TW201825013A - Elastic conductive sheet, elastic wiring, elastic wiring-equipped fabric, and method for restoring conductivity - Google Patents

Elastic conductive sheet, elastic wiring, elastic wiring-equipped fabric, and method for restoring conductivity Download PDF

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TW201825013A
TW201825013A TW106135387A TW106135387A TW201825013A TW 201825013 A TW201825013 A TW 201825013A TW 106135387 A TW106135387 A TW 106135387A TW 106135387 A TW106135387 A TW 106135387A TW 201825013 A TW201825013 A TW 201825013A
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stretchable
conductivity
wiring
recovery rate
sheet
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TW106135387A
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Chinese (zh)
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米倉弘倫
權義哲
入江達彥
木南萬紀
石丸園子
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日商東洋紡股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/04—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by a layer being specifically extensible by reason of its structure or arrangement, e.g. by reason of the chemical nature of the fibres or filaments
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Abstract

To provide an elastic conductive material for forming elastic wiring in a garment-type electronic device, wherein the product life thereof which is limited by deterioration of the electrical wiring can be extended on the user side. An electrode, electrical wiring, or the like is formed in a garment by using an elastic conductive sheet as the wiring, said elastic conductive sheet being configured from a conductive filler and a binder resin, characterized in that the unevenness in the film thickness of the sheet is 10% or less and the elastic recovery thereof after 20% elongation at 25 DEG C is 92% or greater, and preferably, further characterized in that Mw/Mn > 4 or higher, given that the number average molecular weight of the binder resin is Mn and the weight average molecular weight thereof is Mw. Furthermore, when the conductivity of this electrode or wiring decreases due to repeated stretching or laundering, it is possible to restore the conductivity thereof to a useful level by heating to 60 DEG C or higher.

Description

伸縮性導體片、伸縮性配線、設有伸縮性配線之布帛及導電性恢復方法Stretchable conductor sheet, stretchable wiring, fabric provided with stretchable wiring, and conductivity recovery method

本發明關於一種導電材料，該導電材料使用於在衣服中納入電子功能或電氣功能而使用之衣服型穿戴式電子設備，更詳細而言，係關於形成有具伸縮性之電氣配線，且有自然穿戴感的衣服型電子設備。The present invention relates to a conductive material, which is used in a clothing-type wearable electronic device that incorporates an electronic function or an electrical function into clothing. More specifically, it relates to the formation of flexible electrical wiring and natural Wearable clothing-type electronic device.

如今，人們正開發意欲將具有輸入輸出、演算、通訊功能之電子設備以極接近或密接於身體之狀態使用的穿戴式電子設備。就穿戴式電子設備而言，已知有如手錶、眼鏡、耳機之具配件型外形的設備、於衣服納入電子功能的紡織品整合型設備。專利文獻1中揭示了該紡織品整合型設備之一例。Today, people are developing wearable electronic devices intended to use electronic devices with input, output, calculation, and communication functions in close proximity or close contact with the body. As for wearable electronic devices, there are known accessories-like devices such as watches, glasses, and earphones, and textile-integrated devices that incorporate electronic functions in clothing. Patent Document 1 discloses an example of this textile-integrated device.

電子設備需要電力供給用、訊號傳輸用的電氣配線。尤其在紡織品整合型穿戴式電子設備中，配合伸縮的衣服亦要求電氣配線具有伸縮性。通常由金屬線、金屬箔構成之電氣配線本質上並無實用的伸縮性，故使用將金屬線、金屬箔配置成波形、或重複馬蹄形而使其具有擬似的伸縮功能的方法。 金屬線的情況下，藉由將金屬線視為刺繡線並縫在衣服上，可形成配線。但，顯然該方法不適合大量生產。 利用金屬箔之蝕刻形成配線的方法，係一般印刷電路板之製法。下列方法為已知：將金屬箔貼合於具伸縮性之樹脂片，以和印刷電路板同樣的方法形成波形配線，而製成擬似的伸縮性配線。該方法係利用波形配線部的扭轉變形而使其具有擬似的伸縮特性，但由於扭轉變形會導致金屬箔在厚度方向也產生變形，故作為衣服的一部分使用的話，會有非常不協調的穿戴感而不佳。又，如洗滌時之經受過度變形的情況下，金屬箔會產生永久性塑性變形，配線的耐久性也會有問題。Electronic equipment requires electrical wiring for power supply and signal transmission. Especially in textile-integrated wearable electronic devices, telescopic clothes are also required to have elasticity in conjunction with telescopic clothes. Generally, electrical wiring composed of metal wires and metal foils does not have practical elasticity in nature. Therefore, a method of arranging metal wires and metal foils in a corrugated shape or repeating a horseshoe shape to have a similar telescopic function is used. In the case of a metal thread, a wire can be formed by treating the metal thread as an embroidery thread and sewing it on clothes. However, it is clear that this method is not suitable for mass production. A method for forming a wiring by etching a metal foil is a general printed circuit board manufacturing method. The following method is known: bonding a metal foil to a stretchable resin sheet, forming a wave-shaped wiring in the same manner as a printed circuit board, and making a pseudo-stretchable wiring. This method uses the torsional deformation of the wave-shaped wiring part to make it have similar telescopic characteristics. However, the torsional deformation will cause the metal foil to deform in the thickness direction. Therefore, if it is used as part of clothes, it will have a very uncomfortable wearing feeling. Not good. In addition, if it is subjected to excessive deformation during washing, the metal foil will undergo permanent plastic deformation, and the durability of the wiring will also have problems.

作為實現伸縮性導體配線的方法，有人提出使用特殊的導電糊劑的方法。係將銀粒子、碳粒子、奈米碳管等導電性粒子、與帶伸縮性之胺甲酸酯樹脂等彈性體、天然橡膠、合成橡膠、溶劑等予以混練而製成糊劑狀，將配線直接或與伸縮性薄膜基材等組合後印刷描繪在衣服上。 由導電粒子與伸縮性黏結劑樹脂構成之導電性組成物，能實現巨觀上可伸縮之導體。該由糊劑獲得之導電性組成物，從微觀上看的話，受到外力時樹脂黏結劑部發生變形，在導電性粒子之電氣連結不中斷的範圍內維持導電性。巨觀上觀察到之電阻率，相較於金屬線、金屬箔為更高的值，但組成物本身即帶有伸縮性，故無需採用波形配線等形狀，配線寬度與厚度的自由度高，因此在實用上相較於金屬線可實現更低電阻的配線。As a method for realizing a flexible conductor wiring, a method using a special conductive paste has been proposed. Conductive particles such as silver particles, carbon particles, nano carbon tubes, and elastomers such as urethane resin with elasticity, natural rubber, synthetic rubber, and solvents are mixed to form a paste, and the wiring is made. Print or draw on clothing directly or in combination with a stretchable film substrate. A conductive composition composed of conductive particles and a stretchable binder resin can realize a telescopically stretchable conductor. From a microscopic perspective, the conductive composition obtained from the paste is deformed when an external force is applied, and the conductivity is maintained within a range where the electrical connection of the conductive particles is not interrupted. The resistivity observed on Juguan is higher than that of metal wires and metal foils, but the composition itself has elasticity, so there is no need to use shapes such as wave wiring, and the freedom of wiring width and thickness is high. Therefore, it is practically possible to realize wiring with lower resistance than metal wires.

專利文獻2中揭示了藉由將銀粒子與聚矽氧橡膠組合，並進一步以聚矽氧橡膠被覆聚矽氧橡膠基板上之導電性膜，以抑制伸長時之導電率降低的技術。專利文獻3中揭示了銀粒子與聚胺甲酸酯乳液的組合，為可獲得高導電率且高伸長率之導電膜。進一步有許多組合奈米碳管、銀填料等高縱橫比之導電性粒子以嘗試特性改善的示例被提出。Patent Document 2 discloses a technique in which silver particles are combined with a silicone rubber, and a conductive film on a silicone rubber substrate is further covered with a silicone rubber to suppress a decrease in conductivity during elongation. Patent Document 3 discloses that a combination of silver particles and a polyurethane emulsion is a conductive film capable of obtaining high conductivity and high elongation. Furthermore, many examples have been proposed in which high aspect ratio conductive particles such as nano carbon tubes and silver fillers are combined to try to improve characteristics.

專利文獻4中揭示了利用印刷法直接於衣服形成電氣配線的技術。 [先前技術文獻] [專利文獻]Patent Document 4 discloses a technique for forming electrical wiring directly on clothes using a printing method. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開平2-234901號公報 [專利文獻2]日本特開2007-173226號公報 [專利文獻3]日本特開2012-54192號公報 [專利文獻4]日本專利第3723565號公報[Patent Document 1] Japanese Patent Application Laid-Open No. 2-234901 [Patent Literature 2] Japanese Patent Application Laid-Open No. 2007-173226 [Patent Literature 3] Japanese Patent Application Laid-Open No. 2012-54192 [Patent Literature 4] Japanese Patent No. 3723565

[發明所欲解決之課題] 伸縮性導體組成物主要由導電粒子與柔軟性樹脂構成。作為如此之伸縮性導體，一般已知有使用橡膠等交聯型彈性體作為樹脂黏結劑，並摻合有碳黑、金屬粒子而成之組成物。如此之伸縮性導體組成物，係藉由使金屬系導電粒子與交聯型彈性體之前驅體、和視需要之溶劑等混合溶解分散所獲得之糊劑或漿液而形成。製成糊劑時，容易利用網版印刷等形成配線圖案。[Problems to be Solved by the Invention] The stretchable conductor composition is mainly composed of conductive particles and a flexible resin. As such a stretchable conductor, a composition using a crosslinked elastomer such as rubber as a resin binder and blending carbon black and metal particles is generally known. Such a stretchable conductor composition is formed by dissolving and dispersing a paste or a slurry obtained by mixing and dispersing metallic conductive particles with a precursor of a crosslinked elastomer, and a solvent, if necessary. When making a paste, it is easy to form a wiring pattern by screen printing or the like.

利用由使用伸縮性黏結劑之伸縮性導電糊劑獲得之伸縮性的導體組成物，於構成衣服之布帛利用印刷法形成配線時，相較於類似的技術，例如使用導電糊劑之膜電路(membrane circuit)的形成技術，存在各種差異，該等差異造成技術的困難性。 通常在使用PET薄膜等工程塑膠薄膜作為基材之膜電路中，電路全體具有折曲性，但基材本身相對於伸張負荷之彈性模量非常高，因此實質上不展示伸縮性。另一方面，使用布帛、柔軟的高分子片作為基材而形成由伸縮性導體組成物構成之配線時，可實現具有伸縮性之配線。經適當設計、製造之該伸縮性導體配線即使從伸張10%左右到最大達100%以上，仍可維持導電性。The use of a stretchable conductor composition obtained from a stretchable conductive paste using a stretchable adhesive, compared to similar techniques when fabricating the fabric of a garment using printing, such as a film circuit using a conductive paste ( There are various differences in the formation technology of membrane circuit, and these differences cause technical difficulties. Generally, in a film circuit using an engineering plastic film such as a PET film as a base material, the entire circuit has flexibility, but the base material itself has a very high elastic modulus with respect to a tensile load, and therefore does not substantially exhibit elasticity. On the other hand, when a wiring made of a stretchable conductor composition is formed using a fabric or a flexible polymer sheet as a base material, a wiring having stretchability can be realized. The properly designed and manufactured stretchable conductor wiring can maintain electrical conductivity even when stretched from about 10% to a maximum of 100% or more.

但，由導電粒子與伸縮性黏結劑樹脂構成之伸縮性導電被膜為分散系，彈性範圍窄，亦即虎克定律(Hooke's law)成立之拉伸荷重與應變(伸展)呈線性比例的範圍窄，充其量只有數%。超過彈性範圍、還有發生變形時，被膜內部會產生微小的裂紋，因裂紋產生之間隙擴大，致使塗膜持續變形。就該狀態而言，裂紋周圍的被膜由於尚為柔軟的緣故，被膜不會完全斷裂，裂紋的數目、寬度的增加等微觀上的內部結構變化不會在巨觀上給被膜帶來致命性的破壞，看似會持續柔軟地伸張的區域。雖然在該區域內不會發生被膜的斷裂，但由於內部結構上微小裂紋的成長，致使因導電粒子之連結所產生之導電路徑逐漸變窄，就結果而言塗膜的導電性降低。However, a stretchable conductive film composed of conductive particles and a stretchable binder resin is a dispersion system and has a narrow elastic range, that is, the range in which the tensile load and strain (elongation) in which Hooke's law is established is linear is narrow. , At best only a few percent. When the elastic range is exceeded and deformation occurs, minute cracks will be generated inside the film, and the gap generated by the cracks will expand, resulting in continuous deformation of the coating film. In this state, because the film around the crack is still soft, the film will not completely break, and the microscopic internal structural changes such as the increase in the number of cracks and the width will not cause the film to be fatal on a large scale. Destroyed, seemingly continuously stretched areas. Although the fracture of the film does not occur in this area, due to the growth of microcracks in the internal structure, the conductive path caused by the connection of conductive particles is gradually narrowed, and as a result, the conductivity of the coating film is reduced.

伸張至塑性變形區域之伸縮性導電被膜，若除掉拉伸荷重，則發生收縮並恢復到幾乎接近初始長度的長度，但由於導電粒子的連接被切斷，電阻值無法恢復到初始值，成為比起初始值更高的值。如此，重複超過彈性區域之伸張的話，伸縮性導電膜的電阻值會逐漸變高，最終成為非導通。如此，以往的伸縮性導電被膜存在因重複伸縮導致導電性降低的問題，將該伸縮性導體皮膜使用於衣服型電子設備之配線時，由於實際使用時發生之重複伸縮、進一步洗滌時等所加諸之水流，導致對於重複伸縮之耐久性成為問題。 [解決課題之手段]The stretchable conductive film stretched to the area of plastic deformation will shrink and recover to a length close to the initial length if the tensile load is removed. However, since the connection of the conductive particles is cut off, the resistance value cannot be restored to the initial value and becomes Higher value than the initial value. In this way, if the stretch beyond the elastic region is repeated, the resistance value of the stretchable conductive film will gradually increase and eventually become non-conductive. In this way, the conventional stretchable conductive film has a problem of reduced conductivity due to repeated expansion and contraction. When the stretchable conductive film is used for wiring of clothes-type electronic equipment, it is added due to repeated expansion and contraction that occurs during actual use and further washing. The flow of water causes problems with durability against repeated expansion and contraction. [Means for solving problems]

本案發明人等為了達成該目的而進行努力研究，結果發現藉由賦予伸縮性導電被膜特定的特性，重複伸縮耐久性在實用上得到大幅改善，而達成了下列發明。 亦即，本發明具有下列構成。 [1]一種伸縮性導體片，係由導電填料與黏結劑樹脂構成之伸縮性的導體片，其特徵為：該片之膜厚不均為10%以下，於25℃伸張20%後之伸張回復率為92%以上。 [2]如[1]之伸縮性導體片，於25℃伸張20%後，在除去伸張荷重的狀態下進行60℃加熱時的伸張回復率為96%以上。 [3]如[1]或[2]之伸縮性導體片，其中，伸縮性導體片之片材面方向之初始導電率為1×102 S/cm以上，因機械負荷所致之導電率降低比為初始導電率之1/1000以上之範圍時，60℃加熱所致之導電性回復率為10%以上。 [4]如[1]～[3]中任一項之伸縮性導體片，係由65～85質量%的黏結劑樹脂與15～35質量%的導電填料構成，該導電填料的90質量%以上由金屬粒子構成，該黏結劑樹脂之20%伸張後之伸張回復率為99%以上，玻璃轉移溫度為0℃以下。 [5]如[1]～[4]中任一項之伸縮性導體片，其中，令該黏結劑樹脂之數量平均分子量為Mn，重量平均分子量為Mw時，為Mw/Mn＞4。 [6]一種伸縮性導體/布帛疊層體，具有：50%伸張時之伸張回復率為99%以上，且具有60℃以上之耐熱性的絕緣性布帛層；及如[1]～[5]中任一項之伸縮性導體片的層。 [7]一種如[1]～[5]中任一項之伸縮性導體片或如[6]之伸縮性導體/布帛疊層體的導電性恢復方法，係藉由在已除去伸縮性導體片之伸張荷重的狀態下加熱至60℃以上。The inventors of the present invention conducted diligent research in order to achieve the object, and as a result, it was found that the repeatable stretch durability was greatly improved in practical use by imparting specific characteristics to a stretchable conductive film, and the following inventions were achieved. That is, the present invention has the following constitutions. [1] A stretchable conductor sheet, which is a stretchable conductor sheet composed of a conductive filler and a binder resin, characterized in that the film thickness of the sheet is not more than 10%, and it is stretched after being stretched by 20% at 25 ° C. The response rate was above 92%. [2] The stretchable conductor sheet according to [1], after being stretched by 20% at 25 ° C, the stretch recovery rate when the heating is performed at 60 ° C with the tensile load removed is 96% or more. [3] The stretchable conductor sheet according to [1] or [2], wherein the initial conductivity of the sheet surface direction of the stretchable conductor sheet is 1 × 10 2 S / cm or more, and the conductivity due to mechanical load When the reduction ratio is in the range of 1/1000 or more of the initial conductivity, the conductivity recovery rate by heating at 60 ° C is 10% or more. [4] The stretchable conductor sheet according to any one of [1] to [3], which is composed of 65 to 85% by mass of a binder resin and 15 to 35% by mass of a conductive filler, and 90% by mass of the conductive filler The above is composed of metal particles. After 20% elongation of the adhesive resin, the elongation recovery rate is more than 99%, and the glass transition temperature is 0 ° C or lower. [5] The stretchable conductor sheet according to any one of [1] to [4], wherein the number average molecular weight of the binder resin is Mn, and when the weight average molecular weight is Mw, Mw / Mn> 4. [6] A stretchable conductor / fabric laminated body having: an insulation fabric layer having a stretch recovery rate of 50% or more and a heat resistance of 60 ° C or more; and [1] to [5] ] Layer of any one of the stretchable conductor sheets. [7] A method for recovering the conductivity of the stretchable conductor sheet according to any one of [1] to [5] or the stretchable conductor / cloth laminate according to [6], by removing the stretchable conductor The sheet is heated to a temperature of 60 ° C or higher under a tensile load.

