JP2022055597A - Elastic conductive thread, conductive structure, and wearable device - Google Patents

Abstract

To provide an elastic conductive thread excellent in elastic electrical property.SOLUTION: An elastic conductive thread comprises one or a plurality of threads. The thread has an insulating elastomer layer and a conductive elastomer layer laminated on the surface of the insulating elastomer layer in a radial cross section of the thread.SELECTED DRAWING: Figure 1

Description

The present invention relates to stretchable conductive threads, conductive structures, and wearable devices.

So far, various developments have been made on conductive yarns. As this kind of technique, for example, the technique described in Patent Document 1 is known. Patent Document 1 describes a conductive thread made of a metal material containing stainless steel fibers (claim 1 of Patent Document 1).

Special Table 2005-525479A

However, as a result of the study by the present inventor, it has been found that the metallic conductive yarn described in Patent Document 1 has room for improvement in terms of stretchable electrical characteristics.

As a result of further studies, the present inventor has found that by using a stretchable conductive yarn having a structure in which a conductive elastomer layer is laminated on the surface of an insulating elastomer layer, elasticity and electrical characteristics at the time of expansion and contraction can be improved. The invention was completed.

According to the present invention
Elastic conductive yarn containing one or more yarns,
A stretchable conductive yarn is provided in which the yarn has an insulating elastomer layer and a conductive elastomer layer laminated on the surface of the insulating elastomer layer in one of the radial cross sections of the yarn.

Further, according to the present invention.
Provided is a conductive structure composed of a knit or woven fabric made of the above stretchable conductive yarn.

Further, according to the present invention.
A wearable device comprising the stretchable conductive yarn described above or the conductive structure described above is provided.

According to the present invention, a stretchable conductive yarn having excellent stretchable electrical characteristics, a conductive structure using the stretchable conductive yarn, and a wearable device are provided.

It is a figure which shows typically the structure of the stretchable conductive yarn which concerns on this embodiment. (A) is a cross-sectional view taken along the line AA of FIG. 1, and FIGS. (B) to (d) are cross-sectional views of a modified example of the stretchable conductive yarn. It is a figure which shows typically the structure of the conductive structure which concerns on this embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by the same reference numerals, and description thereof will be omitted as appropriate. Further, the figure is a schematic view and does not match the actual dimensional ratio.

The stretchable conductive yarn of this embodiment will be described.

The stretchable conductive yarn of the present embodiment includes one or more yarns, and the yarn is laminated on the surface of the insulating elastomer layer and the insulating elastomer layer in one of the radial cross sections of the yarn. It has a conductive elastomer layer.

According to the present embodiment, it is possible to realize a stretchable conductive yarn having excellent stretchable electrical characteristics, in which continuity is maintained even after stretching or repeated stretching.

The stretchable conductive yarn may be used as it is as a linear yarn, or may be used as a knit or a woven fabric, for example.

The stretchable conductive yarn can be used for various electric equipment applications, and can be used, for example, for wearable devices, smart textiles, strain sensors, biosensor devices, stretchable wiring, flexible electrodes, conductive cloths, and the like.

Hereinafter, the stretchable conductive yarn of the present embodiment will be described in detail.

FIG. 1 is a perspective view schematically showing an example of the stretchable conductive yarn 100 of the present embodiment.
FIG. 2A is a cross-sectional view taken along the line AA of the stretchable conductive yarn 100 of FIG. 1A.

In the present specification, the radial cross section of the thread is defined as the cross section parallel to the radial direction of the thread and orthogonal to the axial direction in the portion where the thread is in a straight line state.

The stretchable conductive thread 100 of FIG. 1 has a thread 50 having a tube structure.

In the present specification, having elasticity means that the elongation rate when the yarn is stretched in the extending direction is, for example, 10% or more, preferably 20% or more, more preferably, with respect to the length when the yarn is not stretched. Means that it can be expanded to 50% or more, more preferably 100%. When the stretchable conductive yarn 100 is stretched in the extending direction of the yarn, the conductive elastomer layer 20 can be maintained in a state in which the conductive elastomer layer 20 is not broken within the above-mentioned stretch ratio range.

The thread 50 of FIG. 1 includes both an insulating tube structure including an insulating elastomer layer 10 and a conductive tube structure including a conductive elastomer layer 20. That is, the thread 50 is composed of a tube structure in which a conductive tube structure is laminated on the outer periphery of the insulating tube structure.

As shown in FIG. 2A, the yarn 50 has at least a laminated structure in which the conductive elastomer layer 20 is laminated on the surface of the insulating elastomer layer 10 in the radial cross section of the yarn 50.

The insulating elastomer layer 10 and the conductive elastomer layer 20 are each made of an elastic elastomer. Conduction can be achieved by the conductive elastomer layer 20. Moreover, since the conductive elastomer layer 20 is laminated on the insulating elastomer layer 10, it is possible to improve the durability even during elongation.

The state in which the insulating elastomer layer 10 and the conductive elastomer layer 20 are laminated in the yarn 50 means that the layers are in surface contact with each other and are chemically and / or physically bonded and in close contact with each other. There may be. Therefore, the yarn 50 can suppress the possibility of breakage such as peeling between the insulating elastomer layer 10 and the conductive elastomer layer 20 even during stretching or repeated stretching. Therefore, it is possible to realize the stretchable conductive yarn 100 having highly reliable extension electrical characteristics.

The inside of the conductive tube structure of the thread 50 may be provided with one or two or more through holes (holes 30) penetrating both ends of the thread 50. This makes it possible to increase the ease of elongation of the thread 50 with respect to external stress.

Next, a modification of the structure of the stretchable conductive thread 100 will be described.
FIG. 2 is a cross-sectional view showing an example of a modification of the stretchable conductive yarn 100.

The yarn in the stretchable conductive yarn may have at least one of an insulating tube structure including an insulating elastomer layer and a conductive tube structure including a conductive elastomer layer. The yarn may be composed of a multi-layer tube structure, may have one or more insulating tube structures inside, and / or have one or more conductive tube structures. You may.

The threads 50, 51, 52 of FIG. 2 have an insulating tube structure containing the insulating elastomer layers 10, 11, 12, respectively. Further, each of the threads 50, 51, 52, and 53 in FIG. 2 has a conductive tube structure including the conductive elastomer layers 20, 21, 22, 23, 24, respectively. The conductive tube structure having two or more layers enables multi-layer wiring of yarn.

The yarn in the stretchable conductive yarn may be provided with either an insulating tube structure or a conductive tube structure on the outermost layer of the yarn.

The threads 50, 51, and 53 of FIG. 2 have a conductive tube structure in the outermost layer. The conductive elastomer layers 20, 21 and 24 in the conductive tube structure provided on the outermost layer can realize a structure that can be easily connected to the outside.
The thread 52 of FIG. 2 has an insulating tube structure in the outermost layer. The insulating elastomer layer 12 in the insulating tube structure provided on the outermost layer functions as a protective member for protecting the conductive elastomer layer 23 provided on the inner side.

The yarn in the stretchable conductive yarn may have at least one of an insulating tube structure including an insulating elastomer layer and a solid insulating core structure including an insulating elastomer layer.

The threads 50, 51, 52 of FIG. 2 have an insulating tube structure containing the insulating elastomer layers 10, 11, 12, respectively. The insulating tube structure makes it possible to increase the ease of elongation of the yarn against external stress.
The thread 53 of FIG. 2 has a solid insulating core structure including an insulating elastomer layer 13. The insulating core structure makes it possible to increase the mechanical strength of the yarn.

The yarn in the stretchable conductive yarn comprises an insulating tube structure and a conductive elastomer layer configured to cover at least one surface on the outer surface and the inner surface of the insulating tube structure. It may have a sex tube structure. Further, the thread in the stretchable conductive thread has an insulating core structure and a conductive tube structure including a conductive elastomer layer configured to cover the outer surface of the insulating core structure. You may.

The thread 50 of FIG. 2 has an insulating tube structure including an insulating elastomer layer 10 and a conductive elastomer layer 20 configured to cover at least a part of a surface on the outer surface of the insulating tube structure. It comprises a conductive tube structure including.
The thread 51 of FIG. 2 is configured to cover at least a part of the insulating tube structure including the insulating elastomer layer 11 and each surface on the outer surface and the inner surface of the insulating tube structure. The conductive tube structure including the conductive elastomer layers 21 and 22 is provided.
The thread 52 of FIG. 2 has an insulating tube structure including an insulating elastomer layer 12 and a conductive elastomer layer 23 configured to cover at least a part of a surface on the inner surface of the insulating tube structure. It comprises a conductive tube structure including.
The thread 53 of FIG. 2 includes a solid insulating core structure including the insulating elastomer layer 13 and a conductive elastomer layer 24 configured to cover the outer surface of the insulating core structure. It has a tube structure and.

In the present specification, in a state where the conductive elastomer layer laminated on the insulating elastomer layer covers at least one surface of the outer surface and / or the inner surface of the insulating elastomer layer, coating is at least a part of the surface. Or it means a state that covers the entire surface.

The conductive elastomer layer may be composed of a tube structure in the same layer, but is not limited to this, and may have various shapes. The conductive elastomer layer will be described in detail later, but since it is formed by a coating means such as printing using a conductive filler, it can be formed in various wiring patterns such as linear and wavy.

