CN1840589A - Paint composition with excellent electromagnetic absorption and electro-conductivity and metal plate coated with the same - Google Patents
Paint composition with excellent electromagnetic absorption and electro-conductivity and metal plate coated with the same Download PDFInfo
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- CN1840589A CN1840589A CNA2006100683649A CN200610068364A CN1840589A CN 1840589 A CN1840589 A CN 1840589A CN A2006100683649 A CNA2006100683649 A CN A2006100683649A CN 200610068364 A CN200610068364 A CN 200610068364A CN 1840589 A CN1840589 A CN 1840589A
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- paint composite
- ferrite dust
- soft magnetism
- metal plate
- electromagnetic wave
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
- A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
- A47L13/20—Mops
- A47L13/24—Frames for mops; Mop heads
- A47L13/254—Plate frames
- A47L13/256—Plate frames for mops made of cloth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B25—HAND TOOLS; PORTABLE POWER-DRIVEN TOOLS; MANIPULATORS
- B25G—HANDLES FOR HAND IMPLEMENTS
- B25G3/00—Attaching handles to the implements
- B25G3/38—Hinged, pivoted, swivelling, or folding joints
Abstract
The invention relates to a dope compound with soft magnetic iron powder at 20-60mass%, whose surface is covered by conductive metal. The invention has electromagnetic wave adsorption and better conductivity, with high heat emission.
Description
Technical field
The present invention relates to the paint composite of a kind of electromagnetic wave absorbability and excellent electric conductivity, and the coated metal plate that covers by this paint composite, this coated metal plate especially can be preferably as the raw material use that constitutes electronics.
Background technology
In recent years, in the high performance of electronics and the process of miniaturization, requirement has the hertzian wave that takes place from electronics not to the characteristic (electromagnetic wave shielding performance) of external leaks, how to realize that this characteristic becomes important problem for electronic device design person.If the hertzian wave that leaks from electronics becomes many, then cause being disposed at the mishandle of the precision instrument etc. of this electronics periphery easily.From this viewpoint, in Japan, will forbid the electromagnetic rank of radiating from electronics, stipulate that by the VCCI standard assigned frequency zone is the leakage electromagnetic wave of 30MHz～1GHz in this standard as autonomous required standard.
On the other hand, in electronics, also require good thermal diffusivity, in order to make this thermal diffusivity good, the structure that pore is set at the housing of electronics is very effective.But in this structure, because pore becomes electromagnetic leak position, so if from the such viewpoint of electromagnetic wave shielding performance then be not preferred.That is, in the housing of electronics, if the structure that thermal diffusivity is good from electromagnetic wave shielding performance, becomes the major cause that it weakens on the contrary, if from structural level, thermal diffusivity and electromagnetic wave shielding performance are opposite characteristic.
Owing to have above-mentioned restriction, so proposed a kind ofly to make the electromagnetic wave shielding performance good technical from other angles from the structural level of such electronics.
For example be conceived to, hertzian wave not only leaks from pore and the wiring hole of being located at housing, also leaks from the junction surface between the steel plate, and the steel plate that uses the surface conductivity excellence is studied.That is, if the junction surface between the steel plate has potential difference to produce, then hertzian wave takes place, so the hertzian wave that takes place is from the clearance leakage at junction surface.Therefore if adopt the steel plate of surface conductivity excellence, then owing to the conducting of steel plate junction surface, potential difference can not take place, so hertzian wave does not take place, can prevent the electromagnetic leakage from the junction surface.Specifically, raw material as casting of electronic device, use for example raw material of the surface conductivity excellence of electrogalvanizing steel plate etc., but this raw material, can only reduce from the hertzian wave of the clearance leakage between the steel plate, for example, because can't prevent electromagnetic leakage, so can not obtain good electromagnetic wave shielding performance from pore and wiring hole.
As other technology, also proposed to have the thin slice or the band of electromaganic wave absorbing property, be mounted on hertzian wave radioactive source and gap, the technology that leakage electromagnetic wave is reduced.
