TWI826445B - Conductor substrate, stretchable wiring substrate, and stretchable resin film for wiring substrate - Google Patents
Conductor substrate, stretchable wiring substrate, and stretchable resin film for wiring substrate Download PDFInfo
- Publication number
- TWI826445B TWI826445B TW108116003A TW108116003A TWI826445B TW I826445 B TWI826445 B TW I826445B TW 108116003 A TW108116003 A TW 108116003A TW 108116003 A TW108116003 A TW 108116003A TW I826445 B TWI826445 B TW I826445B
- Authority
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- Taiwan
- Prior art keywords
- meth
- acrylate
- stretchable
- resin film
- rubber
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 127
- 239000011347 resin Substances 0.000 title claims abstract description 127
- 239000004020 conductor Substances 0.000 title claims abstract description 59
- 239000000758 substrate Substances 0.000 title claims abstract description 28
- 229920001971 elastomer Polymers 0.000 claims abstract description 74
- 239000005060 rubber Substances 0.000 claims abstract description 55
- 239000000945 filler Substances 0.000 claims abstract description 45
- 239000011888 foil Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 24
- 238000004132 cross linking Methods 0.000 claims description 24
- 239000004593 Epoxy Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000011342 resin composition Substances 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000010408 film Substances 0.000 description 158
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 131
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- 238000000034 method Methods 0.000 description 18
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- MOFOBJHOKRNACT-UHFFFAOYSA-N nickel silver Chemical compound [Ni].[Ag] MOFOBJHOKRNACT-UHFFFAOYSA-N 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000889 permalloy Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- JZFHXRUVMKEOFG-UHFFFAOYSA-N tert-butyl dodecaneperoxoate Chemical compound CCCCCCCCCCCC(=O)OOC(C)(C)C JZFHXRUVMKEOFG-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- KDKQKAXHHJSODN-UHFFFAOYSA-N tert-butyl hydrogen carbonate;2-propan-2-ylperoxypropane Chemical compound CC(C)OOC(C)C.CC(C)(C)OC(O)=O KDKQKAXHHJSODN-UHFFFAOYSA-N 0.000 description 1
- FQFILJKFZCVHNH-UHFFFAOYSA-N tert-butyl n-[3-[(5-bromo-2-chloropyrimidin-4-yl)amino]propyl]carbamate Chemical compound CC(C)(C)OC(=O)NCCCNC1=NC(Cl)=NC=C1Br FQFILJKFZCVHNH-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003249 vinylidene fluoride hexafluoropropylene elastomer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0277—Bendability or stretchability details
- H05K1/0283—Stretchable printed circuits
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- 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
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/06—Thermal details
- H05K2201/068—Thermal details wherein the coefficient of thermal expansion is important
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Structure Of Printed Boards (AREA)
Abstract
本發明揭示一種伸縮性配線基板,其包括伸縮性樹脂膜及設置於伸縮性樹脂膜上的導體層。伸縮性樹脂膜含有橡膠成分及填料。橡膠成分可經交聯。The present invention discloses a stretchable wiring substrate, which includes a stretchable resin film and a conductor layer provided on the stretchable resin film. The stretchable resin film contains rubber components and fillers. The rubber component can be cross-linked.
Description
本發明是有關於一種導體基板、伸縮性配線基板及配線基板用伸縮性樹脂膜。 The present invention relates to a conductor substrate, a stretchable wiring substrate, and a stretchable resin film for the wiring substrate.
近年來,於穿戴式設備及健康照護(health care)關聯設備等領域中,要求例如可沿著身體的曲面或關節部來使用,並且即便穿脫亦難以產生連接不良的伸縮性電子裝置(可拉伸元件(stretchable device))。為了製造此種具有高伸縮性的可拉伸元件而要求具有高伸縮性的伸縮性配線基板。因此,例如專利文獻1提出有一種伸縮自如的包含熱塑性彈性體的伸縮性柔性電路基板。 In recent years, in the fields of wearable devices and health care-related devices, there has been a demand for stretchable electronic devices that can be used along curved surfaces or joints of the body and are less likely to cause poor connection even when put on and taken off. stretchable device). In order to produce such a stretchable element with high stretchability, a stretchable wiring board with high stretchability is required. Therefore, for example, Patent Document 1 proposes a stretchable flexible circuit board containing a thermoplastic elastomer.
[現有技術文獻] [Prior art documents]
[專利文獻] [Patent Document]
[專利文獻1]日本專利特開2013-187380號公報 [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-187380
伸縮性配線基板大多於製造可拉伸元件的過程中隨著安裝各種電子零件等而暴露於例如超過100℃的高溫中。但是,明確得知:伸縮性配線基板若變得高溫,則大幅熱膨脹,其可成為穩定 製造可拉伸元件的阻礙。另外,先前的構成伸縮性配線基板的伸縮性樹脂膜特別是於高溫下具有高黏性,因此高溫下的伸縮性配線基板的處理性亦存在問題。 The stretchable wiring board is often exposed to high temperatures, for example, exceeding 100° C. during the installation of various electronic components during the manufacturing process of the stretchable element. However, it is clearly known that when a stretchable wiring board becomes high-temperature, it thermally expands significantly and becomes stable. Obstacles to creating stretchable elements. In addition, the stretchable resin film constituting the conventional stretchable wiring board has high viscosity especially at high temperatures, so there is also a problem with the handleability of the stretchable wiring board at high temperatures.
因此,本發明的一方面的目的在於提供一種具有優異的伸縮性並且熱膨脹係數小、而且高溫下的黏性低且處理性優異的伸縮性配線基板,以及用以獲得所述伸縮性配線基板的導體基板及伸縮性樹脂膜。 Therefore, an object of one aspect of the present invention is to provide a stretchable wiring board that has excellent stretchability, a small thermal expansion coefficient, low viscosity at high temperatures, and excellent handleability, and a method for obtaining the stretchable wiring board. Conductor substrate and stretchable resin film.
本發明的一方面提供一種導體基板,其包括伸縮性樹脂膜及設置於所述伸縮性樹脂膜上的導體層。所述伸縮性樹脂膜含有橡膠成分及填料。所述橡膠成分可經交聯。 One aspect of the present invention provides a conductor substrate, which includes a stretchable resin film and a conductor layer disposed on the stretchable resin film. The stretchable resin film contains rubber components and fillers. The rubber component may be cross-linked.
根據所述本發明的一方面的導體基板,可獲得具有優異的伸縮性並且熱膨脹係數小、而且高溫下的黏性低且處理性優異的伸縮性配線基板。 According to the conductive substrate according to one aspect of the present invention, a stretchable wiring substrate can be obtained that has excellent stretchability, a small thermal expansion coefficient, low viscosity at high temperatures, and excellent handleability.
本發明的另一方面提供一種伸縮性配線基板,其包括所述導體基板,所述導體層形成配線圖案。 Another aspect of the present invention provides a stretchable wiring substrate including the conductor substrate, and the conductor layer forms a wiring pattern.
所述導體基板具有優異的伸縮性並且熱膨脹係數小,而且高溫下的黏性低且處理性優異。 The conductor substrate has excellent stretchability and a small thermal expansion coefficient, has low viscosity at high temperatures, and has excellent handleability.
本發明的進而又一方面提供一種配線基板用伸縮性樹脂膜,其含有橡膠成分及填料。換言之,本發明的進而又一方面提供伸縮性樹脂膜的用途,其用於製造配線基板,所述伸縮性樹脂膜含有橡膠成分及填料,所述橡膠成分可經交聯。所述橡膠成 分可經交聯。 A further aspect of the present invention provides a stretchable resin film for wiring boards, which contains a rubber component and a filler. In other words, a further aspect of the present invention provides the use of a stretchable resin film for manufacturing a wiring substrate, the stretchable resin film containing a rubber component and a filler, and the rubber component can be cross-linked. The rubber is The points can be cross-linked.
所述伸縮性樹脂膜可提供具有優異的伸縮性並且熱膨脹係數小、而且高溫下的黏性低且處理性優異的伸縮性配線基板。 The stretchable resin film can provide a stretchable wiring board that has excellent stretchability, a small thermal expansion coefficient, low viscosity at high temperatures, and excellent handleability.
根據本發明的一方面,可提供具有優異的伸縮性並且熱膨脹係數小、而且高溫下的黏性低且處理性優異的伸縮性配線基板。 According to one aspect of the present invention, it is possible to provide a stretchable wiring board that has excellent stretchability, a small thermal expansion coefficient, low viscosity at high temperatures, and excellent handleability.
1:伸縮性配線基板 1: Flexible wiring board
3:伸縮性樹脂膜 3: Stretchable resin film
5:導體層 5: Conductor layer
X:位移量 X: displacement amount
圖1是表示伸縮性配線基板的一實施形態的平面圖。 FIG. 1 is a plan view showing an embodiment of a stretchable wiring board.
圖2是表示恢復率的測定例的應力-應變曲線。 FIG. 2 is a stress-strain curve showing a measurement example of recovery rate.
以下,對本發明的若干實施形態進行詳細說明。其中,本發明並不限定於以下的實施形態。 Several embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.
圖1是表示伸縮性配線基板的一實施形態的平面圖。圖1所示的伸縮性配線基板1為包括伸縮性樹脂膜3及設置於伸縮性樹脂膜3上且形成配線圖案的導體層5的導體基板。伸縮性樹脂膜3含有橡膠成分及填料。主要因橡膠成分而容易對伸縮性樹脂膜賦予伸縮性。導體層5形成包含可伸縮的波形部分的配線圖案。 FIG. 1 is a plan view showing an embodiment of a stretchable wiring board. The stretchable wiring board 1 shown in FIG. 1 is a conductor board including a stretchable resin film 3 and a conductor layer 5 provided on the stretchable resin film 3 and forming a wiring pattern. The stretchable resin film 3 contains rubber components and fillers. The rubber component makes it easy to impart stretchability to the stretchable resin film. The conductor layer 5 forms a wiring pattern including stretchable wave portions.
伸縮性樹脂膜3可具有例如拉伸變形至應變20%為止後的恢復率為80%以上的伸縮性。該恢復率是於使用伸縮性樹脂膜的測定樣品的拉伸試驗中求出。圖2是表示恢復率的測定例的應 力-應變曲線。於在第一次的拉伸試驗中達到位移量(應變)X的時間點開放拉伸應力而使試驗片返回至初始位置,其後,進行第二次的拉伸試驗,此時,於將開始施加負荷的時間點的位置與X的差設為Y時,將由式:R=(Y/X)×100計算的R定義為恢復率。恢復率例如可將X設為50%來測定。就相對於重覆使用的耐性的觀點而言,恢復率可為80%以上、85%以上或90%以上。恢復率於定義上的上限為100%。 The stretchable resin film 3 may have stretchability such that, for example, the recovery rate after being stretched and deformed to a strain of 20% is 80% or more. The recovery rate is determined in a tensile test using a measurement sample of a stretchable resin film. Figure 2 is an application diagram showing an example of recovery rate measurement. Force-strain curve. The tensile stress is released at the time when the displacement (strain) When the difference between the position at the time when load application starts and X is set to Y, R calculated from the formula: R=(Y/X)×100 is defined as the recovery rate. The recovery rate can be measured by setting X to 50%, for example. From the perspective of resistance to repeated use, the recovery rate may be above 80%, above 85%, or above 90%. Recovery rate is by definition capped at 100%.
