JP2022078683A - Flexible telescopic heater device or - Google Patents

Abstract

To provide a flexible telescopic heater device excellent in telescopic durability.SOLUTION: A flexible telescopic heater device includes an elastic substrate containing an insulating elastomer, and elastic heater wiring containing a conductive elastomer formed on the elastic substrate.SELECTED DRAWING: Figure 1

Description

The present invention relates to a flexible telescopic heater device.

Various developments have been made on heater devices. As this kind of technique, for example, the technique described in Patent Document 1 is known. Patent Document 1 describes that a heating type wearable device including a main body and a heating portion attached to the surface of the main body is composed of a heating layer obtained by knitting a wire made of a metal material. (Paragraph 0029 of Patent Document 1, FIG. 4, etc.).

Japanese Unexamined Patent Publication No. 2018-183036

However, as a result of the study by the present inventor, it has been found that there is room for improvement in the expansion / contraction durability of the heater device data described in Patent Document 1.

As a result of further studies, the present inventor has found that a flexible telescopic heater device having excellent stretchability durability can be realized by constructing a substrate and a heater wiring with a stretchable material, and has completed the present invention.

According to the present invention
An elastic substrate containing an insulating elastomer and
The elastic heater wiring including the conductive elastomer formed on the elastic substrate is provided.
Flexible telescopic heater device.
Is provided.

According to the present invention, a flexible telescopic heater device having excellent telescopic durability is provided.

It is a figure which shows an example of the structure of the flexible telescopic heater device of this embodiment. (A) is a cross-sectional view taken along the line AA of FIG. 1, (b) is a cross-sectional view taken along the line BB of FIG. 1, and (c) is a cross-sectional view showing a configuration of a modified example. It is a block diagram for demonstrating the function of the flexible telescopic heater device of this embodiment. It is a figure which shows typically an example of the manufacturing process of the flexible telescopic heater device 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 heater device of this embodiment will be outlined.

The flexible telescopic heater device of the present embodiment includes a stretchable substrate containing an insulating elastomer and a stretchable heater wiring including a conductive elastomer formed on the stretchable substrate.

In the flexible telescopic heater device, the elastic heater wiring can be generated by passing an electric current, and this can be used as a heat source body. The elastic heater wiring can generate heat both when it is not stretched and when it is stretched.

Here, since the heating portion of the heating type wearable device described in Patent Document 1 is made of a non-stretchable material such as a metal material, the heating portion may be disconnected due to elongation or bending deformation.

On the other hand, in the present embodiment, a flexible telescopic heater device that is expandable and / or bendable can be realized by configuring the substrate and the heater wiring with elastic materials, respectively. The elastic heater wiring can stably exhibit heat generation characteristics even during deformation such as extension. Further, even during deformation such as elongation, the elastic heater wiring is suppressed from peeling from the elastic substrate, and the adhesion to each other is maintained.
As described above, according to the present embodiment, it is possible to realize a flexible expansion / contraction heater device having excellent expansion / contraction durability.

According to the present embodiment, since the stretchable heater wiring can be formed by a printing method using a conductive paste, it is possible to provide a flexible stretchable heater device having excellent wiring design flexibility and design.

The flexible telescopic heater device of the present embodiment can be used for various purposes, and can heat an object to be heated such as a body or an article other than the body.

The flexible telescopic heater device can be used as a wearable device that can be worn on either the body or clothing. The flexible telescopic heater device may be worn directly on the body or may be worn on the body via a body-wearing member (clothes). Due to its elasticity, such a flexible telescopic heater device can follow the surface shape of the body and the movement of the body.

Further, according to the present embodiment, a washable flexible telescopic heater device can be realized.

Each configuration of the flexible telescopic heater device of this embodiment will be described in detail.

FIG. 1 is a top view showing an example of the configuration of the flexible telescopic heater device 100. 2A is a cross-sectional view taken along the line AA of FIG. 1, and FIG. 2B is a cross-sectional view taken along the line BB of FIG.

The flexible telescopic heater device 100 of FIG. 1 includes a stretchable substrate 10, a stretchable heater wiring 20, and an external electrode 50.

The stretchable substrate 10 is composed of a stretchable insulating layer containing an insulating elastomer.

The stretchable substrate 10 has a wiring forming region in which the stretchable heater wiring 20 is formed and a wiring peripheral region in which the stretchable heater wiring 20 is not formed in the top view.
The wiring forming region of the stretchable substrate 10 is in close contact with the stretchable heater wiring 20 when it is not stretched or stretched, and its mechanical strength can be enhanced. Further, a mounting portion such as a sewing thread or a snap button for installing on clothes or the like can be attached to the wiring peripheral area of the elastic substrate 10.

