WO2010101103A1 - 放電ギャップ充填用組成物および静電放電保護体 - Google Patents
放電ギャップ充填用組成物および静電放電保護体 Download PDFInfo
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- WO2010101103A1 WO2010101103A1 PCT/JP2010/053209 JP2010053209W WO2010101103A1 WO 2010101103 A1 WO2010101103 A1 WO 2010101103A1 JP 2010053209 W JP2010053209 W JP 2010053209W WO 2010101103 A1 WO2010101103 A1 WO 2010101103A1
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- discharge gap
- composition
- electrostatic discharge
- oxide film
- discharge
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
- H01T4/00—Overvoltage arresters using spark gaps
- H01T4/02—Details
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
- H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
- H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
- H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
- H01C17/06526—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
- H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
- H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
- H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
- H01C17/06553—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of a combination of metals and oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
- H01C7/1006—Thick film varistors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
- H01C7/12—Overvoltage protection resistors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
- H01T4/00—Overvoltage arresters using spark gaps
- H01T4/10—Overvoltage arresters using spark gaps having a single gap or a plurality of gaps in parallel
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02H—EMERGENCY PROTECTIVE CIRCUIT ARRANGEMENTS
- H02H9/00—Emergency protective circuit arrangements for limiting excess current or voltage without disconnection
- H02H9/04—Emergency protective circuit arrangements for limiting excess current or voltage without disconnection responsive to excess voltage
- H02H9/06—Emergency protective circuit arrangements for limiting excess current or voltage without disconnection responsive to excess voltage using spark-gap arresters
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05F—STATIC ELECTRICITY; NATURALLY-OCCURRING ELECTRICITY
- H05F3/00—Carrying-off electrostatic charges
- H05F3/02—Carrying-off electrostatic charges by means of earthing connections
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0067—Devices for protecting against damage from electrostatic discharge
Definitions
- the present invention relates to a discharge gap filling composition and an electrostatic discharge protector, and more specifically, an electrostatic discharge protector that is excellent in adjustment accuracy of operating voltage and can be reduced in size and cost, and the electrostatic discharge
- the present invention relates to a discharge gap filling composition used for a protector.
- Electrostatic discharge (hereinafter sometimes referred to as ESD) is one of the destructive and inevitable phenomena to which electrical systems and integrated circuits are exposed. From an electrical point of view, ESD is a transient high current phenomenon lasting from 10 to 300 ns with a peak current of several amperes. Therefore, when ESD occurs, if a current of almost several amperes is not conducted outside the integrated circuit within several tens of nanoseconds, the integrated circuit will be damaged by repair or will malfunction or deteriorate and function normally. No longer. In recent years, electronic components and electronic devices have been rapidly reduced in weight, thickness, and size.
- an electrostatic protection element for protecting an IC or the like in a circuit from ESD there has been an element having a bulk structure made of a sintered body of a metal oxide or the like as disclosed in JP-A-2005-353845.
- This element is a laminated chip varistor made of a sintered body, and includes a laminated body and a pair of external electrodes.
- a varistor has a property that when an applied voltage reaches a certain value or more, a current that has not flowed until then suddenly flows out, and has an excellent deterrent against electrostatic discharge.
- the multilayer chip varistor which is a sintered body, cannot avoid a complicated manufacturing process consisting of sheet molding, internal electrode printing, sheet lamination, and the like, and is also likely to suffer from problems such as delamination during the mounting process. There was a problem.
- discharge protection elements include electrostatic protection elements that protect ICs in circuits from ESD.
- Discharge-type devices have the advantages that they have a small leakage current, are simple in principle, and are less likely to fail.
- the discharge voltage can be adjusted by the distance of the discharge gap.
- the distance of the discharge gap is determined according to the gas pressure and the gas type.
- As an element on the market there is a device in which a cylindrical ceramic surface conductor film is formed, a discharge gap is provided in the film by a laser or the like, and this is glass sealed.
- this commercially available glass sealed tube type discharge gap type element has excellent electrostatic discharge characteristics, its form is complicated, so there is a limit in terms of size as a small surface mount element, There is also a problem that it is difficult to reduce the cost.
- Japanese Unexamined Patent Publication No. 3-89588 discloses that the distance of the discharge gap is 4 mm
- Japanese Unexamined Patent Publication No. 5-67851 discloses that the distance of the discharge gap is 0.15 mm.
- a discharge gap of 5 to 60 ⁇ m is preferable for protecting normal electronic elements
- a discharge gap of 1 to 30 ⁇ m is used for protecting ICs and LSIs sensitive to static electricity.
- it is exemplified that it can be increased to about 150 ⁇ m for an application where only a large pulse voltage portion needs to be removed.
- this electrostatic discharge protector requires high insulation resistance at a normal operating voltage, for example, generally less than DC 10 V, a voltage-resistant insulating member is provided in the discharge gap of the electrode pair. Is effective. If a normal resist is directly filled in the discharge gap as an insulating member in order to protect the discharge gap, the discharge voltage is significantly increased, which is not practical. When normal resists are filled in an extremely narrow discharge gap of about 1 to 2 ⁇ m or less, the discharge voltage can be lowered, but the filled resists are slightly degraded and the insulation resistance is lowered. In some cases, there is a problem of conduction.
- Japanese Patent Application Laid-Open No. 2007-266479 discloses a protective element in which a functional film containing ZnO as a main component and containing silicon carbide is provided between a pair of electrode patterns whose ends are opposed to each other with a discharge gap of 10 ⁇ m to 50 ⁇ m formed on an insulating substrate. Is disclosed. This has a simple structure as compared with the multilayer chip varistor, and has an advantage that it can be manufactured as a thick film element on the substrate.
- these ESD countermeasure elements have been reduced in mounting area in accordance with the evolution of electronic equipment, but the form is only an element, and since it is mounted on a wiring board by solder etc., design freedom There is a limit to downsizing including the height and the height. Therefore, it is desired not to fix the element, but to be able to take ESD countermeasures at a necessary location and for a necessary area in a free form including miniaturization.
- Patent Document 1 JP-T-2001-523040
- the resin composition here is a base material made of a mixture of insulating binders. It is characterized by including conductive particles having an average particle diameter of less than 10 ⁇ m and semiconductor particles having an average particle diameter of less than 10 ⁇ m.
- Patent Document 2 Hyatt et al., US Pat. No. 4,726,991 (Patent Document 2) is introduced, and conductive particles and semiconductors whose surfaces are coated with an insulating oxide film.
- a composition material in which a mixture of particles is bound by an insulating binder, a composition material in which a particle diameter range is defined, a composition material in which an interplanar spacing between conductive particles is defined, and the like are disclosed.
- a high electrical resistance value cannot be obtained at a low voltage, or a low electrical resistance value can be obtained at a high voltage.
- There are technical instability factors such as no.
- a lightning arrester described in Japanese Patent Publication No. 7-118361 (Patent Document 3) is known as a device for protecting other devices from a surge by utilizing a dielectric breakdown phenomenon of a high resistance film on a metal surface.
- Patent Document 3 molybdenum is selected as the metal having an oxide film to realize a molybdenum lightning arrester.
- This molybdenum lightning arrester can be used repeatedly because it will automatically form again in a short time as long as it is placed in an oxidizing atmosphere, even if the oxide film once breaks down. There is no need for replacement over time, making it a very useful device.
- the voltage level of the surge is almost the same as that of electrostatic discharge, the current may reach the scale of 1,000 to 10,000 A, so that only the metal with the oxide film can sufficiently protect other devices from the surge.
- the electrostatic current is significantly smaller than that of the surge, the electrostatic discharge protection characteristics may not be sufficient with only the metal having an oxide film against electrostatic discharge.
- Patent Document 4 Japanese Patent Application Laid-Open No. 2007-262446
- a mixture of metal oxide particles coated with a material or metal particles having a surface oxide film and a carbon material is baked in an oxidizing gas containing oxygen and then baked in an inert gas, the carbon material oxidizes the metal. It is described that the film is reduced and exhibits excellent conductivity.
- Patent Document 5 Japanese Patent Application Laid-Open No. 2003-59616
- Patent Document 5 describes a surge absorbing element in which a discharge inducing body made of an easy electron generating material including a carbon material is provided so as not to be short-circuited between discharge gaps.
- the discharge voltage can be set to less than 1 KV.
