TW201823304A - Method for manufacturing insulating layer and multilayered printed circuit board - Google Patents
Method for manufacturing insulating layer and multilayered printed circuit board Download PDFInfo
- Publication number
- TW201823304A TW201823304A TW106126268A TW106126268A TW201823304A TW 201823304 A TW201823304 A TW 201823304A TW 106126268 A TW106126268 A TW 106126268A TW 106126268 A TW106126268 A TW 106126268A TW 201823304 A TW201823304 A TW 201823304A
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- Prior art keywords
- insulating layer
- group
- layer
- manufacturing
- resin layer
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 72
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- 235000010290 biphenyl Nutrition 0.000 description 1
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- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
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- 239000013522 chelant Substances 0.000 description 1
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- ILIVWCHUHYQQPB-UHFFFAOYSA-N cyclohexa-2,4-diene-1,1-diamine Chemical compound NC1(N)CC=CC=C1 ILIVWCHUHYQQPB-UHFFFAOYSA-N 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
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- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
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- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010329 laser etching Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- JAOPKYRWYXCGOQ-UHFFFAOYSA-N n,n-dimethyl-1-(4-methylphenyl)methanamine Chemical compound CN(C)CC1=CC=C(C)C=C1 JAOPKYRWYXCGOQ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
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- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- IAYUQKZZQKUOFL-UHFFFAOYSA-N pyridine-2,3,5,6-tetramine Chemical compound NC1=CC(N)=C(N)N=C1N IAYUQKZZQKUOFL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
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- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4664—Adding a circuit layer by thick film methods, e.g. printing techniques or by other techniques for making conductive patterns by using pastes, inks or powders
- H05K3/4667—Adding a circuit layer by thick film methods, e.g. printing techniques or by other techniques for making conductive patterns by using pastes, inks or powders characterized by using an inorganic intermediate insulating layer
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
-
- 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
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
-
- 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
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/0023—Etching of the substrate by chemical or physical means by exposure and development of a photosensitive insulating layer
-
- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
-
- 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
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
- H05K3/4676—Single layer compositions
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Ceramic Engineering (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本申請案主張基於向韓國智慧財產局(Korean Intellectual Property Office)於2016年8月9日提出申請之韓國專利申請案10-2016-0101419號及於2017年7月28日提出申請之韓國專利申請案10-2017-0096355號之優先權權益,該等申請案之揭示係以其全文引用的方式併入本文中。 This application is based on Korean Patent Application No. 10-2016-0101419 filed with the Korean Intellectual Property Office on August 9, 2016 and Korean Patent Application filed on July 28, 2017 Case No. 10-2017-0096355, the disclosure of these applications is incorporated herein by reference in its entirety.
本發明係關於絕緣層的製造方法以及多層印刷電路板的製造方法。更具體而言,本發明係關於絕緣層的製造方法,其可實現均勻且精細圖案,同時改善成本及生產力方面之效率以及確保優異機械性質;以及使用自該絕緣層的製造方法所獲得之絕緣層的多層印刷電路板之製造方法。 The present invention relates to a method for manufacturing an insulating layer and a method for manufacturing a multilayer printed circuit board. More specifically, the present invention relates to a method of manufacturing an insulating layer, which can achieve a uniform and fine pattern, while improving efficiency in terms of cost and productivity, and ensuring excellent mechanical properties; and using the insulation obtained from the method of manufacturing the insulating layer Manufacturing method of multilayer printed circuit board.
近來的電子裝置已日益小型化、輕量化、以及高度功能化。為此,隨著增層PCB(增層電路板(build-up printed circuit board))之應用領域主要在小型裝置中迅速擴展,多層印刷電路板的使用迅速增加。 Recently, electronic devices have been increasingly miniaturized, lightened, and highly functional. For this reason, as the application field of build-up PCB (build-up printed circuit board) is mainly expanded in small devices, the use of multilayer printed circuit boards is rapidly increasing.
多層印刷電路板可自平面佈線進行立體佈線。尤其是在工業電子裝置領域中,多層印刷電路板改善功能元件(諸如積體電路(IC)以及大型積體電路(LSI))的集成度,以及亦為用於電子裝置之小型化、減輕重量、高功能性、結構電功能件之集成(integration of structural electrical function)、縮短裝配時間及降低成本的有利產品。 The multilayer printed circuit board can be three-dimensionally wired from a planar wiring. Especially in the field of industrial electronic devices, multilayer printed circuit boards improve the integration of functional components such as integrated circuits (ICs) and large integrated circuits (LSIs), and are also used for miniaturization and weight reduction of electronic devices. , High functionality, integration of structural electrical function (integration of structural electrical function), shorten the assembly time and reduce the cost of favorable products.
此等應用領域中所使用之增層PCB必須形成通路孔以供個別層之間的連接。該通路孔對應於多層印刷電路板之層間電性連接路徑。過去,其係用機械鑽機械加工,但隨著因電路微加工而使孔直徑變小,因機械鑽孔及精細孔機械加工的限制所造成的加工成本提高,故而出現雷射加工法作為替代。 The build-up PCBs used in these applications must form vias for connections between individual layers. The via hole corresponds to an inter-layer electrical connection path of the multilayer printed circuit board. In the past, it was machined with a mechanical drill. However, as the hole diameter became smaller due to the micromachining of the circuit, the processing cost caused by the limitations of mechanical drilling and fine hole machining increased, so the laser machining method appeared as an alternative. .
在雷射加工法的情況下,使用CO2或YAG雷射鑽。然而,由於通路孔的大小係由雷射鑽決定,例如在CO2雷射鑽的情況下,存在難以製造直徑為40μm或更小之通路孔的限制。此外,亦存在當必須形成大量通路孔時成本負擔重的限制。 In the case of laser processing, a CO 2 or YAG laser drill is used. However, since the size of the via hole is determined by a laser drill, for example, in the case of a CO 2 laser drill, there is a limitation that it is difficult to manufacture a via hole having a diameter of 40 μm or less. In addition, there is a limitation that the cost burden is heavy when a large number of via holes must be formed.
因此,已提出使用光敏性絕緣材料之低成本具有精細直徑的通路孔之形成方法代替上述雷射加工技 術。尤其是,作為光敏性絕緣材料,可提及稱之為「阻焊劑」之光敏性絕緣膜,該光敏性絕緣膜能利用光敏性而形成精細開口圖案。 Therefore, a method of forming a low-cost via hole having a fine diameter using a photosensitive insulating material has been proposed instead of the above-mentioned laser processing technology. In particular, as the photosensitive insulating material, a photosensitive insulating film called "solder resist" can be mentioned, and the photosensitive insulating film can form a fine opening pattern by utilizing the photosensitivity.
此種光敏性絕緣材料或阻焊劑可分成使用碳酸鈉顯影劑之情況及使用另外的顯影之情況以形成圖案。在使用另外的顯影劑之情況中,光敏性絕緣材料或阻焊劑具有因環境及成本因素而難以應用在實際製程的限制。 Such a photosensitive insulating material or solder resist can be divided into a case where a sodium carbonate developer is used and a case where another development is used to form a pattern. In the case of using another developer, the photosensitive insulating material or the solder resist has a limitation that it is difficult to apply to the actual process due to environmental and cost factors.
在另一方面,當使用碳酸鈉顯影劑時,具有環保的優點。在情況中,為了賦予光敏性,使用含有大量羧酸及丙烯酸基之經酸改質的丙烯酸酯樹脂,但是由於大部分丙烯酸酯基及羧基係用酯鍵鏈結,包括聚合抑制劑等以聚合成有利形式,以及另外包括光引發劑等以藉紫外線輻射導致自由基反應。 On the other hand, when a sodium carbonate developer is used, it has the advantage of environmental protection. In some cases, in order to impart photosensitivity, acid-modified acrylate resins containing a large amount of carboxylic acid and acrylic groups are used. However, since most acrylate groups and carboxyl groups are linked by ester bonds, polymerization inhibitors and the like are used for polymerization. Into advantageous forms, and additionally include photoinitiators and the like to cause free radical reactions by ultraviolet radiation.
然而,聚合抑制劑、光引發劑等在高溫條件下會在樹脂外部擴散,因而可能導致在半導體封裝製程期間及之後絕緣層與傳導層之間的界面分離。此外,在該樹脂內之酯鍵在高濕度下導致水解反應並降低該樹脂的交聯密度,此導致該樹脂的吸濕率提高。當如上述吸濕率高時,聚合抑制劑、光引發劑等係在高溫條件下在該樹脂外部轉化並導致在半導體封裝製程期間及之後絕緣層與傳導層之間的界面分離,且存在HAST性質惡化的限制。 However, polymerization inhibitors, photoinitiators, etc. diffuse outside the resin under high temperature conditions, which may cause interface separation between the insulating layer and the conductive layer during and after the semiconductor packaging process. In addition, the ester bonds in the resin cause a hydrolysis reaction under high humidity and reduce the crosslinking density of the resin, which results in an increase in the moisture absorption rate of the resin. When the moisture absorption rate is high as described above, polymerization inhibitors, photoinitiators, etc., are converted outside the resin under high temperature conditions and cause interface separation between the insulating layer and the conductive layer during and after the semiconductor packaging process, and HAST is present. Restrictions on deterioration of nature.
因此,需要發展能用低成本獲致均勻且精細圖案,同時防止絕緣層與傳導層之間界面分離的絕緣層之製造方法。 Therefore, there is a need to develop a manufacturing method of an insulating layer capable of obtaining a uniform and fine pattern at a low cost while preventing the interface between the insulating layer and the conductive layer from being separated.
1‧‧‧聚合物樹脂層 1‧‧‧ polymer resin layer
2‧‧‧銅線 2‧‧‧ copper wire
3‧‧‧銅箔積層物 3‧‧‧ copper foil laminate
4‧‧‧超薄銅箔 4‧‧‧ ultra-thin copper foil
5‧‧‧載體銅箔 5‧‧‧ carrier copper foil
6‧‧‧光敏性乾燥膜阻劑(DFR) 6‧‧‧Photosensitive Dry Film Resistant (DFR)
7‧‧‧通路孔 7‧‧‧via hole
8‧‧‧晶種層 8‧‧‧ seed layer
9‧‧‧光敏性樹脂圖案 9‧‧‧ photosensitive resin pattern
10‧‧‧金屬基底 10‧‧‧ metal substrate
<1>至<8>‧‧‧製程進行順序 <1> to <8> ‧‧‧ Process sequence
圖1示意圖示實施例1之絕緣層的製造方法。 FIG. 1 is a schematic view showing a method for manufacturing an insulating layer of Example 1. FIG.
圖2示意圖示實施例2之多層印刷電路板的製造方法。 FIG. 2 schematically illustrates a method for manufacturing a multilayer printed circuit board according to the second embodiment.
本發明一目的係提供能實現均勻且精細圖案,同時改善成本及生產力方面的效率以及確保優異機械性質之絕緣層的製造方法。 An object of the present invention is to provide a manufacturing method of an insulating layer capable of achieving uniform and fine patterns while improving efficiency in terms of cost and productivity, and ensuring excellent mechanical properties.
本發明另一目的係提供使用自該絕緣層的製造方法所獲得之絕緣層的多層印刷電路板之製造方法。 Another object of the present invention is to provide a method for manufacturing a multilayer printed circuit board using an insulating layer obtained from the method for manufacturing the insulating layer.
本發明之實施態樣提供絕緣層的製造方法,該方法包括下列步驟:將金屬層之黏附有載體膜之一表面的相反表面黏附至含有鹼溶性樹脂及熱可固化黏合劑之聚合物樹脂層;在該載體膜上形成經圖案化之光敏性樹脂層;移除被該經圖案化之光敏性樹脂層暴露的該載體膜及該金屬層以形成經圖案化之金屬層;自該經圖案化之金屬層分離及移除該載體膜;對被該經圖案化之金屬層暴露之該聚合物樹脂層進行鹼性顯影;以及在該鹼性顯影之後熱固化該聚合物樹脂層。 An embodiment of the present invention provides a method for manufacturing an insulating layer, the method including the following steps: adhering an opposite surface of a metal layer to a surface of a carrier film adhered to a polymer resin layer containing an alkali-soluble resin and a heat-curable adhesive Forming a patterned photosensitive resin layer on the carrier film; removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer; from the patterned The metalized layer separates and removes the carrier film; performs alkaline development on the polymer resin layer exposed by the patterned metal layer; and thermally cures the polymer resin layer after the alkaline development.
本發明另一實施態樣提供多層印刷電路板的 製造方法,該方法包括在自該絕緣層的製造方法所獲得之絕緣層上形成具有圖案之金屬基底的步驟。 Another aspect of the present invention provides a method for manufacturing a multilayer printed circuit board, the method including the step of forming a patterned metal substrate on an insulating layer obtained from the method for manufacturing the insulating layer.
根據本發明具體實施態樣之絕緣層的製造方法以及多層印刷電路板的製造方法將於下文中更詳細說明。 A method for manufacturing an insulating layer and a method for manufacturing a multilayer printed circuit board according to specific embodiments of the present invention will be described in more detail below.
本說明書中,鹵素基包括氟、氯、溴、及碘。 In the present specification, the halogen group includes fluorine, chlorine, bromine, and iodine.
本說明書中,烷基可為直鏈或支鏈,且碳原子數無特別限制,但較佳為1至40個。根據一實施態樣,烷基具有1至20個碳原子。根據另一實施態樣,烷基具有1至10個碳原子。根據另一實施態樣,烷基具有1至6個碳原子。烷基之具體實例包括甲基、乙基、丙基、正丙基、異丙基、丁基、正丁基、異丁基、三級丁基、二級丁基、1-甲基-丁基、1-乙基-丁基、戊基、正戊基、異戊基、新戊基、三級戊基、己基、正己基、1-甲基戊基、2-甲基戊基、4-甲基-2-戊基、3,3-二甲基丁基、2-乙基丁基、庚基、正庚基、1-甲基己基、環戊基甲基、環己基甲基、辛基、正辛基、三級辛基、1-甲基庚基、2-乙基己基、2-丙基戊基、正壬基、2,2-二甲基庚基、1-乙基-丙基、1,1-二甲基丙基、異己基、2-甲基戊基、4-甲基己基、5-甲基己基等,但不侷限於此。 In the present specification, the alkyl group may be a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tertiary butyl, secondary butyl, 1-methyl-butyl Base, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4 -Methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, Octyl, n-octyl, tertiary octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl -Propyl, 1,1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.
在本說明書中,芳基無特別限制,但較佳具有6至60個碳原子,且可為單環芳基或多環芳基。根據一實施態樣,芳基具有6至30個碳原子。根據另一實施態 樣,芳基具有6至20個碳原子。該芳基可為苯基、聯苯基、聯三苯基等作為該單環芳基,但不侷限於此。該多環芳基之特殊實例包括萘基、蒽基、菲基、芘基、苝基、廾快基(crycenyl)、茀基等,但不侷限於此。 In this specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to another embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be phenyl, biphenyl, bitriphenyl, or the like as the monocyclic aryl group, but is not limited thereto. Specific examples of the polycyclic aryl group include, but are not limited to, naphthyl, anthracenyl, phenanthryl, fluorenyl, fluorenyl, crycenyl, fluorenyl, and the like.
根據本發明之實施態樣,提供絕緣層的製造方法,該方法包括下列步驟:將金屬層之黏附有載體膜之一表面的相反表面黏附至含有鹼溶性樹脂及熱可固化黏合劑之聚合物樹脂層;在該載體膜上形成經圖案化之光敏性樹脂層;移除被該經圖案化之光敏性樹脂層暴露的該載體膜及該金屬層以形成經圖案化之金屬層;自該經圖案化之金屬層分離及移除該載體膜;對被該經圖案化之金屬層暴露之該聚合物樹脂層進行鹼性顯影;以及在該鹼性顯影之後熱固化該聚合物樹脂層。 According to an embodiment of the present invention, a method for manufacturing an insulating layer is provided. The method includes the following steps: adhering the opposite surface of a metal layer to a surface of a carrier film adhered to a polymer containing an alkali-soluble resin and a thermosetting adhesive A resin layer; forming a patterned photosensitive resin layer on the carrier film; removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer; from the The patterned metal layer separates and removes the carrier film; performs alkaline development on the polymer resin layer exposed by the patterned metal layer; and thermally cures the polymer resin layer after the alkaline development.
根據一實施態樣之絕緣層的製造方法,本發明人發現當被引至鹼溶性聚合物樹脂層上之具有圖案的金屬層用作對該聚合物樹脂層進行鹼性顯影的遮罩時,該聚合物樹脂層被該金屬層圖案暴露之經由鹼性顯影移除,且聚合物樹脂層未被該金屬層圖案暴露之部分受到保護免於鹼性顯影劑影響,因而可經由化學方法在該聚合物樹脂層中形成精細圖案。 According to a method for manufacturing an insulating layer according to an embodiment, the inventors have found that when a patterned metal layer introduced onto an alkali-soluble polymer resin layer is used as a mask for alkaline development of the polymer resin layer, the The polymer resin layer is removed by alkaline development after the metal layer pattern is exposed, and the portion of the polymer resin layer that is not exposed by the metal layer pattern is protected from the influence of the alkaline developer, so that the polymer can be polymerized through the chemical method. A fine pattern is formed in the resin layer.