The upper limit of the thickness of the stretchable substrate 10 can be set according to the application, and may be, for example, 10 mm or less, preferably 1 mm or less, but more preferably 400 μm or less from the viewpoint of wearable device applications. A thin film heat device can be realized by setting the thickness to 400 μm or less.
From the viewpoint of mechanical strength, the lower limit of the thickness of the stretchable substrate 10 is, for example, 10 μm or more, preferably 50 μm or more, and more preferably 100 μm or more.

The upper limit of the durometer hardness A of the insulating elastomer is not particularly limited, but may be, for example, 80 or less, preferably 70 or less. As a result, it is possible to increase the ease of deformation, which facilitates deformation such as bending and stretching.
On the other hand, the lower limit of the durometer hardness A is, for example, 20 or more, preferably 30 or more. As a result, the frictional durability and mechanical strength of the insulating elastomer can be enhanced. In addition, the washing resistance of the flexible telescopic heater device 100 can be improved.

The lower limit of the tensile strength of the insulating elastomer is, for example, 5.0 MPa or more, preferably 6.0 MPa or more, and more preferably 7.0 MPa or more. As a result, it is possible to realize a structure having excellent elongation durability during repeated expansion and deformation.
On the other hand, the upper limit of the tensile strength is not particularly limited, but may be, for example, 25 MPa or less. This makes it possible to balance various properties of the insulating elastomer.

The lower limit of the elongation at break of the insulating elastomer is, for example, 500% or more, preferably 600% or more, and more preferably 700% or more. This makes it possible to improve the elongation durability at the time of repeated elongation deformation.
On the other hand, the upper limit of the elongation at break is not particularly limited, but may be, for example, 2000% or less, or 1800% or less. This makes it possible to balance various properties of the insulating elastomer.

The lower limit of the tear strength of the insulating 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 34 N / mm or more. This makes it possible to sew the elastic substrate 10 to clothes. That is, it is possible to realize a flexible telescopic heater device 100 that can be sewn. In addition, it is possible to improve durability, scratch resistance and mechanical strength during repeated use of silicone rubber.
On the other hand, the upper limit of the tear strength 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 insulating elastomer.

In the present embodiment, for example, the following method can be adopted as a method for measuring the characteristics of each member of the flexible telescopic heater device 100 and the characteristics of the elastomer used for each member. For the measurement of the characteristics of each member, each member such as a substrate may be used as it is as a test piece.

(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).

When the weight of the elastic substrate 10 before the water exposure treatment is W1 and the weight of the elastic substrate 10 after the water exposure treatment at 40 ° C. for 120 minutes is W2, W1 and W2 are, for example, -3≤ (W2). -W1) / W1 * 100≤1, preferably -2.8≤ (W2-W1) /W1 * 100≤0.9, more preferably -2.5≤ (W2-W1) /W1 * 100≤0 It may be configured to satisfy .5. Thereby, the washing resistance of the flexible telescopic heater device 100 can be improved.

The stretchable heater wiring 20 is formed by laminating on one surface of the stretchable substrate 10.

The stretchable heater wiring 20 may have an external connection portion 30 at an end portion. An external electrode 50 is formed on the external connection portion 30. The external connection portion 30 may have a rectangular pad shape when viewed from above.

The external electrode 50 is not particularly limited as long as it can be connected to the outside. An example of the external electrode 50 is a metal snap button or the like. For example, the external electrode 50 and the power supply can be electrically connected via a wiring cable.

The elasticity in the present specification is expressed by the elongation rate when stretched in a predetermined direction. As the predetermined direction, for example, in the top view of FIG. 1, the extending direction in which the elastic heater wiring 20 has the maximum length may be adopted.
When stretched in this extending direction, having elasticity means that the stretchability can be stretched to, for example, 10% or more, preferably 20% or more, more preferably 50% or more, and the stretchability thereof. It means a state in which the elastic heater wiring 20 is not broken at times.

The stretchable heater wiring 20 is composed of a conductive layer containing a conductive elastomer.

In the flexible telescopic heater device 100, the state in which the stretchable substrate 10 and the stretchable heater wiring 20 are laminated is a state in which the surfaces of each other are in surface contact with each other, and are chemically and / or physically bonded and adhered to each other. It may be in a state. Therefore, even during stretching or repeated stretching, it is possible to suppress the possibility of damage such as peeling of the stretchable heater wiring 20 from the surface of the stretchable substrate 10. Thereby, the flexible expansion / contraction heater device 100 having excellent expansion / contraction durability can be realized.

In FIG. 2A, which is one of the cross sections of the flexible telescopic heater device 100, when the substrate thickness of the stretchable substrate 10 when not stretched is X and the wiring thickness of the stretchable heater wiring 20 when not stretched is Y, X. , Y are configured to satisfy, for example, 0.02 ≦ Y / X ≦ 5.
The lower limit of Y / X is, for example, 0.02 or more, preferably 0.05 or more, and more preferably 0.1 or more. On the other hand, the upper limit of Y / X is, for example, 5 or less, preferably 4 or less, and more preferably 3 or less. Within such a range, it is possible to balance the heat generation characteristics and the mechanical strength.

