WO2022098042A1 - 높은 치수 안정성을 가지는 폴리이미드 필름 및 그 제조방법 - Google Patents
높은 치수 안정성을 가지는 폴리이미드 필름 및 그 제조방법 Download PDFInfo
- Publication number
- WO2022098042A1 WO2022098042A1 PCT/KR2021/015673 KR2021015673W WO2022098042A1 WO 2022098042 A1 WO2022098042 A1 WO 2022098042A1 KR 2021015673 W KR2021015673 W KR 2021015673W WO 2022098042 A1 WO2022098042 A1 WO 2022098042A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mol
- less
- dianhydride
- content
- polyimide film
- Prior art date
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 230000009477 glass transition Effects 0.000 claims abstract description 16
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 78
- 150000004985 diamines Chemical class 0.000 claims description 43
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 42
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 39
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 claims description 32
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 239000011888 foil Substances 0.000 claims description 29
- 229920005575 poly(amic acid) Polymers 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 24
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 23
- BCJIMAHNJOIWKQ-UHFFFAOYSA-N 4-[(1,3-dioxo-2-benzofuran-4-yl)oxy]-2-benzofuran-1,3-dione Chemical compound O=C1OC(=O)C2=C1C=CC=C2OC1=CC=CC2=C1C(=O)OC2=O BCJIMAHNJOIWKQ-UHFFFAOYSA-N 0.000 claims description 20
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 18
- GYFUIPAIOWWVFV-UHFFFAOYSA-N 1-phenoxycyclohexa-3,5-diene-1,3-diamine Chemical compound C1C(N)=CC=CC1(N)OC1=CC=CC=C1 GYFUIPAIOWWVFV-UHFFFAOYSA-N 0.000 claims description 10
- 230000005606 hygroscopic expansion Effects 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000203 mixture Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 239000000945 filler Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000004642 Polyimide Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000012024 dehydrating agents Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 108010025899 gelatin film Proteins 0.000 description 4
- 125000005462 imide group Chemical group 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- -1 diamine compound Chemical class 0.000 description 2
- 125000006159 dianhydride group Chemical class 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000051 modifying effect Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- NMFFUUFPJJOWHK-UHFFFAOYSA-N 2-phenoxyaniline Chemical compound NC1=CC=CC=C1OC1=CC=CC=C1 NMFFUUFPJJOWHK-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
-
- 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
Definitions
- the present invention relates to a polyimide film having high dimensional stability, and more particularly, to a polyimide film having high thermal dimensional stability and high dimensional stability against moisture, and a method for manufacturing the same.
- Polyimide (PI) is a polymer material with the highest level of heat resistance, chemical resistance, electrical insulation, chemical resistance, and weather resistance among organic materials based on an imide ring with excellent chemical stability along with a rigid aromatic main chain. am.
- the polyimide film is spotlighted as a material for various electronic devices requiring the above-described properties.
- microelectronic components to which the polyimide film is applied include thin circuit boards that have high circuit integration and are flexible to respond to weight reduction and miniaturization of electronic products. there is.
- the thin circuit board generally has a structure in which a circuit including a metal foil is formed on an insulating film.
- a thin circuit board is called a Flexible Metal Foil Clad Laminate
- a thin copper plate is made of metal foil.
- FCCL Flexible Copper Clad Laminate
- a manufacturing method of a flexible metal foil laminate for example, (i) a casting method in which polyamic acid, a precursor of polyimide, is cast or coated on a metal foil, and then imidized, (ii) sputtering a metallizing method in which a metal layer is directly provided on the polyimide film by the method;
- the metallizing method produces a flexible metal foil laminate by sequentially depositing a tie layer and a seed layer by sputtering a metal such as copper on a polyimide film having a thickness of 20 to 38 ⁇ m, for example.
- This method has an advantage in forming ultra-fine circuits having a circuit pattern pitch of 35 ⁇ m or less, and is widely used in manufacturing flexible metal foil laminates for COF (chip on film).
- the polyimide film used for the flexible metal foil laminate by the metallizing method should have high dimensional stability.
- dimensional stability is measured by thermal dimensional stability expressed by thermal expansion coefficient, but dimensional stability to moisture expressed by hygroscopic expansion coefficient is increasingly important as well as thermal dimensional stability.
- Patent Document 1 Republic of Korea Patent No. 10-1375276
- Patent Document 2 Republic of Korea Patent Publication No. 2016-0002402
- an object of the present invention is to provide a polyimide film having both high thermal dimensional stability and high dimensional stability against moisture.
- One aspect of the present invention for achieving the above object is that the coefficient of thermal expansion is 1 ppm / °C or more, 5 ppm / °C or less,
- the modulus of elasticity is 9 GPa or more and 11.5 GPa or less
- the glass transition temperature is 340 °C or more and 400 °C or less
- a polyimide film is provided.
- the polyimide film may have a coefficient of hygroscopic expansion of 4 ppm/RH% or more and 6 ppm/RH% or less.