- surge current flows, it is necessary to provide instability and pores due to deformation caused by deformation of the discharge inducer.
- the manufacturing process for forming the element is complicated.
- the present invention is intended to solve the above-described problems, and it is possible to easily take ESD countermeasures in various shapes for electronic circuit boards of various designs, and to reduce the operating voltage.
- the inventor sets a discharge gap of a pair of electrodes to a specific interval, fills the gap with a composition made of a specific component, and solidifies or It has been found that by curing, an electrostatic discharge protector that is excellent in adjustment accuracy of the operating voltage, and that can be reduced in size and cost can be obtained.
- a composition for filling a discharge gap of an electrostatic discharge protector comprising metal particles (A) having an oxide film, a layered substance (B), and a binder component (C).
- the electrostatic discharge protector of the present invention forms a discharge gap according to the required operating voltage between necessary electrodes, and fills the discharge gap with the composition for filling the discharge gap of the present invention to solidify or cure. Can be formed. For this reason, if the composition for filling a discharge gap of the present invention is used, a small electrostatic discharge protector can be manufactured at low cost, and electrostatic discharge protection can be easily realized.
- the discharge gap filling composition of the present invention the operating voltage can be adjusted by setting the discharge gap to a specific interval. Therefore, the electrostatic discharge protector of the present invention is excellent in the adjustment accuracy of the operating voltage. .
- the electrostatic discharge protector of the present invention can be suitably used in digital devices such as mobile phones, mobile devices that are often touched by human hands and easily accumulate static electricity.
- FIG. 1 is a longitudinal sectional view of an electrostatic discharge protector 11 which is a specific example of the electrostatic discharge protector according to the present invention.
- FIG. 2 is a longitudinal sectional view of an electrostatic discharge protector 21 which is a specific example of the electrostatic discharge protector according to the present invention.
- FIG. 3 is a longitudinal sectional view of an electrostatic discharge protector 31 which is a specific example of the electrostatic discharge protector according to the present invention.
- the present invention will be specifically described below.
- Metal particles having oxide film (A) The metal particles (A) having an oxide film used in the present invention are particles in which a film made of an oxide of a metal is formed on the surface of particles made of a metal.
- the metal particles (A) having an oxide film are insulative at a normal voltage because the oxide film is insulative, but are electrically conductive due to the destruction of the oxide film at high voltage load during electrostatic discharge. Further, it is considered that the oxide film is formed again by releasing the high voltage, and the insulating property is restored.
- the metal particles used in the present invention have an oxide film on the surface, and even when the particles are closely packed and connected to each other, the volume resistance value is 10 8 ⁇ / Particles showing cm 2 or more are preferred.
- Metal oxides are passive because the movement of free electrons is constrained, but the more easily ionized metal becomes a stronger insulator when oxidized.
- the metal particles in the present invention are preferably so-called passivated metal particles that can form a dense oxide film on the surface and protect the inside despite having a high ionization tendency.
- metals that form such metal particles include manganese, niobium, zirconium, hafnium, tantalum, molybdenum, vanadium, nickel, cobalt, chromium, magnesium, titanium, and aluminum. Most preferred are aluminum, nickel, tantalum, and titanium.
- the metal may be an alloy of those metals. Several kinds of metal particles may be used in combination.
- vanadium used in thermistors whose resistance value changes suddenly at a specific temperature can be used effectively.
- the metal particles (A) having the above oxide film can be used either individually or in combination.
- the metal particles (A) having an oxide film can be prepared by heating the metal particles in the presence of oxygen, but an oxide film having a more stable structure can be prepared by the following method. That is, for the purpose of preventing the dielectric breakdown voltage of the oxide film on the metal surface from becoming uneven within one product or between products, for example, the metal particles having the oxide film are cleaned with an organic solvent such as acetone. Then, the surface is slightly etched with dilute hydrochloric acid, in a mixed gas atmosphere composed of 20% hydrogen and 80% argon, at a temperature lower than the melting point of the metal itself, for example, 750 ° C. in the case of a metal other than aluminum, In this case, for example, by heating at 600 ° C. for about 1 hour and further heating for 30 minutes in a high purity oxygen atmosphere, a uniform oxide film can be formed with high controllability and good reproducibility.
- the particle diameter of the metal particles (A) having a preferable oxide film varies depending on the distance between a pair of provided counter electrodes, but is preferably 0.01 ⁇ m or more and 30 ⁇ m or less as an average particle diameter.
- the average particle size is larger than 30 ⁇ m, the amount of the oxide film per unit weight of the metal particles is small compared with the amount of the non-oxidized conductor part inside, so that it was reduced and destroyed at the time of ESD occurrence. There is a tendency for the oxidation of the surface film to be delayed and the restoration of insulation to be delayed.
- the weight ratio between the oxide film and the conductor portion per unit weight may be biased toward the larger oxide film weight, which may increase the operating voltage when ESD occurs.
- the average particle size is 1% by mass of metal particles to be measured in methanol, dispersed with an ultrasonic homogenizer with an output of 150 W for 4 minutes, and then laser diffraction light scattering particle size distribution analyzer Microtrac MT3300 [Nikkiso Co., Ltd. ] The cumulative diameter of 50% by mass obtained by measurement is evaluated.
- the volume occupancy of the metal particles (A) having an oxide film is The solid content of the discharge gap filling composition is preferably less than 80% by volume.
- the obtained electrostatic discharge protector needs to show conductivity as a whole.
- the amount is in a preferred range, and the volume occupancy of the metal particles (A) having an oxide film is desirably 30% by volume or more in the solid content of the discharge gap filling resin composition. That is, it is preferable that the volume occupancy of the metal particles (A) having the oxide film in a state where the electrostatic discharge protector is formed is 30% by volume or more and less than 80% by volume.
- the volume occupancy is observed by occupying the cross section of the cured product of the discharge gap filling composition by energy dispersive X-ray analysis using a scanning electron microscope JSM-7600F (JEOL Ltd.). It can be evaluated by the volume ratio of the visual field.
- Layered material (B) The layered substance (B) is a substance formed by combining a plurality of layers with van der Waals force, and is not originally in the structure of the crystal at a specific position in the crystal by ion exchange or the like. It is a compound that can enter atoms, molecules, and ions and does not change its crystal structure. The position where atoms, molecules and ions enter, that is, the host position, has a planar layer structure.
- layered material (B) examples include layered carbon materials (B2) such as clay mineral crystals (B1) and graphite (graphite), and chalcogenides of transition metals. These compounds each exhibit unique properties by incorporating metal atoms, inorganic molecules, organic molecules, and the like into the crystal as guests.
- B2 layered carbon materials
- B1 clay mineral crystals
- graphite graphite
- chalcogenides of transition metals These compounds each exhibit unique properties by incorporating metal atoms, inorganic molecules, organic molecules, and the like into the crystal as guests.
- the layered substance (B) is characterized in that the distance between the layers corresponds flexibly depending on the size of the guest and the interaction of the guest, and the compound obtained by including the guest by the host is called an interlayer compound.
- interlayer compound the compound obtained by including the guest by the host.
- the guest species between the layers are different from those adsorbed on the surface and are in a unique environment constrained in two directions by the host layer. Therefore, it is considered that the characteristics of the intercalation compound not only depend on the structures and properties of the host and guest, but also reflect the host-guest interaction.
- the layered material (B) has been researched in that it absorbs electromagnetic waves well, and in the case of an oxide, it becomes an oxygen absorbing and releasing material that absorbs and exhales oxygen at a certain temperature. These characteristics are considered to affect the destruction and regeneration of the oxide film of the metal particles (A) having the oxide film.
- examples of the clay mineral crystal (B1) include smectite clay, which is a swellable silicate, and swellable mica.
- Specific examples of the smectite group clay include, for example, montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, saconite, stevensite, bentonite, and the like, and substitutions and derivatives thereof, and mixtures thereof.
- swellable mica examples include lithium-type teniolite, sodium-type teniolite, lithium-type tetrasilicon mica, and sodium-type tetrasilicon mica, and substitutions and derivatives thereof, and mixtures thereof.
- Some of the above-mentioned swellable mica have a structure similar to that of percurites, and such percurites and the like can also be used.
- the layered carbon material (B2) can be used as the layered substance (B) used in the present invention.
- the layered carbon material (B2) can emit free electrons to the interelectrode space when ESD occurs.
