JP6948224B2 - Manufacturing method of insulating composition and chip resistor - Google Patents

Description

The present invention relates to an insulating composition, a chip resistor, a method for producing a display body, and a method for producing a chip resistor.

Due to the recent demand for miniaturization, high efficiency, and high output for electrical equipment, adhesion that can cope with severe physical or chemical stress is applied to electrical coating with an insulating composition or insulating material. High mechanical strength typified by property, (heat) impact resistance, or wear resistance is required.

Typical targets for coating with insulating compositions or insulating materials are not only terminals of various electrical contacts, but also rotors and stators of various electric motors, field coils for motors, electric wires for construction, home appliances and industry. -Electric wires for electric power equipment, electric wires such as underground power transmission cables, transformers, high voltage generators for medical equipment, etc., or electronic parts such as resistors, capacitors, inductors, semiconductor parts, etc. that are generally used in electronic circuits. Further, it is a mounting circuit board substrate, a wiring circuit, and various chip-shaped electronic components used for general electronic control and the like.

For example, as shown in FIG. 5, a general chip resistor 900 includes a resistor 950 formed on a ceramic base material 910, a glass material layer 960 covering the resistor 950, and further the glass material. It has a protective film 970 that covers the layer. In addition, the chip resistor 900 has a metal electrode layer 920 electrically connected to the resistor 950 and a metal electrode layer 920 on a part of a flat surface, a part of a bottom surface, and a side surface of a ceramic base material 910. A nickel layer 930 and a tin-plated layer 940 are provided. When the glass material layer 960 is omitted and the protective film 970 is directly formed and coated on the resistor 950, or between the metal electrode layer 920 and the nickel plating layer 930, a resin electrode layer containing conductive fine particles. May be formed.

The protective film described above is provided to prevent corrosion by the plating solution or deterioration of the resistor due to the external environment (humidity, etc.). Examples of the material of the protective film are an alicyclic epoxy resin, a phenol aralkyl resin, and an epoxy resin containing a curing accelerator (Patent Document 1), or a cresol novolac type epoxy resin, a phenol aralkyl resin, and a phenol-modified xylene resin. (Patent Document 2) is disclosed.

In addition, chip-shaped electronic components such as resistors or integrated circuits (ICs) that are surface-mounted on a substrate have their identification numbers, product code, and / or product numbers, etc. (hereinafter collectively referred to as "numbers, etc."). ) Is displayed on the surface of the electronic component. As far as the inventors know, until now, in order to display the above-mentioned numbers and the like, thermosetting or ultraviolet-curable epoxy resins and the like have been mainly used on the surface of the electronic component (the surface of the above-mentioned protective film). The process of applying and transferring the stamping paste or ink as an ingredient has been generally adopted.

Further, in an electronic component with a lead, a method of displaying an identification number or the like by transferring an ink containing a pigment onto the surface of the electronic component using a roller or a stamp, or forming the ink on the surface of the electronic component. A method of displaying an identification number or the like by irradiating a coating film containing a color-developing agent or a heat-absorbing agent with a laser to develop a color or forming an uneven surface is adopted.

Japanese Unexamined Patent Publication No. 7-278260 Japanese Unexamined Patent Publication No. 2009-091424

However, the stamping paste or ink formed on the surface of the electronic component may cause problems with adhesion to the surface of the electronic component. In addition, defects due to so-called coating, such as bleeding and / or chipping of the stamp paste or ink, reduce or make the visibility of the person who handles the electronic component (for example, a worker in the manufacturing factory of the electronic component) reduced or invisible. Will let you. In addition, when the electronic components are mass-produced, problems such as defects due to mechanical contact may occur when the electronic components are collectively processed and manufactured. Further, the above-mentioned problem may occur not only at the time of manufacturing the electronic component but also at the time when the electronic component is mounted on a circuit board or an electronic device module and actually used.

The above-mentioned technical problem is not limited to the numbers and the like formed on the surface of the electronic component, but also to the numbers and the like for various electric devices whose at least a part is covered with the insulating composition. The part fits.

The present invention can greatly contribute to enhancing the visibility of numbers and the like used in various devices such as electric devices by solving at least one of the above-mentioned technical problems.

