JP6607402B2 - Self-temperature-controllable resin resistor forming composition sheet and self-temperature-controllable resin resistor sheet - Google Patents

Description

  In the present invention, the temperature at which the rate of increase in the resistance value when the self-temperature-regulating resin resistor is heated and the temperature of the atmosphere is increased (hereinafter also referred to as self-regulating temperature) is 150 ° C. The present invention relates to a self-temperature-controlling resin resistor sheet as described above, and also relates to a self-temperature-controlling resin resistor-forming composition sheet for forming the self-temperature-controlling resin resistor sheet.

  A conductive composition in which a conductive material such as carbon black or metal powder is dispersed in an organic polymer such as polyethylene or polypropylene has a PTC (positive temperature coefficient) characteristic that the resistance value changes with temperature and the resistance value increases. It is known to have Such a composition is disclosed in Patent Document 1.

An element having such a PTC characteristic (hereinafter referred to as a PTC element) has an excessive current flowing in the PTC element, and when the temperature of the PTC element itself reaches a certain temperature T ₀ (inflection point), or When the environmental temperature of the device rises and the temperature of the PTC element reaches T ₀ , the PTC element suddenly becomes a high resistance (trip state), thereby interrupting the current flowing through the element, thereby incorporating the PTC element. It is used as a protection circuit that protects electrical circuits.

  By utilizing the PTC characteristics, the conductive composition has the function of maintaining the set (material design) temperature, and has been commercialized and marketed by various manufacturers as a ribbon-like or film-like flexible heater as a self-temperature control heater. ing.

By the way, in a trip state higher than the inflection point T ₀ , the polymer softens or expands, the conductive material moves, and the resistance value increases. And if the temperature of a PTC element falls from an inflection point, softening and expansion | swelling of a polymer will be eliminated, and since a conductive material re-aggregates, resistance value will fall. Depending on the PTC element, it may be necessary to set the inflection point to 150 ° C. or higher.
Therefore, Patent Document 2 discloses a technique of a temperature self-controllable molded body made of non-thermoplastic polyimide and conductive powder as a PTC resistor that operates at a high temperature of 150 ° C. or higher. However, in the technique disclosed in Patent Document 2, since the inflection point is controlled by changing the molecule of the polyimide resin, there is a problem that the degree of freedom of design when assuming the inflection point is low.

  In addition, products with similar characteristics are being marketed with ceramic heaters that use resistance change characteristics at the Curie point of barium titanate. However, with a ceramic heater, it is difficult to freely select the shape of the self-temperature-controlling resin resistor.

Japanese Patent Publication No. 55-012683 JP 2006-173586 A

  Conventionally, in a trip state at a high temperature of 150 ° C. or higher, the polymer softens and the conductive material easily moves, and changes such as a decrease in the resistance value due to reaggregation cause an organic resin composition that exhibits stable PTC characteristics. There is a problem that it is difficult to obtain. In addition, it is necessary to design a molecule for the self-temperature-regulating resin resistor that operates at an inflection point of 150 ° C. or higher.

  In view of the above situation, the present invention forms a thin film having a self-temperature control function in a temperature range of 150 to 300 ° C. by optimizing three types of materials and composition of resin, conductive powder, and inorganic filler. A self-temperature-controllable resin resistor forming composition sheet is provided, and a self-temperature-controllable resin resistor sheet using the forming composition sheet is provided.

According to a first aspect of the present invention, there is provided an inorganic material which suppresses reaggregation in a trip state of an uncured resin pressure-sensitive adhesive containing an uncured resin, a conductive material, and the conductive material on at least one surface of the substrate. A self-regulating resin resistor forming composition containing a filler, wherein the uncured resin adhesive is an uncured thermosetting resin, an adhesive in which the thermosetting resin is dissolved in an organic solvent, a glass transition point Is an adhesive obtained by dissolving a thermoplastic resin of 250 ° C. or more in an organic solvent, or an adhesive obtained by dissolving a mixture of the thermosetting resin and the thermoplastic resin in an organic solvent , and the inorganic filler is a plate-like powder. The content of the inorganic filler is 3 to 20% by volume with respect to the volume of the self-temperature-controlling resin resistor, which is a cured product of the self-temperature-controlling resin resistor-forming composition, and the conductivity The substance is a conductive powder Ri, wherein the conductive powder comprises metal powder, the metal powder, the particle size distribution d ₅₀ of the particle size 0.1~10μm the primary particles are aggregated and characterized Rukoto such from the secondary particles of 5~60μm It is a self-regulating resin resistor forming composition sheet.