- the layered carbon material (B2) has an insulating property by reducing the metal oxide because it stores heat when ESD occurs, or by changing the Schottky rectification characteristics by causing a phase transition of the lattice structure at the oxide film interface by the heat. It is possible to change so that the metal particle (A) which has the oxide film which showed this may show electroconductivity.
- the layered carbon material (B2) is oxidized by oxygen generated at the time of overcharge and the internal resistance is increased, but after the occurrence of ESD, it becomes an oxygen supply source for regenerating the oxide film of the metal particles.
- Examples of the layered carbon material (B2) include low-temperature treated coke, carbon black, metal carbide, carbon whisker, and SiC whisker, which are also operative with respect to ESD. These have a hexagonal network surface of carbon atoms as a basic structure, but have a relatively small number of layers and a slightly low regularity, so that they tend to be slightly short-circuited.
- the layered carbon material (B2) carbon nanotubes, vapor-grown carbon fibers, carbon fullerene, graphite, or carbine-based carbon materials having more regular layers are preferable, and at least one of these, or these It is desirable to include a mixture of
- fibrous layered carbon materials (B2) such as carbon nanotubes, graphite whiskers, filamentous carbon, graphite fibers, ultrafine carbon tubes, carbon tubes, carbon fibrils, carbon microtubes, and carbon nanofibers have recently been mechanically used. Not only the strength but also the field emission function and the hydrogen occlusion function have attracted industry attention, and are considered to be related to the oxidation-reduction reaction of the metal particles (A) having an oxide film. Further, these layered carbon materials (B2) and artificial diamond may be mixed and used.
- hexagonal, trigonal, or rhombohedral crystals with high stacking regularity such as hexagonal plate-like flat crystals, and carbon atoms form a straight chain.
- carbine-based carbon materials in which carbon atoms are alternately repeated or carbon atoms are connected by a double bond, intercalation of other atoms, ions, molecules, etc. can be easily inserted between layers. It is suitable as a catalyst for promoting reduction. That is, the layered carbon material (B2) exemplified here is characterized in that both an electron donor and an electron acceptor can be intercalated.
- the layered carbon material (B2) is subjected to high temperature treatment at about 2500 to 3200 ° C. in an inert gas atmosphere, and is inert together with graphitization catalysts such as boron, boron carbide, beryllium, aluminum, and silicon.
- High temperature treatment at about 2500 to 3200 ° C. in a gas atmosphere may be performed in advance.
- clay mineral crystals (B1) such as swellable silicate and swellable mica
- layered carbon material (B2) may be used alone or in combination of two or more. Good.
- smectite group clay, graphite, and vapor grown carbon fiber are preferably used in terms of dispersibility in the binder component (C) and easy availability.
- the average particle diameter is preferably 0.01 ⁇ m or more and 30 ⁇ m or less.
- the average particle diameter of the layered substance (B) exceeds 30 ⁇ m, conduction between the particles tends to occur particularly in the case of the layered carbon material (B2), and it may be difficult to obtain a stable ESD protector.
- the thickness is less than 0.01 ⁇ m, there are cases where production problems such as strong cohesive force and high chargeability may occur.
- the layered substance (B) is spherical or scaly, the average particle size is 50 mg of sample, added to 50 mL of distilled water, and further 2% Triton (GE Healthcare Biosciences, Inc.
- the average fiber diameter is preferably 0.01 ⁇ m or more and 0.3 ⁇ m or less
- the average fiber length is preferably 0.01 ⁇ m or more and 20 ⁇ m or less, and more preferably the average fiber diameter is 0.00. It is preferably 06 ⁇ m or more and 0.2 ⁇ m or less, and the average fiber length is 1 ⁇ m or more and 20 ⁇ m or less.
- the average fiber diameter and average fiber length of the fibrous layered substance (B) can be calculated by measuring with an electron microscope, for example, calculating the average with 20 to 100 measurements.
- the layered carbon material (B2) When the layered carbon material (B2) is used as the layered substance (B), it is necessary to avoid conduction between the carbon materials (B2) between the electrodes in order to ensure insulation during normal operation. Therefore, in addition to the dispersibility and the average particle diameter of the layered carbon material (B2), the volume occupation ratio is important. In addition, when a clay mineral crystal (B1) such as swellable silicate or swellable mica is used as the layered substance (B), the addition amount that partially destroys the oxide film of the metal particles is sufficiently effective.
- a clay mineral crystal (B1) such as swellable silicate or swellable mica
- the volume occupancy of the layered carbon material (B2) is 0.1% by volume or more and 10% by volume or less in the solid content of the discharge gap filling resin composition. It is desirable to be. If the volume is larger than 10% by volume, conduction between carbons is likely to occur, and the heat storage during ESD discharge increases, resulting in the destruction of the resin and the substrate, or the restoration of the insulation of the ESD protector due to the high temperature after ESD occurs. Tend to be late. On the other hand, if it is less than 0.1% by volume, the operability for ESD protection may become unstable.
- Binder component (C) In the binder component (C) of the present invention, a metal particle (A) having an oxide film and a layered substance (B) are dispersed therein, and a medium of the metal particle (A) having an oxide film and the layered substance (B). It is an insulator material that functions as Examples of the binder component (C) include organic polymers, inorganic polymers, and composite polymers thereof. Of these, polysiloxane compounds are preferred for the following reasons.
- the binder component (C) preferably has a functional group that reacts with a metal oxide.
- the sol-gel reaction product of alkoxysilane reacts with the metal oxide to fix the metal particles (A), and the polysilane obtained from the alkoxysilane having a specific functional group in the side chain.
- the siloxane compound stably immobilizes the metal particles (A) having an oxide film, and brings out the characteristics as an ESD protector more remarkably.
- a polysiloxane compound having a ladder structure has a molecular structure advantageous in terms of heat resistance, and is very preferable for protecting an ESD protector from heating by ESD discharge.
- carbocyclic or heterocyclic polymers having a ladder structure polyacene and polyperinaphthalene can be used, although they are difficult to produce.
- trialkoxysilane represented by the general formula (1) is preferable.
- R is an alkyl group having 1 to 8 carbon atoms such as methyl group, ethyl group, n-isopropyl group, phenyl group, ⁇ -chloropropyl group, vinyl group, 3,3,3-chloropropyl group, ⁇ - A glycidoxypropyl group or a 3,4-epoxycyclohexylethyl group, and R ′ is an alkyl group having 1 to 8 carbon atoms.
- a polysiloxane compound When these trialkoxysilanes are hydrolyzed and condensed in the presence of an acid, a polysiloxane compound is obtained. Furthermore, after further increasing the molecular weight by condensation by adding a base, the coexisting water and salt may be removed to obtain a polysiloxane compound. Further, dialkyl dialkoxysilane and tetraalkoxysilane may be used together and co-condensed.
- the polysiloxane compound preferably has a polystyrene-equivalent weight average molecular weight of 500 to 50,000 as measured by GPC, and if it is less than 500, cracks may occur in the discharge gap filling member. In particular, when only the polysiloxane compound is used as the binder component (C), it is preferable to use a polysiloxane compound having the above molecular weight range.
- a silicone elastomer or a silicone resin can be used, and a silicone oil may be further used in combination.
- Polysilsesquioxane can also be used.
- Silicone oils include straight silicone oils substituted with hydrocarbon groups (polydimethylsiloxane, polymethylphenylsiloxane, polymethylhydrogensiloxane, etc.) and non-reactive modified silicone oils, as well as amino groups, epoxy groups, alcohols, and mercapto groups. And reactive modified silicone oils modified with carboxyl groups, polyoxyalkylenes, higher alcohols, fatty acid copolymerized modified silicone oils and the like.
- silicone elastomer examples include a crosslinking reaction product of a base polymer such as polysiloxane having a substituted or unsubstituted monovalent hydrocarbon group as described above and a crosslinking agent.
- a base polymer such as polysiloxane having a substituted or unsubstituted monovalent hydrocarbon group as described above
- a crosslinking agent examples include room temperature condensation curable liquid silicone rubber, heat vulcanized silicone rubber, and liquid heat vulcanized silicone rubber.
- silicone resin examples include those obtained by copolymerizing a polyfunctional siloxane component in the structure to obtain a high-order cross-linked resin. Generally, a straight silicone resin substituted with a hydrocarbon group is used. Although used, an epoxy-modified or alkyd-modified resin may be used.