As a result of intensive research and analysis by the present inventors, the present inventors have found that at least a part of the electric device is covered with an insulating composition or an insulating material (hereinafter, collectively referred to as "insulating composition"). We focused on the fact that there is a limit to adopting a display body that is separate from the above, no matter how the adhesiveness with electrical equipment is improved. Based on such awareness of the problem, the present inventors have conducted extensive research and analysis on the possibility that the insulating composition itself can display a number or the like, so to speak, as a display body. In addition, the present inventors have also paid attention to the laser resistance of the insulating composition, and have conducted extensive research in order to create an insulating composition in consideration of improving the laser resistance. As a result, the present inventors substantially impair the insulating property by containing a specific substance whose state can be visually changed by applying a predetermined energy from the outside. It has been found that at least some of the above technical problems can be solved without any need. The present invention was created based on the above viewpoint.

One insulating composition of the present invention comprises a thermosetting and / or photocurable polyfunctional epoxy resin (a), a curing agent (b), inorganic particles (c), a solvent (d), and the like. _{It contains titanium oxide (TiO 2} ) and / or titanium oxynitride (e) that produces lower-order titanium oxide by being given the energy of.

According to this insulating composition, it is possible to realize with high accuracy the display of numbers and the like for various devices such as electric devices, which are at least partially covered with the insulating composition. More specifically, since the insulating composition itself has a function of displaying, the problem of adhesiveness between a component provided separately from the insulating composition and the insulating composition as in the conventional case does not occur. A special technical effect is achieved.

Further, one method for producing a display body of the present invention is a thermosetting and / or photocurable polyfunctional epoxy resin (a), a curing agent (b), inorganic particles (c), and a solvent (d). ) And titanium oxynitride (e) in a planar insulating composition, with respect to a part of the titanium oxynitride (e), titanium oxide (TiO ₂ ) and / or lower order. Titanium oxide (TiO _X , x in the formula includes an energy supply step that provides energy for the production of 0 <x <2).

According to this method for manufacturing a display body, a display body capable of highly accurately displaying a number or the like for various devices such as electrical equipment, which is at least partially covered with the above-mentioned insulating composition, is manufactured. be able to. More specifically, since the display body manufactured by this manufacturing method has the function of displaying the display body itself, the components and the insulating composition which are provided separately from the insulating composition as in the conventional case. It has a special technical effect that the problem of adhesion to objects does not occur.

Further, one method for producing a chip resistor of the present invention is a thermosetting and / or photocurable polyfunctional epoxy resin (a), a curing agent (b), inorganic particles (c), and a solvent ( The above-mentioned acid in the coating step of covering at least a part of the surface of the chip resistor with an insulating composition containing d) and titanium oxynitride (e) and forming a surface. For a part of titanium nitride (e), titanium oxide (TiO ₂ ) and / or lower titanium oxide (TiO _X , x in the formula gives energy for producing 0 <x <2). Including the energy supply process.

According to this method for manufacturing a chip resistor, it is possible to manufacture a chip resistor capable of highly accurately displaying a number or the like for a chip resistor whose at least a part is covered with the above-mentioned insulating composition. .. More specifically, since the chip resistor manufactured by this manufacturing method has a function of displaying the insulating composition itself, the insulation is provided with a component separately provided from the insulating composition as in the conventional case. A special technical effect is achieved in which the problem of adhesion to the composition does not occur.

According to one insulating composition of the present invention, it is possible to realize with high accuracy the display of numbers and the like for various devices such as electric devices, which are at least partially covered with the insulating composition.

Further, according to one method of manufacturing a display body of the present invention, a display such as a number for various devices such as electrical equipment whose at least a part is covered with an insulating composition can be realized with high accuracy. The body can be manufactured.

Further, according to one method for manufacturing a chip resistor of the present invention, a chip resistor capable of highly accurately displaying a number or the like for a chip resistor whose at least a part is covered with an insulating composition is manufactured. can do.

It is sectional drawing of the chip resistor of 2nd Embodiment. It is a schematic diagram (perspective view) of the chip resistor provided with the insulating protective film in the state which exhibits the display function as a display body in 3rd Embodiment. It is a schematic diagram (perspective view) of the electric wire provided with the insulating protective film in the state which exhibits the display function as a display body in the modification of the 3rd Embodiment. It is a photograph of the insulating composition (display body) exhibiting the display function according to the fifth embodiment. It is sectional drawing of the conventional chip resistor.

Hereinafter, an example of the insulating composition according to the embodiment of the present invention will be described in detail.

<First Embodiment>
The insulating composition of the present embodiment contains a thermosetting and / or photocurable polyfunctional epoxy resin (a), a curing agent (b), inorganic particles (c), a solvent (d), and a predetermined amount. _{It contains titanium oxide (TiO 2} ) and / or titanium oxynitride (e) that produces lower-order titanium oxide when energy is applied. An example of application of the insulating composition of this embodiment to various typical products is an insulating protective paste composition.

