JP2019029540A - Stretchable wiring board and manufacturing method thereof - Google Patents

Abstract

To suppress deformation of a stretchable base material when a stretchable wiring board having a wiring pattern formed from a metal foil is continuously manufactured by using a long stretchable base material.SOLUTION: A manufacturing method of a stretchable wiring board 1 includes a step of transferring a metal foil-attached base material 20 having an elongated stretchable base material 3 and a metal foil 10 laminated on the stretchable base material 3 along the longitudinal direction MD, removing a part of the metal foil 10, and forming a metal foil pattern 5 including two guide portions 5E respectively extending on both end portions of the stretchable base material 3 along the longitudinal direction MD of the stretchable base material 3 and a wiring pattern 5C formed between the two guide portions 5E.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a stretchable wiring board and a manufacturing method thereof.

  In recent years, in the field of wearable devices and healthcare-related devices, for example, there is a demand for flexibility and stretchability that can be used along curved surfaces or joints of the body, and that connection failure hardly occurs even when detached. In order to configure such a device, a flexible substrate having high stretchability, that is, a stretchable wiring substrate having a stretchable base material is used (for example, Patent Document 1).

  The stretchable wiring board generally has a stretchable base material and a stretchable wiring pattern formed on the stretchable base material. As a method for forming a stretchable wiring pattern, a pre-stretch method has been proposed in which a metal thin film is deposited on a stretchable base material that has been stretched in advance, and then the stretching is relaxed to form a wrinkled metal wiring. . As another method, a method of easily forming a wiring pattern by printing using a conductive paste containing conductive particles has been proposed.

International Publication No. 2016/080346

  However, since the method for depositing a metal thin film includes a vacuum process that takes a long time, it is difficult to improve the production efficiency. In addition, the wiring pattern formed by printing the conductive paste has a problem that the resistance value is higher than that of the metal wiring, and the resistance value increases when it is stretched.

  It is expected that a stretchable wiring board having metal wiring can be efficiently produced by processing a metal foil laminated on a stretchable base material by etching or the like to form a wiring pattern. In particular, a stretchable wiring board including a large number of wiring patterns by continuously processing a metal foil while conveying a long stretchable base material and a metal foil-attached base material having a metal foil in its longitudinal direction. Can be manufactured very efficiently. However, if the metal foil is processed while conveying a long metal foil-attached base material, the stretchable base material subjected to tension causes deformation such as necking or twisting. It became clear that it might be difficult.

  Therefore, one aspect of the present invention is that when an elastic wiring board having a wiring pattern formed from a metal foil is continuously manufactured using a long elastic base material, the elastic base material is deformed. The purpose is to suppress.

  One aspect of the present invention is to convey a metal foil-attached substrate having a long stretchable substrate and a metal foil laminated on the stretchable substrate along the longitudinal direction of the metal foil. By removing a part, two guide portions respectively extending on both ends of the stretchable base material along the longitudinal direction of the stretchable base material and wiring formed between the two guide portions Provided is a method for manufacturing a stretchable wiring board, comprising a step of forming a metal foil pattern including a pattern.

  According to this method, by providing guide portions extending on both ends of the stretchable base material, a wiring pattern is continuously formed on the stretchable base material while suppressing deformation of the stretchable base material. can do.

  According to the present invention, in the case of continuously producing a stretchable wiring board having a wiring pattern formed from a metal foil using a long stretchable base material, while suppressing deformation of the stretchable base material. The stretchable wiring board can be efficiently manufactured.

It is a top view which shows one Embodiment of the method of manufacturing an elastic board | substrate. It is sectional drawing along the II-II line | wire of FIG. 1 which shows one Embodiment of the method of manufacturing an elastic board | substrate. It is a stress-strain curve which shows the example of a measurement of a recovery rate.

  Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  1 and 2 are plan views showing an embodiment of a method for producing a stretchable substrate. FIG. 2 is a sectional view taken along line II-II in FIG. The method shown in FIG.1 and FIG.2 conveys the base material 20 with a metal foil which has the elongate elastic base material 3 and the metal foil 10 laminated | stacked on the elastic base material 3 along the longitudinal direction MD. However, by removing a part of the metal foil 10, the two guide portions 5E extending on both ends of the stretchable base material 3 along the longitudinal direction MD of the stretchable base material 3 and the two guide portions 5E, respectively. A step of forming a metal foil pattern 5 including a wiring pattern 5C formed between the guide portions 5E. Until the metal foil pattern 5 is formed, the metal foil-attached base material 20 may be transported so as to continuously move without stopping, or is transported intermittently while temporarily stopping. May be.