橡膠成分包含一種或兩種以上的橡膠。橡膠成分中所含的橡膠可為熱塑性彈性體。作為熱塑性彈性體的例子,可列舉氫化型苯乙烯系彈性體。氫化型苯乙烯系彈性體是使氫與具有包含不飽和雙鍵的軟鏈段的苯乙烯系彈性體的不飽和雙鍵進行加成反應而獲得的彈性體。氫化型苯乙烯系彈性體亦可期待耐候性提高等效果。作為氫化型苯乙烯彈性體的例子,可列舉:苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物彈性體(SEBS(Styrene Ethylene Butylene Styrene),有時亦稱為「氫化苯乙烯丁二烯橡膠」)。 The rubber component contains one or more than two types of rubber. The rubber contained in the rubber component may be a thermoplastic elastomer. Examples of thermoplastic elastomers include hydrogenated styrenic elastomers. The hydrogenated styrenic elastomer is an elastomer obtained by adding hydrogen to an unsaturated double bond of a styrenic elastomer having a soft segment containing an unsaturated double bond. Hydrogenated styrenic elastomers can also be expected to have effects such as improved weather resistance. Examples of hydrogenated styrene elastomers include styrene-ethylene-butylene-styrene block copolymer elastomer (SEBS (Styrene Ethylene Butylene Styrene)), sometimes also called "hydrogenated styrene butadiene rubber" ”).
橡膠成分可包含選自由丙烯酸橡膠、異戊二烯橡膠、丁基橡膠、苯乙烯丁二烯橡膠、丁二烯橡膠、丙烯腈丁二烯橡膠、矽酮橡膠、胺基甲酸酯橡膠、氯丁二烯橡膠、乙烯丙烯橡膠、氟橡膠、硫化橡膠、表氯醇橡膠及氯化丁基橡膠所組成的群組中至少一種橡膠。 The rubber component may include acrylic rubber, isoprene rubber, butyl rubber, styrene butadiene rubber, butadiene rubber, acrylonitrile butadiene rubber, silicone rubber, urethane rubber, chlorine rubber, At least one rubber from the group consisting of butadiene rubber, ethylene propylene rubber, fluorine rubber, vulcanized rubber, epichlorohydrin rubber and chlorinated butyl rubber.
就避免因吸濕等而對配線造成的損傷的觀點而言,橡膠成分可包含選自苯乙烯丁二烯橡膠、丁二烯橡膠及丁基橡膠中的 至少一種橡膠。藉由使用苯乙烯丁二烯橡膠,伸縮性樹脂膜對於鍍敷步驟中所使用的各種化學液的耐性提高,可良率佳地製造配線基板。 From the viewpoint of avoiding damage to wiring due to moisture absorption, etc., the rubber component may include styrene-butadiene rubber, butadiene rubber, and butyl rubber. At least one kind of rubber. By using styrene-butadiene rubber, the resistance of the stretchable resin film to various chemical liquids used in the plating step is improved, and wiring substrates can be manufactured with good yield.
作為丙烯酸橡膠的市售品,例如可列舉日本瑞翁(Zeon)股份有限公司的「尼珀爾(Nipol)AR系列」、可樂麗(Kuraray)股份有限公司的「可樂麗緹(Kurarity)系列」。作為異戊二烯橡膠的市售品,例如可列舉日本瑞翁(Zeon)股份有限公司的「尼珀爾(Nipol)IR系列」。作為丁基橡膠的市售品,例如可列舉JSR股份有限公司的「丁基(BUTYL)系列」。作為苯乙烯丁二烯橡膠的市售品,例如可列舉:JSR股份有限公司的「戴納龍(Dynaron)SEBS系列」、「戴納龍(Dynaron)HSBR系列」、日本科騰聚合物(Kraton polymers Japan)股份有限公司的「科騰(Kraton)D聚合物系列」、阿隆化成(Aronkasei)股份有限公司的「AR系列」。作為丁二烯橡膠的市售品,例如可列舉日本瑞翁(Zeon)股份有限公司的「尼珀爾(Nipol)BR系列」。作為丙烯腈丁二烯橡膠的市售品,例如可列舉JSR股份有限公司的「JSR NBR系列」。作為矽酮橡膠的市售品,例如可列舉信越矽酮股份有限公司的「KMP系列」。作為乙烯丙烯橡膠的市售品,例如可列舉JSR股份有限公司的「JSR EP系列」。作為氟橡膠的市售品,例如可列舉大金(Daikin)股份有限公司的「DAI-EL系列」。作為表氯醇橡膠的市售品,例如可列舉日本瑞翁(Zeon)股份有限公司的「海德林(Hydrin)系列」。 Examples of commercially available acrylic rubber products include the "Nipol AR series" of Zeon Co., Ltd. and the "Kurarity series" of Kuraray Co., Ltd. . As a commercial product of isoprene rubber, "Nipol IR series" of Japan Zeon Co., Ltd. can be mentioned, for example. Examples of commercially available butyl rubber include "Butyl (BUTYL) Series" of JSR Co., Ltd. Commercially available products of styrene butadiene rubber include, for example, JSR Co., Ltd.'s "Dynaron SEBS series", "Dynaron HSBR series", Japan's Kraton Polymers (Kraton) Polymers Japan Co., Ltd.'s "Kraton D polymer series" and Aronkasei Co., Ltd.'s "AR series". As a commercial product of butadiene rubber, for example, "Nipol BR series" of Japan Zeon Co., Ltd. can be cited. As a commercial product of acrylonitrile butadiene rubber, "JSR NBR series" of JSR Co., Ltd. is mentioned, for example. As a commercial product of silicone rubber, "KMP series" of Shin-Etsu Silicone Co., Ltd. is mentioned, for example. As a commercially available product of ethylene propylene rubber, "JSR EP series" of JSR Co., Ltd. is mentioned, for example. Examples of commercially available fluororubber include Daikin Co., Ltd.'s "DAI-EL series". As a commercially available product of epichlorohydrin rubber, "Hydrin series" of Japan Zeon Co., Ltd. can be mentioned, for example.
橡膠成分亦可藉由合成而製作。例如,丙烯酸橡膠可藉由使(甲基)丙烯酸、(甲基)丙烯酸酯、芳香族乙烯基化合物、氰化乙烯基化合物等反應而獲得。 Rubber components can also be produced synthetically. For example, acrylic rubber can be obtained by reacting (meth)acrylic acid, (meth)acrylic acid ester, aromatic vinyl compound, cyanide vinyl compound, and the like.
橡膠成分可藉由交聯基的反應而交聯。藉由使用經交聯的橡膠成分,有伸縮性樹脂膜的耐熱性容易提高的傾向。交聯基只要為可利用將橡膠成分的分子鏈交聯的反應或橡膠成分的分子鏈與後述的交聯成分的反應來進行交聯結構體的形成的反應性基即可。作為所述交聯基的例子,可列舉:(甲基)丙烯醯基、乙烯基、環氧基、苯乙烯基、胺基、異氰脲酸酯基、脲基、氰酸酯基、異氰酸酯基、巰基、羥基、羧基及酸酐基。 The rubber component can be cross-linked through the reaction of cross-linking groups. By using a crosslinked rubber component, the heat resistance of the stretchable resin film tends to be easily improved. The cross-linking group may be a reactive group that can form a cross-linked structure by a reaction that cross-links the molecular chain of the rubber component or a reaction between the molecular chain of the rubber component and a cross-linking component described below. Examples of the crosslinking group include: (meth)acryl group, vinyl group, epoxy group, styrene group, amine group, isocyanurate group, urea group, cyanate group, and isocyanate group, mercapto group, hydroxyl group, carboxyl group and acid anhydride group.
橡膠成分可藉由酸酐基或羧基中的至少一交聯基的反應而交聯。作為具有酸酐基的橡膠的例子,可列舉經順丁烯二酸酐部分地改質的橡膠。作為經順丁烯二酸酐部分地改質的橡膠的市售品,例如有旭化成股份有限公司製造的苯乙烯系彈性體「塔芙普林(TufPrene)912」。 The rubber component can be cross-linked by reaction of at least one cross-linking group among an acid anhydride group or a carboxyl group. Examples of rubber having an acid anhydride group include rubber partially modified with maleic anhydride. As a commercially available rubber partially modified with maleic anhydride, there is, for example, the styrenic elastomer "TufPrene 912" manufactured by Asahi Kasei Co., Ltd.
經順丁烯二酸酐部分地改質的橡膠可為經順丁烯二酸酐改質的氫化型苯乙烯系彈性體。作為經順丁烯二酸酐改質的氫化型苯乙烯系彈性體的例子,可列舉順丁烯二酸酐改質苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物彈性體。作為經順丁烯二酸酐改質的氫化型苯乙烯系彈性體的市售品的例子,有日本科騰聚合物(Kraton polymers Japan)股份有限公司的「FG1901」、「FG1924」、旭化成股份有限公司的「塔芙泰科(TufTech)M1911」、「塔芙泰科 (TufTech)M1913」、「塔芙泰科(TufTech)M1943」。 The rubber partially modified with maleic anhydride may be a hydrogenated styrenic elastomer modified with maleic anhydride. Examples of hydrogenated styrene-based elastomers modified with maleic anhydride include maleic anhydride-modified styrene-ethylene butylene-styrene block copolymer elastomers. Examples of commercially available hydrogenated styrenic elastomers modified with maleic anhydride include "FG1901" and "FG1924" of Kraton Polymers Japan Co., Ltd., Asahi Kasei Co., Ltd. The company's "TufTech (TufTech) M1911", "TufTech (TufTech)M1913", "TufTech (TufTech)M1943".
就塗膜性的觀點而言,橡膠成分的重量平均分子量可為20000~200000、30000~150000或50000~125000。此處的重量平均分子量(Mw)是指藉由凝膠滲透層析法(Gel Permeation Chromatography,GPC)而求出的標準聚苯乙烯換算值。 From the viewpoint of coating properties, the weight average molecular weight of the rubber component may be 20,000 to 200,000, 30,000 to 150,000, or 50,000 to 125,000. The weight average molecular weight (Mw) here refers to a standard polystyrene conversion value calculated by gel permeation chromatography (Gel Permeation Chromatography, GPC).
以伸縮性樹脂膜中的填料以外的成分的質量為基準,伸縮性樹脂膜中的橡膠成分的含量可為30質量%~100質量%、50質量%~100質量%或70質量%~100質量%。若橡膠成分的含量處於該範圍內,則伸縮性樹脂膜容易具有特別優異的伸縮性。 Based on the mass of components other than fillers in the stretchable resin film, the content of the rubber component in the stretchable resin film may be 30 mass% to 100 mass%, 50 mass% to 100 mass%, or 70 mass% to 100 mass% %. When the content of the rubber component is within this range, the stretchable resin film tends to have particularly excellent stretchability.
伸縮性樹脂膜包含分散於含有橡膠成分的樹脂相中的一種或兩種以上的填料。填料可為無機填料、有機填料或該些的組合。填料可特別包含選自由二氧化矽、玻璃、氧化鋁、氧化鈦、碳黑、雲母及氮化硼所組成的群組中的至少一種無機填料。 The stretchable resin film contains one or more fillers dispersed in a resin phase containing a rubber component. Fillers can be inorganic fillers, organic fillers, or a combination of these. The filler may particularly include at least one inorganic filler selected from the group consisting of silica, glass, alumina, titanium oxide, carbon black, mica and boron nitride.