- silicone resin As the silicone resin. Specific examples include product name TSE3033, product name X14-B2334 or product name X14-B3445 manufactured by Momentive Performance Materials Japan GK. Are preferably used.
- the polysiloxane compound a siloxane-containing polyimide is also preferable.
- the resin can be cross-linked while fixing the metal particles (A) having an oxide film at the siloxane bond site. Since it has an imide structure, it exhibits excellent adhesion particularly when the base material is a polyimide material such as a printed wiring board.
- Specific examples of commercially available siloxane-containing polyimides include the product name poly (imide-siloxane) SPI manufactured by Nippon Steel Chemical Co., Ltd.
- an alkoxy group-containing silane-modified epoxy resin obtained by subjecting a polyfunctional epoxy resin having a secondary hydroxyl group to a dealcoholization condensation reaction of an alkoxysilane partial condensate in the absence of a solvent also corresponds to the polysiloxane compound of the present invention
- the electrostatic discharge protector can be obtained under slow curing conditions by using the binder component (C) obtained.
- alkoxy group-containing silane-modified resins include epoxy resins and polyamic acids, as well as phenol resins and urethane resins, and are commercially available from Arakawa Chemical Co., Ltd. as a composeran series.
- polysiloxane compounds and resins other than polysiloxane compounds.
- resins other than polysiloxane compounds include phenol resins, unsaturated polyester resins, epoxy resins, vinyl ester resins, alkyd resins, acrylic resins, and melamine resins. , Xylene resin, guanamine resin, diallyl phthalate resin, allyl ester resin, furan resin, imide resin, urethane resin, urea resin and the like.
- the addition amount of the polysiloxane compound is 5 parts by mass or more with respect to 100 parts by mass of the metal particles (A) having an oxide film. It is preferable to do. When the amount is less than 5% by mass, the metal particles (A) having a blended oxide film are not sufficiently fixed, and thus a short circuit may occur when a high voltage is repeatedly applied.
- the composition for filling a discharge gap according to the present invention comprises a metal catalyst (A) having an oxide film, a layered substance (B) and a binder component (C), as well as a curing catalyst and a curing accelerator as necessary.
- discharge gap filling composition for example, in addition to metal particles (A) having an oxide film, layered substance (B) and binder component (C), Other components such as a solvent, a filler, and a curing catalyst are dispersed and mixed using a disper, a kneader, a three-roll mill, a bead mill, a rotation / revolution stirrer, or the like.
- the electrostatic discharge protector of the present invention is used as a protection circuit for releasing an overcurrent to the ground in order to protect the device during electrostatic discharge.
- the electrostatic discharge protector of the present invention exhibits a high electrical resistance value at a low voltage during normal operation, and supplies current to the device without letting it escape to ground. On the other hand, when an electrostatic discharge occurs, it immediately exhibits a low electrical resistance value, allowing overcurrent to escape to ground and preventing overcurrent from being supplied to the device.
- the discharge gap is filled with the discharge gap filling member formed from the composition for filling the discharge gap containing the insulating binder component (C). No current is generated.
- the resistance value when a voltage of DC 10 V or less is applied between the electrodes can be made 10 10 ⁇ or more, and electrostatic discharge protection can be realized.
- the electrostatic discharge protector of the present invention is formed of at least two electrodes and one discharge gap filling member.
- the two electrodes are arranged at a certain distance.
- the space between the two electrodes becomes a discharge gap.
- the discharge gap filling member is filled in the discharge gap. That is, the two electrodes are connected via the discharge gap filling member.
- the discharge gap filling member is formed of the aforementioned discharge gap filling composition.
- the electrostatic discharge protector of the present invention can be produced by using the above-mentioned discharge gap filling composition to form a discharge gap filling member as follows.
- a discharge gap filling composition is prepared by the above-described method, and the composition is applied by a method such as potting or screen printing so as to be in contact with two electrodes on the substrate forming the discharge gap. In response to this, it is heated and solidified or cured to form a discharge gap filling member on a substrate such as a flexible wiring board.
- the preferable discharge gap distance of the electrostatic discharge protector is 500 ⁇ m or less, more preferably 5 ⁇ m or more and 300 ⁇ m or less, and further preferably 10 ⁇ m or more and 150 ⁇ m or less. If the distance of the discharge gap exceeds 500 ⁇ m, it may operate if the width of the electrode that forms the discharge gap is set wide, but it tends to cause non-uniform electrostatic discharge performance for each product, and electrostatic discharge protection It becomes difficult to reduce the size of the body. In addition, even when the thickness is less than 5 ⁇ m, non-uniformity of electrostatic discharge performance is easily caused for each product due to the dispersibility of the metal particles (A) having an oxide film and the layered substance (B), and short-circuiting easily occurs.
- the distance of the discharge gap means the shortest distance between the electrodes.
- the preferred electrode shape of the electrostatic discharge protector can be arbitrarily set according to the state of the circuit board, but when considering miniaturization, the cross-sectional shape orthogonal to the thickness method is a rectangular film shape, for example, the thickness Examples are those having a thickness of 5 to 200 ⁇ m.
- the preferred electrode width of the electrostatic discharge protector is 5 ⁇ m or more, and the wider the electrode width, the more suitable the energy during electrostatic discharge can be diffused.
- the width of the electrode of the electrostatic discharge protector is a pointed shape of less than 5 ⁇ m, the energy at the time of electrostatic discharge is concentrated, so that damage to peripheral members including the electrostatic discharge protector itself becomes large.
- the composition for filling a discharge gap of the present invention has insufficient adhesion to the substrate depending on the material of the substrate provided with the discharge gap, the electrostatic discharge is very high energy, and the oxide film. Since the volume occupancy of the metal particles (A) is high, if a protective layer of the resin composition is provided so as to cover the discharge gap filling member after forming the discharge gap filling member, higher voltage resistance is imparted. Thus, the repetition resistance is improved and the contamination of the electronic circuit board due to the drop-off of the metal particles (A) having an oxide film having a high volume occupation ratio can be prevented.
- Examples of the resin used as the protective layer include natural resins, modified resins, and oligomer synthetic resins.
- Rosin is a typical natural resin.
- the modified resin include rosin derivatives and rubber derivatives.
- the oligomer synthetic resin for example, an epoxy resin, an acrylic resin, a maleic acid derivative, a polyester resin, a melamine resin, a polyurethane resin, a polyimide resin, a polyamic acid resin, used together with a polysiloxane compound of an electrostatic discharge protector, Examples include polyimide / amide resins.
- the resin composition preferably contains a curable resin that can be cured by heat or ultraviolet rays in order to maintain the strength of the coating film.
- Thermosetting resins include carboxyl group-containing polyurethane resins, epoxy compounds, acid anhydride groups, carboxyl groups, alcoholic groups or combinations of amino compounds and epoxy compounds, and carboxyl groups, alcoholic groups or amino acids.
- a combination of a compound containing a group and a compound containing carbodiimide may be mentioned.
- Epoxy compounds include bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, phenol novolac type epoxy resins, cresol novolak type epoxy resins, Alicyclic epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, Examples thereof include epoxy compounds having two or more epoxy groups in one molecule, such as silicone-modified epoxy resins and ⁇ -caprolactone-modified epoxy resins.
- an epoxy compound in which atoms such as halogen such as chlorine and bromine and phosphorus are introduced into the structure may be used for imparting flame retardancy.
- bisphenol S type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, tetraglycidyl xylenoyl ethane resin, and the like may be used.
- an epoxy compound having two or more epoxy groups in one molecule it is preferable to use an epoxy compound having two or more epoxy groups in one molecule.
- an epoxy compound having only one epoxy group in one molecule may be used in combination.
- the compound containing a carboxyl group include acrylate compounds, and are not particularly limited.
- a compound containing an alcoholic group and a compound containing an amino group are not particularly limited.
- ultraviolet curable resin examples include acrylic copolymers, epoxy (meth) acrylate resins, and urethane (meth) acrylate resins, which are compounds containing two or more ethylenically unsaturated groups.
- the resin composition forming the protective layer may be a curing accelerator, a filler, a solvent, a foaming agent, an antifoaming agent, a leveling agent, a lubricant, a plasticizer, an antirust agent, a viscosity modifier, a colorant, etc. Can be contained.
- the thickness of the protective layer is not particularly limited, but it is preferable that the protective layer completely covers the discharge gap filling member formed by the discharge gap filling composition. If there is a defect in the protective layer, the possibility of generating cracks with high energy during electrostatic discharge increases.