  The laminate with metal foil ((a) of FIGS. 1 and 2) has a long sheet-like stretchable base material 3 and a metal foil 10 that covers one main surface of the stretchable base material 3. The metal foil 10 does not necessarily need to cover the entire main surface of the stretchable base material 3, and a part of the stretchable base material 3 may be left partially exposed. Moreover, the metal foil 10 may be laminated on both surfaces of the stretchable base material 3. The total length of the long stretchable base material 3 is not particularly limited, but may be, for example, 5 to 300 m. The width of the stretchable base material 3 is not particularly limited, but may be, for example, 100 to 1000 mm.

  As the metal foil 10, copper foil, titanium foil, stainless steel foil, nickel foil, permalloy foil, 42 alloy foil, Kovar foil, nichrome foil, beryllium copper foil, phosphor bronze foil, brass foil, white 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, hastelloy foil, and the like. From the viewpoint of appropriate conductivity and elastic modulus, the metal foil 10 is preferably selected from copper foil, gold foil, nickel foil, and iron foil. From the viewpoint of wiring formability, copper foil is preferable.

  There is no restriction | limiting in particular as copper foil, For example, the electrolytic copper foil and rolled copper foil generally used for a copper clad laminated board, a flexible wiring board, etc. can be used. Examples of commercially available electrolytic copper foil include F0-WS-18 (Furukawa Electric Co., Ltd., trade name), NC-WS-20 (Furukawa Electric Co., Ltd., trade name), YGP-12 (Nippon Electrolytic Co., Ltd.). Company-made, product name), GTS-18 (Furukawa Electric Co., Ltd., trade name), and F2-WS-12 (Furukawa Electric Co., Ltd., trade name). As rolled copper foil, for example, TPC foil (manufactured by JX Metals Co., Ltd., trade name), HA foil (manufactured by JX Metals Co., Ltd., trade name), HA-V2 foil (manufactured by JX Metals Co., Ltd., trade name), and C1100R (Mitsui Sumitomo Metal Mining Shindoh Co., Ltd., trade name). From the viewpoint of further improving the adhesion to the stretchable substrate, it is preferable to use a copper foil that has been subjected to a roughening treatment.

  From the viewpoint of adhesiveness to the stretchable substrate 3, the surface of the metal foil 10 on the stretchable substrate 3 side may be a surface that has been subjected to a silane coupling treatment.

  The base material 20 with metal foil is obtained by, for example, laminating the metal foil 10 on the long elastic base material 3 or forming the elastic base material 3 on the long metal foil 10. Can do. Details of the stretchable substrate 3 and the resin composition for forming the stretchable substrate 3 will be described later. You may convey the base material 20 with metal foil continuously or intermittently along longitudinal direction MD, unwinding the base material 20 with metal foil from a roll-shaped base material with metal foil.

  When laminating the metal foil 10 on the stretchable substrate 3, for example, the metal foil can be laminated on a stretchable substrate formed in advance on a carrier film. The lamination method is not particularly limited, and a roll laminator, a vacuum laminator, a vacuum press, or the like is used. From the viewpoint of production efficiency, a roll laminator or a vacuum laminator is preferable.

  When the stretchable base material 3 is formed on the metal foil 10, for example, a resin composition varnish for forming the stretchable base material is applied to the metal foil, and the applied resin composition is dried. The stretchable base material 3 is formed by a method including: If necessary, the resin composition is cured by heating or light irradiation.

  Although the thickness of the elastic base material 3 is not specifically limited, Usually, it is 5-1000 micrometers. When the thickness is within this range, sufficient stretchability and strength of the stretchable substrate 3 can be easily obtained.

  The stretchable base material 3 can have stretchability such that, for example, the recovery rate after tensile deformation to 20% strain is 80% or more. This recovery rate is calculated | required in the tension test using the measurement sample of an elastic base material. FIG. 3 is a stress-strain curve showing an example of measuring the recovery rate. The strain (displacement amount) applied in the first tensile test is X, and the difference between X and the position where the load is applied to the measurement sample when the tensile test is performed again after returning to the initial position is defined as Y. R calculated as (%) = Y / X × 100 is defined as the recovery rate. The recovery rate can be measured with X as 20%. If the recovery rate is 80% or more, it can withstand repeated use, so the recovery rate is more preferably 85% or more, and still more preferably 90% or more.

