JPH07216174A - Heat-sensitive resin material, heat-sensitive body and heat-sensitive heat-generating body - Google Patents

Abstract

PURPOSE:To obtain the subject material having highly sensitive properties as a thermistor, reduced in the deterioration or change in the intrinsic impedance ¦Z¦ due to external factors such as high temperature and high humidity and having high stability CONSTITUTION:This resin material is prepared by adding an ionic additive being an ionically conductive solid polyelectrolyte prepared by dissolving sodium perchlorate in a subsidiary polymer comprising polyolefin oxide to a polymer matrix comprising a vinyl chloride resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive resin material, a heat-sensitive material, and a heat-sensitive heating element used for electric carpets and the like.

[0002]

2. Description of the Related Art For a large area heating appliance such as an electric carpet, a thermosensitive resin material containing a polyvinyl chloride resin as a main component, which is conventionally provided in Japanese Patent Laid-Open No. 2-209939, is used as a thermistor. The sheet-shaped heat-sensitive heating element, the cord-shaped heat-sensitive element, or the heat-sensitive heating element used is used.

And in the electric carpet of recent years,
As a surface material made of a carpet material or a cover material used for covering an electric carpet, a thick material tends to be preferred from the real intention or the high-class intention, and it is necessary to raise the temperature of the heating element higher than before. .

[0004]

However, when the temperature of the heating element is made higher than that of the conventional one, the temperature of the high temperature part of the partially adiabatic state, which occurs when the part is in the adiabatic state, becomes extremely high, and as a polymer matrix polymer. In a conventional heat-sensitive resin material containing a polyvinyl chloride resin as a main component, the characteristic of the relationship between the intrinsic impedance value (hereinafter abbreviated as | Z |) as a temperature sensor and temperature changes with time due to heat aging at high temperature. ,
There is a risk that the temperature to be sensed may become dangerously high due to the change of | Z |. The phenomenon is that the plasticizer in the polyvinyl chloride resin bleeds out due to the action of high temperature, and the glass transition point of the polyvinyl chloride resin shifts to the high temperature side. The polyvinyl chloride resin is exposed to high temperatures. It is considered that the cause is that the dechlorination reaction causes heat aging.

Therefore, various proposals for improvement have hitherto been made. For example, as a countermeasure, a heat-resistant plasticizer having a large molecular weight is used, or a plasticizer-impermeable film is used to prevent the plasticizer from bleeding out. Is proposed. Also, as a countermeasure, improve the thermal stability to prevent dechlorination reaction and prevent sudden deterioration,
It has been proposed to improve ionic additives in the direction of higher heat resistance. However, a typical composition with such an improvement, namely, a high-molecular-weight heat-resistant plasticizer of trimellitic acid ester or more, tribasic lead sulfate as a heat stabilizer, and an organic compound as a heat-resistant ionic additive In the heat-sensitive resin material in which the perchlorate (particularly quaternary ammonium salt) was added to the polyvinyl chloride resin, there were the following problems and the upper limit temperature for use could not be raised too much. . B) Since the temperature-impedance characteristics are determined by the amount of plasticizer added and the amount of ionic additive added to the polyvinyl chloride resin, the design of detection sensitivity in the partially adiabatic high temperature part and the thermosensitive resin material used at high temperatures It is difficult to achieve both heat deformation strength. C) Organic perchlorates such as quaternary ammonium salts have low heat resistance of the alkyl group and lose the stability of | Z | due to thermal deterioration. D) Organic perchlorate easily absorbs moisture, and even when added to polyvinyl chloride resin, it absorbs moisture. If moisture is absorbed in this way, the ionic conductivity of the ionic additive increases, and | Fluctuates toward the lower side, and quality control of characteristics is difficult. E) To increase the heat resistance of the organic perchlorate, it is necessary to use one with a large molecular weight of the alkyl group, but this one also has a large ionic radius and becomes difficult to conduct, and temperature-impedance characteristics It is difficult to increase the sensitivity of (thermistor characteristics).

The present invention has been made in view of the above points, and it is possible to increase the sensitivity of the thermistor characteristics and to deteriorate or change the specific impedance value | Z | due to external factors such as high temperature and high humidity. The purpose is to provide a highly stable thermosensitive resin material that can
It is another object of the present invention to provide a heat sensitive body and a heat sensitive heat generating body that can be used at a higher temperature than conventional ones.