Further, the conductive elastomer layer in the same layer may be composed of one integrated member, or may be composed of a plurality of members separated from each other. When the plurality of members include, for example, a first conductive elastomer layer and a second conductive elastomer layer, a gap may be formed between them, but insulation such as a material constituting the insulating elastomer layer may be formed between them. It may be filled with an elastomer. This makes it possible to form two or more wiring patterns in the same layer of conductive elastomer layers.

The conductive elastomer layer in the yarn may be composed of a single layer, or two or three or more layers. In the case of a multi-layer structure, an insulating elastomer layer or another layer may be formed between the layers.

The stretchable conductive yarn may be composed of one linear yarn (conductive yarn), or may be composed of a twisted yarn obtained by twisting a plurality of linear yarns (conductive yarn).

Next, the materials and properties constituting the stretchable conductive yarn 100 will be described.

The insulating elastomer layer may be composed of an insulating elastomer, and is composed of a thermosetting elastomer such as, for example, silicone rubber, urethane rubber, fluororubber, nitrile rubber, acrylic rubber, styrene rubber, chloroprene rubber, ethylene propylene rubber and the like. May be done. Among these, as the elastomer, one or more thermosetting elastomers selected from the group consisting of silicone rubber, urethane rubber, and fluororubber may be used. Preferably, the insulating elastomer layer may be made of silicone rubber. Silicone rubber is chemically stable among elastomers and has excellent mechanical strength.

The insulating elastomer layer may contain a non-conductive filler. This enhances the mechanical properties of the conductive elastomer layer. As the non-conductive filler, known materials can be used, but for example, silica particles, silicone rubber particles, talc and the like may be used.

The conductive elastomer layer may be composed of a conductive elastomer, and is conductive with a thermosetting elastomer such as silicone rubber, urethane rubber, fluororubber, nitrile rubber, acrylic rubber, styrene rubber, chloroprene rubber, or ethylene propylene rubber. It may be configured to include a sex filler. Among these, as the elastomer, one or more thermosetting elastomers selected from the group consisting of silicone rubber, urethane rubber, and fluororubber may be used. Among these, the conductive elastomer layer may be configured to contain silicone rubber. As a result, the elasticity and conductivity of the conductive elastomer layer can be enhanced.
The conductive elastomer layer may contain a non-conductive filler as well as a conductive filler. This makes it possible to increase the durability of expansion and contraction.

Examples of the conductive filler include powdery or fibrous metal-based fillers, carbon-based fillers, metal oxide fillers, metal-plated fillers and the like. Among these, as the conductive filler, a metal-based filler, preferably silver powder, may be used.

The insulating elastomer layer and the conductive elastomer layer may be configured to contain the same thermosetting elastomer.

In the present specification, the inclusion of the same thermosetting elastomer means to include at least one or more of the same types of elastomers among the types of thermosetting elastomers exemplified above.

Hereinafter, the components of the silicone rubber-based curable composition will be described in detail.

The insulating elastomer layer and the conductive elastomer layer may be configured to contain the same silicone rubber.

In the present specification, the inclusion of the same silicone rubber means that the silicone rubber-based curable composition contains at least the same kind of vinyl group-containing linear organopolysiloxane, and further, the same kind of cross-linking agent. It may contain one or more selected from the group consisting of the same type of non-conductive filler, the same type of silane coupling agent, and the same type of catalyst.

The insulating elastomer may be composed of a cured product of a silicone rubber-based curable composition containing a vinyl group-containing organopolysiloxane.
Further, the conductive elastomer may be composed of a conductive filler and a cured product of a silicone rubber-based curable composition containing a vinyl group-containing organopolysiloxane.

The vinyl group-containing linear organopolysiloxane of the same type may contain at least the same vinyl group as the functional group and may have a linearity, and the vinyl group amount, the molecular weight distribution, or the addition amount thereof in the molecule may be. It may be different.

The cross-linking agent of the same type may have at least a common structure such as a linear structure or a branched structure, may contain a molecular weight distribution in the molecule or a different functional group, and the addition amount thereof is different. You may.

The non-conductive fillers of the same type may have at least a common constituent material, and may differ in particle size, specific surface area, surface treatment agent, or addition amount thereof.

The silane coupling agent of the same type may have at least a common functional group, and other functional groups in the molecule and the amount added may be different.

The catalysts of the same type may have at least a common constituent material, and the catalysts may contain different compositions or may have different addition amounts.

The silicone rubber-based curable composition constituting the same silicone rubber further comprises different types of vinyl group-containing linear organopolysiloxanes, cross-linking agents, non-conductive fillers, silane coupling agents, and catalysts. It may contain one or more selected from the group.

The silicone rubber-based curable composition of the present embodiment can contain a vinyl group-containing organopolysiloxane (A). The vinyl group-containing organopolysiloxane (A) is a polymer which is a main component of the silicone rubber-based curable composition of the present embodiment.

The vinyl group-containing organopolysiloxane (A) can include a vinyl group-containing linear organopolysiloxane (A1) having a linear structure.

The vinyl group-containing linear organopolysiloxane (A1) has a linear structure and contains a vinyl group, and the vinyl group serves as a cross-linking point at the time of curing.

The content of the vinyl group of the vinyl group-containing linear organopolysiloxane (A1) is not particularly limited, but is preferably, for example, having two or more vinyl groups in the molecule and 15 mol% or less. .. As a result, the amount of vinyl groups in the vinyl group-containing linear organopolysiloxane (A1) is optimized, and a network with each component described later can be reliably formed.

In the present specification, the vinyl group content is the mol% of the vinyl group-containing siloxane unit when all the units constituting the vinyl group-containing linear organopolysiloxane (A1) are 100 mol%. .. However, it is considered that there is one vinyl group for each vinyl group-containing siloxane unit.

The degree of polymerization of the vinyl group-containing linear organopolysiloxane (A1) is not particularly limited, but is preferably in the range of, for example, preferably about 1000 to 10000, and more preferably about 2000 to 5000. The degree of polymerization can be determined, for example, as a polystyrene-equivalent number average degree of polymerization (or number average molecular weight) in GPC (gel permeation chromatography) using chloroform as a developing solvent.

In the present specification, "to" means that an upper limit value and a lower limit value are included unless otherwise specified.

Further, the specific gravity of the vinyl group-containing linear organopolysiloxane (A1) is not particularly limited, but is preferably in the range of about 0.9 to 1.1.

By using a vinyl group-containing linear organopolysiloxane (A1) having a degree of polymerization and specific gravity within the above range, the silicone rubber obtained has heat resistance, flame retardancy, chemical stability, etc. Can be improved.

The vinyl group-containing linear organopolysiloxane (A1) preferably has a structure represented by the following formula (1).

In formula (1), R ¹ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, an aryl group, or a hydrocarbon group in which these are combined. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group and the like, and among them, a methyl group is preferable. Examples of the alkenyl group having 1 to 10 carbon atoms include a vinyl group, an allyl group, a butenyl group and the like, and among them, a vinyl group is preferable. Examples of the aryl group having 1 to 10 carbon atoms include a phenyl group and the like.

Further, R ² is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, an aryl group, or a hydrocarbon group in which these are combined. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group and the like, and among them, a methyl group is preferable. Examples of the alkenyl group having 1 to 10 carbon atoms include a vinyl group, an allyl group, and a butenyl group. Examples of the aryl group having 1 to 10 carbon atoms include a phenyl group.

Further, R ³ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an aryl group, or a hydrocarbon group in which these are combined. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group and the like, and among them, a methyl group is preferable. Examples of the aryl group having 1 to 8 carbon atoms include a phenyl group.

Further, examples of the substituent of R ¹ and R ² in the formula (1) include a methyl group, a vinyl group and the like, and examples of the substituent of R ³ include a methyl group and the like.

In the equation (1), the plurality of R ^1s are independent of each other and may be different from each other or may be the same. The same applies to R ² and R ³ .

Further, m and n are the number of repeating units constituting the vinyl group-containing linear organopolysiloxane (A1) represented by the formula (1), m is an integer of 0 to 2000, and n is 1000 to 10000. Is an integer of. m is preferably 0 to 1000, and n is preferably 2000 to 5000.

Moreover, as a specific structure of the vinyl group-containing linear organopolysiloxane (A1) represented by the formula (1), for example, the one represented by the following formula (1-1) can be mentioned.

In formula (1-1), R ¹ and R ² are each independently a methyl group or a vinyl group, and at least one of them is a vinyl group.

The vinyl group-containing linear organopolysiloxane (A1) is a first vinyl group-containing linear siloxane having a vinyl group content of 2 or more in the molecule and 0.4 mol% or less. Organopolysiloxane (A1-1) may be included. The vinyl group amount of the first vinyl group-containing linear organopolysiloxane (A1-1) may be 0.1 mol% or less.

The vinyl group-containing linear organopolysiloxane (A1) has a vinyl group content of 0.5 to 15 mol% with the first vinyl group-containing linear organopolysiloxane (A1-1). May contain a vinyl group-containing linear organopolysiloxane (A1-2).

As raw rubber which is a raw material of silicone rubber, a first vinyl group-containing linear organopolysiloxane (A1-1) and a second vinyl group-containing linear organopolysiloxane (A1-2) having a high vinyl group content are used. ), The vinyl groups can be unevenly distributed, and the cross-linking density can be more effectively formed in the cross-linking network of the silicone rubber. As a result, the tear strength of the silicone rubber can be increased more effectively.