  The tensile elastic modulus of the stretchable base material 3 is preferably 0.1 MPa or more and 1000 MPa or less. When the tensile elastic modulus is 0.1 MPa or more and 1000 MPa or less, the handleability and flexibility as a substrate tend to be particularly excellent. In this respect, the elastic modulus is more preferably 0.3 MPa or more and 100 MPa or less, and further preferably 0.5 MPa or more and 50 MPa or less.

  The elongation at break of the elastic substrate 3 is preferably 100% or more. When the elongation at break is 100% or more, sufficient stretchability tends to be obtained. From this viewpoint, the elongation at break is more preferably 150% or more, and further preferably 200% or more. The upper limit of the elongation at break is not particularly limited, but is usually about 1000% or less.

  As shown in FIG. 1 and FIG. 2B, the etching resist 7 is formed on the metal foil 10 while conveying the base 20 with metal foil along the longitudinal direction MD. The etching resist 7 has a pattern including a guide covering portion 7E and a wiring covering portion 7C that respectively cover the guide portion 5E and the wiring pattern 5C. For example, the etching resist 7 is formed by a method including laminating a photosensitive film and exposing and developing the photosensitive film to form an etching resist. Exposure and development of the photosensitive film may be performed while transporting the substrate 20 with the metal foil, or may be performed after the transport is temporarily stopped.

  The photosensitive film for forming the etching resist 7 may be selected from dry film resists usually used for forming the etching resist. Examples of commercially available products include “Photec RY” manufactured by Hitachi Chemical Co., Ltd. is there.

  Subsequently, as shown in FIG. 1 and FIG. 2C, a part of the metal foil 10 is removed by etching the metal foil 10 using the etching resist 7 as a mask. Thereafter, as shown in FIGS. 1 and 2D, the etching resist 7 is removed, so that the two guide portions 5E and the plurality of wiring patterns 5C formed between the two guide portions 5E are opposed to each other. The stretchable wiring board 1 having the metal foil pattern 5 is obtained. By etching using an etching resist, the guide portion 5E and the wiring pattern 5C can be efficiently formed collectively. Etching of the metal foil may be performed while conveying the substrate 20 with metal foil, or may be performed after the conveyance is stopped. As an etchant for etching the metal foil 10, for example, a mixed solution of concentrated sulfuric acid and hydrogen peroxide solution or a ferric chloride solution can be used.

  The wiring pattern 5C includes a waveform portion that can be expanded and contracted. However, the shape of the wiring pattern C is not limited to this, and any shape that can be expanded and contracted can be adopted.

  The stretchable base material where the metal foil has been removed by etching has low rigidity and stretchability, so that if the tension for transportation is applied to the stretchable base material after etching, it will be like necking or twisting. Deformation tends to occur. By leaving the metal foil as the guide portion 5E extending along the longitudinal direction MD of the stretchable base material 3, rigidity is imparted to the stretchable base material 3, so that the stretchable base material 3 that has received tension is provided. Deformations such as necking and twisting are less likely to occur. The two guide portions 5E are respectively provided on both end portions in the width direction of the stretchable base material 3 (direction perpendicular to the longitudinal direction MD). However, the guide part 5E is provided inside both ends of the stretchable base material 3, and there is no metal foil between the guide part 5E and both ends of the stretchable base material 3, and the stretchable base material 3 is exposed. There may be parts. The guide portion 5E is preferably formed continuously along the longitudinal direction of the stretchable base material 3, but the guide portion 5E may be partially interrupted within a range not impairing the gist of the present invention. . The width of the guide portion 5E is not particularly limited. For example, the ratio of the width of the guide portion 5E to the width of the stretchable base material 3 may be 5 to 50%. Further, the width of the guide portion 5E may be 10 to 250 mm.

  The formed long stretchable wiring board 1 includes a plurality of wiring patterns 5C. Usually, each elastic wiring board is cut out from the long elastic wiring board 1. Various stretchable devices are manufactured by mounting electronic elements such as semiconductor elements on the cut out individual stretchable wiring boards. It is also possible to obtain a roll-shaped elastic wiring board by winding up the long elastic wiring board before cutting out the individual elastic wiring boards in a roll shape. From unwinding of the stretchable base material to winding up the stretchable wiring board, the metal foil may be processed continuously without winding up the stretchable base material and the metal foil. You may wind up once. Also when unwinding the long stretchable wiring substrate wound up in a roll shape, the occurrence of deformation such as necking and twisting is suppressed by providing the guide portion.

