CN111742029B - 粘接剂组合物、热固性粘接片以及印刷电路板 - Google Patents
粘接剂组合物、热固性粘接片以及印刷电路板 Download PDFInfo
- Publication number
- CN111742029B CN111742029B CN201980009500.2A CN201980009500A CN111742029B CN 111742029 B CN111742029 B CN 111742029B CN 201980009500 A CN201980009500 A CN 201980009500A CN 111742029 B CN111742029 B CN 111742029B
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- adhesive composition
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- epoxy resin
- styrene
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- 239000000853 adhesive Substances 0.000 title claims abstract description 74
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 74
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 43
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000003822 epoxy resin Substances 0.000 claims abstract description 48
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 48
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 229920001971 elastomer Polymers 0.000 claims abstract description 25
- 239000000806 elastomer Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims description 23
- 239000012790 adhesive layer Substances 0.000 claims description 18
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 16
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 10
- 239000011241 protective layer Substances 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 238000005452 bending Methods 0.000 abstract description 28
- -1 acryl Chemical group 0.000 description 18
- 238000001723 curing Methods 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 10
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 10
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- 229910052802 copper Inorganic materials 0.000 description 7
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- 150000003440 styrenes Chemical class 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- 230000005856 abnormality Effects 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
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- 239000011342 resin composition Substances 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C09J7/35—Heat-activated
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
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- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C09J165/02—Polyphenylenes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C09J171/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
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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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
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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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
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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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- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2453/00—Presence of block copolymer
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Abstract
本发明提供介电常数和介电损耗角正切低,耐弯折性良好的粘接剂组合物。在粘接剂组合物中,相对于该粘接剂组合物的合计100质量份,含有:75~90质量份的苯乙烯系弹性体、3~25质量份的末端具有聚合性基团的改性聚苯醚树脂、以及合计10质量份以下的环氧树脂和环氧树脂固化剂。
Description
技术领域
本技术涉及粘接剂组合物、热固性粘接片以及印刷电路板。本申请基于在日本于2018年2月5日申请的日本专利申请号特愿2018-018177主张优先权,该申请通过参照被援用于本申请中。
背景技术
由于信息通信的高速、大容量化,加速了流过印刷电路板的信号的高频化的趋势。为了应对该情况,对刚性基板、柔性印刷电路板(FPC)的构成材料(例如粘接剂组合物)要求低介电常数、低介电损耗角正切这样的低介电特性(例如,参照专利文献1、2)。
再者,聚苯醚作为具有低介电特性的基板用材料,虽然优点也多,但熔点(软化点)非常高,在常温下具有硬的性质,因此存在耐弯折性差的缺点。例如,如专利文献2中记载的树脂组合物那样,若相对于树脂整体,3~5成左右由聚苯醚构成,则耐弯折性趋于变差。
现有技术文献
专利文献
专利文献1:日本特开2017-57346号公报
专利文献2:日本特开2016-79354号公报
发明内容
发明所要解决的问题
本技术是鉴于这样的现有实际情况而提出的,提供介电常数和介电损耗角正切低、耐弯折性良好的粘接剂组合物、热固性粘接片以及印刷电路板。
用于解决问题的方案
在本技术的粘接剂组合物中,相对于该粘接剂组合物的合计100质量份,含有:75~90质量份的苯乙烯系弹性体、3~25质量份的末端具有聚合性基团的改性聚苯醚树脂、以及合计10质量份以下的环氧树脂和环氧树脂固化剂。
本技术的热固性粘接片在基材上形成有由上述的粘接剂组合物形成的热固性粘接层。
本技术的印刷电路板借助上述的粘接剂组合物的固化物层叠有:具备基材和布线图案的带有布线的树脂基板的上述布线图案侧、以及保护层(coverlay)。
发明效果
根据本技术,能提供介电常数和介电损耗角正切低、耐弯折性良好的粘接剂组合物。
附图说明