Specifically, as the vinyl group-containing linear organopolysiloxane (A1), for example, in the above formula (1-1), a unit in which R1 is a vinyl group and / or a unit in which R2 is a vinyl group is a molecule. A first vinyl group-containing linear organopolysiloxane (A1-1) having two or more of them and containing 0.4 mol% or less, and a unit in which R1 is a vinyl group and / or R2 is a vinyl group. It is preferable to use a second vinyl group-containing linear organopolysiloxane (A1-2) containing 0.5 to 15 mol% as the unit.

Further, the first vinyl group-containing linear organopolysiloxane (A1-1) preferably has a vinyl group content of 0.01 to 0.2 mol%. Further, the vinyl group-containing linear organopolysiloxane (A1-2) preferably has a vinyl group content of 0.8 to 12 mol%.

Further, when the first vinyl group-containing linear organopolysiloxane (A1-1) and the second vinyl group-containing linear organopolysiloxane (A1-2) are blended in combination (A1-1). The ratio of and (A1-2) is not particularly limited, but for example, the weight ratio of (A1-1) :( A1-2) is preferably 50:50 to 95: 5, and 80:20 to 90: It is more preferably 10.

The first and second vinyl group-containing linear organopolysiloxanes (A1-1) and (A1-2) may be used alone or in combination of two or more. good.

Further, the vinyl group-containing organopolysiloxane (A) may contain a vinyl group-containing branched organopolysiloxane (A2) having a branched structure.

<< Organohydrogen Polysiloxane (B) >>
The silicone rubber-based curable composition of the present embodiment can contain organohydrogenpolysiloxane (B).
The organohydrogenpolysiloxane (B) is classified into a linear organohydrogenpolysiloxane (B1) having a linear structure and a branched organohydrogenpolysiloxane (B2) having a branched structure. Either one or both can be included.

The linear organohydrogenpolysiloxane (B1) has a linear structure and a structure (≡Si—H) in which hydrogen is directly bonded to Si, and is a vinyl group-containing organopolysiloxane (A). In addition to the vinyl group, it is a polymer that undergoes a hydrosilylation reaction with the vinyl group contained in the components contained in the silicone rubber-based curable composition to crosslink these components.

The molecular weight of the linear organohydrogenpolysiloxane (B1) is not particularly limited, but for example, the weight average molecular weight is preferably 20000 or less, and more preferably 1000 or more and 10000 or less.

The weight average molecular weight of the linear organohydrogenpolysiloxane (B1) can be measured, for example, by polystyrene conversion in GPC (gel permeation chromatography) using chloroform as a developing solvent.

Further, the linear organohydrogenpolysiloxane (B1) is usually preferably one having no vinyl group. This makes it possible to accurately prevent the cross-linking reaction from proceeding in the molecule of the linear organohydrogenpolysiloxane (B1).

As the linear organohydrogenpolysiloxane (B1) as described above, for example, one having a structure represented by the following formula (2) is preferably used.

In formula (2), ^R4 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, an aryl group, a hydrocarbon group combining these, or a hydride group. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group and the like, and among them, a methyl group is preferable. Examples of the alkenyl group having 1 to 10 carbon atoms include a vinyl group, an allyl group, a butenyl group and the like. Examples of the aryl group having 1 to 10 carbon atoms include a phenyl group.

Further, R5 is a substituted or unsubstituted alkyl group having 1 to ¹⁰ carbon atoms, an alkenyl group, an aryl group, a hydrocarbon group combining these, or a hydride group. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group and a propyl group, and among them, a methyl group is preferable. Examples of the alkenyl group having 1 to 10 carbon atoms include a vinyl group, an allyl group, a butenyl group and the like. Examples of the aryl group having 1 to 10 carbon atoms include a phenyl group.

In the equation (2), the plurality of R ^4s are independent of each other and may be different from each other or may be the same. The ^same applies to R5. However, of the plurality of ^R4 and R5, at ^least two or more are hydride groups.

Further, R ⁶ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an aryl group, or a hydrocarbon group in which these are combined. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group and the like, and among them, a methyl group is preferable. Examples of the aryl group having 1 to 8 carbon atoms include a phenyl group. The plurality of ^R6s are independent of each other and may be different from each other or may be the same.

Examples of the substituent of R ⁴ , R ⁵ , and R ⁶ in the formula (2) include a methyl group and a vinyl group, and a methyl group is preferable from the viewpoint of preventing an intramolecular cross-linking reaction.

Further, m and n are the number of repeating units constituting the linear organohydrogenpolysiloxane (B1) represented by the formula (2), where m is an integer of 2 to 150 and n is an integer of 2 to 150. Is. Preferably, m is an integer of 2 to 100 and n is an integer of 2 to 100.

The linear organohydrogenpolysiloxane (B1) may be used alone or in combination of two or more.

Since the branched organohydrogenpolysiloxane (B2) has a branched structure, it forms a region having a high crosslink density and is a component that greatly contributes to the formation of a dense structure having a crosslink density in the silicone rubber system. Further, like the linear organohydrogenpolysiloxane (B1), it has a structure (≡Si—H) in which hydrogen is directly bonded to Si, and in addition to the vinyl group of the vinyl group-containing organopolysiloxane (A), silicone. It is a polymer that hydrosilylates with the vinyl group of the component contained in the rubber-based curable composition and crosslinks these components.

The specific gravity of the branched organohydrogenpolysiloxane (B2) is in the range of 0.9 to 0.95.

Further, the branched organohydrogenpolysiloxane (B2) is usually preferably one having no vinyl group. This makes it possible to accurately prevent the cross-linking reaction from proceeding in the molecule of the branched organohydrogenpolysiloxane (B2).

The branched organohydrogenpolysiloxane (B2) is preferably represented by the following average composition formula (c).

Average composition formula (c)
(H _a (R ⁷ ) _3-a SiO _1/2 ) _m (SiO _4/2 ) _n
(In the formula (c), R ⁷ is a monovalent organic group, a is an integer in the range of 1 to 3, m is _a number of Ha (R ⁷ ) _3-a SiO _1/2 units, and n is SiO _{4 /.} It is a number of ₂ units)

In formula (c), R ⁷ is a monovalent organic group, preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group, or a hydrocarbon group in combination thereof. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group and the like, and among them, a methyl group is preferable. Examples of the aryl group having 1 to 10 carbon atoms include a phenyl group.

In the formula (c), a is the number of hydride groups (hydrogen atoms directly bonded to Si), and is an integer in the range of 1 to 3, preferably 1.

Further, in the formula ( _c ), m is the number of Ha (R ⁷ ) _3-a SiO _1/2 unit, and n is the number of SiO _4/2 unit.

The branched organohydrogenpolysiloxane (B2) has a branched structure. The linear organohydrogenpolysiloxane (B1) and the branched organohydrogenpolysiloxane (B2) differ in that their structure is linear or branched, and the Si is the same as when the number of Si is 1. The number of alkyl groups R to be bonded (R / Si) is 1.8 to 2.1 for the linear organohydrogenpolysiloxane (B1) and 0.8 to 1 for the branched organohydrogenpolysiloxane (B2). It is in the range of 0.7.

Since the branched organohydrogenpolysiloxane (B2) has a branched structure, for example, the residual amount when heated to 1000 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere is 5% or more. Will be. On the other hand, since the linear organohydrogenpolysiloxane (B1) is linear, the amount of residue after heating under the above conditions is almost zero.

Further, specific examples of the branched organohydrogenpolysiloxane (B2) include those having a structure represented by the following formula (3).

In formula (3), R ⁷ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an aryl group, or a hydrocarbon group in combination thereof, or a hydrogen atom. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group and the like, and among them, a methyl group is preferable. Examples of the aryl group having 1 to 8 carbon atoms include a phenyl group. Examples of the substituent of R ⁷ include a methyl group and the like.

In the equation (3), the plurality of R ^7s are independent of each other and may be different from each other or may be the same.

Further, in the equation (3), "-O-Si≡" indicates that Si has a branched structure that spreads three-dimensionally.

The branched organohydrogenpolysiloxane (B2) may be used alone or in combination of two or more.

Further, in the linear organohydrogenpolysiloxane (B1) and the branched organohydrogenpolysiloxane (B2), the amount of hydrogen atoms (hydride groups) directly bonded to Si is not particularly limited. However, in the silicone rubber-based curable composition, the linear organohydrogenpolysiloxane (B1) and the branched organohydrogenpoly are added to 1 mol of the vinyl group in the vinyl group-containing linear organopolysiloxane (A1). The total amount of hydride groups of siloxane (B2) is preferably 0.5 to 5 mol, more preferably 1 to 3.5 mol. This ensures that a crosslinked network is formed between the linear organohydrogenpolysiloxane (B1) and the branched organohydrogenpolysiloxane (B2) and the vinyl group-containing linear organopolysiloxane (A1). Can be made to.

<< Silica particles (C) >>
The silicone rubber-based curable composition of the present embodiment may contain silica particles (C) as a non-conductive filler, if necessary.

The silica particles (C) are not particularly limited, but for example, fumed silica, calcined silica, precipitated silica and the like are used. These may be used alone or in combination of two or more.