The component (a) of the present embodiment is a thermosetting and / or photocurable epoxy resin. The type of the epoxy resin is not particularly limited. Examples of typical epoxy resins are bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, hydroxyphenyl type epoxy resin, alicyclic epoxy resin, alkyl type epoxy resin and the like.

In this embodiment, a predetermined energy is applied to the above-mentioned insulating composition from the outside. Typical examples of the energy applying means are laser irradiation, heating with various known heaters, or ultraviolet rays.

Therefore, in order for the insulating composition of the present embodiment to exhibit the display function with higher accuracy, an epoxy resin having the following performances (1) and / or (2) is adopted as the component (a) of the present embodiment. Is a preferred embodiment.
(1) Performance that can withstand exposure to locally high energy due to the above-mentioned laser irradiation, etc., and / or performance that can withstand exposure to locally high temperature (2) Thermal history of the insulating composition (heat cycle) ) Tolerance

Further, the type of the curing agent for the component (b) of the present embodiment is not particularly limited. Examples of the curing agent in a typical thermal curing, acid anhydride curing agent, imidazole curing agent, phenol type curing agent, amine curing agent, and dicyandiamide: from the group of (Dicyandiamide also referred to as [Dicy].) At least one selected. It is preferable to adopt the above-mentioned example of a typical curing agent because the effect of ensuring sufficient curability of the epoxy resin in the insulating composition of the present embodiment can be obtained.

The component (b) of the present embodiment has a viewpoint of increasing resistance to external energy (for example, resistance to laser irradiation) and resistance to heat caused by external energy (for example, heat during laser irradiation). It is preferable to select from the viewpoint of enhancing or enhancing the resistance to deterioration of mechanical properties. From each of the above viewpoints, for example, adopting a dicyandiamide-based curing agent or an imidazole-based curing agent is a more preferable embodiment. The amount of the curing agent in the thermosetting is not particularly limited. However, when the total mass of the component (a) of the present embodiment is 100 parts by mass, the total mass of the component (b) of the present embodiment may be adjusted in the range of 1 part by mass or more and 20 parts by mass or less. It is preferable because sufficient curability and appropriate reactivity can be achieved at the same time.

An example of a photocurable curing agent is a known curing agent, which is a so-called "photopolymerization initiator", which generates radicals and / or acids when irradiated with ultraviolet rays or the like to initiate polymerization. A typical example of a photopolymerization initiator is a triallyl sulfonium salt or the like. Further, if necessary, a known polymerization inhibitor, light stabilizer, and / or photosensitizer and the like can be further added. The blending amount of the photopolymerization initiator is not particularly limited. However, when the total mass of the photocurable epoxy resin and the epoxy monomer of the present embodiment is 100 parts by mass, the photocurable curing agent of the present embodiment is prepared in the range of 1 part by mass or more and 15 parts by mass or less. This is preferable because appropriate reactivity and sufficient curability can be achieved at the same time.

Further, the type of the inorganic particles of the component (c) of the present embodiment is not particularly limited. From the standpoint of maintaining electrical insulation with high accuracy, examples of suitable inorganic particles are at least one selected from the group of silica, magnesium silicate (talc), alumina, and titania. By adopting ceramic particles such as silica, magnesium silicate, alumina, and titania as the component (c) of the present embodiment, the insulating property of the insulating composition of the present embodiment is further enhanced.

Further, the type of the solvent of the component (d) of the present embodiment is not particularly limited. The solvent of the present embodiment is applied in various ways when the component (a) of the present embodiment (epoxy resin) and the component (c) of the present embodiment (inorganic particles) are mixed and used as a paste-like substance. Alternatively, it is used to provide appropriate coatability for forming a coating film in a transfer step. Examples of coating or transfer means for a substrate such as ceramic, resin, or metal are coating or transfer means by a screen printing method, a roller transfer method, a dip method, a dipping method, a spray coating method, or the like. Therefore, the solvent of the component (d) of the present embodiment can be adopted as long as it gives an appropriate viscosity and stability to the insulating composition in a general working environment.

In addition, examples of typical solvents are
Aliphatic alcohols such as ethanol, n-propanol, isopropanol, isobutanol;
Terpenols such as tarpioners;
Glycol ethers such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and hexyl carbitol;
Esters such as isopropyl acetate, ethyl propionate, butyl benzoate, diethyl adipic acid;
And / or hydrocarbons such as n-hexane, dodecane, and tetradecene.