進一步，本發明具有下列構成。 [8]一種伸縮性配線，係至少由下列層構成：拉伸降伏伸度為70%以上，熱變形溫度為60℃以上之伸縮性絕緣高分子層；及由導電填料與黏結劑樹脂構成之伸縮性導體層。 [9]如[8]之伸縮性配線，其中，該伸縮性導體層之於25℃伸張20%後之伸張回復率為92%以上。 [10]如[8]或[9]之伸縮性配線，其中，伸縮性導體層之面方向之初始導電率為1×102 S/cm以上，因機械負荷所致之導電率降低比為初始導電率之1/1000以上之範圍時，60℃加熱所致之導電性回復率為10%以上。 [11]如[8]～[10]中任一項之伸縮性配線，其中，該伸縮性導體層係由65～85質量%的黏結劑樹脂與15～35質量%的導電填料構成，該導電填料的90質量%以上由金屬粒子構成，該黏結劑樹脂之20%伸張後之伸張回復率為99%以上，玻璃轉移溫度為0℃以下。 [12]如[8]～[11]中任一項之伸縮性配線，其中，令該黏結劑樹脂之數量平均分子量為Mn，重量平均分子量為Mw時，為Mw/Mn＞4。 [13]一種設有伸縮性配線之布帛，係在50%伸張時之伸張回復率為99%以上，且具有60℃以上之耐熱性的絕緣性布帛上具有如[8]～[12]中任一項之伸縮性配線。 [14]一種如[8]～[12]中任一項之伸縮性配線的導電性恢復方法，係藉由在已除去伸縮性配線之伸張荷重的狀態下加熱至60℃以上。 [15]一種如[13]之設有伸縮性配線之布帛的導電性恢復方法，係藉由在已除去設有伸縮性配線之布帛之伸張荷重的狀態下加熱至60℃以上。 [發明之效果]Furthermore, this invention has the following structures. [8] A flexible wiring composed of at least the following layers: a stretchable insulating polymer layer with a tensile drop of 70% or more and a thermal deformation temperature of 60 ° C or more; and a conductive filler and a binder resin Stretchable conductor layer. [9] The stretchable wiring according to [8], wherein the stretch recovery rate of the stretchable conductor layer after being stretched by 20% at 25 ° C is 92% or more. [10] The stretchable wiring according to [8] or [9], wherein the initial conductivity in the plane direction of the stretchable conductor layer is 1 × 10 2 S / cm or more, and the conductivity reduction ratio due to mechanical load is In the range of 1/1000 or more of the initial conductivity, the conductivity recovery rate by heating at 60 ° C is 10% or more. [11] The stretchable wiring according to any one of [8] to [10], wherein the stretchable conductor layer is composed of 65 to 85% by mass of a binder resin and 15 to 35% by mass of a conductive filler, and the More than 90% by mass of the conductive filler is composed of metal particles, and the 20% stretch of the adhesive resin has a stretch recovery rate of 99% or higher, and a glass transition temperature of 0 ° C or lower. [12] The flexible wiring according to any one of [8] to [11], wherein the number average molecular weight of the binder resin is Mn, and when the weight average molecular weight is Mw, Mw / Mn> 4. [13] A fabric with stretchable wiring, which has an extension recovery rate of 99% or more when 50% stretched, and an insulation fabric with heat resistance of 60 ° C or more has [8] to [12] Flexible wiring of any one. [14] A method for recovering the conductivity of the stretchable wiring according to any one of [8] to [12], which is performed by heating the stretched wiring to a temperature of 60 ° C or higher in a state where the tensile load is removed. [15] A method for recovering the conductivity of a fabric provided with a stretchable wiring as in [13], by heating to a temperature of 60 ° C or more under a state where the tensile load of the fabric provided with the stretchable wiring has been removed. [Effect of the invention]

本發明之伸縮性導體片及伸縮性導體層，具有由導電粒子與伸縮性黏結劑樹脂構成之分散系結構。如上所述，使如此之具有分散系結構之柔軟性被膜伸張的話，因應伸張度，會有虎克定律成立之彈性變形區域、及落在虎克定律之外的塑性變形區域。彈性區域較窄，而在塑性區域中於被膜內部產生微小裂紋之情事如前述。此處觀察到之塑性區域，係從巨觀上的觀點觀察到之塑性區域。由於被膜內部產生微小的裂紋而導致發生不可逆的結構變化，但未產生裂紋的黏結劑樹脂部分則發生彈性變形。 以下，除非另有說明，伸縮性導體片與伸縮性導體層同義，同樣由伸縮性導體組成物構成，伸縮性的疊層體、伸縮性配線中之伸縮性導體層係加工成預定大小之伸縮性導體片。The stretchable conductor sheet and the stretchable conductor layer of the present invention have a dispersed structure composed of conductive particles and a stretchable adhesive resin. As described above, if such a flexible film having a dispersed structure is stretched, depending on the stretch, there will be an elastic deformation region where Hooke's law is established, and a plastic deformation region falling outside of Hooke's law. The elastic region is relatively narrow, and the occurrence of micro-cracks in the film in the plastic region is as described above. The plastic region observed here is a plastic region observed from a macroscopic viewpoint. Irreversible structural changes occur due to micro-cracks inside the film, but the resin part of the adhesive that does not crack is elastically deformed. Hereinafter, unless otherwise stated, a stretchable conductor sheet is synonymous with a stretchable conductor layer, and is also composed of a stretchable conductor composition. The stretchable laminate and the stretchable conductor layer in the stretchable wiring are processed into a predetermined size of stretch. Sexual conductor sheet.

本發明之主要目的在於，藉由將巨觀上觀察到之伸縮性導體片之伸張回復率調整成為92%以上，以抑制實用上之導電性能的降低。亦即，即使是在因伸縮性導體片伸張時所產生之微小裂紋導致由粒子接觸所產生之導電路徑被切斷的情況下，伸縮性導體片本身具有足夠高的伸張回復率時，可再現一度被切斷的導電粒子間之接觸，並實現電阻率的降低亦即導電性之回復。伸縮性導體片之伸張回復，主要依賴於黏結劑樹脂之柔軟性，藉由使用回復率高同時展示強收縮力之黏結劑樹脂，該效果提升。高分子因拉伸荷重延伸時，原來為捲縮狀態之高分子鏈成為鏈被拉伸的形態。於該狀態下進行提升高分子鏈之自由度的操作，亦即，進行加熱、或利用溶劑等之塑化操作的話，被拉伸的高分子鏈欲恢復到原來的捲縮狀態並展現收縮力。如本發明般，就伸縮性導體片而言，展示預定之伸張回復率的黏結劑樹脂也兼具該效果，故藉由將因重複伸張等實際使用導致導電性降低之伸縮性導體片，於除去伸張荷重之狀態加熱至適當溫度，可進一步提高伸張回復率，同時也可使被切斷之導電性粒子間之接觸狀態恢復。The main object of the present invention is to suppress the reduction in practical conductive performance by adjusting the stretch recovery rate of the stretchable conductor sheet observed on a large scale to 92% or more. That is, even when the conductive path generated by the contact of the particles is cut due to the micro-cracks generated when the stretchable conductor sheet is stretched, the stretchable conductor sheet itself has a sufficiently high stretch recovery rate, and can be reproduced. The contact between the conductive particles once cut off, and the reduction of the resistivity, that is, the recovery of the conductivity. The stretch recovery of the stretchable conductor sheet mainly depends on the softness of the adhesive resin. The effect is improved by using an adhesive resin that has a high recovery rate and exhibits strong shrinkage. When a polymer is stretched by a tensile load, the polymer chain that was originally in a crimped state becomes a state where the chain is stretched. In this state, the operation of increasing the degree of freedom of the polymer chain is performed, that is, if the heating or plasticizing operation using a solvent is performed, the stretched polymer chain is expected to return to the original crimped state and exhibit contraction force. . As in the present invention, with respect to the stretchable conductive sheet, a binder resin exhibiting a predetermined stretch recovery rate also has this effect. Therefore, by using a stretchable conductive sheet having reduced conductivity due to actual use such as repeated stretching, Heating to an appropriate temperature without removing the tensile load can further increase the tensile recovery rate, and can also restore the contact state between the cut conductive particles.

又，本發明中，藉由擴大黏結劑樹脂之分子量分布，可進一步提高回復效果。亦即，相對較高分子量之樹脂成分主導著伸縮性，同時相對較低分子量之成分展示自我修復性地填埋微小裂紋之功能，藉此，機械尺寸之回復與導電性能之回復同時得到促進。藉由在除去伸張荷重之狀態下加熱至適當溫度，可進一步促進該效果。Further, in the present invention, by increasing the molecular weight distribution of the binder resin, the recovery effect can be further improved. That is, a relatively higher molecular weight resin component dominates the stretchability, while a relatively lower molecular weight component exhibits a function of self-healingly filling tiny cracks, whereby the recovery of mechanical dimensions and the recovery of conductive properties are promoted simultaneously. This effect can be further promoted by heating to an appropriate temperature while removing the tensile load.

本發明中之伸縮性導體片、伸縮性導體層、伸縮性配線，係至少由拉伸降伏伸度為70%以上，熱變形溫度為60℃以上之伸縮性絕緣高分子層與伸縮性導體層構成，該伸縮性導體層由導電填料與黏結劑樹脂構成。The stretchable conductive sheet, the stretchable conductive layer, and the stretchable wiring in the present invention are made of a stretchable insulating polymer layer and a stretchable conductive layer having a stretch of at least 70% and a heat distortion temperature of 60 ° C or more. The elastic conductor layer is composed of a conductive filler and a binder resin.

本發明中之拉伸降伏伸度，係在利用一般的拉伸試驗獲得之縱軸為荷重(或強度)，橫軸為應變(或伸度或延伸)時之曲線(S-S曲線)中，於荷重不增加之情形下觀察到延伸增加之最初的點的伸度，亦即於降伏點之伸度。一般而言，降伏點係取概略地表示從彈性變形轉變成塑性變形之邊界的點。 圖1A係顯示利用拉伸試驗獲得之典型的S-S曲線的概略圖，圖中， SR：拉伸斷裂強度 SB：拉伸強度 SS：拉伸降伏強度 ER：拉伸斷裂伸度 EB：拉伸伸度 ES：拉伸降伏伸度。 本發明中之伸縮性絕緣高分子層之拉伸降伏伸度宜為80%以上，為95%以上更佳，為120%以上尤佳。 拉伸降伏伸度的上限為450%，較佳為360%。拉伸降伏強度高到超過必要的話，會有損及作為絕緣保護層之機械強度的情況。The tensile yielding elongation in the present invention is the curve (SS curve) when the vertical axis is the load (or strength) and the horizontal axis is the strain (or elongation or extension) obtained by a general tensile test. When the load is not increased, the extension of the initial point where the extension increases is observed, that is, the extension at the drop point. In general, the drop point is a point that roughly represents a boundary where elastic deformation is transformed into plastic deformation. FIG. 1A is a schematic diagram showing a typical SS curve obtained by a tensile test. In the figure, SR: tensile fracture strength SB: tensile strength SS: tensile drop strength ER: tensile elongation at break EB: tensile elongation Degree ES: stretch and yield. In the present invention, the stretch-elongation degree of the stretchable insulating polymer layer is preferably 80% or more, more preferably 95% or more, and even more preferably 120% or more. The upper limit of the stretch yield is 450%, preferably 360%. If the tensile drop strength is higher than necessary, the mechanical strength of the insulating protective layer may be impaired.

本發明中之熱變形溫度，係指於該溫度下，樹脂展現流動性、黏著性、黏接性中之任意者。關於熱變形溫度，係根據使調整成預定溫度之伸縮性絕緣高分子層與同樣調整成預定溫度之金屬接觸時，伸縮性絕緣高分子層是否發生顯著變形，或伸縮性絕緣高分子層與金屬之間是否產生黏著性或黏接性來判定。本發明就簡便的方法而言，可使用下列方法：使伸縮性絕緣高分子層接觸已加熱至預定溫度之熨斗，保持使伸縮性絕緣高分子層充分加熱的時間(1分鐘)後，將熨斗從伸縮性絕緣高分子層移走，根據觸感判斷伸縮性絕緣高分子層有無變形、移走熨斗時是否展示黏著、黏接性，以判斷是否達到熱變形溫度。 本發明中之伸縮性絕緣高分子層之熱變形溫度需為60℃以上，為75℃以上較佳，為90℃以上尤佳，為110℃以上更佳。熱變形溫度的上限取決於布料之耐熱性，較佳為180℃。更佳為160℃。熱變形溫度低於該範圍的話，會有伸縮性配線產生黏連的情況，又，熱變形溫度超過該範圍的話，會有柔軟性受到影響的情況。The thermal deformation temperature in the present invention means that at this temperature, the resin exhibits any one of flowability, adhesion, and adhesion. The thermal deformation temperature is based on whether the elastic insulating polymer layer is significantly deformed when the elastic insulating polymer layer adjusted to a predetermined temperature is brought into contact with a metal also adjusted to a predetermined temperature, or whether the elastic insulating polymer layer is in contact with a metal. Determine whether there is adhesion or adhesion between them. For the simple method of the present invention, the following method can be used: contact the stretchable insulating polymer layer with an iron that has been heated to a predetermined temperature, and maintain the time for fully heating the stretchable insulating polymer layer (1 minute), and then turn the iron Remove it from the stretchable insulating polymer layer, and determine if the stretchable insulating polymer layer is deformed according to the tactile sensation. If the iron is removed, it will show adhesion and adhesion to determine whether it has reached the thermal deformation temperature. The thermal deformation temperature of the stretchable insulating polymer layer in the present invention needs to be 60 ° C or higher, preferably 75 ° C or higher, more preferably 90 ° C or higher, and more preferably 110 ° C or higher. The upper limit of the heat distortion temperature depends on the heat resistance of the cloth, and is preferably 180 ° C. More preferably, it is 160 ° C. If the heat distortion temperature is lower than this range, the stretchable wiring may be stuck, and if the heat distortion temperature exceeds this range, the flexibility may be affected.

就本發明中之拉伸降伏伸度為70%以上，熱變形溫度為60℃以上之伸縮性絕緣高分子層而言，可使用非交聯型或交聯型彈性體。可使用彈性模量理想為1～1000MPa，玻璃轉移溫度理想為-60℃至15℃之範圍內的熱塑性彈性體樹脂作為本發明中使用之非交聯型彈性體，可列舉熱塑性之合成樹脂、合成橡膠、天然橡膠等。更具體而言，可列舉：胺甲酸酯橡膠、丙烯酸橡膠、聚矽氧橡膠、丁二烯橡膠、腈橡膠或氫化腈橡膠等含有腈基之橡膠、異戊二烯橡膠、硫化橡膠、苯乙烯丁二烯橡膠、丁基橡膠、氯磺化聚乙烯橡膠、乙烯丙烯橡膠、偏二氟乙烯共聚物等。其中，含有腈基之橡膠、氯丁橡膠、氯磺化聚乙烯橡膠、苯乙烯丁二烯橡膠為較佳，含有腈基之橡膠為特佳。 就本發明中之交聯型彈性體而言，可理想地使用對於前述非交聯型彈性體摻合交聯劑而獲得之交聯橡膠。交聯劑可使用硫、硫系交聯劑(所謂硫化劑)、有機過氧化物、金屬氧化物、有機胺化合物等。本發明中宜使用非硫系交聯劑。硫或含有硫之交聯劑的情況下，游離的含硫成分會和導電層之導電粒子作用，而發生導電性降低等不便的情況。 本發明中之交聯型彈性體中，為了將降伏伸度保持在預定範圍以上，交聯密度宜相對較低。本發明中，就使用四氫呋喃作為溶劑之凝膠分率而言，宜以使凝膠分率成為90質量%以下，較佳為80質量%以下的方式使交聯密度得到保持。As for the stretchable insulating polymer layer having a tensile yielding elongation of 70% or more and a thermal deformation temperature of 60 ° C or more, a non-crosslinked or crosslinked elastomer can be used. As the non-crosslinked elastomer used in the present invention, a thermoplastic elastomer resin having an elastic modulus of preferably 1 to 1000 MPa and a glass transition temperature in the range of -60 ° C to 15 ° C can be used. Examples include thermoplastic synthetic resins, Synthetic rubber, natural rubber, etc. More specific examples include rubbers containing nitrile groups, such as urethane rubber, acrylic rubber, silicone rubber, butadiene rubber, nitrile rubber, or hydrogenated nitrile rubber, isoprene rubber, vulcanized rubber, and styrene. Butadiene rubber, butyl rubber, chlorosulfonated polyethylene rubber, ethylene propylene rubber, vinylidene fluoride copolymer, etc. Among them, a rubber containing a nitrile group, a neoprene rubber, a chlorosulfonated polyethylene rubber, and a styrene butadiene rubber are preferred, and a rubber containing a nitrile group is particularly preferred. As the crosslinked elastomer in the present invention, a crosslinked rubber obtained by blending a crosslinking agent with the aforementioned non-crosslinked elastomer is preferably used. Examples of the crosslinking agent include sulfur, sulfur-based crosslinking agents (so-called vulcanizing agents), organic peroxides, metal oxides, and organic amine compounds. In the present invention, a non-sulfur-based crosslinking agent is preferably used. In the case of sulfur or a sulfur-containing crosslinking agent, free sulfur-containing components may interact with the conductive particles of the conductive layer, causing inconvenience such as a decrease in conductivity. In the crosslinked elastomer of the present invention, in order to keep the yielding elongation above a predetermined range, the crosslink density should be relatively low. In the present invention, in terms of the gel fraction using tetrahydrofuran as a solvent, the crosslinking density is preferably maintained such that the gel fraction becomes 90% by mass or less, and preferably 80% by mass or less.