For example, the specific surface area of the silica particles (C) by the BET method is preferably, for example, 50 to 400 m ² / g, and more preferably 100 to 400 m ² / g. The average primary particle size of the silica particles (C) is preferably, for example, 1 to 100 nm, and more preferably about 5 to 20 nm.

By using the silica particles (C) within the range of the specific surface area and the average particle size, it is possible to improve the hardness and mechanical strength of the formed silicone rubber, particularly the tensile strength.

<< Silane Coupling Agent (D) >>
The silicone rubber-based curable composition of the present embodiment can contain a silane coupling agent (D).
The silane coupling agent (D) can have a hydrolyzable group. The hydrolyzing group is hydrolyzed by water to become a hydroxyl group, and this hydroxyl group undergoes a dehydration condensation reaction with the hydroxyl group on the surface of the silica particles (C), whereby the surface of the silica particles (C) can be modified.

Further, the silane coupling agent (D) can include a silane coupling agent having a hydrophobic group. As a result, this hydrophobic group is imparted to the surface of the silica particles (C), so that the cohesive force of the silica particles (C) is reduced in the silicone rubber-based curable composition and thus in the silicone rubber (hydrogen due to the silanol group). Aggregation due to bonding is reduced), and as a result, it is presumed that the dispersibility of the silica particles in the silicone rubber-based curable composition is improved. As a result, the interface between the silica particles and the rubber matrix increases, and the reinforcing effect of the silica particles increases. Further, it is presumed that the slipperiness of the silica particles in the matrix is improved when the rubber matrix is deformed. Then, by improving the dispersibility and slipperiness of the silica particles (C), the mechanical strength (for example, tensile strength, tear strength, etc.) of the silicone rubber due to the silica particles (C) is improved.

Further, the silane coupling agent (D) can include a silane coupling agent having a vinyl group. As a result, a vinyl group is introduced on the surface of the silica particles (C). Therefore, when the silicone rubber-based curable composition is cured, that is, the vinyl group of the vinyl group-containing organopolysiloxane (A) and the hydride group of the organohydrogenpolysiloxane (B) undergo a hydrosilylation reaction. When the network (crosslinked structure) formed by these is formed, the vinyl group of the silica particles (C) is also involved in the hydrosilylation reaction with the hydride group of the organohydrogenpolysiloxane (B). Silica particles (C) will also be incorporated into. As a result, it is possible to reduce the hardness and increase the modulus of the formed silicone rubber.

As the silane coupling agent (D), a silane coupling agent having a hydrophobic group and a silane coupling agent having a vinyl group can be used in combination.

Examples of the silane coupling agent (D) include those represented by the following formula (4).

Y _n -Si- (X) _4-n ... (4)
In the above equation (4), n represents an integer of 1 to 3. Y represents any functional group having a hydrophobic group, a hydrophilic group or a vinyl group, and when n is 1, it is a hydrophobic group, and when n is 2 or 3, at least one of them is. It is a hydrophobic group. X represents a hydrolyzable group.

The hydrophobic group is an alkyl group having 1 to 6 carbon atoms, an aryl group, or a hydrocarbon group in which these are combined, and examples thereof include a methyl group, an ethyl group, a propyl group, a phenyl group, and the like. Methyl groups are preferred.

Examples of the hydrophilic group include a hydroxyl group, a sulfonic acid group, a carboxyl group, a carbonyl group and the like, and a hydroxyl group is particularly preferable. The hydrophilic group may be contained as a functional group, but is preferably not contained from the viewpoint of imparting hydrophobicity to the silane coupling agent (D).

Further, examples of the hydrolyzable group include an alkoxy group such as a methoxy group and an ethoxy group, a chloro group or a silazane group, and among them, a silazane group is preferable because it has high reactivity with the silica particles (C). Those having a silazane group as a hydrolyzable group have two structures of ( _Yn —Si—) in the above formula (4) due to their structural characteristics.

Specific examples of the silane coupling agent (D) represented by the above formula (4) include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, and methyltri, as those having a hydrophobic group as a functional group. Alkoxysilanes such as ethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane; methyltrichlorosilane , Chlorosilanes such as dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane; hexamethyldisilazane, examples of which have a vinyl group as a functional group include methacrypropyltriethoxysilane, methacrypropyltrimethoxysilane, methacryoxy. Ekalkylsilanes such as propylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane; chlorosilanes such as vinyltrichlorosilane, vinylmethyldichlorosilane; divinyltetramethyldi Examples thereof include silazanes, but in consideration of the above description, hexamethyldisilazane is particularly preferable as having a hydrophobic group, and divinyltetramethyldisilazane is preferable as having a vinyl group.

In the present embodiment, the lower limit of the content of the silane coupling agent (D) is preferably 1% by mass or more with respect to 100 parts by weight of the total amount of the vinyl group-containing organopolysiloxane (A). It is more preferably 5% by mass or more, and further preferably 5% by mass or more. The upper limit of the content of the silane coupling agent (D) is preferably 100% by mass or less, preferably 80% by mass or less, based on 100 parts by mass of the total amount of the vinyl group-containing organopolysiloxane (A). It is more preferably present, and further preferably 40% by mass or less.
By setting the content of the silane coupling agent (D) to the above lower limit value or more, the silicone rubber has an appropriate adhesion to the substrate, and when the silica particles (C) are used, the silicone rubber as a whole It can contribute to the improvement of the mechanical strength of. Further, by setting the content of the silane coupling agent (D) to the above upper limit value or less, the silicone rubber can have appropriate mechanical properties.

<< Platinum or platinum compound (E) >>
The silicone rubber-based curable composition of the present embodiment can contain platinum or a platinum compound (E).
Platinum or the platinum compound (E) is a catalytic component that acts as a catalyst during curing. The amount of platinum or the platinum compound (E) added is the amount of the catalyst.

As the platinum or the platinum compound (E), known ones can be used, for example, platinum black, platinum supported on silica, carbon black or the like, platinum chloride acid or an alcohol solution of platinum chloride acid, chloride. Examples thereof include a complex salt of platinum acid and olefin, and a complex salt of platinum chloride acid and vinyl siloxane.

As the platinum or the platinum compound (E), only one type may be used alone, or two or more types may be used in combination.

<< Water (F) >>
Further, the silicone rubber-based curable composition of the present embodiment may contain water (F) in addition to the above components (A) to (E).

Water (F) functions as a dispersion medium for dispersing each component contained in the silicone rubber-based curable composition, and is a component that contributes to the reaction between the silica particles (C) and the silane coupling agent (D). .. Therefore, in the silicone rubber, the silica particles (C) and the silane coupling agent (D) can be more reliably connected to each other, and uniform characteristics can be exhibited as a whole.

Further, when water (F) is contained, the content thereof can be appropriately set, but specifically, for example, 10 to 100 parts by weight with respect to 100 parts by weight of the silane coupling agent (D). It is preferably in the range of 30 to 70 parts by weight, and more preferably in the range of 30 to 70 parts by weight. This makes it possible to more reliably proceed the reaction between the silane coupling agent (D) and the silica particles (C).

(Other ingredients)
Further, the silicone rubber-based curable composition of the present embodiment may further contain other components in addition to the above components (A) to (F). Other components include silica particles (C) such as diatomaceous earth, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, cerium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, glass wool, and mica. Examples thereof include additives such as inorganic fillers, reaction inhibitors, dispersants, pigments, dyes, antioxidants, antioxidants, flame retardants, and thermal conductivity improvers.

In the silicone rubber-based curable composition, the content ratio of each component is not particularly limited, but is set as follows, for example.

In the present embodiment, the upper limit of the content of the silica particles (C) may be, for example, 60 parts by weight or less, preferably 50 parts by weight, based on 100 parts by weight of the total amount of the vinyl group-containing organopolysiloxane (A). The following may be used, and more preferably 40 parts by weight or less. This makes it possible to balance mechanical strength such as hardness and tensile strength. The lower limit of the content of the silica particles (C) is not particularly limited with respect to 100 parts by weight of the total amount of the vinyl group-containing organopolysiloxane (A), but may be, for example, 10 parts by weight or more.

The silane coupling agent (D) is preferably contained in a proportion of, for example, 5 parts by weight or more and 100 parts by weight or less of the vinyl group-containing organopolysiloxane (A) with respect to 100 parts by weight. More preferably, it is contained in a proportion of 5 parts by weight or more and 40 parts by weight or less. Thereby, the dispersibility of the silica particles (C) in the silicone rubber-based curable composition can be surely improved.

The content of the organohydrogenpolysiloxane (B) is specifically, for example, with respect to 100 parts by weight of the total amount of the vinyl group-containing organopolysiloxane (A), the silica particles (C) and the silane coupling agent (D). , 0.5 part by weight or more and preferably 20 parts by weight or less, and more preferably 0.8 parts by weight or more and 15 parts by weight or less. When the content of (B) is within the above range, a more effective curing reaction may be possible.

