JP2016145331A - Resin composition, manufacturing method of structure, structure, and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition and a structure usable for achieving downsizing an electronic component, a manufacturing method of the structure, and an electronic component containing the structure.SOLUTION: There is provided a resin composition for manufacturing a structure exhibiting nonlinear voltage-current characteristics not following ohm principle, containing a thermosetting resin, and a semiconductor ceramic particle having a plurality of crystal parts and a grain boundary part separating the crystal parts with the semiconductor ceramic particle of 60 mass% to 97 mass% based on the total amount of the resin composition.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a method for producing a structure, a structure, and an electronic component.

In recent years, with the progress of technology capable of high-density mounting, electronic components have been reduced in size and weight. Therefore, the circuit mounted in the electronic component tends to be densified.
Here, when the circuit mounted in the electronic component is densified, an overvoltage such as static electricity is applied to cause malfunction of the electronic component, damage to the electronic component, etc. The possibility of inconvenience tends to increase.
In view of such circumstances, in order to protect an electronic element mounted in a circuit mounted in an electronic component from an overvoltage such as static electricity, a withstand voltage protection element (varistor element) mounted on the circuit together with the electronic element. Etc.) are being studied (Patent Document 1, etc.).

JP 2004-247346 A

  The conventional withstand voltage protection element is assumed to be used in a circuit together with an electronic element. Therefore, it is necessary to secure a space for arranging the withstand voltage protection element in the conventional electronic component. However, the technical level required for downsizing and weight reduction of electronic components is increasing.

  Therefore, the present inventors can provide an electronic component if it can be provided with a structure having a function of protecting against an overvoltage such as static electricity inside the electronic element itself mounted in a circuit mounted in the electronic component. We thought it could be further downsized.

  In light of the above, the present invention provides a resin composition and a structure that can be used to reduce the size of an electronic component, a method for manufacturing the structure, and an electronic component that includes the structure. is there.

According to the present invention, a resin composition for producing a structure exhibiting non-linear voltage-current characteristics that does not follow Ohm's law,
A thermosetting resin;
Semiconductor ceramic particles having a plurality of crystal parts and a grain boundary part separating the crystal parts,
A resin composition comprising 60% by mass or more and 97% by mass or less of the semiconductor ceramic particles with respect to the total amount of the resin composition is provided.

Further, according to the present invention, there is provided a method for manufacturing a structure that exhibits non-linear voltage-current characteristics that do not follow Ohm's law,
Preparing the resin composition;
And obtaining the structure by compression molding or transfer molding of the resin composition.

Furthermore, according to the present invention, there is a structure that exhibits non-linear voltage-current characteristics that do not follow Ohm's law,
A thermosetting resin, and a semiconductor ceramic particle having a plurality of crystal parts and grain boundary parts separating the crystal parts, and a cured product of a resin composition,
A structure comprising the semiconductor ceramic particles in an amount of 60% by mass to 97% by mass with respect to the total amount of the resin composition is provided.

Furthermore, according to the present invention, a substrate and an electronic device provided on the substrate and having a first terminal and a second terminal spaced apart from each other;
The structure provided on the substrate of the electronic element so as to be in contact with the first terminal and the second terminal;
A part of the semiconductor ceramic particles is disposed between the first terminal and the second terminal. An electronic component is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition and structure which can be used in order to implement | achieve size reduction of an electronic component, the manufacturing method of this structure, Furthermore, an electronic component provided with this structure can be provided.

It is an expanded sectional view of the semiconductor ceramic particle concerning this embodiment. It is a schematic diagram which shows an example of the structure which concerns on this embodiment. It is a schematic diagram which shows an example of the structure which concerns on this embodiment. It is a figure for demonstrating the method of calculating a non-linear coefficient and a varistor voltage from the measurement result of an electric current value.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

<< Resin composition >>
The resin composition according to this embodiment (hereinafter also referred to as “the present resin composition”) is for producing a structure 300 that exhibits nonlinear voltage-current characteristics that do not follow Ohm's law. (See FIG. 2). Specifically, the present resin composition includes a thermosetting resin and semiconductor ceramic particles having a plurality of crystal parts and a grain boundary part separating the crystal parts. Further, the present resin composition contains the semiconductor ceramic particles in an amount of 60% by mass to 97% by mass with respect to the total amount.

  By using the resin composition adopting such a configuration, a configuration (structure 300) having a function of protecting from an overvoltage such as static electricity is provided inside the electronic element itself arranged in the circuit of the electronic component with a high yield. It becomes possible to make it. For this reason, it is not necessary to arrange an electronic element and a withstand voltage protection element in a circuit like the conventional electronic component, As a result, size reduction of an electronic component can be implement | achieved.

  Here, the non-linear voltage-current characteristic (varistor characteristic) that does not follow Ohm's law of the structure 300 obtained by the manufacturing method according to this embodiment is an electronic component including at least two electrode terminals. When a voltage that gradually increases is applied, the current flowing through an overvoltage protection element, generally called a varistor element, increases non-linearly. In the present embodiment, the structure 300 having the varistor characteristics is specifically a structure that is mounted on an electronic component having a first terminal and a second terminal, and the structure 300 is an electron. When mounted on a component, if the voltage between the first terminal and the second terminal is less than the withstand voltage of the device, it exhibits insulation, and between the first terminal and the second terminal When the voltage is higher than the driving voltage of the device, it indicates the one showing conductivity.

  Note that the characteristics of the structure 300 according to the present embodiment are the voltage that is converted from insulating to conductive and the voltage that is converted from conductive to insulating as described above. Called.

  Hereinafter, the resin composition (resin composition for forming a high-voltage protection member) according to this embodiment will be described in detail.

  In the conventional electronic component, as described in the background art section and the problem to be solved by the invention, in order to protect the electronic component from an overvoltage such as static electricity, an electronic element is included in the circuit of the electronic component. In addition, it has been usual to employ a configuration in which a withstand voltage protection element is provided. Therefore, it is necessary to secure a space for arranging the withstand voltage protection element in the conventional electronic component. Therefore, there has been a limit to the further miniaturization of electronic components that has been required in recent years.