For example, open in the 2000-200990 communique the spy, proposed a kind of electromagnetic wave absorb, it is to make that to contain Cr be the soft magnetic powder that the Fe base alloy about 5～35 quality % is formed, and is scattered in rubber and the resin.Open in the 2002-111276 communique the spy in addition, disclose a kind of electromagnetic wave absorb, it is in the insulativity thin slice that is made of thermosetting resin, and soft magnetic metal powder is disperseed.But, open in 2000-200990 communique and the 2002-111276 communique above-mentioned spy, in order to obtain sufficient electromagnetic wave absorbability, need make the soft magnetic powder that contains a large amount of (more than the 10 volume %) in the resin, and thickness also becomes (for example, more than the 1mm) greatly, the processing difficulty that becomes, therefore, exist in the shortcoming that is difficult to be suitable for outside the extremely limited position such as electromagnetic wave emission source and electronics gap.
Also have, in the housing of electronics, except that above-mentioned characteristic,, also require the surface conductivity excellence in order to ensure ground connection.But, open in 2000-200990 communique and the 2002-111276 communique above-mentioned spy, the surface conductivity of electromagnetic wave absorb does not receive publicity.
Also have, open the spy and propose a kind of technology in the 2004-27064 communique, the paint composite of ferrite dust and carbon black allotment is coated on the surface of metal sheet, and thermal diffusivity and electromagnetic wave absorbability are had concurrently.Carbon black powders is known as conductive particle generally, and still, allotment carbon black and the rank of the surface conductivity that shows for static prevents degree, is not that the potential difference that can prevent the junction surface between the steel plate takes place is guaranteed the rank of ground connection.
Summary of the invention
The present invention is in view of such situation, and its purpose is to propose a kind of except that electromagnetic wave absorbability, the paint composite that electroconductibility is also excellent.Other purpose is, also proposes the also excellent paint composite of a kind of thermal diffusivity.Other purpose is in addition, proposes a kind of coated metal plate that is covered by this paint composite.
Present inventors, for being provided, the paint composite that has both electromagnetic wave absorbability and electroconductibility studies repeatedly, it found that, if allotment soft magnetism ferrite dust in paint composite, then can guarantee electromagnetic wave absorbability, and, if cover the surface of this soft intermediate stage ferrite dust with conductive metal, then also can improve the electroconductibility of paint composite, thereby finish the present invention.
That is, so-called paint composite of the present invention has following main points: except that resin, contain the soft magnetism ferrite dust of 20～60 quality %, and described soft magnetism ferrite dust, its surface is covered by conductive metal.Described paint composite, also preferred package contains the thermal diffusivity additive.
In the present invention, also comprise the one side at least of metal sheet, by the coated metal plate of above-mentioned coating constituent covering.In this coated metal plate, preferred described paint composite is that 3～50 μ m cover with thickness.In view of the above, processibility improves.Coated metal plate of the present invention preferably is used in the electromagnetic wave shielding of electronics.
In addition, coated metal plate of the present invention is suitable for use in the housing for electronic equipment that electromagnetic wave emission source is built in enclosed space.At this moment, all or part of coverage rate by described paint composite of the inner face of its housing is constituted.
According to the present invention,, can provide the paint composite of a kind of magnetic wave absorptivity and excellent electric conductivity by being allocated in paint composite by the soft magnetism ferrite that conductive metal covers.Also have,, then can provide a kind of except that electromagnetic wave absorbability and electroconductibility, the paint composite that thermal diffusivity is also excellent if in described paint composite, allocate the thermal diffusivity additive.In the present invention, also comprise the coated metal plate that this paint composite is covered in the surface of metal sheet.
Description of drawings
Fig. 1 is the figure that the principle of the electromagnetic wave absorbability that utilizes coated metal plate of the present invention is described.
