CN110003650A - 聚酰亚胺薄化软性基板及其制造方法 - Google Patents
聚酰亚胺薄化软性基板及其制造方法 Download PDFInfo
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- CN110003650A CN110003650A CN201811416311.0A CN201811416311A CN110003650A CN 110003650 A CN110003650 A CN 110003650A CN 201811416311 A CN201811416311 A CN 201811416311A CN 110003650 A CN110003650 A CN 110003650A
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- polyimides
- conductor layer
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- flexible base
- bis
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- 239000009719 polyimide resin Substances 0.000 claims abstract description 47
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 27
- 239000010410 layer Substances 0.000 claims description 137
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 26
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 21
- 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 19
- 239000000758 substrate Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- -1 hexafluoro propylidene Chemical group 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
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- 239000010949 copper Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- 150000003949 imides Chemical class 0.000 claims description 6
- 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 5
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- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010931 gold Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
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- 239000007787 solid Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 3
- UMGYJGHIMRFYSP-UHFFFAOYSA-N 2-(4-aminophenyl)-1,3-benzoxazol-5-amine Chemical class C1=CC(N)=CC=C1C1=NC2=CC(N)=CC=C2O1 UMGYJGHIMRFYSP-UHFFFAOYSA-N 0.000 claims description 3
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000006159 dianhydride group Chemical group 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