  According to a second aspect of the present invention, there is provided a self-temperature-controlling resin resistor, wherein the conductive material in the first invention is contained in an amount of 5 to 20% by volume with respect to the volume of the self-temperature-controlling resin resistor. It is a composition sheet for formation.

  According to a fourth aspect of the present invention, the inorganic filler in the first to third aspects is a layered clay mineral selected from boron nitride, bentonite, mica, and kaolin. It is a resistor-forming composition sheet.

  The fifth invention of the present invention is an epoxy resin if the resin contained in the uncured resin adhesive in the first to fourth inventions is a thermosetting resin, and a polyamide-imide resin if it is a thermoplastic resin. It is a composition sheet for forming a self-temperature-controlling resin resistor, characterized in that it is present.

  According to a sixth aspect of the present invention, when the conductive powder in the third aspect includes a metal powder, the metal powder is any one of a nickel powder, a nickel-based alloy powder, and a nickel-based coated powder. A composition sheet for forming a self-temperature adjusting resin resistor.

  In a seventh aspect of the present invention, when the conductive powder in the third aspect includes a non-metallic powder, the non-metallic powder is selected from the group consisting of carbon black powder, titanium nitride powder, and zirconium nitride powder. It is a self-temperature-controllable resin resistor-forming composition sheet, which is at least one kind of powder.

According to an eighth aspect of the present invention, there is provided a base material and a PTC characteristic in which an inorganic filler for suppressing reaggregation in a trip state of the conductive material and the conductive material is dispersed in a resin on at least one surface of the base material. A self-temperature-controlling resin resistor, wherein the resin is a thermosetting resin, a thermoplastic resin having a glass transition point of 250 ° C. or higher, and a mixture of the thermosetting resin and the thermoplastic resin. an inorganic filler 3-20% by volume of the plate-like powder of the volume adjustment type resistor, 5-20 volume% of conductive material included, said conductive material is a conductive powder, said conductive powder is A self-regulating resin resistor comprising a metal powder, wherein the metal powder comprises secondary particles having a particle size distribution d50 of ₅ to 60 μm in which primary particles having a particle size of 0.1 to 10 μm are aggregated It is a sheet.

  In a tenth aspect of the present invention, the inorganic filler in the eighth and ninth aspects is boron nitride, or at least one layered clay mineral selected from bentonite, mica, and kaolin. It is an adjustment type resin resistor sheet.

  The eleventh invention of the present invention is characterized in that the resin in the eighth to tenth inventions is an epoxy resin if it is a thermosetting resin, and is a polyimide resin or a polyamide-imide resin if it is a thermoplastic resin. It is a self-temperature adjusting type resin resistor sheet.

  According to a twelfth aspect of the present invention, when the conductive powder in the ninth aspect includes a metal powder, the metal powder is any one of a nickel powder, a nickel-based alloy powder, and a nickel-based coated powder. It is a self-temperature adjusting type resin resistor sheet.

  In a thirteenth aspect of the present invention, when the conductive powder in the ninth aspect includes a nonmetallic powder, the nonmetallic powder is at least selected from the group consisting of carbon black powder, titanium nitride powder, and zirconium nitride powder. A self-temperature-controllable resin resistor sheet characterized by being one kind of powder.

  A fourteenth aspect of the present invention is a self-temperature-regulating resin resistor characterized in that the self-regulating temperature at which the rate of increase in resistance value due to temperature rise in the eighth to thirteenth aspects changes is 150 ° C or higher. It is a sheet.

  According to the present invention, there is provided a self-temperature-adjustable resin resistor sheet capable of controlling the self-adjusting temperature in a temperature range of 150 ° C. to 300 ° C. by selecting the resin and selecting the content of the conductive powder and the inorganic filler. realizable.

It is a figure which shows the "electric resistance-temperature characteristic" of the self-temperature adjustment type | mold resin resistor which concerns on Example 1 of this invention, and represents the evaluation method of self-temperature adjustment temperature. FIG. 6 is a diagram showing “electric resistance-temperature characteristics” according to Example 2. FIG. 6 is a diagram illustrating “electric resistance-temperature characteristics” according to Example 3; 6 is a diagram showing “electric resistance-temperature characteristics” according to Comparative Example 1. FIG. FIG. 10 is a diagram showing “electric resistance-temperature characteristics” according to Comparative Example 5;

  In the present invention, when obtaining a self-temperature-controlling resin resistor, a conductive material such as carbon black or metal powder is dispersed in a single composition of epoxy, polyamideimide, polyimide, or a mixture of organic polymers. It is necessary to form a conductive composition, and as a substance for improving the electrical properties, a plate crystal or a plate-like inorganic filler is added in a predetermined amount adjusted in consideration of the content of the conductive material. The self-temperature-regulating resin resistor sheet is produced by producing a self-temperature-regulating resin resistor-forming composition sheet by forming a conductive composition.

