JP6759575B2 - Resin compositions for forming high voltage protection members, semiconductor devices and electronic components - Google Patents

Description

The present invention relates to a resin composition for forming a high voltage protective member, a semiconductor device, and an electronic component.

In recent years, with the progress of technology that can be mounted at high density, the size and weight of electronic components have been reduced. Therefore, the circuits mounted in electronic components tend to be denser.
Here, when the circuit mounted in the electronic component is densified, an overvoltage such as static electricity is applied, which causes inconvenience such as malfunction of the electronic component or damage to the electronic component. Tends to increase.

In view of these circumstances, some reports have been made on techniques for protecting electronic elements mounted in circuits mounted in electronic components from overvoltages such as static electricity (Patent Documents 1 to 3 and the like).

Patent Documents 1 to 3 describe a technique relating to a resin material having a varistor function, which is used to seal and cover the entire external terminal of an electronic component body. That is, Patent Documents 1 to 3 disclose a technique for directly covering the above-mentioned electronic element with a withstand voltage protection member to suppress the above-mentioned inconvenience when a transient voltage is applied to the electronic element. ing.

Japanese Unexamined Patent Publication No. 06-244001 Japanese Unexamined Patent Publication No. 06-244002 Japanese Unexamined Patent Publication No. 06-244003

However, the present inventors obtained by burying the region between the two terminals in the electronic component having the first terminal and the second terminal with the conventional resin material described in Patent Documents 1 to 3. It has been found that when the above-mentioned structure is produced, the voltage-current characteristic may not exhibit good non-linearity (varistor characteristic) that does not obey Ohm's law. Therefore, as a result of diligent studies on the factors that the varistor characteristics are not exhibited in the structure produced by using the conventional resin material, the present inventors have found that the resin is poorly embedded in the inter-terminal region and the varistor particles in the inter-terminal region. It was found that there is a possibility that problems such as poor filling of (semiconductor ceramic particles exhibiting a varistor function) may occur.

Therefore, the present invention is for forming a high voltage protection member which is excellent in the balance between the resin embedding property in the inter-terminal region and the particle filling property and which is useful for producing a structure having an overvoltage protection function with good yield. Provided are a resin composition, and a semiconductor device and an electronic component using the resin composition.

As a result of intensive studies to achieve the above problems, the present inventors have conducted the above-mentioned varistor particles in order to improve the balance between the resin embedding property and the particle filling property of the resin composition containing the varistor particles. The present invention was completed with the finding that controlling the sedimentation behavior of the particles is effective as a design guideline.

According to the present invention, the cured product is a resin composition for forming a high voltage protective member, which exhibits non-linearity in which the voltage-current characteristic does not obey Ohm's law.
Thermosetting resin and
A semiconductor ceramic particle having a grain boundary portion and a plurality of crystal portions separated by the grain boundary portion,
Including
The thermosetting resin contains a silicone resin and contains
The silicone resin has at least one reactive group selected from a vinyl group, a hydrogen atom, a hydroxy group, an alkoxy group, and an epoxy group.
The average particle size d50 of the semiconductor ceramic particles is D [μm], and the minimum melt viscosity value of the resin composition for forming a high voltage protective member at a temperature of 25 ° C. or higher and 150 ° C. or lower is η [Pa · s]. Then, the value of the sedimentation index S [(μm) ² / (Pa · s)] represented by S = D ² / η is 300 (μm) ² / (Pa · s) or more, and the minimum melt viscosity. Provided is a resin composition for forming a high voltage protective member, wherein the value of η [Pa · s] is 0.01 Pa · s or more and 5 Pa · s or less.

Further, according to the present invention, there is provided a semiconductor device provided with a cured product of the resin composition for forming a high voltage protective member.

Further, according to the present invention, there is provided an electronic component provided with a cured product of the resin composition for forming a high voltage protective member.

According to the present invention, for forming a high voltage protection member useful for producing a structure having an excellent balance between resin embedding property and particle filling property in the inter-terminal region and having an overvoltage protection function with good yield. A resin composition, and a semiconductor device and an electronic component using the resin composition can be provided.

It is an enlarged sectional view of the semiconductor ceramic particle 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 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 varistor voltage from the measurement result of a current value.

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

<< Resin composition for forming high voltage protection member >>
The cured product of the resin composition for forming a high voltage protective member according to the present embodiment (hereinafter, also referred to as “the present resin composition”) exhibits non-linearity in which the voltage-current characteristic does not obey Ohm's law. is there.
Specifically, the present resin composition contains a thermosetting resin and semiconductor ceramic particles having a grain boundary portion and a plurality of crystal portions separated by the grain boundary portion. Then, in this resin composition, the average particle size d50 of the semiconductor ceramic particles is set to D [μm], and the value of the minimum melt viscosity of the resin composition for forming a high voltage protective member at a temperature of 25 ° C. or higher and 150 ° C. or lower is set. When η [Pa · s], the value of the sedimentation index S [(μm) ² / (Pa · s)] represented by S = D ² / η is 300 (μm) ² / (Pa · s). That is all.
As a result, a resin composition for forming a high voltage protective member, which has an excellent balance between resin embedding property in the inter-terminal region and particle filling property, and is useful for producing a structure having an overvoltage protection function with good yield. Can be realized. That is, according to the present resin composition, it is possible to provide a configuration having a function of protecting from overvoltage such as static electricity in a good yield inside the electronic element itself arranged in the circuit of the electronic component.
Specific examples of the above electronic components to which this resin composition can be applied include consumer devices such as mobile phones, smartphones, tablet terminals, game machines, personal computers and televisions, servers, router devices, and industrial devices such as robots. In addition, electronic components provided in electronic devices such as moving bodies such as automobiles, aircraft, trains, and ships can be mentioned.