亦已經由實驗發現,相較於使用經雷射加工製造的絕緣層,以上述方法在其上形成精細圖案的絕緣層可以低成本快速形成,以及所製造之最終絕緣層可實現優異的物理性質。本發明已基於此發現研發。 It has also been found through experiments that, compared to using an insulating layer manufactured by laser processing, an insulating layer on which a fine pattern is formed by the above method can be quickly formed at low cost, and the final insulating layer manufactured can achieve excellent physical properties. . The present invention has been developed based on this finding.
此外,由於最終製造之絕緣層含有是為非光敏性絕緣材料之熱可固化樹脂的固化產物,光引發劑或聚合抑制劑之含量比起使用傳統光敏性絕緣材料製造絕緣層的情況大幅減少。此使得可製造具有優異的機械性質之絕緣層,該性質係諸如減少會因光引發劑或聚合抑制劑所產生之絕緣層與傳導層之間的界面分離的性質。 In addition, since the final insulation layer contains a cured product of a heat-curable resin that is a non-photosensitive insulation material, the content of the photoinitiator or polymerization inhibitor is greatly reduced compared to the case where the insulation layer is manufactured using a conventional photosensitive insulation material. This makes it possible to manufacture an insulating layer having excellent mechanical properties, such as a property of reducing an interface separation between the insulating layer and the conductive layer which may be caused by a photoinitiator or a polymerization inhibitor.
特別是,在實施態樣之絕緣層的製造方法中,當引入金屬層作為聚合物樹脂層上之遮罩時,因該製程係在載體膜黏附至該金屬層的情況下進行,不只該金屬層可被該載體膜輕易地積層,該載體膜亦可隨著該金屬層被同一蝕刻劑同時移除。因此,即使在黏附該載體膜的狀態下,該金屬層亦可輕易地蝕刻。 In particular, in the manufacturing method of the insulating layer of the embodiment, when the metal layer is introduced as a mask on the polymer resin layer, the process is performed while the carrier film is adhered to the metal layer, not only the metal The layer can be easily laminated by the carrier film, and the carrier film can be simultaneously removed as the metal layer is removed by the same etchant. Therefore, the metal layer can be easily etched even in a state where the carrier film is adhered.
此外,為了在該載體膜及該金屬層上形成圖案,引至該載體膜上之光敏性樹脂層可經由該載體膜與該金屬層之間的物理性剝離而輕易地移除。如此,即使不使用獨立的剝離液體處理以移除該光敏性樹脂層,在製程效率方面亦是有利的。 In addition, in order to form a pattern on the carrier film and the metal layer, the photosensitive resin layer introduced onto the carrier film can be easily removed through physical peeling between the carrier film and the metal layer. As such, it is advantageous in terms of process efficiency even if the photosensitive resin layer is removed without using a separate peeling liquid treatment.
此外,由於一實施態樣之絕緣層的製造方法中所使用之鹼溶性樹脂在分子結構中含有經胺基取代之特徵環狀醯亞胺官能基連同酸官能基,鹼溶性可由酸官能基實現,且當與熱可固化黏合劑反應時,固化密度可因經胺基取代之環狀醯亞胺基而提高,從而改善耐熱性可靠度及機械性質以及改善在另外的界面之黏著性。 In addition, since the alkali-soluble resin used in the manufacturing method of the insulating layer according to one embodiment contains a characteristic cyclic fluorene imine functional group together with an acid functional group in the molecular structure, the alkali solubility can be achieved by the acid functional group. And, when reacting with a heat-curable adhesive, the curing density can be increased by the cyclic fluorene imide group substituted with an amine group, thereby improving the reliability of heat resistance and mechanical properties, and improving the adhesion at another interface.
因而,含有鹼溶性樹脂之聚合物樹脂層可具 有提高之與積層在上側的金屬層界面黏著性,以及尤其是,可具有比金屬層與積層在該金屬層上方部分的載體膜之間的界面黏著性更高之黏著力。因此,如下述,該載體膜與該金屬層之間可能物理性剝離。 Therefore, the polymer resin layer containing the alkali-soluble resin may have improved interface adhesion with the metal layer on the upper side of the laminate, and in particular, may have an interface between the metal layer and the carrier film laminated on the upper portion of the metal layer. Higher adhesion. Therefore, as described below, physical separation may occur between the carrier film and the metal layer.
具體而言,該絕緣層的製造方法可包括下列步驟:將金屬層之黏附有載體膜之一表面的相反表面黏附至含有鹼溶性樹脂及熱可固化黏合劑之聚合物樹脂層;在該載體膜上形成經圖案化之光敏性樹脂層;移除被該經圖案化之光敏性樹脂層暴露的該載體膜及該金屬層以形成經圖案化之金屬層;自該經圖案化之金屬層分離及移除該載體膜;對被該經圖案化之金屬層暴露之該聚合物樹脂層進行鹼性顯影;以及在該鹼性顯影之後熱固化該聚合物樹脂層。 Specifically, the method for manufacturing the insulating layer may include the following steps: adhering the opposite surface of the metal layer to which one surface of the carrier film is adhered to a polymer resin layer containing an alkali-soluble resin and a heat-curable adhesive; on the carrier; Forming a patterned photosensitive resin layer on the film; removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer; and from the patterned metal layer Separating and removing the carrier film; subjecting the polymer resin layer exposed by the patterned metal layer to alkaline development; and thermally curing the polymer resin layer after the alkaline development.
各步驟之細節將於下文說明。 The details of each step will be explained below.
將金屬層之黏附有載體膜之一表面的相反表面黏附至含有鹼溶性樹脂及熱可固化黏合劑之聚合物樹脂層的步驟 Step of adhering the opposite surface of the metal layer to which one surface of the carrier film is adhered to a polymer resin layer containing an alkali-soluble resin and a heat-curable adhesive
在該將金屬層之黏附有載體膜之一表面的相反表面黏附至含有鹼溶性樹脂及熱可固化黏合劑之聚合物樹脂層的步驟中,聚合物樹脂層意指經由將含有鹼溶性樹脂及熱可固化黏合劑之聚合物樹脂組成物乾燥所形成的膜。 In the step of adhering the opposite surface of the metal layer to which one surface of the carrier film is adhered to a polymer resin layer containing an alkali-soluble resin and a heat-curable adhesive, the polymer resin layer means that the alkali-soluble resin and A film formed by drying a polymer resin composition of a heat-curable adhesive.
該聚合物樹脂層可單獨存在或可呈在含有半導體材料之基底(諸如電路板、片、多層印刷電路板等)上形成的狀態存在。在基底上形成聚合物樹脂層的方法之實 例無特別限制,但可使用例如將聚合物樹脂組成物直接塗布在該基底上之方法,或將聚合物樹脂組成物塗布在載體膜上或黏附有載體膜之金屬層上,然後與該基底積層之方法等。 The polymer resin layer may exist alone or in a state formed on a substrate (such as a circuit board, a sheet, a multilayer printed circuit board, and the like) containing a semiconductor material. Examples of the method of forming a polymer resin layer on a substrate are not particularly limited, but, for example, a method of directly coating a polymer resin composition on the substrate, or coating the polymer resin composition on a carrier film or adhering A method of laminating a carrier film on a metal layer and then laminating the substrate.
此外,將金屬層之黏附有載體膜之一表面的相反表面黏附至含有鹼溶性樹脂及熱可固化黏合劑之聚合物樹脂層的方法之實例可包括將含有鹼溶性樹脂及熱可固化黏合劑之聚合物樹脂組成物塗布至金屬層之黏附有載體膜之一表面的相反表面並乾燥該塗層。 In addition, an example of a method of adhering the opposite surface of the metal layer to which one surface of the carrier film is adhered to the polymer resin layer containing an alkali-soluble resin and a heat-curable adhesive may include an alkali-soluble resin and a heat-curable adhesive The polymer resin composition is applied to the opposite surface of the metal layer to which one surface of the carrier film is adhered and the coating is dried.
該聚合物樹脂層可包括鹼溶性樹脂及熱可固化黏合劑。 The polymer resin layer may include an alkali-soluble resin and a heat-curable adhesive.
該聚合物樹脂層可包括以100重量份之該鹼溶性樹脂計為1至150重量份、10至100重量份、或20至50重量份之量的熱可固化黏合劑。當該熱可固化黏合劑的含量太高時,該聚合物樹脂層之顯影性惡化且強度會降低。反之,當該熱可固化黏合劑的含量過低時,不只該聚合物樹脂層過度顯影,塗層均勻度亦會降低。 The polymer resin layer may include a heat-curable adhesive in an amount of 1 to 150 parts by weight, 10 to 100 parts by weight, or 20 to 50 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the content of the heat-curable adhesive is too high, the developability of the polymer resin layer is deteriorated and the strength is reduced. Conversely, when the content of the heat-curable adhesive is too low, not only the polymer resin layer is excessively developed, but also the uniformity of the coating layer may be reduced.
該熱可固化黏合劑可包括至少一個選自由下列所組成之群組的官能基:熱可固化官能基、氧環丁烷基、環狀醚基、環狀硫醚基、氰基、順丁烯二醯亞胺基、及苯并基、及環氧基。即,該熱可固化黏合劑必定包括環氧基,以及除了環氧基之外還可含有氧環丁烷基、環狀醚基、環狀硫醚基、氰基、順丁烯二醯亞胺基、苯并 基、或其二或更多者的混合物。此等熱可固化黏合劑可 藉由熱固化而與鹼溶性樹脂等形成交聯鍵,從而確保絕緣層的耐熱性或機械性質。 The heat-curable adhesive may include at least one functional group selected from the group consisting of: a heat-curable functional group, an oxycyclobutane group, a cyclic ether group, a cyclic thioether group, a cyano group, and cis-butyl Arylene diimide, and benzo And epoxy. That is, the heat-curable adhesive must include an epoxy group, and in addition to the epoxy group, it may also contain an oxycyclobutane group, a cyclic ether group, a cyclic thioether group, a cyano group, and maleic acid. Amine, benzo Base, or a mixture of two or more thereof. These heat-curable adhesives can form a cross-linking bond with an alkali-soluble resin or the like by heat curing, thereby ensuring heat resistance or mechanical properties of the insulating layer.
更具體而言,可使用分子中含有上述官能基中之二或更多者的多官能基樹脂化合物作為該熱可固化黏合劑。 More specifically, a polyfunctional resin compound containing two or more of the above-mentioned functional groups in a molecule may be used as the heat-curable adhesive.
該多官能基樹脂化合物可包括分子中含有二或更多個環狀醚基及/或環狀硫醚基(下文稱為環狀(硫)醚基)之樹脂。 The polyfunctional resin compound may include a resin containing two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in the molecule.
該分子中含有二或更多個環狀(硫)醚基之熱可固化黏合劑可為分子中具有選自3、4、或5員環狀醚基或環狀硫醚基的任一種或兩種中之二或更多者的化合物。 The thermosetting adhesive containing two or more cyclic (thio) ether groups in the molecule may be any one having 3, 4, or 5 member cyclic ether groups or cyclic thioether groups in the molecule or A compound of two or more of the two.
分子中具有二或更多個環狀硫醚基之化合物的實例包括雙酚A型環硫化物樹脂(episulfide resin)YL 7000(由Japan Epoxy Resins Co.,Ltd.製造)等。 Examples of the compound having two or more cyclic sulfide groups in the molecule include bisphenol A-type episulfide resin YL 7000 (manufactured by Japan Epoxy Resins Co., Ltd.) and the like.
此外,該多官能基樹脂化合物可包括分子中含有至少二或更多個環氧基之多官能基環氧化合物(epoxy compound)、分子中含有至少二或更多個氧環丁烷基之多官能基氧環丁烷化合物、或含有至少兩個硫醚基之環硫化物樹脂、分子中含有至少二或更多個氰基之多官能基氰酸酯化合物、或分子中含有至少二或更多個苯并基之多官能基苯并化合物等。 In addition, the polyfunctional resin compound may include a polyfunctional epoxy compound containing at least two or more epoxy groups in a molecule, and a polyfunctional epoxy compound containing at least two or more oxycyclobutane groups in a molecule. Functional oxycyclobutane compounds, or episulfide resins containing at least two thioether groups, polyfunctional cyanate compounds containing at least two or more cyano groups in the molecule, or at least two or more in the molecule Multiple benzo Polyfunctional benzo Compounds etc.
該多官能基環氧化合物之具體實例可包括雙酚A型環氧樹脂、氫化雙酚A型環氧樹脂、溴化雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、酚醛清漆 型環氧樹脂、酚系酚醛清漆環氧樹脂(phenol novolac epoxy resin)、甲酚酚醛清漆環氧樹脂、N-環氧丙基環氧樹脂、雙酚A之酚醛清漆環氧樹脂、聯茬酚環氧樹脂、聯苯酚環氧樹脂、螯合物環氧樹脂、乙二醛環氧樹脂、含胺基之環氧樹脂、經橡膠改質之環氧樹脂、二環戊二烯酚系環氧樹脂、酞酸二環氧丙酯樹脂、雜環環氧樹脂、四環氧丙基茬酚基乙烷樹脂(tetraglycidyl xylenoyl ethane resin)、經聚矽氧改質之環氧樹脂、經ε-己內酯改質之環氧樹脂等。此外,為了賦予阻燃性,可使用具有其中導入諸如磷等原子之結構的化合物。此等環氧樹脂可藉由熱固化而改善諸如經固化塗膜之黏附性、軟焊耐熱性、無電鍍覆抗性等。 Specific examples of the polyfunctional epoxy compound may include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol S Type epoxy resin, novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, N-epoxypropyl epoxy resin, bisphenol A novolac Epoxy resin, biphenol epoxy resin, biphenol epoxy resin, chelate epoxy resin, glyoxal epoxy resin, amine-containing epoxy resin, rubber modified epoxy resin, bicyclic Pentadiene phenolic epoxy resin, phthalic acid diglycidyl resin, heterocyclic epoxy resin, tetraglycidyl xylenoyl ethane resin, polysiloxane modified ring Epoxy resin, epoxy resin modified by ε-caprolactone, etc. Further, in order to impart flame retardancy, a compound having a structure in which an atom such as phosphorus is introduced may be used. These epoxy resins can be improved by heat curing such as adhesion of cured coating film, soldering heat resistance, electroless plating resistance, and the like.
該多官能基氧環丁烷化合物之實例可包括多官能基氧環丁烷,諸如雙[(3-甲基-3-氧環丁烷基甲氧基)甲基]醚、雙[(3-乙基-3-氧環丁烷基甲氧基)甲基]醚、1,4-雙[(3-甲基-3-氧環丁烷基甲氧基)甲基]苯、1,4-雙[(3-乙基-3-氧環丁烷基甲氧基)甲基]苯、(3-甲基-3-氧環丁烷基)丙烯酸甲酯、(3-乙基-3-氧環丁烷基)丙烯酸甲酯、(3-甲基-3-氧環丁烷基)甲基丙烯酸甲酯、(3-乙基-3-氧環丁烷基)甲基丙烯酸甲酯、及其寡聚物或共聚物,以及除此之外,可包括氧環丁烷醇與含羥基之樹脂(諸如酚醛清漆樹脂)的醚化產物、聚(對羥基苯乙烯)、Cardo型雙酚(cardo-type bisphenol)、杯芳烴(calixarene)、杯間苯二酚芳烴(calixresorcinarene)、倍半矽氧烷等。此外,可包括具有 氧環丁烷環之不飽和單體與(甲基)丙烯酸烷酯的共聚物。 Examples of the polyfunctional oxycyclobutane compound may include polyfunctional oxycyclobutane, such as bis [(3-methyl-3-oxocyclobutylmethoxy) methyl] ether, bis [(3 -Ethyl-3-oxocyclobutylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3-oxocyclobutylmethoxy) methyl] benzene, 1, 4-bis [(3-ethyl-3-oxocyclobutylmethoxy) methyl] benzene, (3-methyl-3-oxocyclobutyl) methyl acrylate, (3-ethyl- (3-Oxycyclobutane) methyl acrylate, (3-methyl-3-oxocyclobutyl) methyl methacrylate, (3-ethyl-3-oxocyclobutyl) methacrylate Esters, and their oligomers or copolymers, and in addition, may include etherified products of oxycyclobutanol and hydroxyl-containing resins such as novolac resins, poly (p-hydroxystyrene), Cardo type Cardo-type bisphenol, calixarene, calixresorcinarene, silsesquioxane, etc. Further, a copolymer of an unsaturated monomer having an oxocyclobutane ring and an alkyl (meth) acrylate may be included.
該多官能基氰酸酯化合物之實例可包括雙酚A型氰酸酯樹脂、雙酚E型氰酸酯樹脂、雙酚F型氰酸酯樹脂、雙酚S型氰酸酯樹脂、雙酚M型氰酸酯樹脂、酚醛清漆型氰酸酯樹脂、酚系酚醛清漆型氰酸酯樹脂、甲酚酚醛清漆型氰酸酯樹脂、雙酚A之酚醛清漆型氰酸酯樹脂、聯苯酚型氰酸酯樹脂、其寡聚物或共聚物等。 Examples of the polyfunctional cyanate compound may include bisphenol A type cyanate resin, bisphenol E type cyanate resin, bisphenol F type cyanate resin, bisphenol S type cyanate resin, bisphenol M type cyanate resin, novolac type cyanate resin, phenol novolac type cyanate resin, cresol novolac type cyanate resin, bisphenol A novolac type cyanate resin, biphenol type Cyanate resin, its oligomer or copolymer, and the like.