In FIG. 2B, which is one of the cross sections of the flexible telescopic heater device, when the wiring thickness of the stretchable heater wiring 20 when not stretched is Y and the wiring width of the stretchable heater wiring 20 is Z, Y and Z are For example, it is configured to satisfy 0.4 ≦ Z / Y ≦ 250.
The lower limit of Z / Y is, for example, 0.4 or more, preferably 1 or more, and more preferably 2 or more. On the other hand, the upper limit of Z / Y is, for example, 250 or less, preferably 230 or less, and more preferably 200 or less. Within such a range, it is possible to balance the heat generation characteristics and the mechanical strength.

The lower limit of the resistance value of the elastic heater wiring 20 when not extended at 25 ° C. is, for example, 1 Ω or more, preferably 2 Ω or more, and more preferably 5 Ω or more. Thereby, the heat generation characteristic can be improved.
On the other hand, the upper limit of the resistance value of the elastic heater wiring 20 when the temperature is 25 ° C. and is not extended is, for example, 200 Ω or less, preferably 180 Ω or less, and more preferably 150 Ω or less. This makes it possible to balance the expansion / contraction durability of the expansion / contraction heater wiring 20 with the heat generation characteristics.

When the resistance value of the elastic heater wiring 20 at 25 ° C. and not extended is R1, and the resistance value of the elastic heater wiring 20 at 25 ° C. and 50% extension is R2, R1 and R2 are, for example, 1 ≦. It may be configured to satisfy R2 / R1 ≦ 10.
The lower limit of R2 / R1 is, for example, 1 or more, preferably 1.3 or more, and more preferably 1.5 or more. On the other hand, the upper limit of R2 / R1 is, for example, 10 or less, preferably 8 or less, and more preferably 6 or less. Within such a range, it is possible to achieve a balance between heat generation characteristics and expansion / contraction durability.

The lower limit of the volume resistivity of the elastic heater wiring 20 at 25 ° C. when unstretched is, for example, 1.0 × 10 ^-5 Ω · cm or more, preferably 2.0 × 10 ^-5 Ω · cm or more, more preferably. Is 5.0 × 10 ^-5 Ω · cm or more. Thereby, the heat generation characteristic can be improved.
On the other hand, the upper limit of the volume resistivity of the elastic heater wiring 20 at 25 ° C. when unstretched is, for example, 1.0 × 10 ¹ Ω · cm or less, preferably 1.0 × 10 ^-1 Ω · cm or less. It is preferably 1.0 × 10 ^-2 Ω · cm or less. This makes it possible to balance the expansion / contraction durability of the expansion / contraction heater wiring 20 with the heat generation characteristics.

An example of the function of the flexible telescopic heater device 100 will be described with reference to FIG.
FIG. 3 shows a functional block diagram of the flexible telescopic heater device 100.

An example of the flexible telescopic heater device 100 includes a control unit 320. The flexible telescopic heater device 100 may further include at least one or more other functional units such as a power supply unit 350, a communication unit 340, and a display unit.

The control unit 320 controls the surface temperature of the elastic heater wiring 20. The control unit 320 can control the surface temperature based on the information input from the input unit 330, for example.

The flexible telescopic heater device 100 may further include a storage unit 360.
The control unit 320 determines the surface temperature of the elastic heater wiring 20 based on the temperature conditions stored in the storage unit 360 according to the information from the temperature sensor that measures the surface temperature of the elastic heater wiring 20 (not shown). Can be controlled.

Here, the temperature condition may include the value of the set temperature of the surface temperature of the elastic heater wiring 20, the numerical range of the set temperature, the temperature rise condition, the temperature profile with respect to the time axis, and the like. For example, when the set temperature is set to 30 ° C., the control unit 320 can control the elastic heater wiring 20 to energize and raise the surface temperature until the surface temperature of the elastic heater wiring 20 reaches 30 ° C. .. After reaching the set temperature, the control unit 320 may stop the energization, or may control the energization amount or the on / off of the energization so that the temperature is within a predetermined range.

The input unit 330 may be provided directly on the flexible telescopic heater device 100, or may be provided on an external terminal such as a smartphone. The information input from the input unit 330 is transmitted to the control unit 320 via the communication unit 340 included in the flexible telescopic heater device 100. The input unit 330 may be composed of, for example, a button or a touch panel.
The communication unit 340 includes various communication means such as Bluetooth (registered trademark) and Wi-Fi.

The power supply unit 350 may be composed of a mobile battery or may include an electrode that can be connected to an external power source.