The content of platinum or the platinum compound (E) means the amount of catalyst and can be appropriately set, but specifically, vinyl group-containing organopolysiloxane (A), silica particles (C), and silane coupling agent ( The amount of the platinum group metal in this component is 0.01 to 1000 ppm by weight, preferably 0.1 to 500 ppm, based on the total amount of D). By setting the content of platinum or the platinum compound (E) to the above lower limit value or more, the obtained silicone rubber composition can be sufficiently cured. By setting the content of platinum or the platinum compound (E) to the above upper limit value or less, the curing rate of the obtained silicone rubber composition can be improved.

Further, when water (F) is contained, the content thereof can be appropriately set, but specifically, for example, 10 to 100 parts by weight with respect to 100 parts by weight of the silane coupling agent (D). It is preferably in the range of 30 to 70 parts by weight, and more preferably in the range of 30 to 70 parts by weight. This makes it possible to more reliably proceed the reaction between the silane coupling agent (D) and the silica particles (C).

<Manufacturing method of silicone rubber>
Next, a method for manufacturing the silicone rubber of the present embodiment will be described.
As a method for producing a silicone rubber of the present embodiment, a silicone rubber-based curable composition can be prepared, and the silicone rubber-based curable composition can be cured to obtain a silicone rubber.
The details will be described below.

First, each component of the silicone rubber-based curable composition is uniformly mixed by an arbitrary kneading device to prepare a silicone rubber-based curable composition.

[1] For example, a vinyl group-containing organopolysiloxane (A), silica particles (C), and a silane coupling agent (D) are weighed in a predetermined amount and then kneaded by an arbitrary kneading device. A kneaded product containing each of these components (A), (C) and (D) is obtained.

The kneaded product is preferably obtained by kneading the vinyl group-containing organopolysiloxane (A) and the silane coupling agent (D) in advance, and then kneading (mixing) the silica particles (C). This further improves the dispersibility of the silica particles (C) in the vinyl group-containing organopolysiloxane (A).

Further, when obtaining this kneaded product, water (F) may be added to the kneaded product of each component (A), (C), and (D) as needed. This makes it possible to more reliably proceed the reaction between the silane coupling agent (D) and the silica particles (C).

Further, it is preferable that the kneading of each component (A), (C), and (D) goes through a first step of heating at the first temperature and a second step of heating at the second temperature. Thereby, in the first step, the surface of the silica particles (C) can be surface-treated with the coupling agent (D), and in the second step, the silica particles (C) and the coupling agent (D) are combined. By-products produced by the reaction can be reliably removed from the kneaded product. Then, if necessary, the component (A) may be added to the obtained kneaded product and further kneaded. This makes it possible to improve the familiarity of the components of the kneaded product.

The first temperature is preferably, for example, about 40 to 120 ° C., and more preferably about 60 to 90 ° C., for example. The second temperature is, for example, preferably about 130 to 210 ° C, more preferably about 160 to 180 ° C.

Further, the atmosphere in the first step is preferably under an inert atmosphere such as under a nitrogen atmosphere, and the atmosphere in the second step is preferably under a reduced pressure atmosphere.

Further, the time of the first step is preferably, for example, about 0.3 to 1.5 hours, and more preferably about 0.5 to 1.2 hours. The time of the second step is, for example, preferably about 0.7 to 3.0 hours, and more preferably about 1.0 to 2.0 hours.

By setting the first step and the second step under the above-mentioned conditions, the above-mentioned effect can be obtained more remarkably.

[2] Next, the organohydrogenpolysiloxane (B) and platinum or the platinum compound (E) are weighed in a predetermined amount, and then the kneaded product prepared in the above step [1] using an arbitrary kneading device. By kneading each component (B) and (E), a silicone rubber-based curable composition is obtained. The obtained silicone rubber-based curable composition may be a paste containing a solvent.

When kneading the respective components (B) and (E), the kneaded product previously prepared in the above step [1] and the organohydrogenpolysiloxane (B) were prepared in the above step [1]. It is preferable to knead the kneaded product with platinum or the platinum compound (E), and then knead the respective kneaded products. This ensures that each component (A) to (E) is contained in the silicone rubber-based curable composition without proceeding with the reaction between the vinyl group-containing organopolysiloxane (A) and the organohydrogenpolysiloxane (B). Can be dispersed in.

The temperature at which each component (B) and (E) is kneaded is preferably, for example, about 10 to 70 ° C., more preferably about 25 to 30 ° C. as the roll set temperature.

Further, the kneading time is preferably, for example, about 5 minutes to 1 hour, and more preferably about 10 to 40 minutes.

By setting the temperature within the above range in the above step [1] and the above step [2], the progress of the reaction between the vinyl group-containing organopolysiloxane (A) and the organohydrogenpolysiloxane (B) is more accurately performed. Can be prevented or suppressed. Further, in the above steps [1] and the above steps [2], by setting the kneading time within the above range, each component (A) to (E) is more reliably dispersed in the silicone rubber-based curable composition. Can be done.

The kneading device used in each of the steps [1] and [2] is not particularly limited, and for example, a kneader, a two-roll, a Banbury mixer (continuous kneader), a pressurized kneader, or the like can be used.

Further, in this step [2], a reaction inhibitor such as 1-ethynylcyclohexanol may be added to the kneaded product. As a result, even if the temperature of the kneaded product is set to a relatively high temperature, the progress of the reaction between the vinyl group-containing organopolysiloxane (A) and the organohydrogenpolysiloxane (B) is more accurately prevented or suppressed. be able to.

[3] Next, the silicone rubber is formed by curing the silicone rubber-based curable composition.

In the present embodiment, the curing step of the silicone rubber-based curable resin composition is, for example, heating (primary curing) at 100 to 250 ° C. for 1 to 30 minutes and then post-baking (secondary) at 200 ° C. for 1 to 4 hours. It is done by curing).

Through the above steps, a silicone rubber made of a cured product of a silicone rubber-based curable resin composition can be obtained.

[3] Next, the insulating paste can be obtained by dissolving the silicone rubber-based curable composition obtained in the step [2] in a solvent.
Further, [3] Next, the silicone rubber-based curable composition obtained in the step [2] is dissolved in a solvent, and a conductive filler is added to obtain a conductive paste.

(Conductive filler)
As the conductive filler, a known conductive material may be used, but metal powder (G) may be used. ..
The metal constituting the metal powder (G) is not particularly limited, but for example, copper, silver, gold, nickel, tin, lead, zinc, bismuth, antimon, or at least one kind of metal powder alloyed with these. Alternatively, two or more of these can be included.
Of these, the metal powder (G) preferably contains silver or copper, that is, silver powder or copper powder, because of its high conductivity and high availability.
As these metal powders (G), those coated with other kinds of metals can also be used.

In the present embodiment, the shape of the metal powder (G) is not limited, but conventionally used metal powders (G) such as dendritic, spherical, and lint-like can be used. Among these, phosphorus flake-shaped metal powder (G) may be used.

Further, the particle size of the metal powder (G) is not limited, but for example, the average particle size _D50 is preferably 0.001 μm or more, more preferably 0.01 μm or more, still more preferably 0.1 μm or more. be. The particle size of the metal powder (G) is, for example, preferably 1,000 μm or less, more preferably 100 μm or less, and further preferably 20 μm or less with an average particle size _D50 .
By setting the average particle size D ₅₀ in such a range, it is possible to exhibit appropriate conductivity as a silicone rubber.
The particle size of the metal powder (G) is determined by, for example, observing a conductive paste or a silicone rubber formed by using the conductive paste with a transmission electron microscope or the like, performing image analysis, and arbitrarily selecting a metal. It can be defined as the average value of 200 pieces of flour.

The content of the conductive filler in the conductive paste is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more in 100% by mass of the conductive paste. More preferred. The content of the conductive filler in the conductive paste is preferably 85% by mass or less, more preferably 75% by mass or less, and 65% by mass or less in 100% by mass of the conductive paste. Is even more preferable.
By setting the content of the conductive filler to the above lower limit value or more, the silicone rubber can have an appropriate conductive property. Further, by setting the content of the conductive filler to the above upper limit value or less, the silicone rubber can have appropriate flexibility.

The lower limit of the content of the silica particles (C) in the conductive paste is, for example, 1% by mass or more, preferably 3% by mass or more, based on 100% by mass of the total amount of the silica particles (C) and the conductive filler. It is more preferably 5% by mass or more. Thereby, the mechanical strength of the silicone rubber can be improved. On the other hand, the upper limit of the content of the silica particles (C) in the conductive paste is preferably 20% by mass or less in the total amount of 100% by mass of the silica particles (C) and the conductive filler. Is 15% by mass or less, more preferably 10% by mass or less. This makes it possible to balance the elastic electrical characteristics and the mechanical strength of the silicone rubber.

The content of the silicone rubber-based curable composition in the conductive paste / insulating paste is preferably 1% by mass or more, preferably 3% by mass or more, based on 100% by mass of the conductive paste / insulating paste. Is more preferable, and 5% by mass or more is further preferable. The content of the silicone rubber-based curable composition in the conductive paste / insulating paste is preferably 25% by mass or less, preferably 20% by mass or less, based on 100% by mass of the conductive paste / insulating paste. It is more preferably present, and further preferably 15% by mass or less.
By setting the content of the silicone rubber-based curable composition to the above lower limit value or more, the silicone rubber can have appropriate flexibility. Further, by setting the content of the silicone rubber-based curable composition to the above upper limit value or less, the mechanical strength of the silicone rubber can be improved.