多官能基順丁烯二醯亞胺化合物之實例可包括4,4'-二苯甲烷雙順丁烯二醯亞胺、甲苯雙順丁烯二醯亞胺、間甲苯雙順丁烯二醯亞胺、雙酚A二苯基醚雙順丁烯二醯亞胺、3,3'-二甲基-5,5'-二乙基-4,4'-二苯甲烷雙順丁烯二醯亞胺、4-甲基-1,3-伸苯基雙順丁烯二醯亞胺、1,6'-雙順丁烯二醯亞胺-(2,2,4-三甲基)己烷)等。 Examples of the polyfunctional cis-butene difluorene imine compound may include 4,4'-diphenylmethane bis-cis-butene difluorene imine, toluene bis-cis-butene difluorene imine, m-toluene bis-cis butylene difluorene Imine, bisphenol A diphenyl ether biscis-butene diimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane biscis-butene di Fluorenimine, 4-methyl-1,3-phenylenebiscis-butenedifluoreneimine, 1,6'-biscisbutenedifluorenimine- (2,2,4-trimethyl) Hexane) and the like.
該多官能基苯并化合物之實例可包括雙酚A型苯并樹脂、雙酚F型苯并樹脂、酚酞型苯并樹脂、硫二酚型苯并樹脂、二環戊二烯型苯并 樹脂、3,3-(亞甲基-1,4-聯伸苯基)雙(3,4-二氫-2H-1,3-苯并)樹脂等。 The multifunctional benzo Examples of the compound may include bisphenol A type benzo Resin, bisphenol F type benzo Resin, phenolphthalein type benzo Resin, thiodiol type benzo Resin, dicyclopentadiene type benzo Resin, 3,3- (methylene-1,4-biphenylene) bis (3,4-dihydro-2H-1,3-benzo ) Resin and so on.
該多官能基樹脂化合物之更具體實例可包括YDCN-500-80P(Kukdo Chemical Co.Ltd.)、酚系酚醛清漆型氰化物酯樹脂PT-30S(Lonza Ltd.)、甲苯型順丁烯二醯亞胺樹脂BMI-2300(Daiwa Kasei Co.,Ltd.)、Pd型苯并 樹脂(Shikoku Chemicals)等。 More specific examples of the multifunctional resin compound may include YDCN-500-80P (Kukdo Chemical Co. Ltd.), a phenol-based novolac cyanide ester resin PT-30S (Lonza Ltd.), and toluene-type maleic acid Perylene imine resin BMI-2300 (Daiwa Kasei Co., Ltd.), Pd type benzo Resin (Shikoku Chemicals) and the like.
同時,該鹼溶性樹脂可包括至少一或多個、 或二或更多個選自酸官能基及經胺基取代之環狀醯亞胺官能基者。酸官能基之實例可包括但不侷限於羧基或酚基。該鹼溶性樹脂包括至少一或多個、或二或更多個酸官能基,因此該聚合物樹脂層展現較高鹼性顯影性質且該聚合物樹脂層之顯影速率可控制。 Meanwhile, the alkali-soluble resin may include at least one or more, or two or more selected from acid functional groups and cyclic amidine imine functional groups substituted with amine groups. Examples of the acid functional group may include, but are not limited to, a carboxyl group or a phenol group. The alkali-soluble resin includes at least one or more, or two or more acid-functional groups, so the polymer resin layer exhibits higher alkaline developing properties and the development rate of the polymer resin layer can be controlled.
經胺基取代之環狀醯亞胺官能基在官能基結構中包括胺基及環狀醯亞胺基,且可包括其至少一或多者、或二或更多者。由於鹼溶性樹脂含有至少一或多個、或二或更多個經胺基取代之環狀醯亞胺官能基,該鹼溶性樹脂具有存在大量包含在胺基中的活性氫之結構。因此,當在熱固化期間與熱可固化黏合劑之反應性提高時,固化密度可提高,從而改善耐熱性可靠度及機械性質。 The amine-substituted cyclic amidine imide functional group includes an amine group and a cyclic amidine imine group in the functional group structure, and may include at least one or more, or two or more thereof. Since the alkali-soluble resin contains at least one or more, or two or more cyclic fluorene imine functional groups substituted with an amine group, the alkali-soluble resin has a structure in which a large amount of active hydrogen contained in the amine group is present. Therefore, when the reactivity with the heat-curable adhesive is improved during heat curing, the curing density can be increased, thereby improving the reliability of heat resistance and mechanical properties.
此外,由於大量環狀醯亞胺官能基存在該鹼溶性樹脂中,極性因包含在該環狀醯亞胺官能基中之羰基及三級胺基而提高,因此該鹼溶性樹脂之界面黏著性可提高。含有鹼溶性樹脂之聚合物樹脂層因而可具有提高之與積層在上側的金屬層界面黏著性,以及尤其是,可具有比介於金屬層與積層在該金屬層上方部分的載體膜之間的界面黏著性更高之黏著力。因此,如下述,該載體膜與該金屬層之間可能物理性剝離。 In addition, since a large number of cyclic fluorene imine functional groups are present in the alkali-soluble resin, the polarity is increased by the carbonyl group and tertiary amine group contained in the cyclic fluorene imine functional group, so the interface adhesion of the alkali-soluble resin Can be improved. The polymer resin layer containing an alkali-soluble resin may therefore have improved interface adhesion with the metal layer on the upper side of the laminate, and in particular, may have a ratio between the metal layer and the carrier film of the laminate above the metal layer. Interface adhesion is higher. Therefore, as described below, physical separation may occur between the carrier film and the metal layer.
更具體而言,經胺基取代之環狀醯亞胺官能基可包括以下示化學式1表示之官能基。 More specifically, the cyclic amidine imide functional group substituted with an amine group may include a functional group represented by Chemical Formula 1 shown below.
在化學式1中,R1為具有1至10個碳原子、1至5個碳原子、或1至3個碳原子之伸烷基或烯基,且「*」意指鍵結點。伸烷基為衍生自烷烴之二價官能基,例如直鏈、支鏈、或環狀基團,且包括亞甲基、伸乙基、伸丙基、伸異丁基、伸二級丁基、伸三級丁基、伸戊基、伸己基等。該伸烷基中所含的一或多個氫原子可經另一取代基取代,該另一取代基之實例包括具有1至10個碳原子之烷基、具有2至10個碳原子之烯基、具有2至10個碳原子之炔基、具有2至12個碳原子之芳基、具有2至12個碳原子之雜芳基、具有6至12個碳原子之芳基烷基、鹵素原子、氰基、胺基、甲脒基、硝基、醯胺基、羰基、羥基、磺醯基、胺基甲酸酯基、具有具有1至10個碳原子之烷氧基等。 In Chemical Formula 1, R 1 is an alkylene or alkenyl group having 1 to 10 carbon atoms, 1 to 5 carbon atoms, or 1 to 3 carbon atoms, and "*" means a bonding point. Dialkylene is a divalent functional group derived from an alkane, such as a linear, branched, or cyclic group, and includes methylene, ethylidene, propylidene, isobutylene, dibutylene, Tertiary butyl, pentyl, and hexyl. One or more hydrogen atoms contained in the alkylene group may be substituted with another substituent. Examples of the other substituent include an alkyl group having 1 to 10 carbon atoms, and an olefin having 2 to 10 carbon atoms. Radical, alkynyl radical having 2 to 10 carbon atoms, aryl radical having 2 to 12 carbon atoms, heteroaryl radical having 2 to 12 carbon atoms, arylalkyl radical having 6 to 12 carbon atoms, halogen Atoms, cyano, amine, formamyl, nitro, sulfonylamino, carbonyl, hydroxyl, sulfonyl, carbamate, alkoxy groups having 1 to 10 carbon atoms, and the like.
本文所使用之用語「經取代」意指鍵結另一官能基代替化合物中的氫原子,且待取代之位置無限制,只要其係氫原子被取代的位置(即,取代基可取代的位置)即可。當二或更多個取代基取代時,該二或更多個取代基可彼此相同或不同。 The term "substituted" as used herein means that another functional group is bonded to replace a hydrogen atom in a compound, and the position to be substituted is not limited as long as it is a position where a hydrogen atom is substituted (i.e., a position where a substituent can be substituted ). When two or more substituents are substituted, the two or more substituents may be the same as or different from each other.
烯基意指在其中間或末端含有至少一個碳-碳雙鍵的前文提及之伸烷基,且其實例包括乙烯、丙烯、丁烯、己烯、乙炔等。烯基中之一或多個氫原子可以如同伸烷基中之相同方式經取代基取代。 Alkenyl means the aforementioned alkylene group containing at least one carbon-carbon double bond at its middle or terminal, and examples thereof include ethylene, propylene, butene, hexene, acetylene, and the like. One or more hydrogen atoms in the alkenyl group may be substituted with a substituent in the same manner as in the alkylene group.
較佳的,經胺基取代之環狀醯亞胺官能基可為以下示化學式2表示之官能基。 Preferably, the cyclic amidine imide functional group substituted with an amine group may be a functional group represented by Chemical Formula 2 shown below.
在化學式2中,「*」意指鍵結位點。 In Chemical Formula 2, "*" means a bonding site.
如上述,該鹼溶性樹脂包括經胺基取代之環狀醯亞胺官能基連同酸官能基。具體而言,酸官能基可鍵結至該經胺基取代之環狀醯亞胺官能基的至少一末端。此時,該經胺基取代之環狀醯亞胺官能基和該酸官能基可經由經取代或未經取代之伸烷基或經取代或未經取代之伸芳基鍵結。例如,酸官能基可經由經取代或未經取代之伸烷基或經取代或未經取代之伸芳基而鍵結至該經胺基取代之醯亞胺官能基中所含的胺基之末端。酸官能基可經由經取代或未經取代之伸烷基或經取代或未經取代之伸芳基而鍵結至該經胺基取代之醯亞胺官能基中所含的環狀醯亞胺官能基之末端。 As described above, the alkali-soluble resin includes an amine-substituted cyclic amidine imine functional group together with an acid functional group. Specifically, an acid functional group may be bonded to at least one terminal of the amine substituted cyclic amidine imine functional group. At this time, the cyclic fluoreneimine functional group substituted with the amine group and the acid functional group may be bonded through a substituted or unsubstituted alkylene group or a substituted or unsubstituted aryl group. For example, an acid functional group may be bonded to an amino group contained in the amine-substituted amidine functional group via a substituted or unsubstituted alkylene group or a substituted or unsubstituted alkylene group. End. The acid functional group may be bonded to the cyclic amidine imide contained in the amido-substituted amidine functional group via a substituted or unsubstituted alkylene group or a substituted or unsubstituted alkylene group. The end of the functional group.
更具體而言,該經胺基取代之環狀醯亞胺官能基中所含的胺基之末端意指化學式1中之胺基中所含的氮原子,以及該經胺基取代之環狀醯亞胺官能基中所含的醯亞胺官能基之末端意指化學式1中之環狀醯亞胺官能基中所含的氮原子。 More specifically, the terminal of the amine group contained in the amine-substituted cyclic amidine imide functional group means a nitrogen atom contained in the amine group in Chemical Formula 1, and the amine-substituted cyclic group The terminal of the fluorene imine functional group contained in the fluorene imine functional group means a nitrogen atom contained in the cyclic fluorene imine functional group in Chemical Formula 1.
伸烷基為衍生自烷烴之二價官能基,例如直鏈、支鏈、或環狀基團,且包括亞甲基、伸乙基、伸丙基、伸異丁基、伸二級丁基、伸三級丁基、伸戊基、伸己基等。該伸烷基中所含的一或多個氫原子可經另一取代基取代,該另一取代基之實例包括具有1至10個碳原子之烷基、具有2至10個碳原子之烯基、具有2至10個碳原子之炔基、具有2至12個碳原子之芳基、具有2至12個碳原子之雜芳基、具有6至12個碳原子之芳基烷基、鹵素原子、氰基、胺基、甲脒基、硝基、醯胺基、羰基、羥基、磺醯基、胺基甲酸酯基、具有具有1至10個碳原子之烷氧基等。 Dialkylene is a divalent functional group derived from an alkane, such as a linear, branched, or cyclic group, and includes methylene, ethylidene, propylidene, isobutylene, dibutylene, Tertiary butyl, pentyl, and hexyl. One or more hydrogen atoms contained in the alkylene group may be substituted with another substituent. Examples of the other substituent include an alkyl group having 1 to 10 carbon atoms, and an olefin having 2 to 10 carbon atoms. Radical, alkynyl radical having 2 to 10 carbon atoms, aryl radical having 2 to 12 carbon atoms, heteroaryl radical having 2 to 12 carbon atoms, arylalkyl radical having 6 to 12 carbon atoms, halogen Atoms, cyano, amine, formamyl, nitro, sulfonylamino, carbonyl, hydroxyl, sulfonyl, carbamate, alkoxy groups having 1 to 10 carbon atoms, and the like.
伸芳基意指衍生自芳烴之二價官能基,例如環狀基團,且可包括苯基、萘基等。該伸芳基中所含之一或多個氫原子可經另一取代基取代。該取代基之實例包括具有1至10個碳原子之烷基、具有2至10個碳原子之烯基、具有2至10個碳原子之炔基、具有2至12個碳原子之芳基、具有2至12個碳原子之雜芳基、具有6至12個碳原子之芳基烷基、鹵素原子、氰基、胺基、甲脒基、硝基、醯胺基、羰基、羥基、磺醯基、胺基甲酸酯基、具有具有1至10個 碳原子之烷氧基等。 The aryl group means a divalent functional group derived from an aromatic hydrocarbon, such as a cyclic group, and may include a phenyl group, a naphthyl group, and the like. One or more hydrogen atoms contained in the arylene group may be substituted with another substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 2 to 12 carbon atoms, Heteroaryl groups with 2 to 12 carbon atoms, arylalkyl groups with 6 to 12 carbon atoms, halogen atoms, cyano, amine, formamidine, nitro, amido, carbonyl, hydroxyl, sulfo A fluorenyl group, a urethane group, an alkoxy group having 1 to 10 carbon atoms, and the like.
鹼溶性樹脂的製造方法之實例無特別限制,但例如,該鹼溶性樹脂可經由環狀不飽和醯亞胺化合物和胺化合物之反應來製造。在此情況下,該環狀不飽和醯亞胺化合物及胺化合物中之至少一者可含有在其末端取代的酸官能基。即,酸官能基可在該環狀不飽和醯亞胺化合物、該胺化合物、或此等化合物二者的末端取代。酸官能基之細節係如上述。 Examples of the method for producing the alkali-soluble resin are not particularly limited, but, for example, the alkali-soluble resin can be produced through a reaction between a cyclic unsaturated fluorene imine compound and an amine compound. In this case, at least one of the cyclic unsaturated fluorene imine compound and the amine compound may contain an acid functional group substituted at its terminal. That is, the acid functional group may be substituted at the terminal of the cyclic unsaturated fluorene imine compound, the amine compound, or both of these compounds. The details of the acid functional group are as described above.
環狀醯亞胺化合物為含有上述環狀醯亞胺官能基的化合物,而環狀不飽和醯亞胺化合物意指該環狀醯亞胺化合物中含有至少一個不飽和鍵(即,雙鍵或三鍵)的化合物。 A cyclic fluorene imine compound is a compound containing the above cyclic fluorene imine functional group, and a cyclic unsaturated fluorene imine compound means that the cyclic fluorene imine compound contains at least one unsaturated bond (i.e., a double bond or Triple bond).
該鹼溶性樹脂可經由該胺化合物中所含之胺基與該環狀不飽和醯亞胺化合物中所含之雙鍵或三鍵的反應來製造。 The alkali-soluble resin can be produced through a reaction between an amine group contained in the amine compound and a double or triple bond contained in the cyclic unsaturated fluorene imine compound.
用於反應該環狀不飽和醯亞胺化合物與該胺化合物之重量比無特別限制,但例如,該胺化合物可藉由混合以100重量份之該環狀不飽和醯亞胺化合物計為10至80重量份、或30至60重量份之量而反應。 The weight ratio of the cyclic unsaturated fluorene imine compound to the amine compound is not particularly limited, but for example, the amine compound may be 10 by mixing 100 parts by weight of the cyclic unsaturated fluorene imine compound. To 80 parts by weight, or 30 to 60 parts by weight.
該環狀不飽和醯亞胺化合物之實例包括N經取代之順丁烯二醯亞胺化合物。本文所使用之用語「N經取代」意指官能基係代替氫原子鍵結至順丁烯二醯亞胺化合物中所含的氮原子,並且視N經取代之順丁烯二醯亞胺化合物之數目而定,N經取代之順丁烯二醯亞胺化合物可分 類成單官能基N經取代之順丁烯二醯亞胺化合物及多官能基N經取代之順丁烯二醯亞胺化合物。 Examples of the cyclic unsaturated fluorene imine compound include an N-substituted cis-butene difluorene imine compound. The term "N substituted" as used herein means that a functional group is bonded to a nitrogen atom contained in a maleimide compound instead of a hydrogen atom, and is regarded as an N substituted maleimide compound Depending on the number, N-substituted maleimide compounds can be classified into monofunctional N-substituted maleimide compounds and polyfunctional N-substituted maleimide compounds Compound.
單官能基N經取代之順丁烯二醯亞胺化合物為一種順丁烯二醯亞胺化合物中所含之氮原子係經官能基取代的化合物,以及多官能基N經取代之順丁烯二醯亞胺化合物為二或更多種順丁烯二醯亞胺化合物各者中所含的氮原子係經由官能基鍵結的化合物。 A monofunctional N-substituted maleimide compound is a compound in which a nitrogen atom contained in a maleimide compound is a functional group substituted, and a polyfunctional N-substituted maleimide The difluorene imine compound is a compound in which a nitrogen atom contained in each of two or more maleimide diimine compounds is bonded via a functional group.