[0007]

The heat-sensitive resin material according to the present invention comprises a polymer matrix polymer made of polyvinyl chloride resin, and sodium perchlorate in a subpolymer made of polyolefin oxide as an ionic additive. It is characterized by adding an ion conductive polymer solid electrolyte prepared by dissolution.

In the present invention, it is preferable to use a heat-resistant plasticizer as a plasticizer and a lead silicate type heat stabilizer in combination. Further, in the present invention, polyethylene oxide or a copolymer of polyethylene oxide and polypropylene oxide can be used as the sub-polymer comprising polyolefin oxide.

Further, in the present invention, it is preferable to adjust the content of sodium perchlorate in the subpolymer to 3% by weight to 25% by weight. In addition, in the present invention, it is preferable that the addition amount of the ion conductive polymer solid electrolyte is adjusted to 0.3 to 10 parts by weight with respect to 100 parts by weight of the polymer matrix polymer.

The heat-sensitive body according to the present invention is characterized in that a pair of electrodes are arranged with the above heat-sensitive resin material interposed therebetween. The heat-sensitive heating element according to the present invention includes a pair of electrodes arranged via the above heat-sensitive resin material to form a heat-sensitive element, and at least one of the pair of electrodes is used as a heat-generating resistor, and these are covered with an insulator. It is characterized by being formed.

The present invention will be described in detail below. Ion-conducting polymer prepared by dissolving sodium perchlorate (NaClO ₄ ) in a sub-polymer made of polyolefin oxide as an ionic additive in polyvinyl chloride resin that constitutes the matrix polymer The heat-sensitive resin material according to the present invention can be prepared by adding a solid electrolyte, further adding a plasticizer or a heat stabilizer, and kneading the mixture.

As described above, according to the present invention, sodium perchlorate is dissolved in a sub-polymer made of polyolefin oxide, and this is added to a polymer matrix polymer made of polyvinyl chloride resin.
This is because, compared with the case where only sodium perchlorate is directly added to the polymer matrix polymer made of polyvinyl chloride resin, there are the following remarkable merits.

That is, polyethylene oxide (PE
O), polypropylene oxide (PPO), and other polyolefin oxides have ether oxygen, and the sodium ion of sodium perchlorate can move through this ether oxygen. As a result, the temperature dependence of the volume specific impedance value | Z | of the polyvinyl chloride resin can be made highly sensitive, and the thermistor B constant can be increased. The B constant can be calculated by the following equation when the relationship between | Z | and temperature is set as shown in FIG.

B = (ln | Z | -ln | Za |) / (1
/ T-1 / Ta) Further, in organic perchlorates such as quaternary ammonium salts used as ionic additives in conventional heat-sensitive resin materials, the design of the volume specific impedance value | Z | The only option is to increase or decrease the amount of organic perchlorate or plasticizer, but if the amount of organic perchlorate is too small, the temperature dependence of | Z | Since it is necessary to add it to supersaturation because the stability of the sex relationship becomes poor, and the addition amount of the plasticizer is restricted by the flexibility, cold resistance, processability, etc. of the polyvinyl chloride resin. The range of adjustment of the addition amount of is small, and the degree of freedom in designing | Z | is very limited. However, by using polyolefin oxide as the subpolymer as in the present invention, | Z | is designed by changing the average molecular weight of the polyolefin oxide, in other words, changing the glass transition point (Tg point) of the subpolymer. It is possible to increase the degree of freedom in designing | Z |.

Furthermore, the quaternary ammonium salt used as an ionic additive in the conventional heat-sensitive resin material has a high hygroscopic property, and when placed in a high humidity atmosphere and absorbs moisture, the ionic conductivity of the ionic additive is increased. Of the heat-sensitive resin material
There is a problem that Z | fluctuates to the lower side, and similar problems may occur with sodium perchlorate, although not to the same extent as quaternary ammonium salts. However, in the present invention, by using PEO or a copolymer of PEO and PPO as the polyolefin oxide, the fluctuation of | Z | due to moisture absorption can be prevented. That is, PEO has a property that its viscosity increases by absorbing moisture, and by utilizing the phenomenon of thickening gelation due to moisture absorption,
By suppressing the movement of ions that become active due to the absorption of sodium perchlorate, the mobility of the ions is reduced, and the decrease of | Z | due to the improvement of ionic conductivity is positively canceled, and the heat-sensitive resin material | The change in Z | can be apparently prevented.

