CN117120929A - Laminated structure, dry film, cured product, and electronic component - Google Patents
Laminated structure, dry film, cured product, and electronic component Download PDFInfo
- Publication number
- CN117120929A CN117120929A CN202280025323.9A CN202280025323A CN117120929A CN 117120929 A CN117120929 A CN 117120929A CN 202280025323 A CN202280025323 A CN 202280025323A CN 117120929 A CN117120929 A CN 117120929A
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- resin
- resin layer
- resin composition
- film
- laminated structure
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- LMIOYAVXLAOXJI-UHFFFAOYSA-N 3-ethyl-3-[[4-[(3-ethyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(CC)COC2)C=CC=1COCC1(CC)COC1 LMIOYAVXLAOXJI-UHFFFAOYSA-N 0.000 description 1
- AOXLOPQXIGICOF-UHFFFAOYSA-N 3-methyl-3-[(3-methyloxetan-3-yl)methoxymethoxymethoxymethyl]oxetane Chemical compound C1OCC1(C)COCOCOCC1(C)COC1 AOXLOPQXIGICOF-UHFFFAOYSA-N 0.000 description 1
- UVJGOUQARONWII-UHFFFAOYSA-N 3-methyl-3-[[4-[(3-methyloxetan-3-yl)methoxymethyl]phenyl]methoxymethyl]oxetane Chemical compound C=1C=C(COCC2(C)COC2)C=CC=1COCC1(C)COC1 UVJGOUQARONWII-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Natural products OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- WYBZFSGKJOYRQH-UHFFFAOYSA-N [nitro(phenyl)methyl] carbamate Chemical group NC(=O)OC([N+]([O-])=O)C1=CC=CC=C1 WYBZFSGKJOYRQH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000006307 alkoxy benzyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class 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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- 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
-
- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Materials For Photolithography (AREA)
Abstract
Providing: a laminated structure having excellent photopatternability while achieving both the opposite characteristics of B-HAST resistance and crack resistance at a high level. A laminated structure is characterized by comprising: a resin layer in which 2 layers of a resin layer (a) formed from a resin composition (a) and a resin layer (B) formed from a resin composition (B) are laminated, wherein the resin composition (B) of the resin layer (B) includes: an alkali-soluble resin; a photo-alkali generator having a function as a photopolymerization initiator, or a photopolymerization initiator and a photo-alkali generator; and a thermosetting resin, wherein the resin composition (a) of the resin layer (A) comprises: the difference between the gloss sensitivity and the residual sensitivity, which were obtained by measuring the thickness of the coating film of the pattern formed by exposing the 2 resin layers to light from the resin layer (B) side through a stepwise exposure meter and then performing the PEB step and the thickness of the coating film of the pattern formed by exposing and then developing the resin layer after the PEB step, was 20 or less.
Description
Technical Field
The present invention relates to a laminated structure, a dry film, a cured product, and an electronic component using the same, which are suitable for use in a semiconductor package or the like.
Background
In recent years, as printed circuit boards having a smaller size and lighter weight have been more densely packed, solder resists have been required to have higher workability and higher performance. In addition, recently, along with miniaturization, weight saving, and high performance of electronic devices, miniaturization and mass-production of semiconductor packages have been advanced. Various semiconductor packages have been proposed to cope with such a high density.
In recent years, there has been a demand for a solder resist layer used for various semiconductor packages which cope with a high density, which has high reliability in a use environment and high reliability for a long period of time. One of the reliability tests relating to reliability in a use environment is a bias applied high acceleration stress test (hereinafter referred to as B-HAST), and one of the reliability tests for a long time is a crack resistance test in a cold and hot cycle. As a photocurable/thermosetting resin composition excellent in B-HAST resistance, there is a resin composition comprising a carboxyl group-containing photosensitive resin obtained as follows: a reaction product is obtained by reacting a compound (a) having 2 or more phenolic hydroxyl groups in 1 molecule with an alkylene oxide (b) or a cyclic carbonate compound (c), and an unsaturated group-containing monocarboxylic acid (d) and a polybasic acid anhydride (e) (patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent No. 5183073
Disclosure of Invention
Problems to be solved by the invention
The resin composition described in comparative document 1 contains a carboxyl group-containing photosensitive resin having a rigid skeleton, and therefore has excellent B-HAST resistance, but on the contrary, crack resistance in the cold and hot cycles is not necessarily sufficient from the level of recent requirements.
The resin composition comprising the carboxyl group-containing polyurethane resin and having a softer skeleton is formed instead of the carboxyl group-containing photosensitive resin having a rigid skeleton, and as a result, crack resistance is improved, but B-HAST resistance tends to be lowered.
It is therefore an object of the present invention to provide: not only can the opposite characteristics of B-HAST resistance and crack resistance be simultaneously achieved at a high level, but also the laminated structure, dry film, cured product and electronic component have excellent photo-patterning property.
Solution for solving the problem
The present inventors have studied intensively to solve the above problems, and as a result, have confirmed that: by forming a laminate of two layers having different compositions, the opposite properties of B-HAST resistance and crack resistance can be achieved at a high level. In a laminated structure in which only a layer suitable for B-HAST resistance and a layer suitable for crack resistance are laminated, it is naturally difficult to control the sensitivity of each layer, and therefore it is determined that: it is difficult to obtain good photo-patternability. In recent years, in the use of semiconductor packages, excellent photopatternability is demanded that the opening diameter of a Solder Resist Opening (SRO) is 50 μm or less.
Accordingly, the present invention has been completed as a result of further continued research and development to obtain a laminated structure having not only B-HAST resistance and crack resistance but also excellent photopatternability.
That is, the laminated structure of the present invention is characterized by comprising: a resin layer comprising 2 layers of a resin layer (A) formed from a resin composition (a) and a resin layer (B) formed from a resin composition (B) are laminated,
the resin composition (B) of the resin layer (B) contains: an alkali-soluble resin; a photo-alkali generator having a function as a photopolymerization initiator, or a photopolymerization initiator and a photo-alkali generator; a thermosetting resin, and a method for producing the same,
the resin composition (a) of the resin layer (a) contains: a carboxyl group-containing resin and a thermosetting resin, substantially free of a photopolymerization initiator,
the difference between the gloss sensitivity and the residual sensitivity, which was obtained by measuring the thickness of the coating film of the pattern formed by exposing the 2 resin layers from the resin layer (B) side through the step exposure meter and performing the PEB (POST EXPOSURE BAKE) step, and the thickness of the coating film of the pattern formed by exposing and performing the PEB step and then developing, was 20 or less. Details of the PEB step are as follows.
Here, the definition of the gloss sensitivity and the residual sensitivity is as follows.
When the thickness of the 2-layer resin layer before the pattern formed by exposing the 2-layer resin layer from the resin layer (B) side through a stepwise exposure meter and performing the PEB step is 100%, the maximum value of the number of exposure meter steps of the thickness of the coating film remaining 95% or more after the exposure and the PEB step and after the development is defined as gloss sensitivity, and the maximum value of the number of exposure meter steps of the thickness of the coating film remaining 5% or less after the development is defined as residual sensitivity, and the thickness of the coating film before the development is defined as 100%.