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- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 229920006259 thermoplastic polyimide Polymers 0.000 claims description 3
- LOCTYHIHNCOYJZ-UHFFFAOYSA-N (4-aminophenyl) 4-aminobenzoate Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(N)C=C1 LOCTYHIHNCOYJZ-UHFFFAOYSA-N 0.000 claims description 2
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- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 claims 1
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 229940113088 dimethylacetamide Drugs 0.000 description 6
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- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical group C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
-
- 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
- C08K3/08—Metals
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0277—Bendability or stretchability details
- H05K1/028—Bending or folding regions of flexible printed circuits
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
-
- 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
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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
- C08K3/08—Metals
- C08K2003/0831—Gold
-
- 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
- C08K3/08—Metals
- C08K2003/085—Copper
-
- 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
- C08K3/08—Metals
- C08K2003/0862—Nickel
-
- 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
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Abstract
本发明提供一种聚酰亚胺薄化软性基板及其制造方法。聚酰亚胺薄化软性基板,包含聚酰亚胺树脂、导体层与聚酰亚胺绝缘层。聚酰亚胺树脂的线热膨胀系数小于40ppm/K。导体层由多个金属纳米粒子堆叠而成,堆叠的金属纳米粒子之间具有多个孔隙,孔隙的尺寸介于0.1μm至1μm。聚酰亚胺树脂的一部分填入此孔隙中。聚酰亚胺绝缘层由覆盖于导体层上的聚酰亚胺树脂所形成。
Description
技术领域
本发明涉及一种聚酰亚胺基板以及其制造方法。特别涉及一种用特定制程制作且有特定结构的聚酰亚胺薄化软性基板。
背景技术
软性基板的发展过程中,从早期的有胶系软性基板(3-layer FCCL),发展至无胶系软性基板(2-layer FCCL)。其中,2-layer FCCL少了一层接着剂层,不但减少软性基板材料整体厚度,且具有更佳的耐热性、尺寸稳定性、难燃性、耐折性等特性,恰好符合电子产品对于轻量化、薄型化、功能强化等需求与发展趋势。但是,不论是2-layer FCCL或者是3-layer FCCL,其仍须通过传统的蚀刻制程进行图案化:将导体层的部分铜箔去除以形成导线、通孔、网格等图案化线路。此制程方式不但不符合环保趋势,面对目前图案的细线化、小孔径等趋势,也遇到很大瓶颈。