In the present invention, sodium perchlorate, which is an inorganic perchlorate as described above, is used as the ionic substance of the ionic additive. Ion conduction, which determines the conductivity of the heat-sensitive resin material, is determined by the number of carriers and the moving speed of carrier ions, but in order to increase the number of carriers, increase the dielectric constant ε of the polymer matrix polymer, It is effective to use a salt having a small dissociation energy, and it is effective to use a charged particle having a small ionic radius in order to increase the moving speed.
That is, in the present invention, by dispersing a polyolefin oxide having ether oxygen in a polymer matrix polymer, sodium ions having a small ionic radius move along the segmental motion through the uniformly arranged ether oxygen, and high ion It is possible to obtain a highly sensitive thermosensitive resin material having a large B constant by exhibiting conductivity.

In the present invention, the polyolefin oxide is PEO or PEO and P as described above.
It is preferable to use a copolymer of PO. PEO has a strong cation coordination ability because it has a conformation in which adjacent ether oxygens cooperatively coordinate a salt, and also has a large ionic dissociation ability, and increases the number of carrier ions and also increases the ion mobility. Is something that can be done. Also PEO
As described above, there is a thickening gelation action due to moisture absorption, and it is possible to reduce the fluctuation of | Z | due to moisture absorption of the thermosensitive resin material.

The copolymer of PEO and PPO is slightly inferior to PEO in the cation coordination ability of PPO due to the obstacle of the side chain methyl group, but at the same average molecular weight, the viscosity is much smaller than that of PEO, and the average molecular weight is much smaller. Can exist in a liquid state at room temperature at the level of several thousand, so PEO and P
By using a copolymer of PO, a subpolymer having a large ion dissociation ability and a low viscosity and being kneaded into a polyvinyl chloride resin and having good uniform dispersibility can be obtained. Of course, the polyolefin oxide is not limited to the above PEO or the copolymer of PEO and PPO.

In the present invention, the content of sodium perchlorate in the polyolefin oxide subpolymer is preferably 3% by weight or more and 25% by weight or less. If the content of sodium perchlorate is less than 3% by weight, the number of carrier ions will be insufficient, the ionic conductivity will not be sufficient, and highly sensitive thermistor characteristics cannot be obtained. On the other hand, when the content of sodium perchlorate exceeds 25% by weight, many salts that cannot be dissociated are present, which hinders the ionic conduction and rather reduces the ionic conductivity. The interaction with oxygen becomes too strong, unnecessarily increasing the viscosity of the solid polymer electrolyte. Therefore, in the present invention, the content of sodium perchlorate is 3% by weight to 25%.
By adjusting the content in the range of wt%, it is possible to obtain a heat-sensitive resin material having high sensitivity and thermistor characteristics with high ion conductivity.

Further, in the present invention, the amount of the ion conductive polymer solid electrolyte added is adjusted to the range of 0.3 to 10 parts by weight with respect to 100 parts by weight of the polymer matrix polymer made of polyvinyl chloride resin. Is preferred. If the added amount is less than 0.3 parts by weight, the ionic conductivity is insufficient, high-sensitivity thermistor characteristics cannot be obtained, and the temperature at which the dielectric loss tangent tan δ = 1 or more in the temperature dependence of | Z | Is too high and not practical. On the contrary, when the addition amount exceeds 10 parts by weight, the dielectric loss tangent tan δ = 1
Temperature becomes too low, which makes it unsuitable for use as a thermistor for electric carpets and economically unfavorable. Further, | Z | in the high temperature region becomes too small. When AC power of 100 V (50 or 60 Hz) is applied, the possibility of thermistor break increases. Therefore, by selecting the addition amount of the ion conductive polymer solid electrolyte from the range of 0.3 to 10 parts by weight, the temperature at which the dielectric loss tangent tan δ = 1 is about 40.
Between 80 ° C and 80 ° C, and the B constant in the high temperature range is large,
It is possible to obtain a heat-sensitive resin material having highly sensitive thermistor characteristics.