- FIG. 1 shows a longitudinal sectional view of an electrostatic discharge protector 11 which is a specific example of the electrostatic discharge protector of the present invention.
- the electrostatic discharge protector 11 is formed of an electrode 12A, an electrode 12B, and a discharge gap filling member 13.
- the electrode 12A and the electrode 12B are arranged so that their axial directions coincide with each other and their tip surfaces face each other.
- a discharge gap 14 is formed between the opposing end surfaces of the electrode 12A and the electrode 12B.
- the discharge gap filling member 13 is filled in the discharge gap 14, and further, the tip portion of the electrode 12A facing the tip surface of the electrode 12B and the tip of the electrode 12B facing the tip surface of the electrode 12A. It is provided in contact with these tip parts so as to cover the part from above.
- the width of the discharge gap 14, that is, the distance between the tip surfaces of the electrodes 12A and 12B facing each other, is preferably 5 ⁇ m or more and 300 ⁇ m or less.
- FIG. 2 shows a longitudinal sectional view of an electrostatic discharge protector 21 which is another specific example of the electrostatic discharge protector of the present invention.
- the electrostatic discharge protector 21 is formed of an electrode 22A, an electrode 22B, and a discharge gap filling member 23.
- the electrode 22A and the electrode 22B are arranged in parallel with each other so that the tip portions thereof overlap in the vertical direction.
- a discharge gap 24 is formed at a portion where the electrodes 22A and 22B overlap in the vertical direction.
- the discharge gap filling member 23 has a rectangular cross section and fills the discharge gap 24.
- the width of the discharge gap 24, that is, the distance between the electrode 22A and the electrode 22B where the electrode 22A and the electrode 22B overlap in the vertical direction is preferably 5 ⁇ m or more and 300 ⁇ m or less.
- FIG. 3 shows a longitudinal sectional view of an electrostatic discharge protector 31 which is a specific example of the electrostatic discharge protector of the present invention.
- the electrostatic discharge protector 31 is an aspect in which a protective layer is provided on the electrostatic discharge protector 11 and is formed of an electrode 32A, an electrode 32B, a discharge gap filling member 33, and a protective layer 35.
- the electrode 32A and the electrode 32B are arranged so that their axial directions coincide with each other and their tip surfaces face each other.
- a discharge gap 34 is formed between the opposing end faces of the electrode 32A and the electrode 32B.
- the discharge gap filling member 33 is filled in the discharge gap 34, and further, the tip of the electrode 32A facing the tip surface of the electrode 32B and the tip of the electrode 32B facing the tip surface of the electrode 32A. It is provided in contact with these tip parts so as to cover the part from above.
- the protective layer 35 is provided so as to cover the surface other than the bottom surface of the discharge gap filling member 33.
- the width of the discharge gap 34 that is, the distance between the tip surfaces of the electrodes 32A and 32B facing each other, is preferably 5 ⁇ m or more and 300 ⁇ m or less.
- A The electric resistance value indicates 10 10 ⁇ or more.
- B The electric resistance value indicates less than 10 10 ⁇ .
- ⁇ Evaluation Method of Operating Voltage> Using a static electricity tester for semiconductors ESS-6008 (manufactured by NOISE LABORATORY), after measuring the peak current of any applied voltage, attach the obtained electrostatic discharge protector and give the same applied voltage, When a current of 70% or more of the Peak current in the absence of the electrostatic discharge protector was observed when measured, the applied voltage was evaluated as an “operating voltage”.
- the obtained electrostatic discharge protector was attached to an electrostatic tester ESS-6008 for semiconductor (manufactured by NOISE LABORATORY), applied with an applied voltage of 8 kV 10 times, and then applied with DC 10 V using an insulation resistance meter MEGOHMETER SM-8220. The resistance value was measured. This was evaluated as “high voltage resistance”.
- Binder Component (C)> Polysiloxane Compound A reflux condenser and a stirrer were provided.
- 100 parts of methyltrimethoxysilane, 60 parts of alumina sol 520 (an acidic aqueous solution manufactured by Nissan Chemical Industries, Ltd., solid content concentration 20%) and 15 parts of isopropyl alcohol are added and heated to 60 ° C. for 4 hours. After that, 5 parts of ⁇ -glycidoxypropyltrimethoxysilane was added and further reacted at 60 ° C. for 1 hour.
- Example 1 50.0 g of the polysiloxane compound obtained in the synthesis example, 25 g of a product name “08-0076” (aluminum powder average particle diameter 2.5 ⁇ m, manufactured by Toyo Aluminum Co., Ltd.) as a metal particle (A) having an oxide film, a layered substance As (B), 2.5 g of the trade name “Lucentite SPN” (smectite group scaly mean particle size 2 um manufactured by Co-op Chemical Co., Ltd.) is added, and the mixture is stirred for 15 minutes at 2000 rpm with a homogenizer to obtain the volume occupancy in the solid content.
- Example 2 60 g of product name “08-0076” (aluminum powder average particle diameter 2.5 ⁇ m, manufactured by Toyo Aluminum Co., Ltd.) as metal particles (A) having an oxide film on 25.0 g of the polysiloxane compound obtained in the synthesis example, layered material As (B), 4.0 g of a trade name “UF-G5” (artificial graphite fine powder, flaky mean particle size 3 ⁇ m, manufactured by Showa Denko KK) was added, and the mixture was stirred with a homogenizer at 2000 rpm for 15 minutes.
- product name “08-0076” aluminum powder average particle diameter 2.5 ⁇ m, manufactured by Toyo Aluminum Co., Ltd.
- U-G5 artificial graphite fine powder, flaky mean particle size 3 ⁇ m, manufactured by Showa Denko KK
- Example 3 70 g of product name “08-0076” (aluminum powder average particle diameter 2.5 ⁇ m, manufactured by Toyo Aluminum Co., Ltd.) as metal particles (A) having an oxide film on 15.0 g of the polysiloxane compound obtained in the synthesis example, layered material (B) as trade name “VGCF” (registered trademark) (vapor-grown carbon fiber, average fiber diameter 0.15 ⁇ m, average fiber length 10 ⁇ m, manufactured by Showa Denko KK) 0.1 g was added and homogenizer at 2000 rpm for 15 minutes. Stir.
- Example 4 To 25.0 g of the polysiloxane compound obtained in the synthesis example, 200 g of a product name “4SP-10” (nickel powder average particle diameter 10 ⁇ m, manufactured by Nikko Guatemala Co., Ltd.) as a metal particle (A) having an oxide film, layered material (B ) 4.0 g of trade name “UF-G5” (artificial graphite fine powder scaly mean particle size 3 ⁇ m, manufactured by Showa Denko KK) was added, and the mixture was stirred with a homogenizer at 2000 rpm for 15 minutes.
- 4SP-10 nickel powder average particle diameter 10 ⁇ m, manufactured by Nikko Guatemala Co., Ltd.
- U-G5 artificial graphite fine powder scaly mean particle size 3 ⁇ m, manufactured by Showa Denko KK
- Example 5 25.0 g of the polysiloxane compound obtained in the synthesis example, 35 g of a product name “08-0075” (aluminum powder average particle size 6.8 ⁇ m, manufactured by Toyo Aluminum Co., Ltd.) as a metal particle (A) having an oxide film, a layered substance As (B), 3.5 g of a trade name “UF-G5” (artificial graphite fine powder scaly mean particle size 3 ⁇ m, manufactured by Showa Denko KK) was added, and the mixture was stirred with a homogenizer at 2000 rpm for 15 minutes.
- a product name “08-0075” aluminum powder average particle size 6.8 ⁇ m, manufactured by Toyo Aluminum Co., Ltd.
- U-G5 artificial graphite fine powder scaly mean particle size 3 ⁇ m, manufactured by Showa Denko KK
- Example 6 70 g of product name “08-0076” (aluminum powder average particle diameter 2.5 ⁇ m, manufactured by Toyo Aluminum Co., Ltd.) as metal particles (A) having an oxide film on 25.0 g of the polysiloxane compound obtained in the synthesis example, layered material As (B), 0.1 g of a trade name “UF-G5” (artificial graphite fine powder, flaky mean particle size 3 ⁇ m, manufactured by Showa Denko KK) was added, and the mixture was stirred with a homogenizer at 2000 rpm for 15 minutes.