(solvent)
Conductive pastes and insulating pastes contain solvents.
As the solvent, various known solvents can be used, and for example, a high boiling point solvent can be included. These may be used alone or in combination of two or more.

The lower limit of the boiling point of the high boiling point solvent is, for example, 100 ° C. or higher, preferably 130 ° C. or higher, and more preferably 150 ° C. or higher. This makes it possible to improve printing stability such as screen printing. On the other hand, the upper limit of the boiling point of the high boiling point solvent is not particularly limited, but may be, for example, 300 ° C. or lower, 290 ° C. or lower, or 280 ° C. or lower. As a result, excessive heat history at the time of wiring formation can be suppressed, so that damage to the base and the shape of the wiring formed of the conductive paste can be maintained satisfactorily.

The solvent can be appropriately selected from the viewpoint of solubility and boiling point of the silicone rubber-based curable resin composition. For example, an aliphatic hydrocarbon having 5 or more and 20 or less carbon atoms, preferably 8 or more and 18 or less carbon atoms. It is possible to contain an aliphatic hydrocarbon of the above, more preferably an aliphatic hydrocarbon having 10 or more and 15 or less carbon atoms.

Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, methylcyclohexane, ethylcyclohexane, octane, decane, dodecane and tetradecane; benzene, toluene, ethylbenzene, xylene, mecitylene and tri. Aromatic hydrocarbons such as fluoromethylbenzene and benzotrifluoride; diethyl ether, diisopropyl ether, dibutyl ether, cyclopentylmethyl ether, cyclopentyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether, dipropylene Ethers such as glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran; dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1 , 1-Trichloroethane, haloalkanes such as 1,1,2-trichloroethane; carboxylic acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide; Esters and the like can be exemplified. These may be used alone or in combination of two or more.
The solvent used here may be appropriately selected from the solvents capable of uniformly dissolving or dispersing the composition components in the above conductive paste.

The upper limit of the polarity term (δ _p ) of the Hansen solubility parameter of the solvent is, for example, 10 MPa ^1/2 or less, preferably 7 MPa ^1/2 or less, and more preferably 5.5 MPa ^1/2 or less. It can contain a first solvent. This makes it possible to improve the dispersibility and solubility of the silicone rubber-based curable resin composition in the paste. The lower limit of the polarity term (δ _p ) of the first solvent is not particularly limited, but may be, for example, 0 Pa ^1/2 or more.

The upper limit of the hydrogen bond term (δ _h ) of the Hansen solubility parameter in the first solvent is, for example, 20 MPa ^1/2 or less, preferably 10 MPa ^1/2 or less, and more preferably 7 MPa ^1/2 or less. be. This makes it possible to improve the dispersibility and solubility of the silicone rubber-based curable resin composition in the paste. The lower limit of the hydrogen bond term (δ _h ) of the first solvent is not particularly limited, but may be, for example, 0 Pa ^1/2 or more.

The Hansen solubility parameter (HSP) is an indicator of how soluble a substance is in another substance. HSP represents solubility as a three-dimensional vector. This three-dimensional vector can be typically represented by a dispersion term (δ _d ), a polarity term (δ _p ), and a hydrogen bond term (δ _h ). And it can be judged that those having similar vectors have high solubility. It is possible to judge the similarity of vectors by the distance of Hansen solubility parameter (HSP distance).

The Hansen solubility parameter (HSP value) used in the present specification can be calculated using software called HSPiP (Hansen Solubility Parameter in Practice). Here, the computer software HSPiP developed by Hansen and Abbott includes a function to calculate the HSP distance and a database describing various resin and solvent or non-solvent Hansen parameters.
The solubility of each resin in a pure solvent and a mixed solvent of a good solvent and a poor solvent was investigated, and the results were input to the HSPiP software. Is calculated.

As the solvent of the present embodiment, for example, an elastomer or a solvent having a small difference in HSP distance, polarity term and hydrogen bond term between the constituent unit constituting the elastomer and the solvent can be selected.

The lower limit of the viscosity of the conductive paste and / or the insulating paste when measured at a room temperature of 25 ° C. and a shear rate of 20 [1 / s] is, for example, 1 Pa · s or more, preferably 5 Pa · s or more. , More preferably 10 Pa · s or more. Thereby, the film forming property can be improved. In addition, the shape retention can be improved even when a thick film is formed. On the other hand, the upper limit of the viscosity of the conductive paste and / or the insulating paste at room temperature of 25 ° C. is, for example, 100 Pa · s or less, preferably 90 Pa · s or less, and more preferably 80 Pa · s or less. .. Thereby, the printability in the paste can be improved.

At room temperature of 25 ° C., the viscosity measured at a shear rate of 1 [1 / s] is η1, the viscosity measured at a shear rate of 5 [1 / s] is η5, and the thixotropic index is the viscosity ratio (η1 / η5). ).
At this time, the lower limit of the thixotropic index of the conductive paste and / or the insulating paste is, for example, 1.0 or more, preferably 1.1 or more, and more preferably 1.2 or more. As a result, the shape of the wiring obtained by the printing method can be stably maintained. On the other hand, the upper limit of the thixotropic index of the conductive paste and / or the insulating paste is, for example, 3.0 or less, preferably 2.5 or less, and more preferably 2.0 or less. This makes it possible to improve the printability of the paste.

In the present embodiment, an insulating elastomer can be obtained by curing the above-mentioned silicone rubber-based curable composition.
Further, using the above-mentioned silicone rubber-based curable composition, an insulating elastomer having a tube structure or a solid core structure can be obtained by various molding methods such as extrusion molding and compression molding.
Further, an insulating elastomer can be obtained by forming a coating film using various coating means such as printing, spraying, and dipping with an insulating paste and drying the coating film.
Similar to the insulating paste, the conductive paste is used to form a coating film using various coating means such as printing, spraying, and dipping, and the coating film is dried to obtain a conductive elastomer.
These insulating elastomers and conductive elastomers can be used to form an insulating elastomer layer and a conductive elastomer layer.

As an example of the manufacturing process of the stretchable conductive yarn 100, for example, a silicone rubber-based curable composition is extruded into a tube shape using an extruder to form an insulating tube structure containing an insulating elastomer layer 10. obtain. By applying a conductive paste on the outer surface of the obtained insulating tube structure and drying it, a conductive tube structure containing the conductive elastomer layer 20 is formed on the outer surface of the insulating tube structure. The laminated threads 50 can be formed.
Further, as an example of the manufacturing process of the stretchable conductive yarn 100, an insulating tube structure including the insulating elastomer layer 12 is obtained by extrusion molding, and a conductive paste is applied to the inner holes of the obtained insulating tube structure. By applying and drying, a thread 52 in which the conductive tube structure including the conductive elastomer layer 23 is laminated can be formed on the inner surface of the insulating tube structure.

As described above, the conductive elastomer layer in the stretchable conductive yarn may be composed of a coating layer (conductive silicone rubber) made of a conductive paste. The pattern shape of the conductive elastomer layer can be freely selected. Further, when the insulating elastomer layer is composed of the cured product of the above-mentioned silicone rubber-based curable composition, the adhesion between the coating layer composed of the conductive paste and the insulating elastomer layer can be enhanced.

The lower limit of the content of the conductive filler in the yarn is, for example, 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more in 100% by mass of the conductive elastomer layer. As a result, the stretchable electrical characteristics of the stretchable conductive yarn can be enhanced. On the other hand, the upper limit of the content of the conductive filler in the yarn is, for example, 90% by mass or less, preferably 88% by mass or less, and more preferably 85% by mass or less in 100% by mass of the conductive elastomer layer. This makes it possible to suppress deterioration of rubber properties such as elasticity of the elastic conductive yarn.

The lower limit of the breaking strength of one yarn in the stretchable conductive yarn is, for example, 4 MPa or more, preferably 5 MPa or more, and more preferably 15 MPa or more. On the other hand, the upper limit of the breaking strength of one yarn in the stretchable conductive yarn is, for example, 17 MPa or less, preferably 15 MPa or less, and more preferably 13 MPa or less.

The lower limit of the breaking elongation of one yarn in the stretchable conductive yarn is, for example, 200% or more, preferably 300% or more, and more preferably 400% or more. On the other hand, the upper limit of the breaking elongation of one yarn in the stretchable conductive yarn is, for example, 1500% or less, preferably 1400% or less, and more preferably 1300% or less.

The electric resistance value R0 of one yarn in the stretchable conductive yarn when not stretched is, for example, 0.1 Ω / cm to 50 Ω / cm, preferably 0.3 Ω / cm to 35 Ω / cm, and more preferably 0. It is 5Ω / cm to 20Ω / cm.
The electric resistance value R0 is calculated from the following formula.
R0 (Ω / cm) = resistance value of unstretched thread (Ω) / length of unstretched thread (cm)

The electric resistance value R50 of one yarn in the stretchable conductive yarn at the time of 50% elongation is, for example, 0.1 Ω / cm to 400 Ω / cm, preferably 0.3 Ω / cm to 200 Ω / cm, and more preferably 0. It is 5.5 Ω / cm to 100 Ω / cm.
The electric resistance value R50 is calculated from the following formula.
R50 (Ω / cm) = resistance value of thread at 50% elongation (Ω) / length of thread at 50% elongation (cm)

The electric resistance value R100 of one yarn in the stretchable conductive yarn at 100% elongation is 0.5Ω / cm to 800Ω / cm, preferably 1Ω / cm to 450Ω / cm, and more preferably 1.5 to 250Ω. / Cm.
The electric resistance value R100 is calculated from the following formula.
R100 (Ω / cm) = resistance value of thread at 100% elongation (Ω) / length of thread at 100% elongation (cm)

The rate of change in the electrical resistance value of a single yarn before and after performing a 50% expansion / contraction operation 100 times for the stretchable conductive yarn is, for example, 200% or less, preferably 180% or less, more preferably. Is less than 150%.
The rate of change in the electrical resistance value is (R0'-R0) / R0 when the resistance value of the yarn when unstretched is R0 and the resistance value when the yarn is not stretched after 100 expansions and contractions is R0'. It is defined as × 100.