为了满足图案的细线化、小孔径的需求,在软性基板图案化制程中,逐渐发展出全加成法、半加成法等加工方式。而应用于上述制程的导体层薄化材料,包含以湿制程达成聚酰亚胺膜金属化,或者以溅镀法将薄铜形成在聚酰亚胺膜表面。前者,目前仍有信赖性相关问题,尚未被大量运用于上述制程技术中,而溅镀法所制成的铜箔基材,虽然已经是使用多年的成熟技术,且大量应用于COF(Chip On Film)载板上,但是此材料的产出,必须有巨额的设备投资,包含真空溅镀设备、电镀设备等。因此,如果大量采用此材料于未来细线化软性基板的话,势必将面临高成本、低产能等问题。此外,除了上述两种方式外,另一种方式为直接图案化方式,以金属粒子或离子所配制的金属墨水或金属膏(金属胶),利用网印或喷印的方式直接在高分子基材,例如聚酰亚胺膜、聚酯膜等基板上形成图案化线路,再经过烧结形成连续致密导线。此方式虽能减少微影制程、降低环境污染,但是金属粒子仅堆积于基材表面,高分子基材无法进入导体层的孔隙中,因此导体层与基材的附着度不佳而容易产生脱落等问题。
发明内容
本发明提供一种新颖结构的聚酰亚胺薄化软性基板及其制造方法,其聚酰亚胺树脂嵌入导体层的孔隙,进而形成绝缘层,具有良好的附着力。
根据本发明,提供一种聚酰亚胺薄化软性基板,包含聚酰亚胺树脂、导体层与聚酰亚胺绝缘层。聚酰亚胺树脂的线热膨胀系数小于40ppm/K。导体层由多个金属纳米粒子堆叠而成,堆叠的金属纳米粒子之间具有多个孔隙。孔隙的尺寸介于0.1μm至1μm之间。聚酰亚胺树脂的一部分填入此孔隙中。聚酰亚胺绝缘层由覆盖于导体层上的聚酰亚胺树脂所形成。
在一个实施例中,上述聚酰亚胺薄化软性基板中的聚酰亚胺树脂为热固型聚酰亚胺树脂、热塑型聚酰亚胺树脂或可溶性聚酰亚胺树脂中的一种。
在一个实施例中,上述聚酰亚胺树脂由下述至少一种二酐单体及至少一种二胺单体聚合而成:
二酐单体包括对-亚苯基双(苯偏三酸酯二酐)、2,2'-双-(3,4-二羧苯基)六氟丙烷二酐、4,4'-二苯醚四酸酐、苯四甲酸二酐、联苯四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、3,3',4,4'-二苯基砜四酸酐、4,4'-(六氟亚丙基)双-邻苯二甲酸酐及4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐);
二胺单体包括4,4'-二胺基二苯基醚、4,4'-二胺基二苯甲烷、2,2’-双[4-(4-胺基苯氧基)苯基]丙烷、2,2'-双[4-(4-胺基苯氧基)苯基]丙烷、4,4'-二胺基二苯砜、3,3’-二胺基二苯砜、1,3-双(4-胺基苯氧基)苯、4,4'-二胺基苯甲酰胺苯、4-氨基苯甲酸(4-氨基苯基)酯、2-(4-氨基苯基)-5-氨基苯并恶唑、对苯二甲酸二对氨基苯酯、对-苯二胺、2,2'-双(三氟甲基)联苯胺、4,4'-二氨基-2,2'-二甲基-1,1'-联苯及2,2-双[4-(4-胺基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷。
在一个实施例中,聚酰亚胺树脂的粘度值介于0.4-1.0dL/g之间。
在一个实施例中,金属纳米粒子为银、铜、镍、金或钛中的一种或其组合。
在一个实施例中,金属纳米粒子的粒径介于100-1000nm之间。
在一个实施例中,导体层的厚度介于500nm-3μm之间。
根据本发明的另一个实施例,提供一种聚酰亚胺薄化软性基板的制造方法,包含下列步骤:
(a)提供载板;
(b)将多个金属纳米粒子涂布在该载板上而形成导体层。所述金属纳米粒子间因堆叠形成有多个孔隙,且各孔隙的尺寸介于0.1μm至1μm之间;
(c)将聚酰亚胺树脂覆盖于步骤(b)的导体层上,使聚酰亚胺树脂中的一部分渗透并填入所述孔隙中,且聚酰亚胺树脂的另一部分在导体层上形成聚酰亚胺绝缘层;以及
(d)使该载板与步骤(c)的该导体层分离,从而形成该聚酰亚胺薄化软性基板。
在一个实施例中,聚酰亚胺薄化软性基板的制造方法还包括下列步骤:
(e)图案化导体层;以及
(f)在步骤(e)的图案化的该导体层上形成导电金属层。
在一个实施例中,聚酰亚胺薄化软性基板的制造方法还包括下列步骤:
(g)在该导体层上形成导电金属层。
在一个实施例中,上述导电金属层通过电镀方式而形成。
在一个实施例中,载板的材质为玻璃、PET、聚酰亚胺、铜、铝或不锈钢。
在一个实施例中,在步骤(e)中,利用激光雕刻或药液蚀刻方式图案化该导体层。