填料的平均粒徑可為10nm~500nm。若填料的平均粒徑處於該範圍內,則於伸縮性樹脂膜的熱膨脹係數的減低及伸縮性樹脂膜的高溫下的黏性抑制的方面可獲得更進一步顯著的效果。就相同的觀點而言,填料的平均粒徑可為400nm以下、300nm以下、200nm以下、150nm以下或80nm以下。於本說明書中,填料的平均粒徑是指藉由雷射繞射.散射法而求出的粒徑的平均值(平均一次粒子徑)。填料的平均粒徑的測定例如可使用奈米粒子徑分佈測定裝置SALD-7500nano(島津製作所股份有限公司製造)來進行。 The average particle size of the filler can be 10nm~500nm. If the average particle diameter of the filler is within this range, further significant effects can be obtained in reducing the thermal expansion coefficient of the stretchable resin film and suppressing the viscosity of the stretchable resin film at high temperatures. From the same point of view, the average particle size of the filler may be 400 nm or less, 300 nm or less, 200 nm or less, 150 nm or less, or 80 nm or less. In this specification, the average particle size of the filler is determined by laser diffraction. The average value of the particle diameter (average primary particle diameter) determined by the scattering method. The average particle size of the filler can be measured, for example, using a nanoparticle size distribution measuring device SALD-7500nano (manufactured by Shimadzu Corporation).
填料的形狀並無特別限定,填料可具有大致球形、纖維狀、不定形等任意形狀。 The shape of the filler is not particularly limited, and the filler may have any shape such as approximately spherical, fibrous, or irregular.
填料的表面可經官能基修飾。作為可導入於填料的表面上的官能基,例如可列舉胺基、苯基胺基、苯基。具有經官能基修飾的表面的填料可有助於伸縮性樹脂膜與導體層的密接性提高。 The surface of the filler can be modified with functional groups. Examples of the functional group that can be introduced onto the surface of the filler include an amino group, a phenylamino group, and a phenyl group. The filler having a functional group-modified surface can contribute to improving the adhesion between the stretchable resin film and the conductor layer.
相對於橡膠成分100質量份,伸縮性樹脂膜中的填料的含量可為1質量份~200質量份。若填料的含量處於該範圍內,則於伸縮性樹脂膜的熱膨脹係數的減低及伸縮性樹脂膜的高溫下的黏性抑制的方面可獲得更進一步顯著的效果。就相同的觀點而言,相對於橡膠成分100質量份,填料的含量可為150質量份以下或100質量份以下。 The content of the filler in the stretchable resin film may be 1 to 200 parts by mass relative to 100 parts by mass of the rubber component. If the content of the filler is within this range, further significant effects can be obtained in terms of reducing the thermal expansion coefficient of the stretchable resin film and suppressing the viscosity of the stretchable resin film at high temperatures. From the same viewpoint, the content of the filler may be 150 parts by mass or less or 100 parts by mass or less relative to 100 parts by mass of the rubber component.
伸縮性樹脂膜可為含有橡膠成分及填料的樹脂組成物的硬化物。於該情況下,樹脂組成物亦可進而含有交聯成分。樹脂組成物的硬化物包含藉由橡膠成分的交聯基彼此的反應、橡膠成分的交聯基與交聯成分的反應、交聯成分的聚合反應或該些的組合而形成的交聯結構體。若伸縮性樹脂膜為樹脂組成物的硬化物,則有伸縮性樹脂膜的耐熱性容易提高的傾向。 The stretchable resin film may be a cured product of a resin composition containing a rubber component and a filler. In this case, the resin composition may further contain a crosslinking component. The cured product of the resin composition includes a cross-linked structure formed by the reaction of the cross-linked groups of the rubber component, the reaction of the cross-linked group of the rubber component and the cross-linked component, the polymerization reaction of the cross-linked component, or a combination thereof. . If the stretchable resin film is a cured product of the resin composition, the heat resistance of the stretchable resin film tends to be easily improved.
用以形成伸縮性樹脂膜的樹脂組成物可含有的交聯成分為具有一個以上的反應性基的化合物。交聯成分例如可為具有選自由環氧基、(甲基)丙烯醯基、乙烯基、苯乙烯基、胺基、異氰脲酸酯基、脲基、氰酸酯基、異氰酸酯基、巰基、羥基及羧基所 組成的群組中的至少一種反應性基的化合物。就伸縮性樹脂膜的耐熱性提高的觀點而言,交聯成分可為具有選自環氧基、胺基、羥基及羧基中的反應性基的化合物。特別是,藉由具有順丁烯二酸酐基或羧基中的至少一者的橡膠與具有環氧基的化合物(環氧樹脂)的組合,於伸縮性樹脂膜的耐熱性及低透濕度、伸縮性樹脂膜與導電層的密接性及硬化後的伸縮性樹脂膜的低黏性的方面可獲得特別優異的效果。若伸縮性樹脂膜的耐熱性提高,則例如可抑制如氮迴流般的加熱步驟中的伸縮性樹脂膜的劣化。若硬化後的伸縮性樹脂膜具有低黏性,則可操作性良好地對導體基板或配線基板進行處理。 The crosslinking component that can be contained in the resin composition used to form a stretchable resin film is a compound having one or more reactive groups. The cross-linking component may, for example, have a group selected from the group consisting of epoxy group, (meth)acrylyl group, vinyl group, styrene group, amine group, isocyanurate group, urea group, cyanate group, isocyanate group, and mercapto group. , hydroxyl and carboxyl groups Compounds consisting of at least one reactive group in the group. From the viewpoint of improving the heat resistance of the stretchable resin film, the crosslinking component may be a compound having a reactive group selected from an epoxy group, an amine group, a hydroxyl group, and a carboxyl group. In particular, a combination of a rubber having at least one of a maleic anhydride group or a carboxyl group and a compound having an epoxy group (epoxy resin) improves the heat resistance, low moisture permeability, and stretchability of the stretchable resin film. Particularly excellent effects can be obtained in terms of the adhesion between the flexible resin film and the conductive layer and the low viscosity of the cured stretchable resin film. If the heat resistance of the stretchable resin film is improved, for example, deterioration of the stretchable resin film in a heating step such as nitrogen reflux can be suppressed. If the cured stretchable resin film has low viscosity, the conductor substrate or the wiring substrate can be processed with good workability.
可用作交聯成分的含有環氧基的化合物可為單官能、二官能或三官能以上的多官能環氧樹脂。為了獲得充分的硬化性,交聯成分可包含二官能或三官能以上的環氧樹脂。 The epoxy group-containing compound that can be used as a cross-linking component can be a monofunctional, difunctional, or trifunctional or higher multifunctional epoxy resin. In order to obtain sufficient curability, the cross-linking component may contain a bifunctional or trifunctional or higher epoxy resin.
環氧樹脂例如可為選自雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛清漆型環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧樹脂、甲酚酚醛清漆型環氧樹脂及具有脂肪鏈的環氧樹脂中的至少一種。作為市售的具有脂肪鏈的環氧樹脂,例如可列舉迪愛生(DIC)股份有限公司製造的EXA-4816。 The epoxy resin may be, for example, selected from the group consisting of bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phenol novolak-type epoxy resin, naphthalene-type epoxy resin, dicyclopentadiene-type epoxy resin, and cresol At least one kind of novolak-type epoxy resin and epoxy resin having an aliphatic chain. Examples of commercially available epoxy resins having an aliphatic chain include EXA-4816 manufactured by DIC Co., Ltd.
提供具有高玻璃轉移溫度的硬化物的環氧樹脂可有助於伸縮性樹脂膜的熱膨脹係數減低及高溫下的黏性抑制。例如可根據與作為硬化劑的苯酚酚醛清漆樹脂的反應來選擇形成具有180℃以上或200℃以上的玻璃轉移溫度的硬化物的環氧樹脂。作 為此種環氧樹脂的具體例,可列舉二環戊二烯型環氧樹脂及萘型環氧樹脂。 Epoxy resins that provide hardened materials with high glass transition temperatures can contribute to reducing the thermal expansion coefficient of stretchable resin films and suppressing viscosity at high temperatures. For example, an epoxy resin that forms a cured product having a glass transition temperature of 180° C. or higher or 200° C. or higher can be selected based on the reaction with a phenol novolac resin as a hardener. do Specific examples of such epoxy resins include dicyclopentadiene-type epoxy resin and naphthalene-type epoxy resin.
交聯成分亦可包含具有(甲基)丙烯醯基的化合物。具有(甲基)丙烯醯基的化合物可為(甲基)丙烯酸酯。具有(甲基)丙烯醯基的化合物可為具有一個、兩個或三個以上的(甲基)丙烯醯基的化合物(例如,單官能、二官能或三官能以上的(甲基)丙烯酸酯)。為了獲得充分的硬化性,交聯成分可為具有兩個或三個以上的(甲基)丙烯醯基的化合物。 The cross-linking component may include a compound having a (meth)acrylyl group. The compound having a (meth)acrylyl group may be a (meth)acrylate. The compound having a (meth)acrylyl group may be a compound having one, two, or three or more (meth)acrylyl groups (for example, a monofunctional, difunctional, or trifunctional or higher (meth)acrylate ). In order to obtain sufficient curability, the cross-linking component may be a compound having two or more (meth)acrylyl groups.
作為單官能(甲基)丙烯酸酯,例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛基庚酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸山萮基酯、(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-3-氯-2-羥基丙酯、(甲基)丙烯酸-2-羥基丁酯、甲氧基聚乙二醇(甲基)丙烯酸酯、乙氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、乙氧基聚丙二醇(甲基)丙烯酸酯及丁二酸單(2-(甲基)丙烯醯氧基乙基)酯等脂肪族(甲基)丙烯酸酯;(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲 基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸異冰片酯、四氫鄰苯二甲酸單(2-(甲基)丙烯醯氧基乙基)酯及六氫鄰苯二甲酸單(2-(甲基)丙烯醯氧基乙基)酯等脂環式(甲基)丙烯酸酯;(甲基)丙烯酸苄基酯、(甲基)丙烯酸苯基酯、(甲基)丙烯酸鄰聯苯基酯、(甲基)丙烯酸-1-萘基酯、(甲基)丙烯酸-2-萘基酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸對枯基苯氧基乙酯、(甲基)丙烯酸鄰苯基苯氧基乙酯、(甲基)丙烯酸-1-萘氧基乙酯、(甲基)丙烯酸-2-萘氧基乙酯、苯氧基聚乙二醇(甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯、苯氧基聚丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸-2-羥基-3-苯氧基丙酯、(甲基)丙烯酸-2-羥基-3-(鄰苯基苯氧基)丙酯、(甲基)丙烯酸-2-羥基-3-(1-萘氧基)丙酯及(甲基)丙烯酸-2-羥基-3-(2-萘氧基)丙酯等芳香族(甲基)丙烯酸酯;(甲基)丙烯酸-2-四氫糠酯、N-(甲基)丙烯醯氧基乙基六氫鄰苯二甲醯亞胺及2-(甲基)丙烯醯氧基乙基-N-咔唑等雜環式(甲基)丙烯酸酯;以及該些化合物的己內酯改質體。該些中,就與苯乙烯系彈性體的相容性、以及透明性及耐熱性的觀點而言,可自所述脂肪族(甲基)丙烯酸酯及所述芳香族(甲基)丙烯酸酯中選擇單官能(甲基)丙烯酸酯。 Examples of the monofunctional (meth)acrylate include: (methyl)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylate )Terth-butyl acrylate, (meth)butoxyethyl acrylate, (meth)isoamyl acrylate, (meth)hexyl acrylate, (meth)-2-ethylhexyl acrylate, (meth)acrylate Heptyl (meth)acrylate, octylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, ( Tridecyl methacrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate ester, behenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxy(meth)acrylate Propyl ester, 2-hydroxybutyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate Aliphatic (meth)acrylates such as acrylic acid ester, ethoxy polypropylene glycol (meth)acrylate and succinic acid mono(2-(meth)acryloyloxyethyl) ester; (meth) Cyclopentyl acrylate, cyclohexyl (meth)acrylate, (meth)acrylate Dicyclopentyl acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, mono(2-(meth)acryloxyethyl) tetrahydrophthalate and alicyclic (meth)acrylates such as hexahydrophthalic acid mono(2-(meth)acryloyloxyethyl) ester; benzyl (meth)acrylate, phenyl (meth)acrylate Ester, o-biphenyl (meth)acrylate, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, phenoxyethyl (meth)acrylate, (meth)acrylate p-Cunylphenoxyethyl acrylate, o-phenylphenoxyethyl (meth)acrylate, 1-naphthyloxyethyl (meth)acrylate, 2-naphthoxyethyl (meth)acrylate Ethyl ester, phenoxy polyethylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, phenoxy polypropylene glycol (meth)acrylate, (meth)acrylate 2-hydroxy-3-phenoxypropyl acrylate, (meth)acrylic acid-2-hydroxy-3-(o-phenylphenoxy)propyl ester, (meth)acrylic acid-2-hydroxy-3-(meth)acrylate Aromatic (meth)acrylates such as 1-naphthyloxy)propyl ester and (meth)acrylic acid-2-hydroxy-3-(2-naphthyloxy)propyl ester; (meth)acrylic acid-2-tetrahydrogen Heterocyclic (methyl) compounds such as furfuryl ester, N-(meth)acryloxyethyl hexahydrophthalimide and 2-(meth)acryloxyethyl-N-carbazole Acrylates; and caprolactone modifications of these compounds. Among these, from the viewpoint of compatibility with styrenic elastomer, transparency and heat resistance, the aliphatic (meth)acrylate and the aromatic (meth)acrylate can be selected. Select monofunctional (meth)acrylates.