本發明中之伸縮性絕緣高分子層，在單獨成膜後，可自我黏著、黏接於布料或伸縮性導體層上，或藉由熱熔黏接層等其他黏接手段貼合。 又，可將形成伸縮性絕緣高分子層之高分子材料熔融擠壓至布料或伸縮性導體層上來形成本發明中之伸縮性絕緣高分子層。 進一步，可藉由將形成伸縮性絕緣高分子層之高分子材料與視需要之溶劑、視需要添加之交聯劑、添加劑等加以摻合並予以印墨化，再印刷或塗布於布料或伸縮性導體層上，使其乾燥硬化來形成本發明中之伸縮性絕緣高分子層。針對可使用之溶劑、添加劑等係比照後述可用於伸縮性導體層之材料。After the flexible insulating polymer layer in the present invention is formed into a single film, it can be self-adhesive, adhered to the cloth or the stretchable conductor layer, or adhered by other adhesive means such as a hot-melt adhesive layer. In addition, the polymer material forming the stretchable insulating polymer layer can be melt-extruded onto the cloth or the stretchable conductor layer to form the stretchable insulating polymer layer in the present invention. Further, the polymer material forming the stretchable insulating polymer layer and the solvent, the cross-linking agent, and the additive added as needed can be mixed and printed, and then printed or coated on the cloth or stretchable. The conductive layer is dried and hardened to form the stretchable insulating polymer layer in the present invention. For the solvents and additives that can be used, the materials that can be used for the stretchable conductor layer are compared with those described later.

就本發明之伸縮性導體片、伸縮性導體層而言，該片或導體層的膜厚不均需為10%以下，於25℃伸張20%後之伸張回復率需為92%以上。 本發明中，伸縮性導體片之膜厚不均宜為8%以下。原因為：膜厚不均較大的情況下，由於施加伸張荷重時膜厚較薄之部分的伸度選擇性地變高，部分地劣化會加速，整體觀之時導電性降低程度會變高，且片的機械損傷、電氣損傷亦變大。本發明中，藉由使該片的膜厚不均成為10%以下，可更為顯著地展現相關效果。As for the stretchable conductor sheet and the stretchable conductor layer of the present invention, the film thickness variation of the sheet or the conductor layer needs to be 10% or less, and the stretch recovery rate after being stretched by 20% at 25 ° C needs to be 92% or more. In the present invention, the film thickness unevenness of the stretchable conductor sheet is preferably 8% or less. The reason is: in the case of large film thickness unevenness, since the elongation of the thinner part of the film thickness is selectively increased when the tensile load is applied, the partial degradation will be accelerated, and the degree of decrease in conductivity will be higher in the overall view. , And the mechanical damage and electrical damage of the sheet also become larger. In the present invention, by making the film thickness unevenness of the sheet less than or equal to 10%, the relevant effects can be more significantly exhibited.

本發明中之膜厚不均[%]，係在10cm四方形的片中隨機測定10點的厚度，並依照100×(最大膜厚-最小膜厚)/平均膜厚(10點平均)求出。 本發明之伸縮性導體片之膜厚不均宜為8%以下，為6%以下尤佳，為4%以下更佳。The film thickness non-uniformity [%] in the present invention is determined by randomly measuring the thickness of 10 points in a 10 cm square sheet, and is calculated according to 100 × (maximum film thickness-minimum film thickness) / average film thickness (10-point average). Out. The film thickness unevenness of the stretchable conductor sheet of the present invention is preferably 8% or less, more preferably 6% or less, and even more preferably 4% or less.

本發明中之伸張回復率，如圖1B所示般將伸縮性導電片懸垂，施以施加荷重使其伸張，除去荷重使其收縮的作用時，令初始長度為L0 ，伸張20%或預定%時之長度為L1 ，除去伸張荷重時的長度為L2 時，定義如下： 【數1】 伸張回復率＝((L1 -L2 )/(L1 -L0 ))×100 [%] 【數2】 殘留應變率＝((L2 -L0 )/L0 )×100 [%] L0 初始長度 L3 延伸＝L1 -L0 L4 回復長度＝L1 -L2 L5 殘留應變＝L2 -L0 類似的測定法規定在JIS L 1096織物及編物之布料試驗法中，但不是因一定荷重負荷所致之伸張後的回復率，而是使其伸張至一定長度時的回復率，在該點上有所不同。實際使用時往往與施加於伸縮性導體層之負荷、荷重沒有關係，而是重複伸張至預定的長度，故利用一定荷重負荷法之伸張回復率無法表現實用性能。除非另有說明，伸張回復率係於25℃±3℃之環境下進行評價。As shown in FIG. 1B, the stretch recovery rate in the present invention hangs the stretchable conductive sheet, applies a load to make it stretch, and removes the effect of the load to shrink, so that the initial length is L 0 , and the stretch is 20% or predetermined The length at% is L 1 , and the length without extension load is L 2. The definition is as follows: [Number 1] Stretch recovery rate = ((L 1 -L 2 ) / (L 1 -L 0 )) × 100 [ %] [Number 2] Residual strain rate = ((L 2 -L 0 ) / L 0 ) × 100 [%] L 0 initial length L 3 extension = L 1 -L 0 L 4 recovery length = L 1 -L 2 L 5 residual strain = L 2- L 0 Similar measurement method is specified in JIS L 1096 fabric and knitted fabric test method, but not the recovery rate after stretching due to a certain load, but to make it stretch to a certain extent The response rate at length varies at this point. In actual use, it is often not related to the load and load applied to the stretchable conductor layer, but it is repeatedly stretched to a predetermined length, so the stretch recovery rate using a certain load method cannot express practical performance. Unless otherwise stated, the tensile recovery rate is evaluated in an environment of 25 ° C ± 3 ° C.

本發明中之伸縮性導體片、伸縮性導體層、伸縮性配線，於25℃伸張20%後，在除去伸張荷重之狀態下進行60℃加熱時的伸張回復率宜為96%以上。 此處，除去伸張荷重之狀態，係指將懸垂時使其伸張所施加之荷重除去，並且亦除去作為伸張荷重而作用之自身重量的狀態。理想為無重力狀態、或在與伸縮導體片同水平之高比重流體中漂浮的狀態，但實際使用時將試樣水平方向平躺在水平放置的台上的話，可作為事實上已除去伸張荷重之狀態處理。In the stretchable conductor sheet, the stretchable conductor layer, and the stretchable wiring of the present invention, after stretching at 25 ° C for 20%, the stretch recovery rate when heating at 60 ° C without removing the stretch load is preferably 96% or more. Here, the state of removing the tensile load refers to a state in which the load applied to the stretch when it is draped is removed, and its own weight acting as the tensile load is also removed. Ideally, it is in a state of no gravity or floating in a fluid with a high specific gravity that is at the same level as the telescopic conductor sheet. However, when the sample is lying horizontally on a horizontally placed table in actual use, it can be used as the fact that the tensile load has been removed Status processing.

就加熱至60℃的手段而言，可使用利用熱板、熨斗、熨褲機(trouser press)等所為之直接加熱、利用乾燥機、熱風槍(hot blast)等所為之熱風噴吹、蒸氣燻蒸、強光照射、紅外加熱、來自加熱器之輻射加熱等。又，浸漬於熱水中也是有效的方法。 關於加熱後之伸張回復率，係使用加熱後之回復長度，除此之外，可利用與於25℃之伸張回復率相同的方法求出。加熱後之伸張回復率宜為97%以上，為98%以上更佳，為98.8%以上尤佳。For heating to 60 ° C, direct heating using a hot plate, iron, or trouser press, hot air blowing using a dryer, hot blast, or steam fumigation can be used. , Strong light irradiation, infrared heating, radiant heating from heaters, etc. It is also effective to immerse in hot water. The stretch recovery rate after heating is the same as the stretch recovery rate at 25 ° C except that the stretched recovery rate after heating is used. The stretch recovery rate after heating should be more than 97%, more preferably 98% or more, and more preferably 98.8% or more.

伸縮性導體片、伸縮性導體層、伸縮性配線之面方向之初始導電率宜為1×10-3 S/cm以上。導電率係電阻率的倒數。本發明之伸縮性導體片之初始導電率較佳為1×10-2 S/cm以上，尤佳為1×10-1 S/cm以上，更佳為1×100 S/cm以上。 令寬度W[cm]、長度L[cm]、厚度t[cm]之導電被膜之長度L方向的電阻值為R[Ω]時，可利用下式求出導電率S[1/(Ω･cm)]。 S＝(1/R)･(L/(t･W))The initial conductivity of the stretchable conductor sheet, the stretchable conductor layer, and the stretchable wiring in the plane direction should be 1 × 10 -3 S / cm or more. Electrical conductivity is the inverse of resistivity. The initial conductivity of the stretchable conductor sheet of the present invention is preferably 1 × 10 -2 S / cm or more, particularly preferably 1 × 10 -1 S / cm or more, and more preferably 1 × 10 0 S / cm or more. When the resistance value of the length L direction of the conductive film with a width W [cm], a length L [cm], and a thickness t [cm] is R [Ω], the conductivity S [1 / (Ω ･ cm)]. S = (1 / R) ･ (L / (t ･ W))

本發明中，因機械負荷試驗所致之伸縮性導體片之片材面方向之導電率降低比為初始導電率之1/1000以上之範圍時，60℃加熱所致之導電性回復率宜為10%以上。此處， 因機械負荷試驗所致之導電率降低比＝機械負荷試驗後之導電率/初始導電率， 機械負荷試驗後之導電性回復率＝於機械負荷試驗後進行60℃×10分鐘加熱後之導電率/初始導電率。 本發明中之展示伸張回復率之伸縮性導體片，在伸張回復時會恢復導電粒子間的電性接觸，並進一步藉由因加熱而產生之收縮力，使導電性粒子間的接觸更為緊密，故可展現相關特性。 機械負荷試驗後之60℃加熱所致之導電性回復率為15%以上更佳，為25%以上尤佳，為35%以上又更佳。In the present invention, when the reduction ratio of the electrical conductivity in the sheet surface direction of the stretchable conductor sheet caused by the mechanical load test is in the range of 1/1000 or more of the initial electrical conductivity, the conductivity recovery rate caused by heating at 60 ° C is preferably 10% or more. Here, the reduction ratio of the electrical conductivity due to the mechanical load test = the electrical conductivity after the mechanical load test / the initial electrical conductivity, and the electrical conductivity recovery after the mechanical load test = after heating at 60 ° C for 10 minutes after the mechanical load test Conductivity / initial conductivity. In the present invention, the stretchable conductor sheet exhibiting the stretch recovery rate will restore the electrical contact between the conductive particles during the stretch recovery, and further make the contact between the conductive particles closer by the contraction force generated by the heating. , So it can show the relevant characteristics. After the mechanical load test, the conductivity recovery rate caused by heating at 60 ° C is more than 15%, more preferably 25% or more, more preferably 35% or more.

進一步，本發明中，洗滌試驗後之伸縮性導體片之片材面方向之導電率降低比為初始導電率之1/1000以上之範圍時，60℃加熱所致之導電性回復率宜為10%以上。此處， 洗滌試驗後之導電率降低比＝洗滌試驗後之導電率/初始導電率， 洗滌試驗後之導電性回復率＝於洗滌試驗後進行60℃×10分鐘加熱後之導電率/初始導電率。 就洗滌試驗而言，係在水中、或含有洗滌劑之水中於伸縮方向、壓縮方向之兩面施加機械負荷，雖然對於導電片施以比起單純的機械負荷更為複雜的變形，但本發明之展示回復率之伸縮性導體片，在伸張回復時會恢復導電粒子間的電性接觸，並進一步藉由因加熱而產生之收縮力，使導電性粒子間的接觸更為緊密，故可展現相關特性。 洗滌試驗後之60℃加熱所致之導電性回復率為15%以上更佳，為25%以上尤佳，為35%以上又更佳。Further, in the present invention, when the reduction ratio of the conductivity in the sheet surface direction of the stretchable conductor sheet after the washing test is in the range of 1/1000 or more of the initial conductivity, the conductivity recovery rate by heating at 60 ° C is preferably 10 %the above. Here, the reduction ratio of the conductivity after the washing test = the conductivity after the washing test / the initial conductivity, and the conductivity recovery after the washing test = the conductivity / the initial conductivity after heating at 60 ° C for 10 minutes after the washing test rate. For the washing test, a mechanical load is applied to both sides of the expansion and contraction directions in the water or detergent-containing water. Although the conductive sheet is subjected to more complicated deformation than a simple mechanical load, The stretchable conductor sheet exhibiting the recovery rate will restore the electrical contact between the conductive particles when stretched back, and further the contraction between the conductive particles will be made closer by the contraction force caused by heating, so it can show the correlation. characteristic. After the washing test, the conductivity recovery rate caused by heating at 60 ° C is more than 15%, more preferably 25% or more, more preferably 35% or more.

本發明之伸縮性導體片、伸縮性導體層、伸縮性配線，係至少由以金屬粒子作為主體之導電填料與黏結劑樹脂構成。 本發明之導電性粒子係由電阻率為1×10-2 Ωcm以下之物質構成之粒徑為0.5μm以上5μm以下之粒子。就電阻率為1×10-2 Ωcm以下之物質而言，可例示金屬、合金、經摻雜之半導體等。就本發明中較佳使用之導電性粒子而言，可使用銀、金、鉑、鈀、銅、鎳、鋁、鋅、鉛、錫等金屬、黃銅、青銅、白銅、焊料等合金粒子、如被覆銀的銅之混合粒子，進一步可使用經金屬鍍敷之高分子粒子、經金屬鍍敷之玻璃粒子、經金屬被覆之陶瓷粒子等。The stretchable conductor sheet, the stretchable conductor layer, and the stretchable wiring of the present invention are composed of at least a conductive filler and a binder resin mainly composed of metal particles. The conductive particles of the present invention are particles composed of a material having a resistivity of 1 × 10 -2 Ωcm or less and having a particle diameter of 0.5 μm or more and 5 μm or less. Examples of the material having a resistivity of 1 × 10 -2 Ωcm or less include metals, alloys, and doped semiconductors. As the conductive particles preferably used in the present invention, metal particles such as silver, gold, platinum, palladium, copper, nickel, aluminum, zinc, lead, tin, alloy particles such as brass, bronze, white copper, solder, For example, silver-coated copper particles may be polymer particles coated with metal, glass particles coated with metal, ceramic particles coated with metal, and the like.

本發明宜使用薄片狀銀粒子或無定形團聚銀粉為主體。此外，此處所稱使用為主體，係以導電性粒子之90質量%以上的量使用。無定形團聚粉係指球狀或無定形狀之初級粒子團聚成3維者。無定形團聚粉及薄片狀粉，比起球狀粉等，前者比表面積更大，故即使是低填充量亦可形成導電性網絡，故較佳。無定形團聚粉並非單分散的形態，故粒子彼此係物理性地接觸，因此易形成導電性網絡，故更佳。The present invention preferably uses flaky silver particles or amorphous agglomerated silver powder as the main body. In addition, as used herein, the term “mainly used” is used in an amount of 90% by mass or more of the conductive particles. Amorphous agglomerated powder refers to the spherical or amorphous primary particles agglomerated into three dimensions. Amorphous agglomerated powder and flake-shaped powder have a larger specific surface area than spherical powder and the like. Therefore, even a low filling amount can form a conductive network, which is preferable. Amorphous agglomerated powder is not a monodispersed form, so particles are in physical contact with each other, so it is easy to form a conductive network, so it is more preferable.