Here, the non-linearity (varistor characteristic) in which the voltage-current characteristic does not obey Ohm's law, which is possessed by a structure that can be produced using the present resin composition, includes at least two electrode terminals. It refers to the characteristic that the current flowing through the overvoltage protection element, which is generally called a varistor element, increases non-linearly when a gradually increasing voltage is applied to the electronic component. In the present embodiment, the structure having the varistor characteristics is specifically a structure mounted on an electronic component having a first terminal and a second terminal, and the structure is used as an electronic component. When mounted, if the voltage between the first terminal and the second terminal is less than or equal to the withstand voltage of the device, it shows insulation and the voltage between the first terminal and the second terminal. Refers to a device that exhibits conductivity when the voltage exceeds the drive voltage of the device. The voltage at which the characteristics of the structure according to the present embodiment are converted from insulating to conductive as described above and the voltage from conductive to insulating are hereinafter referred to as varistor voltage. ..

Hereinafter, the resin composition for forming a high voltage protective member according to the present embodiment will be described in detail.

When the present inventors produce a structure obtained by burying between two terminals provided in an electronic component using a conventional resin material, the structure does not exhibit good varistor characteristics. It was found that there are cases. As a result of diligent studies on the factors that the varistor characteristics are not exhibited in the structure manufactured by using the conventional resin material, the present inventors have not sufficiently embedded the region between the two terminals with the resin (embedding defect has occurred). ), It was found that there is a possibility that a problem such as insufficient filling of varistor particles in the region between the two terminals (poor filling of particles) may occur.

Here, in order to produce the member (structure) exhibiting the above-mentioned varistor characteristics, it is necessary to produce a resin composition having the following three characteristics. The first characteristic required for the resin composition is excellent enough to control the shape of the member so as to correspond to the shape of the electrode terminal provided in the electronic element to which the member exhibiting the varistor characteristic is used. It is moldable. The second characteristic required for the resin composition is the function of the sealing material used for protecting the electrode terminals in the conventional electronic component, that is, the requirement for durability, moisture resistance, adhesion and the like. It retains its characteristics. The third property required for the resin composition is that the resin composition can exhibit sufficient varistor properties.

The present inventors have diligently studied a design guideline for producing a resin material having an excellent balance between resin embedding property and particle filling property in the inter-terminal region on the premise of satisfying the above-mentioned three required characteristics. As a result, it was found that it is effective to control the sedimentation behavior of semiconductor ceramic particles having varistor characteristics. Specifically, the present inventors have found that controlling the balance between the size of the semiconductor ceramic particles blended in the resin material and the viscosity of the resin material is effective as a design guideline.
In addition, the present inventor has described potting, screen printing, and compression as a method for producing a member exhibiting the above-mentioned varistor characteristics from the viewpoint of satisfying the above-mentioned first characteristic, that is, from the viewpoint of realizing sufficient moldability. It was also found that it is desirable to adopt a molding method or a transfer molding method. Therefore, the present resin composition can be processed into a liquid, granular, tablet-like or sheet-like form. When using a sheet-shaped material, a method of performing lamination using a laminator may be adopted.

As described above, the present resin composition has a value D [μm] of the average particle size d50 of the semiconductor ceramic particles and the minimum melt viscosity η [Pa · s] of the resin composition at a temperature of 25 ° C. or higher and 150 ° C. or lower. The value of the sedimentation index S (S = D ² / η) [(μm) ² / (Pa · s)] calculated from the value of 300 (μm) ² / (Pa · s) or more. It controls. By doing so, a structure having an overvoltage protection function can be produced with good yield without impairing moldability, and a resin composition having an excellent balance between resin embedding property and particle filling property in the inter-terminal region. Can be.

The lower limit of the sedimentation index S (S = D ² / η) [(μm) ² / (Pa · s)] relating to this resin composition is 300 (μm) ² / (Pa · s) or more. It is preferably 500 (μm) ² / (Pa · s) or more, and more preferably 600 (μm) ² / (Pa · s) or more. By doing so, it is possible to improve the balance between the filling property of the semiconductor ceramic particles and the resin embedding property in the region between the two electrode terminals. On the other hand, the upper limit of the sedimentation index S (S = D ² / η) [(μm) ² / (Pa · s)] according to the present resin composition is preferably 1 million (μm) ² / (Pa · s). ) Or less, more preferably 100,000 (μm) ² / (Pa · s) or less, and particularly preferably 20,000 (μm) ² / (Pa · s) or less.
By doing so, it is possible to improve the resin embedding property of the region between the two electrode terminals and the filling property of the semiconductor ceramic particles. Further, it is possible to obtain a resin composition having excellent uniformity after preparation of the resin composition and storage stability at room temperature or low temperature.

Further, in this resin composition, the value of the minimum melt viscosity at a temperature of 25 ° C. or higher and 150 ° C. or lower is preferably 0.001 Pa · s or more and 10 Pa · s or less, and 0.01 Pa · s or more and 5 Pa · s or more. The following is more preferable. By doing so, the settling speed of the semiconductor ceramic particles can be kept within a range that is neither too fast nor too slow. Therefore, when the minimum melt viscosity is within the above numerical range, as a result, a resin composition having an excellent balance between resin embedding property and particle filling property as well as moldability can be obtained.
The minimum melt viscosity is determined by using, for example, a viscoelasticity measuring device (Rheo stress RS-10 HAAKE, manufactured by Thermo Fisher Scientific Co., Ltd.) under the conditions of a heating rate of 10 ° C./min and a frequency of 0.1 Hz. Constant strain-can be measured by stress detection.

