JPS6226706A - Flexible heat sensitive wire - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a flexible heat-sensitive wire used in cloth electric heating devices such as electric blankets and electric blankets.

Conventional technology Conventionally, electric blankets, electric blankets, and electric heating devices made of cloth were
There was a strong demand for washing products so that they could not come in direct contact with the skin. In contrast, electric blankets that can be washed with water have been developed by preventing corrosion of the connection pins of electrical components inside the blankets and tracking between terminals, and by using flexible heat-sensitive wires using polymer thermosensitive materials with excellent moisture resistance. Electric bed blankets have been developed.

Problems to be Solved by the Invention Blankets are generally washed by dry cleaning companies unless otherwise specified. However, the problem with conventional electric blankets is that when they are dry-cleaned, the properties of the flexible heat-sensitive wires arranged inside the blanket change significantly due to the solvents used in the dry cleaning, such as perchloroethylene (tetrachlorethylene) and petroleum-based solvents. was there.

Specifically, it is as follows.

(1) The dry cleaning solvent passes through the outer covering of the temperature sensitive part and the resin mold of the terminal part, and reaches the polymer temperature sensitive layer.
It diffuses and significantly changes its electrical properties.

(2) Since the outer cover of the temperature sensitive part is made of plasticized polyvinyl chloride, the plasticizer is eluted by the dry cleaning solvent, resulting in a loss of flexibility and a significant reduction in its thickness.

An object of the present invention is to provide a flexible heat-sensitive wire that can be used in cloth electric heating devices such as electric blankets and electric bed blankets and can be dry cleaned.

Means to Solve the Problem Electrodes are provided through a polymer temperature-sensitive layer, and a temperature-sensing part is provided with an outer cover over these, and these electrodes and metal terminals are connected, including that part. In a flexible heat-sensitive wire consisting of a hot part and a terminal part in which a metal terminal is fixed by a resin mold, a barrier layer against a dry cleaning solvent is provided on at least a part of both the outer covering of the heat-sensing part and the resin mold of the terminal part. , and oxidizes at least the barrier layer of the temperature-sensitive portion of the resin-molded portion.

Function Highly crystalline polymer materials have a low affinity with dry cleaning solvents and have a dense structure, so they have excellent solvent resistance and an extremely small amount of solvent permeation. Therefore, by providing a barrier layer made of these polymeric materials on the temperature-sensitive layer, the influence of solvents that permeate through the outer covering of the temperature-sensitive part of the flexible heat-sensitive wire can be kept to a very low level. I can do that.

In addition, since the amount of solvent permeation is extremely small, even if the thickness is reduced, it still provides sufficient solvent barrier properties during the dry cleaning process. It won't happen.

On the other hand, the influence on the properties due to the permeation and infiltration of the solvent from the terminal portion increases as the length of the flexible heat-sensitive wire becomes shorter. Therefore, it is necessary to provide a barrier layer at the terminal portion. A polymeric material that satisfies the following requirements is suitable for this barrier layer.

(1) The resin mold fixes the metal terminal and the temperature sensing part,
It is formed with a large wall thickness because it has the function of protecting these connecting parts. Therefore, the material for the barrier layer of the terminal portion may be any material that exhibits barrier properties due to its large thickness.

(2) In order to prevent the solvent from entering through the contact areas between the metal terminals and the temperature sensing part and the barrier layer of the terminal part, it is desirable to bond those parts. Therefore, a polymeric material with good adhesiveness is suitable for the barrier layer of the terminal portion.

When metals are left in the air, their surfaces are usually oxidized and have polar groups. Therefore, among the resin-molded parts, at least the barrier layer of the temperature-sensitive part is oxidized to give it polarity, and the barrier layer of the terminal part is made of a polymer having polar groups such as carboxyl, carbonyl, hydroxyl, and amide groups. When molecular materials are used, adhesion occurs through van der Waalska and hydrogen bonds. These can prevent the permeation and infiltration of solvent from the terminal portion from affecting the properties.

EXAMPLES Polymer temperature sensitive layers used in the flexible heat sensitive wire of the present invention include thermistor materials, temperature fuse materials, and resistive materials with a positive temperature coefficient of resistance. Thermistor material is
It is a material whose resistance, capacitance, or impedance decreases when the temperature rises, and it is a polymer composition that uses polyvinyl chloride or polyamide as a pace polymer, and the temperature fuse material is a crystalline thermoplastic resin such as nylon or polypropylene. It is a polymer composition consisting of: Further, the resistive material is made of a composite composition in which conductive particles such as carbon black are dispersed in a polymer matrix.

On the other hand, dry cleaning generally requires about 30 degrees of labor per process and uses percrene (tetrachlorethylene) or petroleum-based solvents as the solvent. Therefore, it is necessary for the flexible heat-sensitive wire to have at least a small change in the properties of the polymeric temperature-sensitive layer over this period of time, and to not lose its flexibility due to elution of the plasticizer in the outer coating due to repetition of this process.