作為二官能(甲基)丙烯酸酯,例如可列舉:乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、四丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基) 丙烯酸酯、乙氧基化聚丙二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、3-甲基-1,5-戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、2-丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、三環癸烷二甲醇(甲基)丙烯酸酯及乙氧基化-2-甲基-1,3-丙二醇二(甲基)丙烯酸酯等脂肪族(甲基)丙烯酸酯;環己烷二甲醇(甲基)丙烯酸酯、乙氧基化環己烷二甲醇(甲基)丙烯酸酯、丙氧基化環己烷二甲醇(甲基)丙烯酸酯、乙氧基化丙氧基化環己烷二甲醇(甲基)丙烯酸酯、三環癸烷二甲醇(甲基)丙烯酸酯、乙氧基化三環癸烷二甲醇(甲基)丙烯酸酯、丙氧基化三環癸烷二甲醇(甲基)丙烯酸酯、乙氧基化丙氧基化三環癸烷二甲醇(甲基)丙烯酸酯、乙氧基化氫化雙酚A二(甲基)丙烯酸酯、丙氧基化氫化雙酚A二(甲基)丙烯酸酯、乙氧基化丙氧基化氫化雙酚A二(甲基)丙烯酸酯、乙氧基化氫化雙酚F二(甲基)丙烯酸酯、丙氧基化氫化雙酚F二(甲基)丙烯酸酯及乙氧基化丙氧基化氫化雙酚F二(甲基)丙烯酸酯等脂環式(甲基)丙烯酸酯;乙氧基化雙酚A二(甲基)丙烯酸酯、丙氧基化雙酚A二(甲基)丙烯酸酯、乙氧基化丙氧基化雙酚A二(甲基)丙烯酸酯、乙氧基化雙酚F二(甲基)丙烯酸酯、丙氧基化雙酚F二(甲基)丙烯酸酯、乙氧基化丙氧基化雙酚F二(甲基)丙烯酸酯、乙氧基化雙酚AF二(甲基)丙烯酸酯、丙氧基化雙酚AF二(甲基)丙烯酸酯、乙氧基化丙氧基化雙酚AF二(甲基)丙烯酸酯、乙氧基 化芴型二(甲基)丙烯酸酯、丙氧基化芴型二(甲基)丙烯酸酯及乙氧基化丙氧基化芴型二(甲基)丙烯酸酯等芳香族(甲基)丙烯酸酯;乙氧基化異氰脲酸二(甲基)丙烯酸酯、丙氧基化異氰脲酸二(甲基)丙烯酸酯及乙氧基化丙氧基化異氰脲酸二(甲基)丙烯酸酯等雜環式(甲基)丙烯酸酯;該些化合物的己內酯改質體;新戊二醇型環氧基(甲基)丙烯酸酯等脂肪族環氧基(甲基)丙烯酸酯;環己烷二甲醇型環氧基(甲基)丙烯酸酯、氫化雙酚A型環氧基(甲基)丙烯酸酯及氫化雙酚F型環氧基(甲基)丙烯酸酯等脂環式環氧基(甲基)丙烯酸酯;間苯二酚型環氧基(甲基)丙烯酸酯、雙酚A型環氧基(甲基)丙烯酸酯、雙酚F型環氧基(甲基)丙烯酸酯、雙酚AF型環氧基(甲基)丙烯酸酯及芴型環氧基(甲基)丙烯酸酯等芳香族環氧基(甲基)丙烯酸酯。就與苯乙烯系彈性體的相容性、以及透明性及耐熱性的觀點而言,可自所述脂肪族(甲基)丙烯酸酯及所述芳香族(甲基)丙烯酸酯中選擇二官能(甲基)丙烯酸酯。 Examples of the difunctional (meth)acrylate include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. Ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate Ester, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate Acrylates, ethoxylated polypropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol Alcohol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-butyl-2 -Ethyl-1,3-propanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, glycerol di(meth)acrylate Aliphatic (meth)acrylates such as meth)acrylate, tricyclodecane dimethanol (meth)acrylate and ethoxylated-2-methyl-1,3-propanediol di(meth)acrylate ; Cyclohexane dimethanol (meth)acrylate, ethoxylated cyclohexanedimethanol (meth)acrylate, propoxylated cyclohexanedimethanol (meth)acrylate, ethoxylated propylene Oxylated cyclohexanedimethanol (meth)acrylate, tricyclodecane dimethanol (meth)acrylate, ethoxylated tricyclodecane dimethanol (meth)acrylate, propoxylated tricyclohexanedimethanol (meth)acrylate Cyclodecanedimethanol (meth)acrylate, ethoxylated propoxylated tricyclodecane dimethanol (meth)acrylate, ethoxylated hydrogenated bisphenol A di(meth)acrylate, propoxylated Oxylated hydrogenated bisphenol A di(meth)acrylate, ethoxylated propoxylated hydrogenated bisphenol A di(meth)acrylate, ethoxylated hydrogenated bisphenol F di(meth)acrylate , propoxylated hydrogenated bisphenol F di(meth)acrylate and ethoxylated propoxylated hydrogenated bisphenol F di(meth)acrylate and other alicyclic (meth)acrylates; ethoxy Bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxylated propoxylated bisphenol A di(meth)acrylate, ethoxylated Bisphenol F di(meth)acrylate, propoxylated bisphenol F di(meth)acrylate, ethoxylated propoxylated bisphenol F di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate Phenol AF di(meth)acrylate, propoxylated bisphenol AF di(meth)acrylate, ethoxylated propoxylated bisphenol AF di(meth)acrylate, ethoxylated Aromatic (meth)acrylates such as fluorene-based di(meth)acrylate, propoxylated fluorene-based di(meth)acrylate, and ethoxylated propoxylated fluorene-based di(meth)acrylate Esters; ethoxylated isocyanuric acid di(meth)acrylate, propoxylated isocyanuric acid di(meth)acrylate and ethoxylated propoxylated isocyanuric acid di(meth)acrylate ) Heterocyclic (meth)acrylates such as acrylates; caprolactone modified forms of these compounds; aliphatic epoxy (meth)acrylates such as neopentyl glycol epoxy (meth)acrylates Esters; alicyclic rings such as cyclohexanedimethanol-type epoxy (meth)acrylate, hydrogenated bisphenol A-type epoxy (meth)acrylate, and hydrogenated bisphenol F-type epoxy (meth)acrylate. Formula epoxy (meth)acrylate; resorcinol-type epoxy (meth)acrylate, bisphenol A-type epoxy (meth)acrylate, bisphenol F-type epoxy (meth)acrylate ) acrylate, bisphenol AF type epoxy (meth)acrylate and fluorene type epoxy (meth)acrylate and other aromatic epoxy (meth)acrylates. From the viewpoint of compatibility with styrene-based elastomer, transparency, and heat resistance, the difunctional acrylate can be selected from the aliphatic (meth)acrylate and the aromatic (meth)acrylate. (meth)acrylate.
作為三官能以上的多官能(甲基)丙烯酸酯,例如可列舉:三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、乙氧基化季戊四醇三(甲基)丙烯酸酯、丙氧基化季戊四醇三(甲基)丙烯酸酯、乙氧基化丙氧基化季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯、丙氧基化季戊四醇四(甲基)丙烯酸酯、乙氧基化丙氧基化季 戊四醇四(甲基)丙烯酸酯、二-三羥甲基丙烷四丙烯酸酯及二季戊四醇六(甲基)丙烯酸酯等脂肪族(甲基)丙烯酸酯;乙氧基化異氰脲酸三(甲基)丙烯酸酯、丙氧基化異氰脲酸三(甲基)丙烯酸酯及乙氧基化丙氧基化異氰脲酸三(甲基)丙烯酸酯等雜環式(甲基)丙烯酸酯;該些化合物的己內酯改質體;苯酚酚醛清漆型環氧基(甲基)丙烯酸酯及甲酚酚醛清漆型環氧基(甲基)丙烯酸酯等芳香族環氧基(甲基)丙烯酸酯。就與苯乙烯系彈性體的相容性、以及透明性及耐熱性的觀點而言,可自所述脂肪族(甲基)丙烯酸酯及所述芳香族(甲基)丙烯酸酯中選擇多官能(甲基)丙烯酸酯。 Examples of trifunctional or higher polyfunctional (meth)acrylates include: trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylate Trimethylolpropane tri(meth)acrylate, ethoxylated propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol Tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, ethoxylated propoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated Pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated propoxylated quaternary Aliphatic (meth)acrylates such as pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetraacrylate and dipentaerythritol hexa(meth)acrylate; ethoxylated isocyanuric acid triacrylate Heterocyclic (meth)acrylate, propoxylated isocyanurate tri(meth)acrylate, ethoxylated propoxylated isocyanurate tri(meth)acrylate, etc. Acrylic esters; caprolactone modified forms of these compounds; aromatic epoxy (meth)acrylates such as phenol novolak type epoxy (meth)acrylate and cresol novolac type epoxy (meth)acrylate. base) acrylate. From the viewpoint of compatibility with styrene-based elastomer, transparency, and heat resistance, a polyfunctional polyester may be selected from the aliphatic (meth)acrylate and the aromatic (meth)acrylate. (meth)acrylate.