- BPDA biphenyltetracarboxylic dianhydride
- PMDA pyromellitic dianhydride
- ODPA oxydiphthalic anhydride
- BTDA benzophenonetetracarboxylic dianhydride
- a dianhydride component comprising two or more selected from the group consisting of, paraphenylene diamine (PPD), m-tolidine, oxydianiline (ODA), and 1,3-bisaminophenoxybenzene (TPE-R) obtained by imidation reaction of a polyamic acid solution containing a diamine component containing two or more selected from the group consisting of,
- the content of paraphenylene diamine is 10 mol% or more and 70 mol% or less
- the content of m-tolidine is 25 mol% or more and 80 mol% or less
- a polyimide film is provided.
- the content of the biphenyltetracarboxylic dianhydride is 30 mol% or more and 60 mol% or less, and the content of the pyromellitic dianhydride is 40 mol% It may be more than 60 mol%.
- the content of the oxydiphthalic anhydride is 20 mol% or less, and the content of the benzophenonetetracarboxylic dianhydride is 30 mol% or less
- the content of oxydianiline (ODA) may be 20 mol% or less, and the content of 1,3-bisaminophenoxybenzene may be 20 mol% or less.
- the molar ratio of the paraphenylene diamine to the biphenyltetracarboxylic dianhydride may be 0.3 or more and 2.5 or less, and the molar ratio of the m-tolidine to the pyromellitic dianhydride may be 0.6 or more and 1.5 or less.
- reaction molar ratio of the paraphenylene diamine to the biphenyltetracarboxylic dianhydride is 1.05 or more and 1.2 or less, and the paraphenylene diamine and the m-tolidine to the pyromellitic dianhydride are The reaction molar ratio may be 0.9 or more and 0.99 or less.
- Another aspect of the present invention is (a) biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), oxydiphthalic anhydride (ODPA) and benzophenonetetracarboxylic dianhydride
- BPDA biphenyltetracarboxylic dianhydride
- PMDA pyromellitic dianhydride
- ODPA oxydiphthalic anhydride
- benzophenonetetracarboxylic dianhydride A dianhydride component comprising two or more selected from the group consisting of ride (BTDA), paraphenylene diamine (PPD), m-tolidine, oxydianiline (ODA), and 1,3-bis preparing a polyamic acid by polymerizing a diamine component including at least two selected from the group consisting of aminophenoxybenzene (TPE-R) in an organic solvent; and
- the content of the biphenyltetracarboxylic dianhydride is 30 mol% or more and 60 mol% or less, and the content of the pyromellitic dianhydride is 40 mol% or more and 60 mol% or less,
- the content of paraphenylene diamine is 10 mol% or more and 70 mol% or less
- the content of m-tolidine is 25 mol% or more and 80 mol% or less
- a method for manufacturing a polyimide film is provided.
- Another aspect of the present invention provides a flexible metal foil laminate comprising the polyimide film and an electrically conductive metal foil.
- Another aspect of the present invention provides an electronic component comprising the flexible metal foil laminate.
- the present invention provides a polyimide film excellent in both thermal dimensional stability and moisture dimensional stability by providing a polyimide film in which the composition ratio and reaction ratio of dianhydride and diamine components are controlled.
- Such a polyimide film is applicable to various fields requiring a polyimide film having excellent dimensional stability properties, for example, a flexible metal foil laminate manufactured by a metallizing method or an electronic component including such a flexible metal foil laminate.
- dianhydride is intended to include precursors or derivatives thereof, which may not technically be dianhydride acids, but will nevertheless react with a diamine to form a polyamic acid, which in turn is a polyamic acid can be converted into mids.
- diamine is intended to include precursors or derivatives thereof, which may not technically be diamines, but will nevertheless react with dianhydrides to form polyamic acids, which in turn are polyamic acids. can be converted to mid
- the polyimide film according to an embodiment of the present invention is biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), oxydiphthalic anhydride (ODPA) and benzophenonetetracarboxylic
- a dianhydride component comprising two or more selected from the group consisting of dianhydride (BTDA), paraphenylene diamine (PPD), m-tolidine, oxydianiline (ODA), and 1,3 -It is obtained by imidization reaction of a polyamic acid solution containing a diamine component including two or more selected from the group consisting of bisaminophenoxybenzene (TPE-R), and based on 100 mol% of the total content of the dianhydride component , wherein the content of the biphenyltetracarboxylic dianhydride is 30 mol% or more and 60 mol% or less, the content of the pyromellitic dianhydride is 40
- the content of the biphenyltetracarboxylic dianhydride is 30 mol% or more and 55 mol% or less, and the content of the pyromellitic dianhydride is It may be 45 mol% or more and 55 mol% or less.
- the content of the paraphenylene diamine may be 15 mol% or more and 70 mol% or less.
- the paraphenylene diamine of the present invention is a rigid monomer, and as the content of paraphenylene diamine increases, the synthesized polyimide has a more linear structure, contributing to the improvement of the mechanical properties of the polyimide.