就導電性粒子之粒徑而言，利用動態光散射法測得之平均粒徑(50%D)為0.5～5μm，更佳為0.7～3μm。平均粒徑超過預定之範圍的話，微細配線的形成會變得困難，且網版印刷等時會發生堵塞。平均粒徑未達0.5μm時，會有低填充時粒子間無法接觸、導電性惡化的情況。As for the particle diameter of the conductive particles, the average particle diameter (50% D) measured by a dynamic light scattering method is 0.5 to 5 μm, and more preferably 0.7 to 3 μm. When the average particle diameter exceeds a predetermined range, formation of fine wiring becomes difficult, and clogging may occur during screen printing or the like. When the average particle diameter is less than 0.5 μm, there is a case where the particles cannot be contacted during low filling and the conductivity is deteriorated.

本發明中，可使用DBP吸油量為100～550之範圍的碳黑作為導電性填料。碳黑有原料、製造方法不同之多個種類，各自具有其特徵。DBP吸油量係表示碳黑之液體吸收與保持性能的參數，根據ISO4656：2012進行測定。本發明中較佳DBP吸油量為160以上530以下，尤佳為210以上510以下，更佳為260以上500以下。DBP吸油量未達該範圍的話，印刷細線時線間容易被填埋，細線印刷性降低。又，DBP吸油量超過該範圍的話，糊劑的黏度容易上升，導致調整黏度時需要增加溶劑的摻合量，故印刷微細線時線間容易發生溶劑滲出，同樣地細線印刷性會降低。 碳黑的摻合量相對於金屬系填料與碳黑之總量，為0.5質量%以上2.0質量%以下，較佳為0.7質量%以上1.6質量%以下。In the present invention, carbon black having a DBP oil absorption in the range of 100 to 550 can be used as the conductive filler. There are several types of carbon black with different raw materials and manufacturing methods, each with its own characteristics. DBP oil absorption is a parameter representing the liquid absorption and retention performance of carbon black, and it is measured in accordance with ISO4656: 2012. In the present invention, the preferred DBP oil absorption is 160 or more and 530 or less, particularly preferably 210 or more and 510 or less, and more preferably 260 or more and 500 or less. If the amount of DBP oil absorption does not fall within this range, it is easy to be buried between the lines when printing the fine lines, and the printability of the fine lines is reduced. In addition, if the amount of DBP oil absorption exceeds this range, the viscosity of the paste tends to increase, and it is necessary to increase the amount of the solvent when adjusting the viscosity. Therefore, when the fine lines are printed, solvent bleeding between the lines is likely to occur, and the printability of the fine lines is similarly reduced. The blending amount of the carbon black is 0.5 mass% or more and 2.0 mass% or less, and preferably 0.7 mass% or more and 1.6 mass% or less with respect to the total amount of the metal-based filler and the carbon black.

本發明中，亦可含有平均粒徑為0.3μm以上10μm以下之非導電性粒子。本發明中之非導電性粒子，主要是金屬氧化物的粒子，可使用氧化矽、氧化鈦、氧化鎂、氧化鈣、氧化鋁、氧化鐵、金屬之硫酸鹽、金屬之碳酸鹽、金屬之鈦酸鹽等。本發明在該等非導電性粒子之中，宜使用硫酸鋇粒子。The present invention may contain non-conductive particles having an average particle diameter of 0.3 μm to 10 μm. The non-conductive particles in the present invention are mainly metal oxide particles, and silicon oxide, titanium oxide, magnesium oxide, calcium oxide, aluminum oxide, iron oxide, metal sulfate, metal carbonate, and metal titanium can be used. Acid salt etc. Among the non-conductive particles of the present invention, barium sulfate particles are preferably used.

本發明之伸縮性導體片、伸縮性導體層、伸縮性配線中所使用之黏結劑樹脂，20%伸張後之伸張回復率宜為99%以上，為99.5%以上更佳，為99.85%以上尤佳。黏結劑樹脂之伸張回復率，係將黏結劑樹脂成型在厚度20至200μm、且膜厚不均10%以下之片上，並於25±3℃之環境下進行測定。黏結劑樹脂之伸張回復率未達該範圍的話，難以使伸縮性導體片之伸張回復率成為預定之範圍以上。In the stretchable conductor sheet, the stretchable conductor layer, and the adhesive resin used in the stretchable wiring of the present invention, the stretch recovery rate after 20% stretch is preferably 99% or more, more preferably 99.5% or more, and more preferably 99.85% or more. good. The tensile recovery rate of the binder resin is formed by molding the binder resin on a sheet having a thickness of 20 to 200 μm and a film thickness unevenness of 10% or less, and the measurement is performed in an environment of 25 ± 3 ° C. If the stretch recovery rate of the binder resin does not fall within this range, it is difficult to make the stretch recovery rate of the stretchable conductive sheet to be above a predetermined range.

本發明中之黏結劑樹脂可使用非交聯型彈性體。就非交聯型彈性體而言，可使用彈性模量理想為1～1000MPa，玻璃轉移溫度理想為-40℃至0℃之範圍內的熱塑性彈性體樹脂，可列舉熱塑性之合成樹脂、合成橡膠、天然橡膠等。為了展現塗膜(片)的伸縮性，宜為橡膠、聚酯樹脂。橡膠可列舉：胺甲酸酯橡膠、丙烯酸橡膠、聚矽氧橡膠、丁二烯橡膠、腈橡膠或氫化腈橡膠等含有腈基之橡膠、異戊二烯橡膠、硫化橡膠、苯乙烯丁二烯橡膠、丁基橡膠、氯磺化聚乙烯橡膠、乙烯丙烯橡膠、偏二氟乙烯共聚物等。其中，含有腈基之橡膠、氯丁橡膠、氯磺化聚乙烯橡膠、苯乙烯丁二烯橡膠為較佳，含有腈基之橡膠為特佳。 柔軟性樹脂之彈性模量較佳為3～600MPa，更佳10～500MPa，尤佳為15～300MPa，又更佳為20～150MPa，特佳為25～100MPa。As the binder resin in the present invention, a non-crosslinked elastomer can be used. For non-crosslinked elastomers, thermoplastic elastomer resins with an ideal elastic modulus of 1 to 1000 MPa and a glass transition temperature of -40 ° C to 0 ° C can be used. Examples include thermoplastic synthetic resins and synthetic rubbers. , Natural rubber, etc. In order to exhibit the stretchability of the coating film (sheet), rubber or polyester resin is preferred. Examples of the rubber include nitrile-based rubbers such as urethane rubber, acrylic rubber, silicone rubber, butadiene rubber, nitrile rubber, or hydrogenated nitrile rubber, isoprene rubber, vulcanized rubber, and styrene butadiene rubber. , Butyl rubber, chlorosulfonated polyethylene rubber, ethylene propylene rubber, vinylidene fluoride copolymer, etc. Among them, a rubber containing a nitrile group, a neoprene rubber, a chlorosulfonated polyethylene rubber, and a styrene butadiene rubber are preferred, and a rubber containing a nitrile group is particularly preferred. The elastic modulus of the flexible resin is preferably 3 to 600 MPa, more preferably 10 to 500 MPa, even more preferably 15 to 300 MPa, still more preferably 20 to 150 MPa, and particularly preferably 25 to 100 MPa.

含腈基之橡膠只要是含有腈基的橡膠、彈性體即可，並無特別限定，宜為腈橡膠與氫化腈橡膠。腈橡膠為丁二烯與丙烯腈之共聚物，鍵結丙烯腈量多的話，與金屬的親和性提升，但有助於伸縮性之橡膠彈性反而減小。故，在含腈橡膠(例如丙烯腈丁二烯共聚物橡膠)100質量%中，鍵結丙烯腈量宜為18～50質量%，為30～50質量%更佳，為40～50質量%特佳。The nitrile group-containing rubber is not particularly limited as long as it is a nitrile group-containing rubber or elastomer, and is preferably a nitrile rubber or a hydrogenated nitrile rubber. Nitrile rubber is a copolymer of butadiene and acrylonitrile. If there is a large amount of acrylonitrile bonded, the affinity with the metal will increase, but the rubber elasticity that contributes to the stretchability will decrease. Therefore, in 100% by mass of a nitrile-containing rubber (such as acrylonitrile butadiene copolymer rubber), the amount of bonded acrylonitrile is preferably 18 to 50% by mass, more preferably 30 to 50% by mass, and 40 to 50% by mass. Extraordinary.

聚酯樹脂與胺甲酸酯橡膠中，玻璃轉移溫度宜為-40℃至0℃。又，宜具有由硬鏈段與軟鏈段構成之嵌段共聚物結構。本發明之非交聯型彈性體之彈性模量宜為1～1000MPa之範圍，更佳為3～600MPa，尤佳為10～500MPa，又更佳為30～300MPa之範圍。又，本發明之非交聯型彈性體的玻璃轉移溫度宜為零℃以下，為-5℃以下更佳，為-10℃以下尤佳。In polyester resins and urethane rubbers, the glass transition temperature is preferably -40 ° C to 0 ° C. Moreover, it is preferable to have a block copolymer structure which consists of a hard segment and a soft segment. The elastic modulus of the non-crosslinked elastomer of the present invention is preferably in the range of 1 to 1000 MPa, more preferably 3 to 600 MPa, even more preferably 10 to 500 MPa, and still more preferably 30 to 300 MPa. The glass transition temperature of the non-crosslinked elastomer of the present invention is preferably 0 ° C or lower, more preferably -5 ° C or lower, and even more preferably -10 ° C or lower.

該黏結劑樹脂之玻璃轉移溫度宜為0℃以下，為-8℃以下尤佳，為-16℃以下更佳，為-24℃以下又更佳。玻璃轉移溫度高於該範圍的話，會難以展現伸張回復特性。 本發明之伸縮性導體片，宜至少由65～85質量%的黏結劑樹脂與15～35質量%的導電填料構成，該導電填料的90質量%以上由金屬粒子構成。 玻璃轉移溫度可依照常法藉由差示掃描熱量分析(DSC)求得。The glass transition temperature of the binder resin is preferably below 0 ° C, particularly preferably below -8 ° C, more preferably below -16 ° C, and even more preferably below -24 ° C. When the glass transition temperature is higher than this range, it becomes difficult to exhibit the stretch recovery characteristics. The stretchable conductor sheet of the present invention is preferably composed of at least 65 to 85% by mass of a binder resin and 15 to 35% by mass of a conductive filler, and more than 90% by mass of the conductive filler is composed of metal particles. The glass transition temperature can be obtained by differential scanning calorimetry (DSC) according to a conventional method.

本發明中，令前述黏結劑樹脂之數量平均分子量為Mn，重量平均分子量為Mw時，需為Mw/Mn＞4，為Mw/Mn＞4.4尤佳，為Mw/Mn＞4.8更佳，為Mw/Mn＞5.2又更佳。Mw/Mn係表示分子量分布的係數，Mw/Mn越大分子量分布越廣。具有較廣分子量分布之黏結劑樹脂成分中，相對較高分子量之成分主導著伸張回復性。另一方面，相對較低分子量成分具有以下作用：滲出至伸張時產生之微小裂紋部分，於伸張回復時將微小裂紋間自我修復地予以再次連接。 數量平均分子量、重量平均分子量，可依照常法藉由GPC(凝膠滲透層析)分析法求得。In the present invention, when the number average molecular weight of the aforementioned binder resin is Mn and the weight average molecular weight is Mw, Mw / Mn> 4 is required, Mw / Mn> 4.4 is particularly preferred, and Mw / Mn> 4.8 is more preferred, as Mw / Mn> 5.2 is even better. Mw / Mn is a coefficient representing the molecular weight distribution. The larger the Mw / Mn, the wider the molecular weight distribution. Among the binder resin components having a broad molecular weight distribution, relatively high molecular weight components dominate stretch recovery. On the other hand, relatively low-molecular-weight components have the effect of exuding to the microcracks generated during stretching, and reconnecting the microcracks to self-healing when the stretch recovers. The number-average molecular weight and weight-average molecular weight can be determined by GPC (gel permeation chromatography) analysis according to a conventional method.

黏結劑樹脂不必為單一的樹脂，可將伸張回復率高之高分子量樹脂和與之不同的自我修復功能高之低分子樹脂混合使用。本發明中，宜使用分子量分布具有二個以上之峰部之黏結劑樹脂，該黏結劑樹脂係藉由將重量平均分子量在800～4000處具有峰部之樹脂、及重量平均分子量在4000～100000之範圍處具有峰部之樹脂予以摻合而獲得。The binder resin need not be a single resin, and a high-molecular-weight resin having a high stretch recovery rate and a low-molecular-weight resin having a high self-repairing function can be mixed for use. In the present invention, it is preferable to use a binder resin having a molecular weight distribution having two or more peaks. The binder resin is a resin having a peak portion having a weight average molecular weight of 800 to 4000 and a weight average molecular weight of 4,000 to 100,000. A resin having a peak in the range is obtained by blending.

本發明係使用非交聯型彈性體作為主要的黏結劑樹脂，但為了獲得高分子量的黏結劑樹脂，可加入分支成分。分支成分多時，有時會有成為幾乎與交聯結構同等的分子結構之情況。如此，本發明可適當摻合半數已交聯之高分子量之彈性體與低分子量之非交聯型彈性體來使用。The present invention uses a non-crosslinked elastomer as the main binder resin, but in order to obtain a high-molecular-weight binder resin, a branching component may be added. When there are many branching components, the molecular structure may be almost the same as the crosslinked structure. In this way, the present invention can be suitably used by blending half of the crosslinked high molecular weight elastomer and low molecular weight non-crosslinked elastomer.

本發明中之伸縮性導體片，係由伸縮性導體組成物構成之片狀或薄膜狀之狀態的單體膜。 本發明之伸縮性導體片，可將導電性填料、黏結劑樹脂直接熔融混合，並利用擠壓成型等方法片材化。該方法可理想地適用於黏結劑樹脂在相對低溫下為相對較低熔融黏度的情形。 本發明中理想的製造方法，可例示下列方法：藉由至少於導電性填料、黏結劑樹脂中加入溶劑成分，進行混合攪拌、混練，得到伸縮性導體形成用之糊劑，使用獲得之糊劑並利用塗覆法進行片材化。 又，可藉由下列方法等獲得片或電氣配線圖案：同樣地獲得伸縮性導體形成用之糊劑，使用獲得之糊劑，並利用印刷法進行直接圖案化。 此處，就印刷法而言，可使用網版印刷法、平版膠印印刷法、糊劑噴出(paste-jet)法、柔版印刷法、凹版印刷法、凹版膠印印刷法、壓印(stamping)法、模版(stencil)法等。進一步，使用點膠機(dispenser)等直接描繪配線的方法也可解釋為廣義的印刷而使用。The stretchable conductor sheet in the present invention is a sheet-like or film-like monomer film composed of a stretchable conductor composition. The stretchable conductor sheet of the present invention can be directly melt-mixed with a conductive filler and a binder resin, and can be formed into a sheet by a method such as extrusion molding. This method can be ideally applied to the case where the binder resin has a relatively low melt viscosity at a relatively low temperature. The ideal manufacturing method in the present invention can be exemplified by the following method: adding a solvent component to at least the conductive filler and the binder resin, mixing and kneading to obtain a paste for forming a stretchable conductor, and using the obtained paste Sheeting is performed by a coating method. In addition, a sheet or an electrical wiring pattern can be obtained by a method such as obtaining a paste for forming a stretchable conductor in the same manner, and using the obtained paste, and directly patterning it by a printing method. Here, as for the printing method, a screen printing method, a lithographic offset printing method, a paste-jet method, a flexographic printing method, a gravure printing method, a gravure offset printing method, and stamping can be used. Method, stencil method, etc. Furthermore, a method of directly drawing wiring using a dispenser or the like can be interpreted as printing in a broad sense and used.

使用於本發明之伸縮性導體形成用之糊劑的溶劑，宜為沸點為200℃以上，於20℃之飽和蒸氣壓為20Pa以下的有機溶劑。有機溶劑的沸點過低的話，在糊劑製造步驟、糊劑使用時，會有溶劑揮發，構成導電性糊劑之成分比容易發生變化之疑慮。另一方面，有機溶劑的沸點過高的話，會有乾燥硬化塗膜中之殘留溶劑量變多，導致塗膜的可靠性降低之疑慮。又，由於乾燥硬化的時間長，乾燥過程中的邊緣鬆垂(sag of the edge)變大，難以保持窄的配線間距。The solvent used in the paste for forming a stretchable conductor of the present invention is preferably an organic solvent having a boiling point of 200 ° C or higher and a saturated vapor pressure of 20Pa or lower at 20 ° C. If the boiling point of the organic solvent is too low, there is a concern that the solvent will volatilize during the paste manufacturing process and use of the paste, and there is a possibility that the component ratio of the conductive paste is likely to change. On the other hand, if the boiling point of the organic solvent is too high, the amount of residual solvent in the dry-hardened coating film may increase, which may cause a decrease in the reliability of the coating film. In addition, since the drying and curing time is long, the sag of the edge during drying becomes large, and it is difficult to maintain a narrow wiring pitch.