The composition sheet for forming a self-temperature-adjustable resin resistor is a self-temperature-adjustable resin comprising an uncured resin adhesive containing an uncured resin on at least one surface of a substrate and a conductive material such as conductive powder. A resistor-forming composition is provided.
On the other hand, the self-temperature-controlling resin resistor sheet is provided with a self-temperature-controlling resin resistor on at least one surface of the substrate.
In order to describe the self-temperature adjusting resin resistor forming composition sheet according to the present invention, the self-temperature adjusting resin resistor forming composition and the self-temperature adjusting resin resistor will be described.

  With regard to the mechanism of the improvement effect of the electrical properties due to the addition of plate-like crystals and plate-like inorganic fillers contained in the self-temperature-regulating resin resistor, there should be uniformly plate-like inorganic fillers between the conductive materials. Thus, an effect of suppressing reaggregation in the trip state of the conductive substance can be considered.

[Inorganic filler]
As an inorganic filler to be used, it may be a plate-like crystal or plate-like form, and boron nitride is particularly desirable, but a layered clay mineral is also preferred. Examples of the layered clay mineral include bentonite, mica, and kaolin.
Also useful are organic bentonites of clay minerals with organic modifications.

These inorganic fillers are plate-like powders including lamellar clay minerals. In the self-temperature-controlling resin resistor according to the present invention, the inorganic fillers of this plate-like powder are oriented in approximately one direction in the resistor. Is distributed. Therefore, the orientation direction influences the manner of thermal expansion when the self-temperature-controlling resin resistor generates heat or when the self-temperature-controlling resin resistor is exposed to heat.
Therefore, the self-adjusting temperature can be set to 150 ° C. or higher by the influence of the orientation direction of the plate-like inorganic filler and the selection of the resin.

When boron nitride powder is used as the inorganic filler to be used, the particle size distribution is preferably 0.01 μm to 20 μm at d ₅₀ . On the other hand, when the average particle diameter of the boron nitride powder exceeds 20 μm, it is difficult to obtain the effect of the PTC characteristics. Here, the particle size distribution d ₅₀ is a median value of the particle size distribution measured using a laser diffraction / scattering type particle size distribution measuring apparatus.
The particle size of the layered clay mineral is 2 μm or less in the major axis direction.

The self-temperature-regulating resin resistor according to the present invention adjusts the self-regulating temperature based on the content of the inorganic filler.
When the content of the inorganic filler increases, the self-adjusting temperature tends to increase. However, when the inorganic filler exceeds 20% by volume in the self-temperature adjusting resin resistor, the resistance of the self-temperature adjusting resin resistor is increased. The value exceeds 10 ⁷ Ω and is too high to form a PTC element. On the other hand, when the content of the inorganic filler is less than 3% by volume, the self-adjusting temperature is confirmed, but the resistance value has a peak at a temperature exceeding the self-adjusting temperature, and the resistance value decreases at a temperature higher than the peak temperature. It will not function as a PTC element.

[Conductive substance]
Although the present invention includes a conductive substance, the conductive powder is particularly suitable for being easily dispersed in the self-temperature-controllable resin resistor forming composition.

(Conductive powder)
The conductive powder may be composed of metal powder, non-metal powder, or both. As for the content rate of the electroconductive powder, it is desirable that 5-20 volume% is contained in the self-temperature-controlling resin resistor.
When the content of the conductive powder is less than 5% by volume, a self-adjusting temperature is generated at a temperature of 150 ° C. or higher. However, the resistance value is 4 in a temperature range from 40 ° C. to 40 ° C. It does not rise twice and does not function as a PTC element. Further, when the content of the conductive powder is less than 5% by volume, the obtained resistance value exceeds 10 ⁷ Ω and is too high to function as a PTC element.
On the other hand, when the conductive powder contains more than 20% by volume, a self-adjusting temperature is generated at a temperature of 150 ° C. or higher. The value does not increase four times and does not function as a PTC element.

<Metal powder>
When metal powder is used for the conductive powder, nickel powder, copper powder, platinum powder, silver powder, cobalt powder, nickel alloy powder, silver alloy powder, or nickel coat powder can be used. In particular, nickel powder, nickel alloy powder, and nickel coat powder are desirable.
A nickel-chromium alloy or a nickel-copper alloy can be used as the nickel-based alloy powder. A silver-palladium alloy can be used as the silver alloy.