  In view of such circumstances, the present inventor can further provide an electronic component if it can be provided with a configuration having a function of protecting against an overvoltage such as static electricity inside the electronic element itself arranged in the circuit of the electronic component. I thought it could be downsized. Specifically, the present inventor has provided the first terminal and the second terminal in an electronic device such as a semiconductor device, for example, provided with at least two electrode terminals (first terminal and second terminal). It has been found that it is effective as a design guideline to realize, for example, a film-like member that can be arranged so as to be in contact with both of them and exhibit varistor characteristics.

  However, in order to produce the member (structure 300) exhibiting the above varistor characteristics, it was necessary to produce a resin composition having the following three characteristics. The first characteristic required for the resin composition is such that the shape of the member can be controlled so that it can correspond to the shape of the electrode terminal mounted in the electronic device that is the target of use of the member exhibiting varistor characteristics. Excellent moldability. The second characteristic required for the resin composition is that the sealing material used to protect the electrode terminal in the conventional electronic component has functions such as durability, moisture resistance and adhesion. It has the characteristics. The 3rd characteristic requested | required of the said resin composition is that the said resin composition can express sufficient varistor characteristic.

  In view of such circumstances, as a result of earnestly examining the design guidelines for producing a resin material that satisfies the above three required characteristics, the present inventor has obtained semiconductor ceramic particles 100 having varistor characteristics (see FIG. 1), When blended in a resin composition, the function of protecting the electronic element from an external load of an overvoltage such as static electricity or stress applied from the external environment inside the electronic element itself mounted in a circuit mounted in the electronic component It has been found that a member capable of having a structure having the above can be manufactured with high yield.

  In addition, from the viewpoint of satisfying the first characteristic described above, that is, from the viewpoint of realizing sufficient formability, the present inventor has employed a compression molding method or a transfer molding as a method for producing a member exhibiting the above varistor characteristics. We also found it desirable to adopt the law. Therefore, the present resin composition is desirably processed into a granular, tablet or sheet form.

<Thermosetting resin>
Specific examples of the thermosetting resin contained in the resin composition include novolac type phenol resins such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, triazine skeleton-containing phenol novolak resin; unmodified resole phenol resin, Phenolic resins such as oil-modified resole phenolic resins modified with tung oil, linseed oil, walnut oil, etc .; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin Bisphenol type epoxy resins such as bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol Z type epoxy resin; phenol novolac type epoxy resin, cresol Novolak type epoxy resins such as volak type epoxy resins; biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, arylalkylene type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, phenoxy type epoxy resins, dicyclopentadiene type epoxy resins, Epoxy resins such as norbornene type epoxy resin, adamantane type epoxy resin and fluorene type epoxy resin; resins having triazine ring such as urea (urea) resin and melamine resin; unsaturated polyester resin; maleimide resin such as bismaleimide compound; polyurethane resin Diallyl phthalate resin; silicone resin; benzoxazine resin; cyanate ester resin; polyimide resin; polyamideimide resin; benzocyclobutene resin; Rack type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, bisphenol type cyanate resin such as tetramethyl bisphenol F type cyanate resins. One of these may be used alone, two or more having different weight average molecular weights may be used in combination, and one or two or more thereof and a prepolymer thereof may be used in combination.

  The content of the thermosetting resin is preferably 1% by mass or more and 38% by mass or less, more preferably 1.5% by mass or more and 35% by mass or less, and still more preferably with respect to the present resin composition. Is 2% by mass or more and 30% by mass or less, and most preferably 3% by mass or more and 25% by mass or less. By making content of a thermosetting resin more than the said lower limit, the fluid fall of a thermosetting resin can be suppressed. Moreover, by making content of a thermosetting resin below the said upper limit, while being able to suppress the heat-dissipation fall of a thermosetting resin, the varistor characteristic with which the structure 300 which consists of this resin composition is equipped falls. It is possible to suppress this.

  As the thermosetting resin contained in the resin composition, an epoxy resin is preferably used. As said epoxy resin, it is possible to use the monomer, oligomer, and polymer in general which have 2 or more of epoxy groups in 1 molecule irrespective of the molecular weight and molecular structure.

  Specific examples of such epoxy resins include biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, stilbene type epoxy resins, hydroquinone type epoxy resins and the like; cresol novolac type epoxy resins, Novolak type epoxy resins such as phenol novolac type epoxy resin and naphthol novolak type epoxy resin; Phenol aralkyl type epoxy such as phenylene skeleton-containing phenol aralkyl type epoxy resin, biphenylene skeleton containing phenol aralkyl type epoxy resin, phenylene skeleton containing naphthol aralkyl type epoxy resin Resin; Trifunctional epoxy resin such as triphenolmethane type epoxy resin and alkyl-modified triphenolmethane type epoxy resin; Examples include modified phenolic epoxy resins such as diene-modified phenolic epoxy resins and terpene-modified phenolic epoxy resins; and heterocyclic-containing epoxy resins such as triazine nucleus-containing epoxy resins. These can be used alone or in two types. A combination of the above may also be used.

  On the other hand, a silicone resin can be used as the thermosetting resin contained in the resin composition. Thereby, it can be set as the resin composition which has the favorable affinity with respect to the inorganic type material resulting from the inorganic property derived from Si.

  The main component and curing agent of the curable silicone resin are at least one of a unit derived from a monofunctional silane, a unit derived from a bifunctional silane, a unit derived from a trifunctional silane, and a unit derived from a tetrafunctional silane. May be included as a repeating unit.

  Here, the unit derived from monofunctional silane refers to a repeating unit (M unit) represented by the following general formula (1).

R ₃ SiO _1/2 (1)
[However, R represents a non-reactive functional group such as a methyl group, an ethyl group, a propyl group, a cyclohexyl group, or a phenyl group, or a reactive functional group such as a vinyl group, a hydrogen atom, a hydroxy group, an alkoxy group, or an epoxy group. Show. ]

  Moreover, the unit derived from bifunctional silane means the repeating unit (D unit) represented by following General formula (2).