- m-tolidine has a particularly hydrophobic methyl group, it contributes to the low moisture absorption properties related to the dimensional stability of the polyimide film against moisture.
- the polyimide chain derived from the biphenyltetracarboxylic dianhydride of the present invention has a structure called a charge transfer complex (CTC), that is, an electron donor and an electron acceptor. It has a regular linear structure positioned close to each other, and the intermolecular interaction is strengthened.
- CTC charge transfer complex
- this structure has an effect of preventing hydrogen bonding with moisture, it is possible to maximize the effect of lowering the hygroscopicity of the polyimide film, which affects the dimensional stability of the polyimide film by affecting the lowering of the moisture absorption.
- pyromellitic dianhydride is a dianhydride component having a relatively rigid structure, and is preferable in that it can impart appropriate elasticity to the polyimide film.
- the content ratio of dianhydride is important.
- the content ratio of biphenyltetracarboxylic dianhydride decreases, it is difficult to expect a low moisture absorption rate due to the CTC structure, and dimensional stability with respect to moisture is also reduced.
- biphenyltetracarboxylic dianhydride contains two benzene rings corresponding to the aromatic moiety
- pyromellitic dianhydride contains one benzene ring corresponding to the aromatic moiety
- An increase in the content of pyromellitic dianhydride in the dianhydride component can be understood as an increase in the imide group in the molecule based on the same molecular weight, which is an image derived from the pyromellitic dianhydride in the polyimide polymer chain. It can be understood that the ratio of the group is relatively increased compared to the imide group derived from biphenyltetracarboxylic dianhydride.
- the increase in the content of pyromellitic dianhydride can be viewed as a relative increase in imide groups for the entire polyimide film, and therefore, it is difficult to expect high dimensional stability against moisture due to low moisture absorption.
- the content of the oxydiphthalic anhydride is 20 mol% or less, and the content of the benzophenonetetracarboxylic dianhydride is 30 mol% or less
- the content of oxydianiline (ODA) may be 20 mol% or less, and the content of 1,3-bisaminophenoxybenzene may be 20 mol% or less.
- reaction molar ratio of the dianhydride component and the diamine component of the polyimide film the reaction molar ratio of the paraphenylene diamine to the biphenyltetracarboxylic dianhydride is 1.05 or more and 1.2 or less, and the pyromellitic A reaction molar ratio of the paraphenylene diamine and the m-tolidine to the dianhydride may be 0.9 or more and 0.99 or less.
- the reaction molar ratio of the paraphenylene diamine and the m-tolidine to the pyromellitic dianhydride may be 0.9 or more and 0.95 or less.
- the polyimide film has a coefficient of thermal expansion of 1 ppm/°C or more and 5 ppm/°C or less, an elastic modulus of 9 GPa or more and 11.5 GPa or less, and a hygroscopic expansion coefficient of 4 ppm/RH% or more and 6 ppm/RH% or less.
- the glass transition temperature of the polyimide film may be 340 °C or more, 400 °C or less, preferably less than 390 °C.
- the preparation of the polyamic acid is, for example,
- BPDA biphenyltetracarboxylic dianhydride
- PMDA pyromellitic dianhydride
- ODPA oxydiphthalic anhydride
- BTDA benzophenonetetracarboxylic dianhydride
- a dianhydride component comprising two or more selected from, paraphenylene diamine (PPD), m-tolidine, oxydianiline (ODA) and 1,3-bisaminophenoxybenzene (TPE- R) preparing a polyamic acid by polymerizing a diamine component comprising two or more selected from the group consisting of in an organic solvent; and
- the content of the biphenyltetracarboxylic dianhydride is 30 mol% or more and 60 mol% or less, and the content of the pyromellitic dianhydride is 40 mol% or more and 60 mol% or less,
- the content of paraphenylene diamine is 10 mol% or more and 70 mol% or less
- the content of m-tolidine is 25 mol% or more and 80 mol% or less
- It may be a method of manufacturing a polyimide film.
- the polymerization method of the polyamic acid as described above can be defined as a random polymerization method, and the polyimide film prepared from the polyamic acid of the present invention prepared by the above process is the present invention that improves dimensional stability It can be preferably applied in terms of maximizing the effect of
- the polymerization method of the polyamic acid may be a block polymerization method.
- combining a polyamic acid is not specifically limited, Any solvent can be used as long as it is a solvent in which a polyamic acid is dissolved, It is preferable that it is an amide type solvent.
- the organic solvent may be an organic polar solvent, specifically an aprotic polar solvent, for example, N,N-dimethylformamide (DMF), N,N -Dimethylacetamide, N-methyl-pyrrolidone (NMP), gamma butyrolactone (GBL), may be at least one selected from the group consisting of Diglyme (Diglyme), but is not limited thereto. Or it can be used in combination of 2 or more types.