In the present invention, the thickness of the coating film of the pattern formed is in accordance with JIS K5600-1-7: 2014, the measurement is performed by a difference meter between a measured value obtained as the thickness of the whole coating film and a measured value obtained as the thickness of the substrate. The measurement method is as follows: according to the mechanical measurement method, the film thickness before development of the pattern formed after exposure of the 2 resin layers from the resin layer (B) side through a stepwise exposure meter and the PEB step at 90 ℃ for 30 minutes and the film thickness of the residual film formed after the PEB step after exposure and development were measured by a thickness measuring instrument (manufactured by DIGIMICRO MF-501, nikon Corporation), respectively, and when the film thickness before development was set to 100%, the maximum value of the number of exposure meter steps remaining after the development was set to 95% or more, and when the film thickness before development was set to 100%, the maximum value of the number of exposure meter steps after the development was set to 5% or less, respectively, were set to the residual sensitivity.
In the laminated structure of the present invention, the thickness of the resin layer (B) is 2 μm or more and half or less of the thickness of the resin layer (A), and the thickness of the resin layer (A) is preferably 10 to 80 μm, more preferably 20 to 60 μm.
The dry film of the present invention is characterized by comprising: the laminated structure of the present invention; and a film provided in contact with at least one of the surface of the resin layer (B) and the surface of the resin layer (A) of the laminated structure.
The cured product of the present invention is obtained by curing the laminated structure of the present invention or the laminated structure of the dry film of the present invention.
The electronic component of the present invention is characterized by comprising the cured product of the present invention.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there may be provided: a laminated structure having excellent photopatternability as well as B-HAST resistance and crack resistance, a dry film, a cured product thereof, and an electronic component using the cured product.
Detailed Description
Embodiments of the laminated structure, dry film, cured product, and electronic component according to the present invention are described in detail below.
(laminate Structure)
The laminated structure of the present invention comprises: a resin layer comprising 2 layers of a resin layer (A) formed from a resin composition (a) and a resin layer (B) formed from a resin composition (B) are laminated,
The resin composition (B) of the resin layer (B) contains: an alkali-soluble resin; a photo-alkali generator having a function as a photopolymerization initiator, or a photopolymerization initiator and a photo-alkali generator; a thermosetting resin, and a method for producing the same,
the resin composition (a) of the resin layer (a) contains: a carboxyl group-containing resin and a thermosetting resin, substantially free of a photopolymerization initiator,
the difference between the gloss sensitivity and the residual sensitivity, which is obtained by measuring the thickness of the coating film of the pattern formed by exposing the 2 resin layers from the resin layer (B) side through the step exposure meter and then performing the PEB step, and the thickness of the coating film of the pattern formed by exposing and then performing the PEB step, is 20 or less, more preferably 14 or less.
When the laminated structure is formed on a substrate, the layer in contact with the substrate is a resin layer (a), and the layer in contact with the surface of the resin layer (a) opposite to the surface in contact with the substrate is a resin layer (B). That is, the laminated structure has a structure in which a resin layer (a) and a resin layer (B) are laminated in this order on a base material. Examples of the substrate include a printed circuit board, a flexible printed circuit board, and the like, each of which has a circuit formed in advance of copper or the like.
The resin layer (B) is formed from a resin composition (B) containing: an alkali-soluble resin; a photo-alkali generator having a function as a photopolymerization initiator, or a photopolymerization initiator and a photo-alkali generator; and a thermosetting resin. The resin composition (B) of the resin layer (B) containing these components is a photosensitive thermosetting resin composition as follows: the photopolymerization initiator reacts with the alkali-soluble resin by irradiation with light to have photosensitivity, and the photoacid generator serving as a polymerization initiator by heating functions as a catalyst to perform heat curing.
The resin layer (a) is formed from a resin composition (a) containing: the carboxyl group-containing resin and the thermosetting resin are substantially free of photopolymerization initiator. The substantial absence of the photopolymerization initiator means that the photopolymerization initiator is less than 0.5 parts by mass per 100 parts by mass of the carboxyl group-containing resin contained in the resin composition (a).
Since the resin composition (a) of the resin layer (a) containing these components does not contain a photopolymerization initiator, the resin composition (a) has no photosensitivity in a single layer, but is laminated in contact with the resin layer (B), and therefore, an active material such as a radical generated by the photopolymerization initiator contained in the resin layer (B) diffuses into the resin layer (a), and the resin layer (a) also has photosensitivity. In addition, heat curing can be performed by heating. Therefore, the laminated structure can simultaneously form a predetermined pattern in the resin layer (B) and the resin layer (a) by development. Particularly, in the case of performing the PEB step after exposure, the effect of simultaneously forming the pattern is remarkable by thermal diffusion at this time.
[ resin layer (A) ]
(resin composition (a) of resin layer (A))
The resin layer (a) is formed of the resin composition (a). It is desirable that the resin composition (a) of the resin layer (a) not only functions as an adhesive layer with a substrate but also has a characteristic of coping with various circuit patterns. Therefore, the resin composition (a) of the resin layer (a) is preferably a photosensitive thermosetting resin composition as follows: the resin having carboxyl groups, the resin containing carboxyl groups therein and the thermosetting component are subjected to an addition reaction by heating after exposure using a base generated from an alkaline generator as a catalyst, and the unexposed portion is removed by an alkaline solution, whereby development can be performed.
Specific examples of the carboxyl group-containing resin contained in the resin composition (a) of the resin layer (a) include the following compounds.
(1) Carboxyl group-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth) acrylic acid with unsaturated group-containing compounds such as styrene, alpha-methylstyrene, lower alkyl (meth) acrylate, isobutylene and the like.
(2) Carboxyl group-containing polyurethane resins obtained by polyaddition reaction of a diisocyanate such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate or aromatic diisocyanate, a carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutyric acid, and a diol compound such as a polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol a alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(3) Polyurethane resins are obtained by polyaddition reaction of a diisocyanate compound such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, or aromatic diisocyanate with a diol compound such as a polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol a alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group or an alcoholic hydroxyl group, and a carboxyl group-containing polyurethane resin having a terminal end which is obtained by reacting the terminal end of the polyurethane resin with an acid anhydride.
(4) The carboxyl group-containing polyurethane resin is obtained by the polyaddition reaction of a diisocyanate with a 2-functional epoxy resin such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisxylenol epoxy resin, bisphenol epoxy resin or the like, or a partial anhydride-modified product thereof, a carboxyl group-containing diol compound, and a diol compound.
(5) A carboxyl group-containing polyurethane resin obtained by adding a compound having 1 hydroxyl group and 1 or more (meth) acryloyl groups in the molecule, such as hydroxyalkyl (meth) acrylate, to the synthesis of the resin of the above (2) or (4) and subjecting the resultant resin to terminal (meth) acrylation.
(6) A carboxyl group-containing polyurethane resin obtained by adding a compound having 1 isocyanate group and 1 or more (meth) acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, to the synthesis of the resin of (2) or (4) above, and subjecting the resultant resin to terminal (meth) acrylation.
(7) A carboxyl group-containing resin obtained by reacting a multifunctional epoxy resin with (meth) acrylic acid, and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, or the like to a hydroxyl group present in a side chain.