相對於橡膠成分100質量份,用以形成伸縮性樹脂膜的樹脂組成物中的交聯成分的含量可為10質量份以上、15質量份以上或20質量份以上,可為70質量份以下、60質量份以下或50質量份以下。若交聯成分的含量為所述範圍,則有在維持伸縮性樹脂膜的特性的狀態下提高與導體層的密接力的傾向。 The content of the crosslinking component in the resin composition for forming the stretchable resin film may be 10 parts by mass or more, 15 parts by mass or more, or 20 parts by mass or more relative to 100 parts by mass of the rubber component, and may be 70 parts by mass or less. 60 parts by mass or less or 50 parts by mass or less. When the content of the crosslinking component is within the above range, the adhesive force with the conductor layer tends to increase while maintaining the characteristics of the stretchable resin film.
用以形成伸縮性樹脂膜的樹脂組成物亦可進而含有用以實現交聯成分的聚合反應(硬化反應)的硬化劑、硬化促進劑或所述兩者。硬化劑為其自身成為與交聯成分反應的聚合反應(硬化反應)的反應基質的化合物。硬化促進劑為作為硬化反應的觸媒發揮功能的化合物。亦可使用具有硬化劑及硬化促進劑這兩者的功能的化合物。相對於橡膠成分及交聯成分的合計量100質量份,硬化劑及硬化促進劑的含量分別可為0.1質量份~10質量份。 The resin composition used to form a stretchable resin film may further contain a hardener, a hardening accelerator, or both of the above to achieve polymerization reaction (hardening reaction) of the crosslinking component. The hardening agent is a compound that itself serves as a reaction matrix for the polymerization reaction (hardening reaction) in which the cross-linking component reacts. A hardening accelerator is a compound that functions as a catalyst for a hardening reaction. A compound having the functions of both a hardener and a hardening accelerator can also be used. The content of the hardener and the hardening accelerator may be 0.1 to 10 parts by mass, respectively, relative to 100 parts by mass of the total amount of the rubber component and the cross-linked component.
於使用具有環氧基的化合物(環氧樹脂)作為交聯成分 的情況下,作為其硬化劑,可使用選自由脂肪族多胺、聚胺基醯胺、聚硫醇、芳香族多胺、酸酐、羧酸、苯酚酚醛清漆樹脂、酯樹脂及二氰二胺(dicyandiamide)所組成的群組中的至少一種。作為具有環氧基的化合物的硬化劑或硬化促進劑,可使用選自由三級胺、咪唑及膦所組成的群組中的至少一種。就硬化前的樹脂組成物的保存穩定性及硬化性的觀點而言,可使用咪唑。於橡膠成分包含經順丁烯二酸酐改質的橡膠的情況下,可選擇與該橡膠相容的咪唑。相對於橡膠成分及交聯成分的合計量100質量份,咪唑的含量可為0.1質量份~10質量份。 To use a compound with an epoxy group (epoxy resin) as a cross-linking component In this case, as the hardener, aliphatic polyamine, polyamine amide, polythiol, aromatic polyamine, acid anhydride, carboxylic acid, phenol novolac resin, ester resin and dicyandiamine can be used. (dicyandiamide) at least one of the group consisting of. As the hardener or hardening accelerator of the compound having an epoxy group, at least one selected from the group consisting of tertiary amines, imidazole, and phosphine can be used. From the viewpoint of storage stability and curability of the resin composition before curing, imidazole can be used. In the case where the rubber component includes rubber modified by maleic anhydride, an imidazole compatible with the rubber may be selected. The content of imidazole may be 0.1 to 10 parts by mass relative to 100 parts by mass of the total amount of the rubber component and the cross-linked component.
於使用具有(甲基)丙烯醯基的化合物作為交聯成分的情況下,作為其硬化劑,可使用熱自由基聚合起始劑或光自由基聚合起始劑。 When using a compound having a (meth)acrylyl group as a cross-linking component, a thermal radical polymerization initiator or a photo radical polymerization initiator can be used as the hardener.
作為熱自由基聚合起始劑,例如可列舉:甲基乙基酮過氧化物、環己酮過氧化物及甲基環己酮過氧化物等酮過氧化物;1,1-雙(第三丁基過氧基)環己烷、1,1-雙(第三丁基過氧基)-2-甲基環己烷、1,1-雙(第三丁基過氧基)-3,3,5-三甲基環己烷、1,1-雙(第三己基過氧基)環己烷及1,1-雙(第三己基過氧基)-3,3,5-三甲基環己烷等過氧化縮酮;對薄荷烷氫過氧化物等氫過氧化物;α,α'-雙(第三丁基過氧基)二異丙基苯、二枯基過氧化物、第三丁基枯基過氧化物及二-第三丁基過氧化物等二烷基過氧化物;辛醯基過氧化物、月桂醯基過氧化物、硬脂基過氧化物及苯甲醯基過氧化物等二醯基過氧化物;過氧化二碳酸雙(4-第三丁基環己基)酯、過氧化 二碳酸二-2-乙氧基乙酯、過氧化二碳酸二-2-乙基己酯及過氧化碳酸二-3-甲氧基丁酯等過氧化碳酸酯;過氧化三甲基乙酸第三丁酯、過氧化三甲基乙酸第三己酯、過氧化-2-乙基己酸-1,1,3,3-四甲基丁酯、2,5-二甲基-2,5-雙(2-乙基己醯基過氧基)己烷、過氧化-2-乙基己酸第三己酯、過氧化-2-乙基己酸第三丁酯、過氧化異丁酸第三丁酯、過氧化異丙基單碳酸第三己酯、過氧化-3,5,5-三甲基己酸第三丁酯、過氧化月桂酸第三丁酯、過氧化異丙基單碳酸第三丁酯、過氧化-2-乙基己基單碳酸第三丁酯、過氧化苯甲酸第三丁酯、過氧化苯甲酸第三己酯、2,5-二甲基-2,5-雙(苯甲醯基過氧基)己烷及過氧化乙酸第三丁酯等過氧化酯;2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2,4-二甲基戊腈)及2,2'-偶氮雙(4-甲氧基-2'-二甲基戊腈)等偶氮化合物。就硬化性、透明性及耐熱性的觀點而言,可自所述二醯基過氧化物、所述過氧化酯及所述偶氮化合物中選擇熱自由基聚合起始劑。 Examples of thermal radical polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methyl cyclohexanone peroxide; 1,1-bis (th Tributylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-2-methylcyclohexane, 1,1-bis(tert-butylperoxy)-3 ,3,5-trimethylcyclohexane, 1,1-bis(third hexylperoxy)cyclohexane and 1,1-bis(third hexylperoxy)-3,3,5-tri Peroxyketals such as methylcyclohexane; hydroperoxides such as p-menthane hydroperoxide; α,α'-bis(tert-butylperoxy)diisopropylbenzene, dicumyl peroxide Dialkyl peroxides such as tert-butylcumyl peroxide and di-tert-butyl peroxide; octyl peroxide, lauryl peroxide, stearyl peroxide and benzyl peroxide Dihydryl peroxides such as hydroxyl peroxide; peroxydicarbonate bis(4-tert-butylcyclohexyl) ester, peroxy Peroxycarbonates such as di-2-ethoxyethyl dicarbonate, di-2-ethylhexyl peroxydicarbonate and di-3-methoxybutyl peroxycarbonate; peroxytrimethylacetic acid Tributyl ester, tert-hexyl peroxytrimethylacetate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5 -Bis(2-ethylhexylperoxy)hexane, tert-hexyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, peroxyisobutyric acid tert-butyl ester, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, isopropyl peroxide tert-butyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2, Peroxyesters such as 5-bis(benzoylperoxy)hexane and tert-butyl peracetate; 2,2'-azobisisobutyronitrile, 2,2'-azobis(2, Azo compounds such as 4-dimethylvaleronitrile) and 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile). From the viewpoint of hardening, transparency, and heat resistance, the thermal radical polymerization initiator can be selected from the dicarboxylic peroxide, the peroxyester, and the azo compound.
作為光自由基聚合起始劑,例如可列舉:2,2-二甲氧基-1,2-二苯基乙烷-1-酮等安息香縮酮;1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙烷-1-酮及1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙烷-1-酮等α-羥基酮;2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮及1,2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮等α-胺基酮;1-[4-(苯硫基)苯基]-1,2-辛二酮-2-(苯甲醯基)肟等肟酯;雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦及2,4,6-三甲基苯甲醯基二苯基 氧化膦等氧化膦;2-(鄰氯苯基)-4,5-二苯基咪唑二聚體、2-(鄰氯苯基)-4,5-二(甲氧基苯基)咪唑二聚體、2-(鄰氟苯基)-4,5-二苯基咪唑二聚體、2-(鄰甲氧基苯基)-4,5-二苯基咪唑二聚體及2-(對甲氧基苯基)-4,5-二苯基咪唑二聚體等2,4,5-三芳基咪唑二聚體;二苯甲酮、N,N,N',N'-四甲基-4,4'-二胺基二苯甲酮、N,N,N',N'-四乙基-4,4'-二胺基二苯甲酮及4-甲氧基-4'-二甲基胺基二苯甲酮等二苯甲酮化合物;2-乙基蒽醌、菲醌、2-第三丁基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-苯并蒽醌、2-苯基蒽醌、2,3-二苯基蒽醌、1-氯蒽醌、2-甲基蒽醌、1,4-萘醌、9,10-菲醌、2-甲基-1,4-萘醌及2,3-二甲基蒽醌等醌化合物;安息香甲醚、安息香***及安息香苯醚等安息香醚;安息香、甲基安息香及乙基安息香等安息香化合物;苄基二甲基縮酮等苄基化合物;9-苯基吖啶及1,7-雙(9,9'-吖啶基庚烷)等吖啶化合物;N-苯基甘胺酸;以及香豆素。 Examples of the photoradical polymerization initiator include benzoin ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one; 1-hydroxycyclohexyl phenyl ketone, 2 -Hydroxy-2-methyl-1-phenylpropan-1-one and 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1- Ketones and other α-hydroxyketones; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one and 1,2-methyl-1-[4 -(Methylthio)phenyl]-2-morpholinylpropane-1-one and other α-aminoketones; 1-[4-(phenylthio)phenyl]-1,2-octanedione-2 -Oxime esters such as (benzyl)oxime; bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2 ,4,4-trimethylpentylphosphine oxide and 2,4,6-trimethylbenzoyldiphenyl Phosphine oxides such as phosphine oxide; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer polymer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer and 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer p-methoxyphenyl)-4,5-diphenylimidazole dimer and other 2,4,5-triarylimidazole dimer; benzophenone, N,N,N',N'-tetramethyl Base-4,4'-diaminobenzophenone, N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone and 4-methoxy-4' -Dimethylaminobenzophenone and other benzophenone compounds; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone , 2,3-benzoanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10 - Quinone compounds such as phenanthrenequinone, 2-methyl-1,4-naphthoquinone and 2,3-dimethylanthraquinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin, methyl benzoin and ethyl benzoin Benzoin compounds such as benzoin; benzyl compounds such as benzyl dimethyl ketal; acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinylheptane); N-benzene glycine; and coumarin.
伸縮性樹脂膜或用以形成所述伸縮性樹脂膜的樹脂組成物除以上成分以外,視需要亦可於不顯著損及本發明的效果的範圍內進而包含抗氧化劑、熱穩定劑、紫外線吸收劑、抗水解劑、黃變防止劑、可見光吸收劑、著色劑、塑化劑、阻燃劑、調平劑等。 In addition to the above components, the stretchable resin film or the resin composition used to form the stretchable resin film may further contain antioxidants, heat stabilizers, and ultraviolet absorbers as necessary within the range that does not significantly impair the effects of the present invention. Agents, anti-hydrolysis agents, anti-yellowing agents, visible light absorbers, colorants, plasticizers, flame retardants, leveling agents, etc.