- DMF N,N-dimethylformamide
- NMP N-methyl-pyrrolidone
- GBL gamma butyrolactone
- N,N-dimethylformamide and N,N-dimethylacetamide may be particularly preferably used.
- a filler may be added for the purpose of improving various properties of the film, such as sliding properties, thermal conductivity, corona resistance, and loop hardness.
- the filler to be added is not particularly limited, but preferred examples thereof include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, and the like.
- the particle size of the filler is not particularly limited, and may be determined according to the characteristics of the film to be modified and the type of filler to be added. Generally, the average particle diameter is 0.05 to 100 ⁇ m, preferably 0.1 to 75 ⁇ m, more preferably 0.1 to 50 ⁇ m, particularly preferably 0.1 to 25 ⁇ m.
- the modifying effect becomes difficult to appear, and when the particle size exceeds this range, the surface properties may be greatly impaired or the mechanical properties may be greatly reduced.
- the added amount of a filler is 0.01 to 100 parts by weight, preferably 0.01 to 90 parts by weight, and more preferably 0.02 to 80 parts by weight based on 100 parts by weight of polyimide.
- the method of adding a filler is not specifically limited, Any well-known method can also be used.
- the polyimide film may be prepared by thermal imidization and chemical imidization.
- it may be prepared by a complex imidization method in which thermal imidization and chemical imidization are combined.
- the thermal imidization method is a method in which a chemical catalyst is excluded and the imidization reaction is induced by a heat source such as hot air or an infrared dryer.
- the amic acid group present in the gel film can be imidized by heat-treating the gel film at a variable temperature in the range of 100 to 600 ° C., specifically 200 to 500 ° C., more specifically , it is possible to imidize the amic acid group present in the gel film by heat treatment at 300 to 500 °C.
- the polyamic acid composition is dried at a variable temperature in the range of 50 °C to 200 °C. and may also be included in the scope of the thermal imidization method.
- a polyimide film may be prepared by using a dehydrating agent and an imidizing agent according to a method known in the art.
- a polyimide film can be manufactured by heating.
- the present invention provides a flexible metal foil laminate comprising the above-described polyimide film and an electrically conductive metal foil.
- the metal foil to be used is not particularly limited, but when the flexible metal foil laminate of the present invention is used for electronic or electrical equipment applications, for example, copper or copper alloy, stainless steel or an alloy thereof, nickel or a nickel alloy (alloy 42) also included), may be a metal foil comprising aluminum or an aluminum alloy.
- copper foils such as rolled copper foils and electrolytic copper foils are often used, and they can be preferably used in the present invention as well.
- the antirust layer, the heat-resistant layer, or the adhesive layer may be apply
- the thickness of the metal foil is not particularly limited, and may have a thickness capable of exhibiting a sufficient function according to its use.
- the flexible metal foil laminate according to the present invention may have a structure in which a metal foil is laminated on at least one surface of the polyimide film.
- the polyimide film of the present invention can be prepared by a conventional method known in the art as follows. First, a polyamic acid solution is obtained by reacting the above-described dianhydride acid with the diamine component in an organic solvent.
- the solvent is generally an amide solvent, and an aprotic polar solvent, for example, N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methyl-pyrrolidone, or Combinations of these may be used.
- the input form of the dianhydride and the diamine component may be in powder, lump, or solution form. At the beginning of the reaction, it is added in powder form to proceed with the reaction, and thereafter, it is preferable to input in the form of a solution to control polymerization viscosity. .
- the obtained polyamic acid solution may be mixed with an imidization catalyst and a dehydrating agent and applied to a support.
- the catalyst used include tertiary amines (eg, isoquinoline, ⁇ -picoline, pyridine, etc.), and examples of the dehydrating agent include, but are not limited to, acid anhydride.
- the support used in the above may include, but is not limited to, a glass plate, an aluminum foil, a circulation stainless belt or a stainless drum.
- the film applied on the support is gelled on the support by dry air and heat treatment.
- the gelled film is separated from the support and heat-treated to complete drying and imidization.
- the film may be heat treated under a certain tension to remove residual stress inside the film generated during the film forming process.
- BPDA biphenyltetracarboxylic dianhydride
- PMDA fatigue Melitic dianhydride
- ODPA oxydiphthalic anhydride
- BTDA benzophenonetetracarboxylic dianhydride
- PPD paraphenylene diamine
- m-tolidine m-tolidine
- jade Cydianiline ODA
- TPE-R 1,3-bisaminophenoxybenzene
- the polyamic acid thus prepared was stirred so as to have a final viscosity of 100,000 to 120,000 cP.
- a polyimide film was prepared using an applicator.
- the reaction molar ratio of paraphenylene diamine to biphenyltetracarboxylic dianhydride is 1.05 or more and 1.2 or less, and paraphenylene diamine and m-tolidine to pyromellitic dianhydride.
- the reaction was controlled so that the reaction molar ratio of was 0.9 or more and 0.99 or less.