Therefore, each of the above-mentioned solvents can be used alone or in combination of two or more. It is particularly preferable to use glycol ethers and / or terpenols in the insulating composition of the present embodiment from the viewpoint of exhibiting an advantageous feature that it becomes difficult to thicken with time.

Further, the titanium oxynitride of the component (e) of the present embodiment is generally called titanium black. By applying a predetermined energy (for example, energy from laser irradiation) from the outside to the titanium oxynitride, at least a part of the titanium oxynitride is made of titanium oxide (TiO ₂ ) and / or lower titanium oxide (dio _X). , X in the equation can be chemically changed to 0 <x <2). As a result, the insulating composition of the present embodiment contains the titanium oxide and / or the lower-order titanium oxide produced by applying energy to a part of the titanium oxynitride component (e). become. In this embodiment, the above-mentioned chemical changes are positively utilized. Specifically, the insulating composition of the present embodiment is more likely to form a concavo-convex shape by simply irradiating a laser and perceive it by causing a visual difference in color vision between humans before and after the chemical reaction. Is highly accurate and can function as a display body.

More specifically, when a predetermined energy is applied from the outside, the above-mentioned titanium oxide and / or lower order which changed to white with respect to the black matrix, coupled with the excellent light-shielding property of titanium oxynitride in a wide wavelength range. Titanium oxide will look more visually. The high contrast formed between the white color caused by the titanium oxide and / or the lower titanium oxide and the black color caused by the titanium oxynitride can be relatively easily realized by the external energy as described above. Deserves special mention. As will be described later, the function as a display body utilizing the insulating composition of the present embodiment is not limited to the difference due to the contrast (that is, lightness) between white and black, but the hue and / or by developing a color. It is also possible to realize a display function using saturation.

In addition, since the insulating composition of the present embodiment contains titanium oxynitride having material stability, the insulating composition may temporarily cover some device (for example, a resistor of a chip resistor). When provided, it can suppress or mitigate the influence of external environmental factors such as humidity and can exhibit a function as an insulating protective film having high electrical insulation. Therefore, if the insulating composition of the present embodiment is provided so as to cover at least a part of some device, the insulating composition has both a function as a durable protective film and a display function. It can play the role of a realized composition.

By the way, it is preferable that the titanium oxynitride is uniformly dispersed in the insulating composition of the present embodiment. The content of the titanium oxynitride is not particularly limited. However, from the viewpoint of realizing a visually clearer display by a human, the oxynitride is applied to the total mass of the insulating composition before the insulating composition of the present embodiment is cured and dried. The titanium content is preferably 0.5% by mass or more and 20% by mass or less, and more preferably 2% by mass or more and 15% by mass or less. The content of the titanium oxynitride is 7% by mass or more and 30% by mass or less with respect to the total mass of the insulating composition at the stage after the insulating composition of the present embodiment is cured and dried. It is preferable, and it is more preferable that it is 2.8% by mass or more and 40% by mass or less.

Further, the particle shape and particle size of the titanium oxynitride of the present embodiment are not particularly limited.
Usually, the primary particle size is 1 μm or less. However, when a coating film is formed using the insulating composition of the present embodiment, it is a more preferable aspect that the primary particle size is 200 nm or less from the viewpoint of improving the workability.

Further, the predetermined energy given to the insulating composition of the present embodiment is that at least a part of titanium oxynitride is titanium oxide (TiO ₂ ) and / or lower titanium oxide (TiO _X , x in the formula is x in the formula). Energy that can change to 0 <x <2). Given that energy, at least some of the effects of this embodiment are achieved. When laser irradiation is adopted as a means for applying energy, from the viewpoint of exerting the function as a display body with higher accuracy, the part of titanium oxynitride of the component (e) of the present embodiment is used. it is preferred that 50 J / cm ² or more 500 J / cm ² or less of the optical energy density is given. By adopting the light energy density in the numerical range, it is possible to obtain a concave shape having an appropriate depth that can obtain visibility by color development with higher accuracy, and / or the device itself to be protected or the device is formed. It is possible to suppress damage to the underlying material (including the resistor). In addition, so long as the light energy density is 50 J / cm ² or more 300 J / cm ² or less, more accurate high, it becomes difficult depending on the "viewing angle" as a display function, it can realize clearer visibility Therefore, the numerical range is a more preferable aspect.