伸縮性樹脂膜3的厚度可為5μm~1000μm。若伸縮性樹脂膜的厚度為該範圍,則容易獲得作為伸縮性基材的充分的強度,且可充分進行乾燥,因此可減低伸縮性樹脂膜中的殘留溶媒量。 The thickness of the stretchable resin film 3 may be 5 μm to 1000 μm. When the thickness of the stretchable resin film is within this range, sufficient strength as a stretchable base material can be easily obtained and sufficient drying can be performed. Therefore, the amount of residual solvent in the stretchable resin film can be reduced.
伸縮性樹脂膜3的與導體層5相反的一側的主面的表面粗糙度Ra值可為0.1μm以上。藉由該Ra值為0.1μm以上,有伸縮性樹脂膜表面的黏性進一步減低的傾向。就相同的觀點而言,該Ra值可為0.2μm以上、0.3μm以上或0.4μm以上。該Ra值的上限值並無特別限定,就伸縮性樹脂膜的強度的觀點而言,可為2.0μm以下。表面粗糙度Ra值例如可使用階差計(小阪研究所股份有限公司製造,ET-200)來測定。 The surface roughness Ra value of the main surface of the stretchable resin film 3 on the side opposite to the conductor layer 5 may be 0.1 μm or more. When the Ra value is 0.1 μm or more, the viscosity of the surface of the stretchable resin film tends to further decrease. From the same point of view, the Ra value may be 0.2 μm or more, 0.3 μm or more, or 0.4 μm or more. The upper limit of the Ra value is not particularly limited, but from the viewpoint of the strength of the stretchable resin film, it may be 2.0 μm or less. The surface roughness Ra value can be measured using a step meter (ET-200, manufactured by Kosaka Laboratory Co., Ltd.), for example.
藉由對伸縮性樹脂膜賦予凹凸,可使伸縮性樹脂膜的表面粗糙度Ra值成為所述範圍內。作為對伸縮性樹脂膜賦予凹凸的方法,例如有:使用凹凸轉印基材將凹凸圖案轉印於B階段狀態的伸縮性樹脂膜或硬化反應後的伸縮性樹脂膜後,將凹凸轉印基板剝離的方法;對硬化後的伸縮性樹脂膜實施蝕刻處理、熱壓印加工等壓印加工的方法;及將金屬箔的粗糙化面壓接於伸縮性樹脂膜並對金屬箔進行蝕刻的方法。 By providing unevenness to the stretchable resin film, the surface roughness Ra value of the stretchable resin film can be within the above range. An example of a method for imparting unevenness to a stretchable resin film is to use an unevenness transfer substrate to transfer the unevenness pattern to the stretchable resin film in the B-stage state or the stretchable resin film after the curing reaction, and then transfer the unevenness transfer substrate to the stretchable resin film. A method of peeling off; a method of subjecting the hardened stretchable resin film to an embossing process such as etching or hot embossing; and a method of pressing the roughened surface of the metal foil onto the stretchable resin film and etching the metal foil. .
伸縮性樹脂膜的表面的黏性值於30℃下可為0.7gf/mm2以下(6.9kPa以下)、0.5gf/mm2以下(4.9kPa以下)或0.4gf/mm2以下(3.9kPa以下)。伸縮性樹脂膜的表面的黏性值於200℃下可為4.5gf/mm2以下(44kPa以下)或4.0gf/mm2以下(39kPa以下)。黏性值的下限值並無特別限定,可為0gf/mm2(0kPa)。黏性值例如可使用黏著試驗機(力世科(Rhesca)股份有限公司製造的「TACII」)來測定。 The surface viscosity value of the stretchable resin film can be 0.7gf/mm 2 or less (below 6.9kPa), 0.5gf/mm 2 or less (below 4.9kPa), or 0.4gf/mm 2 or less (below 3.9kPa) at 30°C. ). The surface viscosity value of the stretchable resin film may be 4.5 gf/mm 2 or less (44 kPa or less) or 4.0 gf/mm 2 or less (39 kPa or less) at 200°C. The lower limit of the viscosity value is not particularly limited, but may be 0gf/mm 2 (0kPa). The viscosity value can be measured using an adhesion testing machine ("TACII" manufactured by Rhesca Co., Ltd.), for example.
伸縮性樹脂膜的彈性係數(拉伸彈性係數)可為0.1MPa 以上且1000MPa以下。若彈性係數為0.1MPa以上且1000MPa以下,則有作為基材的處理性及可撓性特別優異的傾向。就該觀點而言,彈性係數可為0.3MPa以上且100MPa以下或0.5MPa以上且50MPa以下。 The elastic coefficient (tensile elastic coefficient) of the stretchable resin film can be 0.1MPa Above and below 1000MPa. When the elastic coefficient is 0.1 MPa or more and 1000 MPa or less, the base material tends to have particularly excellent handleability and flexibility. From this point of view, the elastic coefficient may be 0.3 MPa or more and 100 MPa or less, or 0.5 MPa or more and 50 MPa or less.
伸縮性樹脂膜的斷裂伸長率可為100%以上。若斷裂伸長率為100%以上,則有容易獲得充分的伸縮性的傾向。就該觀點而言,斷裂伸長率可為150%以上、200%以上、300%以上或500%以上。斷裂伸長率的上限並無特別限制,通常為1000%左右以下。 The stretchable resin film may have an elongation at break of 100% or more. When the elongation at break is 100% or more, sufficient stretchability tends to be easily obtained. From this perspective, the elongation at break may be above 150%, above 200%, above 300%, or above 500%. The upper limit of the elongation at break is not particularly limited, but is usually about 1000% or less.
伸縮性樹脂膜可以包括載體膜及設置於載體膜上的伸縮性樹脂膜的積層膜的狀態供給。 The stretchable resin film may be supplied in a laminated film state including a carrier film and a stretchable resin film provided on the carrier film.
作為載體膜,並無特別限制,例如可列舉:聚對苯二甲酸乙二酯(Polyethylene Terephthalate,PET)、聚對苯二甲酸丁二酯及聚萘二甲酸乙二酯等聚酯;聚碳酸酯;聚乙烯及聚丙烯等聚烯烴;聚醯胺;聚醯亞胺;聚醯胺醯亞胺;聚醚醯亞胺;聚醚硫醚;聚醚碸;聚醚酮;聚苯醚;聚苯硫醚;聚芳酯;聚碸;以及液晶聚合物。就柔軟性及強韌性的觀點而言,可將聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、聚丙烯、聚碳酸酯、聚醯胺、聚醯亞胺、聚醯胺醯亞胺、聚苯醚、聚苯硫醚、聚芳酯或聚碸的膜用作載體膜。 The carrier film is not particularly limited, and examples thereof include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; polycarbonate ester; polyolefins such as polyethylene and polypropylene; polyamide; polyimide; polyamide imine; polyether imine; polyether sulfide; polyether sulfide; polyether ketone; polyphenylene ether; Polyphenylene sulfide; polyarylate; polyurethane; and liquid crystal polymers. From the viewpoint of softness and strength, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, polycarbonate, polyamide, Films of polyimide, polyimide, polyphenylene ether, polyphenylene sulfide, polyarylate or polystyrene are used as carrier films.
載體膜的厚度並無特別限制,可為3μm~250μm。若載體膜的厚度為3μm以上,則有載體膜容易具有充分的膜強度的傾向。若載體膜的厚度為250μm以下,則有容易獲得充分的柔軟 性的傾向。就以上觀點而言,載體膜的厚度可為5μm~200μm或7μm~150μm。就與伸縮性樹脂膜的剝離性提高的觀點而言,視需要可使用藉由矽酮系化合物、含氟化合物等對基材膜實施了脫模處理的膜。 The thickness of the carrier film is not particularly limited and can range from 3 μm to 250 μm. When the thickness of the carrier film is 3 μm or more, the carrier film tends to have sufficient film strength. If the thickness of the carrier film is 250 μm or less, sufficient softness can be easily obtained. sexual orientation. From the above point of view, the thickness of the carrier film may be 5 μm ~ 200 μm or 7 μm ~ 150 μm. From the viewpoint of improving the peelability from the stretchable resin film, a film in which the base film has been subjected to a release treatment using a silicone compound, a fluorine-containing compound, or the like may be used if necessary.
所述積層膜亦可進而具有覆蓋伸縮性樹脂膜的保護膜。 The laminated film may further have a protective film covering the stretchable resin film.
作為保護膜,並無特別限制,例如可列舉:聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等聚酯;聚乙烯及聚丙烯等聚烯烴。就柔軟性及強韌性的觀點而言,可將聚對苯二甲酸乙二酯等聚酯或聚乙烯及聚丙烯等聚烯烴的膜用作保護膜。就與伸縮性樹脂膜的剝離性提高的觀點而言,可藉由矽酮系化合物、含氟化合物等對保護膜實施脫模處理。 The protective film is not particularly limited, and examples thereof include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; and polyolefins such as polyethylene and polypropylene. . From the viewpoint of flexibility and strength, films of polyesters such as polyethylene terephthalate or polyolefins such as polyethylene and polypropylene can be used as protective films. From the viewpoint of improving the peelability from the stretchable resin film, the protective film can be subjected to a release treatment using a silicone compound, a fluorine-containing compound, or the like.
保護膜的厚度可根據目標柔軟性而適宜地改變,可為10μm~250μm。若保護膜的厚度為10μm以上,則有保護膜容易具有充分的膜強度的傾向。若保護膜的厚度為250μm以下,則有保護膜容易具有充分的柔軟性的傾向。就以上觀點而言,保護膜的厚度可為15μm~200μm或20μm~150μm。 The thickness of the protective film can be appropriately changed according to the target softness, and can be 10μm~250μm. When the thickness of the protective film is 10 μm or more, the protective film tends to have sufficient film strength. When the thickness of the protective film is 250 μm or less, the protective film tends to have sufficient flexibility. From the above point of view, the thickness of the protective film can be 15 μm ~ 200 μm or 20 μm ~ 150 μm.
伸縮性配線基板1(或導體基板)所具有的導體層5例如可為導體箔或導體鍍膜。 The conductor layer 5 included in the flexible wiring board 1 (or the conductor board) may be, for example, a conductor foil or a conductor plating film.
導體箔可為金屬箔。作為金屬箔的例子,可列舉:銅箔、鈦箔、不鏽鋼箔、鎳箔、高導磁合金(permalloy)箔、42合金箔、鈷箔、鎳鉻合金(nichrome)箔、鈹銅箔、磷青銅箔、黃銅箔、鎳銀合金箔、鋁箔、錫箔、鉛箔、鋅箔、焊料箔、鐵箔、鉭箔、鈮 箔、鉬箔、鋯箔、金箔、銀箔、鈀箔、蒙鎳合金(Monel)箔、英高鎳合金(Inconel)箔及赫史特合金(Hastelloy)箔。就適當的彈性係數等的觀點而言,導體箔只要選自銅箔、金箔、鎳箔及鐵箔中即可。就配線形成性的觀點而言,導體箔可為銅箔。銅箔可藉由光微影而簡易地形成配線圖案且不會損及伸縮性樹脂基材的特性。作為銅箔,並無特別限制,例如可使用覆銅積層板及柔性配線板等中所使用的電解銅箔及壓延銅箔。 The conductor foil can be a metal foil. Examples of metal foils include copper foil, titanium foil, stainless steel foil, nickel foil, permalloy foil, 42 alloy foil, cobalt foil, nichrome foil, beryllium copper foil, phosphorus foil Bronze foil, brass foil, nickel silver alloy foil, aluminum foil, tin foil, lead foil, zinc foil, solder foil, iron foil, tantalum foil, niobium Foil, molybdenum foil, zirconium foil, gold foil, silver foil, palladium foil, Monel foil, Inconel foil and Hastelloy foil. From the viewpoint of an appropriate elastic coefficient and the like, the conductor foil may be selected from copper foil, gold foil, nickel foil and iron foil. From the viewpoint of wiring formability, the conductor foil may be copper foil. Copper foil can easily form wiring patterns through photolithography without impairing the properties of the stretchable resin base material. The copper foil is not particularly limited, and for example, electrolytic copper foil and rolled copper foil used in copper-clad laminates, flexible wiring boards, and the like can be used.