  Hereinafter, an embodiment of the stretchable substrate 3 and a resin composition for forming the stretchable substrate 3 will be described.

  The stretchable base material according to one embodiment or the resin composition for forming the same can contain a rubber component. Mainly by this rubber component, stretchability is easily imparted to the stretchable substrate. 30 mass% or more may be sufficient with respect to the total mass of a stretchable base material or a resin composition. Further, the content of the rubber component may be less than 100% by mass with respect to the total mass of the stretchable base material or the resin composition. In the present specification, the “total mass of the resin composition” means the mass of a portion excluding the organic solvent described later used for forming the varnish.

  Rubber components include, for example, acrylic rubber, isoprene rubber, butyl rubber, styrene butadiene rubber, butadiene rubber, acrylonitrile butadiene rubber, silicone rubber, urethane rubber, chloroprene rubber, ethylene propylene rubber, fluorine rubber, sulfurized rubber, epichlorohydrin rubber, and chlorinated rubber. At least one of butyl rubber can be included. From the viewpoint of protecting the wiring from damage due to moisture absorption or the like, it is preferable that the gas permeability of the rubber component is low. From this viewpoint, the rubber component may be at least one selected from styrene butadiene rubber, butadiene rubber, and butyl rubber.

  Examples of commercially available acrylic rubber include “Nipol AR series” manufactured by Nippon Zeon Co., Ltd. and “Clarity series” manufactured by Kuraray Co., Ltd.

  As a commercial item of isoprene rubber, for example, “Nipol IR series” manufactured by Nippon Zeon Co., Ltd. can be mentioned.

  Examples of commercially available butyl rubber include “BUTYL series” manufactured by JSR Corporation.

  Examples of commercially available styrene butadiene rubber include “Dynalon SEBS Series”, “Dynalon HSBR Series” manufactured by JSR Corporation, “Clayton D Polymer Series” manufactured by Kraton Polymer Japan, and “AR Series” manufactured by Aron Kasei Co., Ltd. It is done.

  Examples of commercially available butadiene rubber include “Nipol BR series” manufactured by Nippon Zeon Co., Ltd.

  Examples of commercially available acrylonitrile butadiene rubber include “JSR NBR series” manufactured by JSR Corporation.

  Examples of commercially available silicone rubber include “KMP series” manufactured by Shin-Etsu Silicone Co., Ltd.

  Examples of commercially available ethylene propylene rubber include “JSR EP series” manufactured by JSR Corporation.

  As a commercial item of fluororubber, for example, “DAIEL series” manufactured by Daikin Corporation can be mentioned.

  As a commercial item of epichlorohydrin rubber, for example, “Hydrin series” manufactured by Nippon Zeon Co., Ltd. may be mentioned.

  The rubber component can also be produced by synthesis. For example, acrylic rubber can be obtained by reacting (meth) acrylic acid, (meth) acrylic acid ester, aromatic vinyl compound, vinyl cyanide compound and the like.

  The stretchable substrate or the resin composition for forming the stretched substrate may further contain a coupling agent. A coupling agent is a compound having a function of binding an organic material and an inorganic material. The coupling agent includes, for example, a hydrolyzable group having affinity or reactivity with an inorganic material (inorganic filler, glass, metal, etc.) and an organic functional group capable of chemically bonding with an organic material (organic synthetic resin, etc.). It may be a compound having It is considered that the adhesion between the stretchable base material and the metal foil is improved when the stretchable base material contains a coupling agent.

  Examples of the hydrolysis group of the coupling agent include an alkoxy group and an acetoxy group. Examples of the organic functional group of the coupling agent include (meth) acryl group, vinyl group, epoxy group, amino group, ureido group, mercapto group, sulfide group, isocyanurate group, isocyanate group, acid anhydride group and the like.

  The coupling agent may be, for example, a silane coupling agent from the viewpoint of further improving the adhesion between the stretchable base material and the metal foil and the versatility.

  Specific examples of the coupling agent include vinyl silane, (meth) acryl silane, epoxy silane, mercapto silane, sulfur silane, amino silane, ureido silane, isocyanurate silane, isocyanate silane and acid anhydride.