In the present invention, it is preferable to use a heat-resistant plasticizer such as trimellitic acid ester or pyromellitic acid ester as the plasticizer to be blended with the polyvinyl chloride resin which is the high molecular matrix polymer. . The expression of thermistor properties in the thermosensitive resin material according to the present invention is due to the ionic conductivity of sodium chlorate, which is an ionic additive, and polychlorinated polymer solid electrolyte in which sodium perchlorate is dissolved is dispersed. The thermistor properties also depend on the glass transition temperature of the matrix polymer of the vinyl resin, which is related to the type and amount of the plasticizer added to the polyvinyl chloride resin.
That is, when the high temperature acts on the heat-sensitive resin material and the plasticizer bleeds out and escapes, the glass transition temperature of the polyvinyl chloride resin changes, and | Z | changes. In the invention, by using the heat-resistant plasticizer which does not bleed out even when a high temperature is applied as described above, the fluctuation of | Z | can be reduced and the thermistor characteristics can be stabilized.

The blending amount of the heat resistant plasticizer is preferably in the range of 20 to 100 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin. If the blending amount of the heat resistant plasticizer is too small, uniform dispersibility with other blending agents, extrusion moldability, cold resistance,
There is a possibility that problems such as flexibility may occur, and conversely, if the amount of the heat-resistant plasticizer is too large, even though it is a heat-resistant plasticizer, it tends to bleed out due to the action of high temperature, and the polyvinyl chloride resin If the glass transition temperature becomes too low, | Z |
The high-sensitivity region in which the value of changes sharply with temperature shifts to the low temperature side. Therefore, the blending amount of the heat-resistant plasticizer is preferably set within the above range, and the range of 35 to 60 parts by weight is particularly suitable.

In the present invention, a heat stabilizer containing lead silicate composed of lead oxide (PbO) and silicon dioxide (SiO ₂ ) is used as a heat stabilizer to be blended with the polyvinyl chloride resin which serves as a polymer matrix polymer. It is preferable to use an agent. Tribasic lead sulfate, which has been conventionally used as a heat stabilizer for polyvinyl chloride resins, may decompose the plasticizer because it is basic, but lead silicate does not decompose the plasticizer. It is possible to use the above heat-resistant plasticizer without fear, and lead silicate can obtain high thermal stability because the lead component in the molecule is rich. .

The amount of lead silicate compounded is preferably in the range of 5 to 20 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin. If the blending amount of lead silicate is too small, the thermal stability of the heat-sensitive resin material will be insufficient, and since lead silicate is in powder form, it is difficult to uniformly blend a large amount of lead silicate. Therefore, the upper limit and the lower limit of the lead silicate content are set as described above, and particularly 10 parts by weight to 20 parts by weight.
A range of parts by weight is suitable.

As shown in FIG. 3, the heat-sensitive material A according to the present invention is prepared by winding a metal wire around an insulative core thread 6 to form an inner winding electrode 2, and using the heat-sensitive resin material 1 prepared as described above. It can be prepared by covering the outer side of the inner winding electrode 2 and winding a metal wire on the outer side to form the outer winding electrode 3. Since | Z | changes with the temperature change in the heat-sensitive resin material 1 as described above, the heat generation temperature is detected by measuring the potential difference between the inner winding electrode 2 and the outer winding electrode 3 to detect the impedance. Is something that can be done.

In the heat-sensitive heating element B according to the present invention, at least one of the inner winding electrode 2 and the outer winding electrode 3 of the heat-sensitive element A is used as a heat-generating resistor to generate heat, and these are heated by the insulator 4. It can be prepared by coating with. In FIG. 3, reference numeral 5 denotes a separation layer formed by winding a resin film on the outer side of the outer winding electrode 3.