- U-G5 artificial graphite fine powder, flaky mean particle size 3 ⁇ m, manufactured by Showa Denko KK
- Example 7 The composition for filling the discharge gap was the same as in Example 2, but an electrostatic discharge protector was obtained without providing a protective layer, and the resistance, operating voltage, and high voltage resistance at normal times were evaluated. The results are shown in Table 1.
- Table 1 To 25.0 g of the polysiloxane compound obtained in the synthesis example, 100 g of a product name “08-0076” (aluminum powder average particle diameter 2.5 ⁇ m, manufactured by Toyo Aluminum Co., Ltd.) was added as metal particles (A) having an oxide film. The mixture was stirred for 15 minutes at 2000 rpm with a homogenizer.
- the electrostatic discharge protector formed using the discharge gap filling composition containing the metal particles (A) having an oxide film, the layered substance (B), and the binder component (C) is usually It can be seen that the resistance during operation, the operating voltage and the high voltage resistance are excellent.
- an electrostatic discharge protector having a free shape can be obtained, and a small size for ESD countermeasures. And cost reduction.
- Electrostatic discharge protector 12A ... Electrode 12B ... Electrode 13 ... Discharge gap filling member 14 ... Discharge gap 21 . Electrostatic discharge protector 22A ... Electrode 22B ... Electrode 23 ... .... Discharge gap filling member 24 ... Discharge gap 31 . Electrostatic discharge protector 32A ... Electrode 32B ... Electrode 33 ... Discharge gap filling member 34 ... Discharge gap 35 ... Protective layer
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Abstract
Description
[1]酸化皮膜を有する金属粒子(A)、層状物質(B)およびバインダー成分(C)を含むことを特徴とする、静電放電保護体の放電ギャップ充填用組成物。
[2]前記酸化皮膜を有する金属粒子(A)が、マンガン、ニオブ、ジルコニウム、ハフニウム、タンタル、モリブデン、バナジウム、ニッケル、コバルト、クロム、マグネシウム、チタンおよびアルミニウムからなる群から選ばれる1種類の金属から形成される単一粒子、または相互に異なる金属から形成される少なくとも2種類の前記単一粒子が混合してなる混合粒子である、[1]に記載の放電ギャップ充填用組成物。
[3]前記層状物質(B)が、粘土鉱物結晶(B1)及び層状カーボン材料(B2)からなる群から選ばれる少なくとも1つである、[1]または[2]に記載の放電ギャップ充填用組成物。
[4]前記層状物質(B)が、層状カーボン材料(B2)である、[3]に記載の放電ギャップ充填用組成物。
[5]前記層状カーボン材料(B2)が、カーボンナノチューブ、気相成長カーボンファイバー、カーボンフラーレン、黒鉛およびカルビン系炭素材料からなる群から選ばれる少なくとも1つである、[4]に記載の放電ギャップ充填用組成物。
[6]前記バインダー成分(C)が、ポリシロキサン化合物を含む、[1]~[5]のいずれかに記載の放電ギャップ充填用組成物。
[7] 放電ギャップと、該放電ギャップに充填された放電ギャップ充填部材とを有してなる静電放電保護体であって、前記放電ギャップ充填部材が[1]~[6]のいずれかに記載の放電ギャップ充填用組成物から形成され、前記放電ギャップの距離が5~300μmであることを特徴とする静電放電保護体。
[8][7]に記載の静電放電保護体を設けた電子回路基板。
[9]フレキシブル電子回路基板である[8]に記載の電子回路基板。
[10][8]または[9]に記載の電子回路基板を設けてなる電子機器。
<放電ギャップ充填用組成物>
酸化皮膜を有する金属粒子(A)
本発明に用いられる酸化皮膜を有する金属粒子(A)とは、金属からなる粒子の表面に、その金属の酸化物からなる皮膜が形成されてなる粒子である。酸化皮膜を有する金属粒子(A)は、該酸化皮膜が絶縁性であることによって、通常電圧では絶縁性であるが、静電放電時の高電圧負荷の際には酸化皮膜の破壊によって導電性となり、さらに高電圧解除によって再び酸化皮膜が形成され絶縁性が復活すると考えられる。
層状物質(B)
層状物質(B)とは、複数の層がファンデルワールス力で結合して形成されている物質であり、イオン交換などによって、その結晶内の特定の位置に本来その結晶の構成にあずからない原子や分子やイオンを入り込ませることができ、それによって結晶構造が変化しない化合物である。原子や分子やイオンが入り込む位置、すなわちホスト位置は、平面的な層構造をしている。そのような層状物質(B)の典型的なものには、粘土鉱物結晶(B1)やグラファイト(黒鉛)などの層状カーボン材料(B2)あるいは遷移金属のカルコゲン化物などがある。それらの化合物は、ゲストとして金属原子や無機分子、有機分子などを結晶内に取り込むことによってそれぞれ特異な性質を発現する。
バインダー成分(C)
本発明のバインダー成分(C)は、その中に酸化皮膜を有する金属粒子(A)および層状物質(B)を分散させ、酸化皮膜を有する金属粒子(A)と層状物質(B)との媒体として機能する絶縁体物質である。バインダー成分(C)としては、例えば有機系ポリマー、無機系ポリマーおよびそれらの複合ポリマーを挙げることができる。中でも、以下の理由から、ポリシロキサン化合物が好ましい。
その他の成分
本発明に係る放電ギャップ充填用組成物は、酸化皮膜を有した金属粒子(A)、層状物質(B)及びバインダー成分(C)の他、必要に応じて硬化触媒、硬化促進剤、充填剤、溶剤、発泡剤、消泡剤、レベリング剤、滑剤、可塑剤、抗錆剤、粘度調整剤、着色剤等を含有することができる。また、シリカ粒子などの絶縁性粒子を含有することができる。
放電ギャップ充填用組成物の製造方法
本発明の放電ギャップ充填用組成物を製造するには、例えば、酸化皮膜を有する金属粒子(A)、層状物質(B)及びバインダー成分(C)の他、その他の成分である溶剤、充填剤、硬化触媒などを、ディスパー、ニーダー、3本ロールミル、ビーズミル、自転公転型撹拌機などを用いて分散、混合する。混合の際は、相溶性を良好にするために十分な温度に加温してもよい。上記の分散、混合ののち、必要に応じてさらに硬化促進剤を加えて混合して、調製することができる。
<静電放電保護体>
本発明の静電放電保護体は、静電放電時にデバイスを保護するため、過電流をアースに逃すための保護回路として用いられる。本発明の静電放電保護体は、通常作動時の低い電圧のときには、高い電気抵抗値を示し、電流をアースに逃がさずデバイスに供給する。一方、静電放電が生じたときには、即座に低い電気抵抗値を示し、過電流をアースに逃し、過電流がデバイスに供給されるのを阻止する。静電放電の過渡現象が解消したときには、高い電気抵抗値に戻り、電流をデバイスに供給する。本発明の静電放電保護体は、放電ギャップに、絶縁性のバインダー成分(C)を含む前記放電ギャップ充填用組成物から形成された放電ギャップ充填部材が充填されているため、通常作動時に漏れ電流は発生しない。例えば、電極間にDC10V以下の電圧を印加した場合の抵抗値を1010Ω以上にすることが可能となり、静電放電保護を実現することができる。
<静電放電保護体の作製>