图1是表示印刷电路板的构成例的剖视图。
图2是表示多层印刷电路板的构成例的剖视图。
图3是表示耐弯折性试验中使用的TEG的构成例的俯视图。
图4是表示耐弯折性试验中使用的测定装置的立体图。
具体实施方式
以下,对本技术的实施方式进行说明。以下说明的成分的重均分子量和数均分子量的值是根据通过凝胶渗透色谱(GPC)法测定的标准聚苯乙烯换算的分子量计算出的值。
<粘接剂组合物>
本技术的粘接剂组合物是热固性的粘接剂组合物,相对于该粘接剂组合物的合计100质量份,含有:75~90质量份的苯乙烯系弹性体(成分A)、3~25质量份的末端具有聚合性基团的改性聚苯醚树脂(成分B;以下,也简称为改性聚苯醚树脂)、以及合计10质量份以下的环氧树脂(成分C)和环氧树脂固化剂(成分D)。通过采用这样的构成,可以制成在热固化后介电常数和介电损耗角正切也低,热固化后耐弯折性也良好的粘接剂组合物。这样的粘接剂组合物例如可适合用作柔性印刷电路板用的粘接剂(层间粘接剂)。
[苯乙烯系弹性体]
苯乙烯系弹性体是苯乙烯与烯烃(例如,丁二烯、异戊二烯等共轭二烯)的共聚物和/或其氢化物。苯乙烯系弹性体是将苯乙烯作为硬链段、将共轭二烯作为软链段的嵌段共聚物。作为苯乙烯系弹性体的例子,可列举出:苯乙烯/丁二烯/苯乙烯嵌段共聚物、苯乙烯/异戊二烯/苯乙烯嵌段共聚物、苯乙烯/乙烯/丁烯/苯乙烯嵌段共聚物、苯乙烯/乙烯/丙烯/苯乙烯嵌段共聚物、苯乙烯/丁二烯嵌段共聚物等。另外,也可以使用通过氢化消除了共轭二烯成分的双键的、苯乙烯/乙烯/丁烯/苯乙烯嵌段共聚物、苯乙烯/乙烯/丙烯/苯乙烯嵌段共聚物、苯乙烯/丁二烯嵌段共聚物(也称为氢化苯乙烯系弹性体)等。
苯乙烯系弹性体的重均分子量优选100000以上,更优选100000~150000,进一步优选110000~150000。通过采用这样的构成,能使剥离强度(连接可靠性)、耐热性更良好。
苯乙烯系弹性体中的苯乙烯比率优选小于30%,更优选5%~30%,进一步优选5%~25%,特别优选10%~20%。通过采用这样的构成,能使耐弯折性更良好,能使剥离强度(连接可靠性)、耐热性更良好。
作为苯乙烯系弹性体的具体例,可列举出Tuftec H1221(Mw120000,苯乙烯比率10%)、Tuftec H1041(Mw90000,苯乙烯比率30%)、Tuftec H1043(Mw110000,苯乙烯比率67%,以上为旭化成社制)、HYBRAR 7125(Mw110000,苯乙烯比率20%,可乐丽社制)。其中,从分子量、苯乙烯比率的观点考虑,优选Tuftec H1221、HYBRAR 7125。
相对于成分A、成分B、成分C以及成分D的合计100质量份,粘接剂组合物中的苯乙烯系弹性体的含量为75~90质量份,可以为80~90质量份。当苯乙烯系弹性体的含量不足75质量份时,耐弯折性趋于变差。另外,当苯乙烯系弹性体的含量超过90质量份时,其他成分(例如成分B)的含量相对减少,因此耐热性趋于变差。苯乙烯系弹性体可以单独使用一种,也可以并用两种以上。
[改性聚苯醚树脂]
改性聚苯醚树脂在分子中具有聚苯醚链,在末端具有聚合性基团。改性聚苯醚树脂优选在1分子中具有2个以上的环氧基和烯属不饱和键中的至少一种作为聚合性基团。特别是,从与上述的苯乙烯系弹性体的相容性、粘接剂组合物的介电特性的观点考虑,改性聚苯醚树脂优选在两末端具有环氧基和烯属不饱和键(例如,(甲基)丙烯酰基、乙烯基苄基)中的至少一种。
需要说明的是,未被具有聚合性基团的化合物改性的聚苯醚树脂,即,末端具有羟基的聚苯醚树脂的极性过强,因此与上述的苯乙烯系弹性体的相容性差,恐怕会无法将粘接剂组合物成膜化,因此不优选。
作为改性聚苯醚树脂的一例的、在两末端具有乙烯基苄基的改性聚苯醚树脂例如通过将使双官能酚化合物和单官能酚化合物氧化偶联而得到的双官能亚苯基醚低聚物的末端酚性羟基进行乙烯基苄基醚化而得到。
从与上述的苯乙烯系弹性体的相容性、借助粘接剂组合物的固化物将具备基材和布线图案的带有布线的树脂基板的布线图案侧和保护层热固化(压制)时的高低差追随性等观点考虑,改性聚苯醚树脂的重均分子量(或数均分子量)优选为1000~3000。
作为改性聚苯醚树脂的具体例,可以使用OPE-2St(两末端具有乙烯基苄基的改性聚苯醚树脂)、OPE-2Gly(两末端具有环氧基的改性聚苯醚树脂)、OPE-2EA(两末端具有丙烯酰基的改性聚苯醚树脂,以上,三菱瓦斯化学社制)、Noryl SA9000(两末端具有甲基丙烯酰基的改性聚苯醚树脂,SABIC社制)等。
相对于成分A、成分B、成分C以及成分D的合计100质量份,粘接剂组合物中的改性聚苯醚树脂的含量为3~25质量份,优选为5~20质量份。当改性聚苯醚树脂的含量超过25质量份时,耐弯折性趋于变差。另外,通过使改性聚苯醚树脂的含量为5质量份以上,能使耐热性更良好。聚苯醚树脂可以单独使用一种,也可以并用两种以上。
