JPWO2014156844A1 - Thermoplastic resin film substrate for photobaking, conductive circuit board using the same, and method for producing the same - Google Patents
Thermoplastic resin film substrate for photobaking, conductive circuit board using the same, and method for producing the same Download PDFInfo
- Publication number
- JPWO2014156844A1 JPWO2014156844A1 JP2015508372A JP2015508372A JPWO2014156844A1 JP WO2014156844 A1 JPWO2014156844 A1 JP WO2014156844A1 JP 2015508372 A JP2015508372 A JP 2015508372A JP 2015508372 A JP2015508372 A JP 2015508372A JP WO2014156844 A1 JPWO2014156844 A1 JP WO2014156844A1
- Authority
- JP
- Japan
- Prior art keywords
- base material
- circuit board
- thermoplastic resin
- circuit pattern
- resin film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000758 substrate Substances 0.000 title claims abstract description 41
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 62
- 229920005989 resin Polymers 0.000 claims abstract description 60
- 239000011347 resin Substances 0.000 claims abstract description 60
- 239000010410 layer Substances 0.000 claims abstract description 41
- 239000002344 surface layer Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 abstract description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 30
- 239000011342 resin composition Substances 0.000 description 28
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 21
- 239000004641 Diallyl-phthalate Substances 0.000 description 20
- 239000000178 monomer Substances 0.000 description 20
- -1 polyethylene terephthalate Polymers 0.000 description 19
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 10
- 239000004020 conductor Substances 0.000 description 10
- 238000010304 firing Methods 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000635 electron micrograph Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
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- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- BRXKVEIJEXJBFF-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-methylbutane-1,4-diol Chemical compound OCC(C)C(CO)(CO)CO BRXKVEIJEXJBFF-UHFFFAOYSA-N 0.000 description 2
- RVGLEPQPVDUSOJ-UHFFFAOYSA-N 2-Methyl-3-hydroxypropanoate Chemical compound COC(=O)CCO RVGLEPQPVDUSOJ-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- YEEPGEMPCOIATE-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(O)C(C)(C)CO Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(O)C(C)(C)CO YEEPGEMPCOIATE-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- VMHYWKBKHMYRNF-UHFFFAOYSA-N (2-chlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC=C1C(=O)C1=CC=CC=C1 VMHYWKBKHMYRNF-UHFFFAOYSA-N 0.000 description 1
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
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- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
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- ONCICIKBSHQJTB-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]propan-1-one Chemical compound CCC(=O)C1=CC=C(N(C)C)C=C1 ONCICIKBSHQJTB-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
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- FNBHVKBYRFDOJK-UHFFFAOYSA-N 1-butoxypropan-2-yl propanoate Chemical compound CCCCOCC(C)OC(=O)CC FNBHVKBYRFDOJK-UHFFFAOYSA-N 0.000 description 1
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- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- DOVZUKKPYKRVIK-UHFFFAOYSA-N 1-methoxypropan-2-yl propanoate Chemical compound CCC(=O)OC(C)COC DOVZUKKPYKRVIK-UHFFFAOYSA-N 0.000 description 1
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
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- OAMHTTBNEJBIKA-UHFFFAOYSA-N 2,2,2-trichloro-1-phenylethanone Chemical compound ClC(Cl)(Cl)C(=O)C1=CC=CC=C1 OAMHTTBNEJBIKA-UHFFFAOYSA-N 0.000 description 1
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- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
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- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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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
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
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- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
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- 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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
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- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0183—Dielectric layers
- H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure
Abstract
光焼成を行っても表面に形成した回路パターンに断線やクラックが生じない光焼成用熱可塑性樹脂フィルム基材、これを用いた導電回路基板およびその製造方法を提供する。基材１の表層に、架橋構造を有する樹脂層５が形成されてなる光焼成用熱可塑性樹脂フィルム基材である。また、導電回路基板は、上記光焼成用熱可塑性樹脂フィルム基材上に回路パターンが形成されてなる。さらに、導電回路基板の製造方法は、上記光焼成用熱可塑性樹脂フィルム基材上に回路パターンを形成した後、回路パターンを光焼成する。Provided are a photobaking thermoplastic resin base material in which a circuit pattern formed on the surface does not break even when photobaking is performed, a conductive circuit board using the thermoplastic resin film base material, and a method for manufacturing the same. It is a thermoplastic resin film substrate for photo-baking in which a resin layer 5 having a crosslinked structure is formed on the surface layer of the substrate 1. The conductive circuit board is formed by forming a circuit pattern on the photo-baking thermoplastic resin film substrate. Furthermore, the manufacturing method of a conductive circuit board forms a circuit pattern on the said thermoplastic resin film base material for photobaking, Then, a circuit pattern is photobaked.
Description
本発明は、光焼成用熱可塑性樹脂フィルム基材（以下、単に「基材」とも称する）、導電回路基板および導電回路基板の製造方法に関し、詳しくは、光焼成を行っても表面に形成した回路パターンに断線やクラックが生じない光焼成用熱可塑性樹脂フィルム基材、これを用いた導電回路基板およびその製造方法に関する。 The present invention relates to a photo-baking thermoplastic resin film base material (hereinafter also simply referred to as “base material”), a conductive circuit board, and a method for producing a conductive circuit board. The present invention relates to a thermoplastic resin film substrate for photo-baking that does not cause disconnection or cracks in a circuit pattern, a conductive circuit board using the same, and a method for manufacturing the same.
従来、フィルム基板やガラス基板等に熱硬化型の導電性樹脂組成物を塗布または印刷して、加熱硬化させることにより、抵抗膜方式タッチパネルの電極やプリント配線板の回路パターン等を形成していた。また、プラズマディスプレイパネル、蛍光表示管、電子部品等における導体パターンの形成には、一般に極めて多量の金属粉またはガラス粉末を含有する導電性ペーストを用いてスクリーン印刷法によってパターン形成が行われていた。 Conventionally, a thermosetting conductive resin composition is applied or printed on a film substrate, a glass substrate, or the like, and heated and cured to form a resistive film type touch panel electrode, a printed wiring board circuit pattern, or the like. . In addition, for the formation of conductor patterns in plasma display panels, fluorescent display tubes, electronic parts, etc., pattern formation is generally performed by screen printing using a conductive paste containing a very large amount of metal powder or glass powder. .
しかしながら、このような方法では、高温での加熱や焼成が必要であるため、基板が高温の影響を受けない材料に限定されるという難点がある。例えば、セルロース（紙）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエステル、および他の多くのプラスチック等のコストがより低い、または可撓性の基板の多くは、これらの温度に耐えることができない。同様に、有機半導体等の基板上の他の成分も、高温で分解してしまうおそれがある。 However, in such a method, since heating and baking at high temperature are necessary, there is a difficulty in that the substrate is limited to a material that is not affected by high temperature. Many of the lower cost or flexible substrates, such as cellulose (paper), polyethylene terephthalate (PET), polyester, and many other plastics, cannot withstand these temperatures. Similarly, other components on the substrate such as an organic semiconductor may be decomposed at a high temperature.