The particle size of the metal powder used is 0.1 μm to 10 μm as primary particles, and the particle size of the primary particles is particularly preferably 0.1 μm to 3 μm. Furthermore, metal powder, if the primary particles it is desirable to form agglomerated secondary particles, using a metal powder of secondary particles thereof primary particles are aggregated, the particle size distribution d ₅₀ of the secondary particles 5μm When the particle size of the secondary particles exceeds 60 μm, the dispersion of the metal powder in the resistor is insufficient, and the resistance value may be too high or the self-adjusting temperature may not be exhibited. On the other hand, if the particle size of the secondary particles is less than 5 μm, the metal powder is less aggregated, so that the number of intertwined portions is reduced, and the resistance value after kneading with the resin may be increased.

  The particle size of primary particles is the particle size of individual particles that are aggregated, and is measured by SEM observation. Alternatively, the SEM image may be image-analyzed to calculate the average particle size to obtain the particle size. Further, it may be obtained from a particle size distribution measured using a laser diffraction / scattering particle size distribution measuring apparatus.

<Non-metallic powder>
In addition to the metal powders described so far, non-conductive metal powders such as carbon black, titanium nitride, and zirconium nitride can also be suitably used as the conductive powder.

Metal powder is preferably the particle size distribution _{d 50} of used ones 0.005～100Myuemu, it is particularly preferable to particularly use those 0.01μm~60μm with a particle size distribution _{d 50.}
If the particle size distribution d ₅₀ is less than 0.005 μm, mixing becomes difficult, and if it exceeds 100 μm, the resistance may be increased.

[resin]
As the resin used for the self-temperature-controlling resin resistor, a thermosetting resin, a thermoplastic resin having a glass transition point of 250 ° C. or higher, or a mixture composed of both is used.
Even when the thermosetting resin is exposed to a temperature exceeding the glass transition point, it can maintain its shape without being softened until it is thermally decomposed. For such a thermosetting resin, an epoxy resin is preferable from the viewpoint of heat resistance and the like. Moreover, the glass transition point of an epoxy resin can be suitably selected from a resistance value change at a temperature higher than the self-adjusting temperature.

<Epoxy resin>
Examples of the epoxy resin include various bisphenol-type epoxies, various phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, epoxidized products of various dicyclopentadiene-modified phenol resins obtained by reacting dicyclopentadiene with various phenols, and novolaks. Modified aromatics derived from a naphthalene skeleton such as modified, and known aromatic epoxy resins such as an epoxy resin obtained by epoxidizing a phenol resin having a fluorene skeleton can be used. Moreover, it is possible to use an alicyclic epoxy resin or a known epoxy resin containing a heterocyclic ring.

Examples of the curing agent used in combination include known curing agents such as amine compounds, amide compounds, dibasic acid compounds, acid anhydride compounds, and phenol compounds.
In the amine compound, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole and the like. Examples of amide compounds include dicyandiamide. Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydro And phthalic anhydride. Examples of phenolic compounds include polyhydric phenolic hydroxyl group-containing compounds such as phenol novolac resins, cresol novolac resins, and phenol resins.

A known curing accelerator may be used in combination with the epoxy resin.
Furthermore, an organic solvent that dissolves an uncured epoxy resin or a reactive organic solvent having an epoxy group may be used in the self-temperature-controlling resin resistor forming composition according to the present invention. For example, esters such as diethylene glycol monoethyl ether acetate can be used as the organic solvent.

These uncured epoxy resins are liquid or solid pellets. The uncured epoxy resin is dissolved in an organic solvent or the like even in a solid pellet form. Therefore, these uncured epoxy resins can constitute the uncured resin pressure-sensitive adhesive according to the present invention, and can be used for the self-temperature-regulating resin resistor forming composition according to the present invention.
It is desirable that the epoxy resin used in the self-temperature-controllable resin resistor forming composition can be cured by selecting a curing agent and heating.

<Thermoplastic resin having a glass transition point of 250 ° C. or higher>
For thermoplastic resins having a glass transition point of 250 ° C. or higher, polyimide resins and polyamideimide resins are desirable. Since the polyimide resin and the polyamideimide resin do not deteriorate at a temperature of 150 ° C. to 300 ° C., they can be used for the resin of the self-temperature-controlling resin resistor according to the present invention.

  When a thermoplastic resin is used as the resin of the self-regulating resin resistor forming composition, as an uncured resin adhesive, an adhesive obtained by dissolving a polyimide resin or a polyamide resin in a known ether such as diethylene glycol monoethyl ether acetate An ionic liquid varnish can be used.