R ₂ SiO _2/2 (2)
[However, R represents a non-reactive functional group such as a methyl group, an ethyl group, a propyl group, a cyclohexyl group, or a phenyl group, or a reactive functional group such as a vinyl group, a hydrogen atom, a hydroxy group, an alkoxy group, or an epoxy group. Show. ]

  Moreover, the unit derived from a trifunctional silane means a repeating unit (T unit) represented by the following general formula (3).

RSiO _3/2 (3)
[However, R represents a non-reactive functional group such as a methyl group, an ethyl group, a propyl group, a cyclohexyl group, or a phenyl group, or a reactive functional group such as a vinyl group, a hydrogen atom, a hydroxy group, an alkoxy group, or an epoxy group. Show. ]

Moreover, the unit derived from tetrafunctional silane means a repeating unit (Q unit) represented by the following general formula (4).
SiO _4/2 (4)

  The resin composition preferably contains a release agent. In this way, a member (structure 300) exhibiting varistor characteristics can be manufactured with a high yield. The reason for this is as follows. As described above, the present resin composition is assumed to be used as a raw material for producing a member (structure 300) exhibiting varistor characteristics by a compression molding method or a transfer molding method. When the compression molding method or the transfer molding method is employed, the member (structure 300) is manufactured using a resin mold. In this case, after molding the member (structure 300) using the resin composition, it is necessary to release the molded product from the mold. And when the mold release force at the time of releasing a molding from a molding die becomes strong, there exists a tendency for the inconvenience that the obtained molding is damaged easily arises. Therefore, when a resin composition containing a release agent is used, it is possible to suppress the above-described inconvenience, and as a result, a member (structure 300) exhibiting varistor characteristics is manufactured with high yield. It becomes possible.

  Specific examples of the release agent according to this embodiment include natural wax, synthetic wax, higher fatty acid or metal salt thereof, paraffin, polyethylene oxide and the like. The content of the release agent is preferably 0.01% by mass or more and 1% by mass or less, and more preferably 0.03% by mass or more and 0.8% by mass with respect to the total amount of the thermosetting resin composition. It is as follows.

  You may make the resin material 200 (refer FIG. 2 and FIG. 3) contained in this resin composition contain a hardening | curing agent. The curing agent only needs to be cured by reacting with a thermosetting resin. Specific examples of curing agents that can be used when an epoxy resin is used as the thermosetting resin include ethylenediamine and trimethylene. C2-C20 linear aliphatic diamine such as diamine, tetramethylenediamine, hexamethylenediamine, metaphenylenediamine, paraphenylenediamine, paraxylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl Propane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1,5-diaminonaphthalene, metaxylenediamine, 1 , 1-Bis (4-aminophenyl) cyclohexane Aminos such as sun and dicyanodiamide; resol type phenol resins such as aniline-modified resole resin and dimethyl ether resole resin; novolac type phenol resins such as phenol novolac resin, cresol novolac resin, tert-butylphenol novolac resin, nonylphenol novolac resin; phenylene skeleton -Containing phenol aralkyl resin, phenol aralkyl resin such as biphenylene skeleton-containing phenol aralkyl resin; phenol resin having a condensed polycyclic structure such as naphthalene skeleton and anthracene skeleton; polyoxystyrene such as polyparaoxystyrene; hexahydrophthalic anhydride (HHPA) , Alicyclic acid anhydrides such as methyltetrahydrophthalic anhydride (MTHPA), trimellitic anhydride (TMA), pyromellitic anhydride Acid anhydrides including aromatic acid anhydrides such as acid (PMDA) and benzophenone tetracarboxylic acid (BTDA), etc .; Polymercaptan compounds such as polysulfide, thioester and thioether; Isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; Examples include organic acids such as carboxylic acid-containing polyester resins. These may be used alone or in combination of two or more.

  Among them, from the viewpoint of improving the moisture resistance and reliability of the structure 300, a compound having at least two phenolic hydroxyl groups in one molecule is preferable, and specific examples thereof include phenol novolac resin, cresol novolac resin, tert-butylphenol. Novolak type resins such as novolak resins and nonylphenol novolak resins; resol type phenol resins; polyoxystyrenes such as polyparaoxystyrene; phenylene skeleton-containing phenol aralkyl resins, biphenylene skeleton-containing phenol aralkyl resins, phenylene skeleton-containing naphthol aralkyl type phenol resins, etc. Is mentioned.

  The resin material 200 included in the resin composition may contain a curing accelerator. In the case of using an epoxy resin as the thermosetting resin, for example, it may be anything that promotes a curing reaction between a functional group such as an epoxy group and a curing agent, and specific examples thereof include 1,8-diazabicyclo (5 , 4, 0) Diazabicycloalkenes such as undecene-7 and derivatives thereof; amine compounds such as tributylamine and benzyldimethylamine; imidazole compounds such as 2-methylimidazole; organic phosphines such as triphenylphosphine and methyldiphenylphosphine Tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / tetrabenzoic acid borate, tetraphenylphosphonium / tetranaphthoic acid borate, tetraphenylphosphonium / tetranaphthoyloxyborate, tetraphenylphospho Um tetra naphthyl Oki tetra-substituted phosphonium tetra-substituted borate such as Chevrolet bets; triphenylphosphine or the like adduct of benzoquinone and the like. These may be used alone or in combination of two or more.

When a silicone resin is used as the thermosetting resin, H ₂ PtCl ₆ · mH ₂ O, K ₂ PtCl ₆ , KHPtCl ₆ · mH ₂ O, K ₂ PtCl ₄ , K ₂ PtCl ₄ · mH ₂ O , PtO ₂ · mH ₂ O (m is a positive integer for each), and complexes of these compounds with hydrocarbons such as olefins, alcohols or vinyl group-containing organopolysiloxanes are preferably used.

  In addition to the above components, the resin material 200 contained in the present resin composition may include a coupling agent such as γ-glycidoxypropyltrimethoxysilane; various colorants; silicone oil, silicone as necessary. Various additives such as low stress agents such as rubber; ion scavengers such as hydrotalcite; flame retardants such as aluminum hydroxide; antioxidants may be added.