このような問題を解決する手段として、近年、いわゆる、光焼成という技術が開発され、注目を集めている。例えば、特許文献１には、少なくとも粒径１μｍ未満のナノ粒子を含有する分散体を基材上にパターン印刷し、パルス発光を照射することにより、大部分の金属ナノ粒子を含む一部のナノ粒子が言わば黒体としての挙動を示し、高い電磁線吸収率を示し、かつ、粒子の熱質量が小さいことにより粒子が急速に加熱、融着されて硬化した回路パターンを形成する方法が提案されている。この方法の場合、基板の熱伝導率が悪く、かつパルス長が短いことにより、最小限のエネルギーしか基板には伝達されないので、従来の熱硬化や焼成による方法の問題を解決することができる。 In recent years, a so-called photobaking technique has been developed and attracts attention as a means for solving such problems. For example, in Patent Document 1, a dispersion containing at least nanoparticles having a particle size of less than 1 μm is pattern-printed on a substrate and irradiated with pulsed light emission, whereby some of the nanoparticles including most metal nanoparticles are included. A method has been proposed in which particles exhibit behavior as a black body, exhibit high electromagnetic radiation absorptivity, and form a circuit pattern in which particles are rapidly heated and fused to harden due to their small thermal mass. ing. In the case of this method, since the thermal conductivity of the substrate is poor and the pulse length is short, only a minimum amount of energy is transmitted to the substrate, so that the problems of the conventional thermosetting and baking methods can be solved.
しかしながら、特許文献１に記載されているような光焼成技術を用いてプラスチック等の可撓性基材に回路パターンを形成した場合、可撓性基材が焼成時にダメージを受けてしまい回路パターンにクラックや断線を誘発してしまう場合がある。したがって、今日、プラスチック等の可撓性の基材に、光焼成という技術を用いて回路パターンを形成するには、このような問題を解決しなければならない。 However, when a circuit pattern is formed on a flexible base material such as plastic using a light baking technique as described in Patent Document 1, the flexible base material is damaged during baking, resulting in a circuit pattern. It may induce cracks and breaks. Therefore, today, in order to form a circuit pattern on a flexible base material such as plastic using a technique called light baking, such a problem must be solved.
そこで、本発明の目的は、光焼成を行っても表面に形成した回路パターンに断線やクラックが生じない光焼成用熱可塑性樹脂フィルム基材、これを用いた導電回路基板およびその製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a thermoplastic resin film base material for photo-baking that does not cause disconnection or cracks in the circuit pattern formed on the surface even after photo-baking, a conductive circuit board using the same, and a method for manufacturing the same There is to do.
本発明者は、上記課題を解消するために鋭意検討した結果、以下の知見を得るに至った。図５は、従来の基材に回路パターンを形成する際における光焼成前後の基材の断面図であり、（ａ）は光焼成前、（ｂ）は光焼成後である。プラスチック等の可撓性の基材１上に回路パターンを形成するに当たって、基材１上に導電性組成物で形成した回路パターンの塗膜２を光焼成すると、導電性組成物中の導電性物質の粒子が急速に加熱、融着して基材１上で固化し、回路パターンに応じた導体３を形成する。この際、導体３は同時に熱により収縮する。一方、導体３の温度上昇に伴い、基材１の温度も上昇するため、プラスチック等の可撓性の基材１を用いた場合、基材１の温度が融点以上に上昇すると、導体３の収縮に伴い、基材１自身も収縮してしまう。 As a result of intensive studies in order to solve the above problems, the present inventors have obtained the following knowledge. FIGS. 5A and 5B are cross-sectional views of the base material before and after light baking when forming a circuit pattern on a conventional base material, where FIG. 5A is before light baking and FIG. 5B is after light baking. In forming a circuit pattern on a flexible base material 1 such as plastic, when the coating film 2 of the circuit pattern formed of the conductive composition on the base material 1 is photobaked, the conductivity in the conductive composition is determined. The particles of the substance are rapidly heated and fused to solidify on the substrate 1 to form the conductor 3 corresponding to the circuit pattern. At this time, the conductor 3 is simultaneously contracted by heat. On the other hand, since the temperature of the base material 1 also rises as the temperature of the conductor 3 rises, when the flexible base material 1 such as plastic is used, if the temperature of the base material 1 rises above the melting point, the conductor 3 Along with the shrinkage, the substrate 1 itself shrinks.
図示例においては、導体３の縁部近傍の基材１が導体３の収縮に伴い引っ張られて、凹み４が生じ、基材１がダメージを受けている。これにより、可撓性の基材１に形成した回路パターンに断線が生じてしまうと考えられる。本発明者はかかる知見に基づき、さらに鋭意検討した結果、基材の表層に架橋構造を有する樹脂層を設けることで、上記課題を解決することができることを見出し、本発明を完成するに至った。 In the illustrated example, the base material 1 in the vicinity of the edge of the conductor 3 is pulled with the contraction of the conductor 3 to form a dent 4, and the base material 1 is damaged. Thereby, it is thought that a disconnection will arise in the circuit pattern formed in the flexible base material 1. FIG. As a result of further intensive studies based on such knowledge, the present inventors have found that the above problem can be solved by providing a resin layer having a crosslinked structure on the surface layer of the substrate, and the present invention has been completed. .
すなわち、本発明の光焼成用熱可塑性樹脂フィルム基材は、基材の表層に、架橋構造を有する樹脂層が形成されてなることを特徴とするものである。ここで、架橋構造とは、架橋基を有する同一高分子間、異種高分子間、高分子−低分子間、及び、同一または異種の低分子間において、熱、光などの電磁エネルギー等により、互いに結合することで形成された、三次元の網目構造のことである。架橋構造を形成することにより、高分子等のもつ融点は消失し、見かけ上の分子量が無限大となるため、流動性や溶解度に変化が起こり耐薬品性、耐溶剤性、耐候性、耐熱性、耐熱老化性等に優れた特性を示すようになる。なお、本明細書中で示されるガラス転移温度は、公知慣用の測定方法により測定可能であるが、好ましくは示差走査熱量測定（ＤＳＣ：Ｄｉｆｆｅｒｅｎｔｉａｌ Ｓｃａｎｎｉｎｇ Ｃａｌｏｒｉｍｅｔｒｙ）により測定された値である。 That is, the thermoplastic resin film substrate for photobaking of the present invention is characterized in that a resin layer having a crosslinked structure is formed on the surface layer of the substrate. Here, the cross-linked structure refers to electromagnetic energy such as heat, light, etc. between the same polymer having a cross-linking group, between different polymers, between a polymer and a low molecule, and between the same or different low molecules. A three-dimensional network structure formed by joining together. By forming a cross-linked structure, the melting point of the polymer disappears and the apparent molecular weight becomes infinite, resulting in changes in fluidity and solubility, chemical resistance, solvent resistance, weather resistance, heat resistance In addition, it exhibits excellent properties such as heat aging resistance. The glass transition temperature shown in the present specification can be measured by a known and commonly used measurement method, but is preferably a value measured by differential scanning calorimetry (DSC).
本発明のフィルム基材においては、前記樹脂層は活性エネルギー線の照射により硬化されてなるものであることが好ましい。 In the film base material of this invention, it is preferable that the said resin layer is hardened | cured by irradiation of an active energy ray.
また、本発明の導電回路基板は、上記本発明の光焼成用熱可塑性樹脂フィルム基材上に回路パターンが形成されてなることを特徴とするものである。 The conductive circuit board of the present invention is characterized in that a circuit pattern is formed on the photobaking thermoplastic resin film substrate of the present invention.
さらに、本発明の導電回路基板の製造方法は、上記本発明の導電回路基板の製造方法であって、前記光焼成用熱可塑性樹脂フィルム基材上に回路パターンを形成した後、該回路パターンを光焼成することを特徴とするものである。 Furthermore, the method for producing a conductive circuit board according to the present invention is the above-described method for producing a conductive circuit board according to the present invention, wherein a circuit pattern is formed on the thermoplastic resin film substrate for photobaking, and then the circuit pattern is formed. It is characterized by light baking.