Fig. 2 is the figure of evaluation method that is used to illustrate the absorption of electromagnetic wave performance of coated metal plate.
Fig. 3 is the figure of the hertzian wave state that volume reflection tails off under the resonant frequency of housing of explanation input.
The explanatory view of the state when Fig. 4 is medelling ground expression mensuration electromagnetic wave absorbability.
Embodiment
Paint composite of the present invention has following feature, promptly contain " the soft magnetism ferrite dust that covers by conducting metal (below, be called metal and cover ferrite dust) ".
That is, the powder of soft magnetism ferrite (being also referred to as soft ferrite), known have an absorption of electromagnetic wave effect, and absorption of electromagnetic wave is considered to be undertaken by electromagnetic energy is become heat.Therefore as can be known, the main absorption frequency of soft magnetic powder zone is near the hertzian wave 1～1000MHz.On the other hand, because the soft magnetism ferrite dust is non-conductive, so allocate with paint composite, this paint composite can not show electroconductibility yet.Therefore, the paint composite that will contain soft ferrite dust is coated on the surperficial resulting coated metal plate of metal sheet, and the raw material use as casting of electronic device can not prevent the generation of the potential difference of the bonding part between steel plate, can not guarantee ground connection.Therefore in the present invention, cover ferrite dust by the metal that conductive metal covers by the surface of allocating the soft magnetism ferrite dust, thus the electroconductibility of performance paint composite.Also have, though the soft magnetism ferrite dust is covered by conductive metal, hertzian wave is delivered to the soft magnetism ferrite dust through the conductive metal layer and is absorbed, so can not hinder the absorption of electromagnetic wave effect that utilizes the soft magnetism ferrite dust to produce.
And,, consider the direct conductive metal powder of allotment in paint composite in order to improve the electroconductibility of paint composite.But, if in paint composite, allocate conductive metal, then because account for paint composite additive to contain quantitative change many, so can produce the such problem of processibility variation of the coating metal that is coated with this paint composite.
As above-mentioned soft magnetism ferrite dust, can list: the Ni-Zn of soft magnetism is that ferrite dust and Mn-Zn are that ferrite dust, Cu-Zn are that ferrite dust, Mn-Mg-Zn are that ferrite dust, Ni-Fe are ferrite dust etc., can they are independent, perhaps mix more than 2 kinds as and use.
Above-mentioned soft magnetism ferrite dust makes it to contain 20～60 quality % in paint composite.Because, then be difficult to bring into play electromaganic wave absorbing property, so make it to contain 20 quality % at least if content is lower than 20 quality %.Preferred content is more than the 25 quality %, and more preferably content is more than 30 quality %.The content of soft magnetism ferrite dust is many more, form the paint composite of electromaganic wave absorbing property excellence more, still, if content surpasses 60 quality %, then be coated with the bendability variation of the coated metal plate that this paint composite is housed, compactness of filming and erosion resistance deterioration.Preferred content is below the 50 quality %, and more preferably content is below the 45 quality %.
The soft magnetism ferrite dust, preferred median size is below the 20 μ m, wishes to remove as far as possible the powder (for example, particle diameter surpasses the powder of 20 μ m) of big particle diameter.The formation of filming to metal sheet surface becomes easily thus, and, can also suppress the reduction of the appearance characteristics of coated metal plate and processibility, erosion resistance.Preferred median size is below the 15 μ m.The lower limit of median size is not specially limited, but is generally about 1 μ m.
The median size of above-mentioned soft magnetism ferrite dust is meant, adopts general size-grade distribution meter, measures the size-grade distribution of the soft magnetism ferrite dust after the classification, from the granularity (D50) of the aggregate-value 50% of the small particle size side that calculates based on its measurement result.This size-grade distribution can be scattered in the pure water by making the soft magnetism ferrite dust, utilizes the intensity map of diffraction that laser radiation produces and scattering and measures.Have as size-grade distribution meter illustration, for example Leeds ﹠amp; Northrup corporate system " Microtrac9220FRA (device name) " and " Microtrac HRA (device name) " etc.