为使本发明的上述及其他方面更为清楚易懂,下文特举实施例,并配合附图作详细说明。
附图简要说明
图1绘示了根据本发明实施例的聚酰亚胺薄化软性基板的结构示意图。
图2为根据本发明实施例的聚酰亚胺薄化软性基板的导体层的SEM图。
图3A至图3C绘示了根据本发明实施例的聚酰亚胺薄化软性基板的制造方式。
具体实施方式
请参阅图1,其是根据本发明的实施例的聚酰亚胺薄化软性基板的结构示意图。聚酰亚胺薄化软性基板100为导体层110及聚酰亚胺绝缘层120所组成的双层结构。导体层由纳米粒子111所堆叠构成,内部因堆叠具有多个孔隙112,孔隙的尺寸为0.1-1μm。聚酰亚胺绝缘层由聚酰亚胺树脂121所构成,部分聚酰亚胺树脂121渗入导体层110中,填入导体层110的孔隙112中。
导体层110可由金属纳米粒子111所配制的金属膏(金属胶),或金属离子态的金属墨水制作而成。金属墨水经加热还原后会恢复为金属纳米粒子。金属纳米粒子111的粒径为100-1000nm,优选为200-500nm。选用金属墨水或特定尺寸的金属纳米粒子,经过烧结成型、堆叠后会在内部产生多个孔隙112。此孔隙在SEM底下进行观察,尺寸介于0.1-1μm之间(如图2所示,黑色部分即为孔隙)。孔隙太小则聚酰亚胺树脂不易填入,孔隙太大则降低导体层的导电度。堆叠后的导体层厚度为500nm-3μm,优选为1-2μm,导体层太薄则无法与聚酰亚胺绝缘层稳固接合,太厚则无法达到薄化效果。
优选地,金属纳米粒子111选自由银、金、铜、镍或钛中的一种,或是上述的组合,但并不限于此。金属纳米粒子的来源不限于金属纳米粒子涂料,也可经由金属离子溶液经还原后形成纳米粒子堆积而形成导体层。
部分的聚酰亚胺树脂121填入导体层110的多数孔隙112中,甚至可穿透导体层110。另一部分的聚酰亚胺树脂121在导体层上形成聚酰亚胺绝缘层120。因此,聚酰亚胺绝缘层120与导体层110间将有强力的附着力,导体层110(或其上的电路图案)不易剥落。
上述聚酰亚胺树脂121,由聚酰亚胺的前驱物的聚酰胺酸的溶液经亚胺化后制得。聚酰胺酸由至少一种二酐单体及至少一种二胺单体以相等摩尔量的方式在有机溶剂中溶解,并在可控制温度条件下进行搅拌直至二酐与二胺聚合结束。
用以溶解二胺单体及二酐单体的有机溶剂可为N,N-二甲基乙酰胺、N,N-二乙基乙酰胺、N,N-二甲基甲酰胺、N-甲基-2-吡咯烷酮等溶剂。
二酐的单体,可选自由对-亚苯基双(苯偏三酸酯二酐)、2,2'-双-(3,4-二羧苯基)六氟丙烷二酐、4,4'-二苯醚四酸酐、苯四甲酸二酐、联苯四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、3,3',4,4'-二苯基砜四酸酐、4,4'-(六氟亚丙基)双-邻苯二甲酸酐及4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)所组成的组。
二胺的单体,可选自由4,4'-二胺基二苯基醚、4,4'-二胺基二苯甲烷、2,2’-双[4-(4-胺基苯氧基)苯基]丙烷、2,2'-双[4-(4-胺基苯氧基)苯基]丙烷、4,4'-二胺基二苯砜、3,3’-二胺基二苯砜、1,3-双(4-胺基苯氧基)苯、4,4'-二胺基苯甲酰胺苯、4-氨基苯甲酸(4-氨基苯基)酯、2-(4-氨基苯基)-5-氨基苯并恶唑、对苯二甲酸二对氨基苯酯、对-苯二胺、2,2'-双(三氟甲基)联苯胺、4,4'-二氨基-2,2'-二甲基-1,1'-联苯及2,2-双[4-(4-胺基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷所组成的组。
上述披露的聚酰胺酸(聚酰亚胺前驱物)组成仅为示例,实际上使用的二酐单体及二胺单体并不限于上述材料。只要线热膨胀系数(CTE)小于40ppm/K的聚酰亚胺树脂(例如热固型聚酰亚胺树脂、热塑型聚酰亚胺树脂或可溶性聚酰亚胺树脂中的任意一种)都可作为本发明的聚酰亚胺树脂。
聚酰亚胺树脂的粘度值优选为0.4-1.0dL/g。若聚酰亚胺树脂为可溶型,则测定聚酰亚胺树脂的粘度;若为不可溶型聚酰亚胺(一般聚酰亚胺),则测定聚酰胺酸的粘度。粘度太低则代表聚酰亚胺分子量太小,而导致无法成膜,即低分子量薄膜容易碎裂的现象。当粘度太高时,则不易流动填入导体层的孔隙中。
以下用图3A至图3C说明一种聚酰亚胺薄化软性基板的制备方法:
首先,如图3A所示,将含有金属纳米粒子111的金属胶涂布于载板130上,并经由烧结形成导体层110。金属胶中的固型份(金属含量)优选为60-85重量百分比。金属胶可经由旋转涂布法、喷涂法、网版印刷法、刮条涂布法、狭缝涂布法、线棒式湿膜涂布法等涂布方法涂布于载板上,并经过干燥与烧结以形成预备导体层。例如,加热干燥的方法为将涂布金属胶的载板置于约80-120℃的烘箱中进行干燥。例如,烧结的方法为将上述干燥后的载板放置于富有氮气、氩气等惰性气体的烘箱,并以200-350的温度对金属胶进行烧结,以形成包含多个孔隙112的导体层110。此孔隙112由金属纳米粒子111堆叠所形成,各孔隙的尺寸介于0.1μm至1μm之间。上述导体层的金属优选但不限于选自银、金、铜、镍或钛中的一种,或上述的组合。导体层厚度优选为500nm-3μm。
载板130是指供金属胶涂覆并干燥于其上的支撑物质,其可包括:聚酰亚胺、聚酰胺等塑胶基板;铜、铝、不锈钢等金属基板,或玻璃基板等。
然后,如图3B所示,将聚酰亚胺树脂121涂布在导体层110上,形成聚酰亚胺绝缘层120。此处先将聚酰亚胺树脂的前驱物聚酰胺酸溶液以旋转涂布法、喷涂法、网版印刷法、柔性版印刷法、刮条涂布法、狭缝涂布法、线棒式湿膜涂布法等方法涂布在步骤导体层110(及载板130)上,然后再使聚酰胺酸溶液酰亚胺化形成聚酰亚胺树脂。酰亚胺化的方式可使用高温熟化,例如连续或分段将聚酰胺酸进行加热,加热温度为250-350℃,也可使用化学转化,加入催化剂帮助脱水反应。部分的聚酰亚胺树脂121渗入导体层110的多个孔隙111中,甚至可穿透进而接触载板130;另一部分的聚酰亚胺树脂121在导体层110上形成聚酰亚胺绝缘层130。特别说明的是,导体层110内堆叠的金属纳米粒子间虽有孔隙,但仍互相接触,即使部分填入聚酰亚胺树脂121(绝缘体),其仍为导体。
最后,如图3C所示,从导体层110上剥离/移除载板130,即完成本发明的聚酰亚胺薄化软性基板。
根据上述步骤,可以制作出具有薄化导体层的聚酰亚胺基板,且聚酰亚胺绝缘层跟导体层之间仍具有良好附着力。
此外,可对上述聚酰亚胺薄化软性基板的导体层进行图案化,形成线路。导体层图案化的方式没有特别限制,通常可通过激光雕刻、药液蚀刻等方式达成。举例来说,可将聚酰亚胺薄化软性基板的导体层面涂布光阻,经过曝光与显影形成光阻图案,光阻图案非形成区域的金属层通过湿式蚀刻而去除,最后再以去光阻剂除去光阻。
图案化本发明聚酰亚胺薄化软性基板的导体层后,可再以湿式镀覆法增厚,其中以电解电镀法为最佳。特别说明的是,增厚导体层的步骤在图案化导体层之前或之后都可进行。
可依上述所介绍的聚酰亚胺薄化软性基板的制造方式,制作双面导体层基板。详细来说,制作完成如图1所示的聚酰亚胺薄化软性基板100之后,可以(1)在聚酰亚胺绝缘层120上涂布接着层,(2)再以另一聚酰亚胺薄化软性基板100的聚酰亚胺面与接着层压合与熟化,最终可制得「导体层-聚酰亚胺绝缘层-接着层-聚酰亚胺绝缘层-导体层」结构的聚酰亚胺双面导体层基板。
上述步骤(1)涂布的接着层材料可包括环氧树脂、聚酰亚胺树脂等接着剂,此接着剂经由旋转涂布法、网版印刷法、柔性版印刷法、刮条涂布法、狭缝涂布法、线棒式湿膜涂布法等涂布方法涂布于聚酰亚胺薄化软性基板的聚酰亚胺面上并进行干燥。
步骤(2)中,以另一聚酰亚胺薄化软性基板的聚酰亚胺面与接着层进行压合,最后进行熟化。熟化温度根据不同接着剂有所不同,一般为150-300℃,熟化后即完成双面导体层基板。
合成例1
将24.20g(0.076mole)的2,2’-双(三氟甲基)联苯胺[TFMB]、1.85g(0.017mole)的对-苯二胺[PDA]、2.36g(0.008mole)的1,3-双(4-胺基苯氧基)苯[TPE-R]及244.37g的N-甲基-2-吡咯烷酮[NMP]置入三颈烧瓶内。在30℃下搅拌至完全溶解后,再加入41.75g(0.091mole)的对-亚苯基双(苯偏三酸酯二酐)[TAHQ]及2.83g(0.005mole)的4,4’-(4,4’-异丙基二苯氧基)双(邻苯二甲酸酐)[PBADA],然后持续搅拌并在25℃下反应24小时,可得到合成例1的聚酰胺酸溶液,其粘度为0.8dL/g。
合成例2
将8.97g(0.028mole)的2,2’-双(三氟甲基)联苯胺[TFMB]、2.40g(0.012mole)的4,4’-二胺基二苯基醚[ODA]及100g的二甲基乙酰胺[DMAc]置入三颈烧瓶内。在30℃下搅拌至完全溶解后,再加入10.66g(0.024mole)的2,2’-双-(3,4-二羧苯基)六氟丙烷二酐[6FDA]与4.7g(0.016mole)的联苯四羧酸二酐[BPDA],然后持续搅拌并在25℃下反应24小时,可得到合成例2的聚酰胺酸溶液,其粘度为0.75dL/g。
合成例3