- Example 1 50 50 - - 40 60 - - Example 2 50 50 - - 35 65 - - Example 3 47 53 - - 35 65 - - Example 4 47 53 - - 40 60 - - Example 5 40 50 10 - 70 30 - - Example 6 30 50 - 20 30 70 - - Example 7 50 50 - - 75 15 10 - Example 8 50 50 - - 75 15 - 10 Comparative Example 1 50 50 - - 0 100 - - Comparative Example 2 50 50 - - 15 85 - - Comparative Example 3 50 50 - - 60 40 - - Comparative Example 4 40 60 - - 100 0 - - Comparative Example 5 20 50 30 - 85 15 - - Comparative Example 6 50 50 - - 85 5 - 10 Comparative Example 7 50 50 - - 15 75 10 -
- the elastic modulus, coefficient of thermal expansion (CTE), coefficient of hydroscopic expansion (CHE) and glass transition temperature (Tg) of the prepared polyimide film were measured and shown in Table 2 below.
- the modulus of elasticity of the polyimide films prepared in all Examples and Comparative Examples was tested three times in accordance with ASTM D 882 regulations using a Standard Instron testing apparatus, and the average value was taken.
- CTE coefficient of thermal expansion
- the coefficient of hygroscopic expansion is measured by adjusting the humidity to 3 %RH and absorbing moisture until completely saturated with the minimum weight applied to prevent the polyimide film from loosening (for a sample of 25 mm ⁇ 150 mm, about 1 g). After measuring, the humidity was adjusted to 90 %RH, and the size was measured after saturated moisture absorption in the same way, and the dimensional change rate was measured at 90%RH per 87% relative humidity difference from both results.
- the glass transition temperature (T g ) was obtained by obtaining the loss modulus and storage modulus of each film using DMA, and the inflection point was measured as the glass transition temperature in their tangent graph.
- the polyimide films of Examples 1 to 8 have a coefficient of thermal expansion of 1 ppm/°C or more and 5 ppm/°C or less, an elastic modulus of 9 GPa or more and 11.5 GPa or less, and a hygroscopic expansion coefficient of 4 ppm/RH% or more, 6 ppm/RH% or less was exhibited.
- Comparative Example 5 including oxydiphthalic anhydride as a dianhydride component while excessively including m-tolidine has lowered thermal dimensional stability and lowered glass transition temperature compared to Examples. (coefficient of thermal expansion: 7.0 ppm/°C, glass transition temperature: 300°C).
- the polyimide films of Examples 1 to 8 prepared within the appropriate range of the present application were excellent in both thermal dimensional stability and dimensional stability to moisture, but outside the appropriate range of the present application, thermal dimensional stability and dimensional stability to moisture It was confirmed that it was difficult to achieve both stability.
- polyimide films of Examples 1 to 8 prepared within the appropriate range of the present application had appropriate ranges applicable to various fields in terms of elastic modulus and glass transition temperature.
- the polyimide film that has excellent dimensional stability and satisfies all the various conditions applicable to the application field is a polyimide film manufactured within the appropriate range of the present application.