本発明によれば、光焼成を行っても表面に形成した回路パターンに断線やクラックが生じない光焼成用熱可塑性樹脂フィルム基材、これを用いた導電回路基板およびその製造方法を提供することができる。 According to the present invention, there are provided a thermoplastic resin film base material for light firing which does not cause breakage or cracks in a circuit pattern formed on the surface even after light firing, a conductive circuit board using the same, and a method for producing the same. Can do.
以下、本発明の実施の形態について、詳細に説明する。
［光焼成用熱可塑性樹脂フィルム基材］
本発明の光焼成用熱可塑性樹脂フィルム基材は、基材の表層に、架橋構造を有する樹脂層が形成されてなるものである。図１は、本発明の基材に回路パターンを形成する際における光焼成前後の基材の断面図であり、（ａ）は光焼成前、（ｂ）は光焼成後である。図示するように、本発明の基材は、基材１の表層に架橋構造を有する樹脂層５が設けられている。この樹脂層５により、光焼成時に導体３が収縮しても基材１は収縮することはなくなり、光焼成時における回路パターンのクラックや断線を防止することができる。かかる効果を良好に得るためには、基材の表層に形成される架橋構造を有する樹脂層のガラス転移温度は、１００℃以上が好ましく、より好ましくは１４０℃以上２５０℃以下である。Hereinafter, embodiments of the present invention will be described in detail.
[Photo-baking thermoplastic resin film substrate]
The photo-baking thermoplastic resin film substrate of the present invention is obtained by forming a resin layer having a crosslinked structure on the surface layer of the substrate. FIG. 1 is a cross-sectional view of a substrate before and after photo-firing when forming a circuit pattern on the substrate of the present invention, (a) before photo-firing and (b) after photo-firing. As shown in the figure, the base material of the present invention is provided with a resin layer 5 having a crosslinked structure on the surface layer of the base material 1. The resin layer 5 prevents the base material 1 from contracting even if the conductor 3 contracts during light baking, and can prevent cracks and breaks in the circuit pattern during light baking. In order to obtain such an effect satisfactorily, the glass transition temperature of the resin layer having a crosslinked structure formed on the surface layer of the substrate is preferably 100 ° C. or higher, more preferably 140 ° C. or higher and 250 ° C. or lower.
本発明の基材においては、基材１の表面に設けられる樹脂層５については、架橋構造を有するもの、好ましくはガラス転移温度が上記範囲を満足するものであれば特に制限はないが、活性エネルギー線の照射により硬化したものであることが好ましい。これは、架橋構造を有する樹脂層５は、基材１上に樹脂層５となる樹脂組成物を塗布してこれを活性エネルギー線の照射により硬化させることによって、容易に形成することができるためである。 In the base material of the present invention, the resin layer 5 provided on the surface of the base material 1 is not particularly limited as long as it has a crosslinked structure, and preferably has a glass transition temperature satisfying the above range. It is preferable that it is hardened | cured by irradiation of an energy ray. This is because the resin layer 5 having a crosslinked structure can be easily formed by applying a resin composition to be the resin layer 5 on the substrate 1 and curing it by irradiation with active energy rays. It is.
上述のとおり、本発明の基材の樹脂層５を形成する樹脂組成物としては、樹脂層５の状態で架橋構造を有するものであれば、特に制限はないが、しかしながら、本発明の基材の樹脂層５を形成する樹脂組成物としては、活性エネルギー線硬化性樹脂組成物が好ましく、活性エネルギー線硬化性樹脂としては、一分子中にひとつ以上のエチレン性不飽和結合を有する化合物が好ましい。例えば、エポキシ（メタ）アクリレート、ウレタンアクリレート、ポリエステルアクリレート、ポリエーテルアクリレート、アクリル樹脂の側鎖にエチレン性不飽和二重結合を導入した変性アクリル樹脂等が挙げられる。中でも、二つ以上のエチレン性不飽和結合を有する化合物がより好ましく、さらに、ジアリルフタレート樹脂が特に好ましい。本発明の基材に係る樹脂層５を形成する樹脂組成物は、（Ａ）ジアリルフタレート樹脂と、（Ｂ）多官能モノマーと、（Ｃ）光重合開始剤と、を含有する。以下、（Ａ）ジアリルフタレート樹脂と、（Ｂ）多官能モノマーと、（Ｃ）光重合開始剤と、を有する樹脂組成物について詳細に説明する。 As described above, the resin composition for forming the resin layer 5 of the base material of the present invention is not particularly limited as long as it has a crosslinked structure in the state of the resin layer 5, however, the base material of the present invention. The resin composition for forming the resin layer 5 is preferably an active energy ray curable resin composition, and the active energy ray curable resin is preferably a compound having one or more ethylenically unsaturated bonds in one molecule. . Examples thereof include epoxy (meth) acrylate, urethane acrylate, polyester acrylate, polyether acrylate, and a modified acrylic resin in which an ethylenically unsaturated double bond is introduced into the side chain of the acrylic resin. Among them, a compound having two or more ethylenically unsaturated bonds is more preferable, and a diallyl phthalate resin is particularly preferable. The resin composition forming the resin layer 5 according to the substrate of the present invention contains (A) diallyl phthalate resin, (B) a polyfunctional monomer, and (C) a photopolymerization initiator. Hereinafter, the resin composition having (A) diallyl phthalate resin, (B) polyfunctional monomer, and (C) photopolymerization initiator will be described in detail.
なお、本明細書において、（メタ）アクリレートとは、アクリレート、メタアクリレートおよびそれらの混合物を総称する用語で、他の類似の表現についても同様である。 In the present specification, “(meth) acrylate” is a general term for acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions.
＜（Ａ）ジアリルフタレート樹脂＞
本発明の基材の樹脂層５を形成する樹脂組成物においては、ジアリルフタレート樹脂としては、ジアリルフタレート系繰り返し単位を含むものであればよく、ジアリルフタレート系モノマーの単独重合体、２種以上のジアリルフタレート系モノマーの共重合体の他、ジアリルフタレート系モノマーと、このモノマーと共重合可能な他のモノマー（例えば、エチレン性二重結合を有する芳香族化合物、エチレン性二重結合を有する脂肪族化合物、または（メタ）アリル化合物）との共重合体であってもよい。ジアリルフタレート系モノマーと、このモノマーと共重合可能な他のモノマーとの共重合体は、通常、ジアリルフタレート系繰り返し単位が主体をなす。<(A) Diallyl phthalate resin>
In the resin composition forming the resin layer 5 of the base material of the present invention, the diallyl phthalate resin may be any one containing a diallyl phthalate-based repeating unit. In addition to copolymers of diallyl phthalate monomers, diallyl phthalate monomers and other monomers copolymerizable with this monomer (for example, aromatic compounds having an ethylenic double bond, aliphatics having an ethylenic double bond) Or a copolymer with a (meth) allyl compound). A copolymer of a diallyl phthalate monomer and another monomer copolymerizable with this monomer usually has a diallyl phthalate repeating unit as a main component.