将16.42g(0.04mole)的2,2’-双[4-(4-胺基苯氧基)苯基]丙烷[BAPP]及100g的二甲基乙酰胺[DMAc]置入三颈烧瓶内。在30℃下搅拌至完全溶解后,再加入11.76g(0.04mole)的联苯四羧酸二酐[BPDA],然后持续搅拌并在25℃下反应24小时,可得到合成例3的聚酰胺酸溶液,其粘度为1.2dL/g。
合成例4
将11.52g(0.036mole)的2,2’-双(三氟甲基)联苯胺[TFMB]及100g的二甲基乙酰胺[DMAc]置入三颈烧瓶内。在30℃下搅拌至完全溶解后,再加入11.76g(0.04mole)的联苯四羧酸二酐[BPDA],然后持续搅拌并在25℃下反应24小时,可得到合成例3的聚酰胺酸溶液,其粘度为0.3dL/g。
实施例1
将金属胶(含粒径为150±20nm的纳米银)以旋转涂布方式涂布在玻璃载板上,并经过100℃的表面干燥与250℃温度的烧结形成导体层。然后将合成例1的聚酰胺酸溶液涂布在导体层上,经过350℃熟化后将导体层与载板分离,即可得实施例1的聚酰亚胺薄化软性基板。
实施例2
将金属墨水以旋转涂布方式涂布在玻璃载板上,并经过100℃的表面干燥与250℃温度的烧结后,金属墨水内的离子还原成粒子形成导体层。然后将合成例2的聚酰胺酸溶液涂布在导体层上,经过350℃熟化后将导体层与载板分离,即可得实施例2的聚酰亚胺薄化软性基板。
比较例1
将金属胶(含粒径为150±20nm的纳米银)以旋转涂布方式涂布在玻璃载板上,并经过100℃的表面干燥与250℃温度的烧结而形成导体层。然后将合成例3的聚酰胺酸溶液涂布在导体层上,经过350℃熟化后将导体层与载板分离,即可得比较例1的聚酰亚胺薄化软性基板。
比较例2
将金属胶(含粒径为50±20nm的纳米银)以旋转涂布方式涂布在玻璃载板上,并经过100℃的表面干燥与250℃温度的烧结而形成导体层。然后将合成例2的聚酰胺酸溶液涂布在导体层上,经过350℃熟化后将导体层与载板分离,即可得比较例2的聚酰亚胺薄化软性基板。
比较例3
将金属胶(含粒径为1500±400nm的纳米银)以旋转涂布方式涂布在玻璃载板上,并经过100℃的表面干燥与250℃温度的烧结而形成导体层。然后将合成例2的聚酰胺酸溶液涂布在导体层上,经过350℃熟化后将导体层与载板分离,即可得比较例3的聚酰亚胺薄化软性基板。
比较例4
将金属胶(含粒径为150±20nm的纳米银)以旋转涂布方式涂布在玻璃载板上,并经过100℃的表面干燥与250℃温度的烧结而形成导体层。然后将合成例4的聚酰胺酸溶液涂布在导体层上,经过350℃熟化后将导体层与载板分离,即可得比较例4的聚酰亚胺薄化软性基板。
表1聚酰亚胺薄化软性基板的特性比较
*拉力值测试是将导体层以电镀增厚至18μm后,测量绝缘层与导体层间的附着力。
*耐热性测试是将测试样品于288℃锡炉中,连续浸泡三个循环,如无剥离现象即判定PASS。
*CTE值即为聚酰亚胺绝缘层的CTE值。
*表面电阻是指将金属胶转印后,在电镀金属前,测量其表面电阻。
表1比较实施例与比较例的聚酰亚胺薄化软性基板的特性。由比较例1可知,若聚酰亚胺的线热膨胀系数及粘度较高,当然耐热性、金属层与聚酰亚胺层的相容性均会较差,且会使聚酰亚胺薄化软性基板表面产生卷曲;根据比较例2,若使用金属纳米颗粒粒径较小的金属胶(导体层孔隙小),则聚酰亚胺无法有效填入导体层孔隙中,使得载板与导体层的附着力大于聚酰亚胺层与金属层的附着力,此时载板与导体层不易分离,即产生部分导体层残留在载板上,或者完全留在载板上,而无法完全转印至聚酰亚胺层的现象;根据比较例3,使用金属纳米颗粒粒径较大的金属胶(导体层孔隙大),则导体层的导电能力下降,表面电阻明显增大;根据比较例4,使用粘度较低的聚酰亚胺树脂,因粘度较低不易成膜,使得聚酰亚胺薄化软性基板产生脆化情形。
实施例3聚酰亚胺薄化软性基板的图案化
将实施例2的聚酰亚胺薄化软性基板的导体层贴上干膜光阻,以温度100℃进行贴合后,通过累计照射量为90mJ的紫外光进行曝光。随后,通过浸渍于碳酸钙显影液中进行显像。使用纯水进行冲洗,在导体层上形成配制有多条线宽30μm的直线光阻图案,使用蚀刻液进行蚀刻金属层。使用纯水进行冲洗后再使用3%NaOH水溶液进行去光阻,如此可得图案化的聚酰亚胺薄化软性基板。最后,再以电镀方式进行导线增厚。
实施例4双面板制作
将实施例2的聚酰亚胺薄化软性基板的PI树脂面涂布环氧树脂接着剂,并在温度90℃环境下进行干燥。然后再将另一聚酰亚胺薄化软性基板的PI树脂面进行粘贴与压合,最后经过熟化后即可得双面导体层基板。
虽然本发明以实施例说明如上,但这些实施例并非用以限制本发明。本领域的通常知识者在不脱离本发明技艺精神的范畴内,可以对这些实施例进行等效实施或变更,因此本发明的保护范围应以其后所附的权利要求为准。
【符号说明】
100:聚酰亚胺薄化软性基板
110:导体层