- the present invention provides a polyimide film excellent in both thermal dimensional stability and moisture dimensional stability by providing a polyimide film in which the composition ratio and reaction ratio of dianhydride and diamine components are controlled.
- Such a polyimide film is applicable to various fields requiring a polyimide film having excellent dimensional stability properties, for example, a flexible metal foil laminate manufactured by a metallizing method or an electronic component including such a flexible metal foil laminate.
Landscapes
- 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)
- Laminated Bodies (AREA)
Abstract
Description
이무수물산 | 디아민 | |||||||
BPDA | PMDA | ODPA | BTDA | m-Tolidine | PPD | ODA | TPE-R | |
실시예 1 | 50 | 50 | - | - | 40 | 60 | - | - |
실시예 2 | 50 | 50 | - | - | 35 | 65 | - | - |
실시예 3 | 47 | 53 | - | - | 35 | 65 | - | - |
실시예 4 | 47 | 53 | - | - | 40 | 60 | - | - |
실시예 5 | 40 | 50 | 10 | - | 70 | 30 | - | - |
실시예 6 | 30 | 50 | - | 20 | 30 | 70 | - | - |
실시예 7 | 50 | 50 | - | - | 75 | 15 | 10 | - |
실시예 8 | 50 | 50 | - | - | 75 | 15 | - | 10 |
비교예 1 | 50 | 50 | - | - | 0 | 100 | - | - |
비교예 2 | 50 | 50 | - | - | 15 | 85 | - | - |
비교예 3 | 50 | 50 | - | - | 60 | 40 | - | - |
비교예 4 | 40 | 60 | - | - | 100 | 0 | - | - |
비교예 5 | 20 | 50 | 30 | - | 85 | 15 | - | - |
비교예 6 | 50 | 50 | - | - | 85 | 5 | - | 10 |
비교예 7 | 50 | 50 | - | - | 15 | 75 | 10 | - |
물성 | ||||
탄성율 (GPa) |
CTE (ppm/℃) |
CHE (ppm/RH%) |
Tg (℃) |
|
실시예 1 | 10.5 | 1.8 | 4.5 | 343 |
실시예 2 | 9.5 | 4.4 | 5.3 | 353 |
실시예 3 | 9.1 | 2.5 | 4.6 | 373 |
실시예 4 | 10.3 | 1.6 | 4.3 | 382 |
실시예 5 | 9.7 | 4.9 | 5.8 | 343 |
실시예 6 | 9.3 | 2.2 | 5.7 | 370 |
실시예 7 | 11.2 | 3.1 | 5.5 | 341 |
실시예 8 | 11.1 | 3.5 | 5.8 | 342 |
비교예 1 | 8.6 | 0.2 | 7.0 | 390 |
비교예 2 | 9.0 | 1.5 | 6.5 | 410 |
비교예 3 | 11.9 | 5.7 | 3.8 | 327 |
비교예 4 | 11.7 | 6.0 | 5.9 | 295 |
비교예 5 | 11.5 | 7.0 | 6.5 | 300 |
비교예 6 | 12.2 | 2.1 | 5.0 | 310 |
비교예 7 | 8.8 | 2.4 | 6.0 | 390 |
Claims (15)
- 열팽창계수가 1 ppm/℃ 이상, 5 ppm/℃ 이하이고,탄성율이 9 GPa 이상, 11.5 GPa 이하이며,유리전이온도가 340℃ 이상, 400℃ 이하인,폴리이미드 필름.
- 제1항에 있어서,흡습팽창계수가 4 ppm/RH% 이상, 6 ppm/RH% 이하인,폴리이미드 필름.
- 비페닐테트라카르복실릭디안하이드라이드(BPDA), 피로멜리틱디안하이드라이드(PMDA), 옥시디프탈릭안하이드라이드(ODPA) 및 벤조페논테트라카복실릭디안하이드라이드(BTDA)로 이루어진 그룹에서 선택된 2종 이상을 포함하는 이무수물산 성분과, 파라페닐렌 디아민(PPD), m-톨리딘(m-tolidine), 옥시디아닐린(ODA) 및 1,3-비스아미노페녹시벤젠(TPE-R)으로 이루어진 그룹에서 선택된 2 종 이상을 포함하는 디아민 성분을 포함하는 폴리아믹산 용액을 이미드화 반응시켜 얻어지고,상기 디아민 성분의 총함량 100몰%를 기준으로, 상기 파라페닐렌 디아민의 함량이 10 몰% 이상 70 몰% 이하이고, 상기 m-톨리딘의 함량이 25 몰% 이상 80 몰% 이하인,폴리이미드 필름.
- 제3항에 있어서,상기 이무수물산 성분의 총함량 100 몰%를 기준으로, 상기 비페닐테트라카르복실릭디안하이드라이드의 함량이 30 몰% 이상 60 몰% 이하이고, 상기 피로멜리틱디안하이드라이드의 함량이 40 몰% 이상 60 몰% 이하인,폴리이미드 필름.
- 제4항에 있어서,상기 이무수물산 성분의 총함량 100 몰%를 기준으로, 상기 옥시디프탈릭안하이드라이드의 함량이 20 몰% 이하이고, 상기 벤조페논테트라카복실릭디안하이드라이드의 함량이 30 몰% 이하이며,상기 디아민 성분의 총함량 100몰%를 기준으로, 상기 옥시디아닐린(ODA)의 함량이 20 몰% 이하이고, 상기 1,3-비스아미노페녹시벤젠의 함량이 20 몰% 이하인,폴리이미드 필름.
- 제3항에 있어서,상기 비페닐테트라카르복실릭디안하이드라이드에 대한 상기 파라페닐렌 디아민의 몰비가 0.3 이상, 2.5 이하인,폴리이미드 필름.
- 제3항에 있어서,상기 피로멜리틱디안하이드라이드에 대한 상기 m-톨리딘의 몰비가 0.6 이상 1.5 이하인,폴리이미드 필름.
- 제3항에 있어서,상기 비페닐테트라카르복실릭디안하이드라이드에 대한 상기 파라페닐렌 디아민의 반응 몰비가 1.05 이상, 1.2 이하인,폴리이미드 필름.
- 제3항에 있어서,상기 피로멜리틱디안하이드라이드에 대한 상기 파라페닐렌 디아민 및 상기 m-톨리딘의 반응 몰비가 0.9 이상, 0.99 이하인,폴리이미드 필름.