From the viewpoint of enhancing the film forming property of the insulating composition of the present embodiment, the mass is taken as 100 parts by mass when the total mass of the components (a) to (d) which are the constituent materials of the insulating composition is 100 parts by mass. The standard can be shown as follows.
Total of (a), (b), and (c): Approximately 50 parts by mass to about 80 parts by mass.
(A) Component: Approximately 30 parts by mass to 50 parts by mass.
(B) Component: Approximately 0.5 parts by mass to 14 parts by mass.
(C) Component: Approximately 30 parts by mass to 50 parts by mass.

Further, in order to further enhance the display function, it is another preferred embodiment that the insulating composition of the present embodiment contains a component that can develop a color when a predetermined energy is applied from the outside. For example, when laser irradiation is adopted as a means for applying energy, the insulating composition of the present embodiment is subjected to laser irradiation in addition to the above-mentioned components (a), (b), (c), and (d). A display function capable of developing a color by further containing at least one selected from the group of magnesium oxalate, zirconium silicate, chromium compound, iron oxide, molybdenum oxide, and bismuth oxide as a color-developing pigment according to the above. It is preferable from the viewpoint of realizing the above or enhancing the display function.

In addition, the above-mentioned color-developing pigment can also play a role as an absorber of energy given from the outside. Therefore, even if the energy given from the outside exceeds the amount of energy required to produce the above-mentioned titanium oxide and / or lower-order titanium oxide, a certain amount of excess is the color-developing pigment. Will be absorbed. As a result, if the insulating composition of the present embodiment contains the above-mentioned color-developing pigment, if the insulating composition is provided so as to cover some device (for example, a resistor of a chip resistor). It is possible to prevent unnecessary or excessive energy from being supplied to the device to be protected or the underlying material on which the device is formed. This effect can greatly contribute to the improvement of the reliability of the device.

The insulating composition of the present embodiment can be produced by kneading and / or mixing each of the above-mentioned components using a rotary stirrer, a planetary kneader, or a known instrument or device such as a three-roll. .. The viscosity of the insulating composition that can be produced in the form of a paste is not particularly limited. The viscosity of the typical paste-like insulating composition has a value measured using a spiral viscometer of about 0.1 Pa · s to about 300 Pa · s.

<Second embodiment>
In this embodiment, an example in which the insulating composition of the first embodiment is used to cover the surface of at least a part of the device (for example, the chip resistor 100) will be described. Therefore, duplicate description of the insulating composition of the first embodiment may be omitted.

FIG. 1 is a schematic cross-sectional view of the chip resistor 100 of the present embodiment. The chip resistor 100 shown in FIG. 1 has the same configuration except that the protective film 970 of the conventional chip resistor 900 shown in FIG. 5 is changed to the insulating protective film 70. Therefore, the chip resistor 100 of the present embodiment has an insulation protection that covers the resistor 50 formed on the ceramic base material 10, the glass material layer 60 that covers the resistor 50, and the glass material layer 60. It has a film 70. Further, the chip resistor 100 electrically connects the metal electrode layer 20 electrically connected to the resistor 50 and the metal electrode layer 20 on a part of the flat surface, a part of the bottom surface, and the side surface of the base material 10. It includes a connected nickel layer 30 and a tin-plated layer 40.

As shown in FIG. 1, at least a part of the surface of the chip resistor 100 is covered with the insulating composition of the first embodiment. More specifically, a part or the whole of the resistor 50 included in the chip resistor 100, or a part or the whole of both the resistor 50 and the glass material layer 60 provided on the resistor 50 is the insulating composition. It is covered with an insulating protective film 70 formed from. In order for the insulating protective film 70 to exert its function as a protective layer, the insulating protective film 70 is formed by the insulating composition so that at least the resistor 50 is isolated from the external environment (for example, humidity). ..

By the way, in the present embodiment, the means or method adopted in the coating step of coating the chip resistor 100 is not particularly limited. Examples of typical coating means are a screen printing method, a roller transfer method, a dipping method, a dipping method, a spray coating method and the like. Further, it can be adopted as long as it gives an appropriate viscosity and stability in a general working environment. Further, the film thickness of the insulating protective film 70 that covers at least a part of the surface of the chip resistor 100 is not particularly limited. However, from the viewpoint of preventing or suppressing deterioration of the resistor due to electrical insulation or external environment such as humidity, it is preferable that the film thickness of the insulating protective film 70 is 5 μm or more and 40 μm or less. This is one aspect.