  Further, as the uncured liquid material, known diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-, which dissolves without precipitating the polyamic acid of the polyimide precursor. Ethers such as propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate And esters Varnish uncured liquid material dissolved can be used.

Even if an adhesive liquid varnish in which polyamic acid is dissolved in an organic solvent is used as an uncured resin adhesive, it is imidized by heating to 300 ° C. after application of the self-temperature-adjustable resin resistor forming composition and dehydrating and ring-closing. It can be a polyimide resin.
In addition, since polyimide resin is known to be cured by being dehydrated and closed by heating, it may be recognized as a thermosetting resin, but in the present invention, polyimide resin is used as a thermoplastic resin. Take as an example.
Moreover, the resin used for the self-temperature-controlling resin resistor according to the present invention may be a mixture of an epoxy resin and a polyimide resin.

[Self-temperature-controllable resin resistor forming composition sheet]
The composition sheet for forming a self-temperature-controlling resin resistor according to the present invention is a self-temperature-controlling resin resistor containing a conductive material and an uncured resin adhesive that contains an uncured resin on at least one surface of a substrate. A body-forming composition is provided.
The base material may have a property of peeling from the self-temperature-adjusting resin resistor forming composition, or the self-temperature-adjusting resin resistor-forming composition is cured without peeling off the base material. It is good also as an adjustment type resin resistor sheet.

  Only the self-temperature-controllable resin resistor forming composition may be transferred to the object to be pasted by using a known laminator or the like. The composition for forming a self-temperature adjusting resin resistor transferred to the adherend is heated and cured to form a self-temperature adjusting resin resistor on the surface of the adherend.

The manufacturing method of the self-temperature-controllable resin resistor-forming composition sheet is obtained by adding a self-temperature-controllable resin resistor-forming composition slurry that is diluted with an organic solvent and flows to at least one surface of the substrate. The organic solvent is removed and fixed to the surface of the substrate by heating and drying by a known doctor blade method or die coater method.
In addition, when the flowing composition slurry for forming a self-temperature adjusting resin resistor is applied, a slurry additive such as a known antifoaming agent may be added.
The composition slurry for forming a self-temperature-controlling resin resistor is prepared by mixing an inorganic filler, conductive powder, and an uncured resin adhesive with a known mixing method such as a self-revolving mixer, a bead mill, a ball mill, a roll mill, etc. Can be manufactured.

[Self-temperature-adjustable resin resistor-forming composition]
<Application>
When the self-temperature-controlling resin resistor is applied with the composition slurry for forming a self-temperature-controlling resin resistor, the plate-like powder of the inorganic filler contained is oriented and dispersed in the coating direction. When the composition for forming a self-temperature-controlling resin resistor in such a coated state is cured, the inorganic filler of the plate-like powder is cured while maintaining the orientation and dispersion state by coating.

<Curing>
The composition for forming a self-temperature-controlling resin resistor is exposed to a heat-curing temperature higher than the heat-drying temperature and cured to become a self-temperature-controlling resin resistor.
When exposed to the heat-curing temperature in this way, the resin curing reaction proceeds in the self-temperature-adjustable resin resistor-forming composition using the thermosetting resin. Moreover, when polyamic acid is used, imidation proceeds and the self-temperature-controllable resin resistor forming composition is cured. If a thermoplastic resin such as polyimide dissolved in an organic solvent is used as the uncured resin adhesive, the organic solvent is further removed and the self-temperature-controlling resin resistor forming composition is cured.

The heating and curing temperature of the self-temperature adjusting resin resistor forming composition needs to be cured at a temperature higher by 50 ° C. or more than the self-adjusting temperature.
This is because if the resin is cured at a temperature lower than the operating temperature (use temperature), the resin may change during long-term use, and sufficient reliability cannot be obtained. In practice, the temperature change is repeated in a range of about + 20 ° C., so that the temperature may be cured at a temperature of + 20 ° C. or higher.
A terminal can be formed after this hardening and a PTC element can be produced.

  Also, in the self-temperature-controlling resin resistor sheet, the base material may have a property of peeling from the self-temperature-controlling resin resistor, or the self-temperature-controlling resin resistor that does not peel off the base material. It is good also as a sheet.

[Self-temperature-regulating resin resistor]
In the self-temperature-regulating resin resistor according to the present invention, the thermosetting resin or the thermoplastic resin having a glass transition point of 250 ° C. or higher contains 3 to 20% by volume of the inorganic filler plate powder, and further contains 5 conductive powders. By including ~ 20% by volume, self-adjusting temperature is exhibited in the temperature range exceeding 150 ° C, and the resistance value of the self-temperature adjusting resin resistor is within the temperature range of 40 ° C to self-adjusting temperature. It is possible to realize a self-temperature-regulating resin resistor that is increased four times or more and does not decrease the increased resistance value even when exposed to a higher temperature.