導體鍍膜可為藉由加成法(additive method)或半加成法(semi-additive method)中所使用的通常的鍍敷法而形成的膜。例如,於進行使鈀附著的鍍敷觸媒賦予處理後,將伸縮性樹脂膜浸漬於無電鍍敷液中而於底塗層(primer)的整個表面析出厚度0.3μm~1.5μm的無電鍍敷層(導體層)。可視需要進一步進行電鍍(電性鍍敷)而調整成所需的厚度。作為無電鍍中所使用的無電鍍敷液,可使用任意的無電鍍敷液,並無特別限制。關於電鍍,亦可採用通常的方法,並無特別限制。就成本方面及電阻值的觀點而言,導體鍍膜(無電鍍膜、電鍍膜)可為鍍銅膜。 The conductor plating film may be a film formed by a common plating method used in an additive method or a semi-additive method. For example, after performing a plating catalyst application process to adhere palladium, the stretchable resin film is immersed in an electroless plating solution to deposit electroless plating with a thickness of 0.3 μm to 1.5 μm on the entire surface of the primer. layer (conductor layer). If necessary, further electroplating (electroplating) can be performed to adjust to the required thickness. As the electroless plating liquid used for electroless plating, any electroless plating liquid can be used without particular limitation. Regarding electroplating, ordinary methods can also be used and are not particularly limited. From the viewpoint of cost and resistance value, the conductor plating film (electroless plating film, electroplating film) may be a copper plating film.
導體層的厚度並無特別限制,可為1μm~50μm。若導體層的厚度為1μm以上,則可更容易形成配線圖案。若導體層的厚度為50μm以下,則特別容易進行蝕刻及處理。 The thickness of the conductor layer is not particularly limited and can be 1 μm to 50 μm. If the thickness of the conductor layer is 1 μm or more, the wiring pattern can be formed more easily. When the thickness of the conductor layer is 50 μm or less, etching and processing are particularly easy.
伸縮性配線基板例如可藉由如下方法而製造,所述方法包括:準備具有伸縮性樹脂膜及設置於伸縮性樹脂膜上的導體層的導體基板;及於導體層形成配線圖案。 A stretchable wiring board can be manufactured, for example, by a method including preparing a conductive board having a stretchable resin film and a conductor layer provided on the stretchable resin film, and forming a wiring pattern on the conductor layer.
具有導體箔作為導體層的導體基板例如可藉由如下方法而獲得,所述方法包括:將用以形成伸縮性樹脂膜的樹脂組成物的清漆塗敷於導體箔,或將導體箔積層於形成於載體膜上的伸縮性樹脂膜上。對用以形成伸縮性樹脂膜的樹脂組成物的塗膜進行乾燥,藉由對所形成的樹脂層進行加熱或光照射而使其硬化,藉此可形成伸縮性樹脂膜。 A conductive substrate having a conductor foil as a conductor layer can be obtained, for example, by applying a varnish of a resin composition for forming a stretchable resin film to the conductor foil, or laminating the conductor foil to form a stretchable resin film. on a stretchable resin film on a carrier film. A stretchable resin film can be formed by drying a coating film of a resin composition for forming a stretchable resin film and curing the formed resin layer by heating or irradiating light.
具有導體鍍膜作為導體層的導體基板例如可藉由如下方法而獲得:藉由加成法或半加成法中所使用的通常的鍍敷法而於形成於載體膜上的伸縮性樹脂膜上形成導體鍍膜。 A conductive substrate having a conductive plating film as a conductive layer can be obtained, for example, by a common plating method used in an additive method or a semi-additive method, on a stretchable resin film formed on a carrier film. Form conductor coating.
於導體層形成配線圖案的方法例如可包括:於導體基板的導體層上形成蝕刻抗蝕劑的步驟;對蝕刻抗蝕劑進行曝光,並對曝光後的蝕刻抗蝕劑進行顯影而形成覆蓋導體層的一部分的抗蝕劑圖案的步驟;利用蝕刻液將未由抗蝕劑圖案覆蓋的部分的導體層去除的步驟;及將抗蝕劑圖案去除的步驟。 The method of forming a wiring pattern on a conductor layer may include, for example: forming an etching resist on the conductor layer of the conductor substrate; exposing the etching resist; and developing the exposed etching resist to form a covering conductor. forming a resist pattern on a portion of the conductor layer; using an etching solution to remove a portion of the conductor layer that is not covered by the resist pattern; and removing the resist pattern.
或者,於導體層形成配線圖案的方法亦可包括:於導體基板的導體層上形成鍍敷抗蝕劑的步驟;對鍍敷抗蝕劑進行曝光,並對曝光後的鍍敷抗蝕劑進行顯影而形成覆蓋導體層的一部分的抗蝕劑圖案的步驟;藉由無電鍍或電鍍而於未由抗蝕劑圖案覆蓋的部分的導體層上進而形成導體鍍膜的步驟;將抗蝕劑圖案去除的步驟;以及將導體層中的、未由藉由所述電鍍而形成的導體鍍膜覆蓋的部分去除的步驟。 Alternatively, the method of forming a wiring pattern on a conductor layer may also include: forming a plating resist on the conductor layer of the conductor substrate; exposing the plating resist; and conducting the exposed plating resist. The step of developing to form a resist pattern covering a portion of the conductor layer; the step of forming a conductor coating on the portion of the conductor layer not covered by the resist pattern by electroless plating or electroplating; removing the resist pattern and the step of removing the portion of the conductor layer that is not covered by the conductor coating formed by the electroplating.
藉由將各種電子零件搭載於配線基板,可獲得可拉伸元 件。 By mounting various electronic components on the wiring board, stretchable elements can be obtained pieces.
[實施例] [Example]
以下,列舉實施例而對本發明進一步進行具體說明。其中,本發明並不限定於該些實施例。 Hereinafter, an Example is given and this invention is demonstrated further concretely. However, the present invention is not limited to these examples.
1.原材料 1.Raw materials
作為用以製作伸縮性樹脂膜的原材料,準備以下材料。 As raw materials for producing a stretchable resin film, the following materials are prepared.
(A)橡膠成分 (A) Rubber component
.順丁烯二酸酐改質苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物彈性體(商品名「FG1924GT」,日本科騰聚合物(Kraton polymers Japan)股份有限公司製造) . Maleic anhydride modified styrene-ethylene butylene-styrene block copolymer elastomer (trade name "FG1924GT", manufactured by Kraton Polymers Japan Co., Ltd.)
(B)交聯成分 (B) Cross-linking component
.二環戊二烯型環氧樹脂(商品名「艾匹克隆(EPICLON)HP7200H」,迪愛生(DIC)(股)製造) . Dicyclopentadiene-type epoxy resin (trade name "EPICLON (EPICLON) HP7200H", manufactured by DIC Co., Ltd.)
(C)硬化促進劑 (C) Hardening accelerator
.1-苄基-2-甲基咪唑(商品名「1B2MZ」,四國化成股份有限公司製造) . 1-Benzyl-2-methylimidazole (trade name "1B2MZ", manufactured by Shikoku Chemical Co., Ltd.)
(D)填料 (D)Packing
.二氧化矽填料漿料SE2050(商品名「SE2050KNK」,阿德瑪科技(Admatechs)股份有限公司製造,平均粒徑500nm,經苯基胺基表面修飾的球狀二氧化矽粒子,二氧化矽濃度70質量%的甲基異丁基酮分散液) . Silica filler slurry SE2050 (trade name "SE2050KNK", manufactured by Admatechs Co., Ltd., average particle size 500nm, spherical silica particles surface-modified with phenylamine groups, silica concentration 70 mass% methyl isobutyl ketone dispersion)
.二氧化矽填料漿料C40(商品名「C40」,CIK納諾達克(CIK Nanotec)股份有限公司製造,經苯基胺基表面修飾的二氧化矽粒子,平均粒徑100nm,二氧化矽濃度65質量%的甲基異丁基酮(Methyl Isobutyl Ketone,MIBK)分散液) . Silica filler slurry C40 (trade name "C40", CIK Nanotec (CIK Manufactured by Nanotec Co., Ltd., silica particles surface-modified with phenylamine groups, average particle diameter 100nm, silica concentration 65% by mass, methyl isobutyl ketone (Methyl Isobutyl Ketone, MIBK) dispersion)
.二氧化矽填料漿料C120(商品名「C120」,CIK納諾達克(CIK Nanotec)股份有限公司製造,經苯基胺基表面修飾的二氧化矽粒子,平均粒徑30nm,二氧化矽濃度30質量%的MIBK分散液) . Silica filler slurry C120 (trade name "C120", manufactured by CIK Nanotec Co., Ltd., silica particles surface-modified with phenylamine groups, average particle size 30nm, silica concentration 30 mass% MIBK dispersion)
.二氧化矽填料漿料F19(商品名「F19」,CIK納諾達克(CIK Nanotec)股份有限公司製造,經苯基表面修飾的二氧化矽粒子,平均粒徑100nm,二氧化矽濃度70質量%的MIBK分散液) . Silica filler slurry F19 (trade name "F19", manufactured by CIK Nanotec Co., Ltd., phenyl surface-modified silica particles, average particle size 100nm, silica concentration 70 mass % MIBK dispersion)
(E)溶劑 (E)Solvent
.甲苯 . Toluene
(載體膜/保護膜) (carrier film/protective film)
.脫模處理聚對苯二甲酸乙二酯(PET)膜(商品名「普雷克斯(Purex)A31」,帝人杜邦膜(Teijin DuPont Films)股份有限公司製造,厚度25μm) . Release-treated polyethylene terephthalate (PET) film (trade name "Purex A31", manufactured by Teijin DuPont Films Co., Ltd., thickness 25 μm)
2.具有伸縮性樹脂膜的積層膜 2. Laminated film with stretchable resin film
實施例1 Example 1
將100質量份的順丁烯二酸酐改質苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物彈性體(FG1924GT)、200質量份的二氧化矽填料漿料(SE2050)及50質量份的甲苯一邊攪拌一邊均勻混合。於所獲得的混合物中添加25質量份的二環戊二烯型環氧樹脂(HP7200H)及3.75質量份的1-苄基-2-甲基咪唑(1B2MZ),對混合物進一步 進行攪拌而獲得樹脂清漆。使用刮刀塗佈機(康井精機股份有限公司製造的「SNC-350」)將所獲得的樹脂清漆塗佈於載體膜的脫模處理面上。於乾燥機(二葉科學股份有限公司製造的「MSO-80TPS」)中,藉由100℃下20分鐘的加熱而將塗膜乾燥,從而形成厚度100μm的樹脂層。於所形成的樹脂層上,以脫模處理面成為樹脂層側的朝向貼附與載體膜相同的脫模處理PET膜作為保護膜,從而獲得積層膜。藉由將積層膜於180℃加熱60分鐘而使樹脂層硬化,從而獲得具有伸縮性樹脂膜(樹脂層的硬化物)的積層膜。 100 parts by mass of maleic anhydride modified styrene-ethylene butylene-styrene block copolymer elastomer (FG1924GT), 200 parts by mass of silica filler slurry (SE2050) and 50 parts by mass of toluene Stir to combine evenly. 25 parts by mass of dicyclopentadiene-type epoxy resin (HP7200H) and 3.75 parts by mass of 1-benzyl-2-methylimidazole (1B2MZ) were added to the obtained mixture, and the mixture was further Stir and obtain resin varnish. The obtained resin varnish was applied to the release-processed surface of the carrier film using a blade coater ("SNC-350" manufactured by Yasui Seiki Co., Ltd.). The coating film was dried by heating at 100° C. for 20 minutes in a dryer ("MSO-80TPS" manufactured by Futaba Science Co., Ltd.) to form a resin layer with a thickness of 100 μm. On the formed resin layer, a release-processed PET film identical to the carrier film was attached as a protective film with the release-processed surface facing the resin layer, thereby obtaining a laminated film. The laminated film was heated at 180° C. for 60 minutes to harden the resin layer, thereby obtaining a laminated film having a stretchable resin film (cured product of the resin layer).