本發明中之有機溶劑，可使用：苯甲醇(蒸氣壓：3Pa、沸點：205℃)、松油醇(蒸氣壓：3.1Pa、沸點：219℃)、二乙二醇(蒸氣壓：0.11Pa、沸點：245℃)、二乙二醇單***乙酸酯(蒸氣壓：5.6Pa、沸點217℃)、二乙二醇單丁醚乙酸酯(蒸氣壓：5.3Pa、沸點：247℃)、二乙二醇二丁醚(蒸氣壓：0.01mmHg以下、沸點：255℃)、三乙二醇(蒸氣壓：0.11Pa、沸點：276℃)、三乙二醇單甲醚(蒸氣壓：0.1Pa以下、沸點：249℃)、三乙二醇單***(蒸氣壓：0.3Pa、沸點：256℃)、三乙二醇單丁醚(蒸氣壓：1Pa、沸點：271℃)、四乙二醇(蒸氣壓：1Pa、沸點：327℃)、四乙二醇單丁醚(蒸氣壓：0.01Pa以下、沸點：304℃)、三丙二醇(蒸氣壓：0.01Pa以下、沸點：267℃)、三丙二醇單甲醚(蒸氣壓：3Pa、沸點：243℃)、二乙二醇單丁醚(蒸氣壓：3Pa、沸點：230℃)。 本發明中之溶劑，亦可視需要含有該等中之2種以上。可適當含有如此之有機溶劑，以使伸縮性導體組成物形成用之糊劑成為適合於印刷等之黏度。The organic solvent in the present invention can be used: benzyl alcohol (vapor pressure: 3Pa, boiling point: 205 ° C), terpineol (vapor pressure: 3.1Pa, boiling point: 219 ° C), diethylene glycol (vapor pressure: 0.11Pa , Boiling point: 245 ° C), diethylene glycol monoethyl ether acetate (vapor pressure: 5.6Pa, boiling point 217 ° C), diethylene glycol monobutyl ether acetate (vapor pressure: 5.3Pa, boiling point: 247 ° C) , Diethylene glycol dibutyl ether (vapor pressure: 0.01mmHg or less, boiling point: 255 ° C), triethylene glycol (vapor pressure: 0.11Pa, boiling point: 276 ° C), triethylene glycol monomethyl ether (vapor pressure: 0.1Pa or less, boiling point: 249 ° C), triethylene glycol monoethyl ether (vapor pressure: 0.3Pa, boiling point: 256 ° C), triethylene glycol monobutyl ether (vapor pressure: 1Pa, boiling point: 271 ° C), tetraethyl Diol (vapor pressure: 1Pa, boiling point: 327 ° C), tetraethylene glycol monobutyl ether (vapor pressure: 0.01Pa or less, boiling point: 304 ° C), tripropylene glycol (vapor pressure: 0.01Pa or less, boiling point: 267 ° C) Tripropylene glycol monomethyl ether (vapor pressure: 3Pa, boiling point: 243 ° C), diethylene glycol monobutyl ether (vapor pressure: 3Pa, boiling point: 230 ° C). The solvent in the present invention may contain two or more of these as necessary. Such an organic solvent may be appropriately contained so that the paste for forming a stretchable conductor composition has a viscosity suitable for printing and the like.

本發明之伸縮性導體形成用糊劑，可藉由利用溶解器(dissolver)、三輥研磨機、自公轉型混合機、碾磨機、球磨機、砂磨機等分散機進行混合分散而獲得。The paste for forming a stretchable conductor according to the present invention can be obtained by mixing and dispersing using a disperser, a three-roll mill, a self-converting mixer, a mill, a ball mill, and a sand mill.

本發明之伸縮性導體形成用糊劑，在不損及發明內容的範圍內，可摻合印刷適性的賦予劑、色調的調整劑、調平劑、抗氧化劑、紫外線吸收劑等公知的有機、無機添加劑。The paste for forming a stretchable conductor according to the present invention may be blended with a known organic, such as a printability imparting agent, a color tone adjusting agent, a leveling agent, an antioxidant, and an ultraviolet absorber, within a range that does not impair the contents of the invention. Inorganic additives.

藉由將以此種方式獲得之伸縮性導體形成用糊劑進行乾燥硬化，可獲得實質上不含溶劑的展示預定之伸張回復率的伸縮性導體片或由伸縮性導體構成之電氣配線圖案。 獲得伸縮性導體片的情況下，可利用模塗機、狹縫塗佈機、缺角輪塗布機、凹版塗佈機等將伸縮性導體形成用糊劑塗布於已塗有脫模劑之薄膜基板等，並進行乾燥、片材化。By drying and curing the paste for forming a stretchable conductor obtained in this manner, a stretchable conductor sheet exhibiting a predetermined stretch recovery rate or an electric wiring pattern composed of a stretchable conductor that is substantially free of a solvent can be obtained. When a stretchable conductor sheet is obtained, a paste for forming a stretchable conductor can be applied to a film coated with a release agent by a die coater, a slit coater, a notch wheel coater, a gravure coater, or the like. The substrate and the like are dried and sheeted.

本發明中，可使用上述說明之伸縮性導體片，在50%伸張時之回復率為99%以上，且具有60℃以上之耐熱性之絕緣性布帛上形成電氣配線。本發明中，布帛之耐熱性係以布料纖維之熱收縮溫度來進行評價。 就電氣配線而言，可藉由將伸縮性導體片裁切成預定的形狀，並利用黏接材等貼附於布帛而製作。又，亦可於布帛直接或預先利用絕緣性樹脂形成基底層後，利用印刷法來獲得預定形狀之電氣配線圖案。 進一步，也可在具有脫模性之另一基材上藉由印刷等形成預定的圖案，並轉印於布帛。本發明視需要會在配線上形成絕緣表覆層。 就印刷法而言，可使用網版印刷法、平版膠印印刷法、糊劑噴出法、柔版印刷法、凹版印刷法、凹版膠印印刷法、壓印法、模版法等。本發明中，宜使用網版印刷法、模版法。又，使用點膠機等直接描繪配線的方法也可解釋為廣義的印刷而使用。 本發明中，藉由該等方法可製造具有由伸縮性導體組成物構成之電氣配線的衣服。In the present invention, the above-described stretchable conductor sheet can be used to form electrical wiring on an insulating fabric having a recovery rate of 99% or more when 50% stretched and having a heat resistance of 60 ° C or higher. In the present invention, the heat resistance of the cloth is evaluated by the heat shrinkage temperature of the cloth fibers. Electrical wiring can be produced by cutting a stretchable conductive sheet into a predetermined shape and attaching it to a fabric using an adhesive material or the like. In addition, an electrical wiring pattern having a predetermined shape may be obtained by using a printing method after the base layer is formed directly or in advance with an insulating resin from the fabric. Furthermore, a predetermined pattern may be formed on another substrate having releasability by printing or the like, and then transferred to a fabric. According to the present invention, an insulating surface coating layer is formed on the wiring as needed. As for the printing method, a screen printing method, a lithographic offset printing method, a paste discharge method, a flexographic printing method, a gravure printing method, a gravure offset printing method, an imprint method, a stencil method, and the like can be used. In the present invention, a screen printing method and a stencil method are preferably used. In addition, a method of directly drawing wiring using a dispenser or the like can be interpreted as printing in a broad sense and used. In the present invention, by these methods, it is possible to produce clothes having electrical wiring composed of a stretchable conductor composition.

本發明中之具有伸縮性導體片、或由伸縮性導體構成之電氣配線的布帛、具有電氣配線的衣服，在除去伸縮性導體部分之伸張荷重之狀態下，藉由利用例如熨斗、熨褲機、吹風機等加熱至60℃以上，可使導電性能從因實際使用時，尤其因重複伸張等負荷導致導電性劣化之狀態，恢復至實用上可使用之狀態。該處理稱為導電性恢復處理。導電性恢復處理中所使用之加熱溫度宜為75℃以上，為90℃以上尤佳，為110℃以上更佳。此外，導電性恢復處理之溫度的上限取決於共用之基材等的耐熱性。由一般的化學纖維等構成之織編物中，150℃左右為上限。當然基材使用棉等相對較高耐熱的纖維，此外，使用聚芳醯胺纖維、聚苯并唑類(polybenzazole)纖維、聚醯亞胺纖維等具有耐熱性之纖維布料、聚矽氧樹脂等耐熱性之柔軟性樹脂時不在此限，只要在180℃～300℃之範圍內使用，並注意不給黏結劑樹脂造成過度的熱損傷即可。 [實施例]In the present invention, the stretchable conductor sheet, the cloth for the electric wiring made of the stretchable conductor, and the clothes with the electric wiring are removed from the stretchable conductor part of the stretched load by using, for example, an iron or a trouser press. , Hair dryer and other heating to 60 ℃ or more, can make the conductivity from actual use, especially due to repeated stretching and other loads caused by the deterioration of conductivity, to return to a practically usable state. This process is called a conductivity recovery process. The heating temperature used in the conductivity recovery treatment is preferably 75 ° C or higher, more preferably 90 ° C or higher, and more preferably 110 ° C or higher. In addition, the upper limit of the temperature of the conductivity recovery treatment depends on the heat resistance of a common substrate or the like. In a woven or knitted fabric made of general chemical fibers or the like, the upper limit is about 150 ° C. Of course, the substrate uses relatively high heat-resistant fibers such as cotton. In addition, it uses heat-resistant fiber cloth such as polyaramide fibers, polybenzazole fibers, polyimide fibers, and silicone resins. The heat-resistant flexible resin is not limited to this, as long as it is used in the range of 180 ° C to 300 ° C, and care should be taken not to cause excessive thermal damage to the adhesive resin. [Example]

以下，例示實施例對本發明進行更加詳細且具體地說明。此外，實施例中之評價結果等係利用下列方法進行測定。Hereinafter, the present invention will be described in more detail and specifically by illustrating examples. The evaluation results and the like in the examples were measured by the following methods.

＜拉伸降伏伸度＞ 將伸縮性絕緣高分子層中使用之樹脂材料成形成厚度20μm至200μm之範圍之任意厚度的片狀，然後沖壓成ISO 527-2-1A規定的啞鈴型，製成試驗片。然後，使用拉伸試驗器求出S-S曲線，如圖1A所示般求出降伏點，並將此時的伸度定為拉伸降伏伸度。<Stretching and Elongation Elongation> The resin material used in the stretchable insulating polymer layer is formed into a sheet having an arbitrary thickness ranging from 20 μm to 200 μm, and then punched into a dumbbell shape specified by ISO 527-2-1A to make Test strip. Then, an S-S curve was obtained by using a tensile tester, and as shown in FIG. 1A, the yield point was obtained, and the elongation at this time was determined as the stretch yielding elongation.

＜熱變形溫度＞ 將伸縮性絕緣高分子片置於加熱板，加熱至預定溫度。然後，將具有已加熱至相同預定溫度之鐵製熱板的電熨斗置於伸縮性絕緣高分子片上1分鐘，之後拿走電熨斗，拿走時伸縮性絕緣高分子片與熨斗的熱板一起被拿起時，判定為有黏著、黏接。又，可目視判定有熨斗所在的痕跡時，判定為發生了熱變形。將預定溫度從60℃以每5℃升高並實施測定，將觀察到熱變形或黏著、黏接性中之任意者時的最低溫度作為熱變形溫度。溫度達到180℃時中止試驗。又，布料發生變形或異常時，於該溫度中止試驗，判定熱變形溫度為該溫度以上。<Heat Deformation Temperature> A stretchable insulating polymer sheet is placed on a heating plate and heated to a predetermined temperature. Then, the electric iron having the iron hot plate heated to the same predetermined temperature is placed on the stretchable insulating polymer sheet for 1 minute, and then the electric iron is removed, and the stretchable insulating polymer sheet is taken together with the hot plate of the iron when it is removed. When picked up, it was judged as sticking or sticking. When it is visually determined that there are traces of the iron, it is determined that thermal deformation has occurred. The predetermined temperature was increased from 60 ° C. to 5 ° C. and measurement was performed. The minimum temperature at which any one of thermal deformation, adhesion, and adhesiveness was observed was taken as the thermal deformation temperature. The test was terminated when the temperature reached 180 ° C. When the cloth is deformed or abnormal, the test is terminated at this temperature, and the thermal deformation temperature is determined to be equal to or higher than this temperature.

＜腈量＞ 將獲得之樹脂材料進行NMR分析而得到之組成比，並由此換算成基於單體之質量比之質量%。<Nitrile content> The composition ratio obtained by NMR analysis of the obtained resin material is converted into a mass% based on the mass ratio of the monomer.

＜慕尼黏度＞ 使用島津製作所製SMV-300RT「Mooney Viscometer」進行測定。<Muni viscosity> It was measured using SMV-300RT "Mooney Viscometer" manufactured by Shimadzu Corporation.

＜彈性模量＞ 將黏結劑樹脂成形成厚度20μm至200μm之範圍之任意厚度的片狀，然後沖壓成ISO 527-2-1A規定的啞鈴型，製成試驗片。 以ISO 527-1規定的方法進行拉伸試驗，求出樹脂材料之應力-應變線圖，依照常法算出彈性模量。<Elastic Modulus> The adhesive resin is formed into a sheet having an arbitrary thickness ranging from 20 μm to 200 μm, and then punched into a dumbbell shape specified in ISO 527-2-1A to prepare a test piece. The tensile test was performed by the method specified in ISO 527-1, the stress-strain diagram of the resin material was obtained, and the elastic modulus was calculated in accordance with the conventional method.

＜玻璃轉移溫度＞ 玻璃轉移溫度係依照常法藉由差示掃描熱量分析(DSC)求得。<Glass transition temperature> The glass transition temperature was determined by differential scanning calorimetry (DSC) according to a conventional method.

＜分子量＞ 將黏結劑樹脂材料之試樣添加至THF(四氫呋喃)中，使溶液中之樹脂的濃度成為0.4質量%，於室溫攪拌1小時後，放置24小時。然後，將獲得之樹脂溶液用THF稀釋4倍後，使其通過0.45μm之濾器，針對該濾液，使用GPC求出數量平均分子量、重量平均分子量、分散比(Mw/Mn)。<Molecular weight> A sample of a binder resin material was added to THF (tetrahydrofuran) so that the concentration of the resin in the solution became 0.4% by mass, and after stirring at room temperature for 1 hour, it was left for 24 hours. Then, the obtained resin solution was diluted 4-fold with THF, and then passed through a 0.45 μm filter. The number average molecular weight, weight average molecular weight, and dispersion ratio (Mw / Mn) of the filtrate were determined using GPC.

若獲得之試樣為經調配後之導電糊劑、或糊劑之硬化物時，則將糊劑材料添加至THF(四氫呋喃)中，使溶液中之試樣的濃度成為2.0質量%，邊攪拌溶液邊使溫度上升至THF的沸點，保持30分鐘後冷卻至室溫，放置24小時。然後，將獲得之樹脂溶液用THF稀釋4倍後，使其通過0.45μm之濾器以除去無機成分，對該濾液進行GPC測定，將添加劑等低分子量成分視為分子量未達500之成分並刪除，並針對於分子量500以上之部分，求出數量平均分子量、重量平均分子量、分散比(Mw/Mn)。If the obtained sample is a prepared conductive paste or a cured product of the paste, the paste material is added to THF (tetrahydrofuran) so that the concentration of the sample in the solution becomes 2.0% by mass, while stirring While the temperature of the solution was raised to the boiling point of THF, the solution was cooled to room temperature for 30 minutes, and left for 24 hours. Then, the obtained resin solution was diluted 4 times with THF, and then passed through a 0.45 μm filter to remove inorganic components. The filtrate was subjected to GPC measurement, and low molecular weight components such as additives were regarded as components having a molecular weight of less than 500 and deleted. The number-average molecular weight, weight-average molecular weight, and dispersion ratio (Mw / Mn) were determined for the portion having a molecular weight of 500 or more.