  Examples of commercially available vinylsilanes include KBM-1003 and KBE-1003 (Shin-Etsu Chemical Co., Ltd., trade name); and A-151, A-171, A-172, and A-2171 (Momentive Performance Materials).・ Product name made in Japan).

  As a commercial item of (meth) acryl silane, for example, KBM-5103, KBM-502, KBM-503, KBE-502 and KBE-503 (Shin-Etsu Chemical Co., Ltd., trade name); Z-6030 and Z-6033 (Trade name, manufactured by Toray Dow Corning Co., Ltd.); and Y-9936 and A-174 (trade name, manufactured by Momentive Performance Materials Japan).

  Examples of commercially available epoxy silane include KBM-303, KBM-402, KBM-403, KBE-402 and KBE-403 (Shin-Etsu Chemical Co., Ltd., trade names); Z-6040, Z-6044 and Z- 6043 (trade name, manufactured by Toray Dow Corning Co., Ltd.); and A-186, A-187, and A-1871 (product names, manufactured by Momentive Performance Materials Japan).

  Examples of commercially available products of mercaptosilane include Z-6062 (trade name, manufactured by Toray Dow Corning Co., Ltd.); and A-189 and A-1891 (product names, manufactured by Momentive Performance Materials Japan). It is done.

  As a commercial item of sulfur silane, A-LINK599 (The product made by Momentive Performance Materials Japan) is mentioned, for example.

  Examples of commercially available aminosilanes include KBM-602, KBM-603, KBM-903, KBM-573, KBM-575, KBE-903 and KBE-9103 (Shin-Etsu Chemical Co., Ltd., trade name); Z-6610 , Z-6011, Z-6020, Z-6094, Z-6883 and Z-6032 (trade names, manufactured by Toray Dow Corning Co., Ltd.); and A-1100, A-1110, A-1120, A-2120 and Y-9669 (made by Momentive Performance Materials Japan, trade name).

  Examples of commercially available products of ureidosilane include KBE-585 (Shin-Etsu Chemical Co., Ltd., trade name); and A-1160 (trade name, manufactured by Momentive Performance Materials Japan).

  Examples of commercially available products of isocyanurate silane include KBM-9659 (Shin-Etsu Chemical Co., Ltd., trade name).

  Examples of commercially available isocyanate silanes include KBE-9007 (Shin-Etsu Chemical Co., Ltd., trade name); and A-1310 and Y-5187 (trade names, manufactured by Momentive Performance Materials Japan).

  Examples of commercially available acid anhydrides include X-12-967C (Shin-Etsu Chemical Co., Ltd., trade name).

  From the viewpoint of further improving the adhesion between the substrate and the conductor, the coupling agent is, for example, a (meth) acryl group, vinyl group, epoxy group, amino group, ureido group, mercapto group, sulfide group, isocyanurate group, isocyanate. It preferably has at least one functional group selected from the group consisting of a group and an acid anhydride group. The functional group may be appropriately selected from the viewpoint of, for example, the type of resin constituting the stretchable substrate. For example, in a resin system containing an unsaturated double bond, the coupling agent preferably has a vinyl group or a (meth) acryl group. In a resin system containing a polar functional group, the coupling agent is an amino group. Alternatively, it preferably has a mercapto group. From the viewpoint of interaction with the conductor foil, the coupling agent may have, for example, a polar functional group.

  Specific examples of the coupling agent include 3-ureidopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3- Isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriet Sisilane, 3-octanoylthio-1-propyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltri Including methoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane and vinyltris (2-methoxyethoxy) silane.

  The content of the coupling agent is preferably 0.2 to 10% by mass and more preferably 0.5 to 5% by mass based on the total mass of the stretchable base material or the curable resin composition. Preferably, it is 0.8-3 mass%. When the content of the coupling agent is within the above range, the adhesion to the metal foil tends to be further improved while maintaining the properties of the stretchable substrate.

  The resin composition for forming the stretchable substrate 3 may be a curable resin composition containing a crosslinking component. In this case, the stretchable base material contains a crosslinked polymer as a crosslinking component. The crosslinking component is, for example, at least one selected from the group consisting of (meth) acrylic groups, vinyl groups, epoxy groups, styryl groups, amino groups, isocyanurate groups, ureido groups, cyanate groups, isocyanate groups, and mercapto groups. A compound having a reactive group may be used. These compounds can be used alone or in combination of two or more.