Materials that meet these conditions include the following:

Nylon 11 or Nylon 1 is used as a barrier layer for the temperature sensitive part.
2, vinyl alcohol copolymers such as random or block copolymers of ethylene and vinyl alcohol, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymers, and polyvinylidene fluoride.

Examples include fluorine-containing polyolefins such as polyvinylidene chloride, vinylidene-based polyolefins, and highly crystalline polyolefins such as high-density polyethylene and polypropylene. Further, as the barrier layer of the terminal portion, there are polymeric materials having polar groups such as carboxyl group-containing polyolefin, ionomer, and polyamide.

A detailed explanation will be given below based on examples.

Example 1 FIG. 1 shows a partially cutaway cross-sectional view of a temperature-sensitive portion of a flexible heat-sensitive wire of the present invention, and FIG. 2 shows a partially cutaway cross-sectional view of a terminal portion. In the figure, 1 is a core thread made of polyester, 2 and 3 are ribbon-shaped electrodes made of stainless steel, 4 is a polymer temperature-sensitive layer made of a plasticized polyvinyl chloride composition containing an organic perchlorate, and 5 6 is a barrier layer made of nylon 12, 6 is a non-leaching material layer made of vinyl chloride-urethane copolymer, 7.8 is a metal terminal connected to electrodes 2 and 3, and 9 is a barrier layer made of polyamide containing dimic acid. , 1o is a resin mold made of the same material as 6. Here, barrier layer 9. Before forming the resin mold 10, the terminal section is heated to 30KHz, 2A.
Corona discharge treatment was carried out.

Using this flexible heat-sensitive wire, an immersion test (
The impedance temperature characteristics before and after the test were measured. For comparison, a conventional example in which plasticized polyvinyl chloride was used in place of the barrier layer 5 and non-eluting material layer 6 of the temperature sensing part in FIG. 1 and the barrier layer 9 and resin mold 1o of the terminal part in FIG. An immersion test was conducted in the same manner as in Example 1. Figure 3 shows the characteristics for a length of 1 m. 11 and 12 in the figure are the characteristics of this example before and after the test, respectively.

Further, 13 is the characteristic after the test of the conventional example. In addition, 14
is the characteristic after subjecting only the terminal portion of the conventional example to an immersion test. As described above, in this example, the change in the electrical properties of the polymer temperature-sensitive layer is extremely small.

Embodiment 2 FIG. 4 shows a partially cutaway cross-sectional view of the temperature-sensitive portion of the flexible heat-sensitive wire of the present invention, and FIG. 5 shows a partially cutaway cross-sectional view of the terminal portion. In the figure, 15 is a core thread made of polyester, 16.17 is a ribbon-shaped electrode made of copper alloy, 18 is a polymer temperature-sensitive layer using nylon 12 as a temperature fuse material, and 19 is made of plasticized polyvinyl chloride. electrical insulating layer; 2o is a barrier layer made of ethylene-vinyl alcohol copolymer; 21
22 is a metal terminal connected to the electrodes 16 and 17, and 23 is a barrier layer (resin mold) made of ionomer. Here, before forming the barrier layer 23, the terminal portion was subjected to corona discharge treatment in the same manner as in Example 1. An immersion test was conducted in the same manner as in Example 1 using this flexible heat-sensitive wire. Temperature fuse performance test after test (atmosphere temperature lower than 160°C)
℃/jnin), the result was 174-1
The fuse operated at 79°C. On the other hand, the same immersion test was carried out in Conventional Example 2 in which plasticized polyvinyl chloride was used instead of the electrical insulating layer 19 and barrier layer 20 of the temperature sensing part in FIG. 4 and the barrier layer 23 of the terminal part in FIG. When we conducted a temperature fuse performance test, we found that the fuse operated at a high temperature of 181 to 197°C, with large variations.

Example 3 FIG. 5 shows a partially cutaway cross-sectional view of the temperature-sensitive part of the flexible heat-sensitive wire of the present invention, and FIG. 7 shows a partially cutaway cross-sectional view of the terminal part. Hail parts.

In the figure, 24 is a polymer temperature-sensitive layer made of a resistance material in which carbon black is dispersed in ethylene-vinyl acetate copolymer, 25 is a barrier layer made of ethylene-vinyl alcohol copolymer, and 2e is a layer made of polyvinyl chloride and polyurethane. Non-extractable material layer consisting of a mixture, 27, 28. is electrode 18
, 17 are connected to metal terminals, and 29 is a barrier layer (resin mold) made of carboxyl group-containing polyolefin.

Here, before forming the barrier layer 29, the terminal portion was subjected to corona discharge treatment in the same manner as in Example 1. Using this flexible heat-sensitive wire, an immersion test (conditions were the same as in Example 1) in a petroleum solvent (Daikyo Sekiyu, Daitsu) was conducted. For comparison, the adhesive layer 25 and the non-eluting material layer 2 of the temperature sensing part in FIG.
A similar immersion test was conducted on Conventional Example 3 in which plasticized polyvinyl chloride was used in place of the barrier layer 29 of the terminal portion shown in FIGS. 6 and 7. Figure 8 shows the resistance temperature characteristics of a 1 m length. In the figure, 30.31 is the characteristic before and after the test of this embodiment, and 32 is the characteristic after the test of the conventional example.