  The self-adjusting temperature is an RT curve indicating the relationship between the resistance value and the temperature, and the temperature at which the change in the rate of increase in the resistance value relative to the temperature when the temperature of the self-temperature adjusting resin resistor is increased starts to change. (Inflection point) (Refer to FIG. 1 for details).

  Hereinafter, the effects will be described with examples.

The composition for forming a self-temperature-regulating resin resistor according to Example 1 is obtained by dissolving an epoxy resin and a curing agent phenol resin in an organic solvent diethylene glycol monoethyl ether acetate as an uncured resin adhesive. An adhesive was prepared. In that case, it mixed so that the numerical value of the epoxy equivalent of an epoxy resin and the phenol equivalent numerical value of a phenol resin might correspond.
As the conductive material, Ni powder having a primary particle size of 1 μm and secondary particle size distribution d ₅₀ of 10 μm was used, and boron nitride having a particle size distribution d ₅₀ of 2 μm was used as the inorganic filler of the plate-like crystals. It added to the uncured resin pressure-sensitive adhesive, and a self-temperature-controlling resin resistor forming composition slurry was prepared.

The prepared self-temperature-controllable resin resistor forming composition slurry was applied on a 37 μm-thick polyimide film used as a substrate by a doctor blade method so that the film thickness after curing was 100 μm. It was dried at a temperature of ° C. to obtain a self-temperature-controllable resin resistor forming composition sheet.
The obtained self-temperature-controlling resin resistor forming composition sheet was cured at 350 ° C. to obtain a self-temperature-controlling resin resistor sheet. The obtained self-temperature-controlling resin resistor sheet was cut into 20 mm × 30 mm, and silver electrodes were formed on both ends in the longitudinal direction to produce a self-temperature-controlling resin resistor resistor.
Evaluation of "resistance-temperature characteristics" of RT (room temperature) -300 degreeC was performed for the produced resistor in a thermostat.

The temperature at which self-temperature adjustment in the “resistance-temperature characteristics (hereinafter referred to as RT curve)” evaluation was performed by specifying the temperature of the resistance value change as follows.
An example of the evaluation method and the results according to Example 1 are shown in FIG.
As shown in FIG. 1, in the RT curve, the intersection temperature of the approximate straight line before and after the resistance value greatly changes is set as the self-adjusting temperature.
It can be seen that the self-regulating temperature of the resistor in Example 1 is 178 ° C.

In addition, self-temperature adjustment is sufficiently possible if the PTC characteristic has a resistance value change of one digit or more in the temperature range of + 40 ° C. from the temperature at which the resistance value change starts. The change starts from 150 ° C., and the resistance value changes by two or more digits in the temperature range of 150 to 190 ° C., so that it can be determined that the PTC characteristic has sufficient temperature adjustment.
The evaluation results according to Example 1 are summarized in Table 1.

Except that the content of the inorganic filler was 14 vol%, a test material according to Example 2 was produced in the same manner as in Example 1, and the characteristics were evaluated.
The results are shown in Table 1 and FIG.

In Example 3, a test material was prepared in the same manner as in Example 1 except that organic bentonite was used instead of the boron filler (BN), and the characteristics were evaluated.
The results are shown in Table 1 and FIG.

In Example 4, a test material was prepared in the same manner as in Example 1 except that the content of the Ni powder of the conductive material was 8 vol%, and the characteristics were evaluated.
The results are shown in Table 1.

In Example 5, a test material was prepared in the same manner as in Example 1 except that the content of the Ni powder of the conductive material was 13 vol%, and the characteristics were evaluated.
The results are shown in Table 1.

In Example 6, instead of the Ni powder to the conductive material, the particle size distribution d ₅₀ of except for using the carbon black of 0.04 .mu.m, the characteristics were evaluated to prepare a test material in the same manner as in Example 1.
The results are shown in Table 1.

In Example 7, instead of the Ni powder to the conductive material, except that the particle size distribution d ₅₀ of using titanium nitride 7μm evaluated the characteristics to prepare a test material in the same manner as in Example 1.
The results are shown in Table 1.

In Example 8, except that the epoxy resin was changed to a polyamide-imide resin having a glass transition point measured by TMA of 280 ° C. and dissolved in an organic solvent diethylene glycol monoethyl ether acetate to prepare an uncured resin adhesive. Sample materials were prepared in the same manner as in Example 1 and their characteristics were evaluated. In addition, the phenol resin of a hardening | curing agent is not contained.
The results are shown in Table 1.