[环氧树脂]
对于环氧树脂,例如,可列举出:具有萘骨架的环氧树脂、双酚A型环氧树脂、双酚F型环氧树脂、苯酚酚醛清漆型环氧树脂、脂环式环氧树脂、硅氧烷型环氧树脂、联苯型环氧树脂、缩水甘油酯型环氧树脂、缩水甘油胺型环氧树脂、乙内酰脲型环氧树脂等。特别是,从膜的成形性的观点考虑,环氧树脂优选为具有萘骨架的环氧树脂、双酚A型环氧树脂或双酚F型环氧树脂,且常温下为液态的环氧树脂。环氧树脂可以单独使用一种,也可以并用两种以上。
[环氧树脂固化剂]
环氧树脂固化剂是促进上述的环氧树脂的固化反应的催化剂。作为环氧树脂固化剂,例如可以使用咪唑系、酚系、胺系、酸酐系、有机过氧化物系等。特别是,从粘接剂组合物的常温下的保管性(寿命)的观点考虑,环氧树脂固化剂优选为具有潜伏性的固化剂,更优选为胶囊化而具有潜伏性的咪唑系的固化剂。由于常温下的保管性良好,可以使粘接剂组合物的供给、使用上的管理更简便。具体而言,作为环氧树脂固化剂,可以使用以潜伏性咪唑改性体为核、用聚氨酯覆盖其表面而成的微胶囊型潜伏性固化剂。作为市售品,例如可以使用Novacure 3941(旭化成E-Materials社制)。环氧树脂固化剂可以单独使用一种,也可以并用两种以上。
相对于成分A、成分B、成分C以及成分D的合计100质量份,粘接剂组合物中的环氧树脂和环氧树脂固化剂的合计含量为10质量份以下,优选5质量份以下。当环氧树脂和环氧树脂固化剂的合计含量超过10质量份时,介电特性趋于变差。
[其他成分]
在不损害本技术的效果的范围内,粘接剂组合物还可以含有上述的成分A~成分D以外的其他成分。作为其他成分,可列举出有机溶剂、硅烷偶联剂、流动性调整用的填料等。有机溶剂没有特别限制,例如可列举出醇系溶剂、酮系溶剂、醚系溶剂、芳香族系溶剂、酯系溶剂等。其中,从溶解性的观点考虑,优选芳香族系溶剂、酯系溶剂。有机溶剂可以单独使用一种,也可以并用两种以上。
<热固性粘接片>
本技术的热固性粘接片在基材上形成有由上述的粘接剂组合物形成的热固性粘接层且为膜形状。例如通过用溶剂将上述的粘接剂组合物稀释,以干燥后的厚度为10~60μm的方式通过棒涂机、辊涂机等涂布于基材的至少一方的面,在50℃~130℃左右的温度下使其干燥而得到热固性粘接片。基材可以使用下述的剥离基材,例如,根据需要用硅酮(silicone)等对聚对苯二甲酸乙二醇酯膜、聚酰亚胺膜等基材进行剥离处理而得到的剥离基材。
构成热固性粘接片的热固性粘接层的厚度可以根据目的适当设定,作为一例,可以设为1~100μm,也可以设为1~30μm。
如上所述,构成热固性粘接片的热固性粘接层由在热固化后介电常数和介电损耗角正切也低、热固化后耐弯折性也良好的粘接剂组合物形成,因此,例如能适用于柔性印刷电路板的层间粘接剂、将柔性印刷电路板的端子部和用于其背衬的连接用基材粘接固定的用途。另外,热固性粘接片的热固化后的剥离强度、耐热性,常温下的保管性也良好。
<印刷电路板>
本技术的印刷电路板借助上述的粘接剂组合物(热固性粘接层)的固化物层叠有:具备基材和布线图案的带有布线的基材的布线图案侧、以及保护层。印刷电路板例如是通过在带有布线的基材的布线图案侧与保护层之间配置热固性粘接片的热固性粘接层并进行热压接,使带有布线的基材和保护层一体化而得到的。
带有布线的基材与上述的粘接剂组合物同样,高频区域的电特性优异。例如,优选在频率1~10GHz的区域中,介电常数和介电损耗角正切低。作为基材的具体例,可列举出以液晶聚合物(LCP:Liquid Crystal Polymer)、聚四氟乙烯、聚酰亚胺以及聚萘二甲酸乙二醇酯中的任意种为主成分的基材。这些基材中,优选以液晶聚合物为主成分的基材(液晶聚合物膜)。这是因为,与聚酰亚胺相比,液晶聚合物的吸湿率非常低,不易被使用环境影响。
对使用本技术的粘接剂组合物的印刷电路板的构成例进行说明。在图1所示的印刷电路板1中,具备液晶聚合物膜2和铜箔(轧制铜箔)3的带有布线的基材(覆铜板:CCL)的铜箔3侧和液晶聚合物膜4借助由上述的粘接剂组合物(热固性粘接层)形成的固化物层5而层叠。
另外,印刷电路板例如可以为图2所示的多层结构。在图2所示的印刷电路板6中,具备聚酰亚胺层7(厚度25μm)、铜箔8(厚度18μm)以及镀铜层9(厚度10μm)的带有布线的基材的镀铜层9侧和保护层10(厚度25μm)借助由上述的粘接剂组合物(热固性粘接层)形成的固化物层5(厚度35μm)而层叠(合计厚度201μm)。
实施例
以下,对本技术的实施例进行说明。需要说明的是,本技术并不限定于这些实施例。
<成分A>
Tuftec H1221:氢化苯乙烯系热塑性弹性体(Mw120000,苯乙烯比率10%),旭化成社制。