- (a) 비페닐테트라카르복실릭디안하이드라이드(BPDA), 피로멜리틱디안하이드라이드(PMDA), 옥시디프탈릭안하이드라이드(ODPA) 및 벤조페논테트라카복실릭디안하이드라이드(BTDA)로 이루어진 그룹에서 선택된 2종 이상을 포함하는 이무수물산 성분과, 파라페닐렌 디아민(PPD), m-톨리딘(m-tolidine), 옥시디아닐린(ODA) 및 1,3-비스아미노페녹시벤젠(TPE-R)으로 이루어진 그룹에서 선택된 2 종 이상을 포함하는 디아민 성분을 유기 용매 중에서 중합하여 폴리아믹산을 제조하는 단계; 및(b) 상기 폴리아믹산을 이미드화하는 단계;를 포함하고,상기 이무수물산 성분의 총함량 100 몰%를 기준으로, 상기 비페닐테트라카르복실릭디안하이드라이드의 함량이 30 몰% 이상 60 몰% 이하이며, 상기 피로멜리틱디안하이드라이드의 함량이 40 몰% 이상 60 몰% 이하이고,상기 디아민 성분의 총함량 100몰%를 기준으로, 상기 파라페닐렌 디아민의 함량이 10 몰% 이상 70 몰% 이하이고, 상기 m-톨리딘의 함량이 25 몰% 이상 80 몰% 이하인,폴리이미드 필름의 제조방법.
- 제10항에 있어서,상기 이무수물산 성분의 총함량 100 몰%를 기준으로, 상기 옥시디프탈릭안하이드라이드의 함량이 20 몰% 이하이고, 상기 벤조페논테트라카복실릭디안하이드라이드의 함량이 30 몰% 이하이며,상기 디아민 성분의 총함량 100몰%를 기준으로, 상기 옥시디아닐린(ODA)의 함량이 20 몰% 이하이고, 상기 1,3-비스아미노페녹시벤젠의 함량이 20 몰% 이하인,폴리이미드 필름의 제조방법.
- 제10항에 있어서,상기 비페닐테트라카르복실릭디안하이드라이드에 대한 상기 파라페닐렌 디아민의 반응 몰비가 1.05 이상 1.2 이하이고,상기 피로멜리틱디안하이드라이드에 대한 상기 파라페닐렌 디아민 및 상기 m-톨리딘의 반응 몰비가 0.9 이상 0.99 이하인,폴리이미드 필름의 제조방법.
- 제10항에 있어서,상기 폴리이미드 필름의 열팽창계수가 1 ppm/℃ 이상, 5 ppm/℃ 이하이고,탄성율이 9 GPa 이상, 11.5 GPa 이하이며,유리전이온도가 340℃ 이상, 400℃ 이하이고,흡습팽창계수가 4 ppm/RH% 이상, 6 ppm/RH% 이하인,폴리이미드 필름의 제조방법.
- 제1항 내지 제9항 중 어느 한 항에 따른 폴리이미드 필름과 전기 전도성의 금속박을 포함하는,연성 금속박 적층판.
- 제14항에 따른 연성 금속박 적층판을 포함하는,전자 부품.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18/034,983 US20230407021A1 (en) | 2020-11-04 | 2021-11-02 | Polyimide film having high dimensional stability, and method for manufacturing same |
CN202180073176.8A CN116490545A (zh) | 2020-11-04 | 2021-11-02 | 具有高尺寸稳定性的聚酰亚胺膜及其制造方法 |
JP2023527073A JP2023547673A (ja) | 2020-11-04 | 2021-11-02 | 高い寸法安定性を有するポリイミドフィルム及びその製造方法 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2020-0145822 | 2020-11-04 | ||
KR20200145822 | 2020-11-04 | ||
KR10-2021-0135635 | 2021-10-13 | ||
KR1020210135635A KR102617724B1 (ko) | 2020-11-04 | 2021-10-13 | 높은 치수 안정성을 가지는 폴리이미드 필름 및 그 제조방법 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022098042A1 true WO2022098042A1 (ko) | 2022-05-12 |
Family
ID=81458048
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2021/015673 WO2022098042A1 (ko) | 2020-11-04 | 2021-11-02 | 높은 치수 안정성을 가지는 폴리이미드 필름 및 그 제조방법 |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP2023547673A (ko) |
TW (1) | TW202227533A (ko) |
WO (1) | WO2022098042A1 (ko) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115594846A (zh) * | 2022-09-14 | 2023-01-13 | 安徽国风新材料股份有限公司(Cn) | 具有改善的粘合力和透湿速率的聚酰亚胺薄膜及制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20080034876A (ko) * | 2005-08-04 | 2008-04-22 | 가부시키가이샤 가네카 | 금속 피복 폴리이미드 필름 |
KR20110012753A (ko) * | 2009-07-31 | 2011-02-09 | 에스케이씨코오롱피아이 주식회사 | 폴리이미드 필름 |
KR20190038383A (ko) * | 2017-09-29 | 2019-04-08 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | 폴리이미드 필름, 금속장 적층판 및 회로 기판 |
KR20200118027A (ko) * | 2018-02-05 | 2020-10-14 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | 폴리이미드 수지 조성물 및 폴리이미드 필름 |
KR20200120492A (ko) * | 2019-04-12 | 2020-10-21 | 피아이첨단소재 주식회사 | 접착력이 우수한 저유전손실 다층 폴리이미드 필름 및 이의 제조방법 |