As shown above, in the flexible heat-sensitive wire of this example,
Changes in properties due to dry cleaning solvents were extremely small, and while in the conventional example the outer jacket diameter decreased by about 12 inches and lost flexibility, the outer jacket diameter of the present example showed almost no change.

The flexible heat-sensitive wire of the present invention can be used as a temperature sensor by using a plurality of built-in electrodes as a signal line, and can be used as a heat-sensitive heater if at least one of these electrodes is also used as a heating wire.

Moreover, if these electrodes (for example, the electrodes of Example 3) are used as power lines, they can also be used as heater wires. Therefore, it is desirable that the material covering the conductive part be a flame-retardant material. Here, the polymer whose main raw material is vinyl chloride is a flame-retardant material and an electrically insulating material, so it is suitable as an outer covering for this type of flexible heat-sensitive wire. For these reasons, if polyvinyl chloride or vinyl chloride copolymer is used as the main material for the electrical insulation layer or non-eluting material layer of the flexible heat-sensitive wire of the present invention, safety will be increased during abnormal heating. . The oxidation treatment imparts polar groups such as carbonyl groups, carboxyl groups, and hydroxyl groups to the treated surface, and corona discharge treatment is easily used. Other methods include flame treatment, hydrochloric acid, and nitric acid.

Acid treatment such as chromic acid mixture is available. Adhesion is caused by chemical adsorption by polar groups on the material surface due to oxidation treatment, as well as
It is also caused by physical adsorption due to roughness on the surface of the material. Therefore, adhesion can also be improved by roughening the surface of the material with sound paper or the like.

Effects of the Invention According to the present invention, it is possible to provide a flexible heat-sensitive wire that can be used in cloth electric heating devices such as electric blankets and electric bed blankets and can be dry-cleaned.

[Brief explanation of the drawing]

Figures 1 and 2 show the flexible heat-sensitive wire of the present invention (Example 1).
), Figure 3 shows the impedance temperature characteristics before and after the solvent immersion test of Example 1 and Conventional Example 1, and Figures 4 and 5 show the flexibility of the present invention. Heat ray (
Partially broken sectional view of the temperature sensing part and terminal part of Example 2), Part 5
7 and 7 are partially broken cross-sectional views of the flexible heat-sensitive wire of the present invention (Example 3), and FIG. 8 shows the resistance temperature characteristics of Example 3 and Conventional Example 3 before and after the solvent immersion test. 1.15... Core thread, 2. 3. 16. 17
・・・・・・Electrode, 4. 18. 24... Polymer temperature sensitive layer, 5. 20°26... Barrier layer of temperature sensing part, 9, 23.29... Barrier layer of terminal part, 7. 8. 21. 22. 27゜28...
・Metal terminal. Name of agent: Patent attorney Toshio Nakao and 1 other person No. 1
figure? π 6o to. Figure 4 Figure 5-

Claims (6)

[Claims] (1) A temperature-sensing section in which electrodes are provided through a polymer temperature-sensing layer and an outer covering is provided over these, and these electrodes and metal terminals are connected, including the connection section, and the temperature-sensing section and the metal In a flexible heat-sensitive wire consisting of a terminal portion fixed by a resin mold, a barrier layer against a dry cleaning solvent is provided on at least a portion of both the outer cover of the temperature-sensing portion and the resin mold of the terminal portion, and the terminal portion is provided with a barrier layer against a dry cleaning solvent. 1. A flexible heat-sensitive wire, wherein at least a barrier layer of a temperature-sensitive part of the resin-molded part is oxidized. (2) The flexible heat-sensitive wire according to claim 1, wherein the barrier layer of the terminal portion is made of a polymeric material having a polar group. (3) The flexible heat-sensitive wire according to claim 2, wherein the polymeric material having a polar group is at least one selected from carboxyl group-containing polyolefins, ionomers, and polyamides. (4) Claims 1 to 3, wherein the barrier layer of the temperature sensing part is at least one selected from polyamide, vinyl alcohol copolymer, fluorine-containing polymer, vinylidene polymer, and highly crystalline polyolefin. The flexible heat-sensitive wire according to any one of the above. (5) According to any one of claims 1 to 4, the outer cover of the temperature sensing part is composed of multiple layers, the outer layer is a non-eluting material layer or a barrier layer, and the inner layer is a barrier layer or an electrically insulating layer. flexible heat-sensitive wire. (6) The flexible heat-sensitive wire according to claim 5, wherein the non-eluting material layer and the electrical insulating layer are made of a polymer composition mainly composed of polyvinyl chloride or vinyl chloride copolymer.