The flexible telescopic heater device 100 may include a display unit. The display unit can display the surface temperature of the elastic heater wiring 20, the set temperature condition, the on / off state of the power supply unit 350, and the like.
The display unit may be composed of a stretchable display or the like.
When the external terminal is provided with a display, the same display content as that of the display unit may be displayed on the display via the communication unit 340.

The components of each part included in the flexible telescopic heater device 100 may be configured by dedicated hardware or may be realized by executing a software program suitable for the components of each part. The components of each unit may be realized by a program execution unit such as a CPU or a processor reading and executing a software program recorded on a recording medium such as a hard disk or a semiconductor memory.

A modification of the flexible telescopic heater device 100 will be described.

As shown in FIG. 2C, the flexible telescopic heater device 100 may include an insulating protective layer 60 formed on at least a part of the surface of the stretchable heater wiring 20.
The insulating protective layer 60 may be formed so as to cover at least a part or all of the upper surface and the side surface of the elastic heater wiring 20.
The insulating protective layer 60 can enhance the washing durability of the flexible telescopic heater device 100.

The insulating protective layer 60 may be made of an elastic material, and may be made of, for example, the same material as the insulating elastomer or the elastic substrate 10. As a result, the adhesion between the elastic substrate 10 and the insulating protective layer 60 can be enhanced. The insulating protective layer 60 may be composed of a printing layer formed by a printing method using an insulating paste, or may be composed of a sheet of insulating elastomer.

The insulating protective layer 60 may be configured to cover the entire elastic heater wiring 20 and the external electrode 50, but it covers the elastic heater wiring 20 and does not cover a part of the external electrode 50 and the external connection portion 30. It may be exposed as follows.
When the insulating protective layer 60 covers the external electrode 50, an electrical connection portion may be formed so as to penetrate the insulating protective layer 60 on the external electrode 50. Examples of the electric connection portion include a metal snap button and the like.

The elastic substrate 10 may be configured as a single layer or may be configured by laminating a plurality of layers.
The flexible telescopic heater device 100 may have a multi-layer wiring structure in which the stretchable substrate 10 and the stretchable heater wiring 20 are alternately laminated.

The shape of the stretchable substrate 10 in the top view is not particularly limited, and can be appropriately deformed according to the intended use.

The flexible telescopic heater device 100 may have one or more stretchable heater wirings 20 on the same surface of the stretchable substrate 10.

At least a part of the stretchable heater wiring 20 may be embedded inside the stretchable substrate 10.

Next, the materials of the stretchable substrate 10 and the stretchable heater wiring 20 will be described.

In an example of the flexible telescopic heater device 100 of the present embodiment, the stretchable substrate 10 is made of an insulating elastomer, and the stretchable heater wiring 20 is made of a conductive elastomer. Further, the insulating protective layer 60 may also be made of an insulating elastomer.

The insulating elastomer can include, for example, a thermosetting elastomer such as silicone rubber, urethane rubber, fluororubber, nitrile rubber, acrylic rubber, styrene rubber, chloroprene rubber, and ethylene propylene rubber. Among these, the insulating elastomer may contain one or more selected from the group consisting of silicone rubber, urethane rubber, and fluororubber, and may be preferably composed of silicone rubber. Silicone rubber is chemically stable among elastomers and has excellent mechanical strength.

The insulating elastomer does not contain a conductive filler and may contain a non-conductive filler. This enhances the mechanical properties of the conductive elastomer.

The conductive elastomer can include, for example, a thermosetting elastomer such as silicone rubber, urethane rubber, fluororubber, nitrile rubber, acrylic rubber, styrene rubber, chloroprene rubber, and ethylene propylene rubber, and a conductive filler. Among these, the conductive elastomer may contain one or more selected from the group consisting of silicone rubber, urethane rubber, and fluororubber, and may be preferably configured to contain silicone rubber and a conductive filler. As a result, the elasticity and electrical characteristics of the conductive elastomer can be enhanced.

The conductive filler may contain, for example, one or more selected from the group consisting of powdery or fibrous metal-based fillers, carbon-based fillers, metal oxide fillers, and metal-plated fillers. Among these, as the conductive filler, a metal-based filler such as silver powder may be used.

The conductive elastomer may further contain a non-conductive filler in addition to the conductive filler. This enhances the mechanical properties of the conductive elastomer.

At least one of the insulating elastomer and the conductive elastomer, preferably both, may contain a non-conductive filler. 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. Among these, silica particles may be included.

In the present embodiment, the stretchable substrate 10 and the stretchable heater wiring 20 may be configured to contain the same thermosetting elastomer, and may preferably contain the same type of silicone rubber. This silicone rubber may be composed of a cured product of a silicone rubber-based curable composition described later.
Further, the insulating protective layer 60 may also contain the same insulating elastomer as the elastic substrate 10, or may contain the same thermosetting elastomer as the elastic heater wiring 20.
As a result, the adhesion to each other can be improved, so that the expansion / contraction durability of the flexible expansion / contraction heater device 100 can be enhanced.