  In Example 9, except that the epoxy resin was replaced with a polyimide resin having a glass transition point of 300 ° C. or higher measured by TMA, dissolved in an organic solvent diethylene glycol monoethyl ether acetate to prepare an uncured liquid material, A material was prepared in the same manner as in Example 1, and the characteristics were evaluated. In addition, the phenol resin of a hardening | curing agent is not contained.

In Example 10, a test material was prepared in the same manner as in Example 1 except that the content of the conductive material was changed to 5 vol%, and the characteristics were evaluated.
The results are shown in Table 1.

In Example 11, a test material was prepared and the characteristics were evaluated in the same manner as in Example 1 except that the content of the conductive material was 20 vol%.
The results are shown in Table 1.

In Example 12, a test material was produced in the same manner as in Example 1 except that the content of the inorganic filler was 3 vol%, and the characteristics were evaluated.
The results are shown in Table 1.

In Example 13, a test material was prepared and evaluated for characteristics in the same manner as in Example 1 except that the content of the inorganic filler was 20 vol%.
The results are shown in Table 1.

(Comparative Example 1)
In Comparative Example 1, a test material was prepared in the same manner as in Example 1 except that the content of the inorganic filler was 2 vol%, and the characteristics were evaluated.
The results are shown in Table 1 and FIG.

(Comparative Example 2)
In Comparative Example 2, a test material was prepared in the same manner as in Example 1 except that the content of the inorganic filler was 25 vol%, and the characteristics were evaluated.
The results are shown in Table 1.

(Comparative Example 3)
In Comparative Example 3, a test material was prepared and the characteristics were evaluated in the same manner as in Example 3 except that organic bentonite was used as the inorganic filler and the content thereof was 2 vol%.
The results are shown in Table 1.

(Comparative Example 4)
In Comparative Example 4, a test material was prepared and the characteristics were evaluated in the same manner as in Example 1 except that the content of the Ni powder of the conductive material was 4 vol%.
The results are shown in Table 1.

(Comparative Example 5)
In Comparative Example 5, a test material was prepared and the characteristics were evaluated in the same manner as in Example 1 except that the content of the Ni powder of the conductive material was 25 vol%.
The results are shown in Table 1 and FIG.

(Comparative Example 6)
In Comparative Example 6, a test material was prepared and the characteristics were evaluated in the same manner as in Example 6 except that the content of the conductive material carbon black was 25 vol%.
The results are shown in Table 1.

(Comparative Example 7)
In Comparative Example 7, a test material was prepared and evaluated for characteristics in the same manner as in Example 7 except that the conductive material was replaced with titanium nitride and the content was 25 vol%.
The results are shown in Table 1.

(Comparative Example 8)
In Comparative Example 8, a test material was prepared and the characteristics were evaluated in the same manner as in Example 8 except that the content of the Ni powder of the conductive material was 25 vol%.
The results are shown in Table 1.

(Comparative Example 9)
In Comparative Example 9, a test material was prepared and the characteristics were evaluated in the same manner as in Example 9 except that the content of the Ni powder of the conductive material was 25 vol%.
The results are shown in Table 1.

(Comparative Example 10)
In Comparative Example 10, a thermoplastic resin polyethylene (glass transition point of TMA measurement—20 ° C.) was used as the resin, and thus a self-temperature-controlling resin resistor forming composition sheet could not be produced.
Therefore, the resin, conductive powder, and inorganic filler are kneaded at a temperature of 180 ° C in a resin kneader, processed into a sheet with a thickness of 0.5 mm, punched into a size of 3 mm x 4 mm, and attached with electrodes to adjust the self-temperature. A resistor of type resin resistor was produced.
When the PTC characteristic of the resistor of the obtained self-temperature-regulating resin resistor according to Comparative Example 10 was measured, the self-regulating temperature was less than 150 ° C.
The results are shown in Table 1.

As is apparent from Table 1, in Examples 1 to 13 according to the present invention, it is understood that good PTC characteristics are obtained for both the self-adjusting temperature and the resistance value change.
On the other hand, when boron nitride (Comparative Example 1) or organic bentonite (Comparative Example 3) as an inorganic filler is 2 vol%, the effect of addition is not recognized. On the other hand, when containing 25% (Comparative Example 2), the resistance value becomes too high. As a result, the PTC characteristics are not exhibited.
Further, when the amount of conductive powder (Ni powder) was as small as 4 vol% (Comparative Example 4), the resistance value was too high and PTC characteristics were not exhibited. On the other hand, in Comparative Examples 5, 8 to 10 (Ni powder), Comparative Example 6 (carbon black), and Comparative Example 7 (titanium nitride) with a high conductive powder of 25 vol%, a sufficient effect can be obtained in the “resistance value change”. There wasn't.
Furthermore, in Comparative Example 10 in which a polyethylene resin was used as the resin, sufficient effects were not obtained for both “self-adjusting temperature” and “resistance value change”.