(8) A carboxyl group-containing resin is obtained by reacting a (meth) acrylic acid with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl groups of a 2-functional epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the hydroxyl groups thus formed.
(9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane compound with a dicarboxylic acid and adding a dibasic acid anhydride to the primary hydroxyl group formed.
(10) A carboxyl group-containing resin is obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with an alkylene oxide such as ethylene oxide or propylene oxide to obtain a reaction product, reacting the reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the reaction product obtained thereby with a polybasic acid anhydride.
(11) A carboxyl group-containing resin is obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate to obtain a reaction product, reacting the reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the reaction product obtained thereby with a polybasic acid anhydride.
(12) And a carboxyl group-containing resin obtained by reacting an epoxy compound having a plurality of epoxy groups in 1 molecule with a compound having at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in 1 molecule such as p-hydroxyphenylethanol, and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting the alcoholic hydroxyl group of the obtained reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, and the like.
(13) A carboxyl group-containing resin having at least any one of an amide structure and an imide structure.
(14) A carboxyl group-containing photosensitive resin having a copolymerization structure, which is obtained by adding a carboxyl group-containing copolymer resin comprising, as monomers, a maleimide such as N-phenylmaleimide or N-benzylmaleimide, or a maleimide derivative, an unsaturated carboxylic acid such as (meth) acrylic acid, or a hydroxyl group-containing unsaturated group-containing compound such as hydroxyalkyl (meth) acrylate, and an unsaturated group-containing compound having an aromatic ring such as styrene, alpha-methylstyrene, or vinyltoluene, to a carboxyl group-containing copolymer resin comprising, as monomers, a glycidyl (meth) acrylate, alpha-methylglycidyl (meth) acrylate, or epoxycyclohexylmethyl (meth) acrylate, or a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in the molecule.
(15) The carboxyl group-containing resin described in (1) to (13) above is obtained by further adding a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in the molecule, such as glycidyl (meth) acrylate and α -methyl glycidyl (meth) acrylate.
In the present specification, (meth) acrylate is a term generically used for acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.
The carboxyl group-containing resin contained in the resin composition (a) of the resin layer (a) may be used not limited to the above-mentioned one, but may be used alone of 1 kind or in combination of plural kinds. Among the carboxyl group-containing resins, the unit having a photosensitive group of (10) an Ethylene Oxide (EO) -Propylene Oxide (PO) modified resin as a phenolic resin starting and the unit having a photosensitive group of (11) an ethylene carbonate-propylene carbonate modified resin as a phenolic resin starting are independent from the developing unit having a carboxyl group, and therefore, after the photosensitive group is crosslinked by exposure, the contrast between the exposed portion and the unexposed portion is preferably obtained without affecting the developability of the developing unit having a carboxyl group, and the sensitivity is preferably adjusted. The carboxyl group-containing resins of the above (10) and (11) may be used in combination with the carboxyl group-containing polyurethane resins of the above (2) to (6).
The amount of the carboxyl group-containing resin contained in the resin composition (a) of the resin layer (a) is 10 to 70% by mass based on the total amount of the solid components of the resin composition (a). By setting the content to 10 mass% or more, the coating film strength can be improved. Further, by setting the content to 70 mass% or less, the tackiness becomes appropriate, and the workability improves. In particular, in the present invention, the resin (10) and (11) is preferably 30 to 100% by mass, more preferably 70 to 100% by mass, of the carboxyl group-containing resin of the resin layer (a) in order to adjust the residual sensitivity. If the amount is within this range, the difference between the gloss sensitivity and the residual sensitivity can be reduced to 20 or less levels with a constant exposure amount.
In the present invention, from the viewpoint of adjusting the gloss sensitivity and residual sensitivity of the resin laminate structure, it is preferable that the resin composition (a) of the resin layer (a) contains substantially no photopolymerization initiator. The substantial absence of the photopolymerization initiator means that the photopolymerization initiator is less than 0.5 parts by mass per 100 parts by mass of the carboxyl group-containing resin contained in the resin composition (a).
This is because, in order to form a pattern simultaneously by development in a laminated structure of the resin layer (B) and the resin layer (a), the resin composition (B) of the resin layer (B) contains a photobase generator having a function as a photopolymerization initiator, and thus it is sufficient to cure the resin laminate. It is assumed that if the photopolymerization initiator is not contained in the resin composition (a) of the resin layer (a), the residual sensitivity tends to be increased, and the fine patterning is adversely affected.
[ thermosetting resin ]
The thermosetting resin contained in the resin composition (a) of the resin layer (a) is a resin having a functional group capable of undergoing a heat-based curing reaction. The thermosetting resin is not particularly limited, and epoxy resins, oxetane compounds, compounds having 2 or more sulfide groups in the molecule, namely episulfide resins, melamine resins, benzoguanamine resins, melamine derivatives, amino resins such as benzoguanamine derivatives, blocked isocyanate compounds, cyclic carbonate compounds, bismaleimides, carbodiimides, and the like may be used, or they may be used in combination.
The epoxy resin is a resin having an epoxy group, and any of conventionally known ones can be used, and examples thereof include a 2-functional epoxy resin having 2 epoxy groups in a molecule, and a multifunctional epoxy resin having a plurality of epoxy groups in a molecule. It is to be noted that hydrogenated 2-functional epoxy resins are also possible.
Examples of the epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol a type epoxy resin, brominated bisphenol a type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, alicyclic type epoxy resin, aliphatic chain type epoxy resin, phosphorus-containing epoxy resin, anthracene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, aminophenol type epoxy resin, amino cresol type epoxy resin, alkylphenol type epoxy resin, and the like. These epoxy resins may be used singly or in combination of 2 or more.
The epoxy resin may be any of a solid epoxy resin, a semi-solid epoxy resin, and a liquid epoxy resin. In the present specification, the solid epoxy resin means an epoxy resin which is solid at 40 ℃, the semisolid epoxy resin means an epoxy resin which is solid at 20 ℃ and liquid at 40 ℃, and the liquid epoxy resin means an epoxy resin which is liquid at 20 ℃.
Examples of the solid epoxy resin include naphthalene type epoxy resins such as EPICLON HP-4700 (naphthalene type epoxy resin) manufactured by DIC Co., ltd., EXA4700 (4-functional naphthalene type epoxy resin) manufactured by DIC Co., ltd., and NC-7000 (naphthalene skeleton-containing multifunctional solid epoxy resin) manufactured by Japanese chemical Co., ltd.; an epoxide (triphenol type epoxy resin) of a condensate of phenols such as EPPN-502H (triphenol epoxy resin) manufactured by Kagaku Co., ltd., and an aromatic aldehyde having a phenolic hydroxyl group; dicyclopentadiene aralkyl type epoxy resins such as EPICLON HP-7200H (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin) manufactured by DIC Co., ltd; biphenyl aralkyl type epoxy resins such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) manufactured by japan chemical company, ltd; biphenyl/phenol novolac type epoxy resins such as NC-3000L manufactured by japan chemical company; novolac type epoxy resins such as EPICLON 660, EPICLON 690, EOCN-104S, manufactured by DIC Co., ltd; biphenyl type epoxy resins such as YX-4000 manufactured by Mitsubishi chemical corporation; NIPPON STEEL Chemical & Material Co., ltd. Phosphorus-containing epoxy resins such as TX 0712; and tris (2, 3-epoxypropyl) isocyanurate such as TEPIC, manufactured by daily chemical company.