  Examples of the colorant include one or more selected from the group consisting of a dye exhibiting a color such as green, red, blue, yellow, and black, a pigment exhibiting a color such as black, and a pigment. Things.

  Among these, examples of the green colorant include those containing one or more known colorants such as anthraquinone, phthalocyanine, and perylene.

  Examples of the black pigment include carbon black, and examples of the black dye include azo-based metal complex black dyes, organic black dyes such as anthraquinone compounds, and the like. Although it does not specifically limit as the said black dye, For example, Kayase Black AN (made by Nippon Kayaku Co., Ltd.), Kayase Black G (made by Nippon Kayaku Co., Ltd.), etc. are mentioned. You may use 1 type, or 2 or more types of black pigments.

<Semiconductor ceramic particles>
FIG. 1 is an enlarged cross-sectional view of semiconductor ceramic particles according to the present embodiment.
As shown in FIG. 1, the semiconductor ceramic particle 100 according to the present embodiment is a particle having a plurality of crystal parts 10 and a grain boundary part 20 that separates the crystal parts 10. In other words, in the semiconductor ceramic particle 100 according to the present embodiment, a plurality of crystals composed of the grain boundary part 20 and two or more crystal parts 10 arranged so as to be separated from each other via the grain boundary part 20 are aggregated. It can be said that it is a particle. When a voltage lower than the varistor voltage is applied to the particle, the semiconductor ceramic particle 100 does not pass current because the grain boundary portion 20 acts as a resistance, but a voltage higher than the varistor voltage is applied. In some cases, the particles have a characteristic that a tunnel effect occurs and current flows as shown by an arrow in FIG.

  In addition, about the member provided with the varistor characteristic like the semiconductor ceramic particle 100 according to the present embodiment, it is included in a withstand voltage protection element (varistor element or the like) to be mounted on the same circuit together with the electronic element in the conventional electronic component. It was. However, a method for producing a member made of the resin composition containing the semiconductor ceramic particles 100 satisfying the following two required characteristics with high yield has not been reported so far. The first required characteristic described above is that it can be provided inside the electronic element itself mounted in the circuit mounted in the electronic component. The second required characteristic described above has a function of protecting the electronic element from stress applied from the external environment in addition to overvoltage such as static electricity when the member is provided inside the electronic element itself. That is.

  The average particle diameter D50 of the semiconductor ceramic particles 100 is preferably 0.01 μm or more and 150 μm or less, more preferably 0.1 μm or more and 120 μm or less, further preferably 1 μm or more and 90 μm or less, and most preferably It is 5 μm or more and 60 μm or less. By doing so, it becomes possible to develop varistor characteristics without depending on the shape of the structure 300 formed of the resin composition including the semiconductor ceramic particles 100.

  The semiconductor ceramic particles 100 are preferably spherical particles. Thereby, it is possible to easily control the varistor characteristics.

  In the semiconductor ceramic particle 100, the crystal part 10 is preferably formed of a material including at least one selected from the group consisting of zinc oxide, silicon carbide, strontium titanate, and barium titanate. Especially, the material which contains zinc oxide as a main component is preferable from a viewpoint of improving the nonlinear coefficient and energy tolerance of the semiconductor ceramic particle 100 itself. Since a material containing silicon carbide as a main component has a high dielectric breakdown voltage, it is suitable when the varistor voltage is set to a high voltage. A material containing strontium titanate as a main component is preferable in terms of absorption and suppression of high voltage / high frequency noise.

  In the semiconductor ceramic particle 100, the grain boundary part 20 is preferably formed of a material containing at least one selected from the group consisting of bismuth, praseodymium, antimony, manganese, cobalt and nickel, or a compound thereof. Especially, it is preferable that the grain boundary part 20 is formed with the material containing 1 or more types selected from the group which consists of bismuth, praseodymium, or these compounds from a viewpoint that a nonlinear resistance characteristic is favorable. . Examples of these compounds include oxides, nitrides, organic compounds, and other inorganic compounds, but oxides are preferable from the viewpoint of satisfactorily expressing varistor characteristics.

  The content of the semiconductor ceramic particles 100 is 60% by mass or more and 97% by mass or less, preferably 70% by mass, based on the total amount of the resin composition from the viewpoint of surely expressing the varistor characteristics of the structure 300. It is 95 mass% or less, More preferably, it is 75 mass% or more and 93 mass% or less. By controlling the content of the semiconductor ceramic particles 100 to be within the above numerical range, the semiconductor ceramic particles are arranged such that a plurality of particles are in contact with each other between the two electrode terminals 30 as shown in the schematic diagram of FIG. A structure 300 filled with 100 can be realized.

  In addition, when the resin composition contains a large amount of the semiconductor ceramic particles 100 as described above, even if the resin composition is melted at the time of manufacturing the structure 300, the semiconductor ceramic particles 100 are contained in the molten resin composition. There is no or very little space to settle. For this reason, the semiconductor ceramic particles 100 are prevented or suppressed from being unevenly distributed in the molten resin composition. As a result, in the manufactured structure 300, the semiconductor ceramic particles 100 are present in a uniformly dispersed state.

  For this reason, when the content of the semiconductor ceramic particles 100 is controlled so as to be within the above numerical range, it is possible to surely exhibit good varistor characteristics of the structure 300.

  The resin composition can contain conductive particles. Thus, when a high voltage exceeding the varistor voltage is applied to an electronic component including the structure 300 formed of the resin composition, the electric conductivity of the structure 300 is improved. can do. Specifically, as shown in FIG. 3, the conductive particles 50 can enter the gap region between the plurality of semiconductor ceramic particles 100 arranged so as to fill the space between the two electrode terminals 30.