在單官能基N經取代之順丁烯二醯亞胺化合物中,在該順丁烯二醯亞胺化合物中所含之氮原子上取代的官能基可包括但不侷限於各種已知之脂族、脂環、或芳族官能基,且在該氮原子上取代的官能基可包括其中脂族、脂環、或芳族官能基經酸官能基取代的官能基。酸官能基之細節係如上述。 In the monofunctional N-substituted maleimide compound, the functional group substituted on the nitrogen atom contained in the maleimide compound may include, but is not limited to, various known aliphatic compounds. , Alicyclic, or aromatic functional group, and the functional group substituted on the nitrogen atom may include a functional group in which an aliphatic, alicyclic, or aromatic functional group is substituted with an acid functional group. The details of the acid functional group are as described above.
單官能基N經取代之順丁烯二醯亞胺化合物之具體實例包括鄰甲苯基順丁烯二醯亞胺、對羥苯基順丁烯二醯亞胺、對羧苯基順丁烯二醯亞胺、十二基順丁烯二醯亞胺等。 Specific examples of the monofunctional N-substituted maleimide compound include o-tolyl maleimide diimide, p-hydroxyphenyl maleimide diimide, p-carboxyphenyl maleimide Fluorene imine, dodecyl cis butene difluorene imine and the like.
在多官能基N經取代之順丁烯二醯亞胺化合物中,中介該二或更多種順丁烯二醯亞胺化合物各者中所含的氮-氮鍵之官能基可包括但不侷限於各種已知之脂族、脂環、或芳族官能基。在具體實例中,可使用4,4'-二苯甲烷官能基等。在氮原子上取代之官能基可包括其中脂族、脂環、或芳族官能基經酸官能基取代的官能基。酸官能基之細節係如上述。 In the polyfunctional N-substituted maleimide compound, the functional group that mediates the nitrogen-nitrogen bond contained in each of the two or more maleimide compounds may include, but not It is limited to a variety of known aliphatic, alicyclic, or aromatic functional groups. In a specific example, a 4,4'-diphenylmethane functional group and the like can be used. The functional group substituted on the nitrogen atom may include a functional group in which an aliphatic, alicyclic, or aromatic functional group is substituted with an acid functional group. The details of the acid functional group are as described above.
多官能基N經取代之順丁烯二醯亞胺化合物之具體實例包括4,4'-二苯甲烷雙順丁烯二醯亞胺(BMI-1000、BMI-1100等,得自Daiwakasei Industry Co.,Ltd.)、甲苯雙順丁烯二醯亞胺、間伸苯基甲烷雙順丁烯二醯亞胺、雙酚A二苯基醚雙順丁烯二醯亞胺、3,3'-二甲基-5,5'-二乙基-4,4'-二苯甲烷雙順丁烯二醯亞胺、4-甲基-1,3-伸苯基雙順丁烯二醯亞胺、1,6'-雙順丁烯二醯亞胺-(2,2,4-三甲基)己烷等。 Specific examples of the polyfunctional N-substituted maleimide compound include 4,4'-diphenylmethanebismaleimide diimide (BMI-1000, BMI-1100, etc., available from Daiwakasei Industry Co. ., Ltd.), Toluene bis-butene difluorene imine, m-phenylene methane bis-butene difluorene imine, bisphenol A diphenyl ether biscis-butene difluorene imine, 3,3 ' -Dimethyl-5,5'-diethyl-4,4'-diphenylmethane biscis butylene diimide, 4-methyl-1,3-phenylene biscis butylene diimide Amines, 1,6'-biscisbutene diamidine- (2,2,4-trimethyl) hexane and the like.
該胺化合物可為分子結構中含有至少一個胺基(-NH2)之一級胺化合物。更佳的,可使用經胺基取代之羧酸化合物、含有至少兩個胺基之多官能基胺化合物、或其混合物。 The amine compound may be a primary amine compound containing at least one amine group (—NH 2 ) in the molecular structure. More preferably, an amine-substituted carboxylic acid compound, a polyfunctional amine compound containing at least two amine groups, or a mixture thereof can be used.
在經胺基取代之羧酸化合物中,該羧酸化合物為分子中含有羧酸(-COOH)官能基的化合物,且視鍵結至該羧酸酸官能基之烴的種類而定,其可包括所有脂族、脂環、及芳族羧酸。由於大量羧酸官能基(其係經由經胺基取代之羧酸化合物而包含在鹼溶性樹脂中的酸官能基)之故,該鹼溶性樹脂的顯影性可獲得改善。 Among the carboxylic acid compounds substituted with an amine group, the carboxylic acid compound is a compound containing a carboxylic acid (-COOH) functional group in the molecule, and it depends on the kind of the hydrocarbon bonded to the carboxylic acid functional group, which may be Includes all aliphatic, alicyclic, and aromatic carboxylic acids. Since a large number of carboxylic acid functional groups, which are acid functional groups contained in an alkali-soluble resin via a carboxylic acid compound substituted with an amine group, the developability of the alkali-soluble resin can be improved.
本文所使用之用語「經取代」意指鍵結另一官能基代替化合物中之氫原子,且該胺基在該羧酸中的取代位置無限制,只要其為氫原子被取代的位置即可。待取代之胺基的數目可為1或更多。 The term "substituted" as used herein means that another functional group is bonded to replace a hydrogen atom in a compound, and the substitution position of the amine group in the carboxylic acid is not limited as long as it is a position where the hydrogen atom is substituted . The number of amine groups to be substituted may be 1 or more.
經胺基取代之羧酸的具體實例包括下列中之20種:α-胺基酸、4-胺基丁酸、5-胺基戊酸、6-胺基己 酸、7-胺基庚酸、8-胺基辛酸、4-胺基苯甲酸、4-胺基苯乙酸、4-胺基環己烷羧酸等,彼等已知為蛋白質的原料。 Specific examples of amine-substituted carboxylic acids include 20 of the following: α-amino acid, 4-aminobutyric acid, 5-aminovaleric acid, 6-aminohexanoic acid, 7-aminoheptanoic acid , 8-aminooctanoic acid, 4-aminobenzoic acid, 4-aminophenylacetic acid, 4-aminocyclohexanecarboxylic acid, etc., which are known as raw materials for proteins.
此外,含有二或更多個胺基之多官能基胺化合物可為分子中含有至少兩個胺基(-NH2)的化合物,且視與該胺基鍵結之烴的類型而定,其可包括所有脂族、脂環、及芳族多官能基胺。該鹼溶性樹脂之可撓性、韌性、銅箔的黏著性可經由該含有至少兩個胺基之多官能基胺化合物而獲得改善。 In addition, the polyfunctional amine compound containing two or more amine groups may be a compound containing at least two amine groups (-NH 2 ) in the molecule, and it depends on the type of the hydrocarbon bonded to the amine group, which All aliphatic, alicyclic, and aromatic polyfunctional amines can be included. The flexibility, toughness, and adhesion of the copper foil of the alkali-soluble resin can be improved by the polyfunctional amine compound containing at least two amine groups.
含有二或更多個胺基之多官能基胺化合物的具體實例包括1,3-環己二胺、1,4-環己二胺、1,3-雙(胺基甲基)-環己烷、1,4-雙(胺基甲基)-環己烷、雙(胺基甲基)-降莰烯、八氫-4,7-亞甲基茚-1(2)(octahydro-4,7-methanoindene-1(2))、5(6)-二甲胺(5(6)-dimethanamine)、4,4'-亞甲基雙(環己胺)、4,4'-亞甲基雙(2-甲基環己胺)、異佛酮二胺、1,3-苯二胺、1,4-苯二胺、2,5-二甲基-1,4-苯二胺、2,3,5,6-甲基-1,4-苯二胺、2,4,5,6-四氟-1,3-苯二胺、2,3,5,6-四氟-1,4-苯二胺、4,6-二胺基間苯二酚、2,5-二胺基-1,4-苯二硫醇、3-胺基苯甲胺、4-胺基苯甲胺、間茬二胺、對茬二胺、1,5-二胺基萘、2,7-二胺基茀、2,6-二胺基蒽醌、間聯甲苯胺、鄰聯甲苯胺、3,3',5,5'-四甲基聯苯胺(TMB)、鄰二甲氧苯胺、4,4'-亞甲基雙(2-氯苯胺)、3,3'-二胺基聯苯胺、2,2'-雙(三氟甲基)-聯苯胺、4,4'-二胺基八氟聯苯、4,4'-二胺基-對聯三苯、3,3'-二胺基二苯甲烷、3,4'-二胺基二苯甲烷、4,4'-二胺基二苯甲烷、4,4'-二 胺基-3,3'-二甲基二苯甲烷、4,4'-亞甲基雙(2-乙基-6-甲基苯胺)、4,4'-亞甲基雙(2,6-二乙基苯胺)、3,3'-二胺基二苯甲酮、4,4'-二胺基二苯甲酮、4,4'-乙二苯胺、4,4'-二胺基-2,2'-二甲基聯苄、2,2'-雙(3-胺基-4-羥苯基)丙烷、2,2'-雙(3-胺苯基)-六氟丙烷、2,2'-雙(3-胺苯基)-六氟丙烷、2,2'-雙(3-胺基-4-甲苯基)-六氟丙烷、2,2'-雙(3-胺基-4-羥苯基)-六氟丙烷、α,α'-雙(4-胺苯基)-1,4-二異丙苯、1,3-雙[2-(4-胺苯基)-2-丙基]苯、1,1'-雙(4-胺苯基)-環己烷、9,9'-雙(4-胺苯基)-茀、9,9'-雙(4-胺基-3-氯苯基)茀、9,9'-雙(4-胺基-3-氟苯基)茀、9,9'-雙(4-胺基-3-甲苯基)茀、3,4'-二胺基二苯基醚、4,4'-二胺基二苯基醚、1,3-雙(3-胺基苯氧基)-苯、1,3-雙(4-胺基苯氧基)-苯、1,4-雙(4-胺基苯氧基)-苯、1,4-雙(4-胺基-2-三氟甲基苯氧基)-苯、4,4'-雙(4-胺基苯氧基)-聯苯、2,2'-雙[4-(4-胺基苯氧基)-苯基]丙烷、2,2'-雙[4-(4-胺基苯氧基)-苯基]六氟丙烷、雙(2-胺苯基)硫醚、雙(4-胺苯基)硫醚、雙(3-胺苯基)碸、雙(4-胺苯基)碸、雙(3-胺基-4-羥基)碸、雙[4-(3-胺基苯氧基)-苯基]碸、雙[4-(4-胺基苯氧基)-苯基]碸、鄰聯甲苯胺碸、3,6-二胺基咔唑、1,3,5-參(4-胺苯基)-苯、1,3-雙(3-胺丙基)-四甲基二矽氧烷、4,4'-二胺基苯甲醯胺苯、2-(3-胺苯基)-5-胺基苯并咪唑、2-(4-胺苯基)-5-胺基苯并唑、1-(4-胺苯基)-2,3-二氫-1,3,3-三甲基-1H-茚-5-胺、4,6-二胺基間苯二酚、2,3,5,6-吡啶四胺、包括Shin-Etsu Silicone(PAM-E、KF-8010、X-22-161A、X-22-161B、KF-8012、 KF-8008、X-22-1660B-3、X-22-9409)之矽氧烷結構的多官能基胺、包括Dow Corning(Dow Corning 3055)之矽氧烷結構的多官能基胺、包括聚醚結構(Huntsman,BASF)之多官能基胺等。 Specific examples of the polyfunctional amine compound containing two or more amine groups include 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) -cyclohexane Alkane, 1,4-bis (aminomethyl) -cyclohexane, bis (aminomethyl) -norbornene, octahydro-4,7-methyleneindene-1 (2) (octahydro-4 , 7-methanoindene-1 (2)), 5 (6) -dimethanamine, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylene Bis (2-methylcyclohexylamine), isophoronediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,3,5,6-methyl-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, 2,3,5,6-tetrafluoro-1 4,4-phenylenediamine, 4,6-diaminoresorcinol, 2,5-diamino-1,4-benzenedithiol, 3-aminobenzylamine, 4-aminobenzyl Amine, diamine, p-diamine, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 2,6-diaminoanthraquinone, m-toluidine, o-toluidine, 3,3 ', 5,5'-tetramethylbenzidine (TMB), o-dimethoxyaniline, 4,4'-methylenebis (2-chloroaniline), 3,3'-diamine group Aniline, 2,2'-bis (trifluoromethyl) -benzidine, 4,4'-diamino octafluorobiphenyl, 4,4'-diamino-p-terphenyl, 3,3'- Amino diphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane , 4,4'-methylenebis (2-ethyl-6-methylaniline), 4,4'-methylenebis (2,6-diethylaniline), 3,3'-diamine Benzophenone, 4,4'-diaminobenzophenone, 4,4'-ethylenediphenylamine, 4,4'-diamino-2,2'-dimethylbibenzyl, 2, 2'-bis (3-amino-4-hydroxyphenyl) propane, 2,2'-bis (3-aminephenyl) -hexafluoropropane, 2,2'-bis (3-aminephenyl)- Hexafluoropropane, 2,2'-bis (3-amino-4-tolyl) -hexafluoropropane, 2,2'-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, α , α'-bis (4-aminophenyl) -1,4-dicumene, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,1'- Bis (4-aminophenyl) -cyclohexane, 9,9'-bis (4-aminephenyl) -fluorene, 9,9'-bis (4-amino-3-chlorophenyl) fluorene, 9 , 9'-bis (4-amino-3-fluorophenyl) fluorene, 9,9'-bis (4-amino-3-tolyl) fluorene, 3,4'-diaminodiphenyl ether 4,4'-diaminodiphenyl ether, 1,3-bis (3-aminophenoxy) -benzene, 1,3-bis (4-aminophenoxy) -benzene, 1, 4-bis (4-aminophenoxy) -benzene, 1,4-bis (4-amino-2-trifluoromethylphenoxy) -benzene, 4,4'-bis (4- Phenylphenoxy) -biphenyl, 2,2'-bis [4- (4-aminophenoxy) -phenyl] propane, 2,2'-bis [4- (4-aminophenoxy ) -Phenyl] hexafluoropropane, bis (2-aminephenyl) sulfide, bis (4-aminephenyl) sulfide, bis (3-aminephenyl) fluorene, bis (4-aminephenyl) fluorene , Bis (3-amino-4-hydroxy) fluorene, bis [4- (3-aminophenoxy) -phenyl] fluorene, bis [4- (4-aminophenoxy) -phenyl] Hydrazone, o-toluidine hydrazone, 3,6-diaminocarbazole, 1,3,5-gins (4-aminophenyl) -benzene, 1,3-bis (3-aminopropyl) -tetramethyl Disylsiloxane, 4,4'-diaminobenzylamine benzene, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5- Aminobenzo Azole, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 4,6-diaminoresorcinol, 2 , 3,5,6-pyridine tetramine, including Shin-Etsu Silicone (PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B -3, X-22-9409) polyfunctional amines with a siloxane structure, polyfunctional amines with a siloxane structure including Dow Corning (Dow Corning 3055), polyether structures (Huntsman, BASF) Functional amines, etc.
此外,該鹼溶性樹脂可包括至少一種以下示化學式3表示之重複單元及至少一種以下示化學式4表示之重複單元。 In addition, the alkali-soluble resin may include at least one repeating unit represented by Chemical Formula 3 below and at least one repeating unit represented by Chemical Formula 4 below.
在化學式3中,R2為直接鍵、具有1至20個碳原子之伸烷基、具有1至20個碳原子之烯基、或具有6至20個碳原子之伸芳基,且「*」意指鍵結點。 In Chemical Formula 3, R 2 is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and "* "Means a key node.
在化學式4中,R3為直接鍵、具有1至20個碳 原子之伸烷基、具有1至20個碳原子之烯基、或具有6至20個碳原子之伸芳基;R4為-H、-OH、-NR5R6、鹵素、或具有1至20個碳原子之烷基;R5及R6可各自獨立地為氫、具有1至20個碳原子之烷基、或具有6至20個碳原子之芳基,且「*」意指鍵結點。 In Chemical Formula 4, R 3 is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms; R 4 is -H, -OH, -NR 5 R 6 , halogen, or an alkyl group having 1 to 20 carbon atoms; R 5 and R 6 may each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, or An aryl group having 6 to 20 carbon atoms, and "*" means a bond point.
較佳的,在化學式3中,R2為伸苯基,以及在化學式4中,R3為伸苯基且R4可為-OH。 Preferably, in Chemical Formula 3, R 2 is a phenylene group, and in Chemical Formula 4, R 3 is a phenylene group and R 4 may be -OH.
同時,該鹼溶性樹脂除了化學式3表示之重複單元及化學式4表示之重複單元以外,還可另外包括乙烯基系重複單元。該乙烯基系重複單元為分子中含有至少一或多個乙烯基之乙烯基系單體的同元聚合物中所含的重複單元,且該乙烯基系單體的實例可包括但不侷限於乙烯、丙烯、異丁烯、丁二烯、苯乙烯、丙烯酸、甲基丙烯酸、順丁烯二酸酐、順丁烯二醯亞胺等。 Meanwhile, the alkali-soluble resin may further include a vinyl-based repeating unit in addition to the repeating unit represented by Chemical Formula 3 and the repeating unit represented by Chemical Formula 4. The vinyl-based repeating unit is a repeating unit contained in a homopolymer of a vinyl-based monomer containing at least one or more vinyls in a molecule, and examples of the vinyl-based monomer may include but are not limited to Ethylene, propylene, isobutylene, butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride, maleimide and the like.