ジアリルフタレート樹脂の原料となるジアリルフタレート系モノマーは、ジアリルオルソフタレートモノマー、ジアリルイソフタレートモノマー、およびジアリルテレフタレートモノマーから選択される化合物である。これら化合物の１種または２種以上を用いてのジアリルフタレート樹脂の合成、およびこれらジアリルフタレート系モノマーと、このモノマーと重合可能な他のモノマーを用いてのジアリルフタレート樹脂の合成は既知の手法を用いればよく、例えば、特公平２−０２４８５０号公報、特開平１１−１４７９１７号公報等に記載された重合反応を採用することができる。 The diallyl phthalate monomer used as the starting material for the diallyl phthalate resin is a compound selected from diallyl orthophthalate monomer, diallyl isophthalate monomer, and diallyl terephthalate monomer. The synthesis of diallyl phthalate resin using one or more of these compounds and the synthesis of diallyl phthalate resin using these diallyl phthalate monomers and other monomers polymerizable with this monomer are known methods. For example, the polymerization reaction described in JP-B-2-024850, JP-A-11-147917 and the like can be employed.
本発明の基材の樹脂層５を形成する樹脂組成物に用いられるジアリルフタレート樹脂としては、例えば、ダイソー社製の「ダップ−Ａ」（登録商標）のような、単独重合体であるジアリルオルソフタレート樹脂、ダイソー社製の「イソダップ」（登録商標）のような、ジアリルイソフタレート樹脂、ジアリルテレフタレート樹脂が好ましく、ジアリルオルソフタレート樹脂、およびジアリルイソフタレート樹脂がより好ましい。 The diallyl phthalate resin used in the resin composition for forming the resin layer 5 of the base material of the present invention is, for example, diallyl ortho which is a homopolymer such as “Dup-A” (registered trademark) manufactured by Daiso Corporation. A diallyl isophthalate resin and a diallyl terephthalate resin such as “Isodap” (registered trademark) manufactured by Daiso Corporation are preferred, and a diallyl orthophthalate resin and a diallyl isophthalate resin are more preferred.
本発明の基材の樹脂層５を形成する樹脂組成物においては、好適に用い得るジアリルフタレート樹脂は、ＧＰＣ（ゲル・パーミエーション・クロマトグラフィー法）で測定した重量平均分子量（ポリスチレン換算）が２０，０００〜６０，０００であり、より好ましくは５０，０００〜６０，０００である。重量平均分子量が６０，０００を超えると硬化性が悪くなるおそれがあり、２０，０００未満であると耐熱性が悪くなるおそれがあるからである。 In the resin composition forming the resin layer 5 of the base material of the present invention, the diallyl phthalate resin that can be suitably used has a weight average molecular weight (polystyrene conversion) of 20 measured by GPC (gel permeation chromatography). 50,000 to 60,000, more preferably 50,000 to 60,000. This is because if the weight average molecular weight exceeds 60,000, the curability may be deteriorated, and if it is less than 20,000, the heat resistance may be deteriorated.
＜（Ｂ）多官能モノマー＞
本発明の基材の樹脂層５を形成する樹脂組成物においては、多官能モノマーとしては、１分子中に少なくとも２つ以上の重合性不飽和基を有する化合物であれば、いかなるものも使用可能である。具体的には、多価アルコールと、α，β−不飽和カルボン酸とを縮合して得られる化合物（例えばエチレングリコールジ（メタ）アクリレート（ジアクリレートまたはジメタクリレートの意味、以下同様）、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ジメチロールプロパンヘキサアクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、１，２−プロピレングリコールジ（メタ）アクリレート、ジ（１，２−プロピレングリコール）ジ（メタ）アクリレート、トリ（１，２−プロピレングリコール）ジ（メタ）アクリレート、テトラ（１，２−プロピレングリコール）ジ（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート、ジエチルアミノプロピル（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等）、スチレン、ジビニルベンゼン、４−ビニルトルエン、４−ビニルピリジン、Ｎ−ビニルピロリドン、２−ヒドロキシエチル（メタ）アクリレート、１，３−（メタ）アクリロイルオキシ−２−ヒドロキシプロパン、メチレンビスアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−メチロールアクリルアミド、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、テトラメチロールプロパンテトラ（メタ）アクリレート等を挙げることができ、より好ましくは、ジメチロールプロパンヘキサアクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、テトラメチロールプロパンテトラ（メタ）アクリレート等の３官能以上であることが好ましい。本発明の基材の樹脂層５を形成する樹脂組成物においては、これらは１種または２種類以上を組み合わせて用いることができる。<(B) Polyfunctional monomer>
In the resin composition for forming the resin layer 5 of the base material of the present invention, any polyfunctional monomer can be used as long as it has at least two polymerizable unsaturated groups in one molecule. It is. Specifically, a compound obtained by condensing a polyhydric alcohol and an α, β-unsaturated carboxylic acid (for example, ethylene glycol di (meth) acrylate (meaning diacrylate or dimethacrylate, hereinafter the same)), triethylene Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dimethylolpropane hexaacrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,2-propylene glycol di (meth) Acrylate, di (1,2-propylene glycol) di (meth) acrylate, tri (1,2-propylene glycol) di (meth) acrylate, tetra (1,2-propylene glycol) di (meth) acrylate, dimethylaminoethyl ( (Meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Pentaerythritol tri (meth) acrylate), styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2 -Hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, Examples include pentaerythritol hexa (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, and more preferably dimethylolpropane hexaacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, It is preferably trifunctional or higher such as dipentaerythritol hexa (meth) acrylate and tetramethylolpropane tetra (meth) acrylate. In the resin composition which forms the resin layer 5 of the base material of the present invention, these can be used alone or in combination of two or more.
本発明の基材の樹脂層５を形成する樹脂組成物においては、多官能モノマーは、ジアリルフタレート樹脂１００質量部に対し、１〜１００質量部の割合で配合することが好ましく、３〜５０質量部の範囲がさらに好ましい。１〜１００質量部の範囲を逸脱すると、本発明の所期の効果が得られない場合があり好ましくない。 In the resin composition for forming the resin layer 5 of the base material of the present invention, the polyfunctional monomer is preferably blended at a ratio of 1 to 100 parts by mass with respect to 100 parts by mass of the diallyl phthalate resin, and 3 to 50 parts by mass. A range of parts is more preferred. Deviating from the range of 1 to 100 parts by mass is not preferable because the desired effect of the present invention may not be obtained.
＜（Ｃ）光重合開始剤＞
本発明の基材の樹脂層５を形成する樹脂組成物においては、光重合開始剤としては、活性エネルギー線の照射によりラジカルを発生する公知の化合物が使用可能であり、例えば、アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、ｐ−ジメチルアミノプロピオフェノン、ジクロロアセトフェノン、トリクロロアセトフェノン、ｐ−ｔｅｒｔ−ブチルトリクロロアセトフェノン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノ−プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、Ｎ，Ｎ−ジメチルアミノアセトフェノン等のアセトフェノン類；ベンゾフェノン、メチルベンゾフェノン、２−クロロベンゾフェノン、４，４’−ジクロロベンゾフェノン、４，４’−ビスジメチルアミノベンゾフェノン、４，４’−ビスジエチルアミノベンゾフェノン、ミヒラーズケトン、４−ベンゾイル−４’−メチルジフェニルサルファイド等のベンゾフェノン類；ベンジル、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾインエーテル類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；チオキサントン、２−クロロチオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２，４−ジイソプロピルチオキサントン等のチオキサントン類；２−メチルアントラキノン、２−エチルアントラキノン、２−ｔｅｒｔ−ブチルアントラキノン、１−クロロアントラキノン、２−アミノアントラキノン、２，３−ジフェニルアントラキノン等のアントラキノン類；ベンゾイルパーオキシド、クメンパーオキシド等の有機過酸化物；２，４，５−トリアリールイミダゾール二量体、リボフラビンテトラブチレート、２−メルカプトベンゾイミダゾール、２−メルカプトベンゾオキサゾール、２−メルカプトベンゾチアゾール等のチオール化合物；２，４，６−トリス−ｓ−トリアジン、２，２，２−トリブロモエタノール、トリブロモメチルフェニルスルホン等の有機ハロゲン化合物；２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド等を挙げることができる。また、その他の例として、アクリジン化合物類、オキシムエステル類等を挙げることができる。本発明の基材の樹脂層５を形成する樹脂組成物においては、これらは１種または２種類以上を組み合わせて用いることができる。<(C) Photopolymerization initiator>
In the resin composition forming the resin layer 5 of the base material of the present invention, as the photopolymerization initiator, a known compound that generates radicals upon irradiation with active energy rays can be used, for example, acetophenone, 2, 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyltrichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2 -Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, N, N -Acetophene such as dimethylaminoacetophenone Benzophenone, methylbenzophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, 4-benzoyl-4'-methyl Benzophenones such as diphenyl sulfide; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; thioxanthone, 2-chlorothioxanthone 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-aminoanthraquinone, 2,3-diphenylanthraquinone; benzoyl peroxide, cumene peroxide, etc. Organic peroxides; Thiol compounds such as 2,4,5-triarylimidazole dimer, riboflavin tetrabutyrate, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; 2,4,6 -Organic halogen compounds such as -tris-s-triazine, 2,2,2-tribromoethanol, tribromomethylphenylsulfone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. Other examples include acridine compounds and oxime esters. In the resin composition which forms the resin layer 5 of the base material of the present invention, these can be used alone or in combination of two or more.