<Thermosetting resin>
Specific examples of the thermosetting resin contained in the present resin composition include novolak-type phenol resins such as phenol novolac resin, cresol novolak resin, bisphenol A-type novolak resin, and triazine skeleton-containing phenol novolak resin; unmodified resol-phenol resin. , Tung oil, linseed oil, walnut oil, etc. modified oil-modified resolephenol resin, etc. Resol type phenol resin, etc. Phenolic resin; Bisphenol A type epoxy resin, Bisphenol F type epoxy resin, Bisphenol S type epoxy resin, Bisphenol E type epoxy Bisphenol type epoxy resin such as resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol Z type epoxy resin; novolak type epoxy resin such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin; Biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, arylalkylene type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, stillben type epoxy resin, hydroquinone type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, phenol Epoxy resins such as aralkyl-type epoxy resin, trifunctional epoxy resin, heterocyclic-containing epoxy resin, modified phenol-type epoxy resin, noboronen-type epoxy resin, adamantan-type epoxy resin, and fluorene-type epoxy resin; Resin having a triazine ring such as; unsaturated polyester resin; maleimide resin such as bismaleimide compound; polyurethane resin; diallylphthalate resin; silicone resin; benzoxazine resin; polyimide resin; polyamideimide resin; benzocyclobutene resin, novolak type cyanate Examples thereof include a resin, a cyanate ester resin such as a bisphenol type cyanate resin such as a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, and a tetramethylbisphenol F type cyanate resin. One of these may be used alone, two or more having different weight average molecular weights may be used in combination, or one or two or more of them may be used in combination with their prepolymers. ..

The content of the thermosetting resin is preferably 10% by mass or more and 80% by mass or less, and more preferably 15% by mass or more and 75% by mass or less, based on the total amount of the present resin composition. By setting the content of the thermosetting resin to the above lower limit value or more, it is possible to suppress a decrease in the fluidity of the thermosetting resin. Further, by setting the content of the thermosetting resin to the above upper limit value or less, it is possible to suppress a decrease in the heat dissipation property of the thermosetting resin and to reduce the varistor characteristics of the structure made of the present resin composition. Can be suppressed.

As the thermosetting resin contained in the present resin composition, it is preferable to use an epoxy resin or a silicone resin. By doing so, it is possible to realize a resin composition for forming a high voltage protective member, which is excellent in terms of productivity, moldability, and shape followability to the object to be sealed. Further, when an epoxy resin or a silicone resin is blended as a thermosetting resin, electrons exhibiting excellent adhesion to a cured product of the present resin composition and good characteristics from the viewpoint of a balance between heat resistance and moisture resistance. Parts can be realized.

In particular, when an epoxy resin is used as the thermosetting resin contained in this resin composition, productivity, moldability, shape followability to the object to be sealed, heat resistance, moisture resistance, adhesion and electrical characteristics It is possible to obtain a resin composition for forming a high voltage protective member, which is excellent in terms of the above.
As the epoxy resin, it is possible to use a monomer, an oligomer, or a polymer having two or more epoxy groups in one molecule, regardless of its molecular weight and molecular structure. Specific examples of such epoxy resins include crystalline epoxy resins such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, stillben type epoxy resin, and hydroquinone type epoxy resin; cresol novolac type epoxy resin, Novolak type epoxy resin such as phenol novolac type epoxy resin, naphthol novolac type epoxy resin; phenol aralkyl type epoxy resin containing phenylene skeleton, phenol aralkyl type epoxy resin containing biphenylene skeleton, phenol aralkyl type epoxy resin such as phenylene skeleton containing naphthol aralkyl type epoxy resin Resins: Trifunctional epoxy resins such as triphenol methane type epoxy resin and alkyl modified triphenol methane type epoxy resin; Modified phenol type epoxy resins such as dicyclopentadiene modified phenol type epoxy resin and terpen modified phenol type epoxy resin; Triazine nuclei Examples thereof include heterocyclic-containing epoxy resins such as containing epoxy resins, and these may be used alone or in combination of two or more.

On the other hand, when a silicone resin is used as the thermosetting resin contained in the present resin composition, in addition to the above-mentioned three required properties, it has a good affinity for inorganic materials due to the inorganic properties derived from Si. From this point of view, it can be an excellent resin composition for forming a high voltage protective member.

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

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

R ₃ SiO _1/2 (1)
[However, R is 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. Shown. ]

The repeating unit derived from bifunctional silane means a repeating unit (D unit) represented by the following general formula (2).

R ₂ SiO _2/2 (2)
[However, R is 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. Shown. ]

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

RSiO _3/2 (3)
[However, R is 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. Shown. ]

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

Specific examples of the silicone resin include silicone rubber and silicone elastomer. These silicone resins are obtained by reacting a silicone rubber monomer or oligomer with a curing agent. Examples of such silicone rubber monomers or oligomers include those containing a methylsiloxane group, an ethylsiloxane group, and a phenylsiloxane group.
As a specific example of the silicone rubber monomer or oligomer, those obtained by introducing a functional group such as a vinyl group or a hydroxyl group or a hydrogen atom are preferably used.

