide film of claim 1, wherein the black polyimide film has a thickness of 3 to 100 μm.
  11. The black polyimide film of claim 1, wherein the black polyimide film has a transmittance in the visible light region of 0.2% or less,
    a gloss (60°) of 50 or less,
    a dielectric constant (Dk) of 4.0 or less, and
    a dielectric loss factor (Df) of 0.01 or less.
  12. A manufacturing method of a black polyimide film, comprising:
    (1) polymerizing a polyamic acid solution from at least one dianhydride monomer and at least one diamine monomer;
    (2) preparing a polyimide precursor composition by mixing the polyamic acid solution with a black pigment containing bituminous coal and lactam black; and
    (3) film-forming the polyimide precursor composition on a support, followed by heat treatment and imidization.
  13. The manufacturing method of claim 12, further comprising, before Step (2), milling with a milling machine to manufacture bituminous coal having an average particle diameter (D50) of 0.5 to 10 μm and lactam black having an average particle diameter (D50) of 30 to 1000 nm, respectively.
  14. The manufacturing method of claim 12, wherein in Step (2), the black pigment includes bituminous coal and lactam black dispersed in an organic solvent.
  15. The manufacturing method of claim 14, wherein the organic solvent is at least one selected from the group consisting of N-methylformamide, N,N'-dimethylformamide (DMF), N-methylformanilide, N,N'-dimethylacetamide (DMAC), N-methyl-pyrrolidone (NMP), propylene glycol methyl ether acetate (PGMEA), ethyleneglycolacetate, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, and acetylacetone.
  16. A coverlay comprising the black polyimide film according to any one of claims 1 to 11.
  17. An electronic device for high-speed transmission comprising the coverlay according to claim 16.
PCT/KR2023/008058 2022-06-13 2023-06-12 Black polyimide film and manufacturing method thereof WO2023243967A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4476265A (en) * 1983-08-25 1984-10-09 Phillips Petroleum Company Pigmented compositions
US20180105657A1 (en) * 2016-10-19 2018-04-19 Taimide Technology Incorporation Polyimide film having low gloss and manufacture thereof
US20180346720A1 (en) * 2017-05-30 2018-12-06 SKC KOLON PI Inc. Ultra-thin black polyimide film and method for preparing the same
WO2020017692A1 (en) * 2018-07-18 2020-01-23 에스케이씨코오롱피아이 주식회사 Polyimide film comprising clay particles and carbon black and manufacturing method therefor
CN111154125A (en) * 2020-01-16 2020-05-15 东莞东阳光科研发有限公司 Black polyimide film and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4476265A (en) * 1983-08-25 1984-10-09 Phillips Petroleum Company Pigmented compositions
US20180105657A1 (en) * 2016-10-19 2018-04-19 Taimide Technology Incorporation Polyimide film having low gloss and manufacture thereof
US20180346720A1 (en) * 2017-05-30 2018-12-06 SKC KOLON PI Inc. Ultra-thin black polyimide film and method for preparing the same
WO2020017692A1 (en) * 2018-07-18 2020-01-23 에스케이씨코오롱피아이 주식회사 Polyimide film comprising clay particles and carbon black and manufacturing method therefor
CN111154125A (en) * 2020-01-16 2020-05-15 东莞东阳光科研发有限公司 Black polyimide film and preparation method thereof

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