本発明の基材の樹脂層５を形成する樹脂組成物においては、上記のような光重合開始剤は、Ｎ，Ｎ−ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ−ジメチルアミノ安息香酸イソアミルエステル、ペンチル−４−ジメチルアミノベンゾエート、トリエチルアミン、トリエタノールアミン等の三級アミン類、およびβ−チオジグリコール等のチオエーテル類、（ケト）クマリン、チオキサンテン等の増感色素類、およびシアニン、ローダミン、サフラニン、マラカライトグリーン、メチレンブルー等のアルキルホウ酸塩のような光増感剤または促進剤の１種または２種以上と組み合わせて用いることができる。 In the resin composition forming the resin layer 5 of the base material of the present invention, the photopolymerization initiator as described above is N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, tertiary amines such as triethanolamine, and thioethers such as β- thiodiglycol, (keto) coumarin, a sensitizing dye such as thioxanthene, and cyanine, rhodamine, It can be used in combination with one kind or two or more kinds of photosensitizers or accelerators such as alkyl borates such as safranine, malachite green and methylene blue.
光重合開始剤の好ましい組合せとしては、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノ−プロパン−１−オン（例えばＢＡＳＦジャパン社製、イルガキュアー９０７）と、２−クロロチオキサントン（例えば、日本化薬（株）製カヤキュアーＣＴＸ）や２，４−ジエチルチオキサントン（例えば、日本化薬（株）製カヤキュアーＤＥＴＸ）、２−イソプロピルチオキサントン、４−ベンゾイル−４’−メチルジフェニルサルファイド等との組合せを挙げることができる。 As a preferable combination of the photopolymerization initiator, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (eg, BASF Japan, Irgacure 907) and 2-chloro thioxanthone (e.g., manufactured by Nippon Kayaku Co., Ltd. Kayacure CTX) and 2,4-diethyl thioxanthone (e.g., manufactured by Nippon Kayaku Co., Ltd. Kayacure DETX), 2-isopropylthioxanthone, 4-benzoyl-4'-methyl diphenyl sulfide And the like.
本発明の基材の樹脂層５を形成する樹脂組成物においては、光重合開始剤の添加量の好適な範囲は、ジアリルフタレート樹脂１００質量部に対して０．０１〜３０質量部、好ましくは０．１〜２０質量部である。光重合開始剤の配合割合が０．０１質量部未満の場合には光硬化性が悪くなり、一方、３０質量部より多い場合には硬化塗膜の特性が悪くなり、また、保存安定性が悪くなるので好ましくない。 In the resin composition forming the resin layer 5 of the base material of the present invention, a suitable range of the addition amount of the photopolymerization initiator is 0.01 to 30 parts by mass, preferably 100 to 30 parts by mass of the diallyl phthalate resin. 0.1 to 20 parts by mass. When the blending ratio of the photopolymerization initiator is less than 0.01 parts by mass, the photocurability is deteriorated. On the other hand, when it is more than 30 parts by mass, the characteristics of the cured coating film are deteriorated, and the storage stability is improved. Since it gets worse, it is not preferable.
＜その他添加剤＞
本発明の基材の樹脂層５を形成する樹脂組成物においては、上記（Ａ）〜（Ｃ）の他に、本発明の所期の効果を損なわない限り、他の添加剤を添加してもよい。添加剤としては、例えば、シリコーン系、フッ素系の消泡剤、レベリング剤、公知慣用の熱重合禁止剤、紫外線吸収剤、シランカップリング剤、可塑剤、発泡剤、難燃剤、帯電防止剤、老化防止剤、抗菌・防黴剤等を挙げることができる。<Other additives>
In the resin composition which forms the resin layer 5 of the base material of the present invention, in addition to the above (A) to (C), other additives are added unless the desired effect of the present invention is impaired. Also good. Examples of additives include silicone-based, fluorine-based antifoaming agents, leveling agents, known and commonly used thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, foaming agents, flame retardants, antistatic agents, Antiaging agents, antibacterial / antifungal agents and the like can be mentioned.
＜フィラー＞
本発明の基材の樹脂層５には、公知慣用の無機または有機フィラーを使用することができるが、特に硫酸バリウム、球状シリカが好ましく、球状シリカは平均一次粒径が１〜１００ｎｍのものが好ましい。ここで、平均一次粒径とは、レーザ散乱法により測定した値である。具体的には、ナノシリカを溶媒中に分散し、その分散溶媒にレーザ光を当てて得られた散乱光を捕捉し、演算することにより、得られる平均粒子径である。ナノシリカは、シランカップリング剤等により表面処理施されたもの、未処理のものいずれも用いることができる。また、２個以上のエチレン性不飽和基を有する化合物や多官能エポキシ樹脂にナノシリカを分散したＨａｎｓｅ−Ｃｈｅｍｉｅ社製のＮＡＮＯＣＲＹＬ（商品名） ＸＰ ０３９６、ＸＰ ０５９６、ＸＰ ０７３３、ＸＰ ０７４６、ＸＰ ０７６５、ＸＰ ０７６８、ＸＰ ０９５３、ＸＰ ０９５４、ＸＰ １０４５（何れも製品グレード名）や、Ｈａｎｓｅ−Ｃｈｅｍｉｅ社製のＮＡＮＯＰＯＸ（商品名） ＸＰ ０５１６、ＸＰ ０５２５、ＸＰ ０３１４（何れも製品グレード名）も使用できる。これらのフィラーを単独でまたは２種以上配合することができる。これらのフィラーは、塗膜の硬化収縮を抑制し、密着性、硬度等の基本的な特性を向上させることができる。<Filler>
For the resin layer 5 of the base material of the present invention, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate and spherical silica are preferable, and the spherical silica has an average primary particle size of 1 to 100 nm. preferable. Here, the average primary particle size is a value measured by a laser scattering method. Specifically, the average particle diameter is obtained by dispersing nanosilica in a solvent and capturing and calculating scattered light obtained by applying laser light to the dispersion solvent. Nanosilica can be used either surface treated with a silane coupling agent or the like or untreated. Further, NANOCRYL (trade name) XP 0396, XP 0596, XP 0733, XP 0746, XP 0765, manufactured by Hanse-Chemie, in which nano silica is dispersed in a compound having two or more ethylenically unsaturated groups or a polyfunctional epoxy resin, XP 0768, XP 0953, XP 0954, XP 1045 (all product grade names) and NANOPOX (trade name) XP 0516, XP 0525, XP 0314 (all product grade names) manufactured by Hanse-Chemie can also be used. These fillers can be used alone or in combination of two or more. These fillers can suppress curing shrinkage of the coating film and improve basic characteristics such as adhesion and hardness.