The present resin composition may contain a cyclic olefin resin. Specific examples of such cyclic olefin resins include monocycles such as cyclohexene and cyclooctene, norbornene, norbornene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclopentadiene, tricyclopentadiene, dihydrotricyclopentadiene, and tetracyclopentadiene. , Polycyclics such as dihydrotetracyclopentadiene, and polymers of cyclic olefin monomers such as substituents in which a functional group is bonded to these monomers. Specific examples of such a polymer of a cyclic olefin monomer include a (co) polymer of a cyclic olefin monomer, a copolymer of a cyclic olefin monomer and a copolymer of another copolymerizable monomer such as α-olefins, and the like. And hydrogenated products of these copolymers and the like. The above-mentioned polymer may be any of a random copolymer, a block copolymer and an alternating copolymer. Further, these cyclic olefin resins can be produced by a known polymerization method, and examples of the polymerization method include an addition polymerization method and a ring-opening polymerization method. Among the cyclic olefin resins, norbornene resins are generally preferable because their main chain skeleton has an alicyclic structure and therefore has low hygroscopicity.

The present resin composition may contain a mold release agent. By doing so, when a granular, tablet-like or sheet-like resin composition is used, a member (structure 300) exhibiting varistor characteristics can be produced with good yield.

Specific examples of the release agent according to the present embodiment include natural wax, synthetic wax, higher fatty acid or metal salts 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 or less, based on the total amount of the present resin composition. is there.

The present resin composition may contain a curing agent. The curing agent may be one that reacts with a thermosetting resin to cure. Here, as a specific example of a curing agent that can be used when an epoxy resin is used as the thermosetting resin, a linear aliphatic group having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, and hexamethylenediamine Diamine, metaphenylenediamine, paraphenylenediamine, paraxylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 4, Aminos such as 4'-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1,5-diaminonaphthalene, metaxylene diamine, paraxylene diamine, 1,1-bis (4-aminophenyl) cyclohexane, dicyanodiamide, etc. Kind: Resol-type phenolic resin such as aniline-modified resol resin and dimethyl ether resol resin; Novolac-type phenolic resin such as phenol novolac resin, cresol novolac resin, tert-butylphenol novolak resin, nonylphenol novolac resin; phenol aralkyl resin containing phenylene skeleton, biphenylene skeleton Phenol aralkyl resin containing phenol aralkyl resin, naphthol aralkyl type phenol resin containing phenylene skeleton; phenol aralkyl resin having condensed polycyclic structure such as naphthalene skeleton and anthracene skeleton; polyoxystyrene such as polyparaoxystyrene; hexahydrophthalic anhydride (phthalic anhydride Alicyclic acid anhydrides such as HHPA) and methyltetrahydrophthalic anhydride (MTHPA), aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA) and benzophenone tetracarboxylic acid (BTDA). Acid anhydrides and the like containing such as; polymercaptan compounds such as polysulfide, thioester and thioether; isocyanate compounds such as isocyanate prepolymer and blocked isocyanate; organic acids such as carboxylic acid-containing polyester resin and the like can be mentioned. 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, a compound having at least two phenolic hydroxyl groups in one molecule is preferable, and specific examples thereof include phenol novolac resin, cresol novolak resin, and tert-butylphenol novolac. Resin, nonylphenol Novolac type phenol resin such as novolak resin; Resol type phenol resin; Polyoxystyrene such as polyparaoxystyrene; Phenylene skeleton-containing phenol aralkyl resin, biphenylene skeleton-containing phenol aralkyl resin, phenylene skeleton-containing naphthol aralkyl type phenol resin, etc. Can be mentioned.

The present resin composition may contain a curing accelerator.
The curing accelerator that can be used when an epoxy resin is used as the thermosetting resin may be one that promotes the curing reaction between a functional group such as an epoxy group and the curing agent, and specific examples thereof include 1,8. − Diazabicyclo [5.4.0] Undecene-7 and other diazabicycloalkenes and their derivatives; amine compounds such as tributylamine and benzyldimethylamine; imidazole compounds such as 2-methylimidazole; triphenylphosphine, methyldiphenylphosphine Organic phosphines such as: tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / tetrabenzoic acid borate, tetraphenylphosphonium / tetranaphthoic acid borate, tetraphenylphosphonium / tetranaphthyloxyborate, tetraphenylphosphonium / tetranaphthyloxyborate. Tetra-substituted phosphoniums such as borates and tetra-substituted borates; triphenylphosphines adducted from benzoquinone and the like can be mentioned. These may be used alone or in combination of two or more.
Specific examples of the curing accelerator that can be used when a silicone resin is used as the thermosetting resin include H ₂ PtCl ₆ · mH ₂ O, K ₂ PtCl ₆ , KH PtCl ₆ · mH ₂ O, and K ₂ PtCl _4. , K ₂ PtCl ₄ · mH ₂ O, PtO ₂ · mH ₂ O (m is a positive integer, respectively), and complexes of these compounds with hydrocarbons such as olefins, alcohols or vinyl group-containing organopolysiloxanes, etc. Can be mentioned.