該含有至少一種以上述化學式3表示之重複單元及至少一種以上述化學式4表示之重複單元的鹼溶性樹脂可藉由使含有以下示化學式5表示之重複單元的聚合物、以下示化學式6表示之胺、與以下示化學式7表示之胺反應來製造。 The alkali-soluble resin containing at least one repeating unit represented by the above-mentioned chemical formula 3 and at least one repeating unit represented by the above-mentioned chemical formula 4 can be obtained by using a polymer containing a repeating unit represented by the following chemical formula 5 and represented by the following chemical formula 6 An amine is produced by reacting with an amine represented by Chemical Formula 7 shown below.
在化學式5至7中,R2至R4係與上述化學式3及4相同,且「*」意指鍵結點。 In Chemical Formulas 5 to 7, R 2 to R 4 are the same as the above Chemical Formulas 3 and 4, and "*" means a bond point.
含有以化學式5表示之重複單元的聚合物之具體實例可包括但不侷限於SMA(Cray Valley)、Xiran(Polyscope)、Scripset(Solenis)、Isobam(Kuraray)、Polyanhydride resin(Chevron Phillips Chemical Company)、Maldene(Lindau Chemicals)等。 Specific examples of the polymer containing a repeating unit represented by Chemical Formula 5 may include, but are not limited to, SMA (Cray Valley), Xiran (Polyscope), Scripset (Solenis), Isobam (Kuraray), Polyanhydride resin (Chevron Phillips Chemical Company), Maldene (Lindau Chemicals) and others.
此外,該含有至少一種以上述化學式3表示之重複單元及至少一種以上述化學式4表示之重複單元的鹼溶性樹脂可藉由使以下示化學式8表示之化合物與以下示化學式9表示之化合物反應來製造。 In addition, the alkali-soluble resin containing at least one repeating unit represented by the above Chemical Formula 3 and at least one repeating unit represented by the aforementioned Chemical Formula 4 can be obtained by reacting a compound represented by the following Chemical Formula 8 with a compound represented by the following Chemical Formula 9 Manufacturing.
在化學式8及9中,R2至R4係與上述化學式3及4相同。 In Chemical Formulas 8 and 9, R 2 to R 4 are the same as the above Chemical Formulas 3 and 4.
此外,該鹼溶性樹脂可為分子中包括羧基或酚基之為人熟知的慣用含羧基樹脂或含酚基樹脂。較佳的,可使用含羧基樹脂或該含羧基樹脂與該含酚基樹脂的混合物。 In addition, the alkali-soluble resin may be a conventionally known carboxyl group-containing resin or a phenol group-containing resin including a carboxyl group or a phenol group in the molecule. Preferably, a carboxyl-containing resin or a mixture of the carboxyl-containing resin and the phenol-based resin can be used.
該含羧基樹脂之實例包括下文(1)至(7)中所列之樹脂。 Examples of the carboxyl group-containing resin include resins listed in (1) to (7) below.
(1)藉由使多官能基環氧樹脂與飽和或不飽和單羧酸反應,然後藉由與多元酸酐反應所獲得之含羧基樹脂,(2)藉由使雙官能基環氧樹脂與雙官能基酚及/或二羧酸反應,然後藉由與多元酸酐反應所獲得之含羧基樹脂, (3)藉由使多官能基酚系樹脂與分子中具有一個環氧基之化合物反應,然後與多元酸酐反應所獲得之含羧基樹脂,(4)藉由使分子中具有二或更多個醇式羥基之化合物與與多元酸酐反應所獲得之含羧基樹脂,(5)藉由使二胺和二酐反應所獲得之聚醯胺酸樹脂(polyamic acid resin)或該聚醯胺酸樹脂之共聚物樹脂,(6)與丙烯酸反應之聚丙烯酸樹脂或該聚丙烯酸樹脂之共聚物,及(7)藉由順丁烯二酸酐及順丁烯二酸酐共聚物之酐與弱酸、二胺、咪唑、或二甲亞碸反應對順丁烯二酸酐樹脂進行開環作用所製備的樹脂,但不侷限於此。 (1) a carboxyl-containing resin obtained by reacting a polyfunctional epoxy resin with a saturated or unsaturated monocarboxylic acid and then reacting with a polybasic acid anhydride; (2) by reacting a bifunctional epoxy resin with a bifunctional epoxy resin; Functional group phenol and / or dicarboxylic acid, and then a carboxyl group-containing resin obtained by reacting with a polybasic acid anhydride; (3) reacting a polyfunctional phenol-based resin with a compound having an epoxy group in the molecule; A carboxyl-containing resin obtained by reacting with a polybasic acid anhydride, (4) a carboxyl-containing resin obtained by reacting a compound having two or more alcoholic hydroxyl groups in a molecule with a polybasic acid anhydride, and (5) a diamine by reacting Polyamic acid resin or copolymer resin of the polyamic acid resin obtained by reaction with dianhydride, (6) polyacrylic resin or copolymer of the polyacrylic resin reacted with acrylic acid, and ( 7) Resin prepared by reacting maleic anhydride and anhydride of maleic anhydride copolymer with weak acid, diamine, imidazole, or dimethylarsine to perform ring opening on maleic anhydride resin, but Not limited to this.
該含羧基樹脂之更具體實例包括CCR-1291H(Nippon Kayaku)、SHA-1216CA60(Shin-A T&C)、Noverite K-700(Lubrizol)、或其二或更多者的混合物。 More specific examples of the carboxyl-containing resin include CCR-1291H (Nippon Kayaku), SHA-1216CA60 (Shin-A T & C), Noverite K-700 (Lubrizol), or a mixture of two or more thereof.
含酚基樹脂的實例無特別限制,但例如,可單獨或組合使用酚醛清漆樹脂,諸如酚系酚醛清漆樹脂、甲酚酚醛清漆樹脂、雙酚F(BPF)酚醛清漆樹脂、或雙酚A系樹脂,諸如4,4'-(1-(4-(2-(4-羥苯基)丙-2-基)苯基)乙-1,1-二基)二酚。 Examples of the phenol-based resin are not particularly limited, but for example, novolac resins such as phenol-based novolac resins, cresol novolac resins, bisphenol F (BPF) novolac resins, or bisphenol A-based resins can be used alone or in combination Resins, such as 4,4 '-(1- (4- (2- (4-hydroxyphenyl) prop-2-yl) phenyl) ethyl-1,1-diyl) diphenol.
該聚合物樹脂層可另外包括至少一種選自由下列所組成之群組的添加劑:熱固化觸媒、無機填料、整平劑、分散劑、脫離劑、及金屬黏著促進劑。 The polymer resin layer may further include at least one additive selected from the group consisting of a thermosetting catalyst, an inorganic filler, a leveling agent, a dispersant, a release agent, and a metal adhesion promoter.
該鹼溶性樹脂可具有藉由KOH滴定測定為50mgKOH/g至250mgKOH/g、或70mgKOH/g至200mgKOH/g 之酸值。該鹼溶性樹脂之酸值的測量方法之實例無特別限制,但例如可使用下述方法。製備濃度為0.1N之KOH溶液(溶劑:甲醇)作為鹼溶液,及製備α-萘酚苯甲醇(pH:0.8至8.2為黃色,10.0為藍綠色)作為指示劑。隨後,收集約1至2g之該鹼溶性樹脂作為樣本,並溶解於50g添加有指示劑之二甲基甲醯胺(DMF)溶劑中,然後用鹼溶劑滴定。酸值係用適當完成時所使用之鹼溶劑的量以mgKOH/g單位測定。 The alkali-soluble resin may have an acid value determined by KOH titration of 50 mgKOH / g to 250 mgKOH / g, or 70 mgKOH / g to 200 mgKOH / g. Examples of the method for measuring the acid value of the alkali-soluble resin are not particularly limited, but, for example, the following methods can be used. A KOH solution (solvent: methanol) having a concentration of 0.1 N was prepared as an alkali solution, and α-naphthol benzyl alcohol (pH: 0.8 to 8.2 was yellow, and 10.0 was blue-green) were used as indicators. Subsequently, about 1 to 2 g of the alkali-soluble resin was collected as a sample and dissolved in 50 g of an indicator-added dimethylformamide (DMF) solvent, followed by titration with an alkali solvent. The acid value is measured in mgKOH / g using the amount of the alkali solvent used when properly completed.
當該鹼溶性樹脂之酸值過度降低至低於50mgKOH/g時,該鹼溶性樹脂的顯影性質降低,因此使得難以進行該顯影法。此外,當該鹼溶性樹脂之酸值過度提高至高於250mgKOH/g時,會因極性提高而發生與另外的樹脂相分離。 When the acid value of the alkali-soluble resin is excessively lowered to less than 50 mgKOH / g, the developing properties of the alkali-soluble resin are reduced, thus making it difficult to perform the developing method. In addition, when the acid value of the alkali-soluble resin is excessively increased to more than 250 mgKOH / g, phase separation from another resin occurs due to an increase in polarity.
熱固化觸媒用以促進熱可固化黏合劑之熱固化。熱固化觸媒之實例包括咪唑衍生物,諸如咪唑、2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、4-苯基咪唑、1-氰乙基-2-苯基咪唑、及1-(2-氰乙基)-2-乙基-4-甲基咪唑;胺化合物,諸如二氰二胺、苯甲基二甲胺、4-(二甲基胺基)-N,N-二甲基苯甲胺、4-甲氧基-N,N-二甲基苯甲胺、及4-甲基-N,N-二甲基苯甲胺;肼化合物,諸如己二酸二醯肼及癸二酸二醯肼;磷化合物,諸如三苯基膦;等。市售產品之實例包括由Shikoku Chemicals Corporation製造之2MZ-A、2MZ-OK、2PHZ、2P4BHZ、及2P4MHZ(咪唑化合物之產品名);由San-Apro Ltd.製造 之U-CAT3503N及UCAT3502T(二甲胺之嵌段異氰酸酯化合物的產品名)、以及DBU、DBN、U-CATS A102、U-CAT5002(雙環脒化合物及其鹽)。然而,熱固化觸媒不侷限於此等,亦可為用於環氧樹脂或氧環丁烷化合物之熱固化觸媒、或加速環氧基及/或氧環丁烷基與羧基之反應的化合物。該等觸媒可單獨使用或作為二或更多者之混合物使用。此外,可使用S-三衍生物,諸如胍胺、乙胍胺、苯并胍胺、三聚氰胺、2,4-二胺基-6-甲基丙烯醯氧乙基-S-三、2-乙烯基-4,6-二胺基-S-三、2-乙烯基-4,6-二胺基-S-三、2-乙烯基-4,6-二胺基-S-三-三聚異氰酸加成物、2,4-二胺基-6-甲基丙烯醯氧乙基-S-三-三聚異氰酸加成物等。較佳的,可用作黏著性賦予劑之化合物亦可與熱固化觸媒組合使用。 Thermal curing catalysts are used to promote thermal curing of thermally curable adhesives. Examples of heat curing catalysts include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1 -Cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; amine compounds such as dicyandiamine, benzyldimethylamine, 4 -(Dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, and 4-methyl-N, N-dimethyl Benzylamine; hydrazine compounds such as dihydrazine adipate and dihydrazine sebacate; phosphorus compounds such as triphenylphosphine; and the like. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (product names of imidazole compounds) manufactured by Shikoku Chemicals Corporation; U-CAT3503N and UCAT3502T (Dimethyl A) manufactured by San-Apro Ltd. Product names of amine block isocyanate compounds), and DBU, DBN, U-CATS A102, U-CAT5002 (bicyclic fluorene compounds and their salts). However, the thermal curing catalyst is not limited to these, and may be a thermal curing catalyst for epoxy resin or oxocyclobutane compound, or a catalyst that accelerates the reaction of epoxy group and / or oxocyclobutane group with carboxyl group. Compound. These catalysts can be used alone or as a mixture of two or more. In addition, S-Three can be used Derivatives such as guanamine, eguanidamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-tri , 2-vinyl-4,6-diamino-S-tri , 2-vinyl-4,6-diamino-S-tri , 2-vinyl-4,6-diamino-S-tri -Trimeric isocyanate adduct, 2,4-diamino-6-methacryloxyethyl-S-tri -Trimeric isocyanate adducts, etc. Preferably, the compound that can be used as an adhesion-imparting agent can also be used in combination with a thermosetting catalyst.
無機填料之實例包括矽石、硫酸鋇、鈦酸鋇、滑石、黏土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁、雲母、或其二或更多者的混合物。 Examples of the inorganic filler include silica, barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, or a mixture of two or more thereof.
無機填料之含量無特別限制。然而,為了獲致該聚合物樹脂層之高剛性,該無機填料可添加量以100重量份之該聚合物樹脂層中所含的所有樹脂組分計為100重量份或更多、100重量份至600重量份、150重量份至500重量份、或200重量份至500重量份。 The content of the inorganic filler is not particularly limited. However, in order to obtain high rigidity of the polymer resin layer, the inorganic filler may be added in an amount of 100 parts by weight or more based on 100 parts by weight of all the resin components contained in the polymer resin layer. 600 parts by weight, 150 parts by weight to 500 parts by weight, or 200 parts by weight to 500 parts by weight.
脫離劑之實例包括聚伸烷基蠟,諸如低分子量聚丙烯及低分子量聚乙烯、酯蠟、巴西棕櫚蠟、石蠟等。 Examples of the release agent include polyalkylene waxes such as low molecular weight polypropylene and low molecular weight polyethylene, ester wax, carnauba wax, paraffin wax, and the like.
金屬黏著促進劑可為不產生金屬材料之表面惡化或透明度問題的材料,例如,矽烷偶合劑、有機金屬偶合劑等。 The metal adhesion promoter may be a material that does not cause surface deterioration or transparency problems of metal materials, such as a silane coupling agent, an organic metal coupling agent, and the like.
整平劑用以移除膜塗布期間在表面上的突起或坑口,及可使用例如可得自BYK-Chemie GmbH之BYK-380N、BYK-307、BYK-378、及BYK-350等。 Leveling agents are used to remove protrusions or pits on the surface during film coating, and for example, BYK-380N, BYK-307, BYK-378, and BYK-350 available from BYK-Chemie GmbH can be used.
此外,該聚合物樹脂層可另外包括能導致相分離之分子量為5000或更大的樹脂或彈性體。因此,可對該聚合物樹脂層之固化產物進行粗糙化處理。分子量為5000或更大的樹脂或彈性體之分子量的測定方法之實例無特別限制,且例如,其意指藉由GPC(凝膠滲透層析術)測量關於聚苯乙烯的重量平均分子量。在藉由GPC測定關於聚苯乙烯之重量平均分子量的方法中,可使用一般已知之分析裝置、偵測器(諸如示差折射率偵測器)、及分析柱。可使用溫度、溶劑、及流率的一般應用條件。測量條件的具體實例包括溫度為30℃、四氫呋喃(THF)、及流率為1mL/min。 In addition, the polymer resin layer may further include a resin or an elastomer having a molecular weight of 5000 or more that can cause phase separation. Therefore, the cured product of the polymer resin layer can be roughened. Examples of the method for measuring the molecular weight of a resin or an elastomer having a molecular weight of 5000 or more are not particularly limited, and for example, it means that the weight average molecular weight with respect to polystyrene is measured by GPC (gel permeation chromatography). In the method for determining the weight-average molecular weight of polystyrene by GPC, a generally known analysis device, a detector such as a differential refractive index detector, and an analytical column can be used. Can be used for general application conditions of temperature, solvent, and flow rate. Specific examples of the measurement conditions include a temperature of 30 ° C, tetrahydrofuran (THF), and a flow rate of 1 mL / min.
此外,為了使該聚合物樹脂層具有光可固化性質,該聚合物樹脂層可另外包括含有光反應性不飽和基團之熱可固化黏合劑、或含有光反應性不飽和基團及光引發劑之鹼溶性樹脂。含有光反應性不飽和基團之熱可固化黏合劑、或含有光反應性不飽和基團及光引發劑之鹼溶性樹脂的具體實例無特別限制,且可使用關於光可固化樹脂組成物之技術領域中所使用的各種化合物而無限制。 In addition, in order to make the polymer resin layer have photo-curable properties, the polymer resin layer may further include a heat-curable adhesive containing a photoreactive unsaturated group, or a photoreactive unsaturated group and a photoinitiator. Agent of alkali-soluble resin. Specific examples of the heat-curable adhesive containing a photo-reactive unsaturated group or the alkali-soluble resin containing a photo-reactive unsaturated group and a photoinitiator are not particularly limited, and a photo-curable resin composition may be used. Various compounds are used in the technical field without limitation.
另一方面,該金屬層之黏附有載體膜之一表面的相反表面可黏附在該聚合物樹脂層上。該金屬層中所述的金屬之實例包括諸如金、銀、銅、錫、鎳、鋁、及鈦等金屬、以及此等金屬之二或更多者的混合物。該金屬層之厚度可為10nm至10μm。若該金屬層之厚度過度增加至大於10μm,需要過量金屬以形成該金屬層,從而提高原料成本以及降低經濟方面的效率。 On the other hand, the opposite surface of the metal layer to which one surface of the carrier film is adhered may be adhered to the polymer resin layer. Examples of the metal described in the metal layer include metals such as gold, silver, copper, tin, nickel, aluminum, and titanium, and mixtures of two or more of these metals. The thickness of the metal layer may be 10 nm to 10 μm. If the thickness of the metal layer is excessively increased to more than 10 μm, excess metal is required to form the metal layer, thereby increasing raw material costs and reducing economic efficiency.