Also have, the above-mentioned soft magnetism ferrite dust that satisfies preferred median size also can use the product of market sale.For example, can exemplify out: as Ni-Zn is the soft magnetism ferrite dust, and " BSN-125 (trade(brand)name) " (median size 13 μ m) of Toda Kogyo Corp.'s system are arranged; As Mn-Zn is the soft magnetism ferrite dust, and " KNS-415 (trade(brand)name) " (median size 9.9 μ m) of Toda Kogyo Corp.'s system etc. are arranged.
As above-mentioned conductive metal, can list: for example, the metal monomer of Au, Ag, Cu, Zn, Fe, Ni etc. and their alloy, the perhaps metallic compound of FeP etc.Wherein the alloy of Ni or Ni preferably, particularly preferably be Ni.
The overlay capacity of above-mentioned conductive metal is not specially limited, but, cover in each particle of ferrite dust (the soft magnetism ferrite dust that is covered by conductive metal) at metal, cover ferrite dust with respect to metal, the adhesion amount of conductive metal is preferably 8～40 quality %.Overlay capacity is lower than 8 quality %, can not improve electroconductibility fully, and the soft magnetism ferrite dust can not be covered by conductive metal.The preferred covering is for more than the 10 quality %, and more preferably overlay capacity is more than the 13 quality %.But, if overlay capacity is too much, then the thickness of conductive metal layer becomes excessive, and hertzian wave can't penetrate the conductive metal layer, is reflected on the surface of conductive metal layer.Therefore electromagnetic wave absorbability reduces.Also have, if make the thickness of conductive metal layer become big, then in the process of the surface coverage conductive metal of soft magnetism ferrite dust, aggegation between the soft magnetism ferrite dust makes electroconductibility reduce on the contrary.In addition, become big if metal covers the particle diameter of ferrite dust, the appearance characteristics and the processibility that then are coated with the coated metal plate of paint composite reduce.
Above-mentioned overlay capacity, " ICPS-1000 (the installing name) " that for example can adopt society of Shimadzu Seisakusho Ltd. system measured by the ICP method.
The median size that metal covers ferrite dust is not specially limited, but is preferably below the 20 μ m, wishes to remove as far as possible the powder (for example, particle diameter surpasses the powder of 20 μ m) of big particle diameter.Formation to the paint composite of metal sheet surface becomes easily like this, and the reduction of can the be suppressed at surface coverage appearance characteristics of coated metal plate of paint composite and processibility, erosion resistance.More preferably median size is below the 15 μ m.
The median size that metal covers ferrite dust is meant, adopts general size-grade distribution instrumentation to decide the size-grade distribution of the metal covering ferrite dust after the classification, from the granularity (D50) of the aggregate-value 50% of the small particle size side that calculates based on its measurement result.This size-grade distribution can be measured equally with above-mentioned soft magnetism ferrite dust.
Metal covers ferrite dust, if the surface of above-mentioned soft magnetism ferrite dust is covered by conductive metal, then covering method is not particularly limited, and for example, can make the plain body powder of soft magnetic iron be scattered in plating bath and carry out electroless plating.
The formation of plating bath, because also will be according to the kind of the conductive metal on the surface that is covered in the soft magnetism ferrite dust, so can not stipulate uniformly, when Ni is covered as the conductive metal layer, for example can adopt the plating bath of sulfur acid nickel 200～250g/L, sodium hypophosphite 200～250g/L, Trisodium Citrate 15～25g/L.
Can establish plating temperature is about 65～75 ℃, and the plating time is 30～100 minutes, if control plating temperature and plating time, then can adjust the thickness of the conductive metal layer on the surface that is covered in the soft magnetism ferrite dust.
For the surface at the soft magnetism ferrite dust is provided with more uniform conductive metal level, the preferred pneumatic blending of plating bath.