膜厚25μmのポリイミドフィルム上に一対の電極パターン(膜厚12μm、放電ギャップの距離50μm、電極幅500μm)を形成した配線基板に、後述する方法で得られた放電ギャップ充填用組成物を、針先が直径2mmで平坦なニードルを用いて塗布し、電極パターンを覆うように放電ギャップに充填した後、120℃恒温器内で60分保持して放電ギャップ充填部材を形成させた。その後、可溶性高透明性ポリイミド(丸善石油化学株式会社製、製品名PI-100)をγブチロラクトンに固形分濃度20%になるように溶解し、このポリイミド溶液を前述の放電ギャップ充填部材を完全に覆うように塗布し、120℃30分間乾燥して、静電放電保護体を得た。
<通常作動電圧時の絶縁性の評価方法>
静電放電保護体の両端の電極部について、絶縁抵抗計「MEGOHMMETER SM-8220」を用いて、DC10V印加における抵抗を「通常作動時の抵抗」として測定した。
B :電気抵抗値が1010Ω未満を示す
<作動電圧の評価方法>
半導体用静電気試験器ESS-6008(NOISE LABORATORY社製)を用いて、任意の印加電圧のPeak電流を測定した後、得られた静電放電保護体をとりつけて同じ印加電圧を与え、Peak電流を測定したとき、静電放電保護体がない場合のPeak電流の70%以上の電流が観測された場合、その印加電圧を「作動電圧」として評価した。
B :作動電圧750以上1000V未満
C :作動電圧1000以上2000V未満
D :作動電圧2000V以上、または1000Vの印加で短絡し絶縁性が回復しない
<耐高電圧性の評価方法>
得られた静電放電保護体を半導体用静電気試験器ESS-6008(NOISE LABORATORY社製)にとりつけ、8kVの印加電圧を10回与えた後、絶縁抵抗計MEGOHMMETER SM-8220を用いて、DC10V印加における抵抗値を測定した。これを、「耐高電圧性」として評価した。
B : 108Ω以上、1010Ω未満を示す
C : 108Ω未満を示す
<バインダー成分(C)の合成例>ポリシロキサン化合物
還流冷却器、攪拌機を備えた反応器に、メチルトリメトキシシラン100部、アルミナゾル520(日産化学工業株式会社製の酸性水溶液、固形分濃度20%)60部、イソプロピルアルコール15部を加え、60℃に加熱して4時間反応させたのち、γ―グリシドキシプロピルトリメトキシシラン5部を加えて、さらに60℃で1時間反応させた。これにイソプロピルアルコールを80部加え、ポリシロキサン化合物溶液を得た。固形分濃度は25%であった。遠心分離機を用いて、該ポリシロキサン化合物溶液のアルミナ分を除去し、上澄み液を孔径0.45μmのフィルターでろ過した。このろ液から得られたポリシロキサン化合物をGPC法で測定したところ、ポリスチレン換算重量平均分子量は9,300だった。
合成例で得られたポリシロキサン化合物50.0gに、酸化皮膜を有する金属粒子(A)として製品名「08-0076」(アルミニウム粉末 平均粒子径2.5μm 東洋アルミ株式会社製)25g、層状物質(B)として商品名「ルーセンタイトSPN」(スメクタイト族 鱗片状 平均粒子径2um コープケミカル社製)2.5gを加えて、ホモジナイザーにて2000rpmで15分間攪拌し、固形分中の体積占有率として、酸化皮膜を有する金属粒子(A)が43体積%、層状物質(B)が4体積%である放電ギャップ充填用組成物を得た。この放電ギャップ用組成物を用いて上記方法により静電放電保護体を得て、通常時の抵抗、作動電圧、耐高電圧性を評価した。結果を表1に示す。
合成例で得られたポリシロキサン化合物25.0gに、酸化皮膜を有する金属粒子(A)として製品名「08-0076」(アルミニウム粉末 平均粒子径2.5μm 東洋アルミ株式会社製)60g、層状物質(B)として商品名「UF-G5」(人造黒鉛微粉末 鱗片状 平均粒子径3μm 昭和電工株式会社製)4.0gを加えて、ホモジナイザーにて2000rpmで15分間攪拌した。さらに、ポリシロキサン化合物として「X14-B3445 A剤」および「X14-B3445 B剤」(共にモメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製シリコーン樹脂)を各々11g加え、ホモジナイザーにて2000rpmで10分間攪拌し、固形分中の体積占有率として、酸化皮膜を有する金属粒子(A)が44体積%、層状物質(B)が5体積%である放電ギャップ充填用組成物を得た。この放電ギャップ用樹脂組成物を用いて上記方法により静電放電保護体を得て、通常時の抵抗、作動電圧、耐高電圧性を評価した。結果を表1に示す。
合成例で得られたポリシロキサン化合物15.0gに、酸化皮膜を有する金属粒子(A)として製品名「08-0076」(アルミニウム粉末 平均粒子径2.5μm 東洋アルミ株式会社製)70g、層状物質(B)として商品名「VGCF」(登録商標)(気相成長カーボンファイバー 平均繊維直径0.15μm、平均繊維長さ10μm 昭和電工株式会社製)0.1gを加えてホモジナイザーにて2000rpmで15分間攪拌した。さらに、ポリシロキサン化合物として「X14-B3445 A剤」および「X14-B3445 B剤」(共にモメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製シリコーン樹脂)を各々15g加え、ホモジナイザーにて2000rpmで10分間攪拌し、固形分中の体積占有率として、酸化皮膜を有する金属粒子(A)が46体積%、層状物質(B)が0.1体積%である放電ギャップ充填用組成物を得た。この放電ギャップ用組成物を用いて上記方法により静電放電保護体を得て、通常時の抵抗、作動電圧、耐高電圧性を評価した。結果を表1に示す。
[実施例4]
合成例で得られたポリシロキサン化合物25.0gに、酸化皮膜を有する金属粒子(A)として製品名「4SP-10」(ニッケル粉末 平均粒子径10μm 日興リカ株式会社製)200g、層状物質(B)として商品名「UF-G5」(人造黒鉛微粉末 鱗片状 平均粒子径3μm 昭和電工株式会社製)4.0gを加えて、ホモジナイザーにて2000rpmで15分間攪拌した。さらに、ポリシロキサン化合物として「X14-B3445 A剤」および「X14-B3445 B剤」(共にモメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製シリコーン樹脂)を各々15gを加え、ホモジナイザーにて2000rpmで10分間攪拌し、固形分中の体積占有率として、酸化皮膜を有する金属粒子(A)が39体積%、層状物質(B)が3体積%である放電ギャップ充填用組成物を得た。この放電ギャップ用組成物を用いて上記方法により静電放電保護体を得て、通常時の抵抗、作動電圧、耐高電圧性を評価した。結果を表1に示す。
[実施例5]
合成例で得られたポリシロキサン化合物25.0gに、酸化皮膜を有する金属粒子(A)として製品名「08-0075」(アルミニウム粉末 平均粒子径6.8μm 東洋アルミ株式会社製)35g、層状物質(B)として商品名「UF-G5」(人造黒鉛微粉末 鱗片状 平均粒子径3μm 昭和電工株式会社製)3.5gを加えてホモジナイザーにて2000rpmで15分間攪拌した。さらに、ポリシロキサン化合物として「X14-B3445 A剤」および「X14-B3445 B剤」(共にモメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製シリコーン樹脂)を各々15gを加え、ホモジナイザーにて2000rpmで10分間攪拌し、固形分中の体積占有率として、酸化皮膜を有する金属粒子(A)が27体積%、層状物質(B)が3体積%である放電ギャップ充填用組成物を得た。この放電ギャップ用組成物を用いて上記方法により静電放電保護体を得て、通常時の抵抗、作動電圧、耐高電圧性を評価した。結果を表1に示す。
[実施例6]
合成例で得られたポリシロキサン化合物25.0gに、酸化皮膜を有する金属粒子(A)として製品名「08-0076」(アルミニウム粉末 平均粒子径2.5μm 東洋アルミ株式会社製)70g、層状物質(B)として商品名「UF-G5」(人造黒鉛微粉末 鱗片状 平均粒子径3μm 昭和電工株式会社製)0.1gを加えてホモジナイザーにて2000rpmで15分間攪拌した。さらに、ポリシロキサン化合物として「X14-B3445 A剤」および「X14-B3445 B剤」(共にモメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製シリコーン樹脂)を各々15gを加え、ホモジナイザーにて2000rpmで10分間攪拌し、固形分中の体積占有率として、酸化皮膜を有する金属粒子(A)が44体積%、層状物質(B)が0.1体積%である放電ギャップ充填用組成物を得た。この放電ギャップ用組成物を用いて上記方法により静電放電保護体を得て、通常時の抵抗、作動電圧、耐高電圧性を評価した。結果を表1に示す。
[実施例7]
放電ギャップ充填用組成物は実施例2と同じであるが、保護層を設けないで静電放電保護体を得て、通常時の抵抗、作動電圧、耐高電圧性を評価した。結果を表1に示す。
[比較例1]
合成例で得られたポリシロキサン化合物25.0gに、酸化皮膜を有する金属粒子(A)として製品名「08-0076」(アルミニウム粉末 平均粒子径2.5μm 東洋アルミ株式会社製)100gを加えてホモジナイザーにて2000rpmで15分間攪拌した。さらに、ポリシロキサン化合物として「X14-B3445 A剤」および「X14-B3445 B剤」(共にモメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製シリコーン樹脂)を各々15gを加え、ホモジナイザーにて2000rpmで10分間攪拌し、固形分中の体積占有率として、酸化皮膜を有する金属粒子(A)が53体積%、層状物質(B)が無添加である放電ギャップ充填用比較組成物を得た。この放電ギャップ用比較組成物を用いて上記方法により比較用静電放電保護体を得て、通常時の抵抗、作動電圧、耐高電圧性を評価した。結果を表1に示す。