載體膜可黏附至該金屬層之一表面。該載體膜可黏附至該金屬層之一表面以防止諸如移動或黏附該金屬層的製程中與該金屬層表面直接接觸,且在黏附該金屬層之後因可物理性剝離之故,該載體膜可輕易地移除。該載體膜的具體實例無特別限制,且例如可不同地應用有機及無機材料,諸如聚合物、金屬、及橡膠。在一實施態樣中,較佳可使用與該金屬層相同材料作為該載體膜的材料。如此,如下述,該載體膜及該金屬層可同時被同一蝕刻劑蝕刻以形成圖案。 The carrier film may be adhered to a surface of the metal layer. The carrier film can be adhered to a surface of the metal layer to prevent direct contact with the surface of the metal layer during a process such as moving or adhering the metal layer, and the carrier film can be physically peeled after being adhered to the metal layer. Can be easily removed. Specific examples of the carrier film are not particularly limited, and, for example, organic and inorganic materials such as polymers, metals, and rubbers can be variously applied. In one embodiment, the same material as that of the metal layer is preferably used as the material of the carrier film. As such, as described below, the carrier film and the metal layer can be simultaneously etched by the same etchant to form a pattern.
另一方面,該與金屬層之黏附有該載體膜之一表面的相反表面可黏附至該聚合物樹脂層。該金屬層之一表面的相反表面意指與金屬層之該一表面平行並面對彼之表面。當該金屬層之黏附有載體膜之一表面的相反表面係黏附至該聚合物樹脂層時,可形成金屬層係積層在該聚合物樹脂層上,然後載體膜積層在該金屬層上的結構。 On the other hand, the surface opposite to the surface of the metal layer to which the carrier film is adhered may be adhered to the polymer resin layer. The opposite surface of one surface of the metal layer means a surface parallel to and facing the one surface of the metal layer. When the opposite surface of the metal layer to which one surface of the carrier film is adhered is adhered to the polymer resin layer, a structure in which a metal layer system is laminated on the polymer resin layer, and then a carrier film is laminated on the metal layer may be formed. .
在該情況下,如下述,由於該載體膜與該金屬層之間的黏著力可小於該聚合物樹脂層與該金屬層之間 的黏著力,可防止在該載體膜與該金屬層物理性剝離期間該聚合物樹脂層與該金屬層剝離。當該聚合物樹脂層與該金屬層之間的黏著力小於該載體膜與該金屬層之間的黏著力時,在該載體膜與該金屬層物理性剝離期間,該聚合物樹脂層與該金屬層剝離,因此會難以在該聚合物樹脂層上形成精細圖案。 In this case, as described below, since the adhesive force between the carrier film and the metal layer can be smaller than the adhesive force between the polymer resin layer and the metal layer, physical properties between the carrier film and the metal layer can be prevented. The polymer resin layer is peeled from the metal layer during peeling. When the adhesive force between the polymer resin layer and the metal layer is smaller than the adhesive force between the carrier film and the metal layer, during the physical peeling of the carrier film from the metal layer, the polymer resin layer and the metal layer Since the metal layer is peeled, it may be difficult to form a fine pattern on the polymer resin layer.
在載體膜上形成經圖案化之光敏性樹脂層的步驟 Step of forming a patterned photosensitive resin layer on a carrier film
光敏性樹脂層可在形成圖案的狀態下積層在載體膜上,或可在積層之後圖案化,但更佳的,圖案可在積層於載體膜上之後形成。 The photosensitive resin layer may be laminated on the carrier film in a state where a pattern is formed, or may be patterned after being laminated, but more preferably, the pattern may be formed after being laminated on the carrier film.
光敏性樹脂層的實例可包括為鹼溶性或非熱固性之光敏性乾燥膜阻劑(DFR等)。 Examples of the photosensitive resin layer may include a photosensitive dry film resist (DFR, etc.) that is alkali-soluble or non-thermosetting.
該在載體膜上形成經圖案化之光敏性樹脂層的步驟可包括曝光及對在該載體膜上形成之該光敏性樹脂層進行鹼性顯影。在該情況下,該光敏性樹脂層可用作該載體膜的保護層,或用作圖案化遮罩。 The step of forming a patterned photosensitive resin layer on the carrier film may include exposing and subjecting the photosensitive resin layer formed on the carrier film to alkaline development. In this case, the photosensitive resin layer can be used as a protective layer of the carrier film or as a patterned mask.
在該在載體膜上形成經圖案化之光敏性樹脂層的步驟中,在該載體膜上形成之光敏性樹脂層的厚度可為1μm至500μm、3μm至500μm、3μm至200μm、1μm至60μm、或5μm至30μm。當該光敏性樹脂層之厚度過度增加時,該聚合物樹脂層的解析度會降低。 In the step of forming a patterned photosensitive resin layer on a carrier film, the thickness of the photosensitive resin layer formed on the carrier film may be 1 μm to 500 μm, 3 μm to 500 μm, 3 μm to 200 μm, 1 μm to 60 μm, Or 5 μm to 30 μm. When the thickness of the photosensitive resin layer is excessively increased, the resolution of the polymer resin layer is reduced.
在曝光及對在該載體膜上形成之該光敏性樹脂層進行鹼性顯影的步驟中,在該載體膜上形成光敏性樹 脂層的方法之實例無特別限制,且例如可使用在載體膜上積層膜狀光敏性樹脂(諸如光敏性乾燥膜)的方法、或藉由噴霧或浸漬在該載體膜上塗布光敏性樹脂組成物並壓製該經塗布之膜的方法等。 In the steps of exposing and subjecting the photosensitive resin layer formed on the carrier film to alkaline development, an example of a method for forming the photosensitive resin layer on the carrier film is not particularly limited, and for example, it can be used on a carrier film A method of laminating a film-like photosensitive resin such as a photosensitive dry film, or a method of coating a photosensitive resin composition by spraying or dipping on the carrier film and pressing the coated film, and the like.
在曝光及對在該載體膜上形成之該光敏性樹脂層進行鹼性顯影的步驟中,曝光及對該光敏性樹脂層進行鹼性顯影的方法之實例無特別限制,但例如,曝光可經由使形成有預定圖案之光罩接觸該光敏性樹脂層上然後用紫外線照射的方法、經由投影物鏡將包括在該遮罩中之預定圖案成像然後用紫外線照射的方法、使用雷射二極體作為光源將包括在該遮罩中之預定圖案直接成像然後用紫外線照射的方法等選擇性進行。在該情況下,紫外線照射條件之實例可包括用5mJ/cm2至600mJ/cm2之光量照射。 In the steps of exposing and subjecting the photosensitive resin layer formed on the carrier film to alkaline development, examples of the method of exposing and subjecting the photosensitive resin layer to alkaline development are not particularly limited, but for example, the exposure may be performed via A method in which a photomask formed with a predetermined pattern is brought into contact with the photosensitive resin layer and then irradiated with ultraviolet rays, a method of imaging a predetermined pattern included in the mask through a projection objective, and then irradiated with ultraviolet rays, using a laser diode as The light source selectively performs a method of directly imaging a predetermined pattern included in the mask and then irradiating it with ultraviolet rays. In this case, examples of the ultraviolet irradiation conditions may include irradiation with a light amount of 5 mJ / cm 2 to 600 mJ / cm 2 .
此外,在曝光及對在該載體膜上形成之該光敏性樹脂層進行鹼性顯影的步驟中,對該光敏性樹脂層進行顯影的方法之實例可包括用鹼性顯影劑處理的方法。鹼性顯影劑之實例無特別限制,但例如,可使用鹼性水溶液,諸如氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、氫氧化四甲銨、胺等,及較佳的,可使用在30℃之1%碳酸鈉顯影劑。鹼性顯影劑之具體用量無特別限制。 In addition, in the steps of exposing and subjecting the photosensitive resin layer formed on the carrier film to alkaline development, examples of a method of developing the photosensitive resin layer may include a method of treating with an alkaline developer. Examples of the alkaline developer are not particularly limited, but, for example, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, amine can be used Etc., and preferably, a 1% sodium carbonate developer at 30 ° C can be used. The specific amount of the alkaline developer is not particularly limited.
在處理鹼性顯影劑之情況下,只有一部分該光敏性樹脂層藉由顯影移除,且位在下方部分的含有鹼溶性樹脂及熱可固化黏合劑之聚合物樹脂層可受到載體膜保 護,從而防止該層被顯影。因此,不需要獨立的用於防止該聚合物樹脂層顯影之步驟,例如事先固化該聚合物樹脂層之步驟、或引入二或更多種不同金屬層以用不同蝕刻劑依序進行圖案化之步驟;通路孔的解析度可藉由使用在該聚合物層上形成精細金屬層作為抗蝕遮罩降低縱橫比而提高。 In the case of processing an alkaline developer, only a part of the photosensitive resin layer is removed by development, and a polymer resin layer containing an alkali-soluble resin and a heat-curable adhesive at the lower part can be protected by a carrier film. This prevents the layer from being developed. Therefore, there is no need for a separate step for preventing the development of the polymer resin layer, such as a step of curing the polymer resin layer in advance, or introducing two or more different metal layers for sequentially patterning with different etchant. Step; The resolution of the via hole can be improved by reducing the aspect ratio by forming a fine metal layer on the polymer layer as a resist mask.
移除被經圖案化之光敏性樹脂層暴露的載體膜及金屬層以形成經圖案化之金屬層的步驟 Step of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer
在移除被經圖案化之光敏性樹脂層暴露的載體膜及金屬層的步驟中,使用該光敏性樹脂圖案作為用於在該載體膜及該金屬層上形成圖案的阻劑。因此,被光敏性樹脂層圖案暴露之載體膜及金屬層意指該載體膜及金屬層的表面未與該光敏性樹脂層接觸之部分。 In the step of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer, the photosensitive resin pattern is used as a resist for forming a pattern on the carrier film and the metal layer. Therefore, the carrier film and the metal layer exposed by the pattern of the photosensitive resin layer mean a portion of the surface of the carrier film and the metal layer that is not in contact with the photosensitive resin layer.
具體而言,移除被光敏性樹脂層圖案暴露的載體膜及金屬層的步驟可包括蝕刻劑通過其上形成有圖案之光敏性樹脂層並與該載體膜及該金屬層接觸的步驟。 Specifically, the step of removing the carrier film and the metal layer exposed by the pattern of the photosensitive resin layer may include a step of an etchant passing through the patterned photosensitive resin layer and contacting the carrier film and the metal layer.
蝕刻劑可視載體膜及金屬層之種類加以選擇,以及若可能的話,較佳係使用對於下方之銅線影響較小且不影響該光敏性樹脂層的物質。 The etchant can be selected according to the type of the carrier film and the metal layer, and if possible, it is preferable to use a substance that has less influence on the underlying copper wire and does not affect the photosensitive resin layer.
然而,如上述,在該實施態樣中,較佳係使用與該金屬層相同的材料作為該載體膜的材料,從而使該載體膜及該金屬層可藉由同一蝕刻劑同時或依序移除,因此可輕易地形成圖案。 However, as mentioned above, in this embodiment, it is preferable to use the same material as the metal layer as the material of the carrier film, so that the carrier film and the metal layer can be simultaneously or sequentially moved by the same etchant. Can be easily formed.
另一方面,在移除被經圖案化之光敏性樹脂層暴露的載體膜及金屬層以形成經圖案化之金屬層的步驟中,聚合物樹脂層之移除率以該聚合物樹脂層的總重計可為0.01重量%或更低。詞語「聚合物樹脂層之移除率以該聚合物樹脂層的總重計為0.01重量%或更低」可意指該聚合物樹脂層被移除的程度非常微不足道,或該聚合物樹脂層未被移除。 On the other hand, in the step of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form the patterned metal layer, the removal rate of the polymer resin layer is based on the polymer resin layer. The total weight may be 0.01% by weight or less. The word "the removal rate of the polymer resin layer is 0.01% by weight or less based on the total weight of the polymer resin layer" may mean that the degree of removal of the polymer resin layer is very insignificant, or the polymer resin layer Not removed.
即,在移除該經圖案化之光敏性樹脂層暴露的載體膜及金屬層以形成經圖案化之金屬層的步驟中所使用的蝕刻劑對該聚合物樹脂層完全不具物理及化學影響。因而,該聚合物樹脂層可安定地保持直到形成精細金屬圖案層,且通路孔的解析度可藉由使用該精細金屬圖案層作為阻劑遮罩降低縱橫比而提高。 That is, the etchant used in the step of removing the exposed carrier film and the metal layer of the patterned photosensitive resin layer to form the patterned metal layer has no physical or chemical influence on the polymer resin layer. Therefore, the polymer resin layer can be stably maintained until the fine metal pattern layer is formed, and the resolution of the via hole can be improved by reducing the aspect ratio by using the fine metal pattern layer as a resist mask.
自經圖案化之金屬層分離及移除載體膜的步驟 Steps to separate and remove carrier film from patterned metal layer
在如上述移除被經圖案化之光敏性樹脂層暴露的載體膜及金屬層以形成經圖案化之金屬層的步驟之後,經圖案化之金屬層、經圖案化之載體膜、及經圖案化之光敏性樹脂層可依序積層。 After the steps of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer as described above, the patterned metal layer, the patterned carrier film, and the pattern The converted photosensitive resin layer may be sequentially laminated.
此時,為了形成絕緣層,必須將除了該聚合物樹脂層及在該聚合物樹脂層上形成的經圖案化之金屬層以外的所有其餘層移除。為此,慣常使用鹼性顯影劑以移除用於形成圖案的光敏性樹脂層。在該情況下,存在鹼性顯影劑容許該聚合物樹脂層同時或依序顯影的問題。此 外,在使用用於形成圖案的金屬層之情況下,由於使用蝕刻劑以移除該金屬層,會發生諸如下方銅線腐蝕的問題。 At this time, in order to form the insulating layer, it is necessary to remove all the remaining layers except the polymer resin layer and the patterned metal layer formed on the polymer resin layer. For this reason, it is customary to use an alkaline developer to remove the photosensitive resin layer for patterning. In this case, there is a problem that the alkaline developer allows the polymer resin layer to be developed simultaneously or sequentially. In addition, in the case where a metal layer for forming a pattern is used, since an etchant is used to remove the metal layer, problems such as corrosion of a copper wire below may occur.
另一方面,在一實施態樣之情況下,除了在聚合物樹脂層上形成的經圖案化之金屬層以外的其餘層可經由將載體膜與金屬層分離及移除的簡單方法而輕易地移除。 On the other hand, in one embodiment, the remaining layers other than the patterned metal layer formed on the polymer resin layer can be easily separated and removed by a simple method of separating and removing the carrier film from the metal layer. Removed.
在上述實施態樣中,由於該載體膜與該金屬層之間的黏著力小於該聚合物樹脂層與該金屬層之間的黏著力,可防止在該載體膜與該金屬層物理性剝離期間該聚合物樹脂層與該金屬層剝離。 In the above embodiment, since the adhesive force between the carrier film and the metal layer is smaller than the adhesive force between the polymer resin layer and the metal layer, it can be prevented during the physical peeling of the carrier film and the metal layer. The polymer resin layer is separated from the metal layer.
此外,在將載體膜與金屬層分離的製程中,由於該載體膜與在該載體膜上形成的光敏性樹脂層係呈黏附或剝離的狀態一起移除,即使不使用蝕刻劑的情況下也只有精細金屬圖案遮罩可輕易地留在該聚合物樹脂層上,因此通路孔的解析度可藉由經由下述圖案化製程降低縱橫比而提高。 In addition, in the process of separating the carrier film from the metal layer, the carrier film is removed together with the photosensitive resin layer formed on the carrier film in a state of adhesion or peeling, even without using an etchant. Only a fine metal pattern mask can be easily left on the polymer resin layer, so the resolution of the via hole can be improved by reducing the aspect ratio through a patterning process described below.
對被經圖案化之金屬層暴露之聚合物樹脂層進行鹼性顯影的步驟 Step of subjecting the polymer resin layer exposed to the patterned metal layer to alkaline development
此外,該絕緣層的製造方法可包括對被經圖案化之金屬層暴露之聚合物樹脂層進行鹼性顯影。於替代慣用雷射蝕刻製程時,經由如上述僅使經由在金屬層上形成之圖案暴露的聚合物樹脂層表面部分與鹼性顯影劑選擇性接觸的製程,可確保同等精確度水準及較高之製程經濟 性。 In addition, the method of manufacturing the insulating layer may include performing alkaline development on the polymer resin layer exposed by the patterned metal layer. When replacing the conventional laser etching process, through the process of selectively contacting only the surface portion of the polymer resin layer exposed through the pattern formed on the metal layer with the alkaline developer as described above, it can ensure the same level of accuracy and high Process economy.
在對被經圖案化之金屬層暴露之聚合物樹脂層進行鹼性顯影的步驟中,使用金屬層圖案作為用於在該聚合物樹脂層上形成圖案的阻劑。因此,被金屬層圖案暴露之聚合物樹脂層意指該聚合物樹脂層的表面不與金屬層接觸之部分。 In the step of performing alkaline development on the polymer resin layer exposed by the patterned metal layer, a metal layer pattern is used as a resist for forming a pattern on the polymer resin layer. Therefore, the polymer resin layer exposed by the metal layer pattern means a portion where the surface of the polymer resin layer is not in contact with the metal layer.