Further, in the present embodiment, the insulating protective film 70 can be formed by curing the paste-like insulating composition covering the chip resistor 100 with heat and / or light. Here, the heating temperature, heating time, or curing atmosphere, which are the curing conditions of the insulating composition by heat, are not particularly limited. A temperature that does not cause deterioration of the resistor 50 and a temperature at which the insulating composition is sufficiently cured and dried are adopted. When the insulating composition is cured by heat, the solvent evaporates with high accuracy, and from the viewpoint of sufficiently curing the insulating composition, the heating temperature of the insulating composition is 80 ° C. or higher and 250 ° C. or higher. The temperature is preferably 100 ° C. or higher, and more preferably 100 ° C. or higher and 210 ° C. or lower.

On the other hand, the means for curing the insulating composition by light is not particularly limited as in the case of curing by heat. For example, ultraviolet curing using a xenon lamp, a metal halide lamp, a high-pressure mercury lamp, and / or an electrodeless lamp can be adopted as a curing means for the insulating composition using the light of the present embodiment. Also in the means for curing the insulating composition with light, a temperature at which the resistor 50 is not deteriorated and a temperature at which the insulating composition is sufficiently cured and dried are adopted. In the case of performing the curing of the insulating composition according to the light, from the viewpoint of sufficiently curing the insulating composition, preferably the amount of light in the range of ^{100mW / cm 2 ~2000mW / cm 2} , the integrated quantity of light it is preferably in the range of ^{100mJ / cm 2 ~10000mJ / cm 2} .

Next, the mode in which the chip resistor 100 of the present embodiment is used to apply energy to the insulating protective film 70 of the chip resistor 100 from the outside to exert the function of the insulating protective film 70 as a display body. Will be described.

FIG. 2 is a schematic view (perspective view) of a chip resistor 100 provided with an insulating protective film 70 in a state of exhibiting a display function as a display body. The cross section AA in FIG. 2 is a schematic cross-sectional view of FIG.

In the present embodiment, as an example of the energy supply process, the insulating protective film 70 (more specifically, a part of the titanium oxynitride contained in the insulating protective film 70) forming the surface of the chip resistor 100 is subjected to. , it is given energy having a 50 J / cm ² or more 500 J / cm ² or less of the optical energy density (in this embodiment, "light energy irradiation step"). As a result, at least a part of the titanium oxynitride contained in the insulating protective film 70 is chemically treated as titanium oxide (TiO ₂ ) and / or lower titanium oxide (TiO _X , x in the formula is 0 <x <2). Can change.

In a typical example, the black color of titanium oxynitride that did not undergo a chemical change because a predetermined energy was not applied from the outside, and the above-mentioned titanium oxide and / or low that changed to white by the application of the energy. The difference in lightness from the next titanium oxide causes a visual difference for humans in terms of color vision. This difference causes the insulating protective film 70 to exhibit a display function as a display body with higher accuracy than when a concave-convex shape is simply formed and perceived by laser irradiation.

In FIG. 2, in the planar insulating protective film 70, the characters “PELNOX” and the model number (number, etc.) of “123-45A” are divided into two stages depending on the portion (white portion) where the above-mentioned chemical change has occurred. The state in which the notation is shown is drawn. As already described, if the color-developing pigment of the first embodiment is utilized, the function of the insulating protective film 70 as a display body is limited to the difference due to the contrast (that is, lightness) between white and black. Instead, it is possible to realize a display function using hue and / or saturation by developing a color.

Here, the type of predetermined energy is not particularly limited as long as it is a means capable of realizing a local supply of the energy in order to exert the display function. Therefore, known energy supply means can be adopted. A typical type of energy is light energy.

The type of light energy supply means (or light energy irradiation means) is not particularly limited. A typical light energy supply means (or light energy irradiation means) is laser irradiation. The type of the laser is also not particularly limited. For example, a carbon dioxide laser, a YAG laser, and / or a semiconductor laser can be used to apply energy to the insulating protective film 70. Further, from the viewpoint of classification by wavelength, energy can be given to the insulating protective film 70 by using an ultraviolet laser, an infrared laser, or the like.

Further, in the present embodiment (more specifically, a portion of the titanium oxynitride containing insulating protective film 70) insulating protective film 70 against, 50 J / cm ² or more 500 J / cm ² or less of the light energy Although energy with density is given, the light energy density is not limited to the above numerical range. For example, if the titanium oxynitride contained in the insulating protective film 70 is supplied with energy capable of producing titanium oxide and / or lower-order titanium oxide in the insulating protective film 70, the effect of the present embodiment can be obtained. At least part of it can be played.

<Third embodiment>
In the present embodiment, instead of the chip resistor 100 of the second embodiment, the building electric wire 200 coated with the insulating composition of the first embodiment is used, and the insulating protective film 270 of the building electric wire 200 is used. A mode in which the function as a display body is exhibited will be described.