Examples of the semi-solid epoxy resin include bisphenol A type epoxy resins such as EPICLON 860, EPICLON 900-IM, EPICLON EXA-4816, EPICLON EXA-4812, NIPPON STEEL Chemical & Material Co., ltd., EPOTOHOTO YD-134, jER834, jER872, and ELA-134, manufactured by Mitsubishi chemical Co., ltd.; naphthalene type epoxy resins such as EPICLON HP-4032 manufactured by DIC Co., ltd; and phenol novolac type epoxy resins such as EPICLON N-740 manufactured by DIC Co., ltd.
Examples of the liquid epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, phenol novolac type epoxy resin, t-butyl catechol type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin, alicyclic type epoxy resin, and the like.
Next, examples of oxetane compounds include polyfunctional oxetanes such as bis [ (3-methyl-3-oxetylmethoxy) methyl ] ether, bis [ (3-ethyl-3-oxetylmethoxy) methyl ] ether, 1, 4-bis [ (3-methyl-3-oxetylmethoxy) methyl ] benzene, 1, 4-bis [ (3-ethyl-3-oxetylmethoxy) methyl ] benzene, 3-methyl-3-oxetanyl) methyl acrylate, 3-ethyl-3-oxetanyl) methyl acrylate, 3-methyl-3-oxetanyl-methyl methacrylate, and 3-ethyl-3-oxetanyl-methyl methacrylate, and oligomers or copolymers thereof, and hydroxyl group-containing resins such as oxetane and novolak resins, poly (p-hydroxystyrene), cardo bisphenols, calixarenes, resorcinol calixarenes, and silsesquioxane. Further, copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate and the like can be mentioned.
Examples of the episulfide resin include bisphenol a episulfide resin. Further, episulfide resins obtained by replacing the oxygen atom of the epoxy group of an epoxy resin with a sulfur atom by the same synthesis method can also be used.
Among thermosetting resins, epoxy resins are preferably used. Further, at least one of a solid epoxy resin and a semisolid epoxy resin is preferable from the viewpoint of obtaining a cured product having a high glass transition temperature (Tg) and excellent crack resistance. The epoxy resin is preferably an aromatic epoxy resin from the viewpoint of preferable physical properties of the cured product, and among them, naphthalene-type epoxy resin and biphenyl-type epoxy resin are more preferable. In the present specification, the aromatic epoxy resin means an epoxy resin having an aromatic ring skeleton in its molecule.
The molecular weight of the thermosetting resin contained in the resin composition (a) of the resin layer (a) is preferably 100 to 2000 in terms of weight average molecular weight in order to adjust the developability and cured coating film characteristics. If the amount is within this range, the number of exposure table stages of the residual sensitivity can be reduced if a component having a low molecular weight, i.e., a weight average molecular weight (Mw) of 100 to 1000 is used, and if a component having a high molecular weight, i.e., a weight average molecular weight of more than 1000 to 2000 is used, the number of exposure table stages of the residual sensitivity can be increased. In the examples of the present invention, the number of exposure table steps of the residual sensitivity was adjusted so as not to excessively increase by using an epoxy resin having a weight average molecular weight of 1000 or less.
The thermosetting resin may be used alone or in combination of 2 or more. The blending ratio of the thermosetting resin is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and still more preferably 19 to 40% by mass, based on the total amount of the resin composition (a), in terms of solid matter conversion.
[ photopolymerizable monomer ]
The resin composition (a) of the resin layer (a) is a photosensitive thermosetting resin composition as described above: the resin having a carboxyl group and the thermosetting component are subjected to an addition reaction by heating after exposure using a base generated from an alkaline generator as a catalyst, and the unexposed portion is removed by an alkaline solution, whereby development can be performed. Thus, there is no need to compound a (meth) acrylate monomer required for a photosensitive resin composition by a polymerization reaction based on radicals generated by a conventional photo radical polymerization initiator. The resin composition of the resin layer (a) may be blended with a (meth) acrylate monomer, mainly for adjusting the sensitivity of the resin layer (a). For example, the (meth) acrylate monomer may be blended in an amount of about 10 to 100 parts by mass per 100 parts by mass of the carboxyl group-containing resin of the resin layer (a).
[ resin layer (B) ]
(resin composition (B) constituting resin layer (B))
The resin layer (B) is formed of the resin composition (B). The resin layer (B) mainly functions as a protective layer for the base material. The resin composition (B) of the resin layer (B) is a photosensitive thermosetting resin composition as follows: the photopolymerization initiator can perform radical polymerization based on light, and the alkali generated by the alkali generator is used as a catalyst, so that the alkali-soluble resin and the thermosetting component undergo an addition reaction by heating after exposure, and the unexposed part is removed by the alkali solution, thereby enabling development.
Examples of the alkali-soluble resin contained in the resin composition (B) of the resin layer (B) include compounds having a phenolic hydroxyl group, compounds having a carboxyl group, compounds having a phenolic hydroxyl group and a carboxyl group, and known and commonly used resins are used. In particular, a carboxyl group-containing resin or a carboxyl group-containing photosensitive resin, which has been conventionally used as a solder resist composition, includes a compound having a carboxyl group. Here, as the carboxyl group-containing resin or carboxyl group-containing photosensitive resin and the compound having an ethylenically unsaturated bond, known and commonly used compounds are used.
Among them, an alkali-soluble resin having an imide ring which is more excellent in properties such as bending resistance and heat resistance can be suitably used as the alkali-soluble resin.
The molecular weight of the carboxyl group-containing resin contained in the resin composition (B) of the resin layer (B) is preferably 1000 to 10000 in terms of weight average molecular weight in order to adjust the micropatternability and surface curability. When the molecular weight of the carboxyl-containing resin component is within this range, the number of exposure levels of the gloss sensitivity can be reduced if a carboxyl-containing resin having a low molecular weight, that is, 1000 to 5000 is used, and the number of exposure levels of the gloss sensitivity can be increased if a carboxyl-containing resin having a high molecular weight, that is, more than 5000 to 10000 is used. When the alkali-soluble resin having an imide ring described later has a carboxyl group, the gloss sensitivity can be adjusted in the same manner as in the above-mentioned range of the weight average molecular weight.
(alkali-soluble resin having imide Ring)
In the present invention, an alkali-soluble resin having an imide ring has: a phenolic hydroxyl group, an alkali-soluble group of 1 or more of carboxyl groups, and an imide ring. The alkali-soluble resin may be introduced with an imide ring by a known method. Examples thereof include: a resin obtained by reacting a carboxylic anhydride component with an amine component and/or an isocyanate component. Imidization may be performed by thermal imidization, chemical imidization, or a combination thereof.
The carboxylic anhydride component includes tetracarboxylic anhydride, tricarboxylic anhydride, and the like, but is not limited to these anhydrides, and may be any compound having an acid anhydride group and a carboxyl group which react with an amino group or an isocyanate group, and may be used as long as it includes a derivative thereof. These carboxylic anhydride components may be used alone or in combination.