具體而言,對被經圖案化之金屬層暴露之聚合物樹脂層進行鹼性顯影的步驟可包括鹼性顯影劑通過其上形成有圖案之金屬層並與聚合物樹脂層接觸的步驟。 Specifically, the step of performing alkaline development on the polymer resin layer exposed by the patterned metal layer may include a step of passing an alkaline developer through the patterned metal layer and contacting the polymer resin layer.
由於該聚合物樹脂層包括鹼溶性樹脂,其具有鹼溶性使其溶解於鹼性顯影劑中,因此該聚合物樹脂層之與該鹼性顯影劑接觸的部分可被溶解並移除。 Since the polymer resin layer includes an alkali-soluble resin, which has alkali solubility to dissolve it in an alkaline developer, a portion of the polymer resin layer that is in contact with the alkaline developer can be dissolved and removed.
另一方面,在對被經圖案化之金屬層暴露之聚合物樹脂層進行鹼性顯影的步驟之後,會留下以被該經圖案化之金屬層暴露之該聚合物樹脂層的總重計為0.1重量%至85重量%、0.1重量%至50重量%、或0.1重量%至10重量%。此被視為因該聚合物樹脂層中所含之鹼溶性樹脂已被該鹼性顯影劑移除,但該具有低鹼性顯影性質的熱可固化黏合劑或無機填料留下未被移除所致。 On the other hand, after the step of alkaline developing the polymer resin layer exposed by the patterned metal layer, it will remain based on the total weight of the polymer resin layer exposed by the patterned metal layer It is 0.1 to 85% by weight, 0.1 to 50% by weight, or 0.1 to 10% by weight. This is considered to be because the alkali-soluble resin contained in the polymer resin layer has been removed by the alkaline developer, but the heat-curable adhesive or inorganic filler having low alkaline development properties has not been removed. Caused by.
因此,當經圖案化之金屬層視需要被蝕刻劑處理移除時,被圖案暴露的下方銅箔可與之一起被蝕刻,因此最小化深蝕刻。 Therefore, when the patterned metal layer is removed by an etchant treatment as needed, the underlying copper foil exposed by the pattern can be etched together with it, thereby minimizing deep etching.
同時,在對被經圖案化之金屬層暴露之聚合物樹脂層進行鹼性顯影的步驟之後留下的聚合物樹脂層可 藉由用剝離液體等的處理予以移除。即,在對被經圖案化之金屬層暴露之聚合物樹脂層進行鹼性顯影的步驟之後,該方法可另外包括處理剝離液體的步驟,且該剝離液體之種類及處理方法無特別限制。 Meanwhile, the polymer resin layer remaining after the step of subjecting the polymer resin layer exposed to the patterned metal layer to alkaline development can be removed by treatment with a peeling liquid or the like. That is, after the step of performing alkaline development on the polymer resin layer exposed by the patterned metal layer, the method may further include a step of processing a peeling liquid, and the kind and processing method of the peeling liquid are not particularly limited.
特別是,為了控制無機填料及熱可固化黏合劑留下的程度,可對熱可固化黏合劑及無機填料相對於鹼溶性樹脂之重量比、在無機填料表面上之酸官能基的比等予以控制。較佳的,以100重量份鹼溶性樹脂計,可添加20重量份至100重量份之熱可固化黏合劑及100重量份至600重量份之無機填料。無機填料表面之酸值可在0mgKOH/g至5mgKOH/g、或0.01mgKOH/g至5mgKOH/g之範圍。酸值之細節與鹼溶性樹脂之酸值的測定方法中的細節相同。 In particular, in order to control the extent to which the inorganic filler and the heat-curable adhesive remain, the weight ratio of the heat-curable adhesive and the inorganic filler to the alkali-soluble resin, the ratio of the acid functional groups on the surface of the inorganic filler, and the like control. Preferably, based on 100 parts by weight of the alkali-soluble resin, 20 to 100 parts by weight of a heat-curable adhesive and 100 to 600 parts by weight of an inorganic filler may be added. The acid value on the surface of the inorganic filler may be in a range of 0 mgKOH / g to 5 mgKOH / g, or 0.01 mgKOH / g to 5 mgKOH / g. The details of the acid value are the same as those in the method of measuring the acid value of the alkali-soluble resin.
鹼性顯影劑之實例無特別限制,但例如,可使用鹼性水溶液,諸如氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、氫氧化四甲銨、胺等,及較佳的,可使用在30℃之1%碳酸鈉顯影劑。鹼性顯影劑之具體用量無特別限制。 Examples of the alkaline developer are not particularly limited, but, for example, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, amine can be used Etc., and preferably, a 1% sodium carbonate developer at 30 ° C can be used. The specific amount of the alkaline developer is not particularly limited.
在鹼性顯影之後熱固化聚合物樹脂層的步驟 Step of thermally curing a polymer resin layer after alkaline development
此外,該絕緣層的製造方法可包括在鹼性顯影之後熱固化聚合物樹脂層。該熱固化聚合物樹脂層的步驟可在100至250℃之溫度進行。 In addition, the method of manufacturing the insulating layer may include thermally curing the polymer resin layer after alkaline development. The step of curing the polymer resin layer may be performed at a temperature of 100 to 250 ° C.
同時,在該熱固化聚合物樹脂層的步驟之 後,該方法可另外包括移除在聚合物樹脂層上的金屬層。金屬層的移除方法包括移除金屬層但不移除聚合物樹脂層之下方銅線或只移除其一部分的方法。 Meanwhile, after the step of thermally curing the polymer resin layer, the method may further include removing a metal layer on the polymer resin layer. The method of removing the metal layer includes a method of removing the metal layer without removing the copper wire under the polymer resin layer or removing only a part thereof.
作為具體實例,藉由將金屬層之銅箔的厚度製成為3μm或更小之極薄厚度,該金屬層被移除然而部分移除下方銅線,或該金屬層被移除但可使用不影響下方銅線的蝕刻劑。 As a specific example, by making the thickness of the copper foil of the metal layer to an extremely thin thickness of 3 μm or less, the metal layer is removed but the underlying copper wires are partially removed, or the metal layer is removed but can be used without Etchant that affects the underlying copper wires.
另一方面,根據本發明另一實施態樣,提供多層印刷電路板的製造方法,該方法包括在該實施態樣中所製造的絕緣層上形成具有圖案之金屬基底的步驟。 On the other hand, according to another aspect of the present invention, a method for manufacturing a multilayer printed circuit board is provided. The method includes the step of forming a patterned metal substrate on the insulating layer manufactured in the aspect.
本發明人發現,由於在上述實施態樣中製造的絕緣層包括特定開口圖案,在將金屬基底新積層在該絕緣層上的製程中,該開口圖案的內部被金屬填充,從而位在上方部分及下方部分的金屬基底係基於該絕緣層連接,以製造多層印刷電路板。本發明已基於此發現而完成。 The inventor has found that, since the insulating layer manufactured in the above embodiment includes a specific opening pattern, in the process of newly laminating a metal substrate on the insulating layer, the inside of the opening pattern is filled with metal, so that it is located in the upper part The metal substrates below and below are connected based on this insulating layer to make a multilayer printed circuit board. The present invention has been completed based on this finding.
絕緣層可用作多層印刷電路板之層間絕緣材料,及可包括鹼溶性樹脂及熱可固化黏合劑之固化產物。鹼溶性樹脂及熱可固化黏合劑之細節包括上述實施態樣中所述者。若必要,可在絕緣層表面上形成厚度為5μm或更小之銅箔。 The insulating layer may be used as an interlayer insulating material of a multilayer printed circuit board, and may include a cured product of an alkali-soluble resin and a heat-curable adhesive. The details of the alkali-soluble resin and the heat-curable adhesive include those described in the above embodiments. If necessary, a copper foil having a thickness of 5 μm or less may be formed on the surface of the insulating layer.
在絕緣層上形成具有圖案之金屬基底的步驟為已知為半加成製程(semi-additive process)(SAP)或經改良的半加成製程(MSAP)之精細電路圖案形成製程。SAP意指以無任何東西存在絕緣層上之狀態形成精細電路圖案的 製程,而MSAP意指以在絕緣層上形成5μm或更小之銅箔的狀態形成精細電路圖案的製程。 The step of forming a patterned metal substrate on the insulating layer is a fine circuit pattern forming process known as a semi-additive process (SAP) or a modified semi-additive process (MSAP). SAP means a process of forming a fine circuit pattern in a state where nothing is present on the insulating layer, and MSAP means a process of forming a fine circuit pattern in a state where a copper foil of 5 m or less is formed on the insulating layer.
在絕緣層上形成其上形成有圖案的金屬基底之步驟的更具體實例包括下列步驟:在該絕緣層上形成金屬薄膜;在該金屬薄膜上形成其上形成有圖案的光敏性樹脂層;將金屬沉積在被該光敏性樹脂層圖案暴露之該金屬薄膜上;移除該光敏性樹脂層;以及移除該暴露的金屬薄膜。 More specific examples of the step of forming a patterned metal substrate on an insulating layer include the following steps: forming a metal thin film on the insulating layer; forming a photosensitive resin layer having a pattern formed thereon on the metal thin film; Metal is deposited on the metal film exposed by the photosensitive resin layer pattern; removing the photosensitive resin layer; and removing the exposed metal film.
在絕緣層上形成金屬薄膜之步驟中,金屬薄膜的形成方法之實例包括乾式沉積法或濕式沉積法,且乾式沉積法的具體實例包括真空沉積、離子鍍、濺鍍等。另一方面,作為濕式沉積法之具體實例,可提及各種金屬之無電鍍覆,更具體而言,可使用無電銅鍍覆。此外,可在氣相沉積之前或之後另外包括粗糙化處理步驟。 In the step of forming the metal thin film on the insulating layer, examples of the method for forming the metal thin film include a dry deposition method or a wet deposition method, and specific examples of the dry deposition method include vacuum deposition, ion plating, sputtering, and the like. On the other hand, as a specific example of the wet deposition method, electroless plating of various metals may be mentioned, and more specifically, electroless copper plating may be used. In addition, a roughening treatment step may be additionally included before or after vapor deposition.
另外,就在絕緣層上形成金屬薄膜的方法而言,在使用金屬層作為該實施態樣之絕緣層的製造方法中之保護層的情況下,當未進行移除金屬層的步驟時,所製造的絕緣層可原樣使用。 In addition, as for the method of forming a metal thin film on an insulating layer, when a metal layer is used as a protective layer in the manufacturing method of the insulating layer in this embodiment, when the step of removing the metal layer is not performed, The manufactured insulating layer can be used as it is.
粗糙化處理法可為乾式及濕式方法,視方法條件而定。乾式方法之實例包括真空處理、大氣壓力處理、氣體電漿處理、氣體準分子UV處理等。濕式方法之實例包括去膠渣處理(desmear treatment)。經由此等粗糙化處理法,可提高金屬薄膜的表面粗糙度並改善對於沉積在該金屬薄膜上的金屬之黏著性。 The roughening method can be a dry method or a wet method, depending on the method conditions. Examples of the dry method include vacuum processing, atmospheric pressure processing, gas plasma processing, gas excimer UV processing, and the like. Examples of the wet method include desmear treatment. By such a roughening treatment method, the surface roughness of the metal thin film can be improved and the adhesion to the metal deposited on the metal thin film can be improved.
在絕緣層上形成金屬薄膜之步驟可另外包括在沉積金屬薄膜之前在絕緣層上形成表面處理層的步驟。因此,金屬薄膜與絕緣層之間的黏著性可獲得改善。 The step of forming a metal thin film on the insulating layer may further include a step of forming a surface treatment layer on the insulating layer before depositing the metal thin film. Therefore, the adhesion between the metal thin film and the insulating layer can be improved.
具體而言,作為在絕緣層上形成表面處理層之方法的實例,可使用選自離子輔助反應法、離子束處理法、及電漿處理法當中的任一者。電漿處理方法可包括大氣電漿處理法、DC電漿處理法、及RF電漿處理法中之任一者。由於表面處理製程之故,在絕緣層表面上可形成含有反應性官能基之表面處理層。作為在絕緣層上形成表面處理層之方法的另一實例,可提及在絕緣層表面上沉積厚度為50nm至300nm之鉻(Cr)及鈦(Ti)金屬的方法。 Specifically, as an example of a method of forming a surface treatment layer on the insulating layer, any one selected from an ion-assisted reaction method, an ion beam treatment method, and a plasma treatment method can be used. The plasma treatment method may include any one of an atmospheric plasma treatment method, a DC plasma treatment method, and an RF plasma treatment method. Due to the surface treatment process, a surface treatment layer containing a reactive functional group can be formed on the surface of the insulating layer. As another example of a method of forming a surface treatment layer on an insulating layer, a method of depositing chromium (Cr) and titanium (Ti) metals with a thickness of 50 nm to 300 nm on the surface of the insulating layer may be mentioned.
同時,形成其中圖案係形成於金屬薄膜上之光敏性樹脂層的步驟可包括曝光及對在金屬薄膜上形成之光敏性樹脂層進行顯影的步驟。光敏性樹脂層及曝光和顯影的細節可包括上述該一實施態樣中者。 Meanwhile, the step of forming the photosensitive resin layer in which the pattern is formed on the metal thin film may include the steps of exposing and developing the photosensitive resin layer formed on the metal thin film. Details of the photosensitive resin layer and exposure and development may include those in the one embodiment described above.
在將金屬沉積在被光敏性樹脂層圖案暴露之金屬薄膜上的步驟中,被光敏性樹脂層圖案暴露之金屬薄膜意指表面未與該光敏性樹脂層接觸的金屬薄膜之部分。待沉積之金屬可為銅。沉積方法的實例無特別限制,且可使用各種為人熟知的物理或化學氣相沉積法而無限制。作為一般實例,可使用電解銅電鍍法。 In the step of depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern, the metal thin film exposed by the photosensitive resin layer pattern means a portion of the metal thin film whose surface is not in contact with the photosensitive resin layer. The metal to be deposited may be copper. Examples of the deposition method are not particularly limited, and various well-known physical or chemical vapor deposition methods can be used without limitation. As a general example, an electrolytic copper plating method can be used.
在移除光敏性樹脂層及移除暴露之金屬薄膜的步驟中,光阻剝離液體可用於移除光敏性樹脂層之方法的實例中,以及蝕刻劑可用於因光敏性樹脂層之移除而暴 露的金屬薄膜之移除方法的實例中。 In the steps of removing the photosensitive resin layer and removing the exposed metal film, a photoresist peeling liquid may be used in an example of a method for removing the photosensitive resin layer, and an etchant may be used due to the removal of the photosensitive resin layer. An example of a method for removing an exposed metal film.
藉由該多層印刷電路板之製造方法所製造的多層印刷電路板可再次用作增層材料(buildup material)。例如,根據該實施態樣之絕緣層的製造方法之在多層印刷電路板上形成絕緣層的第一步驟以及根據另一實施態樣之多層印刷電路板的製造方法之在絕緣層上形成金屬基底的第二步驟可重複進行。 The multilayer printed circuit board manufactured by the manufacturing method of the multilayer printed circuit board can be used again as a buildup material. For example, according to the first step of forming an insulating layer on a multilayer printed circuit board according to the manufacturing method of the insulating layer in this embodiment, and forming the metal substrate on the insulating layer according to the manufacturing method of the multilayer printed circuit board in another embodiment. The second step can be repeated.
因此,包括在藉由多層印刷電路板之製造方法所製造的多層印刷電路板中之積層層數無特別限制,以及根據應用目的及用途,可具有例如一至二十層。 Therefore, the number of laminated layers included in the multilayer printed circuit board manufactured by the manufacturing method of the multilayer printed circuit board is not particularly limited, and may have, for example, one to twenty layers depending on the purpose and application of the application.
根據本發明,可提出絕緣層的製造方法,其可實現均勻且精細圖案,同時改善成本及生產力方面之效率以及確保優異機械性質;以及使用自該絕緣層的製造方法所獲得之絕緣層的多層印刷電路板之製造方法。 According to the present invention, a method for manufacturing an insulating layer can be proposed, which can achieve a uniform and fine pattern while improving efficiency in terms of cost and productivity and ensuring excellent mechanical properties; and a multilayer using the insulating layer obtained from the method for manufacturing the insulating layer Manufacturing method of printed circuit board.
下文,茲以實例方式更詳細說明本發明。然而,該等實例僅供說明目的,且不應被視為限制本發明之範圍。 Hereinafter, the present invention is described in more detail by way of examples. However, these examples are for illustrative purposes only and should not be considered as limiting the scope of the invention.
製備實例1 Preparation Example 1
將632g作為溶劑之二甲基甲醯胺(DMF)、358g作為N經取代之順丁烯二醯亞胺化合物之BMI-1100 (產品名,由Daiwakasei製造)、及151g作為胺化合物之4-胺基苯乙酸置入具有加熱及冷卻能力並配備有溫度計、攪拌器、回流冷凝器、及定量濕氣分析儀的2公升反應容器中並予以混合,且在85℃下攪拌24小時,以製備固體含量為50%之鹼溶性樹脂溶液。 632 g of dimethylformamide (DMF) as a solvent, 358 g of BMI-1100 (product name, manufactured by Daiwakasei) as an N-substituted maleimide compound, and 151 g of 4- Aminophenylacetic acid was placed in a 2 liter reaction vessel with heating and cooling capabilities and equipped with a thermometer, a stirrer, a reflux condenser, and a quantitative moisture analyzer and mixed, and stirred at 85 ° C for 24 hours to prepare Alkali-soluble resin solution with a solids content of 50%.