In the present specification, including the same thermosetting elastomer, including the same insulating elastomer, and containing the same conductive elastomer, respectively, means at least one of the types of thermosetting elastomers exemplified above. Means to contain more than one elastomer of the same type.

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

In the present specification, the inclusion of the same type of silicone rubber means that the silicone rubber-based curable composition contains at least the same type of vinyl group-containing linear organopolysiloxane, and further, the same type 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 amount of vinyl group, the molecular weight distribution, or the amount thereof added 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 include 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 the 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% of 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 hydrosilylates with the vinyl group contained in the components contained in the silicone rubber-based curable composition and crosslinks 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 undergoes a hydrosilylation reaction 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 amount of residue 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 group 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.

The specific surface area of the silica particles (C) by, for example, 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 silanol groups). 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 contained in the vinyl group-containing organopolysiloxane (A) and the hydride group contained in 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 the. 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, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, and methyltri as having a hydrophobic group as a functional group. Ekoxysilanes 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, metharoxypropylmethyldimethoxysilane, 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 an 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). It may be less than or equal to, 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, a 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.

(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 index of the solubility of a substance 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 the vector by the distance (HSP distance) of the Hansen solubility parameter.

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 for calculating 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 25 ° C., the viscosity when measured at a shear rate of 1 [1 / s] is η1, the viscosity when measured at a shear rate of 5 [1 / s] is η5, and the viscosity 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.

The content of the silicone rubber-based curable composition in the insulating paste is preferably 10% by mass or more, more preferably 15% by mass or more, and 20% by mass or more in 100% by mass of the insulating paste. Is more preferable. The content of the silicone rubber-based curable composition in the insulating paste is preferably 50% by mass or less, more preferably 40% by mass or less, and 35% by mass in 100% by mass of the insulating paste. It is more preferably% or less.

(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 flaky 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 with respect to the whole of the conductive paste. Is even more preferable. 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 with respect to the whole of the conductive paste. It is more preferable to have.
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, based on 100% by mass of the total amount of the silica particles (C) and the conductive filler. % Or more, 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, for example, 20% by mass or less with respect to 100% by mass of the total amount of the silica particles (C) and the conductive filler. It is preferably 15% by mass or less, and 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 is preferably 1% by mass or more, more preferably 3% by mass or more, and 5% by mass or more in 100% by mass of the conductive paste. Is more 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 the entire 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.

Next, the manufacturing process of the flexible telescopic heater device 100 of the present embodiment will be described.

The flexible telescopic heater device of the present embodiment includes a step of forming the stretchable substrate 10 and a step of forming the stretchable heater wiring 20 on the stretchable substrate 10.

Here, an example of the manufacturing process of the flexible telescopic heater device 100 will be described with reference to FIG.
FIG. 4 is a cross-sectional view showing an outline of a manufacturing process of the flexible telescopic heater device 100.

First, as shown in FIG. 4A, the support 120 is installed on the workbench 11, and the insulating paste 13 is applied onto the support 12. As the coating method, various methods can be used, and for example, a printing method such as a squeegee method using the squeegee 14 can be used. Subsequently, the coating-like insulating paste 13 can be dried to form an insulating layer 32 (stretchable substrate 10 made of an insulating elastomer) on the support 12. The drying conditions can be appropriately set according to the type and amount of the solvent in the insulating paste 13, and for example, the drying temperature may be 150 ° C. to 180 ° C., the drying time may be 1 minute to 30 minutes, or the like. can.

The insulating layer 32 constituting the elastic substrate 10 may be formed by a molding method such as calendar molding or compression molding using the above-mentioned silicone rubber-based curable composition.

Subsequently, as shown in FIG. 4B, a mask 16 having a predetermined opening pattern shape is arranged on the insulating layer 32. Then, as shown in FIGS. 4 (b) and 4 (c), the conductive paste 15 is applied onto the insulating layer 32 via the mask 16.
As the coating method, the same method as the coating method of the insulating paste 13 can be used, and for example, squeegee printing with the squeegee 14 may be used.
Here, when the insulating paste 13 and the conductive paste 15 each contain a silicone rubber-based curable composition, a conductive coating film (conductive layer 52) having a predetermined pattern shape is laminated on the dried insulating layer 32. After that, these may be collectively cured. The curing treatment can be appropriately set depending on the silicone rubber-based curable composition, and for example, the curing temperature can be 160 ° C. to 220 ° C., the curing time can be 1 hour to 3 hours, or the like. As shown in FIG. 4D, the mask 16 can be removed after the curing treatment or before the curing treatment. As a result, the cured product of the conductive layer 52 (elastic heater wiring 20 composed of the conductive elastomer) having a predetermined pattern shape is formed on the elastic substrate 10 made of the cured product of the insulating layer 32. be able to.
As a result, the flexible telescopic heater device 100 shown in FIG. 1 is obtained.