At least one of the insulating elastomer layer and the conductive elastomer layer contained in the stretchable conductive yarn, preferably both of them, may be composed of an elastomer having the following characteristics.

The lower limit of the tear strength of the elastomer is, for example, 25 N / mm or more, preferably 28 N / mm or more, more preferably 30 N / mm or more, still more preferably 33 N / mm or more, still more preferably 35 N / mm or more. This makes it possible to improve the durability of the elastomer during repeated use. In addition, the mechanical strength of the elastomer can be improved.
On the other hand, the upper limit of the tear strength of the elastomer is not particularly limited, but may be, for example, 80 N / mm or less, or 70 N / mm or less. This makes it possible to balance various properties of the elastomer.

The lower limit of the tensile strength of the elastomer is, for example, 5.0 MPa or more, preferably 10.0 MPa or more, and more preferably 12.0 MPa or more. This makes it possible to improve the mechanical strength of the elastomer. In addition, it is possible to realize an elastomer having excellent durability that can withstand repeated deformation.
On the other hand, the upper limit of the tensile strength of the elastomer is not particularly limited, but may be, for example, 25 MPa or less, or 20 MPa or less. This makes it possible to balance various properties of the elastomer.

The upper limit of the durometer hardness A of the elastomer is not particularly limited, but may be, for example, 80 or less, preferably 75 or less, and more preferably 70 or less. This makes it possible to balance the cured physical properties of the silicone rubber. As a result, it is possible to enhance the deformability of the elastomer, which facilitates deformation such as bending and stretching.
On the other hand, the lower limit of the durometer hardness A of the elastomer is not particularly limited, but is, for example, 20 or more, preferably 25 or more, and more preferably 30 or more. As a result, the mechanical strength of the elastomer can be increased.

In the present embodiment, for example, the following method can be adopted as a method for measuring the characteristics of the yarn (conductive yarn) in the stretchable conductive yarn and the elastomer constituting the yarn. The conductive thread may be used as it is as a test piece for measuring the characteristics of the conductive thread.

(Measurement conditions for tear strength)
A crescent-shaped test piece is prepared using an elastomer, and the tear strength of the obtained crescent-shaped test piece is measured at 25 ° C. in accordance with JIS K6252 (2001).

(Measurement conditions for tensile strength)
A dumbbell-shaped No. 3 test piece is prepared using an elastomer, and the tensile strength of the obtained dumbbell-shaped No. 3 test piece is measured at 25 ° C. in accordance with JIS K6251 (2004).

(Measurement conditions for breaking elongation)
A dumbbell-shaped No. 3 test piece is prepared using an elastomer, and the obtained dumbbell-shaped No. 3 test piece is measured for elongation at break in accordance with JIS K6251 (2004) at 25 ° C.

(Measurement procedure of durometer hardness A)
A sheet-shaped test piece is prepared using an elastomer, and the durometer hardness A of the obtained sheet-shaped test piece at 25 ° C. is measured according to JIS K6253 (1997).

The electrical resistance value R0 of the conductive elastomer when unstretched is, for example, 0.1 Ω / cm to 50 Ω / cm, preferably 0.3 Ω / cm to 35 Ω / cm, and more preferably 0.5 Ω / cm to 20 Ω / cm. Is.

The electrical resistance value R50 of the conductive elastomer at 50% elongation is, for example, 0.1 Ω / cm to 400 Ω / cm, preferably 0.3 Ω / cm to 200 Ω / cm, and more preferably 0.5 Ω / cm to 100 Ω / cm. cm.
The electrical resistance value R100 of the conductive elastomer at 100% elongation is 0.5 Ω / cm to 800 Ω / cm, preferably 1 Ω / cm to 450 Ω / cm, and more preferably 1.5 to 250 Ω / cm.

FIG. 3 is a diagram schematically showing an example of the structure of the conductive structure 200 of the present embodiment.
The conductive structure 200 of the present embodiment is composed of a knit or a woven fabric made of elastic conductive yarn 100.

The wearable device of the present embodiment includes the above-mentioned elastic conductive yarn or a conductive structure.

The sensor or telescopic wiring provided in the wearable device may be composed of the stretchable conductive thread or the conductive structure described above.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like to the extent that the object of the present invention can be achieved are included in the present invention.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the description of these Examples.

(Vinyl group-containing organopolysiloxane (A))
(A1-1): First vinyl group-containing linear organopolysiloxane: Vinyl group-containing dimethylpolysiloxane synthesized by the following synthesis scheme 1 (structure represented by the above formula (1-1)).
(A1-2): Second vinyl group-containing linear organopolysiloxane: Vinyl group-containing dimethylpolysiloxane synthesized by the following synthesis scheme 2 ( ^R1 and R having a structure represented by the above formula (1-1)). Structure in which ² is a vinyl group)

(Organohydrogenpolysiloxane (B))
(B-1): Organohydrogenpolysiloxane: "TC-25D" manufactured by Momentive Co., Ltd.

(Silica particles (C))
(C): Silica fine particles (particle size 7 nm, specific surface area 300 m ² / g), manufactured by Nippon Aerosil Co., Ltd., "AEROSIL300"

(Silane Coupling Agent (D))
(D-1): Hexamethyldisilazane (HMDZ), manufactured by Gelest, "HEXAMETHYLDISILAZANE (SIH6110.1)".
(D-2) Divinyltetramethyldisilazane, manufactured by Gelest, "1,3-DIVINYLTRAMETHYLDISILAZANE (SID4612.0)"

(Platinum or platinum compound (E))
(E-1): Platinum compound (manufactured by Momentive, trade name "TC-25A")

(Water (F))
(F): Pure water

(Metal powder (G))
(G1): Silver powder, manufactured by Tokuri Kagaku Kenkyusho, trade name "TC-101", median diameter d ₅₀ : 8.0 μm, aspect ratio 16.4, average major axis 4.6 μm

(Synthesis of vinyl group-containing organopolysiloxane (A))
[Synthesis scheme 1: Synthesis of first vinyl group-containing linear organopolysiloxane (A1-1)]
The first vinyl group-containing linear organopolysiloxane (A1-1) was synthesized according to the following formula (5).
That is, 74.7 g (252 mmol) of octamethylcyclotetrasiloxane and 0.1 g of potassium silicate were placed in a 300 mL separable flask having a cooling tube and a stirring blade substituted with Ar gas, heated, and heated at 120 ° C. for 30 minutes. Stirred. At this time, an increase in viscosity was confirmed.
Then, the temperature was raised to 155 ° C., and stirring was continued for 3 hours. Then, after 3 hours, 0.1 g (0.6 mmol) of 1,3-divinyltetramethyldisiloxane was added, and the mixture was further stirred at 155 ° C. for 4 hours.
After 4 hours, it was diluted with 250 mL of toluene and then washed 3 times with water. The organic layer after washing was washed with 1.5 L of methanol several times for reprecipitation purification, and the oligomer and the polymer were separated. The obtained polymer was dried under reduced pressure at 60 ° C. overnight to obtain a first vinyl group-containing linear organopolysiloxane (A1-1) ⁽ Mn = 2,2 × 105, Mw = 4.8 ×). 10 ⁵ ). The vinyl group content calculated by 1 H-NMR spectrum measurement was 0.04 mol%.

[Synthesis scheme 2: Synthesis of second vinyl group-containing linear organopolysiloxane (A1-2)]
In the above synthesis step (A1-1), in addition to 74.7 g (252 mmol) of octamethylcyclotetrasiloxane, 2,4,6,8-tetramethyl 2,4,6,8-tetravinylcyclotetrasiloxane 0. By performing the same as the synthesis step of (A1-1) except that 86 g (2.5 mmol) was used, a second vinyl group-containing linear organopolysiloxane (as shown in the following formula (6)) ( A1-2) was synthesized. The vinyl group content calculated by 1 H-NMR spectrum measurement was 0.92 mol%.