Kind as the resin (base resin) that constitutes the above-mentioned coating constituent, do not do special qualification from the viewpoint of electromagnetic wave absorbability, can for example suitably use: acrylic resin, Resins, epoxy, urethane resin, polyolefin resin, vibrin, fluorine resin, silicone resin, the mixing that reaches them or the resin of sex change etc.But, covered the coated metal plate of above-mentioned coating constituent in the metallic surface, when its shell as electronics is used, if consider the characteristic requirement of bendability and the compactness of filming, erosion resistance etc., then preferred polyester resin or sex change vibrin (for example, add Resins, epoxy and make it the resin of sex change) at unsaturated polyester resin.
In paint composite, can add linking agent.As this linking agent, can list for example trimeric cyanamide based compound and isocyanic ester based compound, preferably its a kind or 2 kinds of scopes at 0.5～20 quality % are added.
The above-mentioned coating constituent also preferably contains the thermal diffusivity additive.As the thermal diffusivity additive, can list: carbon black and as lemel of oxide compound, sulfide, carbide and the black of Fe, the Co of black additive, Ni, Cu, Mn, Mo, Ag, Sn etc. etc.; TiO as the thermal diffusivity additive beyond the black additive
2, zirconium white, trichroite, aluminium titanates, beta spodumene, silicon carbide, aluminium nitride, hexagonal boron, ferric oxide, barium sulfate, silicon oxide, aluminum oxide etc. pottery etc., these can be separately or more than 2 kinds and use.
When adopting carbon black as the thermal diffusivity additive, be contained in the content of the carbon black of paint composite, the relation of the thickness in the time of need covering this paint composite according to it and in the metallic surface, and do suitably control, add more than the 1 quality % but be recommended as.Basically the content of carbon black is many more, and heat dissipation characteristics improves, thus more preferably more than the 3 quality %, more preferably more than the 5 quality %.Also have, its upper limit is not particularly limited fastening with the pass of heat dissipation characteristics, but if content surpasses 15 quality %, then except the coating variation, wear-resisting wiping etc. also reduce.Therefore, when considering coating etc., its upper limit is preferably below the 15 quality %, more preferably below the 13 quality %.
Be contained in the content of the carbon black of paint composite, can measure by following method.
At first, being tested adding solvent heating in the body (analytic sample), decompose the organism of being tested in the body.The solvent species that uses, according to the basis is that the kind of resin also is not quite similar, corresponding to each dissolving resin degree, can use appropriate solvent, for example, when adopting, can in the container (eggplant type flask etc.) that adds sodium hydrate methanol solution, put into and be tested body as the polyester based resin of base resin and urethane resin, with 70 ℃ thermostatic baths (water bath) this container of heating, decompose the organism of being tested in the body.Secondly, with glass filter (aperture 0.2 μ m) filtering solution that the carbon in the residue that obtains is quantitative by combustion method, calculate the carbon black concentration in filming.
The median size of above-mentioned carbon black is preferably 5～100nm.Median size is lower than 5nm, and except being difficult to obtain the heat dissipation characteristics, the stability of coating is not good, the application appearance poor.More preferably median size is more than the 10nm, and further preferred median size is more than the 15nm.On the other hand, if median size surpasses 100nm, then not only heat dissipation characteristics reduces, and the outward appearance after the application becomes inhomogeneous.More preferably median size is below the 90nm, and further preferred median size is below the 80nm.Also have,,, recommend the best median size of carbon black to be roughly 20～40nm if synthetically consider to be coated with after membrane stability, the application outward appearance homogeneity etc. except heat dissipation characteristics.
In the present invention,, also can use the product of market sale, for example, recommend to use Mitsubishi Chemical's system " mitsubishi carbon black " (median size 13～75 μ m) etc. as the carbon black that satisfies above-mentioned median size.
During thermal diffusivity additive beyond using carbon black, in order to ensure the heat dissipation characteristics of expectation, content adds up to more than the 10 quality %, is preferably more than the 20 quality %, more preferably more than the 30 quality %.