-
2021
- 2021-11-02 WO PCT/KR2021/015673 patent/WO2022098042A1/ko active Application Filing
- 2021-11-02 JP JP2023527073A patent/JP2023547673A/ja active Pending
- 2021-11-03 TW TW110140873A patent/TW202227533A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20080034876A (ko) * | 2005-08-04 | 2008-04-22 | 가부시키가이샤 가네카 | 금속 피복 폴리이미드 필름 |
KR20110012753A (ko) * | 2009-07-31 | 2011-02-09 | 에스케이씨코오롱피아이 주식회사 | 폴리이미드 필름 |
KR20190038383A (ko) * | 2017-09-29 | 2019-04-08 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | 폴리이미드 필름, 금속장 적층판 및 회로 기판 |
KR20200118027A (ko) * | 2018-02-05 | 2020-10-14 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | 폴리이미드 수지 조성물 및 폴리이미드 필름 |
KR20200120492A (ko) * | 2019-04-12 | 2020-10-21 | 피아이첨단소재 주식회사 | 접착력이 우수한 저유전손실 다층 폴리이미드 필름 및 이의 제조방법 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115594846A (zh) * | 2022-09-14 | 2023-01-13 | 安徽国风新材料股份有限公司(Cn) | 具有改善的粘合力和透湿速率的聚酰亚胺薄膜及制备方法 |
CN115594846B (zh) * | 2022-09-14 | 2024-03-15 | 安徽国风新材料股份有限公司 | 具有改善的粘合力和透湿速率的聚酰亚胺薄膜及制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2023547673A (ja) | 2023-11-13 |
TW202227533A (zh) | 2022-07-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2020054912A1 (ko) | 표면 품질이 개선된 폴리이미드 필름 및 이의 제조방법 | |
WO2021095975A1 (ko) | 저유전 폴리이미드 필름 및 이의 제조방법 | |
WO2021091011A1 (ko) | 고내열 저유전 폴리이미드 필름 및 이의 제조방법 | |
WO2021091014A1 (ko) | 유전특성이 개선된 폴리이미드 필름 및 그 제조방법 | |
WO2019132184A1 (ko) | 연성동박적층판 제조용 폴리이미드 필름 및 이를 포함하는 연성동박적층판 | |
WO2012081763A1 (ko) | 폴리이미드 필름 | |
WO2021060613A1 (ko) | 폴리아믹산 조성물, 이의 제조방법 및 이를 포함하는 폴리이미드 필름 | |
WO2021096245A2 (ko) | 치수 안정성이 향상된 폴리이미드 필름 및 이의 제조방법 | |
WO2020091147A1 (ko) | 폴리이미드 피복물의 내열성을 향상시키기 위한 도체 피복용 폴리이미드 바니쉬 및 이로부터 제조된 폴리이미드 피복물 | |
WO2011013904A2 (ko) | 폴리이미드 필름 | |
WO2020040356A1 (ko) | 방향족 카르복실산을 포함하는 도체 피복용 폴리이미드 바니쉬 및 이의 제조방법 | |
WO2021054515A1 (ko) | 폴리이미드 필름, 이의 제조방법, 및 이를 포함한 연성금속박적층판 | |
WO2021095976A1 (ko) | 고탄성 및 고내열 폴리이미드 필름 및 그 제조방법 | |
WO2020101225A1 (ko) | 가교성 디안하이드라이드계 화합물 및 산화방지제를 포함하는 폴리이미드 전구체 조성물, 이로부터 제조된 폴리이미드 필름 | |
WO2022098042A1 (ko) | 높은 치수 안정성을 가지는 폴리이미드 필름 및 그 제조방법 | |
WO2021091013A1 (ko) | 고내열 저유전 폴리이미드 필름 및 이의 제조방법 | |
WO2021091012A1 (ko) | 저유전 폴리이미드 필름 및 그 제조방법 | |
WO2022065804A1 (ko) | 저유전 폴리이미드 필름 및 이의 제조방법 | |
KR20220060476A (ko) | 높은 치수 안정성을 가지는 폴리이미드 필름 및 그 제조방법 | |
WO2023075542A1 (ko) | 높은 치수 안정성을 가지는 폴리이미드 필름 및 그 제조방법 | |
WO2024117800A1 (ko) | 폴리이미드 필름 및 그 제조방법 | |
WO2021060612A1 (ko) | 폴리아믹산 조성물, 이의 제조방법 및 이를 포함하는 폴리이미드 필름 | |
WO2022114938A1 (ko) | 높은 치수 안정성을 가지는 폴리이미드 필름 및 그 제조방법 | |
WO2020141708A1 (ko) | 폴리아믹산 조성물, 및 이의 제조 방법 | |
WO2024085591A1 (ko) | 폴리이미드 필름 및 그 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21889507 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202180073176.8 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023527073 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 21889507 Country of ref document: EP Kind code of ref document: A1 |