The amine component may be a diamine such as an aliphatic diamine or an aromatic diamine, a polyamine such as an aliphatic polyether amine, a diamine having a carboxylic acid, a diamine having a phenolic hydroxyl group, or the like, but is not limited to these amines. In addition, these amine components may be used alone or in combination.
As the isocyanate component, there may be used diisocyanates such as aromatic diisocyanates and isomers thereof, polymers, aliphatic diisocyanates, alicyclic diisocyanates and isomers thereof, and other general-purpose diisocyanates, but not limited to these isocyanates. In addition, these isocyanate components may be used alone or in combination.
The alkali-soluble resin having an imide ring described above may have an amide bond. The polyamide-imide may be obtained by reacting an imide compound having a carboxyl group with an isocyanate and a carboxylic anhydride, or may be obtained by other reactions. It is also possible to have bonds formed by other additions and condensates.
In the synthesis of such an alkali-soluble resin having an alkali-soluble group and an imide ring, a known and commonly used organic solvent can be used. The organic solvent is not particularly limited as long as it does not react with the carboxylic acid anhydride, amine, or isocyanate as the raw material and dissolves these raw materials. In particular, aprotic solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and γ -butyrolactone are preferable in terms of high solubility of the raw materials.
The acid value of the alkali-soluble resin having 1 or more alkali-soluble groups among the phenolic hydroxyl groups and carboxyl groups and an imide ring described above is preferably 20 to 200mgKOH/g, more preferably 60 to 150mgKOH/g, in order to cope with the photolithography step, and to adjust the gloss sensitivity and the residual sensitivity. When the acid value is 20mgKOH/g or more, the solubility in alkali increases, the development becomes good, and the degree of crosslinking with the heat-curable component after light irradiation becomes high, so that a sufficient development contrast can be obtained. In addition, when the acid value is 200mgKOH/g or less, particularly, so-called hot fogging in the PEB step after light irradiation, which will be described later, can be suppressed, and the process margin becomes large.
In addition, the molecular weight of the alkali-soluble resin is preferably 1000 to 100000, more preferably 2000 to 50000, in order to adjust the developability and cured coating film characteristics. When the molecular weight is 1000 or more, sufficient development resistance and cured physical properties can be obtained after exposure to light and PEB. When the molecular weight is 100000 or less, the alkali solubility increases, and the developability improves.
(photopolymerization initiator)
The photopolymerization initiator used in the resin composition (B) of the resin layer (B) may be any known and commonly used photopolymerization initiator, and examples thereof include benzoin compounds, acylphosphine oxide compounds, acetophenone compounds, α -aminoacetophenone compounds, oxime ester compounds, and thioxanthone compounds. The resin composition (B) of the resin layer (B) enables radical polymerization based on light by containing a photopolymerization initiator.
In particular, when used in the PEB step after light irradiation, which will be described later, a photopolymerization initiator having a function as a photobase generator is suitable. In the PEB step, a photopolymerization initiator and a photobase generator may be used in combination.
The amount of the photopolymerization initiator to be blended is preferably 0.5 to 30 parts by mass relative to 100 parts by mass of the alkali-soluble resin. When the amount is 0.5 parts by mass or more, the surface curability becomes good, and when it is 30 parts by mass or less, halation is less likely to occur, and a good resolution is obtained. Further preferably 1.0 to 20 parts by mass.
(photo-alkaline agent)
The photobase generator having a function as a photopolymerization initiator is a compound of 1 or more alkaline substances that can function as a catalyst for polymerization of a thermally reactive compound described later by changing a molecular structure or splitting a molecule by irradiation with ultraviolet light, visible light, or the like. Examples of the alkaline substance include primary amines and tertiary amines.
Examples of the photobase generator having a function as a photopolymerization initiator include an α -aminoacetophenone compound, an oxime ester compound, a compound having a substituent such as an acyloxyimino group, an N-formylated aromatic amino group, an N-acylated aromatic amino group, a nitrobenzyl carbamate group, and an alkoxybenzyl carbamate group. Among them, oxime ester compounds and α -aminoacetophenone compounds are preferable, and oxime ester compounds are more preferable. As the α -aminoacetophenone compound, a compound having 2 or more nitrogen atoms is particularly preferable.
The α -aminoacetophenone compound may have a benzoin ether bond in a molecule, and may be an alkaline substance (amine) which is cleaved in the molecule when irradiated with light to thereby exert a curing catalyst function.
The oxime ester compound may be any compound that generates an alkaline substance by irradiation with light.
The photobase generator may be used alone or in combination of 1 or 2 or more. The blending amount of the photobase generator in the resin composition is preferably 1.0 to 40 parts by mass, more preferably 1.0 to 20 parts by mass, relative to 100 parts by mass of the alkali-soluble resin. When the amount is 1.0 part by mass or more, the contrast of development resistance of the irradiated portion/non-irradiated portion can be obtained satisfactorily. When the amount is 40 parts by mass or less, the cured product properties are improved.
(thermosetting resin)
The thermosetting resin (B) of the resin layer (B) may be an epoxy resin, an oxetane compound, a compound having 2 or more sulfide groups in the molecule, that is, an episulfide resin, an amino resin such as a melamine resin, a benzoguanamine resin, a melamine derivative, a benzoguanamine derivative, a blocked isocyanate compound, a cyclic carbonate compound, bismaleimide, carbodiimide, or the like, similarly to the thermosetting resin of the resin layer (a), or may be used in combination thereof.
The thermosetting resin (B) of the resin layer (B) may be the same thermosetting resin as the thermosetting resin of the resin layer (a) or may be a different thermosetting resin. In addition, the thermosetting resin may be used singly or in combination of 2 or more.
The blending ratio of the thermosetting resin is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and still more preferably 20 to 40% by mass, based on the total amount of the composition, in terms of solid matter conversion.
The resin composition used for the resin layers (a) and (B) described above may contain the following components as required.
(colorant)
Colorants may be compounded for the purpose of adjusting sensitivity. The colorant may be any of pigments, dyes, and pigments, and may be any of known and commonly used colorants such as red, blue, green, yellow, white, and black.
(other Components)
For the purpose of adjusting the sensitivity and improving the effect coating properties, known and commonly used additives such as antioxidants, ultraviolet absorbers, micro silica, hydrotalcite, silane coupling agents and the like may be blended.
[ laminated Structure ]
The thickness of the resin layer (B) is 2 μm or more and half or less of the thickness of the resin layer (A), and the thickness of the resin layer (A) is preferably 10 to 80 μm, more preferably 20 to 60 μm.
The laminated structure may be formed by dry-film-forming the resin composition of the resin layer (a) and the resin composition of the resin layer (B) on a substrate such as a circuit board, or may be formed by sequentially applying liquid compositions. When the composition is used in a liquid form, it may be one-component or two-component or more, but from the viewpoint of storage stability, two-component or more is preferable.
[ Dry film ]
Next, the dry film of the present invention has a resin layer obtained by coating the resin composition (a) of the resin layer (a) and the resin composition (B) of the resin layer (B) on the 1 st film and drying. In forming the dry film, first, the resin composition (a) of the resin layer (a) and the resin composition (B) of the resin layer (B) are diluted with the above-mentioned organic solvent and adjusted to an appropriate viscosity, and then coated onto a carrier film with a uniform thickness by a comma coater, a doctor blade coater, a lip coater, a bar coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like. Thereafter, the coated composition is dried at a temperature of generally 40 to 130 ℃ for 1 to 30 minutes, whereby a resin layer can be formed. The thickness of the coating film is not particularly limited, and is generally appropriately selected in the range of 5 to 150. Mu.m, preferably 15 to 60. Mu.m, in terms of the film thickness after drying.