＜樹脂之伸張回復率＞ 將樹脂材料成形成厚度20μm至200μm之範圍之任意厚度的片狀，然後沖壓成ISO 527-2-1A規定的啞鈴型，製成試驗片。 之後，在距啞鈴型試驗片中之寬度10mm、長度80mm之部分的中央各為33mm的部位(有效長66mm)作標記，正確測量標記間的初始距離L0 。然後，用夾具夾持標有標記之部位的外側，並使為66mm之標記間距延伸至伸張長度79.2mm(＋13.2mm，相當於伸張度20%)後從夾具取下，於預定之溫度(除非另有說明，否則為25℃)放置在保持為水平方向之氟樹脂片上，測定標記間之伸張後距離L2 ，依下式求出伸張回復率。 初始長度　L0 ＝66.0mm 伸張長度　L1 ＝79.2mm 伸張後之長度　L2 ＝實測 延伸　L3 ＝L1 -L0 ＝13.2mm 回復長度　L4 ＝L1 -L2 伸張回復率＝((L1 -L2 )/(L1 -L0 ))×100[%]<Resin Stretch Recovery Rate> The resin material is formed into a sheet having an arbitrary thickness ranging from 20 μm to 200 μm, and then punched into a dumbbell shape specified by ISO 527-2-1A to prepare a test piece. After that, marks were made on the dumbbell-shaped test piece with a width of 10 mm and a length of 80 mm at the center of each 33 mm (effective length 66 mm), and the initial distance L 0 between the marks was measured correctly. Then, hold the outside of the marked part with a jig, and extend the mark pitch of 66mm to an extension length of 79.2mm (+ 13.2mm, equivalent to 20% extension), then remove it from the jig at a predetermined temperature ( (Unless otherwise noted, 25 ° C) is placed on a fluororesin sheet held in a horizontal direction, the post-stretch distance L 2 between the marks is measured, and the stretch recovery rate is calculated according to the following formula. Initial length L 0 = 66.0 mm Stretched length L 1 = 79.2 mm Length after stretched L 2 = Measured extension L 3 = L 1- L 0 = 13.2 mm Recovery length L 4 = L 1- L 2 Stretched recovery rate = (( L 1 -L 2 ) / (L 1 -L 0 )) × 100 [%]

＜布帛之伸張回復率＞ 將布帛材料沖壓成ISO 527-2-1A規定的啞鈴型，製成試驗片。此外，將布帛之伸長方向設定為啞鈴之長度方向。 然後，與樹脂之伸張回復率之測定同樣，在距啞鈴型試驗片中之寬度10mm、長度80mm之部分的中央各為33mm的部位(有效長66mm)作標記，並延伸至伸張長度99mm(＋33mm，相當於伸張度50%)，除此以外，與樹脂之伸張回復率同樣進行操作，求出伸張回復率。<Extension rate of stretch of fabric> The fabric material was punched into a dumbbell shape specified in ISO 527-2-1A to prepare a test piece. In addition, the stretching direction of the cloth is set to the length direction of the dumbbell. Then, in the same manner as the measurement of the stretch recovery rate of the resin, marks are placed on the dumbbell-shaped test pieces with a width of 10 mm and a length of 80 mm at the center of each 33 mm portion (effective length of 66 mm). (Equivalent to 50% stretch), except that the same operation as the stretch recovery rate of the resin is performed to obtain the stretch recovery rate.

＜布帛之耐熱性＞ 以利用JIS L1013：2010化學纖維纖絲紗試驗方法8.19.2求出之熱收縮溫度作為布帛之耐熱性。<The heat resistance of the fabric> The heat shrinkage temperature of the fabric was determined using the heat shrinkage temperature determined by the JIS L1013: 2010 chemical fiber filament yarn test method 8.19.2.

＜平均粒徑＞ 填料之平均粒徑，係使用堀場製作所製的光散射式粒徑分布測定裝置LB-500進行測定。<Average particle size> The average particle size of the filler was measured using a light scattering type particle size distribution measuring device LB-500 manufactured by Horiba.

＜導電率＞ 導體片之大小足夠時，沖壓成ISO 527-2-1A規定的啞鈴型，並將位於啞鈴型試驗片之中央部的寬度10mm、長度80mm之部分作為試驗片使用。可進行導體片的成型時，係將其加熱壓縮成形成厚度200±20μm之片狀，然後沖壓成ISO 527-2-1A規定的啞鈴型，同樣製成試驗片。若導體片的大小較小，無法獲得規定之啞鈴形狀時，切出能夠採取之寬度及長度的矩形，製成試驗片，並使用已實施導電率測定後之寬度、厚度、長度進行換算。 使用Agilent Technologies公司製Milliohmmeter測定試驗片之寬度10mm、長度80mm之部分的電阻值[Ω]，乘以試驗片之縱橫比(1/8)，求出片電阻值「Ω□」。 又，將電阻值[Ω]乘以截面積(寬度1[cm]×厚度[cm])，並除以長度(8cm)，求出電阻率[Ωcm]。進一步，求出電阻率之倒數，以作為導電率。<Conductivity> When the size of the conductor piece is sufficient, it is punched into a dumbbell shape specified in ISO 527-2-1A, and a portion of the dumbbell-shaped test piece with a width of 10 mm and a length of 80 mm is used as a test piece. When the conductor sheet can be formed, it is heated and compressed to form a sheet with a thickness of 200 ± 20 μm, and then punched into a dumbbell shape specified in ISO 527-2-1A, and a test piece is also made. If the size of the conductor piece is small and a predetermined dumbbell shape cannot be obtained, a rectangle with a width and a length that can be taken is cut out to make a test piece, and the width, thickness, and length after the conductivity measurement is performed are used for conversion. The resistance value [Ω] of a portion of the test piece having a width of 10 mm and a length of 80 mm was measured using a Milliohmmeter manufactured by Agilent Technologies, and was multiplied by the aspect ratio (1/8) of the test piece to obtain a sheet resistance value "Ω □". The resistance value [Ω] is multiplied by the cross-sectional area (width 1 [cm] × thickness [cm]), and divided by the length (8 cm) to obtain the resistivity [Ωcm]. Further, the reciprocal of the resistivity was determined as the conductivity.

＜導電片材料之伸張回復率＞ 使用與導電率之測定中所使用者同樣的試驗片。 然後，與樹脂之伸張回復率之測定同樣，在距啞鈴型試驗片中之寬度10mm、長度80mm之部分的中央各為33mm的部位(有效長66mm)作標記，並延伸至伸張長度99mm(＋33mm，相當於伸張度50%)，除此以外，與樹脂之伸張回復率同樣進行操作，求出導電片之伸張回復率。<Stretch Recovery Rate of Conductive Sheet Material> The same test piece as that used for the measurement of the conductivity was used. Then, in the same manner as the measurement of the stretch recovery rate of the resin, marks are placed on the dumbbell-shaped test pieces with a width of 10 mm and a length of 80 mm at the center of each 33 mm portion (effective length of 66 mm). (Equivalent to 50% elongation). Except for this, the same operation as the elongation recovery rate of the resin is performed to obtain the elongation recovery rate of the conductive sheet.

＜導電片材料之重複伸縮耐久性(機械性負荷試驗)＞ (1)試驗片製作 導體片之大小足夠時，沖壓成ISO 527-2-1A規定的啞鈴型，製成試驗片。可進行導體片的成型時，係將其成形成具有厚度20～200μm之任意厚度的片狀，然後沖壓成ISO 527-2-1A規定的啞鈴型，製成試驗片。若導體片的大小較小，無法獲得規定之啞鈴形狀時，切出能夠採取之寬度及長度的矩形，製成試驗片，並使用已實施導電率測定後之寬度、厚度、長度進行換算。 (2)重複伸縮試驗 使用經改造之裝置，並將鋁箔捲繞在伸縮有效長為66mm之兩端的外側0～5mm處後，以金屬製夾具夾住，邊利用試驗機監測電阻値邊進行重複伸張，該經改造之裝置係將Yamashita Materials製的IPC彎曲試驗機予以改造，將試驗機之往復行程設定為13.2mm，於可動板側利用夾具固定試驗片，並將另一端以夾具固定於另外的固定端，使用啞鈴型試驗片中寬度10mm、長度80mm的部分，以使有效長成為66mm的方式進行調整(相當於伸張度20%)，以使該裝置能進行樣品的重複伸張。電阻値的讀取，於重複伸張600次以下為每10次進行讀取，超過600次為每50次進行讀取，於伸張率為0%之狀態停止，讀取停止後1分鐘後的值並記錄，記錄電阻値達到初始之100倍之時點的次數，並於此結束試驗。<Repetitive expansion and contraction durability of a conductive sheet material (mechanical load test)> (1) Test piece production When the size of the conductive sheet is sufficient, it is punched into a dumbbell shape specified in ISO 527-2-1A to produce a test piece. When the conductor sheet can be formed, it is formed into a sheet shape having an arbitrary thickness of 20 to 200 μm, and then punched into a dumbbell shape specified in ISO 527-2-1A to make a test piece. If the size of the conductor piece is small and a predetermined dumbbell shape cannot be obtained, a rectangle with a width and a length that can be taken is cut out to make a test piece, and the width, thickness, and length after the conductivity measurement is performed are used for conversion. (2) Repeated expansion and contraction test Use a modified device, and wind aluminum foil around 0 to 5 mm outside both ends of the effective expansion and contraction length of 66mm, clamp it with a metal fixture, and repeat it while monitoring the resistance with a testing machine. Stretching, the modified device is an IPC bending tester made by Yamashita Materials, the reciprocating stroke of the tester is set to 13.2mm, the test piece is fixed on the side of the movable plate with a fixture, and the other end is fixed to the The fixed end of the dumbbell-shaped test piece was adjusted with a width of 10mm and a length of 80mm so that the effective length became 66mm (equivalent to 20% extension), so that the device could perform repeated stretching of the sample. The reading of resistance 値 is performed every 10 times when the stretching is repeated less than 600 times, and every 50 times if it is over 600 times, and the reading is stopped when the stretching rate is 0%, and the value is 1 minute after the reading is stopped. And record, record the number of times when the resistance 値 reached 100 times the initial, and end the test here.

＜伸縮性導體層、及伸縮性導體/布帛疊層體之加熱導電性回復率＞ 在導電片之重複伸縮耐久性(機械性負荷)中，當導電率降低比為1/1000以上時，將重複伸縮耐久性(機械性負荷)試驗後之試驗片除去伸張荷重，在不施加自身重量以外之負荷的狀態下，靜置於保持為水平的氟樹脂片上，利用乾燥烘箱於60℃加熱10分鐘之後，恢復至室溫，進行導電率測定，求出導電性回復率。針對伸縮性導體/布帛疊層體，亦同樣在不施加自身重量以外之負荷的狀態下，靜置於保持為水平的氟樹脂片上，利用乾燥烘箱於60℃加熱10分鐘之後，恢復至室溫，進行導電率測定，求出導電性回復率 【數3】 導電率降低比＝測定時導電率/初始導電率 導電性回復率＝60℃×10分鐘加熱後之導電率/初始導電率<Heating conductivity recovery rate of the stretchable conductor layer and the stretchable conductor / fabric laminated body> In the repeated stretch durability (mechanical load) of the conductive sheet, when the conductivity reduction ratio is 1/1000 or more, After repeating the tensile endurance (mechanical load) test, the test piece was removed from the tensile load, and was placed on a fluororesin sheet held horizontally without being subjected to a load other than its own weight, and heated at 60 ° C for 10 minutes in a drying oven. After that, the temperature was returned to room temperature, and the conductivity was measured to determine the conductivity recovery rate. For the stretchable conductor / fabric laminate, similarly, without placing a load other than its own weight, it is placed on a fluororesin sheet that is kept horizontal, heated in a drying oven at 60 ° C for 10 minutes, and then returned to room temperature. ， Conductivity measurement was performed to determine the conductivity recovery rate [Enum. 3] Conductivity reduction ratio = conductivity during measurement / initial conductivity Conductivity recovery = 60 ℃ × 10 minutes after heating / initial conductivity

＜膜厚不均＞ 將伸縮性導體層浸漬於液態氮，充分冷卻後，藉由在任意方向進行彎折而將片折斷，製成可進行剖面觀察的試驗片。利用具有測長功能之顯微鏡觀察獲得之試驗片的剖面，於面方向以約1mm間隔測定10點的伸縮性導體層之導體部分之厚度，並依照下列數學式求出膜厚不均。由獲得之10點的最大膜厚、最小膜厚、平均膜厚，依下式求出膜厚不均。 【數4】 膜厚不均[%]＝100×(最大膜厚-最小膜厚)/平均膜厚<Uneven film thickness> After the stretchable conductor layer was immersed in liquid nitrogen and sufficiently cooled, the sheet was broken by bending in an arbitrary direction to prepare a test piece capable of cross-sectional observation. The cross section of the obtained test piece was observed with a microscope having a length measurement function, and the thickness of the conductor portion of the stretchable conductor layer at 10 points was measured at an interval of about 1 mm in the plane direction. From the obtained maximum film thickness, minimum film thickness, and average film thickness at the 10 points, the film thickness unevenness was calculated according to the following formula. [Number 4] Uneven film thickness [%] = 100 × (maximum film thickness-minimum film thickness) / average film thickness

＜洗滌耐久性＞ (1)試驗片製作 藉由將沖壓成啞鈴型之伸縮性導體層重疊於50mm×200mm之布帛(經編針織物、耐熱性＞100℃、伸張回復率100%)之大致中央部，並重疊已沖壓成40mm×180mm之熱熔黏接層MOB100[日清紡(股)公司製]，再用氟樹脂片夾持後，在120℃進行熱壓製而予以層合，製成試驗片。此外，經編針織物、熱熔黏接層MOB100均為伸張100%時伸張回復率為100%之具有充分的伸張性者。 (2)洗滌試驗 利用JIS L 0217關於纖維製品之操作之表示記號及表示方法中規定的105法，進行30次循環的洗滌試驗。 洗滌液：中性洗滌劑0.5%溶液 水流：弱 浴比：1：60 洗滌循環 洗淨30℃5分鐘 洗清30℃2分鐘，2次 以此循環作為1循環，重複30次。 (3)評價 導電片之洗滌試驗中，當試驗後之導電率降低比為1/1000以上時，將洗滌試驗後之試驗片除去伸張荷重，在不施加自身重量以外之負荷的狀態下，靜置於保持為水平的氟樹脂片上，利用乾燥烘箱於60℃加熱10分鐘之後，恢復至室溫，進行導電率測定，求出導電性回復率。 洗滌試驗後之導電率降低比＝洗滌試驗後之導電率/初始導電率 洗滌試驗後之導電性回復率＝洗滌試驗後進行60℃×10分鐘加熱後之導電率/初始導電率。 此外，計算導電率時，為了方便，片的厚度係使用貼附於布帛前的值。<Washing Durability> (1) Approximately the center of the test piece is produced by laminating a stretchable conductor layer punched into a dumbbell shape on a fabric of 50 mm × 200 mm (warp knitted fabric, heat resistance> 100 ° C, 100% stretch recovery) And laminated with a hot-melt adhesive layer MOB100 [manufactured by Nisshinbo Co., Ltd.] punched into a 40mm × 180mm layer, sandwiched with a fluororesin sheet, and then laminated by hot pressing at 120 ° C to prepare a test piece. . In addition, the warp-knitted fabric and the hot-melt adhesive layer MOB100 are all those with sufficient stretchability when the stretch recovery rate is 100%. (2) Washing test The washing test was performed for 30 cycles using the 105 method specified in JIS L 0217, the symbol and method for handling fiber products. Washing liquid: 0.5% solution of neutral detergent Water flow: weak Bath ratio: 1:60 Washing cycle Washing at 30 ° C for 5 minutes Washing at 30 ° C for 2 minutes, 2 times This cycle is taken as 1 cycle and repeated 30 times. (3) In the washing test for evaluating conductive sheets, when the conductivity reduction ratio after the test is 1/1000 or more, the tensile strength of the test pieces after the washing test is removed, and the load is kept in a state where no load other than its own weight is applied. It was placed on a fluororesin sheet kept at a horizontal level, and heated at 60 ° C. for 10 minutes in a drying oven, and then returned to room temperature. The conductivity was measured to determine the conductivity recovery rate. Conductivity reduction ratio after washing test = conductivity after washing test / initial conductivity Conductivity recovery after washing test = conductivity / initial conductivity after heating at 60 ° C × 10 minutes after washing test. In addition, when calculating the electrical conductivity, for the sake of convenience, the thickness of the sheet is the value before being attached to the fabric.