Among the thermal diffusivity additive beyond the above-mentioned carbon black, TiO preferably
2Deng pottery, TiO further preferably
2For example using TiO
2The time, contain TiO if make
2Be about filming of 30～70 quality %, approximately form 5～50 μ m, then can access general about 0.8 infrared rays integration emissivity.In above-mentioned filming, if also add the black additive of carbon black etc., then infrared rays integration emissivity further becomes big.
As the thermal diffusivity additive that satisfies such median size, also can use the product of market sale, for example as TiO
2Recommend to use the TiO of TAYCA Co., Ltd. system
2(median size 0.2～0.5 μ m) etc.
So-called above-mentioned " infrared rays integration emissivity ", connotation is the easy degree (absorbing easy degree) that infrared rays (heat energy) is emitted.Therefore, above-mentioned infrared rays integration emissivity is high more, and the heat energy quantitative change that (absorption) emitted in then expression is big.For example, when 100% radiation put on the heat energy of object (being coated-body in the present invention), this infrared rays integration emissivity became 1.
Also have, in the present invention, the infrared rays integration emissivity when being heated to 100 ℃ is preferably more than 0.7.This is to consider the coated metal plate that the above-mentioned coating constituent is covered in metal sheet surface, be applicable to that the electrical equipment purposes is (also variant according to member etc., but common atmosphere temperature is substantially at 50～70 ℃, the highest about 100 ℃), should make it consistent, and Heating temperature is decided to be 100 ℃ with the temperature of this realistic scale.
The measuring method of infrared rays integration emissivity is as follows.
Device: NEC (company) system " JIR-5500 type fourier-transform infrared spectrophotometer " and radioassay unit " IRR-200 "
Total range of wavelength: 4.5～15.4 μ m
Measure temperature: the Heating temperature of test portion is set at 100 ℃
Cumulative calculation number of times: 200 times
Resolving power: 16cm
-1
Adopt said apparatus, measure the branch light emission intensity (measured value) of the test portion in the Infrared wavelength territory (4.5～15.4 μ m).Also have, the measured value of above-mentioned test portion, for the intensity of radioactivity of background and device function as addition/additional numerical value and determined, for the purpose of revising these, adopt emissivity to measure program " NEC (company) system emissivity is measured program ", calculate infrared rays integration emissivity.Method of calculation detailed as follows.
[numerical expression 1]
In the formula, be respectively following connotation:
ε (λ): the beam split emissivity of the test portion of wavelength X
E (T): temperature T (℃) the infrared rays integration emissivity of test portion
M (λ, T): wavelength X, temperature T (℃) the branch light emission intensity (measured value) of test portion
A (λ): device function
KFB (λ): the branch light emission intensity of the fixed background of wavelength X (the not background that changes according to test portion)
KTB (λ, TTB): wavelength X, temperature T TB (℃) the branch light emission intensity of capture black matrix
KB (λ, T): wavelength X, temperature T (℃) the luminous intensity of radioactivity (according to the calculated value of the theoretical formula of Planck) of black matrix
λ 1, λ 2: the scope of the wavelength of integration.
At this, above-mentioned A (λ: device function), and above-mentioned KFB (λ: the branch light emission intensity of fixed background), according to the measured value of the branch light emission intensity of 2 blackbody furnaces (80 ℃, 160 ℃), and this temperature province in the branch light emission intensity (according to the calculated value of the theoretical formula of Planck) of black matrix, calculate by following formula.
[numerical expression 2]
In the formula, be respectively following connotation:
M160 ℃ (λ, 160 ℃): the branch light emission intensity (measured value) of 160 ℃ blackbody furnace of wavelength X
M80 ℃ (λ, 80 ℃): the branch light emission intensity (measured value) of 80 ℃ blackbody furnace of wavelength X
K160 ℃ (λ, 160 ℃): the branch light emission intensity of 160 ℃ blackbody furnace of wavelength X (according to the calculated value of the theoretical formula of Planck)
K80 ℃ (λ, 80 ℃): the branch light emission intensity of 80 ℃ blackbody furnace of wavelength X (according to the calculated value of the theoretical formula of Planck).