As the 1 st film, a plastic film, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used. The thickness of the 1 st thin film is not particularly limited, and is generally appropriately selected in the range of 10 to 150. Mu.m. More preferably 15 to 130. Mu.m.
After forming a resin layer formed of the resin composition (a) of the resin layer (a) and the resin composition (B) of the resin layer (B) on the 1 st film, it is preferable to further laminate a releasable cover film on the surface of the film in order to prevent adhesion of dust or the like to the surface of the film. Examples of the release 2 nd film include polyethylene film, polytetrafluoroethylene film, polypropylene film, and surface-treated paper. The 2 nd film may be smaller than the adhesion force between the resin layer and the 1 st film when the cover film is peeled off.
In the present invention, the resin composition (B) of the resin layer (B) and the resin composition (a) of the resin layer (a) may be coated on the 2 nd film and dried to form a laminated structure, and the 1 st film may be laminated on the surface thereof. That is, in the present invention, as the film of the resin composition (a) for coating the resin layer (a) and the resin composition (B) for coating the resin layer (B) in producing the dry film, any of the 1 st film and the 2 nd film may be used.
The resin composition of the resin layer (a) and the resin composition of the resin layer (B) are adjusted to a viscosity suitable for the coating method, for example, using the above-mentioned organic solvent, and coated on a substrate by a method such as dip coating, flow coating, roll coating, bar coating, screen printing, curtain coating, or the like, and then the organic solvent contained in the composition is volatilized and dried (provisionally dried) at a temperature of about 60 to 100 ℃, whereby a hands-free resin layer can be formed. In the case of a dry film obtained by winding up the composition as a film by applying the composition onto a carrier film or a cover film and drying the film, the dry film is bonded to a substrate by a laminator or the like so that a layer of the composition of the present invention is in contact with the substrate, and then the carrier film is peeled off, whereby a resin layer can be formed.
Examples of the substrate include a printed circuit board and a flexible printed circuit board each having a circuit formed in advance of copper or the like: copper-clad laminates of all grades (FR-4 etc.), which use paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven fabric epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits, which use fluororesin, polyethylene, polyphenylene oxide, cyanate ester, etc., and metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer sheets, etc., are used.
The volatilization drying performed after the resin composition is applied to the 1 st film of the substrate or dry film may be performed by a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven or the like (a method of bringing hot air in a dryer into convection contact by using a device having a heat source of an air heating system using steam, or a method of blowing the hot air onto a support by using a nozzle). The heating in the PEB step and the post-curing step described later may be performed using the hot air circulation type drying furnace or the like.
[ cured product ]
The 1 st film of the dry film is peeled off and formed on a substrate for electronic parts, for example, a printed wiring board, and a cured product is formed by exposure to light and alkali development. After alkali development, post-curing is performed as needed. When the dry film is not used, the resin composition (a) of the resin layer (a) and the resin composition (B) of the resin layer (B) are coated and formed on the substrate, and then the cured product is formed by exposure to light and alkali development. After alkali development, post-curing is performed as needed.
(exposure (light irradiation) step)
In this step, the photoacid generator contained in the resin composition (B) of the resin layer (B) is activated into a negative pattern by irradiation with active energy rays, and the exposed portion is cured. When a composition of the PEB step described later is used, a photopolymerization initiator having a function as a photobase generator or a photobase generator is activated into a negative pattern to generate a base.
As the exposure machine used in this step, a direct drawing apparatus, an exposure machine equipped with a metal halide lamp, a light irradiation machine equipped with a (ultra) high-pressure mercury lamp, a light irradiation machine equipped with a mercury short-arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (ultra) high-pressure mercury lamp can be used. The patterned mask for exposure is a negative type mask.
As the active energy ray used in the exposure, a laser light having a maximum wavelength in the range of 350 to 450nm or scattered light is preferably used. By setting the maximum wavelength to this range, the photobase generator can be activated efficiently. The exposure amount varies depending on the film thickness, etc., but is usually set to 100 to 1500mJ/cm 2 。
The resin composition (a) of the laminated resin layer (a) and the resin composition (B) of the resin layer (B) are exposed to light (light irradiation), whereby the exposed portion (the portion where light irradiation is performed) is cured. In this step, the photobase generator contained in the resin layer is activated into a negative pattern by light irradiation, and the light irradiation part is cured. In this step, the photobase generator is not stabilized by the alkali generated in the light irradiation unit, and the alkali is chemically propagated, so that the resin layer can be sufficiently cured deep. The exposure device used for the irradiation may be one that irradiates ultraviolet rays in the range of 350 to 450 nm.
(PEB (POST EXPOSURE BAKE) Process)
In this step, after exposure (light irradiation), the resin layer is heated to cure the exposed portion. In this step, the resin layer can be sufficiently cured by the alkali generated in the light irradiation step. The heating temperature is, for example, 80 to 140 ℃. The heating time is, for example, 2 to 140 minutes. Since the curing of the resin composition of the present invention is, for example, a ring-opening reaction of an epoxy resin by a thermal reaction, strain and curing shrinkage can be suppressed as compared with the case of curing by a photo radical reaction.
(developing step)
In the development step, the unirradiated portion is removed by alkali development, thereby forming a negative pattern-like insulating film. The developing method may be dipping, spraying, brushing, etc., and as the developing solution, aqueous alkali solutions of potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. may be used.
(post-curing Process)
In this step, after the development step, the resin layer is completely thermally cured to obtain a highly reliable coating film. The heating temperature is, for example, 140℃to 180 ℃. The heating time is, for example, 20 to 120 minutes. Further, the light irradiation may be performed before or after the post-curing.
[ electronic component ]
The laminated structure of the present invention is suitable for forming a cured coating film on a printed circuit board as a semiconductor package or the like, more suitable for forming a permanent coating film, and further suitable for forming a solder resist layer, an interlayer insulating layer, and a cover layer. Further, since the curable resin composition of the present invention can provide a cured product having excellent crack resistance, it can be suitably used for forming a permanent coating film such as a solder resist layer used for a printed wiring board having a wiring pattern with a fine pitch, which is adversely affected by occurrence of cracks, for example.
Examples
Hereinafter, the present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Synthesis example 1
220 parts of cresol novolak type epoxy resin (EPICLON N-695, epoxy equivalent: 220, manufactured by DIC Co., ltd.) was placed in a four-necked flask equipped with a stirrer and a reflux condenser, 214 parts of carbitol acetate was added thereto, and the mixture was heated and dissolved. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of dimethylbenzylamine as a reaction catalyst were added. The mixture was heated to 95-105℃and 72 parts of acrylic acid was slowly added dropwise thereto and reacted for 16 hours. The reaction product is cooled to 80-90 ℃, 106 parts of tetrahydrophthalic anhydride is added for reaction for 8 hours, and the reaction product is taken out after cooling.