本発明の基材の樹脂層５においては、これらフィラーの配合量は、（Ａ）ジアリルフタレート樹脂１００質量部に対して、好ましくは０．１〜３００質量部、より好ましくは、０．１〜１５０質量部である。フィラーの配合量が、０．１質量部未満の場合、硬化塗膜特性が低下するので、好ましくない。一方、３００質量部を超えた場合、組成物の粘度が高くなり印刷性が低下たり、硬化物が脆くなるので好ましくない。 In the resin layer 5 of the base material of the present invention, the blending amount of these fillers is preferably 0.1 to 300 parts by mass, more preferably 0.1 to 100 parts by mass of the (A) diallyl phthalate resin. 150 parts by mass. When the amount of the filler is less than 0.1 parts by mass, the cured coating film characteristics are deteriorated, which is not preferable. On the other hand, when it exceeds 300 parts by mass, the viscosity of the composition becomes high, the printability is lowered, and the cured product becomes brittle.
＜有機溶剤＞
本発明の基材の樹脂層５を形成する樹脂組成物においては、必要に応じて樹脂組成物を均一に溶解したり、粘度を調整したりするために、有機溶剤を用いてもよい。有機溶剤は、各成分を均一に溶解することができ、かつ、各成分と反応しないものであれば、特に制限はない。<Organic solvent>
In the resin composition which forms the resin layer 5 of the base material of the present invention, an organic solvent may be used to uniformly dissolve the resin composition or adjust the viscosity as necessary. The organic solvent is not particularly limited as long as it can dissolve each component uniformly and does not react with each component.
これら有機溶剤としては、例えば、メタノール、エタノール等のアルコール類；テトラヒドロフラン等のエーテル類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等のグリコールエーテル類；メチルセロソルブアセテート、エチルセロソルブアセテート等のエチレングリコールアルキルエーテルアセテート類；ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル等のジエチレングリコール類；プロピレングリコールメチルエーテル、プロピレングリコールエチルエーテル、プロピレングリコールプロピルエーテル、プロピレングリコールブチルエーテル等のプロピレングリコールモノアルキルエーテル類；プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、プロピレングリコールブチルエーテルアセテート等のプロピレングリコールアルキルエーテルアセテート類；プロピレングリコールメチルエーテルプロピオネート、プロピレングリコールエチルエーテルプロピオネート、プロピレングリコールプロピルエーテルプロピオネート、プロピレングリコールブチルエーテルプロピオネート等のプロピレングリコールアルキルエーテルアセテート類；トルエン、キシレン等の芳香族炭化水素類；メチルエチルケトン、４−ヒドロキシ−４−メチル−２−ペンタノン等のケトン類；および酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、２−ヒドロキシプロピオン酸エチル、２−ヒドロキシ−２−メチルプロピオン酸メチル、２−ヒドロキシ−２−メチルプロピオン酸エチル、ヒドロキシ酢酸メチル、ヒドロキシ酢酸エチル、ヒドロキシ酢酸ブチル、乳酸メチル、乳酸エチル、乳酸プロピル、乳酸ブチル、３−ヒドロキシプロピオン酸メチル、３−ヒドロキシプロピオン酸エチル、３−ヒドロキシプロピオン酸プロピル、３−ヒドロキシプロピオン酸メチル、３−ブトキシプロピオン酸エチル、３−ブトキシプロピオン酸プロピル、３−ブトキシプロピオン酸ブチル等のエステル類を挙げることができる。 Examples of these organic solvents include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl such as methyl cellosolve acetate and ethyl cellosolve acetate. Ether acetates; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; propylene glycol Ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol alkyl ether acetates such as propylene glycol butyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether Pro Propylene glycol alkyl ether acetates such as pionate and propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and 4-hydroxy-4-methyl-2-pentanone; and methyl acetate , Ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropy Ethyl acetate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, Such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, methyl 3-hydroxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, etc. Mention may be made of esters.
これらの有機溶剤の中でも、溶解性、各成分との反応性および塗膜の形成のしやすさから、グリコールエーテル類、グリコールアルキルエーテルアセテート類、エステル類およびジエチレングリコール類が好ましく用いることができる。本発明の基材の樹脂層５を形成する樹脂組成物においては、これら有機溶剤を１種でまたは２種類以上混合して用いてもよい。 Among these organic solvents, glycol ethers, glycol alkyl ether acetates, esters and diethylene glycols can be preferably used from the viewpoint of solubility, reactivity with each component, and ease of forming a coating film. In the resin composition for forming the resin layer 5 of the substrate of the present invention, these organic solvents may be used alone or in combination of two or more.
本発明の基材の樹脂層５を形成する樹脂組成物を製造するには、上記ジアリルフタレート樹脂を主成分として、これに適宜必要量の多官能モノマー、および光重合開始剤を加えた後、必要に応じて上記添加剤を添加し混合、攪拌すればよい。 In order to produce a resin composition for forming the resin layer 5 of the base material of the present invention, the diallyl phthalate resin as a main component, after adding a necessary amount of a polyfunctional monomer and a photopolymerization initiator as appropriate, What is necessary is just to add and mix and stir the said additive as needed.
［光焼成用熱可塑性樹脂フィルム基材の製造方法］
基材１の表層に架橋構造を有する樹脂層５を形成する方法としては、印刷法等のウェットプロセスを挙げることができる。ウェットプロセスとしては、ディップコート法、フローコート法、ロールコート法、バーコーター法、スクリーン印刷法、カーテンコート法、グラビア印刷法、オフセット印刷法等の既知の方法を採用することができる。[Method for producing thermoplastic resin film substrate for photo-baking]
Examples of the method for forming the resin layer 5 having a crosslinked structure on the surface layer of the substrate 1 include a wet process such as a printing method. As the wet process, known methods such as a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, a gravure printing method, and an offset printing method can be employed.
本発明の基材に用いる基材１については特に制限はなく、例えば、ポリカーボネート（ＰＣ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリイミド（ＰＩ）、ポリエーテルスルフォン（ＰＥＳ）、ポリエチレンナフタレート（ＰＥＮ）等の可撓性のプラスチックフィルムおよびこれらフィルムにガスバリヤー性、ハードコート層を付けた複合フィルムを、合成樹脂基材として用いることができる。 There is no restriction | limiting in particular about the base material 1 used for the base material of this invention, For example, polycarbonate (PC), a polyethylene terephthalate (PET), a polyimide (PI), a polyether sulfone (PES), a polyethylene naphthalate (PEN) etc. Flexible plastic films and composite films obtained by attaching a gas barrier property and a hard coat layer to these films can be used as the synthetic resin substrate.