[製造例1～5] ＜合成橡膠材料的聚合＞ 於配備有攪拌機、水冷套層之不銹鋼製的反應容器中，加入 丁二烯 61質量份 丙烯腈 39質量份 去離子水 270質量份 十二烷基苯磺酸鈉 0.5質量份 萘磺酸鈉縮合物 2.5質量份 第三-十二烷基硫醇 0.3質量份 三乙醇胺 0.2質量份 碳酸鈉 0.1質量份， 邊通入氮氣邊保持浴溫度為5℃，並輕輕地攪拌。然後，歷時30分鐘滴加已將過硫酸鉀3質量份溶解於去離子水19.7質量份而得的水溶液，再繼續反應20小時後，加入已將氫醌0.5質量份溶解於去離子水19.5質量份而得的水溶液，實施聚合停止操作。 然後，為了餾去未反應單體，首先將反應容器內減壓，再導入蒸汽並回收未反應單體，獲得由NBR構成之合成橡膠乳膠(L1)。 於獲得之乳膠加入食鹽與稀硫酸，進行凝聚、過濾，將相對於樹脂之體積比20倍量的去離子水分成5次重複進行使樹脂再分散於去離子水中並過濾的操作以進行洗滌，在空氣中乾燥，獲得合成橡膠樹脂。獲得之合成橡膠樹脂的玻璃轉移溫度、數量平均分子量、重量平均分子量、分散比、凝膠分率、樹脂之伸張回復率顯示於表1。 以下，藉由變更聚合引發劑(過硫酸鉀)的添加量、聚合溫度、原料加入比，得到表1所示之NBR1、NBR2、NBR3、NBR4、SBR1。[Manufacturing Examples 1 to 5] <Polymerization of synthetic rubber material> In a stainless steel reaction vessel equipped with a stirrer and a water-cooled jacket, 61 parts by mass of butadiene, 39 parts by mass of acrylonitrile, and 270 parts by mass of 270 parts by mass of deionized water were charged. 0.5 parts by mass of sodium alkylbenzenesulfonate, 2.5 parts by mass of sodium naphthalenesulfonate, 0.3 parts by mass of tri-dodecyl mercaptan, 0.3 parts by mass of triethanolamine, 0.2 parts by mass of sodium carbonate, and 0.1 part by mass of sodium carbonate. 5 ° C and gently stir. Then, an aqueous solution obtained by dissolving 3 parts by mass of potassium persulfate in 19.7 parts by mass of deionized water was added dropwise over 30 minutes, and the reaction was continued for 20 hours, and then 0.5 part by mass of hydroquinone dissolved in 19.5 parts by mass of deionized water was added. Part of the aqueous solution was subjected to a polymerization stop operation. Then, in order to distill off the unreacted monomers, the inside of the reaction vessel was decompressed, steam was introduced, and the unreacted monomers were recovered to obtain a synthetic rubber latex (L1) composed of NBR. Add salt and dilute sulfuric acid to the obtained latex, perform coagulation and filtration, divide 20 times the volume ratio of the resin with respect to the volume of the deionized water into 5 times, and repeat the operation of redispersing the resin in the deionized water and filtering to perform washing. It was dried in air to obtain a synthetic rubber resin. The glass transition temperature, number average molecular weight, weight average molecular weight, dispersion ratio, gel fraction, and tensile recovery of the resin of the obtained synthetic rubber resin are shown in Table 1. Hereinafter, NBR1, NBR2, NBR3, NBR4, and SBR1 shown in Table 1 were obtained by changing the addition amount of the polymerization initiator (potassium persulfate), the polymerization temperature, and the raw material addition ratio.

【表1】 【Table 1】

[黏結劑樹脂] 依表2所示之摻合比摻合樹脂材料，於足以熔融之溫度進行混練，製成黏結劑樹脂。各黏結劑樹脂的特性顯示於表2。 此外，在表中，關於SBR+交聯劑，SBR係製造例中獲得之SBR1，交聯劑為非硫系之PERBUTYL P[日油(股)公司製]，且相對於樹脂總量為0.1質量%。 表中的胺甲酸酯係使用UR-8700[東洋紡(股)公司製]。[Binder resin] Blend the resin material with the blending ratio shown in Table 2 and knead it at a temperature sufficient to melt to make a binder resin. The characteristics of each binder resin are shown in Table 2. In addition, in the table, regarding SBR + crosslinking agent, SBR1 obtained in the SBR series manufacturing examples, the crosslinker is non-sulfur based PERBUTYL P [manufactured by Nippon Oil Co., Ltd.], and is 0.1 mass relative to the total amount of resin %. In the table, the urethane system was UR-8700 [manufactured by Toyobo Co., Ltd.].

【表2】 【Table 2】

[糊劑化] 首先，藉由將黏結劑樹脂溶解於預定溶劑量之一半量的溶劑，在獲得之溶液中添加金屬系粒子、碳系粒子、其他成分並進行預混合，然後利用三輥研磨機進行分散而糊劑化，得到表3所示之糊劑Pag1。以下同樣依表3所示之組成比製備糊劑。[Paste] First, by dissolving the binder resin in a half of a predetermined solvent amount, the obtained solution is added with metal-based particles, carbon-based particles, and other components and pre-mixed, followed by three-roll grinding The paste was disperse | distributed by the machine, and the paste Pag1 shown in Table 3 was obtained. In the following, a paste was also prepared according to the composition ratio shown in Table 3.

【表3】 【table 3】

此外，表3中， 碳系粒子CB01：中越黑鉛製造所(股)公司製 鱗狀石墨 GRAPHITE BF-1AT(平均粒徑1μm) 碳系粒子CB02：Lion Specialty Chemicals(股)公司製 石墨粉末 KETJENBLACK EC300J BET比表面積 800(m2 /g) 金屬系粒子Ag01：福田金屬箔粉工業(股)公司製 微細薄片狀銀粉 Ag-XF301(平均粒徑6μm) 金屬系粒子Ag02：DOWA Electronics(股)公司製 團聚銀粉G-35(平均粒徑6.0μm) 金屬系粒子Ag03：三井金屬礦業(股)公司製 微小徑銀粉 SPQ03R(平均粒徑0.7μm) 非導電粒子TiO2 ：堺化學工業(股)公司製 氧化鈦粒子 R-62N(平均粒徑為0.3μm) 非導電粒子SiO2 ：NIPPON AEROSIL公司製 氣相二氧化矽(fumed silica)AEROSIL 200(BET比表面積200m2 /g) 溶劑BC：丁基卡必醇乙酸酯 溶劑IP：異佛酮。In addition, in Table 3, carbon-based particles CB01: flaky graphite GRAPHITE BF-1AT (average particle diameter: 1 μm) manufactured by Sino-Vietnam Black Lead Manufacturing Co., Ltd. Carbon-based particles CB02: graphite powder KETJENBLACK manufactured by Lion Specialty Chemicals EC300J BET specific surface area 800 (m 2 / g) Metal particles Ag01: Fine lamella silver powder Ag-XF301 (average particle diameter 6 μm) manufactured by Fukuda Metal Foil Industry Co., Ltd. Metal particles Ag02: DOWA Electronics Co., Ltd. Aggregated silver powder G-35 (average particle size 6.0 μm) Metal particles Ag03: Micro-diameter silver powder SPQ03R (average particle diameter 0.7 μm) made by Mitsui Metals Mining Co., Ltd. Non-conductive particles TiO 2 : Sakai Chemical Industry Co., Ltd. Titanium oxide particles R-62N (average particle size: 0.3 μm) Non-conductive particles SiO 2 : Fumed silica AEROSIL 200 (BET specific surface area 200 m 2 / g) made by NIPPON AEROSIL Co., Ltd. Solvent BC: Butyl Carbitol acetate IP: isophorone.

以使有效寬度成為500mm的方式，利用缺角輪塗佈機將獲得之伸縮性導體形成用糊劑塗布於寬度600mm之經聚矽氧系脫模劑處理之聚酯薄膜上，得到表4所示之伸縮性導體層。 將獲得的片從經脫模處理之聚酯薄膜剝離，進行厚度、厚度不均的評價。結果顯示於表4。然後，對伸縮性導體層之初始導電率、機械性負荷後(重複伸縮耐久性試驗後)之導電率進行評價，求出導電率降低比。進一步，求出機械性負荷後之伸縮性導體層的加熱導電性回復率。結果顯示於表4。使用分子量分布窄之黏結劑樹脂的試樣中，導電率降低係為明顯。此外，關於導電率降低比為1/1000以下之試樣，其加熱所致之導電率回復效果低。又，可知使用分子量分布廣之黏結劑樹脂時，加熱所致之導電率回復率高。The obtained stretchable conductor-forming paste was applied to a polyester film treated with a silicone release agent having a width of 600 mm so that the effective width became 500 mm using a notch wheel coater, and the results shown in Table 4 were obtained. Shown as a stretchable conductor layer. The obtained sheet was peeled from the release-treated polyester film, and the thickness and thickness unevenness were evaluated. The results are shown in Table 4. Then, the initial conductivity of the stretchable conductor layer and the conductivity after a mechanical load (after repeating the stretch durability test) were evaluated to determine the conductivity reduction ratio. Furthermore, the heat conductivity recovery rate of the stretchable conductor layer after a mechanical load was calculated | required. The results are shown in Table 4. In a sample using a binder resin with a narrow molecular weight distribution, the decrease in conductivity was significant. In addition, regarding samples having a conductivity reduction ratio of 1/1000 or less, the conductivity recovery effect by heating was low. It was also found that when a binder resin having a wide molecular weight distribution is used, the conductivity recovery rate due to heating is high.

【表4】 【Table 4】

【表5】 【table 5】

將獲得之伸縮性導體層以預定的方法貼附於經編布料，得到伸縮性導體/布帛疊層體。求出獲得之伸縮性導體/布帛疊層體之伸縮性導體部分的初始導電率、洗滌試驗後之導電率、洗滌試驗後之導電率降低比、洗滌試驗後之導電性回復率，結果顯示於表4。The obtained stretchable conductor layer was attached to a warp-knitted fabric by a predetermined method to obtain a stretchable conductor / cloth laminate. The initial conductivity, the conductivity after the washing test, the conductivity reduction ratio after the washing test, and the conductivity recovery after the washing test of the obtained stretchable conductor / fabric laminated body were obtained. The results are shown in Table 4.

[糊劑化例2]電極表面層用糊劑(伸展性(stretchable)碳糊劑)的製備 依照表3所示之組成製備電極表面層用之碳糊劑。[Paste Example 2] Preparation of Paste (Stretchable Carbon Paste) for Electrode Surface Layer A carbon paste for electrode surface layer was prepared in accordance with the composition shown in Table 3.

[糊劑化例3]伸縮性絕緣高分子層形成用糊劑(伸縮性絕緣印墨：表塗層樹脂印墨、基底層用印墨) 依照表3所示之組成製備伸縮性絕緣高分子層形成用糊劑。由獲得之伸縮性絕緣高分子層形成用糊劑得到的被膜的特性顯示於表5。[Pasting example 3] A paste for forming a stretchable insulating polymer layer (stretchable insulating printing ink: a surface coating resin printing ink, a printing ink for a base layer) According to the composition shown in Table 3, a stretchable insulating polymer layer was prepared. Forming paste. Table 5 shows the characteristics of the film obtained from the obtained paste for forming a stretchable insulating polymer layer.

[應用實施例1] 利用圖2所示之直接印刷法，製作心電圖測定用之衣服型電子設備。將針織材質的運動衫外翻，以不使背面產生皺紋的方式放置在臨時支持體，於襯衫的兩肩與左右下擺用銷固定。 然後，將圖5所示之包含導體圖案之配線，依照圖2所示之程序利用伸縮性導體形成用糊劑Pag5印刷伸縮性導體層，利用伸縮性絕緣高分子層形成用糊劑Pcc1印刷伸縮性表覆層，再利用電極表面層用糊劑Pcb1印刷伸縮性碳層，分別進行網版印刷，於預定之條件使其乾燥、硬化並進行印刷疊層，得到具有心電測定用之電極與配線的運動衫。心電測定用之電極表面層為直徑30mm之圓形。又，就絕緣表覆層而言，在電極部為內徑30mm、外徑36mm之圈餅狀，從電極延伸出來之配線部為寬度14mm，在配線部的終端，為了安裝與感測器連接用之鉤扣，同樣利用碳糊劑印刷直徑10mm之圓形電極。碳糊劑層之厚度以乾燥膜厚計為18μm，絕緣表覆層為30μm，伸縮性導體層為厚度28μm。此外，圖中雖然省略，但在印刷伸縮性導體層之前，先利用伸縮性絕緣高分子層形成用糊劑形成基底層。[Application Example 1] A clothing-type electronic device for measuring an electrocardiogram was produced by the direct printing method shown in FIG. 2. Knit a jersey made of material, and place it on the temporary support so as not to cause wrinkles on the back, and fix it with pins on the shoulders and left and right hem of the shirt. Then, according to the procedure shown in FIG. 2, the wiring including the conductor pattern shown in FIG. 5 is printed with a stretchable conductor layer using the paste Pag5 for forming a stretchable conductor, and the paste Pcc1 is used for forming a stretchable insulating polymer layer. The flexible surface layer is then printed with the electrode surface layer paste Pcb1 to stretch the carbon layer, and then screen-printed, dried and hardened under predetermined conditions, and printed and laminated to obtain an electrode with an electrocardiogram and Wiring sweatshirt. The surface layer of the electrode for electrocardiogram measurement is a circle having a diameter of 30 mm. In addition, as for the insulating surface coating layer, the electrode portion has a doughnut shape with an inner diameter of 30 mm and an outer diameter of 36 mm, and the wiring portion extending from the electrode has a width of 14 mm. At the terminal of the wiring portion, it is connected to the sensor for installation. With the hook, a circular electrode with a diameter of 10 mm was also printed with carbon paste. The thickness of the carbon paste layer was 18 μm in terms of dry film thickness, the insulating surface coating layer was 30 μm, and the stretchable conductor layer was 28 μm in thickness. Although not shown in the figure, the base layer is formed by a paste for forming a stretchable insulating polymer layer before printing the stretchable conductor layer.

獲得之設有電極、配線之運動衫，在左右後腋窩線上與第7肋骨之交叉點具有直徑30mm之圓形電極，且在內側形成有從圓形電極到後頸部中央之寬度10mm之具有伸縮性之導體構成的電氣配線。此外，從左右電極延伸到後頸部中央的配線，在頸部中央具有5mm之間隙，兩者不會短路。 然後，在後頸部中央端之表面側安裝不銹鋼製的鉤扣，為了確保與背面側之配線部電性導通，使用搓捻有金屬細線之導電線將伸縮性導體組成物層與不銹鋼製鉤扣予以電性連接。The obtained jersey with electrodes and wiring has a circular electrode with a diameter of 30mm at the intersection of the left and right rear axillary lines with the seventh rib, and a 10mm width from the circular electrode to the center of the rear neck is formed on the inside. Electrical wiring made of stretchable conductors. In addition, the wiring extending from the left and right electrodes to the center of the back neck has a gap of 5 mm in the center of the neck, and the two will not short-circuit. Then, a stainless steel hook is attached to the surface side of the center end of the back neck. In order to ensure electrical conduction with the wiring portion on the back side, the conductive conductor composition layer is twisted with a stainless steel hook using conductive wires twisted with thin metal wires. The buckle is electrically connected.

藉由不銹鋼製鉤扣連接UNION TOOL公司製的心率感測器WHS-2，利用安裝有該心率感測器WHS-2專用之應用程式「myBeat」的蘋果公司製智慧型手機接收心率數據，並設定為能夠畫面顯示。如上述般製作納入有心率計測功能之運動衫。配線圖案顯示於圖5，配線圖案相對於襯衫的配置顯示於圖4。 讓受試者穿上本運動衫，邊取得心電數據邊實施運動訓練。獲得之心電數據雜訊少，且為高解像度，就心電圖而言，具有可由心跳間隔之變化、心電波形等解析精神狀態、身體狀況、疲勞度、睡意、緊張程度等之品質。 就本運動衫而言，每次訓練後均進行洗滌，並在乾燥後利用已將表面溫度調整為80℃之家庭用熨斗對電極部、及配線部進行熱處理。熱處理係與通常的熨燙同樣將外翻的運動衫置於熨斗台，在配線部分蓋上38μm厚之聚醯亞胺薄膜XENOMAX(東洋紡(股)公司製)作為脫模片，並以從聚醯亞胺薄膜上方推抵熨斗的熱板之方式，以5～10cm/秒的速度使其移動並重複操作5次。 藉由每次進行該洗滌與乾燥後之熨燙，即使在累積使用100次後，仍可維持能良好地進行心電測定之狀態。The heart rate sensor WHS-2 made by UNION TOOL is connected by a stainless steel hook, and the heart rate data is received by an Apple-made smartphone equipped with an application "myBeat" for the heart rate sensor WHS-2. Set to enable screen display. Create a sweatshirt with a heart rate measurement function as described above. The wiring pattern is shown in FIG. 5, and the arrangement of the wiring pattern with respect to the shirt is shown in FIG. 4. The subjects were asked to put on this sweatshirt and exercise training while obtaining ECG data. The obtained ECG data is less noisy and has a high resolution. As for the electrocardiogram, it has the qualities of analyzing mental state, physical condition, fatigue, drowsiness, tension, etc. from changes in heartbeat interval, ECG waveform and the like. In this jersey, after each training, washing is performed, and after drying, the electrode part and the wiring part are heat-treated with a household iron whose surface temperature has been adjusted to 80 ° C. The heat treatment is the same as ordinary ironing. The overturned jersey is placed on the iron table, and the wiring part is covered with a 38 μm thick polyimide film XENOMAX (manufactured by Toyobo Co., Ltd.) as a release sheet. The method of pushing the imine film over the hot plate of the iron, moving it at a speed of 5 to 10 cm / second and repeating the operation 5 times. By performing the washing and drying ironing each time, the state that the ECG measurement can be performed well can be maintained even after the cumulative use of 100 times.

另一方面，除省略熨燙處理以外，其他同樣地使用之運動衫，在洗滌30次後心電測定的雜訊增加，訓練中的心電測定變得困難。31次以後藉由進行熨燙處理，仍可維持能進行心電測定之狀態直到80次。On the other hand, except for omitting the ironing process, other similarly used jerseys increase the noise of ECG measurement after 30 washes, making it difficult to measure ECG during training. After 31 times, by performing the ironing treatment, the state capable of performing ECG measurement can be maintained until 80 times.