[0027]

EXAMPLES The present invention will be further described with reference to examples. (Examples 1 to 4 and Comparative Examples 1 and 2) Examples 1 to 4 and Comparative Example 1 were prepared by mixing the components in the composition shown in Table 1 and further adding a small amount of an antioxidant and a lubricant and kneading. The thermosensitive resin materials of ~ 2 were prepared. In Table 1, octyl pyromellitic acid octyl ester (TOPM) represented by the chemical formula (1) is used as the plasticizer, and lead silicate is PbO.PbSiO ₃ (Pb).
O: 85%) and tribasic lead sulfate (tribase) 3P
using _{bO · PbSO 4 · H 2 O} . Further, in the ionic additive, the quaternary ammonium salt shown in Chemical Formula 2 is used, and the solid polymer electrolyte is a block copolymer (average molecular weight 3500) of PEO and PPO in a weight ratio of 1: 1 and sodium perchlorate. 10% by weight added, the solid polymer electrolyte is a block copolymer of PEO and PPO in a weight ratio of 1: 1 (average molecular weight 3500) to which 15% by weight of sodium perchlorate is added, and the solid polymer electrolyte is PE.
It is obtained by adding 15% by weight of lithium perchlorate to a block copolymer (average molecular weight 3500) of O and PPO in a weight ratio of 1: 1.

[0028]

[Chemical 1]

[0029]

[Table 1]

The heat-sensitive resin materials of Examples 1 to 4 and Comparative Examples 1 and 2 prepared as described above were molded into a press sheet having a thickness of 0.5 mm by a hot roll and a hot press.
A test piece was prepared by cutting out into a size of square cm. The volume characteristic impedance value | Z | at 0 ° C to 100 ° C of this test piece was measured. The results are shown in FIGS. Further, the thermistor B constant at 70 ° C. to 80 ° C. and the thermistor B constant at 80 ° C. to 100 ° C. were obtained based on the above-mentioned calculation formula. The results are shown in the column of "Thermistor B constant" in Table 2.

The test piece was subjected to 16 ° C. at 16 ° C.
The sample was heated in a gear oven for 8 hours (7 days), and the weight loss on heating and the temperature change equivalent value of the change amount of | Z | at the initial 70 ° C. point were measured. The results are shown in Table 2 under "Heating loss" and "70 ° C | Z |
Change ”column. Then, the test piece
Deterioration accelerated test by heating at ℃ (Congo Red method JIS
(200 ° C. heat resistance) was performed, and the time until the decomposition due to dehydrochlorination abruptly occurred was measured to examine the thermal stability. The results are shown in the column of "Thermal stability" in Table 3.

Further, the above test piece was subjected to 40 ° C. × 95%
| Z for the absolutely dry state when left for 168 hours under the atmosphere condition of RH and the atmosphere condition of 60 ° C. × 90% RH
The change rate of | was measured. The results are shown in Table 3 "Z due to moisture absorption | Z
It is shown in the column of “change rate”.

[0033]

[Table 2]

[0034]

[Table 3]

As shown in the column of "Thermistor B constant" in Table 2, Examples 1 to 4 using a polymer solid electrolyte prepared by adding sodium perchlorate to polyolefin oxide as an ionic additive. In comparison with Comparative Example 1 in which a quaternary ammonium salt was added as an ionic additive, the thermistor B constant was much larger, and it was confirmed that the thermistor characteristics were significantly improved in sensitivity. . In addition, Comparative Example 2 using a polymer solid electrolyte prepared by adding lithium perchlorate to polyolefin oxide, which is one of the most sensitive ionic additives up to now, is also shown in Example. As is confirmed by comparing No. 2, it is understood that the polymer solid electrolyte made of sodium perchlorate of the present invention has higher sensitivity in the same composition.

In addition, in Table 2, "heat loss", "70 ° C | Z
Change in | ”and data in the column of“ Thermal stability ”in Table 3 are the same as in Examples 1 to 6 in which the types and compounding compositions of the plasticizer and the stabilizer are the same.
Comparing 3 with Comparative Example 1, it is clearly confirmed that the heat resistance of each Example is excellent. Moreover, it is comparable to Comparative Example 2 which is excellent in heat resistance. Further, as confirmed by comparison between Example 1 and Example 4, even if the same heat-resistant plasticizer is used, the stabilizer is changed from the tribasic lead sulfate of Example 4 to the lead silicate of Example 1. As a result, the heat resistance was significantly improved.