Further, as shown in FIG. 4 (e), the insulating paste 17 is further coated on the insulating layer 32 and the patterned conductive layer 52, and the insulating layer 72 (insulation) is further applied as shown in FIG. 4 (f). An insulating protective layer 60) made of a sex elastomer can be formed.
As a result, the flexible telescopic heater device 100 shown in FIG. 2C is obtained.

After that, the steps of FIGS. 4 (b) to 4 (e) may be repeated as appropriate. As a result, the upper wiring 150 made of the conductive elastomer, the upper insulating layer 160 made of the insulating elastomer, and the like are formed, and the circuit can be multi-layered. Further, the wiring design of the elastic heater wiring 20 can be changed by adjusting the mask pattern and its arrangement position.
The repeating step may be performed after separating the support 120 from the insulating layer 32.

The lower limit of the content of the conductive filler in the conductive cured product obtained by curing the conductive paste constituting the elastic heater wiring 20 is, for example, 65% by mass or more, preferably 70% by mass in 100% by mass of the conductive cured product. As mentioned above, it is more preferably 75% by mass or more. As a result, the telescopic electrical characteristics can be enhanced. On the other hand, the upper limit of the content of the conductive filler in the elastic heater wiring 20 is, for example, 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass in 100% by mass of the conductive elastic heater wiring 20. % Or less. This makes it possible to suppress deterioration of rubber properties such as elasticity.

In the present embodiment, for example, by appropriately selecting the type and blending amount of each component contained in the silicone rubber-based curable composition, the method for preparing the silicone rubber-based curable composition, and the like, the above-mentioned hardness, tensile strength, and the like can be obtained. It is possible to control the breaking elongation and the tear strength. Among these, for example, the type and blending ratio of the resin constituting the silicone rubber, the cross-linking density of the resin, the cross-linking structure, etc. are appropriately controlled, and the blending ratio of the inorganic filler and the bond of the inorganic filler with the rubber are improved. In particular, do not use a second vinyl group-containing linear organopolysiloxane (A1-2) having a vinyl group content of more than 0.4 mol%, and use only two at the ends of the molecule. Use the first vinyl group-containing linear organopolysiloxane (A1-1) having a vinyl group of 0.4 mol% or less, and use a silane coupling agent having a vinyl group. , Appropriate adjustment of the content of the silica particles (C) and the content of the silane coupling agent, etc. are mentioned as factors for setting the hardness, tensile strength, breaking elongation, and tear strength within the desired numerical ranges. Be done.

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.

The raw material components shown in Table 1 are shown below.
(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 Tokuriki 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)
The silicone rubber-based curable composition of Samples 1 to 3 was prepared according to the following procedure.
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 ()) 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, a silicone rubber-based curable composition was obtained.

(Preparation of extinct paste)
The obtained 32 parts by weight of the silicone rubber-based curable composition of Sample 4 was immersed in 68 parts by weight of tetradecane (solvent), and subsequently stirred with a rotation / revolution mixer to obtain an extinct paste.

(Preparation of conductive paste)
The obtained 13.7 parts by weight of the silicone rubber-based curable composition of Sample 5 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. The conductive paste 1 was obtained by adding the metal powder (G1) of No. 1 and kneading with three rolls.

(Manufacturing of flexible telescopic heater device)
Using the obtained silicone rubber-based curable compositions of Samples 1 to 3, they were pressed at 170 ° C. and 10 MPa for 10 minutes to form a sheet having a thickness of 150 μm, and were first cured. Subsequently, it was secondarily cured at 200 ° C. for 4 hours to obtain a sheet-shaped silicone rubber (a cured product of a silicone rubber-based curable composition). The obtained sheet-shaped silicone rubber was cut into a width of 10 cm and a length of 10 cm to prepare two elastic substrates and an insulating protective layer.
Using the obtained conductive paste 1, a wavy line-shaped elastic heater wiring having a width of 2 mm, a length of 980 mm, and a thickness of 0.1 mm is drawn on an elastic substrate through a mask having a predetermined pattern, and is expanded and contracted. A 15 mm × 12 mm square external connection portion was drawn on both ends of the sex heater wiring, dried at 140 ° C. for 20 minutes, and cured at 180 ° C. for 2 hours.
Further, another insulating protective layer was superposed on the surface of the elastic heater wiring, and two metal male snap buttons penetrating the insulating protective layer on the external connection portion were installed.
From the above, the flexible stretchable heater device of Examples 1 to 3 was obtained.

The following items were evaluated for the obtained flexible telescopic heater device. The results are shown in Table 2.