  The content of the conductive particles 50 is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass with respect to the total amount of the resin composition, from the viewpoint of surely expressing the varistor characteristics of the structure 300. The content is from 15% to 15% by mass, and most preferably from 2% to 10% by mass. By controlling the content of the conductive particles 50 to be within the above numerical range, the plurality of semiconductor ceramic particles 100 arranged so as to fill the space between the two electrode terminals 30 as shown in the schematic diagram of FIG. It becomes possible to allow the conductive particles 50 to uniformly enter the gap region.

  The average particle diameter D50 of the conductive particles 50 is preferably 0.01 μm or more and 50 μm or less, more preferably 0.02 μm or more and 40 μm or less, and still more preferably, from the viewpoint of surely expressing the varistor characteristics of the structure. Is 0.05 μm or more and 30 μm or less, and most preferably 0.1 μm or more and 20 μm or less.

  Specific examples of the material forming the conductive particles 50 are selected from the group consisting of nickel, carbon black, aluminum, silver, gold, copper, graphite, zinc, iron, stainless steel, tin, brass, and alloys thereof. And a semiconductive material selected from the group consisting of zinc oxide, silicon carbide, strontium titanate, and barium titanate.

  Moreover, it is preferable that the magnitude | size of the semiconductor ceramic particle 100 and the electrically-conductive particle 50 contained in this resin composition satisfy | fill the following conditions. Specifically, when the average particle diameter D50 of the semiconductor ceramic particles 100 is X and the average particle diameter D50 of the conductive particles 50 is Y, the value of Y / X is preferably 0.05 or more and less than 1. More preferably, it is 0.1 or more and 0.8 or less. By doing so, as shown in the schematic diagram of FIG. 3, the conductive particles 50 can easily enter the gap regions between the plurality of semiconductor ceramic particles 100 arranged so as to fill the gap between the two electrode terminals 30.

  The resin composition according to the present embodiment employs a configuration including a thermosetting resin and semiconductor ceramic particles 100 exhibiting a specific amount of varistor characteristics. By using the resin composition adopting such a configuration, the electronic device is protected from an external load caused by an overvoltage such as static electricity or a stress applied from the external environment inside the electronic device itself disposed in the circuit of the electronic component. Since it is possible to provide a configuration having a function, it is not necessary to arrange an electronic element and a withstand voltage protection element in a circuit as in the case of a conventional electronic component, and as a result, the electronic component is reduced in size. Can be realized.

<< Structure Manufacturing Method >>
The manufacturing method of the structure 300 according to the present embodiment includes a step of preparing a resin composition including the thermosetting resin and the semiconductor ceramic particles 100 as described above, and compression molding or transfer molding of the resin composition. To obtain the structure 300. The structure 300 manufactured by such a manufacturing method is, for example, as a member in the form of a film having a function (varistor characteristic) for protecting against an overvoltage such as static electricity inside an electronic element itself such as a semiconductor element or a light emitting element. It can be provided. Therefore, the electronic component can be reduced in size by using the structure 300 obtained by the manufacturing method according to the present embodiment.

  Hereinafter, a method for producing a member (structure 300) exhibiting varistor characteristics in an electronic component (electronic element) using the resin composition according to the present embodiment will be described.

  When the resin composition according to this embodiment is used, a member (structure 300) exhibiting varistor characteristics can be produced in an electronic component with a high yield by any one of the compression molding method and the transfer molding method. . The structure 300 is an electronic element (for example, a semiconductor element) provided with a substrate 60 and at least two electrode terminals 30 (a first terminal and a second terminal) provided on the substrate 60 and spaced apart from each other. However, according to the resin molding method, the structure 300 corresponding to the shape of the electrode terminal is assumed to be used in contact with both the first terminal and the second terminal. It can be produced (see FIGS. 2 and 3).

  Here, in order to produce the structure 300, when the method of compressing and molding the resin composition is employed, the resin composition is preferably in the form of granules, powders, or sheets. On the other hand, in the case of adopting a transfer molding method of the resin composition in order to produce the structure 300, the resin composition preferably has a tablet shape.

  As an example of a method for producing a member (structure 300) exhibiting varistor characteristics in an electronic component, that is, an example of a method for mounting the structure 300 inside the electronic component, for example, a first terminal and a second terminal The structure 300 (high voltage protection member) is formed by compression molding or transfer molding the resin composition so that both the first terminal and the second terminal are in contact with the electronic element having The method including the process to do is mentioned.

  Hereinafter, as an example of a method for mounting the structure 300 according to the present embodiment inside an electronic component, first, the case where the structure 300 is manufactured by compression molding using a granular resin composition is taken as an example. explain. However, the method of mounting the structure 300 according to the present embodiment inside the electronic component is not limited to the following example.

  First, a resin material supply container containing a granular resin composition is installed between an upper mold and a lower mold of a compression mold. Next, an electronic element having a first terminal and a second terminal is fixed to one of the upper mold and the lower mold of the compression molding mold by a fixing means such as clamp or suction. Hereinafter, the case where the electronic element is fixed to the upper mold of the compression mold so that the surface of the electronic element having the first terminal and the second terminal faces the resin material supply container will be described as an example. To do.

  Next, under reduced pressure, while the interval between the upper and lower molds of the mold is reduced, the weighed granular resin composition is removed from the lower mold by a resin material supply mechanism such as a shutter that constitutes the bottom surface of the resin material supply container. Into the lower mold cavity. As a result, the granular resin composition is heated to a predetermined temperature in the lower mold cavity to be in a molten state. Next, by bonding the upper mold and the lower mold of the mold, the molten resin composition is pressed against the first terminal and the second terminal provided in the electronic element fixed to the upper mold. By carrying out like this, the space | interval formed between the 1st terminal and the 2nd terminal can be filled with the resin composition of a molten state.

  Thereafter, the resin composition is cured over a predetermined time while maintaining the state in which the upper mold and the lower mold are bonded. Thereby, the hardened | cured material of a resin composition can express a varistor characteristic reliably. Here, when performing compression molding, it is preferable to perform resin sealing while reducing the pressure inside the mold, and it is more preferable to perform the sealing under vacuum conditions. As a result, at least the region surrounding the first terminal and the second terminal can be satisfactorily filled without leaving an unfilled portion of the resin composition.