(Preparation of silicone rubber-based curable composition)
According to the following procedure, the silicone rubber-based curable compositions of Examples 1 to 8 in Table 1 and (a) were prepared.
First, a mixture of 90% vinyl group-containing organopolysiloxane (A), silane coupling agent (D) and water (F) is kneaded in advance at the ratio shown in Table 1 below, and then silica particles (silica particles (A)) are added to the mixture. C) was added and further kneaded to obtain a kneaded product (silicone rubber compound).
Here, the kneading after the addition of the silica particles (C) is carried out in the first step of kneading under a nitrogen atmosphere at 60 to 90 ° C. for 1 hour for the coupling reaction, and the removal of the by-product (ammonia). Therefore, it is carried out by going through the second step of kneading under a reduced pressure atmosphere under the condition of 160 to 180 ° C. for 2 hours, and then cooling, and the remaining 10% of the vinyl group-containing organopolysiloxane (A) is added twice. It was added separately and kneaded for 20 minutes.
Subsequently, organohydrogenpolysiloxane (B), platinum or platinum compound (E) was added to 100 parts by weight of the obtained kneaded product (silicone rubber compound) at the ratio shown in Table 2 below, and kneaded with a roll. Then, each silicone rubber-based curable composition was obtained.

(Preparation of conductive paste)
The obtained 13.7 parts by weight of the silicone rubber-based curable composition of (a) was immersed in 31.8 parts by weight of tetradecane (solvent), and subsequently stirred with a rotation / revolution mixer to 54.5 parts by weight. A conductive paste was obtained by kneading with three rolls after adding the metal powder (G1) of the portion.

(Making elastic conductive yarn)
Using the silicone rubber-based curable compositions of Examples 1 to 8, extrusion molding was performed into a tube shape using an extruder to obtain a tube member composed of an insulating silicone rubber.
The obtained conductive paste is applied to the inner layer and / or the outer layer of this tube member so as to have the film thickness shown in Tables 2 and 3, and this is heat-cured at 180 ° C. for 2 hours to conduct conductivity. A sex silicone rubber layer was formed.
As described above, the conductive layer coated tube (stretchable conductive) of Examples 1 to 8 in which the conductive elastomer layer is laminated on the inner surface and / or the outer surface of the insulating tube structure composed of the insulating elastomer layer. Thread) was obtained.
The dimensions of the tube member and the film thickness of the conductive silicone rubber layer were measured using a microscope in the radial cross section of the stretchable conductive yarn.

The following items were evaluated for the obtained stretchable conductive yarn.
The evaluation results are shown in Tables 2 and 3. In each table, diagonal lines mean that the conductive silicone rubber layer was not formed.

(Tensile strength)
The tensile strength at 25 ° C. was measured according to JIS K6251 (2004) using a conductive layer coated tube. The unit is MPa.

(Breaking elongation)
The elongation at break was measured according to JIS K6251 (2004) using a conductive layer coated tube. The breaking elongation was calculated by [moving distance between chucks (mm)] ÷ [initial distance between chucks (35 mm)] × 100. The unit is%.

(Electrical resistance value when unstretched and stretched)
Using a conductive layer coated tube with a length of 5 cm, tape was wrapped around each end by 5 mm to insulate it, and then fixed to the chuck. Measuring clips are attached to both ends of the center 3 cm, and when unstretched, when stretched by 50% at a rate of 0.5 mm / sec in the length direction, and when stretched by 100%, the conductive silicone of the outer layer is used. The resistance value in the rubber layer was measured.
From the obtained resistance values, each electric resistance value (Ω / cm) was calculated based on the following formula.
R0 (Ω / cm) = resistance value of unstretched thread (Ω) / length of unstretched thread (cm)
R50 (Ω / cm) = resistance value of thread at 50% elongation (Ω) / length of thread at 50% elongation (cm)
R100 (Ω / cm) = resistance value of thread at 100% elongation (Ω) / length of thread at 100% elongation (cm)

(50%, rate of change in electrical resistance after 100 expansions and contractions)
Using a conductive layer coated tube with a length of 5 cm, tape was wrapped around each end by 5 mm to insulate it, and then fixed to the chuck. The outer layer is a conductive silicone rubber layer after repeating the test of stretching 50% in the length direction at a rate of 1.33 mm / sec, holding for 10 seconds, releasing the stretch at the same rate, and holding for 10 seconds 100 times. The resistance value in the above was measured, and the rate of change from the initial resistance value was calculated based on the following formula.
The rate of change in the electrical resistance value is (R0'-R0) / R0 when the resistance value of the yarn when unstretched is R0 and the resistance value when the yarn is not stretched after 100 expansions and contractions is R0'. Calculated from × 100.

Using the conductive layer coated tubes of Examples 1 to 4, the resistance values at the time of unstretched, 50% stretched, 100% stretched, and the resistance after 50% stretched 100 times by the same method as above. When the value was measured, it was found that both the inner layer and the outer layer of the conductive silicone rubber layer did not break and were conductive.
Further, it was confirmed that no peeling occurred between the tube member and the conductive silicone rubber layer after stretching and contracting 50% 100 times using the conductive layer coated tubes of Examples 1 to 8.

(Comparative Example 1)
Plyed stainless steel fibers (manufactured by Nippon Seisen Co., Ltd., Naslon (registered trademark), product number: 12-100 / 2, elongation rate: 1.6%) were prepared. The metallic conductive yarn of Comparative Example 1 could not be easily stretched.

It was found that the elastic conductive yarns of Examples 1 to 8 were superior in elasticity and electrical characteristics at the time of extension as compared with Comparative Example 1.

10, 11, 12, 13 Insulating Elastomer Layer 20, 21, 22, 23,24 Conductive Elastomer Layer 30 Holes 50, 51, 52, 53 Thread 100 Elastic Conductive Thread 200 Conductive Structure

Claims (20)

Elastic conductive yarn containing one or more yarns,
A stretchable conductive yarn in which the yarn has an insulating elastomer layer and a conductive elastomer layer laminated on the surface of the insulating elastomer layer in one of the radial cross sections of the yarn. The stretchable conductive yarn according to claim 1.
A stretchable conductive yarn in which the yarn has at least one of an insulating tube structure including the insulating elastomer layer and a conductive tube structure including the conductive elastomer layer. The stretchable conductive yarn according to claim 2.
The thread
At least one of an insulating tube structure containing the insulating elastomer layer and a solid insulating core structure containing the insulating elastomer layer.
Conductive including the conductive elastomer layer configured to cover at least one or more surfaces on the outer surface of the insulating tube structure, on its inner surface, and on the outer surface of the insulating core structure. A stretchable conductive thread having a tube structure. The stretchable conductive yarn according to claim 2 or 3.
A stretchable conductive yarn in which either the insulating tube structure or the conductive tube structure is provided on the outermost layer of the yarn. The stretchable conductive yarn according to any one of claims 1 to 4.
A stretchable conductive yarn in which the insulating elastomer layer contains one or more selected from the group consisting of silicone rubber and urethane rubber. The stretchable conductive yarn according to any one of claims 1 to 5.
A stretchable conductive yarn in which the insulating elastomer layer contains a non-conductive filler. The stretchable conductive yarn according to any one of claims 1 to 6.
A stretchable conductive yarn in which the conductive elastomer layer comprises one or more selected from the group consisting of silicone rubber and urethane rubber, and a conductive filler. The stretchable conductive yarn according to any one of claims 1 to 4.
The insulating elastomer layer is composed of a cured product of a silicone rubber-based curable composition containing a vinyl group-containing organopolysiloxane.
A stretchable conductive yarn in which the conductive elastomer layer is composed of a conductive filler and a cured product of a silicone rubber-based curable composition containing a vinyl group-containing organopolysiloxane. The stretchable conductive yarn according to claim 7 or 8.
A stretchable conductive yarn in which the conductive filler contains silver powder. The stretchable conductive yarn according to any one of claims 7 to 9.
The content of the conductive filler is 70% by mass or more and 90% by mass or less in 100% by mass of the conductive elastomer layer. The stretchable conductive yarn according to any one of claims 1 to 10.
A stretchable conductive yarn in which the conductive elastomer layer is composed of a coating layer made of a conductive paste. The stretchable conductive yarn according to any one of claims 1 to 11.
A stretchable conductive yarn having a breaking strength of 4 MPa or more and 17 MPa or less in one of the stretchable conductive yarns. The stretchable conductive yarn according to any one of claims 1 to 12.
A stretchable conductive yarn having a breaking elongation in one of the stretchable conductive yarns of 200% or more and 1500% or less. The stretchable conductive yarn according to any one of claims 1 to 13.
A stretchable conductive yarn having an electric resistance value of 0.1 Ω / cm or more and 50 Ω / cm or less in one of the stretchable conductive yarns when not stretched. The stretchable conductive yarn according to any one of claims 1 to 14.
A stretchable conductive yarn having an electric resistance value of 0.1 Ω / cm or more and 400 Ω / cm or less in one of the stretchable conductive yarns at the time of 50% elongation. The stretchable conductive yarn according to any one of claims 1 to 15.
A stretchable conductive yarn having an electric resistance value of 0.5 Ω / cm or more and 800 Ω / cm or less in one of the stretchable conductive yarns at the time of 100% elongation. The stretchable conductive yarn according to any one of claims 1 to 16.
A stretchable conductive yarn having a rate of change of 200% or less in the electric resistance value of one yarn before and after performing a 50% stretching operation on the stretchable conductive yarn 100 times. A conductive structure made of a knit or woven fabric using the stretchable conductive yarn according to any one of claims 1 to 17. A wearable device comprising the stretchable conductive yarn according to any one of claims 1 to 17 or the conductive structure according to claim 16. The wearable device according to claim 19.
A wearable device in which the sensor or the telescopic wiring in the wearable device is composed of the stretchable conductive thread or the conductive structure.

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