(hardness)
The silicone rubber-based curable composition of Sample 3 used for the substrate was pressed at 170 ° C. and 10 MPa for 10 minutes to form a sheet and first cured. Subsequently, it was secondarily cured at 200 ° C. for 4 hours, and a sheet-like substrate (cured product of a silicone rubber-based curable composition) having a thickness of 150 μm was used as a test piece.
The test pieces were laminated so as to have a thickness of 6 mm, and the durometer hardness A of the obtained sheet-shaped test pieces at 25 ° C. was measured according to JIS K6253 (1997).
(Tear strength)
Using the above test piece, the tear strength at 25 ° C. was measured according to JIS K6252 (2001). The unit is N / mm.
(Tensile strength)
Using the above test piece, the tensile strength at 25 ° C. was measured according to JIS K6251 (2004). The unit is MPa.
(Breaking elongation)
Using the above test piece, the elongation at break was measured according to JIS K6251 (2004). The breaking elongation was calculated by [moving distance between chucks (mm)] ÷ [initial distance between chucks (35 mm)] × 100. The unit is%.

(Resistance value, volume resistivity)
Using the flexible telescopic heater device of each embodiment, the resistance between the heater wirings in the unstretched region or the stretched region in a 25 ° C environment, when unstretched, or in a state where the heater wiring is stretched by 50% in the extending direction. The value and volume resistivity were measured. In Example 1, the resistance value (R1) of the stretchable heater wiring at 25 ° C. and unstretched is 11Ω, the resistance value (R2) of the stretchable heater wiring at 25 ° C. and 50% stretching is 36Ω, and R2 / R1. The volume resistivity of the elastic heater wiring at 3.3, 25 ° C. and unstretched was 2.4 × 10 ^-4 Ω · cm.

(Rate of change in water content)
The weight (W1) of the stretchable substrate used in the flexible telescopic heater device of each embodiment was measured before the water exposure treatment, and then the water exposure treatment was performed under the condition of immersing the stretchable substrate in distilled water at 40 ° C. for 120 minutes. The weight (W2) of the stretchable substrate was measured. Using the obtained W1 and W2, the rate of change in water content was calculated using the formula: (W2-W1) / W1 * 100.

(Heat generation characteristics)
An external electrode (the end of the cable has a removable metal female snap button) was attached to the external connection portion of the obtained flexible telescopic heater device of each embodiment via a male snap button. A power source was electrically connected to this external electrode via a cable (evaluation device A).
Using the obtained evaluation device A, a voltage of 5 V was applied to the flexible telescopic heater device, and it was confirmed that the surface of the stretchable heater wiring generated heat up to 50 ° C. (at 12 ° C./min).

(Expandable durability)
Using the evaluation device A, the flexible telescopic heater device is stretched by 20% or 50% after repeating the stretching operation 20 times, and then a voltage of 5 V is applied to expand and contract the flexible heater wiring without disconnection. It was confirmed that the surface of the sex heater wiring generated heat up to 50 ° C (at 12 ° C / min).
It was also confirmed that the stretchable substrate and the stretchable heater wiring did not peel off even after repeated stretching operations under the conditions of 20% stretching or 50% stretching.

(Washing durability)
-Of the stretchable substrates of the flexible stretchable heater devices of each of the above obtained examples, the peripheral edge portion where the stretchable heater wiring is not formed is sewn to the cloth with a thread using a sewing machine, and the evaluation device B1 Was produced.
-In the above (manufacturing of a flexible telescopic heater device), after drawing the stretchable heater wiring and drying at 140 ° C. for 20 minutes, the obtained insulating paste is used on the stretchable heater wiring to obtain a thickness of 0.05 mm. An insulating protective layer was formed, dried at 140 ° C. for 20 minutes, and then cured at 180 ° C. for 2 hours to obtain a flexible telescopic heater device with an insulating protective layer. Using this flexible telescopic heater device with an insulating protective layer, the evaluation device B2 was manufactured in the same manner as the evaluation device B1.
-The evaluation device B3 was produced in the same manner as the evaluation device B2 except that the cured product of the silicone rubber-based curable composition of Sample 3 was used for the elastic substrate.
In the evaluation devices B1 to B3, no damage such as cracks was confirmed around the portion of the stretchable substrate that had been sewn.

-Washing resistance test: Using a home washing machine, in accordance with JIS L1930 (C4M method), after washing, rinsing 1 and rinsing 2, the test of hanging and drying is repeated 20 times.
In the evaluation devices B1 to B3 before the washing resistance test and after the washing resistance test, the surface of the elastic heater wiring was exposed when the 20% elongation was repeated 100 times and when the 50% elongation was repeated 100 times. It was confirmed that heat was generated up to 50 ° C (at 12 ° C / min).