製備實例2 Preparation Example 2
將632g作為溶劑之二甲基甲醯胺(DMF)、434g作為N經取代之順丁烯二醯亞胺化合物之對羧苯基順丁烯二醯亞胺、及198g作為胺化合物之4,4-二胺基二苯甲烷置入具有加熱及冷卻能力並配備有溫度計、攪拌器、回流冷凝器、及定量濕氣分析儀的2公升反應容器中並予以混合,且在85℃下攪拌24小時,以製備固體含量為50%之鹼溶性樹脂溶液。 632 g as a solvent of dimethylformamide (DMF), 434 g as an N-substituted maleimide compound, p-carboxyphenyl maleimide, and 198 g as a compound of amine 4, 4-Diaminodiphenylmethane was placed in a 2 liter reaction vessel with heating and cooling capabilities and equipped with a thermometer, a stirrer, a reflux condenser, and a quantitative moisture analyzer, and mixed, and stirred at 85 ° C for 24 hours. Hours to prepare an alkali-soluble resin solution with a solid content of 50%.
製備實例3 Preparation Example 3
將543g作為溶劑之二甲基乙醯胺(DMAc)置入具有加熱及冷卻能力並配備有溫度計、攪拌器、回流冷凝器、及定量濕氣分析儀的2公升反應容器中並予以混合,於其中混合350g之SMA1000(Cray Valley)、144g之4-胺基苯甲酸(PABA)、及49g之4-胺苯酚(PAP)並予以混合。在氮氣氛之下在反應器之溫度固定於80℃之後,使該酸酐和該苯胺反應24小時以形成醯胺酸。然後,在反應器溫度固定於150℃之後,使亞胺化反應持續24小時,以製備固 體含量為50%之鹼溶性樹脂溶液。 543 g of dimethylacetamide (DMAc) as a solvent was placed in a 2 liter reaction vessel having heating and cooling capabilities and equipped with a thermometer, a stirrer, a reflux condenser, and a quantitative moisture analyzer, and mixed. Among them, 350 g of SMA1000 (Cray Valley), 144 g of 4-aminobenzoic acid (PABA), and 49 g of 4-aminophenol (PAP) were mixed and mixed. After the temperature of the reactor was fixed at 80 ° C under a nitrogen atmosphere, the acid anhydride and the aniline were reacted for 24 hours to form amidine. Then, after the reactor temperature was fixed at 150C, the imidization reaction was continued for 24 hours to prepare an alkali-soluble resin solution having a solid content of 50%.
製備實例4 Preparation Example 4
將516g作為溶劑之甲基乙基酮(MEK)置入具有加熱及冷卻能力並配備有溫度計、攪拌器、回流冷凝器、及定量濕氣分析儀的2公升反應容器中並予以混合,添加228g之對羧苯基順丁烯二醯亞胺、85g之對羥苯基順丁烯二醯亞胺、203g之苯乙烯、及0.12g之偶氮雙異丁腈(AIBN)並予以混合。在氮氣氛下反應之溫度逐漸升高至70℃之後,反應持續24小時,以製備固體含量為50%之鹼溶性樹脂溶液。 516 g of methyl ethyl ketone (MEK) as a solvent was placed in a 2 liter reaction vessel equipped with a heating and cooling capacity and equipped with a thermometer, a stirrer, a reflux condenser, and a quantitative moisture analyzer, and mixed, and 228 g was added P-carboxyphenyl maleimide diimide, 85 g of p-hydroxyphenyl maleimide diimide, 203 g of styrene, and 0.12 g of azobisisobutyronitrile (AIBN) and mix them. After the temperature of the reaction was gradually increased to 70 ° C. under a nitrogen atmosphere, the reaction was continued for 24 hours to prepare an alkali-soluble resin solution having a solid content of 50%.
參考圖1,將藉由混合16g在製備實例1中所合成的鹼溶性樹脂、5g作為熱可固化黏合劑之MY-510(由Huntsman製造)、及35g作為無機填料之SC2050 MTO(由Adamatech製造)所獲得的聚合物樹脂組成物塗覆至厚度為3μm且其上黏附載體銅箔5的超薄銅箔4 MT18SD-H(由Mitsui Kinzoku製造),並予以乾燥以製備厚度為15μm之聚合物樹脂層1。然後,聚合物樹脂層1係在85℃下真空積層於電路板上,該電路板上銅線2係形成於銅箔積層3上,並且在110℃下將厚度為15μm之光敏性乾燥膜阻劑KL 1015(由Kolon Industries製造)6積層在該載體銅箔5上。 Referring to FIG. 1, by mixing 16 g of an alkali-soluble resin synthesized in Preparation Example 1, 5 g of MY-510 (manufactured by Huntsman) as a heat-curable adhesive, and 35 g of SC2050 MTO (manufactured by Adamatech) as an inorganic filler The obtained polymer resin composition was applied to an ultra-thin copper foil 4 MT18SD-H (manufactured by Mitsui Kinzoku) having a thickness of 3 μm and a carrier copper foil 5 adhered thereto, and dried to prepare a polymer having a thickness of 15 μm Resin layer 1. Then, the polymer resin layer 1 was vacuum-laminated on a circuit board at 85 ° C, and the copper wire 2 on the circuit board was formed on the copper foil laminate 3, and a photosensitive dry film having a thickness of 15 m was resisted at 110 ° C Agent KL 1015 (manufactured by Kolon Industries) 6 was laminated on the carrier copper foil 5.
使具有30μm直徑之圓形負型光罩與光敏性乾燥膜阻劑6接觸,並用紫外線照射(光量為25mJ/cm2)。然後,經由在30℃之1%碳酸鈉顯影劑對該乾燥膜阻劑6進行顯影,以形成特定圖案。 A circular negative mask having a diameter of 30 μm was brought into contact with the photosensitive drying film resist 6 and irradiated with ultraviolet rays (a light amount of 25 mJ / cm 2 ). Then, the dried film resist 6 is developed through a 1% sodium carbonate developer at 30 ° C. to form a specific pattern.
隨後,載體銅箔5及超薄銅箔4係藉由用蝕刻劑處理來進行蝕刻。此時,其上形成有圖案之光敏性乾燥膜阻劑6係作為載體銅箔5及超薄銅箔4的保護層,以使與該光敏性乾燥膜阻劑6相同圖案均等地形成在載體銅箔5及超薄銅箔4中。 Subsequently, the carrier copper foil 5 and the ultra-thin copper foil 4 are etched by treatment with an etchant. At this time, the patterned photosensitive drying film resist 6 is used as a protective layer for the carrier copper foil 5 and the ultra-thin copper foil 4 so that the same pattern as the photosensitive drying film resist 6 is formed on the carrier equally. Copper foil 5 and ultra-thin copper foil 4.
隨後,將超薄銅箔4及載體銅箔5分離,以使載體銅箔5及積層在載體銅箔5上之光敏性乾燥膜阻劑6被移除。 Subsequently, the ultra-thin copper foil 4 and the carrier copper foil 5 are separated, so that the carrier copper foil 5 and the photosensitive dry film resist 6 laminated on the carrier copper foil 5 are removed.
其次,聚合物樹脂層1係經由在30℃之1%碳酸鈉顯影劑進行顯影。此時,其上形成圖案之超薄銅箔4係作為聚合物樹脂層1的保護層,因此在形成與超薄銅箔4相同圖案時,通路孔7均等地形成在聚合物樹脂層1中。 Next, the polymer resin layer 1 was developed through a 1% sodium carbonate developer at 30 ° C. At this time, the ultra-thin copper foil 4 on which the pattern is formed serves as a protective layer of the polymer resin layer 1. Therefore, when the same pattern as the ultra-thin copper foil 4 is formed, the via holes 7 are uniformly formed in the polymer resin layer 1. .
隨後,在110℃之溫度進行熱固化1小時,然後用蝕刻劑處理以移除超薄銅箔4,並且另外在200℃之溫度熱固化製程1小時以製造絕緣層。 Subsequently, thermal curing was performed at a temperature of 110 ° C. for 1 hour, and then treated with an etchant to remove the ultra-thin copper foil 4, and an additional thermal curing process was performed at a temperature of 200 ° C. for 1 hour to manufacture an insulating layer.
參考圖2,經由濺鍍法,當用氣相沉積設備將氬及氧之混合氣體供應至實施例1中所製造的絕緣層之上表面以及通路孔7之側表面時,將鈦(Ti)金屬沉積為厚度50 nm以及銅(Cu)金屬沉積為厚度0.5μm以形成晶種層8。 Referring to FIG. 2, when a mixed gas of argon and oxygen is supplied to the upper surface of the insulating layer and the side surface of the via hole 7 manufactured in Example 1 by a vapor deposition method through a sputtering method, titanium (Ti) The metal was deposited to a thickness of 50 nm and the copper (Cu) metal was deposited to a thickness of 0.5 μm to form the seed layer 8.
隨後,將該光敏性樹脂層曝光及在晶種層8上顯影以形成光敏性樹脂圖案9。然後,經由電解電鍍將銅所製成的金屬基底10形成於晶種層8上。其次,使用光敏性樹脂剝離液體將光敏性樹脂圖案9移除,從而經由蝕刻移除暴露的晶種層8,從而製造多層印刷電路板。 Subsequently, the photosensitive resin layer is exposed and developed on the seed layer 8 to form a photosensitive resin pattern 9. Then, a metal substrate 10 made of copper is formed on the seed layer 8 by electrolytic plating. Next, the photosensitive resin pattern 9 is removed using a photosensitive resin peeling liquid to remove the exposed seed layer 8 via etching, thereby manufacturing a multilayer printed circuit board.
絕緣層係以與實施例1相同方式製造,惟使用製備實例中2所合成的鹼溶性樹脂代替實施例1之絕緣層的製造方法中之製備實例1中所合成的鹼溶性樹脂。 The insulating layer was manufactured in the same manner as in Example 1, except that the alkali-soluble resin synthesized in Preparation Example 2 was used instead of the alkali-soluble resin synthesized in Preparation Example 1 in the manufacturing method of the insulating layer in Example 1.
絕緣層係以與實施例1相同方式製造,惟使用製備實例中3所合成的鹼溶性樹脂代替實施例1之絕緣層的製造方法中之製備實例1中所合成的鹼溶性樹脂。 The insulating layer was produced in the same manner as in Example 1, except that the alkali-soluble resin synthesized in 3 in Preparation Example was used instead of the alkali-soluble resin synthesized in Preparation Example 1 in the method of manufacturing the insulating layer in Example 1.
絕緣層係以與實施例1相同方式製造,惟使用製備實例中4所合成的鹼溶性樹脂代替實施例1之絕緣層的製造方法中之製備實例1中所合成的鹼溶性樹脂。 The insulating layer was produced in the same manner as in Example 1, except that the alkali-soluble resin synthesized in Preparation Example 4 was used instead of the alkali-soluble resin synthesized in Preparation Example 1 in the manufacturing method of the insulating layer in Example 1.
將藉由混合16g製備實例1中所合成之鹼溶性 樹脂、作為熱可固化黏合劑之5g之MY-510(由Huntsman製造)、及作為無機填料之35g之SC 2050 MTO(由Adamatech製造)所獲得的聚合物樹脂組成物塗布至PET膜(25μm)上並予以乾燥,以製備厚度為15μm的聚合物樹脂層1。然後,該聚合物樹脂層1係在85℃下積層於其上銅線2係形成於銅箔積層物3上的電路板上,並移除該PET膜。 By mixing 16 g of the alkali-soluble resin synthesized in Preparation Example 1, 5 g of MY-510 (manufactured by Huntsman) as a heat-curable adhesive, and 35 g of SC 2050 MTO (manufactured by Adamatech) as an inorganic filler. The obtained polymer resin composition was applied onto a PET film (25 μm) and dried to prepare a polymer resin layer 1 having a thickness of 15 μm. Then, the polymer resin layer 1 is laminated on a circuit board on which a copper wire 2 is formed on a copper foil laminate 3 at 85 ° C., and the PET film is removed.
在110℃下將厚度為15μm之光敏性乾燥膜阻劑KL 1015(由Kolon Industries製造)積層在聚合物樹脂層上。使具有30μm直徑之圓形負型光罩與光敏性乾燥膜阻劑接觸,並用紫外線照射(光量為25mJ/cm2)。然後,該光敏性乾燥膜阻劑及該聚合物樹脂層係經由在30℃之1%碳酸鈉顯影劑依序進行顯影。 A photosensitive dry film resist KL 1015 (manufactured by Kolon Industries) having a thickness of 15 μm was laminated on a polymer resin layer at 110 ° C. A circular negative mask having a diameter of 30 μm was brought into contact with a photosensitive dry film resist, and irradiated with ultraviolet rays (a light amount of 25 mJ / cm 2 ). Then, the photosensitive dry film resist and the polymer resin layer are sequentially developed through a 1% sodium carbonate developer at 30 ° C.
此時,該光敏性乾燥膜阻劑作為該聚合物樹脂層之保護層,並在形成與光敏性乾燥膜阻劑相同圖案時,通路孔均等地形成於該聚合物樹脂層中。 At this time, the photosensitive dry film resist acts as a protective layer of the polymer resin layer, and when the same pattern as the photosensitive dry film resist is formed, via holes are uniformly formed in the polymer resin layer.
隨後,在100℃之溫度下進行熱固化1小時,然後用3%氫氧化鈉阻劑剝離液體處理以移除該光敏性乾燥膜阻劑,並在200℃之溫度下進一步進行熱固化1小時,以製造絕緣層。 Subsequently, heat curing was performed at a temperature of 100 ° C for 1 hour, and then the liquid was stripped with a 3% sodium hydroxide resist to remove the photosensitive dry film resist, and further heat cured at 200 ° C for 1 hour. To make an insulating layer.
多層印刷電路板係以與實施例2相同方式製造,惟使用比較例1中所製造之絕緣層代替實施例1中所製造的絕緣層。 The multilayer printed circuit board was manufactured in the same manner as in Example 2, except that the insulating layer manufactured in Comparative Example 1 was used instead of the insulating layer manufactured in Example 1.
在上述實施例及比較例中所獲得之絕緣層的物理性質係藉由下列方法測量,且結果顯示於下表1。 The physical properties of the insulating layers obtained in the above examples and comparative examples were measured by the following methods, and the results are shown in Table 1 below.
1.通路孔之直徑 Diameter of via hole
使用光學顯微鏡測量實施例1及3至7以及比較例1中所獲得之絕緣層的上開口(通路孔)之直徑。 The diameter of the upper opening (via hole) of the insulating layer obtained in Examples 1 and 3 to 7 and Comparative Example 1 was measured using an optical microscope.
2.吸濕性造成的金屬黏著力 2. Metal adhesion caused by hygroscopicity
使實施例2及比較例2所獲得之多層印刷電路板在135℃與85%吸濕條件下保持48小時,然後根據IPC-TM-650之標準測量金屬的剝離強度。由此獲得金屬黏著力。 The multilayer printed circuit boards obtained in Example 2 and Comparative Example 2 were kept at 135 ° C and 85% moisture absorption for 48 hours, and then the peel strength of the metal was measured according to the standard of IPC-TM-650. As a result, metal adhesion is obtained.
3.高度加速之溫度及濕度應力測試(HAST)抗性 3. Highly accelerated temperature and humidity stress test (HAST) resistance
根據JESD 22-A101之標準確認實施例2及比較例2所獲得之多層印刷電路板的HAST抗性。具體而言,對於寬度為50μm、間隔為50μm、且厚度為12μm之測試件的電路板施加3V電壓,然後使之保持168小時,然後根據下列標準確認測試件之電路板是否存在外觀異常。 The HAST resistance of the multilayer printed circuit boards obtained in Example 2 and Comparative Example 2 was confirmed according to the JESD 22-A101 standard. Specifically, a voltage of 3 V was applied to the circuit board of the test piece having a width of 50 μm, an interval of 50 μm, and a thickness of 12 μm, and then the voltage was maintained for 168 hours. Then, the appearance of the circuit board of the test piece was confirmed according to the following criteria.
OK:膜外觀中未觀察到異常 OK: No abnormality was observed in the appearance of the film
NG:膜中觀察到水泡及剝離 NG: Blistering and peeling were observed in the film
如表1所示,在通路孔僅使用光敏性乾燥膜作為保護層所形成的比較例1之絕緣層的情況下,通路孔之直徑顯示為45μm,然而在實施例1及3至5中所製造的絕緣層中所含之通路孔的直徑降至32μm或33μm。因而,確認在實施例之情況下,可獲致較精細圖案。 As shown in Table 1, in the case of the insulating layer of Comparative Example 1 in which the via hole was formed using only a photosensitive dry film as a protective layer, the diameter of the via hole was 45 μm. However, in Examples 1 and 3 to 5, The diameter of the via hole included in the manufactured insulating layer was reduced to 32 μm or 33 μm. Therefore, it was confirmed that in the case of the embodiment, a finer pattern can be obtained.
此外,確認在自比較例1之絕緣層所獲得的比較例2之多層印刷電路板的情況下,測得金屬黏著力為0.3kgf/cm,然而在實施例2之多層印刷電路板的情況下,測得之金屬黏著力高至0.4kgf/cm,從而改善介於絕緣層與傳導層之間的界面黏著性,並展現優異的HAST抗性。 In addition, it was confirmed that in the case of the multilayer printed wiring board of Comparative Example 2 obtained from the insulating layer of Comparative Example 1, the metal adhesion was measured to be 0.3 kgf / cm. However, in the case of the multilayer printed wiring board of Example 2, The measured metal adhesion is as high as 0.4 kgf / cm, thereby improving the interface adhesion between the insulating layer and the conductive layer, and exhibiting excellent HAST resistance.
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