HYBRAR 7125:氢化苯乙烯系热塑性弹性体(Mw110000,苯乙烯比率20%),可乐丽社制。
Tuftec H1041:氢化苯乙烯系热塑性弹性体(Mw90000,苯乙烯比率30%),旭化成社制。
Tuftec H1043:氢化苯乙烯系热塑性弹性体(Mw110000,苯乙烯比率67%),旭化成社制。
<成分B>
OPE-2St2200:两末端具有乙烯基苄基的改性聚苯醚树脂(Mn=2200),三菱瓦斯化学社制。
SA9000:两末端具有甲基丙烯酰基的改性聚苯醚树脂(Mw1700),SABIC社制。
SA120:两末端具有羟基的聚苯醚树脂,SABIC社制。
S201A:两末端具有羟基的聚苯醚树脂,旭化成社制。
<成分C>
4032D:萘型环氧树脂,DIC社制。
JER828:环氧树脂,三菱化学社制。
YD014:双酚A型环氧树脂,新日铁住金化学社制。
<成分D>
Novacure 3941:以咪唑改性体为核、用聚氨酯覆盖其表面而成的微胶囊型潜伏性固化剂,旭化成E-Materials社制。
2E4MZ:2-乙基-4-甲基咪唑(无潜伏性的咪唑)。
[热固性粘接剂组合物的制备]
按表1所示的质量称量表1所示的各成分,均匀地混合到含有甲苯和乙酸乙酯的有机溶剂中,由此制备出热固性粘接剂组合物(热固性粘接层形成用涂料)。
[热固性片的制作]
将得到的热固性粘接剂组合物涂布在实施了剥离处理的聚对苯二甲酸乙二醇酯膜,在50℃~130℃的干燥炉中干燥,由此制作出具有聚对苯二甲酸乙二醇酯膜和厚度25μm的热固性粘接层的热固性粘接片。
[评价]
<热固性粘接层形成用涂料的涂布性(膜的状态)的评价>
在制作上述的热固性片时,按以下的基准评价了热固性粘接剂组合物的涂布性。将结果示于表1。
A:粘接剂组合物的相容性良好,在膜状态下能进行后述的评价。
B:粘接剂组合物的相容性差,在膜状态下无法进行后述的评价。
<介电常数>
将实施例和比较例中制作的热固性粘接片彼此层压,制作出厚度1mm的试验片后,使该试验片在160℃、1.0MPa的条件下热固化1小时,制作出评价用试验片。使用介电常数测定装置(AET社制),对该评价用试验片求出测定温度23℃、测定频率10GHz下的介电常数。将结果示于表1。
A:介电常数小于2.3。
B:介电常数为2.3以上且小于2.4。
C:介电常数为2.4以上且小于2.6。
D:介电常数为2.6以上。
<介电损耗角正切>
利用与上述的介电常数的测定同样的方法,对评价用试验片求出介电损耗角正切。将结果示于表1。
A:介电损耗角正切小于0.002。
B:介电损耗角正切为0.002以上且小于0.0035。
C:介电损耗角正切为0.0035以上且小于0.005。
D:介电损耗角正切为0.005以上。
<剥离强度>
将得到的热固性粘接片切割成规定大小的长方形(2cm×5cm),用设定为100℃的层压机将该切割后的热固性粘接层临时粘贴到2cm×7cm×50μm厚的液晶聚合物膜上后,去除基材(聚对苯二甲酸乙二醇酯膜)使热固性粘接层露出。对于露出的热固性粘接层从上方重叠相同大小的覆铜板(由厚度12μm的轧制铜箔和厚度50μm的液晶聚合物膜形成的CCL)的轧制铜箔面(未进行粗面化处理的面),在160℃、1.0MPa的条件下热固化1小时。由此,制作出样品。
对得到的样品以剥离速度50mm/min进行90度剥离试验,测定剥离时所需的力(初始的剥离强度和可靠性试验后的剥离强度)。将结果示于表1。
[初始(在上述的160℃、1.0MPa的条件下的热固化后直接进行测定)]
A:剥离强度为8N/cm以上。
B:剥离强度为6N/cm以上且小于8N/cm。
C:剥离强度为4N/cm以上且小于6N/cm。
D:剥离强度小于4N/cm。
[可靠性试验后(85℃,相对湿度85%,240小时(即,在上述的160℃、1.0MPa的条件下的热固化后,投入85℃、相对湿度85%的环境中240小时,取出3小时后进行测定))]
A:剥离强度为7N/cm以上。
B:剥离强度为5N/cm以上且小于7N/cm。
C:剥离强度为3N/cm以上且小于5N/cm。
D:剥离强度小于3N/cm。
<耐热性>
使上述的样品经过三次最高温度260℃-30秒的回流(reflow)工序,确认通过后的样品的外观,按下述基准评价是否未发生剥离、鼓起。将结果示于表1。
A:经过三次后仍无异常。
B:经过两次时无异常,第三次发生剥离、鼓起等异常。
C:经过一次时无异常,第二次发生剥离、鼓起等异常。
D:第一次发生剥离、鼓起等异常。
<耐弯折性>