  Examples of the compound having a (meth) acryl group include a (meth) acrylate compound. The (meth) acrylate compound may be monofunctional, bifunctional or polyfunctional, and is not particularly limited, but bifunctional or polyfunctional (meth) acrylate is preferred in order to obtain sufficient curability.

  Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, butoxyethyl (meth) acrylate, Isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octylheptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate , Lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (Meth) acrylate, behenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Aliphatics such as methoxypolyethylene glycol (meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, methoxypolypropyleneglycol (meth) acrylate, ethoxypolypropyleneglycol (meth) acrylate, mono (2- (meth) acryloyloxyethyl) succinate ( (Meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, dicyclopentanyl (meth) ) Acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, mono (2- (meth) acryloyloxyethyl) tetrahydrophthalate, mono (2- (meth) acryloyloxyethyl) hexahydrophthalate Cyclic (meth) acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, o-biphenyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, 1-naphthoxyethyl (meth) acrylate, 2-naphthoxyethyl (meth) acrylate, phenoxypolyethyleneglycol (Meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (o-phenylphenoxy) propyl Aromatic (meth) acrylates such as (meth) acrylate, 2-hydroxy-3- (1-naphthoxy) propyl (meth) acrylate, 2-hydroxy-3- (2-naphthoxy) propyl (meth) acrylate; 2-tetrahydro Heterocyclic (meth) acrylates such as furfuryl (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, 2- (meth) acryloyloxyethyl-N-carbazole, and caprolacts thereof Modified products thereof. Among these, the aliphatic (meth) acrylate and the aromatic (meth) acrylate are preferable from the viewpoint of compatibility with the styrene-based elastomer, transparency, and heat resistance.

  Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. , Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxylated polypropylene glycol di ( (Meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl Recall 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, glycerin di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, ethoxylated 2-methyl Aliphatic (meth) acrylates such as 1,3-propanediol di (meth) acrylate; cyclohexanedimethanol (meth) acrylate, ethoxylated cyclohexanedimethanol (meth) acrylate, propoxylated cyclohexanedimethanol (meth) acrylate, etoxy Propoxylated cyclohexanedimethanol (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, ethoxylated tricyclodecane dimethanol (meth) acrylate, propoxylated tricyclodecane dimethanol (meth) acrylate, ethoxylated propoxylated tri Cyclodecane dimethanol (meth) acrylate, ethoxylated hydrogenated bisphenol A di (meth) acrylate, propoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated propoxylated hydrogenated bisphenol A di (meth) acrylate, ethoxylated water Alicyclic rings such as hydrogenated bisphenol F di (meth) acrylate, propoxylated hydrogenated bisphenol F di (meth) acrylate, and ethoxylated propoxylated hydrogenated bisphenol F di (meth) acrylate Formula (meth) acrylate; ethoxylated 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 AF di (meth) acrylate, propoxylated bisphenol AF di (meth) acrylate, ethoxylated propoxylated bisphenol AF di (meth) Acrylate, ethoxylated fluorene di (meth) acrylate, propoxylated fluorene di (meth) acrylate, ethoxylated propoxy fluorene di (meth) acrylate Heterocyclic (meth) acrylates such as ethoxylated isocyanuric acid di (meth) acrylate, propoxylated isocyanuric acid di (meth) acrylate, ethoxylated propoxylated isocyanuric acid di (meth) acrylate, etc. Acrylates; these caprolactone modified products; aliphatic epoxy (meth) acrylates such as neopentyl glycol type epoxy (meth) acrylate; cyclohexanedimethanol type epoxy (meth) acrylate, hydrogenated bisphenol A type epoxy (meth) acrylate, hydrogenated Alicyclic epoxy (meth) acrylates such as bisphenol F type epoxy (meth) acrylate; and resorcinol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol Le F type epoxy (meth) acrylate, bisphenol AF type epoxy (meth) acrylates, and aromatic epoxy (meth) acrylates such as fluorene epoxy (meth) acrylate. Among these, the aliphatic (meth) acrylate and the aromatic (meth) acrylate are preferable from the viewpoint of compatibility with the styrene-based elastomer, transparency, and heat resistance.