Further, the present resin composition may contain an inorganic filler from the viewpoint of improving the sealing material characteristics such as durability, moisture resistance and adhesion of the cured product of the resin composition. Examples of this inorganic filler include silica such as melt crushed silica, melt silica, crystalline silica, synthetic silica, and secondary aggregated silica; alumina; titanium white; aluminum hydroxide; talc; clay; mica; glass fiber and the like. Among these, spherical fused silica or synthetic silica is particularly preferable. Moreover, it is preferable that the particle shape is infinitely spherical. Further, the amount of inorganic filling can be increased by mixing particles having different particle sizes, but it is desirable and preferably that the average particle size d50 is 0.01 μm or more and 150 μm or less. , 0.01 μm or more and 50 μm or less, more preferably 0.02 μm or more and 40 μm or less, and further preferably 0.05 μm or more and 30 μm or less.

Further, the present resin composition may contain a coupling agent. Such a coupling agent may be blended by directly adding it at the time of preparing the resin composition, or may be blended by pre-adding treatment to an inorganic filler or semiconductor ceramic particles described later.

Specific examples of the coupling agent include an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a silane coupling agent such as disilazan, a titanate-based coupling agent, and a silicone oil type coupling agent. Be done. One type of these may be used alone, or two or more types may be used in combination. This makes it possible to improve the affinity between the resin and the inorganic filler, semiconductor ceramic particles, or the like, and improve the moldability of the resin composition.

As the silane coupling agent, known ones can be used, and examples thereof include epoxysilane, aminosilane, alkylsilane, ureidosilane, mercaptosilane, vinylsilane and the like.

Specific compounds include, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-amino. Propylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6- (aminohexyl) 3-Aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanan, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glysidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, methyltrimethoxysilane, γ-ureidopropyl Examples thereof include triethoxysilane, vinyl triethoxysilane, and one or a combination of two or more of these can be used. Of these, epoxysilane, mercaptosilane, and aminosilane are preferable, and primary aminosilane is used as the aminosilane. Alternatively, secondary aminosilane is more preferable.

Further, the present resin composition may contain, for example, an adhesion aid from the viewpoint of improving the adhesiveness of the cured product of the resin composition to the adherend. Adhesion aids that can be suitably used when an epoxy resin is used as the thermosetting resin include a functional silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. Can be mentioned. On the other hand, the adhesion aid that can be preferably used when a silicone resin is used as the thermosetting resin includes functional groups such as a hydrogen atom bonded to a silicon atom, an alkenyl group bonded to a silicon atom, an alkoxysilyl group, and an epoxy group. Examples thereof include a siloxane monomer containing a group and a siloxane oligomer.
The content of the adhesion aid is preferably 10 parts by weight or less, and more preferably 0.1 parts by weight or more and 8 parts by weight or less, based on 100 parts by weight of the total amount of the thermosetting resin.

Further, the present resin composition may contain a reaction inhibitor from the viewpoint of improving the storage stability of the resin composition. Reaction inhibitors that can be preferably used when an epoxy resin is used as the thermosetting resin include boron compounds such as trimethylborate and triethylborate, sulfuric acid, acetic acid, adipic acid, tartaric acid, fumaric acid, barbitic acid, and boric acid. Examples include acids, pyrogallols, phenolic resins, acidic compounds such as carboxylic acid anhydrides and the like. On the other hand, reaction inhibitors that can be preferably used when a silicone resin is used as the thermosetting resin include triallyl isocyanurate, alkylmalate, acetylene alcohols, silane-modified products of acetylene alcohols, and acetylene alcohols. Examples thereof include siloxane modified products, hydroperoxides, tetramethylethylenediamines and benzotriazoles.
The content of the reaction inhibitor is preferably 0.001 part by weight or more and 1 part by weight or less, and more preferably 0.005 part by weight or more and 0.% by weight, based on 100 parts by weight of the total amount of the thermosetting resin. It is 5 parts by weight or less.

In addition to the above components, the resin composition contains, if necessary, a colorant such as carbon black; a low stress agent such as silicone oil and silicone rubber; an ion trapping agent such as hydrotalcite; and hydroxylation. Various additives such as flame retardant such as aluminum; antioxidant; dispersant; leveling agent; viscosity modifier; defoamer; pigment, colorant such as dye may be blended.

Examples of the colorant include dyes having a color such as green, red, blue, yellow, and black, pigments having a color such as black, and pigments. These may be used alone or in combination of two or more.

In addition, examples of the green colorant include those containing one or more known colorants such as anthraquinone-based, phthalocyanine-based, and perillene-based.

Examples of the black dye include metal complex salt black dyes such as azo dyes and organic black dyes such as anthraquinone compounds. As such a black dye, for example, Kayaset Black A-N (manufactured by Nippon Kayaku Co., Ltd.), Kayaset Black G (manufactured by Nippon Kayaku Co., Ltd.) and the like can be preferably used. These may be used alone or in combination of two or more.

<Semiconductor ceramic particles>
FIG. 1 is an enlarged cross-sectional view of the 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 grain boundary portion 20 and a plurality of crystal portions 10 separated by the grain boundary portion 20. In other words, in the semiconductor ceramic particles 100 according to the present embodiment, a plurality of crystals composed of a grain boundary portion 20 and two or more crystal portions 10 arranged so as to be separated from each other via the grain boundary portion 20 are aggregated. It can be said that it is a grain. When a voltage lower than the varistor voltage is applied to the semiconductor ceramic particles 100, the grain boundary portion 20 acts as a resistor to prevent current from passing through the semiconductor ceramic particles 100, but a voltage higher than the varistor voltage is applied. In some cases, the particles have a characteristic that a tunnel effect is generated and an electric current is passed as shown by the arrow shown in FIG. A member having varistor characteristics, such as the semiconductor ceramic particles 100 according to the present embodiment, is included in a withstand voltage protection element (varistor element, etc.) mounted on the circuit together with the electronic element in a conventional electronic component. It was. However, a method for producing a member made of a resin composition containing the semiconductor ceramic particles 100 satisfying the following two required characteristics with good yield has not been reported so far. The first required characteristic is that it can be provided inside the electronic element itself mounted in the circuit mounted in the electronic component. The second required characteristic is that when the member is provided inside the electronic element itself, it has a function of protecting the electronic element from stress applied from the external environment in addition to overvoltage such as static electricity. is there.