The building electric wire 200 of the present embodiment includes an insulating protective film 270 made of the same material as the insulating protective film of the first embodiment, which covers the outer periphery of the known building electric wire 200.

In FIG. 3, in the planar insulating protective film 270, the characters "PELNOX" and the model number (number, etc.) of "543-21B" are divided into two stages depending on the portion (white portion) where the above-mentioned chemical change has occurred. The state in which the notation is shown is drawn. In FIG. 3, a wavy line is drawn on the front side of the electric wire 200 of the present embodiment in order to omit the illustration. Further, as already described, if the color-developing pigment of the first embodiment is utilized, the function of the insulating protective film 70 as a display body is limited to the difference due to the contrast (that is, lightness) between white and black. Instead, it is possible to realize a display function using hue and / or saturation by developing a color.

As shown in the second embodiment and the present embodiment, the insulating protective film 70 and the insulating protective film 270 can be used in various situations by applying energy to the insulating composition of the first embodiment from the outside. In, or for various devices, it is possible to exert a function as a display body. Therefore, the use of the insulating protective film 70 and the insulating protective film 270 is not particularly limited.

[Example]
Hereinafter, each of the above-described embodiments will be described in more detail with reference to Examples and Comparative Examples. However, these examples are disclosed only for the purpose of exemplifying each of the above-described embodiments, and do not limit each of the above-described embodiments. In addition, among the numerical values of each component (each raw material) in each Example and Comparative Example, the numerical value other than "titanium oxygen nitride content (%)" means "part by mass". Further, "%" of "oxygen nitride content (%)" means "mass%".

<Preparation of insulating composition>
Each insulating composition shown in each Example and Comparative Example is produced as follows.
First, each component of the insulating composition is blended according to the blending ratio shown in Table 1, and then a planetary kneader (manufactured by Inoue Seisakusho Co., Ltd., model PLM-15) or a kneader mixer (manufactured by Aikosha Seisakusho Co., Ltd.). ) To mix. Then, an insulating composition was obtained by kneading using three rolls (manufactured by EXAKT, model 805).

The product names of each component (each raw material) shown in Table 1 are as follows.
-Bisphenol A type (1) Epoxy resin: manufactured by Mitsubishi Chemical Corporation (model number: jER1256)
-Bisphenol A type (2) Epoxy resin: manufactured by Mitsubishi Chemical Corporation (model number: jER828)
-Cresol novolac type epoxy resin: manufactured by DIC Corporation (model number: N870)
-Alicyclic epoxy resin: Made by Daicel Co., Ltd. (Model number: Celoxide 2021P)
-Thermosetting agent: manufactured by Mitsubishi Chemical Corporation (model number: Dicy # 7)
-Photoacid generator: manufactured by Sun Appro Co., Ltd. (model number: CPI 210S)
-Titanium oxynitride: manufactured by Mitsubishi Materials Corporation (model number: TitanBlack 13M-C)
-Silica: Made by Admatex Co., Ltd. (Model number: SO-C2)
-Magnesium silicate: Made by Japan Talc Co., Ltd. (Model number: Talc P-6)
-Antifoaming agent: BYK-CHEMIE GMBH (model number: BYK-067A)
-Solvent: Daicel Co., Ltd. (Model number: Butyl carbitol acetate)

<Formation of cured product>
Each insulating composition shown in each Example and Comparative Example is a ceramic base material made of alumina through a screen mask plate using a high-precision screen printing device (manufactured by Mino Group Co., Ltd., model: Access AS-11-S5565). (Made by MARUWA: size 60 mm × 70 mm × 0.6 mm) is printed so that the film thickness after curing is about 20 μm.

After that, when thermosetting is adopted as the curing method, it is heat-cured at 180 ° C. for 30 minutes in a smooth-air drying furnace. When photo-curing is adopted as the curing method, it is dried at 80 ° C. for 1 minute in a smooth-air drying furnace, and then an ultraviolet curing device (manufactured by Multiply Co., Ltd., model MPD-031N2-). A cured coating film of the insulating composition was formed by irradiating C1) with ultraviolet rays having an integrated light amount of 300 mJ / cm ^{2 in a nitrogen atmosphere.}

<Laser marking property evaluation>
For the cured product of each insulating composition shown in each example and comparative example, a carbon dioxide laser (manufactured by Panasonic Industrial Devices SUNX Co., Ltd., model number: LP-300 series, wavelength 10.6 μm, maximum output 40 W, oscillation period 10 kHz ) Was used for laser irradiation to perform laser marking treatment.