Further, as shown in the column of "| Z | change rate due to moisture absorption" in Table 3, in each of the examples using PEO, the quaternary ammonium salt was used due to the thickening gel action by the moisture absorption. It is confirmed that the stability of | Z | is much higher than that of Comparative Example 1. Next, using the thermosensitive resin materials prepared in Example 2 and Comparative Examples 1 and 2,
A wire-shaped heat-sensitive heating element B as shown in FIG. 3 was manufactured. That is, three metal wires of 0.12 mmφ made of a copper alloy are spirally wound around the outer periphery of a core yarn 6 formed of a wholly aromatic polyester resin-based 1000 denier fiber at a pitch of 1.25 mm to form an inner winding electrode 2. The heat-sensitive resin material 1 is extruded and covered on the outer side of the outer side, and a Ni-plated metal wire having a width of 0.4 mm and a thickness of 0.05 mm is spirally wound on the outer side at a pitch of 2.0 mm to form the outer wound electrode 3. After further winding a polyethylene terephthalate film having a thickness of 12 μm on the outer side to form the separation layer 5,
A heat-sensitive heating element B using the internally wound electrode 2 as a heating resistor was prepared by insulatingly coating with a heat-resistant polyvinyl chloride resin insulator 4 having a thickness of 0.4 mm.

With respect to the heat-sensitive resin material of the heat-sensitive heating element B thus produced, | Z |
z, and the length of the heat-sensitive heating element B was 36 cm. The results are shown in Fig. 4. Further, the thermistor B constant at 80 ° C. to 100 ° C. was calculated based on the above-mentioned calculation formula. The results are shown in the column of "Thermistor B constant" in Table 4. A heat aging test was performed at 120 ° C. for 1000 hours, and the | Z | to temperature characteristics before the test and after the heat aging test were measured under the conditions of a frequency of 60 Hz and a length of the heat-sensitive heating element B of 36 cm. The results are shown in Fig. 4. Also, the temperature change equivalent value of the change amount of | Z | at the initial 70 ° C. point was measured, and the result is shown in the column of “change of 70 ° C. | Z |” in Table 4.

[0039]

[Table 4]

As can be seen from the column of "Thermistor B constant" in FIG. 4 and Table 3, the second embodiment has a larger thermistor B constant representing the degree of change rate of | Z |, and the thermistor characteristics have higher sensitivity. Is confirmed. That is, the thermistor B constant at 80 ° C. to 100 ° C. is 10350 in Comparative Example 1 and 120 in Comparative Example 2.
50 is 50, while in the second embodiment, 13100
Further, when the amount of the plasticizer used is the same, | Z | in the low temperature range has almost the same level value for all three, so that the thermistor characteristic of Example 2 has high sensitivity. is there.

As can be seen from the column of "Change in 70 ° C. | Z |" in Table 3, the change in | Z | is obviously smaller in Example 2 than in Comparative Example 1. Here, the reason why | Z | in Example 2 is decreasing is that the oligomerization of the polyolefin oxide partially occurs, so that T of the polyolefin oxide as a subpolymer is
This is probably because the g point decreased.

[0042]

INDUSTRIAL APPLICABILITY As described above, the present invention was prepared by dissolving sodium perchlorate in a high molecular matrix polymer made of polyvinyl chloride resin in a subpolymer made of polyolefin oxide as an ionic additive. Since the heat-sensitive resin material was prepared by adding the ion-conductive polymer solid electrolyte, due to the high ion dissociation ability and cation coordination ability of polyolefin oxide, and the synergistic effect of sodium perchlorate having a small ionic radius, Thermistor B, which has extremely high ionic conductivity.
It is possible to obtain a heat-sensitive resin material having a large constant, that is, high sensitivity. Moreover, by selecting the type of polyolefin oxide, the average molecular weight, the addition amount, the concentration of sodium perchlorate, etc., it becomes possible to design the thermistor characteristics with a great degree of freedom.