  In addition, the molding temperature in the case of compression molding using a granular resin composition is not particularly limited, but is preferably 50 to 250 ° C, more preferably 50 to 200 ° C, and particularly preferably 80 to 180 ° C. preferable. The molding pressure is not particularly limited, but is preferably 0.5 to 12 MPa, and particularly preferably 1 to 10 MPa. By setting the molding temperature and pressure within the above ranges, both the occurrence of a portion that is not filled with the molten resin composition and the displacement of the electronic element having the first terminal and the second terminal are caused. Can be prevented.

  Next, an example of a method for mounting the structure 300 according to the present embodiment inside an electronic component will be described by taking as an example a case where the structure 300 is manufactured by compression molding using a sheet-like resin composition. To do.

  First, an electronic element having a first terminal and a second terminal is fixed to one of an upper mold and a lower mold of a compression molding mold by a fixing means such as clamp or suction. Hereinafter, the case where the electronic element is fixed to the upper mold of the compression mold so that the surface of the electronic element having the first terminal and the second terminal faces the resin material supply container will be described as an example. To do.

  Next, a sheet-shaped resin composition is disposed in the lower mold cavity of the mold so that the positions correspond to the first terminal and the second terminal of the electronic element fixed to the upper mold of the mold. Next, by reducing the distance between the upper mold and the lower mold of the mold under reduced pressure, the sheet-shaped resin composition is heated to a predetermined temperature in the lower mold cavity to be in a molten state. Thereafter, the upper mold and the lower mold of the mold are bonded to press the molten resin composition against the first terminal and the second terminal provided in the electronic element fixed to the upper mold. By carrying out like this, the space | interval formed between the 1st terminal and the 2nd terminal can be filled with the resin composition of a molten state.

  Thereafter, the resin composition is cured over a predetermined time while maintaining the state in which the upper mold and the lower mold are bonded. Thereby, the hardened | cured material of a resin composition can express a varistor characteristic reliably. Here, when performing compression molding, it is preferable to perform resin sealing while reducing the pressure inside the mold, and it is more preferable to perform the sealing under vacuum conditions. As a result, at least the region surrounding the first terminal and the second terminal can be satisfactorily filled without leaving an unfilled portion of the resin composition.

  The molding temperature in the case of compression molding using a sheet-shaped resin composition is not particularly limited, but is preferably 50 to 250 ° C, more preferably 50 to 200 ° C, and particularly preferably 80 to 180 ° C. preferable. The molding pressure is not particularly limited, but is preferably 0.5 to 12 MPa, and particularly preferably 1 to 10 MPa. By setting the molding temperature and pressure within the above ranges, both the occurrence of a portion that is not filled with the molten resin composition and the displacement of the electronic element having the first terminal and the second terminal are caused. Can be prevented.

  Next, an example of a method for mounting the structure 300 according to the present embodiment inside an electronic component will be described by taking as an example the case where the structure 300 is manufactured by transfer molding using a tablet-like resin composition. To do.

  First, a molding die provided with an electronic element having a first terminal and a second terminal is prepared. The molding die prepared here was melted with a pot charged with a tablet-shaped resin composition, and then a plunger with an auxiliary ram inserted into the pot to melt the resin composition by applying pressure. A sprue for feeding the resin composition into the molding space is provided.

  Next, the tablet-shaped resin composition is charged into the pot with the molding die closed. Here, the resin composition charged in the pot may be in a semi-molten state by preheating with a preheater or the like in advance. Next, in order to melt the resin composition charged in the pot, a plunger having an auxiliary ram is inserted into the pot to apply pressure to the resin composition. Thereafter, the molten resin composition is introduced into the molding space through a sprue. Next, the resin composition filled in the molding space is cured by being heated and pressurized. After the resin composition is cured, an electronic component including the structure 300 composed of a cured product of the resin composition that surely exhibits varistor characteristics can be obtained by opening the molding die.

  The molding temperature in transfer molding is not particularly limited, but is preferably 50 to 250 ° C, more preferably 50 to 200 ° C, and particularly preferably 80 to 180 ° C. By setting the molding temperature within the above range, it is possible to prevent both occurrence of a portion not filled with the molten resin composition and displacement of the electronic device having the first terminal and the second terminal. can do.

  According to the above method according to the present embodiment, a film shape having a function of protecting the electronic element from an external load such as an overvoltage such as static electricity or a stress applied from the external environment inside the electronic element itself such as a semiconductor element. It is possible to form a member of a form with high yield. By using this technique, it is possible to realize an electronic component that does not require the withstand voltage protection element (varistor element or the like) described in the background section above. That is, if the manufacturing method according to the present embodiment is used, the conventional electronic component can be significantly reduced in size.

  In addition, the resin composition of this invention can be made into a liquid state, if a thermosetting resin (for example, silicone resin etc.) liquid at normal temperature is used. In this case, the structure 300 can also be manufactured by injection-molding such a liquid resin composition. However, by using a thermosetting resin that is solid at room temperature (particularly, an epoxy resin as described above), the resin composition is granulated or pelletized, so that the structure 300 can be stored when the resin composition is stored. During production, the semiconductor ceramic particles 100 can be prevented or suppressed from being unevenly distributed in the resin composition. For this reason, in the manufactured structure 300, the semiconductor ceramic particles 100 can be present in a more uniformly dispersed state. As a result, the structure 300 can surely provide good varistor characteristics.

  As described above, the electronic device having at least two electrode terminals 30 (first terminal and second terminal), and mounted on the electronic device so as to be in contact with the first terminal and the second terminal The electronic component of this embodiment having the structure 300 (arranged) is obtained (see FIGS. 2 and 3).

  In the above-described embodiment, the first terminal and the second terminal are described as the electrode terminals 30, respectively. However, the first terminal and the second terminal respectively constitute a circuit provided on the substrate. The wiring to be used may be used.

  It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  As mentioned above, although embodiment of this invention was described with reference to drawings, these are the illustrations of this invention, Various structures other than the above are also employable.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these.