[應用實施例2] 利用圖3所示之印刷轉印法，針對具有與應用例1同樣圖案之配線的運動衫，使用Pag11作為伸縮性導體形成用糊劑，使用Pcc2作為伸縮性絕緣高分子層形成用糊劑，除此以外，利用相同材料進行試製。使用獲得之運動衫，與應用例1同樣邊取得心電數據邊進行運動訓練，並同樣重複實施洗滌與乾燥、熨燙。結果在應用實施例2中，即使累積使用100次後，運動服也仍維持能進行心電測定之狀態。[Application Example 2] Using the printing transfer method shown in FIG. 3, for a sweatshirt having a wiring pattern similar to that of Application Example 1, Pag11 was used as a paste for forming a stretchable conductor, and Pcc2 was used as a stretchable insulating polymer. Except for the layer-forming paste, trial production was performed using the same material. Using the obtained sweat shirt, exercise training was performed while obtaining ECG data in the same manner as in Application Example 1, and washing, drying, and ironing were repeatedly performed in the same manner. As a result, in the application example 2, even after the cumulative use of 100 times, the sportswear can still maintain a state capable of performing ECG measurement.

[應用實施例3] 利用圖3所示之印刷轉印法，針對具有與應用例1同樣圖案之配線的運動衫，使用Pag11作為伸縮性導體形成用糊劑，使用Pcc3作為伸縮性絕緣高分子層形成用糊劑，除此以外，利用相同材料進行試製。使用獲得之運動衫，與應用例1同樣邊取得心電數據邊進行運動訓練，並同樣重複實施洗滌與乾燥、熨燙。結果在應用實施例3中，即使累積使用100次後，運動服也仍維持能進行心電測定之狀態。[Application Example 3] Using the printing transfer method shown in FIG. 3, for a sweatshirt having a wiring pattern similar to that of Application Example 1, Pag11 was used as a paste for forming a stretchable conductor, and Pcc3 was used as a stretchable insulating polymer. Except for the layer-forming paste, trial production was performed using the same material. Using the obtained sweat shirt, exercise training was performed while obtaining ECG data in the same manner as in Application Example 1, and washing, drying, and ironing were repeatedly performed in the same manner. As a result, in the application example 3, even after the cumulative use of 100 times, the sportswear can still maintain a state capable of performing ECG measurement.

[應用實施例4] 藉由使用實施例1中由伸縮性導體形成用糊劑Pag4獲得之伸縮性導體層，伸縮性絕緣高分子層則使用日清紡(股)公司製設有熱熔層之彈性體片「MOBILON」，省略電極表面層，並將各個片沖壓成預定形狀並進行疊層層合的方法，獲得附設有電極、配線的運動衫。 以下，與應用例1同樣邊取得心電數據邊進行運動訓練，同樣重複實施洗滌與乾燥、熨燙。結果在應用實施例4中，即使累積使用250次後，運動服也仍維持能進行心電測定之狀態。 [產業上利用性][Application Example 4] The elastic conductor layer obtained by using the elastic conductor forming paste Pag4 in Example 1 was used, and the elastic insulating polymer layer was made by Nisshinbo Corporation with a hot-melt layer. The body sheet "MOBILON" is a method of omitting the electrode surface layer and punching each sheet into a predetermined shape and laminating them to obtain a jersey with electrodes and wiring. Hereinafter, as in Application Example 1, exercise training is performed while acquiring ECG data, and washing, drying, and ironing are repeatedly performed in the same manner. As a result, in the application example 4, even after the cumulative use of 250 times, the sportswear still maintained a state capable of performing ECG measurement. [Industrial availability]

如上述般，使用本發明中之伸縮性絕緣高分子層與伸縮性導體層而獲得之伸縮性電氣配線，具有藉由適當地施以加熱處理會回復已降低的導電性的特性，故具有如下有用特性：可使用家庭用之常備品以延長實用上的壽命，而無需使用特殊的裝置。 藉由將本發明之伸縮性電氣配線使用於穿戴式智慧裝置，可應用在：用於以設置在衣服之感測器等檢測人體所帶之資訊，亦即，肌肉電位、心電位等生物電位、體溫、脈搏、血壓等生物資訊的穿戴式裝置、或納入有電溫熱裝置的衣服、納入有用於測定衣服壓力之感測器的穿戴式裝置、利用衣服壓力測量身體大小的衣物、用於測定腳底壓力的襪子型裝置、將撓性太陽能電池模組整合於紡織品而得的衣服、帳篷、包等之配線部、具有關節部之低頻治療器、溫熱療養機等的配線部、彎曲度之感測部等。該等穿戴式裝置不僅能以人體為對象，還可應用在寵物、家畜等動物、或具有伸縮部、彎曲部等之機械裝置，也可用作機械假臂、機械假腿等機械裝置與人體連接所使用之系統的電氣配線。又，亦可作為欲埋設在體內之植入裝置的配線材料而應用。As described above, the stretchable electrical wiring obtained by using the stretchable insulating polymer layer and the stretchable conductor layer in the present invention has the property that the reduced conductivity can be restored by appropriately applying heat treatment, and therefore has the following characteristics: Useful features: You can use household stocks to extend practical life without the need for special equipment. By using the stretchable electrical wiring of the present invention in a wearable smart device, it can be applied to: used to detect information carried by the human body with a sensor or the like installed on clothing, that is, biopotentials such as muscle potentials and cardiac potentials Wearable devices that include biological information such as body temperature, pulse, blood pressure, etc., or clothes that include electrical heating devices, wearable devices that include sensors for measuring the pressure of clothes, clothes that measure body size using clothes pressure, Sock-type device for measuring sole pressure, wiring section of clothes, tents, bags, etc. obtained by integrating a flexible solar cell module into textiles, low-frequency therapeutic device with joints, wiring section of a thermotherapy machine, and bending degree Of the sensing department. These wearable devices can be used not only for the human body, but also for animals such as pets and domestic animals, or mechanical devices with telescoping parts, bending parts, etc., and can also be used as mechanical devices such as mechanical artificial arms, mechanical artificial legs, and human bodies. Connect the electrical wiring of the system used. It can also be used as a wiring material for an implanted device to be buried in the body.

1‧‧‧織品1‧‧‧ Fabric

2‧‧‧臨時支持體2‧‧‧ temporary support

3‧‧‧伸縮性導體組成物層3‧‧‧ Stretchable conductor composition layer

4‧‧‧伸縮性表覆層4‧‧‧ Flexible surface coating

5‧‧‧伸縮性碳層5‧‧‧ Stretchable carbon layer

6‧‧‧脫模支持體6‧‧‧ demoulding support

7‧‧‧黏接層7‧‧‧ Adhesive layer

[圖1A]係用於說明本發明中之拉伸降伏伸度的概略圖。 [圖1B]係用於說明本發明中之伸張回復率的概略圖。 [圖2]係顯示本發明中之利用直接印刷法之設有配線的衣服之製造步驟的概略圖。 [圖3]係顯示本發明中之利用印刷轉印法之設有配線的衣服之製造步驟的概略圖。 [圖4]係顯示於襯衫鋪設有配線之狀態之一例的概略圖。 [圖5]係顯示配線之形狀之一例的概略圖。[FIG. 1A] A schematic diagram for explaining the stretch and drop elongation in the present invention. [Fig. 1B] A schematic diagram for explaining a stretch recovery rate in the present invention. FIG. 2 is a schematic diagram showing a manufacturing process of clothes provided with wiring by a direct printing method in the present invention. Fig. 3 is a schematic view showing the manufacturing steps of clothes provided with wiring by a printing transfer method in the present invention. Fig. 4 is a schematic diagram showing an example of a state where wiring is laid on a shirt. 5 is a schematic diagram showing an example of a shape of a wiring.

Claims (15)

一種伸縮性導體片，係由導電填料與黏結劑樹脂構成之伸縮性的導體片， 其特徵為： 該片之膜厚不均為10%以下，於25℃伸張20%後之伸張回復率為92%以上。A stretchable conductor sheet is a stretchable conductor sheet composed of a conductive filler and a binder resin, and is characterized in that the film thickness of the sheet is not more than 10%, and the stretch recovery rate after stretching at 25 ° C for 20% is More than 92%. 如申請專利範圍第1項之伸縮性導體片，於25℃伸張20%後，在除去伸張荷重的狀態下進行60℃加熱時的伸張回復率為96%以上。For example, the stretchable conductor sheet according to item 1 of the patent application, after stretching at 25 ° C for 20%, the stretch recovery rate when heating at 60 ° C with the stretching load removed is more than 96%. 如申請專利範圍第1或2項之伸縮性導體片，其中，伸縮性導體片之片材面方向之初始導電率為1×102 S/cm以上，因機械負荷所致之導電率降低比為初始導電率之1/1000以上之範圍時，60℃加熱所致之導電性回復率為10%以上。For example, the elastic conductor sheet of item 1 or 2 of the scope of patent application, wherein the initial conductivity of the sheet surface direction of the elastic conductor sheet is 1 × 10 2 S / cm or more, and the conductivity reduction ratio due to mechanical load is When the initial conductivity is in the range of 1/1000 or more, the conductivity recovery rate by heating at 60 ° C is 10% or more. 如申請專利範圍第1或2項之伸縮性導體片，係由65～85質量%的黏結劑樹脂與15～35質量%的導電填料構成，該導電填料的90質量%以上由金屬粒子構成，該黏結劑樹脂之20%伸張後之伸張回復率為99%以上，玻璃轉移溫度為0℃以下。For example, the elastic conductor sheet of the first or second patent application range is composed of 65 to 85% by mass of a binder resin and 15 to 35% by mass of a conductive filler, and more than 90% by mass of the conductive filler is composed of metal particles. After the 20% stretch of the adhesive resin, the stretch recovery rate was above 99%, and the glass transition temperature was below 0 ° C. 如申請專利範圍第1或2項之伸縮性導體片，其中，令該黏結劑樹脂之數量平均分子量為Mn，重量平均分子量為Mw時，為Mw/Mn＞4。For example, the elastic conductor sheet according to item 1 or 2 of the patent application range, wherein the number average molecular weight of the binder resin is Mn, and when the weight average molecular weight is Mw, Mw / Mn> 4. 一種伸縮性導體/布帛疊層體， 具有： 50%伸張時之伸張回復率為99%以上，且具有60℃以上之耐熱性的絕緣性布帛層；及 如申請專利範圍第1至5項中任一項之伸縮性導體片的層。A stretchable conductor / fabric laminated body, having: an insulation fabric layer having a stretch recovery rate of 50% or more when stretched, and having a heat resistance of 60 ° C or more; The layer of any one of the stretchable conductor sheets. 一種如申請專利範圍第1至5項中任一項之伸縮性導體片或如申請專利範圍第6項之伸縮性導體/布帛疊層體的導電性恢復方法，係藉由在已除去伸縮性導體片之伸張荷重的狀態下加熱至60℃以上。A method for recovering the conductivity of a stretchable conductor sheet according to any one of claims 1 to 5 or a stretchable conductor / fabric stack as described in claim 6 The conductor sheet is heated to a temperature of 60 ° C. or more under a tensile load. 一種伸縮性配線，係至少由下列層構成： 拉伸降伏伸度為70%以上，熱變形溫度為60℃以上之伸縮性絕緣高分子層；及 由導電填料與黏結劑樹脂構成之伸縮性導體層。A stretchable wiring composed of at least the following layers: a stretchable insulating polymer layer having a tensile drop of 70% or more and a heat distortion temperature of 60 ° C or more; and a stretchable conductor composed of a conductive filler and a binder resin Floor. 如申請專利範圍第8項之伸縮性配線，其中，該伸縮性導體層之於25℃伸張20%後之伸張回復率為92%以上。For example, the stretchable wiring of the eighth scope of the patent application, wherein the stretch recovery rate of the stretchable conductor layer after being stretched by 20% at 25 ° C is more than 92%. 如申請專利範圍第8或9項之伸縮性配線，其中，伸縮性導體層之面方向之初始導電率為1×102 S/cm以上，因機械負荷所致之導電率降低比為初始導電率之1/1000以上之範圍時，60℃加熱所致之導電性回復率為10%以上。For example, for the flexible wiring of the 8th or 9th in the scope of the patent application, the initial conductivity of the stretchable conductor layer in the plane direction is 1 × 10 2 S / cm or more, and the reduction ratio of the conductivity due to mechanical load is the initial conductivity. In the range of 1/1000 or more, the conductivity recovery rate by heating at 60 ° C is 10% or more. 如申請專利範圍第8或9項之伸縮性配線，其中，該伸縮性導體層係由65～85質量%的黏結劑樹脂與15～35質量%的導電填料構成，該導電填料的90質量%以上由金屬粒子構成，該黏結劑樹脂之20%伸張後之伸張回復率為99%以上，玻璃轉移溫度為0℃以下。For example, the flexible wiring of item 8 or 9 of the scope of patent application, wherein the stretchable conductor layer is composed of 65 to 85% by mass of a binder resin and 15 to 35% by mass of a conductive filler, and 90% by mass of the conductive filler The above is composed of metal particles. After 20% elongation of the adhesive resin, the elongation recovery rate is more than 99%, and the glass transition temperature is 0 ° C or lower. 如申請專利範圍第8或9項之伸縮性配線，其中，令該黏結劑樹脂之數量平均分子量為Mn，重量平均分子量為Mw時，為Mw/Mn＞4。For example, the flexible wiring of the patent application No. 8 or 9, wherein the number average molecular weight of the adhesive resin is Mn, and when the weight average molecular weight is Mw, Mw / Mn> 4. 一種設有伸縮性配線之布帛，係在50%伸張時之伸張回復率為99%以上，且具有60℃以上之耐熱性的絕緣性布帛上具有如申請專利範圍第8至12項中任一項之伸縮性配線。A fabric provided with stretchable wiring, which has an elongation recovery rate of more than 99% when 50% stretched, and an insulation fabric having a heat resistance of 60 ° C or higher. Item of flexible wiring. 一種如申請專利範圍第8至12項中任一項之伸縮性配線的導電性恢復方法，係藉由在已除去伸縮性配線之伸張荷重的狀態下加熱至60℃以上。A method for recovering the conductivity of a stretchable wiring according to any one of claims 8 to 12 of the scope of application for a patent, by heating to a temperature above 60 ° C. in a state where the tensile load of the stretchable wiring has been removed. 一種如申請專利範圍第13項之設有伸縮性配線之布帛的導電性恢復方法，係藉由在已除去設有伸縮性配線之布帛之伸張荷重的狀態下加熱至60℃以上。A method for recovering the electrical conductivity of a fabric provided with a stretchable wiring such as item 13 of the scope of the patent application is by heating to a temperature of 60 ° C or more under a state where the tensile load of the fabric provided with the stretchable wiring has been removed.
TW106135387A 2016-10-18 2017-10-17 Elastic conductive sheet, elastic wiring, elastic wiring-equipped fabric, and method for restoring conductivity TW201825013A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111385968A (en) * 2018-12-26 2020-07-07 信越化学工业株式会社 Stretchable wiring film and method for forming the same
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* Cited by examiner, † Cited by third party
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KR102467334B1 (en) 2019-09-21 2022-11-16 엘지전자 주식회사 Image coding method and device based on transformation
JP2022083344A (en) * 2020-11-24 2022-06-03 東和株式会社 Electrode pad for wearable device
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Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5486268B2 (en) * 2008-11-18 2014-05-07 東海ゴム工業株式会社 Conductive film, transducer including the same, and flexible wiring board
JP5570353B2 (en) * 2010-09-03 2014-08-13 バイエル マテリアルサイエンス株式会社 Conductive member having elastic wiring
JP6303367B2 (en) 2013-09-30 2018-04-04 東洋紡株式会社 Conductive paste, conductive film and touch panel
JP6690528B2 (en) * 2015-01-14 2020-04-28 東洋紡株式会社 Conductive film
CN107112069B (en) * 2015-01-14 2019-04-12 东洋纺株式会社 Conductive silver paste
JP6406359B2 (en) 2015-01-14 2018-10-17 東洋紡株式会社 Conductive fabric
CN107205677B (en) * 2015-01-14 2020-12-25 东洋纺株式会社 Stretchable electrode sheet and contact surface for measuring biological information
JP2016141713A (en) * 2015-01-30 2016-08-08 タツタ電線株式会社 Conductive composition and conductive sheet comprising the same
JP2017073364A (en) * 2015-10-09 2017-04-13 プラスコート株式会社 Conductive paste and conductive film
US10546664B2 (en) * 2016-01-13 2020-01-28 Toyobo Co., Ltd. Stretchable conductor composition, paste for forming stretchable conductor, garment comprising wiring comprising stretchable conductor composition, and method for producing same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112654498A (en) * 2018-11-06 2021-04-13 积水保力马科技株式会社 Telescopic wiring component
US11634842B2 (en) 2018-11-06 2023-04-25 Sekisui Polymatech Co., Ltd. Stretchable wire member
CN111385968A (en) * 2018-12-26 2020-07-07 信越化学工业株式会社 Stretchable wiring film and method for forming the same
CN111385968B (en) * 2018-12-26 2023-04-07 信越化学工业株式会社 Stretchable wiring film and method for forming the same
TWI805064B (en) * 2021-11-08 2023-06-11 財團法人工業技術研究院 Flexible hybrid electronic substrate and electronic textile including the same

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