The specific processing conditions are as follows.
Laser power: 30% -100%,
Scan speed: 500 mm / sec,
Line width: 0.10 mm,
Character height: 2.00 mm,
Character width: 2.00 mm,
Character spacing: 2.00 mm

The results of the laser marking treatment were evaluated visually. The evaluation was performed by classifying into the following three stages.
○ mark: The marking is clear (good visibility).
△ mark: The marking is slightly unclear (visibility can be obtained).
X mark: Not marked, or there is a chip or unclear part (poor visibility).

Table 2 shows the results of evaluating the visibility (results of laser marking treatment) of each Example and Comparative Example. Further, FIG. 4 is a photograph of an insulating composition (display body) exhibiting the display function according to the fifth embodiment. The portion indicated by “X” in FIG. 4 is an example of marking by laser irradiation.

As shown in Table 2, in each example, by irradiating a part of the insulating composition with a laser, the visibility as marking is good or at least obtained due to the difference between the irradiated portion and the non-irradiated portion. It turns out that it can be done. On the other hand, in the comparative example, it is confirmed that the visibility is poor under any irradiation condition.

<Other Embodiments>
By the way, in the second and third embodiments, as an example of the energy supply process, light energy is a typical example of energy given from the outside, but the type of energy in each embodiment is not limited to light energy. .. For example, as an example of the energy supply process, it is another preferable aspect that can be adopted that the example of the energy given from the outside is a known heater or electron beam having enhanced directivity of the heat ray. However, from the viewpoint of the ease of realizing the supply of the energy to an extremely local region represented by small letters or numbers, it is preferable to adopt light energy as the energy given from the outside.

The above-mentioned disclosure of the embodiment or the embodiment is described for the purpose of explaining the embodiment or the embodiment, and is not described for the purpose of limiting the present invention. In addition, modifications that exist within the scope of the invention, including other combinations of embodiments described above, are also within the scope of the claims.

The insulating composition, display body, and chip resistor of the above-described embodiment can be mainly used as an electronic component or a part thereof. However, in particular, the insulating composition and display body of the above-described embodiment are not limited to electronic components, but are not limited to electronic components, but are rotors or stators of various electric motors, field coils for motors, electric wires for construction, electric wires for home appliances / industrial / electric power equipment, and the like. It can be used in a wide range of fields such as electric wires such as underground power transmission cables, transformers, high voltage generators for medical equipment, etc.

10,910 Base material 20,920 Metal electrode layer 30,930 Nickel layer 40,940 Tin plating layer 50,950 Resistor 60,960 Glass material layer 70,270 Insulation protective film 100,900 Chip resistor 200 Building wire 970 Protective film

Claims (6)

Thermosetting and / or photocurable polyfunctional epoxy resin (a) and
Hardener (b) and
Inorganic particles (c) and
Solvent (d) and
_{Containing titanium oxide (TiO 2} ) and / or lower-order titanium oxide (TiO _X , x in the formula is titanium oxynitride (e)) that produces 0 <x <2) when given a given energy. do,
For covering at least some surfaces of one selected from the group of chip resistors, capacitors, inductors, electric motor rotors, electric motor stators, field coils, wires, transformers, and high voltage generators. ,
Insulation composition. Further comprising at least one selected from the group of magnesium oxalate, zirconium silicate, chromium compounds, iron oxide, molybdenum oxide, and bismuth oxide.
The insulating composition according to claim 1. The insulating composition according to claim 1 or 2, wherein the content of the titanium oxynitride (e) is 0.5% by mass or more and 20% by mass or less. It said curing agent (b) is an acid anhydride curing agent, imidazole curing agent, phenol type curing agent is at least one selected from the group of amine curing agent, and dicyandiamide (Dicy),
The insulating composition according to any one of claims 1 to 3. The inorganic particle (c) is at least one selected from the group of silica, magnesium silicate, alumina, and titania.
The insulating composition according to any one of claims 1 to 4. It contains a thermosetting and / or photocurable polyfunctional epoxy resin (a), a curing agent (b), inorganic particles (c), a solvent (d), and titanium oxynitride (e). A coating process that covers at least a portion of the surface of the chip resistor with an insulating composition,
With respect to a part of the titanium oxynitride (e) in the planar insulating composition, titanium oxide (TiO ₂ ) and / or lower titanium oxide (TiO _X , x in the formula is 0). Including an energy supply step that provides energy for the generation of <x <2).
Manufacturing method of chip resistors.

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