<Example 1>
(Preparation of thermosetting resin-containing varnish)
37 parts by mass of a biphenylene skeleton-containing phenol aralkyl type epoxy resin (Nippon Kayaku Co., Ltd., NC3000) as a thermosetting resin, 16 parts by mass of a bisphenol A type liquid epoxy resin (Mitsubishi Chemical Co., Ltd., YL6810), and phenylene as a curing agent 9 parts by mass of skeleton-containing naphthol aralkyl type phenolic resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., SN485), 32 parts by mass of biphenylene skeleton-containing phenol aralkyl resin (Maywa Kasei Co., Ltd., MEH-7851SS), and montanic acid ester as a release agent 1 part by weight of wax (manufactured by Clariant Japan Co., Ltd., WE-4) and 5 parts by weight of a compound represented by the following formula (1) as a curing accelerator are dissolved in propylene glycol monomethyl ether, and a thermosetting resin-containing varnish (A )

  With respect to 40.0 parts by mass of the resin content in the obtained thermosetting resin-containing varnish (A), 60 parts by mass of a microvaristor (manufactured by Ceraon, average particle diameter D50: 50 μm) is introduced as semiconductor ceramic particles. After kneading using three rolls, a solvent-removal and granulation were performed to obtain a granular resin composition.

(Sealing between circuits)
Next, sealing between electrodes was performed using the obtained resin composition. As a substrate, an electronic element having an FR-4 base material (thickness 0.15 mm) and a circuit layer (copper circuit, thickness 12 μm, shortest distance between adjacent circuits 200 μm) was used. On the board | substrate which has such a circuit, the said resin composition was shape | molded so that the adjacent circuit might be covered at 150 degreeC and 100 kN for 5 minutes using the compression molding machine (made by TOWA). Then, it heated at 150 degreeC for 2 hours, the resin composition was hardened, and the board | substrate which sealed between circuits was produced.

<Example 2>
With respect to 30.0 parts by mass of the resin content in the thermosetting resin-containing varnish (A) obtained in the same manner as in Example 1, as a semiconductor ceramic particle, a microvaristor (manufactured by Ceraon, average particle diameter D50: 50 μm) 70 parts by mass was added and kneaded using three rolls, and then the solvent was removed and granulated to obtain a granular resin composition.

(Sealing between circuits)
Using the resin composition obtained above, interelectrode sealing was carried out in the same manner as in Example 1 to produce a substrate in which the circuit was sealed.

<Example 3>
With respect to 15.0 parts by mass of the resin content in the thermosetting resin-containing varnish (A) obtained in the same manner as in Example 1, as a semiconductor ceramic particle, a microvaristor (manufactured by Ceraon, average particle diameter D50: 50 μm) After 85 parts by mass was added and kneaded using three rolls, a granular resin composition was obtained through solvent removal and granulation.

(Sealing between circuits)
Using the resin composition obtained above, interelectrode sealing was carried out in the same manner as in Example 1 to produce a substrate in which the circuit was sealed.

<Example 4>
With respect to 10.0 parts by mass of the resin content in the thermosetting resin-containing varnish (A) obtained in the same manner as in Example 1, as a semiconductor ceramic particle, a microvaristor (manufactured by Ceraon, average particle diameter D50: 50 μm) After 90 parts by mass was added and kneaded using three rolls, a solvent-removal and granulation were performed to obtain a granular resin composition.

(Sealing between circuits)
Using the resin composition obtained above, interelectrode sealing was carried out in the same manner as in Example 1 to produce a substrate in which the circuit was sealed.

<Example 5>
With respect to 7.0 parts by mass of the resin content in the thermosetting resin-containing varnish (A) obtained in the same manner as in Example 1, as a semiconductor ceramic particle, a microvaristor (manufactured by Ceraon, average particle diameter D50: 50 μm) After 93 parts by mass was added and kneaded using three rolls, a solvent was removed and granulated to obtain a granular resin composition.

(Sealing between circuits)
Using the resin composition obtained above, interelectrode sealing was carried out in the same manner as in Example 1 to produce a substrate in which the circuit was sealed.

<Example 6>
With respect to 5.0 parts by mass of the resin content in the thermosetting resin-containing varnish (A) obtained in the same manner as in Example 1, as a semiconductor ceramic particle, a microvaristor (manufactured by Ceraon, average particle diameter D50: 50 μm) After 95 parts by mass was added and kneaded using three rolls, the resin was removed and granulated to obtain a granular resin composition.

(Sealing between circuits)
Using the resin composition obtained above, interelectrode sealing was carried out in the same manner as in Example 1 to produce a substrate in which the circuit was sealed.

<Example 7>
With respect to 15.0 parts by mass of the resin content in the thermosetting resin-containing varnish (A) obtained in the same manner as in Example 1, as a semiconductor ceramic particle, a microvaristor (manufactured by Ceraon, average particle diameter D50: 50 μm) 80 parts by mass, copper particles (Mitsui Mining & Mining Co., Ltd., EAW, average particle diameter D50: 20 μm) 5 parts by mass as conductive particles, kneaded using three rolls, after solvent removal, granulation, A granular resin composition was obtained.

(Sealing between circuits)
Using the resin composition obtained above, interelectrode sealing was carried out in the same manner as in Example 1 to produce a substrate in which the circuit was sealed.

<Example 8>
(Preparation of thermosetting resin-containing varnish)
37.5 parts by mass of biphenylene skeleton-containing phenol aralkyl type epoxy resin (Nippon Kayaku Co., Ltd., NC3000) as thermosetting resin, 16.0 parts by mass of bisphenol A type liquid epoxy resin (Mitsubishi Chemical Co., Ltd., YL6810), 9.0 parts by mass of a phenylene skeleton-containing naphthol aralkyl type phenolic resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., SN485) as a curing agent, 32.5 parts by mass of a biphenylene skeleton-containing phenol aralkyl resin (Maywa Kasei Co., Ltd., MEH-7851SS), As a curing accelerator, 5.0 parts by mass of the compound represented by the above formula (1) was dissolved in propylene glycol monomethyl ether to obtain a thermosetting resin-containing varnish (B).