The average particle size 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, and further preferably 1 μm or more and 90 μm or less. By doing so, the varistor characteristics can be exhibited without depending on the shape of the structure 300 formed of the resin composition for forming a high voltage protective member containing the semiconductor ceramic particles 100. Further, the semiconductor ceramic particles 100 are preferably spherical particles. Thereby, the varistor characteristics can be easily controlled.
When the semiconductor ceramic particles 100 are not spherical, the value of the average particle diameter d50 of the semiconductor ceramic particles 100 in the present embodiment may be a value close to a true sphere.

In the semiconductor ceramic particles 100, the crystal portion 10 is preferably formed of a material containing at least one selected from the group consisting of zinc oxide, silicon carbide, strontium titanate, and barium titanate. When the crystal portion 10 is formed of the above material, it is possible to improve the non-linear coefficient and energy tolerance of the semiconductor ceramic particles 100 itself and suppress high voltage / high frequency noise. Above all, a material containing zinc oxide as a main component is preferable from the viewpoint of improving the non-linear coefficient and energy tolerance of the semiconductor ceramic particles 100 itself. A material containing silicon carbide as a main component has a high dielectric breakdown voltage, and is therefore suitable when the varistor voltage is set to a high voltage. Further, a material containing strontium titanate as a main component is suitable in terms of absorption and suppression of high voltage and high frequency noise.

In the semiconductor ceramic particles 100, the grain boundary portion 20 is selected from the group consisting of bismuth, praseodymium, antimony, manganese, cobalt and nickel, or compounds thereof from the viewpoint of improving the non-linear resistance characteristics of the resin composition. It is preferably formed of a material containing one or more kinds of cobalt. Above all, the grain boundary portion 20 is preferably formed of a material containing at least one selected from the group consisting of bismuth, praseodymium, or a compound thereof from the viewpoint of good non-linear resistance characteristics. .. Examples of these compounds include oxides, nitrides, organic compounds, and other inorganic compounds, but oxides are preferable from the viewpoint of satisfactorily exhibiting varistor characteristics.

The content of the semiconductor ceramic particles 100 is 20% by mass or more and 97% by mass or less, preferably 25% by mass, based on the total amount of the present resin composition, from the viewpoint of surely expressing the varistor characteristics of the structure 300. It is 80% by mass or more, and more preferably 30% by mass or more and 70% by mass or less.
By controlling the content of the semiconductor ceramic particles 100 so as to be within the above numerical range, as shown in the schematic diagram shown in FIG. 2, the two electrode terminals 30 adjacent to each other are in contact with each other. It becomes easy to realize the structure 300 filled with the semiconductor ceramic particles 100. Specifically, when the content of the semiconductor ceramic particles 100 is controlled to be within the above numerical range, the semiconductor ceramic particles 100 are filled between the two electrode terminals 30 adjacent to each other so that the plurality of particles are in contact with each other. It is possible to realize the structure 300 in which the gap region is filled with the resin material 200. Therefore, when the content of the semiconductor ceramic particles 100 is controlled to be within the above numerical range, the varistor characteristics of the structure can be reliably exhibited.
When the content of the semiconductor ceramic particles 100 is 30% by mass or more and 70% by mass or less as described above, the semiconductor ceramic particles 100 are positively applied between the electrode terminals 30 of the electronic component by using this resin composition. Can be settled and filled.

Conductive particles can be contained in the present resin composition. By doing so, when a high voltage exceeding the varistor voltage is applied to the electronic component including the structure 300 formed of the present resin composition, the electrical conductivity of the structure 300 is improved. can do. Specifically, as shown in FIG. 3, the conductive particles 50 can be inserted into the gap region between the plurality of semiconductor ceramic particles 100 arranged so as to fill the space between the two electrode terminals 30. In this case, the resin material 200 is arranged so as to fill the boundary region between the semiconductor ceramic particles 100 and the conductive particles 50.

The content of the conductive particles 50 is preferably 1% by mass or more and 20% by mass or less, and more preferably 2 with respect to the total amount of the present resin composition, from the viewpoint of surely exhibiting the varistor characteristics of the structure 300. It is by mass% or more and 15% by mass or less, and most preferably 2% by mass or more and 10% by mass or less. By controlling the content of the conductive particles 50 so as to be within the above numerical range, as shown in the schematic diagram shown in FIG. 3, the plurality of semiconductor ceramic particles 100 arranged so as to fill the space between the two electrode terminals 30. It is possible to evenly insert the conductive particles 50 into the gap region.

The average particle size 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 further preferably, from the viewpoint of surely exhibiting 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. Examples thereof include conductive materials selected from the group consisting of zinc oxide, silicon carbide, strontium titanate, and barium titanate.