The photosensitive resin solution (A-1) having both an ethylenically unsaturated bond and a carboxyl group thus obtained was as follows: 65% of nonvolatile components, and 100mgKOH/g of acid value of solid material, and the weight average molecular weight (Mw) was about 3500.
Synthesis example 2
6.98g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (hereinafter referred to as "BAPP"), 3.80g of 3, 5-diaminobenzoic acid, 8.21g of JEFFAMINE XTJ-542 (manufactured by Huntsman Co., ltd., molecular weight 1025.64), and 86.49g of gamma-butyrolactone were charged and dissolved in a four-port 300mL flask equipped with a nitrogen inlet pipe, a thermometer, and a stirrer at room temperature.
Then, 17.84g of cyclohexane-1, 2, 4-tricarboxylic acid-1.2-anhydride and 2.88g of trimellitic anhydride were charged, and the mixture was kept at room temperature for 30 minutes. 30g of toluene was further charged, the temperature was raised to 160℃and the water formed with toluene was removed, followed by holding for 3 hours and cooling to room temperature, whereby an imide solution was obtained.
To the obtained imide solution, 9.61g of trimellitic anhydride and 17.45g of trimethylhexamethylene diisocyanate were added, and the mixture was kept at 160℃for 32 hours. Thus, a carboxyl group-containing polyamideimide resin solution (A-2) was obtained. The solid content was 40.1%, the acid value of the solid content was 83.1mgKOH/g, and the weight-average molecular weight (Mw) was 4500.
Synthesis example 3
A novolak-type cresol resin (Aica Kogyo Co.. Ltd.. Trade name., "one hand CRG-951", OH equivalent: 119.4), 119.4g, 1.19g of potassium hydroxide and 119.4g of toluene were charged into an autoclave equipped with a thermometer, a nitrogen introducing device, an alkylene oxide introducing device and a stirring device, and the inside of the system was stirred while being replaced with nitrogen gas, and heated to raise the temperature of the systemTemperature. Then, 63.8g of propylene oxide was slowly added dropwise thereto at 125 to 132℃and 0 to 4.8kg/cm 2 The reaction was carried out for 16 hours. Then, the reaction solution was cooled to room temperature, 1.56g of 89% phosphoric acid was added to the reaction solution and mixed, and potassium hydroxide was neutralized to obtain a propylene oxide reaction solution of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2g/eq. Which is obtained by adding 1.08 moles of alkylene oxide to 1 equivalent of phenolic hydroxyl groups on average. Then, 293.0g of the obtained alkylene oxide reaction solution of novolak-type cresol resin, 43.2g of acrylic acid, 11.53g of methanesulfonic acid, 0.18g of methylhydroquinone and 252.9g of toluene were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml/min, and reacted at 110℃for 12 hours while stirring. 12.6g of water were distilled off as an azeotropic mixture with toluene. Thereafter, the reaction solution was cooled to room temperature, and then, 35.35g of the obtained reaction solution was neutralized with 15% aqueous sodium hydroxide solution, followed by washing with water. After that, toluene was replaced with 118.1g of diethylene glycol monoethyl ether acetate in an evaporator and distilled off to obtain a novolak-type acrylic resin solution. Then, 332.5g of the obtained novolak type acrylic resin solution and 1.22g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml/min, 60.8g of tetrahydrophthalic anhydride was slowly added while stirring, and the mixture was reacted at 95 to 101℃for 6 hours. Thus, a carboxyl group-containing photosensitive resin solution (A-3) having an acid value of 88mgKOH/g in the solid content, a solid content of 71% and a weight-average molecular weight (Mw) of 2000 was obtained.
The materials of each example and each comparative example shown in tables 1 and 2 were compounded in the amounts shown in these tables, and after premixing in a mixer, they were kneaded in a three-roll mill to prepare a resin composition (a) for the resin layer (a) and a resin composition (B) for the resin layer (B). The values in the table are parts by mass of the solid content unless otherwise specified.
< formation of resin layer (A) >)
A substrate formed of an entire surface of copper having a thickness of 18 μm was prepared, and pretreatment was performed using MEC co. Thereafter, the resin compositions of examples and comparative examples were applied to the substrates by a method such as screen printing so that the film thicknesses after drying became the thicknesses (unit: μm) shown in tables 1 and 2, respectively. Thereafter, the resin layer (a) was formed by drying at 90 ℃ for 30 minutes in a hot air circulation type drying furnace.
< formation of resin layer (B) ]
The resin compositions of examples and comparative examples were applied to the resin layer (A) formed as described above by a method such as screen printing so that the film thicknesses after drying became the thicknesses (unit: μm) shown in tables 1 and 2, respectively. Thereafter, the resin layer (B) was formed by drying in a hot air circulation type drying oven at 90 ℃/30 minutes.
A laminate structure formed of each of the resin compositions of examples and comparative examples was produced on a substrate having a copper thickness of 18 μm as described above.
In the case of the dry film lamination method, first, the resin compositions of examples and comparative examples were diluted with an organic solvent and adjusted to an appropriate viscosity, and the resin compositions of examples and comparative examples were applied onto a carrier film in the same manner as described above, and dried to form a resin layer (B), and a resin layer (a) was formed thereon, to produce a dry film. Then, the support film is peeled off after being bonded by a laminator or the like so that the resin layer (a) side contacts the substrate.
Sensitivity >
The obtained layered structure on the substrate was exposed to light by an exposure apparatus (HMW-680-GW 20) equipped with a metal halide lamp via a stage exposure meter (T-4105 manufactured by STOUFFER) of 41 th order, subjected to PEB step at 90 ℃ for 30 minutes, developed in a 1.0% aqueous sodium carbonate solution at 30 ℃ under development conditions (see tables 1 and 2) in accordance with the respective compositions, and then, the gloss sensitivity and residual sensitivity were evaluated from the pattern formed by the stage exposure meter of 41 th order. The exposure amount was adjusted so that the gloss sensitivity became 10 levels.
Gloss sensitivity and residual sensitivity were determined according to the above definition as follows.
When the obtained laminated structure (2-layer resin layer) on the substrate is exposed from the resin layer (B) side through a stepwise exposure meter and the film thickness of the 2-layer resin layer before development of the pattern formed after the PEB step is set to 100%, the maximum value of the number of exposure meter steps after the exposure and after the PEB step, in which the film thickness is 95% or more after the development, is set as the gloss sensitivity, and the maximum value of the number of exposure meter steps, in which the film thickness before the development is set to 100%, and the film thickness after the development is set to 5% or less, is set as the residual sensitivity.
Here, each of the laminated structures formed on the substrate was exposed to light, and after the PEB step, the film thickness of the formed pattern before and after development was in accordance with JIS K5600-1-7: 2014, measuring the difference between the measured value obtained as the thickness of the whole coating film and the measured value obtained as the thickness of the substrate.
According to the mechanical measurement method, each of the laminated structures formed on the substrate was exposed from the resin layer (B) side through a stepwise exposure meter by a thickness measuring instrument (manufactured by DIGIMICRO MF-501, nikon Corporation), and the coating thickness before development of the pattern formed after the PEB step at 90 ℃ for 30 minutes and the coating thickness of the residual coating film formed after the PEB step after the exposure and after the development were measured, respectively, and the maximum value of the number of exposure meter steps in which the coating thickness before the development was 100% and the coating thickness after the development was 95% or more was regarded as the gloss sensitivity, and the maximum value of the number of exposure meter steps in which the coating thickness after the development was 5% or less was regarded as the residual sensitivity.