本発明の基材の樹脂層５を活性エネルギー線硬化性樹脂組成物で形成する場合は、照射光源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプまたはメタルハライドランプ等を好適に用いることができる。本発明のフィルム基材１の樹脂層５を活性エネルギー線硬化性樹脂組成物以外の樹脂組成物で形成した場合は、その他、レーザー光線、電子線等も活性エネルギー線として利用してもよい。 When forming the resin layer 5 of the base material of the present invention in the active energy ray curable resin composition, as the irradiation light source, a low pressure mercury lamp, medium pressure mercury lamps, high pressure mercury lamp, ultra-high pressure mercury lamp, a xenon lamp or metal halide lamp It can be used suitably. When the resin layer 5 of the film substrate 1 of the present invention is formed of a resin composition other than the active energy ray curable resin composition, a laser beam, an electron beam, or the like may be used as the active energy ray.
［導電回路基板およびその製造方法］
次に、本発明の導電回路基板およびその製造方法について説明する。本発明の導電回路基板は、上記本発明の基材上に回路パターンが形成されてなるものである。[Conductive circuit board and manufacturing method thereof]
Next, the conductive circuit board and the manufacturing method thereof according to the present invention will be described. The conductive circuit board of the present invention is obtained by forming a circuit pattern on the base material of the present invention.
本発明の導電回路基板の回路パターンの形成は、例えば、導電性組成物を塗布、印刷等のウェットプロセスにより形成することができる。ウェットプロセスとして、例えば、インクジェット記録法、スクリーン印刷法、スピンコート法、バーコート法、スリットコート法、ディップコート法、スプレーコート法、グラビア印刷法、フレキソ印刷法、グラビアオフセット法、凸版オフセット法、マイクロコンタクトプリント法、凸版反転印刷法等の既知の方法を採用することができる。 The circuit pattern of the conductive circuit board of the present invention can be formed, for example, by a wet process such as coating or printing with a conductive composition. As a wet process, for example, inkjet recording method, screen printing method, spin coating method, bar coating method, slit coating method, dip coating method, spray coating method, gravure printing method, flexographic printing method, gravure offset method, letterpress offset method, Known methods such as a micro contact printing method and a letterpress reverse printing method can be employed.
本発明の導電回路基板の回路パターンの形成に当たって、印刷法を採用する場合、導電性組成物としては、例えば、適当な溶剤中に、金、銀、銅、ニッケル、亜鉛、アルミ、カルシウム、マグネシウム、鉄、白金、パラジウム、スズ、クロム、鉛等の金属粒子および銀／パラジウム等のこれら金属の合金、酸化銀、有機銀、有機金等の比較的低温で熱分化して導電性金属を与える熱分解性金属化合物、酸化亜鉛（ＺｎＯ）、酸化インジュウムスズ（ＩＴＯ）等の導電性金属酸化物粒子を導電性成分として含んでいてもよいし、ポリエチレンジオキシチオフェン／ポリスチレンスルホン酸（ＰＥＤＯＴ／ＰＳＳ）、ポリアニリン等の導電性高分子を含んでいてもよい。また、導電性組成物の溶剤の種類に制限はなく導電性材料の溶解または分散に適した溶剤を適宜選択できる。例えば、水、炭化水素系、アルコール系、ケトン系、エーテル系、エステル系、フッ素系等の各種有機溶剤を使用できる。 When the printing method is employed in forming the circuit pattern of the conductive circuit board of the present invention, examples of the conductive composition include gold, silver, copper, nickel, zinc, aluminum, calcium, magnesium in a suitable solvent. Metal particles such as iron, platinum, palladium, tin, chromium, lead, and alloys of these metals such as silver / palladium, silver oxide, organic silver, organic gold, etc. are thermally differentiated at a relatively low temperature to give a conductive metal. Conductive metal oxide particles such as thermally decomposable metal compounds, zinc oxide (ZnO) and indium tin oxide (ITO) may be included as a conductive component, or polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT / PSS) In addition, a conductive polymer such as polyaniline may be included. Moreover, there is no restriction | limiting in the kind of solvent of an electroconductive composition, The solvent suitable for melt | dissolution or dispersion | distribution of an electroconductive material can be selected suitably. For example, various organic solvents such as water, hydrocarbon, alcohol, ketone, ether, ester, and fluorine can be used.
導電性組成物には導電性材料の他、必要に応じて樹脂等のバインダー成分、酸化防止剤、皮膜形成促進のための各種触媒、各種表面張力調整剤、レベリング剤、離型促進剤等を添加してもよい。これらの導電性組成物の中でも、特にナノ銀粒子を溶剤に分散し、低分子シリコーン等の離型剤、フッ素系界面活性剤等の表面張力調整剤を混合した導電性組成物は凸版反転印刷法に適しており、優れたパターンニング性および低温焼成で高い導電性を示すことから好適に使用できる。 In addition to the conductive material, the conductive composition includes a binder component such as a resin, an antioxidant, various catalysts for promoting film formation, various surface tension adjusting agents, leveling agents, mold release accelerators and the like as necessary. It may be added. Among these conductive compositions, in particular, a conductive composition in which nano silver particles are dispersed in a solvent and a release agent such as low molecular silicone is mixed with a surface tension adjusting agent such as a fluorosurfactant is used for letterpress reverse printing. It can be suitably used because it is suitable for the method, and exhibits excellent patterning properties and high conductivity at low temperature firing.
本発明の導電回路基板の製造方法においては、本発明の基材上に形成された回路パターンの焼成には、光焼成を用いる。光焼成は、フラッシュランプを用いた光照射が好ましい。フラッシュランプは、石英やガラス等の管内に発光ガス（Ｘｅ・Ｋｒ・Ａｒ・Ｎｅ等）を封入したランプで、発光時間１μｓ〜５０００μｓの極めて短い時間、発光するもので、２００ｎｍから１１００ｎｍの波長の広帯域のスペクトルにて照射することができる。入手のし易さからＸｅを封入したキセノンフラッシュランプが好ましい。 In the method for producing a conductive circuit board of the present invention, light firing is used for firing the circuit pattern formed on the substrate of the present invention. The light firing is preferably light irradiation using a flash lamp. A flash lamp is a lamp in which a luminescent gas (Xe, Kr, Ar, Ne, etc.) is sealed in a tube made of quartz, glass or the like, and emits light for a very short time of 1 μs to 5000 μs, and has a wavelength of 200 nm to 1100 nm. Irradiation with a broad spectrum is possible. A xenon flash lamp in which Xe is enclosed is preferable because it is easily available.
以下、実施例を用いて本発明をより詳細に説明する。ただし、本発明は、これら実施例に限定されるものではない。
＜実施例１および実施例２＞
下記表１に示す配合で各成分（単位は質量部）を混合し、各成分を十分に撹拌、溶解させた後、０．４５μｍメンブレインフィルターを用いて濾過し、樹脂組成物を調製した。得られた樹脂組成物を基材である１２５μｍ厚のＰＥＴフィルム（東洋紡社製：コスモシャインＡ４３００）にバーコーターにて塗布し、９０℃で５分間加熱して、溶剤を揮散させた。その後、高圧水銀灯を用いて積算光量２，０００ｍＪ／ｃｍ２の活性エネルギー線で樹脂組成物を硬化させて基材上に樹脂層を形成してフィルム基材を作製した。硬化後の樹脂層の膜厚は２〜３μｍであった。Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
<Example 1 and Example 2>
Each component (unit: part by mass) was mixed in the formulation shown in Table 1 below, and each component was sufficiently stirred and dissolved, followed by filtration using a 0.45 μm membrane filter to prepare a resin composition. The obtained resin composition was applied to a 125 μm-thick PET film (Toyobo Co., Ltd .: Cosmo Shine A4300) as a base material with a bar coater and heated at 90 ° C. for 5 minutes to volatilize the solvent. Thereafter, the resin composition was cured with an active energy ray having an integrated light quantity of 2,000 mJ / cm 2 using a high-pressure mercury lamp to form a resin layer on the base material to produce a film base material. The thickness of the cured resin layer was 2 to 3 μm.