Further, the sizes of the semiconductor ceramic particles 100 and the conductive particles 50 contained in the present resin composition preferably satisfy the following conditions. Specifically, when the average particle size d50 of the semiconductor ceramic particles 100 is X and the average particle size d50 of the conductive particles 50 is Y, the value of Y / X is preferably 0.05 or more and less than 1. , 0.1 or more and 0.8 or less is more preferable. By doing so, as shown in the schematic diagram shown in FIG. 3, the conductive particles 50 can easily enter into the gap region of the plurality of semiconductor ceramic particles 100 arranged so as to fill the space between the two electrode terminals 30.

The resin composition for forming a high voltage protective member according to the present embodiment employs a structure containing a thermosetting resin and semiconductor ceramic particles exhibiting a specific amount of varistor characteristics. By using the resin composition adopting such a configuration, the electronic element itself is protected from an overvoltage such as static electricity and an external load of stress applied from the external environment inside the electronic element itself arranged in the circuit of the electronic component. Since it is possible to provide a configuration having a function, it is not necessary to arrange the electronic element and the withstand voltage protection element in the circuit as in the conventional electronic component, and as a result, the electronic component is downsized. Can be realized.

Hereinafter, a method of molding a member (structure 300) exhibiting varistor characteristics in an electronic component using the resin composition for forming a high voltage protective member according to the present embodiment will be described.

Examples of the method for molding the resin composition for forming a high voltage protective member according to the present embodiment include a method using a discharge device such as a dispenser and an inkjet, a method using a spatula such as a squeegee, and a screen printing machine. Examples thereof include a method using a printing device, a compression molding method, a transfer molding method, an injection molding method, and the like. Of these, the method using a discharge device is preferably used. According to this method, the required amount of the resin composition can be efficiently applied to the target position with high accuracy. Therefore, the coating work can be performed in a short time while minimizing the amount of the resin composition used. As a result, the cost and speed of the coating work can be reduced.

Further, as an example of the structure 300 according to the present embodiment, a semiconductor device including a semiconductor element and a cured product of the present resin composition that seals the semiconductor element, and a region between two electrode terminals of the present resin. Examples thereof include electronic components covered with a cured product of the composition.

The present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.
Hereinafter, an example of the embodiment will be added.
1. 1. The cured product is a resin composition for forming a high voltage protective member, which exhibits non-linearity in which the voltage-current characteristic does not obey Ohm's law.
Thermosetting resin and
A semiconductor ceramic particle having a grain boundary portion and a plurality of crystal portions separated by the grain boundary portion,
Including
The average particle size d50 of the semiconductor ceramic particles is D [μm], and the minimum melt viscosity value of the resin composition for forming a high voltage protective member at a temperature of 25 ° C. or higher and 150 ° C. or lower is η [Pa · s]. High voltage protection in which the value of the sedimentation index S [(μm) ² / (Pa · s)] represented by S = D ² / η is 300 (μm) ² / (Pa · s) or more. Resin composition for forming members.
2. 2. 1. The average particle size d50 of the semiconductor ceramic particles is 0.01 μm or more and 150 μm or less. The resin composition for forming a high voltage protective member according to.
3. 3. 1. The crystal part is formed of a material containing at least one selected from the group consisting of zinc oxide, silicon carbide, strontium titanate, and barium titanate. Or 2. The resin composition for forming a high voltage protective member according to.
4. 1. The grain boundaries are formed of a material containing bismuth, praseodymium, antimony, manganese, cobalt and nickel, or one or more selected from the group consisting of compounds thereof. To 3. The resin composition for forming a high voltage protective member according to any one of.
5. 1. The thermosetting resin contains an epoxy resin or a silicone resin. To 4. The resin composition for forming a high voltage protective member according to any one of.
6. 1. The semiconductor ceramic particles are contained in an amount of 20% by mass or more and 97% by mass or less based on the total amount of the resin composition for forming a high voltage protective member. To 5. The resin composition for forming a high voltage protective member according to any one of.
7. 1. 1. To 6. A semiconductor device comprising a cured product of the resin composition for forming a high voltage protective member according to any one of.
8. 1. 1. To 6. An electronic component comprising a cured product of the resin composition for forming a high voltage protective member according to any one of.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The raw material components used in each Example and each Comparative Example are shown below.
-Thermosetting resin 1: A mixture of bisphenol F type epoxy resin and bisphenol A type epoxy resin (manufactured by DIC Corporation, EPICLON EXA-830LVP, liquid)
-Thermosetting resin 2: Vinyl group-containing silicone resin (manufactured by Momentive Performance Materials Japan, IVSM-4500 (A), liquid)
-Thermosetting resin 3: Hydrogen atom-containing silicone resin (manufactured by Momentive Performance Materials Japan, IVSM-4500 (B), liquid)
-Thermosetting resin 4: Hydroxy group-containing silicone resin (manufactured by Asahi Kasei Wacker Silicone Co., Ltd., SILRES MK, solid)
-Hardener: Phenolic novolak resin (manufactured by Meiwa Kasei Co., Ltd., MEH-8000H, liquid)
-Coupling agent: 3-glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
-Curing accelerator: A compound represented by the following chemical formula (1). In addition, Ph of the following formula (1) represents a phenyl group.

-Semiconductor ceramic particles 1: Ceraon Co., Ltd., micro varistor, average particle size d50: 47.7 μm
-Semiconductor ceramic particles 2: Ceraon Co., Ltd., micro varistor, average particle size d50: 70.7 μm
-Semiconductor ceramic particles 3: manufactured by Ceraon Co., Ltd., micro varistor, average particle size d50: 28.4 μm

(Preparation of thermosetting resin composition varnish)
For Examples 7 to 10 , Reference Examples 1 to 6, and Comparative Examples 1 to 2, each component was kneaded with a planetary mixer according to the blending amounts shown in Table 1 below to prepare a resin composition for forming a high voltage protective member.