< B-HAST resistance >
The resin composition was formed on a comb-shaped evaluation substrate having L/s=12/13 μm, and the resin composition was subjected to an exposure step under the above conditions, a PEB step at 90 ℃ for 30 minutes, and then developed (30 ℃ C., 0.2MPa, 1 mass% Na 2 CO 3 Aqueous solution) to obtain a resist pattern. In the post-curing step, the coating film was cured at 150℃for 60 minutes. Applying a bias voltage of 5.0V to the obtained evaluation substrate, and placing the substrate in a constant temperature and humidity tank at 130deg.C under 85% atmosphere toThe life of the test piece in 1000 hours of treatment was evaluated on the following basis.
And (2) the following steps: 700 hours or more
Delta: over 200 hours and below 700 hours
X: 200 hours or less
< TCT crack resistance (thermal shock resistance) >)
The resin compositions of examples and comparative examples were formed on an evaluation substrate of a BT material, and this test was performed in order to evaluate crack resistance. The exposure step was performed under the conditions of the above-mentioned < sensitivity > evaluation method, and after the PEB step was performed at 90℃for 30 minutes, development (30℃and 0.2MPa, 1% by mass of Na) was performed 2 CO 3 Aqueous solution) to form a 200 μm-sized ∈pattern. In the post-curing step, the coating film was cured under the condition of 150℃for 60 minutes, and the obtained evaluation substrate was evaluated on the basis of the following criteria by taking-65 ℃ (30 minutes) +175 ℃ (30 minutes) as 1 cycle, and after 1000 cycles, the occurrence of cracks at the opening (200 μm square) was confirmed under observation with an optical microscope.
And (3) the following materials: crack occurrence rate is lower than 10%
And (2) the following steps: the crack occurrence rate is more than 10% and less than 20%
Delta: the crack occurrence rate is more than 20% and less than 40%
X: the crack occurrence rate is more than 40 percent
Light patterning
The resin compositions of examples and comparative examples were formed on copper-clad substrates, and in order to evaluate the photopatterning properties, the exposure step was performed under the conditions of the evaluation method of < sensitivity > described above, and after the PEB step at 90℃for 30 minutes, development (30℃at 0.2MPa, 1 mass% Na) was performed 2 CO 3 Aqueous solution) step of forming an SRO pattern on a scale of 10 μm from Φ40 μm to Φ200 μm. In the post-curing step, the coating film was cured at 150℃for 60 minutes, and the minimum size of the opening that could be completely formed was evaluated on the evaluation substrate obtained by observation with an optical microscope adjusted to 100 times.
And (3) the following materials: SRO size phi is below 50 μm
And (2) the following steps: SRO size exceeds phi 50 and is less than phi 60 μm
Delta: SRO size exceeds phi 60 and is less than phi 80 μm
X: SRO size exceeds phi 80 and is less than phi 100 μm
The evaluation results are shown in tables 1 and 2.
TABLE 1
TABLE 2
The materials of tables 1 and 2 are as follows.
* 1) Photosensitive resin solution (A-1) having both ethylenically unsaturated bond and carboxyl group, mw3500
* 2) Carboxyl group-containing polyamideimide resin solution (A-2) Mw4500
* 3) jER834 (bisphenol A epoxy resin, mitsubishi chemical Co., ltd.), mw470
* 4) IRGACURE OXE-02 (1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyloxime), manufactured by BASF Japan Co., ltd.)
* 5) Carboxyl group-containing photosensitive resin solution (A-3) (produced from halogen-free acid/Cheng acrylate resin having a halogen impurity concentration of 5 mass ppm or less), mw2000
* 6) KAYARAD UXE-3000 (carboxyl group-containing bisphenol A type urethane epoxy acrylate, manufactured by Nippon Kagaku Co., ltd.), mw10000
* 7) DPCA-60 (lactone-modified hexaacrylate of dipentaerythritol, manufactured by Japanese chemical Co., ltd.)
* 8) NC-3000L (biphenyl aralkyl epoxy resin, manufactured by Nippon Kagaku Co., ltd.), mw700
* 9) IRGACURE OXE-02 (1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -ethanone 1- (O-acetyloxime), manufactured by BASF Japan Co., ltd.)
The results of the evaluations shown in tables 1 and 2 indicate that the laminated structures of the examples are excellent in B-HAST resistance and crack resistance and have excellent resolution as compared with the laminated structures of the comparative examples.
Claims (5)
1. A laminated structure is characterized by comprising: a resin layer comprising 2 layers of a resin layer (A) formed from a resin composition (a) and a resin layer (B) formed from a resin composition (B) are laminated,
The resin composition (B) of the resin layer (B) contains: an alkali-soluble resin; a photo-alkali generator having a function as a photopolymerization initiator, or a photopolymerization initiator and a photo-alkali generator; a thermosetting resin, and a method for producing the same,
the resin composition (a) of the resin layer (a) comprises: a carboxyl group-containing resin and a thermosetting resin, substantially free of a photopolymerization initiator,
the difference between the gloss sensitivity and the residual sensitivity, which was obtained by measuring the film thickness of the pattern formed by exposing the 2 resin layers from the resin layer (B) side through a step exposure meter and then performing the PEB step, and the film thickness of the pattern formed by exposing and then performing the PEB step and then developing, was 20 or less.
2. The laminated structure according to claim 1, wherein the thickness of the resin layer (B) is 2 μm or more and half or less of the thickness of the resin layer (a), and the thickness of the resin layer (a) is 10 to 80 μm.
3. A dry film, comprising: the laminated structure of claim 1 or 2; and a film provided in contact with at least one of the surface of the resin layer (B) and the surface of the resin layer (A) of the laminated structure.
4. A cured product obtained by curing the laminated structure according to claim 1 or 2 or the resin layer of the dry film according to claim 3.
5. An electronic component comprising the cured product according to claim 4.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2021-062175 | 2021-03-31 | ||
| JP2021062175 | 2021-03-31 | ||
| PCT/JP2022/016968 WO2022211121A1 (en) | 2021-03-31 | 2022-03-31 | Laminated structure, dry film, cured product, and electronic component |
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| JP (1) | JPWO2022211121A1 (en) |
| KR (1) | KR20230165789A (en) |
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| JP5183073B2 (en) | 2006-07-10 | 2013-04-17 | 太陽ホールディングス株式会社 | Photocurable / thermosetting resin composition and cured product thereof |
| WO2013099885A1 (en) * | 2011-12-27 | 2013-07-04 | 太陽インキ製造株式会社 | Dry film, layered structure, printed wiring board, and process for producing layered structure |
| TWI688475B (en) * | 2014-10-16 | 2020-03-21 | 日商太陽油墨製造股份有限公司 | Laminated structure, dry film and flexible printed wiring board |
| JP6387444B1 (en) * | 2017-07-10 | 2018-09-05 | 太陽インキ製造株式会社 | Laminated structure, dry film and flexible printed wiring board |
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