将得到的热固性粘接片切割成规定大小的长方形(1.5cm×12cm),用设定为100℃的层压机将该切割后的热固性粘接层临时粘贴到1.5cm×12cm×50μm厚的液晶聚合物膜上后,去除基材(聚对苯二甲酸乙二醇酯膜)使热固性粘接层露出。对于露出的热固性粘接层,与MIT耐折试验用的FPC-TEG重叠,在160℃、1.0MPa的条件下热固化1小时。将MIT耐折试验用的TEG11的构成示于图3。TEG11是通过由作为基材的液晶聚合物膜(厚度50μm)和轧制铜箔(厚度12μm)形成的CCL形成铜布线而成的。MIT耐折试验是将制作的试验片12放置在图4所示的构造的MIT耐折疲劳试验机13中进行的。在折弯角度135°、折弯钳角度R=0.38、试验速度175cpm的条件下进行。确认了铜布线断裂前的折弯次数。将结果示于表1。
A:断裂前的折弯次数为1200次以上。
B:断裂前的折弯次数为500次以上且少于1200次。
C:断裂前的折弯次数为200次以上且少于500次。
D:断裂前的折弯次数少于200次。
<寿命评价>
将热固性片在常温下保管4个月后,进行了与上述的剥离强度的评价同样的评价。确认了与刚制作完热固性粘接片后就进行了评价的剥离强度相比时的降低率。将结果示于表1。
A:剥离强度的降低小于10%。
B:剥离强度的降低为10%以上且小于30%。
C:剥离强度的降低为30%以上。
[表1]
根据表1所示的结果可知,下述的粘接剂组合物的热固化后的介电常数和介电损耗角正切也低,耐弯折性也良好,在该粘接剂组合物中,相对于粘接剂组合物的合计100质量份,含有:75~90质量份的苯乙烯系弹性体(成分A)、3~25质量份的末端具有聚合性基团的改性聚苯醚树脂(成分B)、以及合计10质量份以下的环氧树脂(成分C)和环氧树脂固化剂(成分D)。
根据实验例6的结果可知,当改性聚苯醚树脂的含量超过25质量份时,耐弯折性变差。
根据实验例8的结果可知,当环氧树脂和环氧树脂固化剂的合计量超过10质量份时,不易使介电损耗角正切降低。
根据实验例11、12的结果可知,当使用末端具有羟基的聚苯醚树脂时,膜状态变差,或介电特性和耐弯折性变差。需要说明的是,在实验例12中,由于膜的状态差,因此无法进行介电常数、介电损耗角正切、剥离强度、耐热性、耐弯折性的评价。
根据实验例的结果可知,通过使改性聚苯醚树脂的含量为5~20质量份,使得介电常数和介电损耗角正切低,耐弯折性良好,进而耐热性也良好。
根据实验例的结果可知,通过使苯乙烯系弹性体的质均分子量为100000以上,能使剥离强度、耐热性以及耐弯折性更良好。
根据实验例的结果可知,通过使苯乙烯系弹性体中的苯乙烯比率小于30%,能使介电特性、剥离强度、耐热性以及耐弯折性更良好。
根据实验例的结果可知,通过使用液态的环氧树脂,能使剥离强度、耐热性以及耐弯折性更良好。
根据实验例的结果可知,通过使用具有潜伏性的环氧树脂固化剂,也能使常温下的保管性良好。
根据实验例3、7、14的结果可知,在10GHz下介电常数(Dk)为2.3以下,介电损耗角正切(Df)小于0.002,显示出非常低的值,对于液晶聚合物膜和未实施粗面化处理的轧制铜箔,示出8N/cm以上的非常高的粘接强度。
附图标记说明
1:印刷电路板,2:液晶聚合物膜,3:铜箔,4:液晶聚合物膜,5:由粘接剂组合物形成的固化物层,6:印刷电路板,7:聚酰亚胺层,8:铜箔,9:镀铜层,10:保护层,11:TEG,12:试验片,13:MIT耐折疲劳试验机,14:柱塞,15:上部夹头,16:旋转夹头,17:弯折挡块。
Claims (7)
1.一种粘接剂组合物,其中,相对于所述粘接剂组合物的合计100质量份,含有:
75~80质量份的苯乙烯系弹性体;
15~20质量份的末端具有聚合性基团的改性聚苯醚树脂;
环氧树脂;以及
具有潜伏性的环氧树脂固化剂,
所述环氧树脂和所述环氧树脂固化剂的合计含量为10质量份以下,所述环氧树脂和所述环氧树脂固化剂的含量均不为0质量份,
所述苯乙烯系弹性体中的苯乙烯比率为5%~25%。
2.根据权利要求1所述的粘接剂组合物,其中,
所述苯乙烯系弹性体的质均分子量为100000以上。
3.根据权利要求1或2所述的粘接剂组合物,其中,
所述苯乙烯系弹性体中的苯乙烯比率为10%~20%。
4.根据权利要求1或2所述的粘接剂组合物,其中,
所述改性聚苯醚树脂在末端具有环氧基和烯属不饱和键中的至少一种。
5.一种热固性粘接片,其在基材上形成有由权利要求1~4中任一项所述的粘接剂组合物形成的热固性粘接层。
6.一种印刷电路板,其借助权利要求1~4中任一项所述的粘接剂组合物的固化物层叠有:具备基材和布线图案的带有布线的树脂基板的所述布线图案侧、以及保护层。
7.根据权利要求6所述的印刷电路板,其中,
所述基材是液晶聚合物膜。
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