Further, since a heat-resistant plasticizer is added as a plasticizer and a lead silicate-based heat stabilizer is added, heat resistance and heat stability can be enhanced, and thermistor characteristics are stable and heat-sensitive. A resin material can be obtained. In addition, since polyethylene oxide or a copolymer of polyethylene oxide and polypropylene oxide is used as the sub-polymer composed of polyolefin oxide, the thickening gelation phenomenon due to the moisture absorption of polyethylene oxide is used to activate the ions activated by the moisture absorption. That suppresses the movement of ions and reduces the mobility of ions, positively cancels the decrease of | Z | due to the improvement of ion conductivity, and prevents the fluctuation of | Z | of the thermosensitive resin material due to moisture absorption. Is.

Furthermore, since the content of sodium perchlorate in the subpolymer is set to 3% by weight to 25% by weight, thermistor characteristics with high ionic conductivity and high sensitivity can be obtained. . Further, since the amount of the ion conductive polymer solid electrolyte added is set to 0.3 to 10 parts by weight with respect to 100 parts by weight of the polymer matrix polymer, a highly sensitive thermistor characteristic having a large thermistor B constant is obtained. Is something that can be done.

Further, since the heat-sensitive body according to the present invention is formed by arranging a pair of electrodes via the above-mentioned heat-sensitive resin material, the heat-sensitive heat-generating body according to the present invention further comprises the above-mentioned heat-sensitive resin. Since a pair of electrodes are arranged through a material to form a heat sensitive body, and at least one of the pair of electrodes is used as a heating resistor and these are covered with an insulator, it is possible to detect a partially adiabatic high temperature portion. The sensitivity and heat aging resistance are improved, the temperature can be used at a higher temperature than before, and the high stability of | Z | with respect to humidity can improve the accuracy of temperature control.

[Brief description of drawings]

FIG. 1 is a graph of specific impedance values | Z | to temperature curves of thermosensitive resin materials of Examples 1 to 4 and Comparative Example 1.

FIG. 2 is a graph of intrinsic impedance values | Z | to temperature curves of the thermosensitive resin materials of Example 2 and Comparative Examples 1 and 2.

FIG. 3 is a partial front view of an embodiment of the heat-sensitive heating element.

FIG. 4 is a graph of an impedance value | Z | to a temperature curve of a heat-sensitive heating element prepared using the heat-sensitive resin material of Example 2 and Comparative Examples 1 and 2.

FIG. 5: A heat-sensitive heating element prepared by using the heat-sensitive resin material of Example 2 and Comparative Examples 1 and 2 is placed in an oven at 120 ° C. for 100 times.
It is a graph of the impedance value | Z | -temperature curve before the treatment and after the heat aging, when the heat aging test is performed after the treatment for standing for 0 hour.

FIG. 6 is a graph of | Z | -temperature curve for explaining the constant B.

[Explanation of reference numerals] 1 heat-sensitive resin material 2 inner winding electrode 3 outer winding electrode 4 insulator

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area // (C08L 27/06 71:02)

Claims (7)

[Claims] 1. An ion conductive polymer solid electrolyte prepared by dissolving sodium perchlorate in a subpolymer composed of polyolefin oxide as an ionic additive in a polymer matrix polymer composed of polyvinyl chloride resin. A thermosensitive resin material characterized by being added. 2. The heat-sensitive resin material according to claim 1, wherein a heat-resistant plasticizer is added as a plasticizer and a lead silicate-based heat stabilizer is added. 3. The heat-sensitive resin material according to claim 1, wherein the sub-polymer comprising polyolefin oxide is polyethylene oxide or a copolymer of polyethylene oxide and polypropylene oxide. 4. The heat-sensitive resin material according to claim 1, wherein the content of sodium perchlorate in the subpolymer is 3% by weight to 25% by weight. 5. The addition amount of the ion conductive polymer solid electrolyte to 100 parts by weight of the polymer matrix polymer is 0.1.
3. The amount is 3 to 10 parts by weight.
5. The heat-sensitive resin material according to any one of 4 to 4. 6. A heat-sensitive body comprising a pair of electrodes arranged with the heat-sensitive resin material according to claim 1 interposed therebetween. 7. A heat sensitive body is formed by disposing a pair of electrodes via the heat sensitive resin material according to claim 1, and at least one of the pair of electrodes is used as a heating resistor, A heat-sensitive heating element characterized by being covered with an insulator.