實施例2 Example 2
將200質量份的二氧化矽填料漿料(SE2050)替換為包含70質量份的填料的108質量份的二氧化矽填料漿料(C40),除此以外,與實施例1同樣地製備樹脂清漆。使用所獲得的樹脂清漆,並利用與實施例1相同的方法而獲得具有伸縮性樹脂膜的積層膜。 A resin varnish was prepared in the same manner as in Example 1, except that 200 parts by mass of the silica filler slurry (SE2050) was replaced with 108 parts by mass of the silica filler slurry (C40) containing 70 parts by mass of the filler. . Using the obtained resin varnish, a laminated film having a stretchable resin film was obtained in the same manner as in Example 1.
實施例3 Example 3
將200質量份的二氧化矽填料漿料(SE2050)替換為包含70質量份的填料的233質量份的二氧化矽填料漿料(C120),除此以外,與實施例1同樣地製備樹脂清漆。使用所獲得的樹脂清漆,並利用與實施例1相同的方法而獲得具有伸縮性樹脂膜的積層膜。 A resin varnish was prepared in the same manner as in Example 1, except that 200 parts by mass of the silica filler slurry (SE2050) was replaced with 233 parts by mass of the silica filler slurry (C120) containing 70 parts by mass of the filler. . Using the obtained resin varnish, a laminated film having a stretchable resin film was obtained in the same manner as in Example 1.
實施例4 Example 4
將200質量份的二氧化矽填料漿料(SE2050)替換為包含70質量份的填料的100質量份的二氧化矽填料漿料(F19),除此以 外,與實施例1同樣地製備樹脂清漆。使用所獲得的樹脂清漆,並利用與實施例1相同的方法而獲得具有伸縮性樹脂膜的積層膜。 200 parts by mass of silica filler slurry (SE2050) is replaced with 100 parts by mass of silica filler slurry (F19) containing 70 parts by mass of filler, except that Except for this, a resin varnish was prepared in the same manner as in Example 1. Using the obtained resin varnish, a laminated film having a stretchable resin film was obtained in the same manner as in Example 1.
實施例5 Example 5
如表1所示般變更二氧化矽填料漿料(SE2050)、二環戊二烯型環氧樹脂(HP7200H)及1-苄基-2-甲基咪唑(1B2MZ)的調配量,除此以外,與實施例1同樣地製備樹脂清漆。使用所獲得的樹脂清漆,並利用與實施例1相同的方法而獲得具有伸縮性樹脂膜的積層膜。 Change the compounding amounts of silica filler slurry (SE2050), dicyclopentadiene-type epoxy resin (HP7200H) and 1-benzyl-2-methylimidazole (1B2MZ) as shown in Table 1, except that , prepare a resin varnish in the same manner as Example 1. Using the obtained resin varnish, a laminated film having a stretchable resin film was obtained in the same manner as in Example 1.
比較例1 Comparative example 1
將100質量份的順丁烯二酸酐改質苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物彈性體(FG1924GT)、25質量份的二環戊二烯型環氧樹脂(HP7200H)及3.75質量份的1-苄基-2-甲基咪唑(1B2MZ)與50質量份的甲苯混合,對混合物進行攪拌而獲得樹脂清漆。使用所獲得的樹脂清漆,並利用與實施例1相同的方法而獲得具有伸縮性樹脂膜的積層膜。 100 parts by mass of maleic anhydride-modified styrene-ethylene butylene-styrene block copolymer elastomer (FG1924GT), 25 parts by mass of dicyclopentadiene-type epoxy resin (HP7200H) and 3.75 parts by mass parts of 1-benzyl-2-methylimidazole (1B2MZ) and 50 parts by mass of toluene were mixed, and the mixture was stirred to obtain a resin varnish. Using the obtained resin varnish, a laminated film having a stretchable resin film was obtained in the same manner as in Example 1.
比較例2及比較例3 Comparative Example 2 and Comparative Example 3
如表1所示般變更順丁烯二酸酐改質苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物彈性體(FG1924GT)及二環戊二烯型環氧樹脂(HP7200H)的調配量,除此以外,與比較例1同樣地獲得樹脂清漆及積層膜。 Change the blending amounts of maleic anhydride-modified styrene-ethylene butylene-styrene block copolymer elastomer (FG1924GT) and dicyclopentadiene-type epoxy resin (HP7200H) as shown in Table 1, except Except for this, a resin varnish and a laminated film were obtained in the same manner as in Comparative Example 1.
3.評價 3.Evaluation
熱膨脹係數(Coefficient of Thermal Expansion,CTE) Coefficient of Thermal Expansion (CTE)
使用由積層膜獲得的伸縮性樹脂膜的樣品,利用以下條件的熱機械分析(Thermomechanical Analysis,TMA)法來測定伸縮性樹脂膜於0℃至120℃的熱膨脹係數。 Using a sample of the stretchable resin film obtained from the laminated film, the thermal expansion coefficient of the stretchable resin film at 0°C to 120°C was measured using the thermomechanical analysis (TMA) method under the following conditions.
裝置:SS6000(精工儀器(Seiko instruments)股份有限公司) Device: SS6000 (Seiko Instruments Co., Ltd.)
樣品尺寸:長度10mm×寬度3mm Sample size: length 10mm x width 3mm
負荷:0.05Mpa Load: 0.05Mpa
溫度:0℃~120℃ Temperature: 0℃~120℃
升溫速度:5℃/min Heating rate: 5℃/min
拉伸彈性係數 Tensile elastic coefficient
準備長度40mm、寬度10mm的短條狀且去除了載體膜及保護膜的伸縮性樹脂膜的試驗片。使用自動繪圖儀(autograph)(島津製作所股份有限公司的「EZ-S」)進行該試驗片的拉伸試驗,獲得應力-應變曲線。根據所獲得的應力-應變曲線來求出室溫下的拉伸彈性係數。拉伸試驗是於卡盤間距離20mm、拉伸速度50mm/min的條件下進行。拉伸彈性係數是根據應力0.5N~1.0N的範圍的應力-應變曲線的斜率而求出。 A short strip-shaped test piece of a stretchable resin film with a carrier film and a protective film removed was prepared with a length of 40 mm and a width of 10 mm. A tensile test was performed on the test piece using an autograph ("EZ-S" manufactured by Shimadzu Corporation) to obtain a stress-strain curve. The tensile elastic coefficient at room temperature was obtained from the obtained stress-strain curve. The tensile test was conducted under the conditions of a distance between chucks of 20mm and a tensile speed of 50mm/min. The tensile elastic coefficient is calculated from the slope of the stress-strain curve in the stress range of 0.5N to 1.0N.
恢復率 recovery rate
準備長度40mm、寬度10mm的短條狀且去除了載體膜及保護膜的伸縮性樹脂膜的試驗片。藉由使用微力試驗機(microforce tester)(伊利諾斯工具公司(Illinois Tool Works Inc)「英斯特朗(Instron)5948」)的拉伸試驗來測定該試驗片的恢復率。於在第一次的拉伸試驗中達到位移量(應變)X的時間點開放拉伸應力 而使試驗片返回至初始位置,其後,進行第二次的拉伸試驗,此時,將開始施加負荷的時間點的位置與X的差設為Y時,將由式:R=(Y/X)×100計算的R的值記錄為恢復率。本實施例中,將應變X設為50%。 A short strip-shaped test piece of a stretchable resin film with a carrier film and a protective film removed was prepared with a length of 40 mm and a width of 10 mm. The recovery rate of the test piece was measured by a tensile test using a microforce tester (Illinois Tool Works Inc. "Instron 5948"). Open the tensile stress at the time when the displacement (strain) X is reached in the first tensile test The test piece is returned to the initial position, and then the second tensile test is performed. At this time, when the difference between the position at the time when the load is applied and The value of R calculated by X)×100 is recorded as the recovery rate. In this example, the strain X is set to 50%.
黏性值 Stickiness value
自積層膜去除保護膜,使用黏著試驗機(力世科(Rhesca)股份有限公司製造的「TACII」)對所露出的伸縮性樹脂膜的表面的黏性值進行測定。測定條件設定為:恆定負荷模式、浸沒速度120mm/min、測試速度600mm/min、負荷100gf、負荷保持時間1秒、溫度30℃或200℃。 The protective film was removed from the laminated film, and the viscosity value of the surface of the exposed stretchable resin film was measured using an adhesion testing machine ("TACII" manufactured by Rhesca Co., Ltd.). The measurement conditions are set as: constant load mode, immersion speed 120mm/min, test speed 600mm/min, load 100gf, load holding time 1 second, temperature 30°C or 200°C.
將用以形成伸縮性樹脂膜的硬化性樹脂組成物的各成分的調配量及伸縮性樹脂膜的評價結果示於表1中。表中的與填 料相關的括號內的數值為漿料中的固體成分(填料)的調配量。 Table 1 shows the compounding amounts of each component of the curable resin composition used to form the stretchable resin film and the evaluation results of the stretchable resin film. and fill in the table The numerical value in parentheses related to the material is the blending amount of the solid component (filler) in the slurry.
如表所示,確認到:含有填料的實施例的伸縮性樹脂膜具有優異的伸縮性並且熱膨脹係數小、而且高溫下的黏性低且處理性優異。即便為不含填料的伸縮性樹脂膜,如比較例3般增量交聯成分,藉此可減低高溫下的黏性,但該情況於熱膨脹係數大的方面存在問題。 As shown in the table, it was confirmed that the stretchable resin film of the Example containing a filler has excellent stretchability and a small thermal expansion coefficient, has low viscosity at high temperatures, and is excellent in handleability. Even if it is a stretchable resin film that does not contain fillers, the viscosity at high temperatures can be reduced by increasing the crosslinking component as in Comparative Example 3. However, in this case, there is a problem in that the thermal expansion coefficient is large.
1‧‧‧伸縮性配線基板 1‧‧‧Flexible wiring board
3‧‧‧伸縮性樹脂膜 3‧‧‧Stretchable resin film
5‧‧‧導體層 5‧‧‧Conductor layer
X‧‧‧位移量 X‧‧‧Displacement
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