(Separation between electrodes)
Next, the electrode-to-electrode sealing was performed using the obtained resin composition for forming a high voltage protective member.
As the substrate, a substrate having an FR-4 substrate (thickness 0.15 mm) and a circuit layer (copper circuit, thickness 12 μm, minimum distance between adjacent circuits 200 μm) was used.
Each of the prepared resin compositions was applied and leveled using a squeegee so as to fill the gap between the circuits. A dispenser was used for this application.

Next, when the resin composition was used as a reference, the applied composition was dried at 100 ° C. for 2 minutes while holding the FR-4 substrate so as to be located vertically below, and then further 60 at 150 ° C. The thermosetting resin was cured by heating for 1 minute. As a result, the electrodes were sealed to prepare a structure.

The measurements and evaluations made on the resin compositions and structures obtained in Examples, Reference and Comparative Examples are detailed below.

<Evaluation items>
-Melty Viscosity: For each of the resin compositions obtained in Examples , Reference Examples and Comparative Examples, in addition to the melt viscosity at room temperature (25 ° C) and the melt viscosity at hot (150 ° C), 25 ° C or higher 150 The minimum melt viscosity (η) at a temperature below ° C. was measured. The unit is Pa · s.
The melt viscosity was measured using a viscoelasticity measuring device (Rheo stress RS-10 HAAKE, manufactured by Thermo Fisher Scientific Co., Ltd.) under the conditions of a heating rate of 10 ° C./min and a frequency of 0.1 Hz. It was carried out by a measurement method based on constant-stress detection.

・ Varistor characteristics (initial): Current / voltage characteristics between circuits are applied from 0V to 100V at a boost speed of 0.5V / sec between adjacent circuits using pAmeter / DC VOLTAGE SOURCE 4140B (manufactured by Azilent Technology). The value of the current that flowed at that time was measured. Based on the results obtained in this way, a graph plotted on the logarithmic axis was created as shown in FIG. Then, the varistor voltage was calculated from the obtained graph. Specifically, the intersection of the tangent line (b) of the graph on the low voltage side and the tangent line (a) on the high voltage side of the inflection point of the obtained graph was calculated as the varistor voltage. Then, the varistor characteristics were determined to be (◯) when the varistor voltage could be calculated and (×) when it was not possible.

Sedimentation index S: The value (D) [μm] of the average particle size d50 of the semiconductor ceramic particles blended in each of the resin compositions obtained in Examples, Reference Examples and Comparative Examples, and the measurement measured by the method described above. Substituting the minimum melt viscosity value (η) [Pa · s] at a temperature of 25 ° C. or higher and 150 ° C. or lower for each resin composition obtained in the comparative examples into the equation of S = D ² / η. Was calculated.

All of the structures of the examples exhibited the varistor characteristics, whereas the structures of the comparative examples did not exhibit the varistor characteristics from the beginning.

10 Crystal part 20 Grain boundary part 30 Electrode terminal 50 Conductive particles 100 Semiconductor ceramic particles 200 Resin material 300 Member (structure) exhibiting varistor characteristics

Claims (7)

The cured product is a resin composition for forming a high voltage protective member, which exhibits non-linearity in which the voltage-current characteristic does not obey Ohm's law.
Thermosetting resin and
A semiconductor ceramic particle having a grain boundary portion and a plurality of crystal portions separated by the grain boundary portion,
Including
The thermosetting resin contains a silicone resin and contains
The silicone resin has at least one reactive group selected from a vinyl group, a hydrogen atom, a hydroxy group, an alkoxy group, and an epoxy group.
The average particle size d50 of the semiconductor ceramic particles is D [μm], and the minimum melt viscosity value of the resin composition for forming a high voltage protective member at a temperature of 25 ° C. or higher and 150 ° C. or lower is η [Pa · s]. Then, the value of the sedimentation index S [(μm) ² / (Pa · s)] represented by S = D ² / η is 300 (μm) ² / (Pa · s) or more, and the minimum melt viscosity. A resin composition for forming a high voltage protective member, wherein the value of η [Pa · s] is 0.01 Pa · s or more and 5 Pa · s or less. The resin composition for forming a high voltage protective member according to claim 1, wherein the average particle size d50 of the semiconductor ceramic particles is 0.01 μm or more and 150 μm or less. The high voltage protection member formation according to claim 1 or 2, wherein the crystal portion is formed of a material containing at least one selected from the group consisting of zinc oxide, silicon carbide, strontium titanate, and barium titanate. Resin composition for. Any one of claims 1 to 3, wherein the grain boundary is formed of a material containing bismuth, praseodymium, antimony, manganese, cobalt and nickel, or one or more selected from the group consisting of compounds thereof. The resin composition for forming a high voltage protective member according to. The high voltage protection member for forming the high voltage protection member according to any one of claims 1 to 4, wherein the semiconductor ceramic particles are contained in an amount of 20% by mass or more and 97% by mass or less based on the total amount of the resin composition for forming the high voltage protection member. Resin composition. A semiconductor device comprising a cured product of the resin composition for forming a high voltage protective member according to any one of claims 1 to 5. An electronic component comprising a cured product of the resin composition for forming a high voltage protective member according to any one of claims 1 to 5.