Claims (12)

A substrate;
Self-temperature-regulating resin resistor comprising an uncured resin adhesive containing an uncured resin, a conductive material, and an inorganic filler that suppresses reaggregation in the trip state of the conductive material on at least one surface of the base material Comprising a body-forming composition;
The uncured resin adhesive is
An uncured thermosetting resin, an adhesive obtained by dissolving the thermosetting resin in an organic solvent, an adhesive obtained by dissolving a thermoplastic resin having a glass transition point of 250 degrees or more in an organic solvent, the thermosetting resin and the heat It is one of adhesives in which a mixture of plastic resins is dissolved in an organic solvent,
The inorganic filler is a plate-like powder,
The content of the inorganic filler is 3 to 20% by volume with respect to the volume of the self-temperature-controlling resin resistor, which is a cured product of the self-temperature-controlling resin resistor-forming composition,
The conductive substance is a conductive powder;
Self said conductive powder comprises metal powder, the metal powder, the particle size distribution d ₅₀ of the particle size 0.1~10μm the primary particles are aggregated is characterized by Rukoto such from the secondary particles of 5~60μm A composition sheet for forming a temperature-adjustable resin resistor.   The conductive substance is contained in the composition for forming a self-temperature-controlling resin resistor at a content of 5 to 20% by volume with respect to the volume of the self-temperature-controlling resin resistor. The composition sheet for forming a self-temperature-controlling resin resistor according to claim 1. The said inorganic filler is 1 type of layered clay mineral chosen from boron nitride or bentonite, mica, and kaolin, The composition sheet for self-temperature-controlling resin resistor formation of Claim 1 or 2 characterized by the above-mentioned. The resin contained in the uncured resin adhesive is
If it is a thermosetting resin, it is an epoxy resin,
The composition sheet for forming a self-temperature-controlling resin resistor according to any one of claims 1 to 3 , wherein the composition sheet is a polyimide resin or a polyamide-imide resin if it is a thermoplastic resin. If they contain metal powder in the conductive powder, the metal powder, nickel powder, nickel alloy powder, self-temperature control type resin according to claim 1, characterized in that either a nickel-based coating powder Resistor forming composition sheet. When the conductive powder includes a nonmetallic powder, the nonmetallic powder is at least one powder selected from the group consisting of carbon black powder, titanium nitride powder, and zirconium nitride powder. Item 2. The self-temperature-controlling resin resistor forming composition sheet according to Item 1 . A substrate;
At least one surface of the base material is provided with a self-temperature-regulating resin resistor having PTC characteristics in which a conductive substance and an inorganic filler that suppresses reaggregation in a trip state of the conductive substance are dispersed in the resin,
The resin is a thermosetting resin, a thermoplastic resin having a glass transition point of 250 ° C. or higher, or a mixture of the thermosetting resin and a thermoplastic resin.
Wherein the inorganic filler of 3-20% by volume of the plate-like powder of the volume of the self-temperature-regulating resistor, 5-20 volume% of conductive material included, said conductive material is a conductive powder, said conductive Self-regulating type characterized in that the conductive powder comprises metal powder, and the metal powder is composed of secondary particles having a particle size distribution d50 of ₅ to 60 μm in which primary particles having a particle size of 0.1 to 10 μm are aggregated Resin resistor sheet. The self-temperature-regulating resin resistor sheet according to claim 7 , wherein the inorganic filler is at least one layered clay mineral selected from boron nitride, bentonite, mica, and kaolin. The resin is
If it is a thermosetting resin, it is an epoxy resin,
The self-regulating resin resistor sheet according to claim 7 or 8 , which is a thermoplastic resin or a polyimide resin or a polyamide-imide resin. The self-temperature-regulating resin resistor according to claim 7 , wherein when the conductive powder includes a metal powder, the metal powder is any one of a nickel powder, a nickel-based alloy powder, and a nickel-based coat powder. Body sheet. When the conductive powder includes a non-metallic powder, the non-metallic powder is at least one powder selected from the group consisting of carbon black powder, titanium nitride powder, and zirconium nitride powder. self temperature adjustment resin resistive sheet according to 7. The self-temperature-regulating resin resistor sheet according to any one of claims 7 to 11 , wherein a self-regulating temperature at which a rate of increase in resistance value due to temperature change is 150 ° C or higher.

Images