  Examples of the trifunctional or higher polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated propoxylated tri Methylolpropane 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 (me ) Aliphatic (meth) acrylates such as acrylate, ethoxylated propoxylated pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexa (meth) acrylate; ethoxylated isocyanuric acid tri (meth) acrylate, propoxylated Heterocyclic (meth) acrylates such as isocyanuric acid tri (meth) acrylate and ethoxylated propoxylated isocyanuric acid tri (meth) acrylate; modified caprolactone thereof; and phenol novolac type epoxy (meth) acrylate and cresol novolac type epoxy ( And aromatic epoxy (meth) acrylates such as (meth) acrylate. Among these, the aliphatic (meth) acrylate and the aromatic (meth) acrylate are preferable from the viewpoint of compatibility with the styrene-based elastomer, transparency, and heat resistance.

  The compound containing an epoxy group is not particularly limited as long as it has an epoxy group in the molecule, and can be, for example, a general epoxy resin. The epoxy resin may be monofunctional, bifunctional, or polyfunctional, and is not particularly limited, but a bifunctional or polyfunctional epoxy resin is preferable in order to obtain sufficient curability.

  Examples of the epoxy resin include bisphenol A type, bisphenol F type, phenol novolac type, and cresol novolac type. An epoxy resin modified with a fatty chain is preferred because flexibility can be imparted. Examples of commercially available fatty chain-modified epoxy resins include EXA-4816 manufactured by DIC Corporation.

  The content of the crosslinking component and the crosslinked polymer formed therefrom is preferably 10 to 50% by mass based on the mass of the stretchable substrate or the curable resin composition for forming the stretchable substrate. If the content of the crosslinked polymer formed from the crosslinking component is within the above range, the adhesion with the metal foil tends to be improved while maintaining the properties of the stretchable substrate. From the above viewpoint, the content of the crosslinking component and the crosslinked polymer is more preferably 15 to 40% by mass.

  The curable resin composition used for forming the stretchable substrate may contain a curing accelerator and / or a polymerization initiator. For example, if it is curable resin composition containing a (meth) acrylate compound etc., you may add a polymerization initiator. The polymerization initiator is not particularly limited as long as it initiates polymerization by heating or irradiation with ultraviolet rays or the like. For example, a thermal radical polymerization initiator or a photo radical polymerization initiator can be used. If it is a thermal radical initiator, it is preferable at the point that reaction of a resin composition advances uniformly. If it is a photo radical initiator, since normal temperature hardening is possible, it is preferable at the point which prevents the deterioration by the heat | fever of a device, and the point which can suppress the curvature of an elastic base material.

  Examples of the thermal radical polymerization initiator include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t- Butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1- Peroxyketals such as bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane; hydroperoxides such as p-menthane hydroperoxide; α, α′-bis (t-butylperoxy) diisopropylbenzene , Dicumyl peroxide, t-butyl cumylper Dialkyl peroxides such as oxide and di-t-butyl peroxide; diacyl peroxides such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide and benzoyl peroxide; bis (4-t-butylcyclohexyl) peroxydicarbonate Peroxycarbonates such as di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxybutyl peroxycarbonate; t-butyl peroxypivalate, t-hexyl peroxy Pivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t-hexylper Oxy-2-e Ruhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, 2,5-dimethyl-2 , 5-bis (benzoylperoxy) hexane, peroxyesters such as t-butylperoxyacetate; and 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) ), 2,2′-azobis (4 Methoxy-2'-dimethylvaleronitrile) azo compounds and the like. Among these, the diacyl peroxide, the peroxyester, and the azo compound are preferable from the viewpoints of curability, transparency, and heat resistance.

  Examples of the radical photopolymerization initiator include benzoin ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one; 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane- Α-hydroxy ketones such as 1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one; 2-benzyl-2-dimethylamino-1 Α-amino ketones such as-(4-morpholinophenyl) -butan-1-one, 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; Oxime esters such as (4-phenylthio) phenyl] -1,2-octadion-2- (benzoyl) oxime; bis (2,4,6 Phosphine oxides such as -trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole 2,4,5-tria such as dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer Reel imidazole dimer; benzophenone, N, N, N ′, N′-tetrame Benzophenone compounds such as lu-4,4′-diaminobenzophenone, N, N, N ′, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone; 2-ethylanthraquinone, Phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, Quinone compounds such as 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin methyl ether, benzoin ethyl ether, benzoy Benzoin ethers such as phenyl ether; benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; benzyl compounds such as benzyldimethyl ketal; 9-phenylacridine, 1,7-bis (9,9′-acridinylheptane), etc. Acridine compounds; N-phenylglycine; and coumarin.