  With respect to 15.0 parts by mass of the resin content in the obtained thermosetting resin-containing varnish (B), 80 parts by mass of microvaristor (made by Ceraon) as semiconductor ceramic particles, and copper powder (Mitsui Metal Mining Co., Ltd.) as conductive particles Manufactured, EAW) 5 parts by mass were added and kneaded using three rolls, followed by solvent removal and granulation to obtain a granular resin composition.

(Sealing between circuits)
Using the resin composition obtained above, interelectrode sealing was carried out in the same manner as in Example 1 to produce a substrate in which the circuit was sealed.

<Comparative Example 1>
In the thermosetting resin-containing varnish (A) obtained in the same manner as in Example 1, the resin content was 40.0 parts by mass, the semiconductor ceramic particles were 55 parts by mass of a microvaristor (Celaon), and the conductive particles were copper powder ( After adding 5 parts by mass of EAW manufactured by Mitsui Kinzoku Mining Co., Ltd. and kneading using three rolls, a solvent-removal and granulation were performed to obtain a granular resin composition.

(Sealing between circuits)
Using the resin composition obtained above, interelectrode sealing was carried out in the same manner as in Example 1 to produce a substrate in which the circuit was sealed.

<Comparative example 2>
Into the thermosetting resin-containing varnish (A) obtained in the same manner as in Example 1, 97.5 parts by mass of a microvaristor (manufactured by Ceraon Co., Ltd.) as semiconductor ceramic particles was added to 2.5 parts by mass of the resin. After kneading using this roll, a granular resin composition was obtained through solvent removal and granulation.

(Sealing between circuits)
Using the resin composition obtained above, interelectrode sealing was carried out in the same manner as in Example 1 to produce a substrate in which the circuit was sealed.

  In the substrates obtained in Examples and Comparative Examples, the moldability, the current / voltage characteristics between circuits, and the peelability were evaluated by the methods described later.

<Evaluation items>
(1) Formability The formability was confirmed by visually observing the appearance of the substrate to determine whether the resin composition was unfilled. The case where there is no unfilling between any of the circuits was judged as (◯), the case where there was unfilled between some of the circuits (△), and the case where there was unfilled among many circuits was judged as (×). .

(2) Electrical characteristics evaluation The current / voltage characteristics between circuits were applied between 0 V and 100 V at a boosting rate of 0.5 V / sec between adjacent circuits using pA meter / DC VOLTAG SOURCE 4140B (manufactured by Agilent Technologies). The current value that occasionally flowed was measured. Based on the results thus obtained, a graph plotted on the logarithmic axis was created as shown in FIG. Next, the nonlinear coefficient and the varistor voltage were calculated from the obtained graph.

  Specifically, the multiplier α when the tangent line (a) of the graph on the high pressure side from the inflection point of the obtained graph is expressed by the following equation (2) is calculated as a nonlinear coefficient, and the graph of the low pressure side graph is calculated. The intersection of the tangent line (b) and the high voltage side tangent line (a) was calculated as the varistor voltage. The varistor characteristics were determined as (◯) when the varistor voltage could be calculated and (×) when it was not possible.

(3) Releasability The releasability was confirmed for ease of release from the mold after molding. When the release property is good (◯), when the resin composition that seals the circuit between the cured product (structure) cannot be released without causing some cracks or deformation (△), the resin composition The case where the mold could not be released without breaking the cured product was determined as (x).
The evaluation results regarding the above evaluation items are shown in Table 1 below together with the blending ratio of each component.

  In addition, a substrate with a circuit sealed was produced by compression molding using a sheet-shaped resin composition and transfer molding using a tablet-shaped resin composition, and the same evaluation as described above was performed. Similar results were obtained. In addition, the thing of the composition similar to the said Example and a comparative example was used for the resin composition.

DESCRIPTION OF SYMBOLS 10 Crystal part 20 Grain boundary part 30 Electrode terminal 50 Conductive particle 60 Substrate 100 Semiconductor ceramic particle 200 Resin material 300 The member (structure) which shows a varistor characteristic

Claims (10)

A resin composition for producing a structure exhibiting non-linear voltage-current characteristics that does not follow Ohm's law,
A thermosetting resin;
Semiconductor ceramic particles having a plurality of crystal parts and a grain boundary part separating the crystal parts,
A resin composition comprising 60% by mass or more and 97% by mass or less of the semiconductor ceramic particles with respect to the total amount of the resin composition.   The resin composition according to claim 1, further comprising a curing accelerator.   The resin composition according to claim 1 or 2, further comprising a release agent.   The said crystal | crystallization part is formed of the material containing 1 or more types selected from the group which consists of a zinc oxide, a silicon carbide, strontium titanate, and a barium titanate. Resin composition.   5. The grain boundary portion is formed of a material containing at least one selected from the group consisting of bismuth, praseodymium, antimony, manganese, cobalt and nickel, or a compound thereof. 6. The resin composition described in 1.   The resin composition according to any one of claims 1 to 5, wherein the resin composition is in the form of granules, tablets, or sheets. A method of manufacturing a structure exhibiting non-linear voltage-current characteristics that does not follow Ohm's law,
Preparing the resin composition according to any one of claims 1 to 6,
And a step of obtaining the structure by compression molding or transfer molding of the resin composition. A structure that exhibits non-linear voltage-current characteristics that do not obey Ohm's law,
A thermosetting resin, and a semiconductor ceramic particle having a plurality of crystal parts and grain boundary parts separating the crystal parts, and a cured product of a resin composition,
A structure comprising 60% by mass or more and 97% by mass or less of the semiconductor ceramic particles with respect to the total amount of the resin composition. A substrate and an electronic device provided on the substrate and having a first terminal and a second terminal spaced apart from each other;
The structure according to claim 8, provided on the substrate of the electronic element so as to contact the first terminal and the second terminal,
An electronic component, wherein a part of the semiconductor ceramic particles is disposed between the first terminal and the second terminal.   The electronic component according to claim 9, wherein the semiconductor ceramic particles disposed between the first terminal and the second terminal are in contact with each other.

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