-Wearability The stretchable substrate of the flexible stretchable heater device of each embodiment obtained above was sewn to the back portion of the T-shirt with a sewing thread. The subject took off and put on the T-shirt on which the flexible telescopic heater device was sewn several times. It was confirmed that the flexible telescopic heater device followed the subject's back during wearing and that the flexible telescopic heater device did not peel off from the T-shirt after attachment / detachment.

The flexible telescopic heater devices of Examples 1 to 3 showed excellent results in telescopic durability and the like.

10 Elastic board 20 Elastic heater wiring 30 External connection 50 External electrode 60 Insulation protective layer 100 Flexible telescopic heater device 320 Control unit 330 Input unit 340 Communication unit 350 Power supply unit 360 Storage unit

Claims (18)

An elastic substrate containing an insulating elastomer and
The elastic heater wiring including the conductive elastomer formed on the elastic substrate is provided.
Flexible telescopic heater device. The flexible telescopic heater device according to claim 1.
A flexible telescopic heater device having a stretchable substrate having a substrate thickness of 400 μm or less. The flexible telescopic heater device according to claim 1 or 2.
A flexible telescopic heater device having a tear strength of 25 N / mm or more of the insulating elastomer measured at 25 ° C. according to JIS K6252 (2001). The flexible telescopic heater device according to any one of claims 1 to 3.
A flexible telescopic heater device having a breaking elongation of the insulating elastomer of 500% or more, measured at 25 ° C. according to JIS K6251 (2004). The flexible telescopic heater device according to any one of claims 1 to 4.
A flexible telescopic heater device having a tensile strength of 5.0 MPa or more of the insulating elastomer measured at 25 ° C. in accordance with JIS K6251 (2004). The flexible telescopic heater device according to any one of claims 1 to 5.
A flexible telescopic heater device having a durometer hardness A of the insulating elastomer of 20 or more, measured at 25 ° C. according to JIS K6253 (1997). The flexible telescopic heater device according to any one of claims 1 to 6.
In one of the cross sections of the flexible telescopic heater device, when the substrate thickness of the stretchable substrate when not stretched is X and the wiring thickness of the stretchable heater wiring when not stretched is Y.
A flexible telescopic heater device in which X and Y are configured to satisfy 0.02 ≦ Y / X ≦ 5. The flexible telescopic heater device according to any one of claims 1 to 7.
In one of the cross sections of the flexible telescopic heater device, when the wiring thickness of the stretchable heater wiring when not extended is Y and the wiring width is Z.
A flexible telescopic heater device in which Y and Z are configured to satisfy 0.4 ≦ Z / Y ≦ 250. The flexible telescopic heater device according to any one of claims 1 to 8.
The insulating elastomer is composed of a cured product of a silicone rubber-based curable composition containing a vinyl group-containing organopolysiloxane.
A flexible telescopic heater device in which the conductive elastomer is composed of a conductive filler and a cured product of a silicone rubber-based curable composition containing a vinyl group-containing organopolysiloxane. The flexible telescopic heater device according to claim 9.
A flexible telescopic heater device in which the conductive filler contains silver powder. The flexible telescopic heater device according to any one of claims 1 to 10.
A flexible telescopic heater device in which at least one of the insulating elastomer and the conductive elastomer contains a non-conductive filler. The flexible telescopic heater device according to any one of claims 1 to 11.
A flexible telescopic heater device in which an insulating protective layer is formed on the surface of the stretchable heater wiring. The flexible telescopic heater device according to any one of claims 1 to 12.
A flexible telescopic heater device in which the resistance value of the stretchable heater wiring at 25 ° C. and unstretched is 1 Ω or more and 200 Ω or less. The flexible telescopic heater device according to any one of claims 1 to 13.
When the resistance value of the elastic heater wiring at 25 ° C. and not extended is R1, and the resistance value of the elastic heater wiring at 25 ° C. and 50% extension is R2.
A flexible telescopic heater device in which R1 and R2 are configured to satisfy 1 ≦ R2 / R1 ≦ 10. The flexible telescopic heater device according to any one of claims 1 to 14.
A flexible telescopic heater device having a volume resistivity of 1.0 × 10 ^-5 Ω · cm or more and 1.0 × 10 ¹ Ω · cm or less at 25 ° C. when unstretched. The flexible telescopic heater device according to any one of claims 1 to 15.
When the weight of the elastic substrate before the water exposure treatment is W1 and the weight of the elastic substrate after the water exposure treatment at 40 ° C. for 120 minutes is W2.
A flexible telescopic heater device in which W1 and W2 are configured to satisfy -3≤ (W2-W1) / W1 * 100≤1. The flexible telescopic heater device according to any one of claims 1 to 16.
A flexible telescopic heater device that is a wearable device that can be worn on either the body or clothing. The flexible telescopic heater device according to any one of claims 1 to 17.
Washable, flexible telescopic heater device.

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