上記手順で作成した基材に、導電性組成物としてＡｇペースト（平均粒径２０ｎｍの銀粒子をターピネオールに分散させた、銀含有率＝４０質量％のナノ銀ペースト）を、メッシュ数３５５（Ｔ３５５Ｂ：乳剤厚５μｍ）のスクリーン版を用いてスクリーン印刷により付与し、膜厚１．０μｍの回路パターンを形成した。この回路パターンをキセノンフラッシュランプ（ランプ出力：７５０Ｖ、パルス長２３００μ秒、２６００μ秒、大気下）にて光焼成して、導電回路基板を作製した。得られた導電回路基板につき、ミリオームハイテスタ３５４０（日置電機社製）を用いてライン抵抗値を、ロレスタＧＰ（三菱化学アナリテック社製）を用いてシート抵抗値を、ライン抵抗値と線幅、膜厚、配線長より計算された比抵抗値につき評価した。得られた結果を表１に併記する。また、図２に、実施例１の導電回路基板の回路パターンの一部の電子顕微鏡写真を、図３に、実施例２の導電回路基板の回路パターンの一部の電子顕微鏡写真を示す。これら電子顕微鏡写真をもとに、電極両わきの基材のえぐれを評価した。えぐれが無く、形状も良好なものを〇、えぐれはないが電極にクラックが生じたものは△、両わきがえぐれてしまったものは×とした。 An Ag paste (a nano silver paste having a silver content of 40% by mass in which silver particles having an average particle diameter of 20 nm are dispersed in terpineol) as a conductive composition is applied to the base material prepared by the above procedure, and the number of meshes is 355 (T355B). : Emulsion thickness 5 μm) was applied by screen printing to form a circuit pattern having a thickness of 1.0 μm. This circuit pattern was photo-baked with a xenon flash lamp (lamp output: 750 V, pulse length 2300 μsec, 2600 μsec, in the atmosphere) to produce a conductive circuit board. For the obtained conductive circuit board, the line resistance value was measured using a milliohm high tester 3540 (manufactured by Hioki Electric Co., Ltd.), the sheet resistance value was measured using Loresta GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), The specific resistance value calculated from the film thickness and the wiring length was evaluated. The obtained results are also shown in Table 1. FIG. 2 shows an electron micrograph of a part of the circuit pattern of the conductive circuit board of Example 1, and FIG. 3 shows an electron micrograph of a part of the circuit pattern of the conductive circuit board of Example 2. On the basis of these electron micrographs, the pitting of the substrate on both sides of the electrode was evaluated. The case where there was no void and the shape was good was marked as ◯, the case where there was no void but a crack occurred in the electrode was marked as Δ, and the case where both sides were cracked was marked as x.
＜比較例＞
基材上に樹脂層を設けなかったこと以外は上記と同様の手順いて導電回路基板を作製し、同様の方法にて、ライン抵抗値、シート抵抗値、比抵抗値につき評価した。得られた結果を表１に併記する。また、図４に、比較例の導電回路基板の回路パターンの一部の電子顕微鏡写真を示す。<Comparative example>
A conductive circuit board was produced in the same procedure as described above except that the resin layer was not provided on the substrate, and the line resistance value, sheet resistance value, and specific resistance value were evaluated in the same manner. The obtained results are also shown in Table 1. FIG. 4 shows an electron micrograph of a part of the circuit pattern of the conductive circuit board of the comparative example.
※２：焼結不足のため測定できず
上記表１より、本発明の光焼成用熱可塑性樹脂フィルム基材は、光焼成を行っても表面に形成した回路パターンにクラックや断線が生じてないことがわかる。また、実施例１では、電極両わきの基材にえぐれは見られず形状も良好であり、実施例２では、電極両わきの基材にえぐれは見られないが、若干電極にクラックが生じていた。比較例は、電極両わきの基材がえぐれてしまっていることがわかる。（図２〜４参照） From Table 1 above, it can be seen that the circuit pattern formed on the surface of the thermoplastic resin film substrate for photobaking of the present invention is not cracked or disconnected even when photobaking is performed. Further, in Example 1, the base material on both sides of the electrode is not seen and the shape is good. In Example 2, the base material on both sides of the electrode is not seen, but the electrode is slightly cracked. It was. In the comparative example, it can be seen that the base material on both sides of the electrode has been removed. (See Figures 2-4)
１ 基材
２ 塗膜
３ 導体
４ 凹み
５ 樹脂層DESCRIPTION OF SYMBOLS 1 Base material 2 Coating film 3 Conductor 4 Depression 5 Resin layer
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| PCT/JP2014/057359 WO2014156844A1 (en) | 2013-03-29 | 2014-03-18 | Thermoplastic resin film base for optical firing, conductive circuit board using same, and method for manufacturing said conductive circuit board |
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| JP2012060084A (en) * | 2010-09-13 | 2012-03-22 | Toshiba Tec Corp | Method for forming conductive pattern and printed material |
| WO2013182896A1 (en) * | 2012-06-05 | 2013-12-12 | Showa Denko K.K. | Substrate film and sintering method |
| JP2014004512A (en) * | 2012-06-22 | 2014-01-16 | Ricoh Co Ltd | Pattern forming method, pattern formed by the same and device |
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| US7439285B2 (en) * | 2004-01-23 | 2008-10-21 | Printar Ltd. | Liquid thermosetting ink |
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| US10231344B2 (en) * | 2007-05-18 | 2019-03-12 | Applied Nanotech Holdings, Inc. | Metallic ink |
| JP2009124032A (en) * | 2007-11-16 | 2009-06-04 | Shinshu Univ | Method of manufacturing printing type electronic circuit board |
| JP2009124029A (en) * | 2007-11-16 | 2009-06-04 | Shinshu Univ | Method of manufacturing electronic circuit board using ink jetting |
| US9730333B2 (en) * | 2008-05-15 | 2017-08-08 | Applied Nanotech Holdings, Inc. | Photo-curing process for metallic inks |
| JP5505778B2 (en) * | 2009-12-24 | 2014-05-28 | 日本ゼオン株式会社 | Film for multilayer printed circuit boards |
| CN102398438A (en) * | 2010-09-15 | 2012-04-04 | 中国科学院化学研究所 | Method for preparing primary circuit by jet-printing metal conductive printing ink by virtue of laser or microwave processing |
| JP2012214870A (en) * | 2011-03-28 | 2012-11-08 | Mitsubishi Paper Mills Ltd | Method for forming metallic coating and metallic ultrafine particle-containing composition |
| JP5880100B2 (en) * | 2012-02-10 | 2016-03-08 | コニカミノルタ株式会社 | Manufacturing method of transparent electrode |
| JP5849834B2 (en) * | 2012-04-09 | 2016-02-03 | コニカミノルタ株式会社 | Transparent electrode, method for producing transparent electrode, and organic electronic device using the transparent electrode |
| JP5489305B2 (en) * | 2012-06-27 | 2014-05-14 | 石原ケミカル株式会社 | Circuit board and conductive film forming method |
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| JP6441212B2 (en) | 2018-12-19 |
| KR102292668B1 (en) | 2021-08-24 |
| WO2014156844A1 (en) | 2014-10-02 |
| KR20150136530A (en) | 2015-12-07 |
| CN105073416A (en) | 2015-11-18 |
| CN105073416B (en) | 2018-01-23 |
| TWI636878B (en) | 2018-10-01 |
| TW201446505A (en) | 2014-12-16 |
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