  In the 2,4,5-triarylimidazole dimer, the substituents of the aryl groups at the two triarylimidazole sites may give the same and symmetric compounds or differently give asymmetric compounds . Like a combination of diethylthioxanthone and dimethylaminobenzoic acid, a thioxanthone compound and a tertiary amine may be combined.

  Among these, the α-hydroxy ketone and the phosphine oxide are preferable from the viewpoints of curability, transparency, and heat resistance. These thermal and photo radical polymerization initiators can be used alone or in combination of two or more. Further, it can be combined with an appropriate sensitizer.

  It is preferable that content of a polymerization initiator is 0.1-10 mass parts with respect to 100 mass parts of total amounts of a rubber component and a crosslinking component. When the content of the polymerization initiator is 0.1 parts by mass or more, sufficient curing tends to be easily obtained. When the content of the polymerization initiator is 10 parts by mass or less, sufficient light transmittance tends to be easily obtained. From the above viewpoint, the content of the polymerization initiator is more preferably 0.3 to 7 parts by mass, and further preferably 0.5 to 5 parts by mass.

  A tertiary amine, imidazole, acid anhydride, or phosphine curing accelerator may be added to the resin composition containing an epoxy resin. From the viewpoint of storage stability and curability of the varnish, it is preferable to use imidazole.

  In addition to the above components, the stretchable base material or the resin composition for forming the base material may contain, as necessary, an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a visible light absorber, a colorant, a plasticizer. Agents, stabilizers, fillers, and the like may be further included within a range that does not significantly impair the effects of the present invention.

  For example, the elastic substrate is obtained by dissolving or dispersing a rubber component and other components as necessary in an organic solvent to obtain a resin varnish, and forming the resin varnish on a metal foil or a carrier film by a method described later. Can be manufactured by a method including the above.

  The organic solvent used here is not particularly limited. For example, aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene and p-cymene; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; ethylene carbonate, propylene carbonate, etc. And carbonates; and amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more. It is preferable that the solid content (components other than the organic solvent) concentration in the resin varnish is usually 20 to 80% by mass.

  Although it does not restrict | limit especially as a carrier film, For example, Polyesters, such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate; Polyolefins, such as polyethylene and a polypropylene; Polycarbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Examples thereof include a resin film selected from ether sulfide, polyether sulfone, polyether ketone, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone, and liquid crystal polymer. Among these, from the viewpoints of flexibility and toughness, a film of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, polycarbonate, polyamide, polyimide, polyamideimide, polyphenylene ether, polyphenylene sulfide, polyarylate or polysulfone is preferable. .

  DESCRIPTION OF SYMBOLS 1 ... Elastic wiring board, 3 ... Elastic base material, 5 ... Metal foil pattern, 5C ... Wiring pattern, 5E ... Guide part, 7 ... Etching resist, 7C ... Wiring covering part, 7E ... Guide covering part, 10 ... Metal Foil, 20 ... substrate with metal foil, MD ... longitudinal direction of stretchable substrate.

Claims (5)

  By removing a part of the metal foil while transporting a metal foil-attached base material having a long stretchable base material and a metal foil laminated on the stretchable base material along its longitudinal direction A metal foil pattern including two guide portions respectively extending on both ends of the stretchable base material along the longitudinal direction of the stretchable base material and a wiring pattern formed between the two guide portions A method for producing a stretchable wiring board, comprising the step of forming a substrate. The step of forming the metal foil pattern comprises:
Laminating a photosensitive film on the metal foil;
Exposing and developing the photosensitive film to form an etching resist;
Etching the metal foil using the etching resist as a mask to remove a part of the metal foil.
The method of claim 1.   The step of forming the base with metal foil by laminating the metal foil on the long stretchable base material or forming the stretchable base material on the long length metal foil. The method according to claim 1, comprising.   The method as described in any one of Claims 1-3 further equipped with the process of winding up the elongate elastic wiring board which has the said metal foil pattern and the said elastic base material in roll shape. A long stretchable base material, and a metal foil pattern laminated on the stretchable base material,
The metal foil pattern has two guide portions respectively extending on both ends of the stretchable base material along the longitudinal direction of the stretchable base material, and a wiring pattern formed between the two guide portions. Including,
Elastic wiring board.

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