111:金属纳米粒子
112:孔隙
120:聚酰亚胺绝缘层
121:聚酰亚胺树脂
130:载板
Claims (15)
1.一种聚酰亚胺薄化软性基板,包含:
聚酰亚胺树脂,其线热膨胀系数小于40ppm/K;
导体层,由多个金属纳米粒子堆叠而成,所述堆叠的多个金属纳米粒子间具有孔隙,各所述孔隙的尺寸介于0.1μm至1μm之间,其中,该聚酰亚胺树脂中的一部分填入所述孔隙中;
聚酰亚胺绝缘层,由覆盖于该导体层上的该聚酰亚胺树脂所形成。
2.如权利要求1所述的聚酰亚胺薄化软性基板,其中该聚酰亚胺树脂为热固型聚酰亚胺树脂、热塑型聚酰亚胺树脂或可溶性聚酰亚胺树脂中的一种。
3.如权利要求1所述的聚酰亚胺薄化软性基板,其中该聚酰亚胺树脂由下述至少一种二酐单体及至少一种二胺单体聚合而成:
所述二酐单体选自由对-亚苯基双(苯偏三酸酯二酐)、2,2'-双-(3,4-二羧苯基)六氟丙烷二酐、4,4'-二苯醚四酸酐、苯四甲酸二酐、联苯四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、3,3',4,4'-二苯基砜四酸酐、4,4'-(六氟亚丙基)双-邻苯二甲酸酐及4,4'-(4,4'-异丙基二苯氧基)双(邻苯二甲酸酐)所组成的组;
所述二胺单体选自由4,4'-二胺基二苯基醚、4,4'-二胺基二苯甲烷、2,2’-双[4-(4-胺基苯氧基)苯基]丙烷、2,2'-双[4-(4-胺基苯氧基)苯基]丙烷、4,4'-二胺基二苯砜、3,3’-二胺基二苯砜、1,3-双(4-胺基苯氧基)苯、4,4'-二胺基苯甲酰胺苯、4-氨基苯甲酸(4-氨基苯基)酯、2-(4-氨基苯基)-5-氨基苯并恶唑、对苯二甲酸二对氨基苯酯、对-苯二胺、2,2'-双(三氟甲基)联苯胺、4,4'-二氨基-2,2'-二甲基-1,1'-联苯及2,2-双[4-(4-胺基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷所组成的组。
4.如权利要求1所述的聚酰亚胺薄化软性基板,其中该聚酰亚胺树脂的粘度值介于0.4dL/g至1.0dL/g之间。
5.如权利要求1所述的聚酰亚胺薄化软性基板,其中所述金属纳米粒子为银、铜、镍、金或钛中的一种或其组合。
6.如权利要求1所述的聚酰亚胺薄化软性基板,其中所述金属纳米粒子的粒径介于100nm至1000nm之间。
7.如权利要求1所述的聚酰亚胺薄化软性基板,其中该导体层的厚度介于500nm至3μm之间。
8.一种聚酰亚胺薄化软性基板的制造方法,包含下列步骤:
(a)提供载板;
(b)将多个金属纳米粒子涂布在该载板上而形成导体层,所述金属纳米粒子间因堆叠形成多个孔隙,且各所述孔隙的尺寸介于0.1μm至1μm之间;
(c)将聚酰亚胺树脂覆盖于步骤(b)的该导体层上,使该聚酰亚胺树脂中的一部分渗透并填入所述孔隙中,且该聚酰亚胺树脂的另一部分在该导体层上形成聚酰亚胺绝缘层;以及
(d)使该载板与步骤(c)的该导体层分离,从而形成该聚酰亚胺薄化软性基板。
9.如权利要求8所述的制造方法,还包括下列步骤:
(e)图案化该导体层;以及
(f)在步骤(e)的图案化的该导体层上形成导电金属层。
10.如权利要求8所述的制造方法,还包括下列步骤:
(g)在该导体层上形成导电金属层。
11.如权利要求9或10所述的制造方法,其中该导电金属层通过电镀方式而形成。
12.如权利要求8所述的制造方法,其中该聚酰亚胺树脂的粘度值介于0.4-1.0dL/g之间。
13.如权利要求8所述的制造方法,其中该载板的材质为玻璃、PET、聚酰亚胺、铜、铝或不锈钢。
14.如权利要求9所述的制造方法,其在步骤(e)中,利用激光雕刻或药液蚀刻方式图案化该导体层。
15.一种聚酰亚胺薄化软性双面金属基板,包含:
两片如权利要求1所述的聚酰亚胺薄化软性基板,各所述聚酰亚胺薄化软性基板的聚酰亚胺绝缘层间以接着剂贴合,而形成一片两面均为所述金属层的聚酰亚胺薄化软性双面金属基板。
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US10412836B2 (en) | 2019-09-10 |
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US20190357358A1 (en) | 2019-11-21 |
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US20190191568A1 (en) | 2019-06-20 |
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