[比較例2]
合成例で得られたポリシロキサン化合物25.0gに、層状物質(B)として商品名「UF-G5」(人造黒鉛微粉末 鱗片状 平均粒子径3μm 昭和電工株式会社製)50gを加えて、ホモジナイザーにて2000rpmで15分間攪拌した。さらに、ポリシロキサン化合物として「X14-B3445 A剤」および「X14-B3445 B剤」(共にモメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製シリコーン樹脂)を各々15gを加え、ホモジナイザーにて2000rpmで10分間攪拌し、固形分中の体積占有率として、酸化皮膜を有する金属粒子(A)が無添加で、層状物質(B)が41体積%である放電ギャップ充填用比較組成物を得た。この放電ギャップ用比較組成物を用いて上記方法により比較用静電放電保護体を得て、通常時の抵抗、作動電圧、耐高電圧性を評価した。結果を表1に示す。
[比較例3]
合成例で得られたポリシロキサン化合物25.0gに、層状物質(B)として商品名「UF-G5」(人造黒鉛微粉末 鱗片状 平均粒子径3μm 昭和電工株式会社製)10gを加えてホモジナイザーにて2000rpmで15分間攪拌した。さらに、ポリシロキサン化合物として「X14-B3445 A剤」および「X14-B3445 B剤」(共にモメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製シリコーン樹脂)を各々15gを加え、ホモジナイザーにて2000rpmで10分間攪拌し、固形分中の体積占有率として、酸化皮膜を有する金属粒子(A)が無添加で、層状物質(B)が12体積%である放電ギャップ充填用比較組成物を得た。この放電ギャップ用比較組成物を用いて上記方法により比較用静電放電保護体を得て、通常時の抵抗、作動電圧、耐高電圧性を評価した。結果を表1に示す。
[比較例4]
合成例で得られたポリシロキサン化合物25.0gに、酸化皮膜を有さない金属粒子としてタングステン粉末(球状 平均粒子径3μm 日本タングステン株式会社製)200g、層状物質(B)として商品名「UF-G5」(人造黒鉛微粉末 鱗片状 平均粒子径3μm 昭和電工株式会社製)3.5gを加えてホモジナイザーにて2000rpmで15分間攪拌した。さらに、ポリシロキサン化合物として「X14-B3445 A剤」および「X14-B3445 B剤」(共にモメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製シリコーン樹脂)を各々15g加え、ホモジナイザーにて2000rpmで10分間攪拌し、固形分中の体積占有率として、酸化皮膜を有さない金属粒子が27体積%、層状物質(B)が3体積%である放電ギャップ充填用組成物を得た。この放電ギャップ用組成物を用いて上記方法により静電放電保護体を得て、通常時の抵抗、作動電圧、耐高電圧性を評価した。結果を表1に示す。
合成例で得られたポリシロキサン化合物25.0gに、酸化皮膜を有する金属粒子(A)として製品名「08-0076」(アルミニウム粉末 平均粒子径2.5μm 東洋アルミ株式会社製)60g、層状ではない物質として、タングステン粉末(球状 平均粒子径3μm 日本タングステン株式会社製)26gを加えて、ホモジナイザーにて2000rpmで15分間攪拌した。さらに、ポリシロキサン化合物として「X14-B3445 A剤」および「X14-B3445 B剤」(共にモメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製シリコーン樹脂)を各々11g加え、ホモジナイザーにて2000rpmで10分間攪拌し、固形分中の体積占有率として、酸化皮膜を有する金属粒子(A)が44体積%、層状ではない物質が5体積%である放電ギャップ充填用組成物を得た。この放電ギャップ用樹脂組成物を用いて上記方法により静電放電保護体を得て、通常時の抵抗、作動電圧、耐高電圧性を評価した。結果を表1に示す。
12A・・電極
12B・・電極
13・・・放電ギャップ充填部材
14・・・放電ギャップ
21・・・静電放電保護体
22A・・電極
22B・・電極
23・・・放電ギャップ充填部材
24・・・放電ギャップ
31・・・静電放電保護体
32A・・電極
32B・・電極
33・・・放電ギャップ充填部材
34・・・放電ギャップ
35・・・保護層
Claims (10)
- 酸化皮膜を有する金属粒子(A)、層状物質(B)およびバインダー成分(C)を含むことを特徴とする、静電放電保護体の放電ギャップ充填用組成物。
- 前記酸化皮膜を有する金属粒子(A)の金属が、マンガン、ニオブ、ジルコニウム、ハフニウム、タンタル、モリブデン、バナジウム、ニッケル、コバルト、クロム、マグネシウム、チタンおよびアルミニウムからなる群から選ばれる少なくとも1つ1種類の金属から形成される単一粒子、または相互に異なる金属から形成される少なくとも2種類の前記単一粒子が混合してなる混合粒子である、請求項1に記載の放電ギャップ充填用組成物。
- 前記層状物質(B)が、粘土鉱物結晶(B1)及び層状カーボン材料(B2)からなる群から選ばれる少なくとも1つである、請求項1または2に記載の放電ギャップ充填用組成物。
- 前記層状物質(B)が、層状カーボン材料(B2)である、請求項3に記載の放電ギャップ充填用組成物。
- 前記層状カーボン材料(B2)が、カーボンナノチューブ、気相成長カーボンファイバー、カーボンフラーレン、黒鉛およびカルビン系炭素材料からなる群から選ばれる少なくとも1つである、請求項4に記載の放電ギャップ充填用組成物。
- 前記バインダー成分(C)が、ポリシロキサン化合物を含む、請求項1~5のいずれかに記載の放電ギャップ充填用組成物。
- 放電ギャップと、該放電ギャップに充填された放電ギャップ充填部材とを有してなる静電放電保護体であって、前記放電ギャップ充填部材が請求項1~6のいずれかに記載の放電ギャップ充填用組成物から形成され、前記放電ギャップの距離が5~300μmであることを特徴とする静電放電保護体。
- 請求項7に記載の静電放電保護体を設けた電子回路基板。
- フレキシブル電子回路基板である請求項8に記載の電子回路基板。
- 請求項8または請求項9に記載の電子回路基板を設けてなる電子機器。
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JP5784688B2 (ja) * | 2012-12-10 | 2015-09-24 | サムソン エレクトロ−メカニックス カンパニーリミテッド. | 静電気放電構造及び静電気放電構造の製造方法 |
CN108475552B (zh) * | 2015-12-29 | 2022-07-12 | 3M创新有限公司 | 用于高频电磁干扰(emi)应用的复合物 |
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- 2010-03-01 CN CN201080010184XA patent/CN102341978A/zh active Pending
- 2010-03-01 WO PCT/JP2010/053209 patent/WO2010101103A1/ja active Application Filing
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CN102802333A (zh) * | 2011-05-25 | 2012-11-28 | Tdk株式会社 | 静电保护部件 |
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JPWO2016203976A1 (ja) * | 2015-06-15 | 2017-12-21 | 株式会社村田製作所 | Esd保護装置 |
CN109890118A (zh) * | 2019-04-09 | 2019-06-14 | 深圳市阿赛姆科技有限公司 | 一种具有静电保护功能的静电抑制器 |
KR20220115408A (ko) * | 2021-02-10 | 2022-08-17 | 주식회사 현대케피코 | 전자 제어 장치 및 그 제조 방법 |
KR102486422B1 (ko) | 2021-02-10 | 2023-01-06 | 주식회사 현대케피코 | 전자 제어 장치 및 그 제조 방법 |
Also Published As
Publication number | Publication date |
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CN102341978A (zh) | 2012-02-01 |
US20110317326A1 (en) | 2011-12-29 |
JPWO2010101103A1 (ja) | 2012-09-10 |
KR20110132431A (ko) | 2011-12-07 |
TW201100495A (en) | 2011-01-01 |
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