Also having, when the calculating of infrared rays integration emissivity E (T=100 ℃), consider KTB (λ, TTB), is in order to measure, and around test portion, configuration is through the capture black matrix of water-cooled.By the setting of above-mentioned capture black matrix, (meaning is the background radiation that changes according to test portion can to control the change background radiation.In order to be reflected on the test portion surface from the radiation around the test portion, the measured value of the branch light emission intensity of test portion is expressed as the numerical value of this background radiation addition) the branch light emission intensity, make its step-down.Above-mentioned capture black matrix uses the approximate black matrix of emissivity 0.96, described KTB[(λ, TTB): wavelength X, temperature T TB (℃) the branch light emission intensity of capture black matrix] by following such calculating.
KTB(λ、TTB)＝0.96×KB(λ、TTB)
In the formula, KB (λ, TTB) connotation is, wavelength X, temperature T TB (℃) the branch light emission intensity of black matrix.
Next, coated metal plate of the present invention is described.
Coated metal plate of the present invention, the one side at least of metal sheet is covered by the above-mentioned coating constituent, also can be that the two sides is covered by the above-mentioned coating constituent.
Preferred 3～50 μ m of the thickness of above-mentioned coating constituent.If above-mentioned thickness is lower than 3 μ m, perhaps surpass 50 μ m, then the compactness of the bendability of coated metal plate, paint composite epithelium and erosion resistance tendency that reduction is arranged.More preferably thickness also according to variations such as the kind of the soft magnetism ferrite dust that uses and content, but is roughly more than the 4 μ m, below the 40 μ m.Further preferred thickness is more than the 5 μ m, below the 30 μ m.
Kind at metal sheet used in the present invention also is not particularly limited, and for example the steel plate class of the various coated steel sheets of cold-rolled steel sheet, hot-rolled steel sheet, electrogalvanizing steel plate (EG), hot-dip galvanized steel sheet (GI), alloyed hot-dip galvanized steel plate (GA), 5 quality %Al-Zn coated steel sheets, 55 quality %Al-Zn coated steel sheets, Al etc., stainless-steel sheet etc. and known metal sheet etc. all can be suitable for.
In addition, above-mentioned metal sheet, the purposes such as compactness lifting that promote, film for erosion resistance, also can implement chromate treating and phosphatizing, but then, consider environmental pollution etc., the metal sheet that also can use non-chromate to handle, any form all is contained in the scope of the present invention.
Below, the metal sheet that non-chromate is handled is described.
The method (based process) of above-mentioned " non-chromate processing " is not particularly limited, and can carry out normally used known based process.Specifically, recommend separately, or and the based process of, silica system phosphate-based with carrying out, titanium system, zirconium system etc.
Also have, handle because a highest wisdom is carried out non-chromate, then erosion resistance reduces, so the purpose that improves for erosion resistance also can be used rust-preventive agent in filming or in the based process.
As above-mentioned rust-preventive agent, can list: silica based compound, phosphate-based compound, phosphite based compound, poly-phosphate based compound, sulphur series organic compound, benzotriazole (benzotriazol), tannic acid, molybdate series compound, tungstate based compound, vanadium sub-group compound, silane coupling agent etc., these can separately or and be used.(for example be preferably the silica based compound especially, calcium ion-exchanged silica etc.), with phosphate-based compound, phosphite based compound, poly-phosphate based compound (for example, also using aluminium triphosphate etc.), and recommendation makes " silica based compound ": " phosphate-based compound, phosphite based compound or polyphosphate based compound ", counting 0.5～9.5 with quality ratio: also use in the scope of 9.5～0.5 (more preferably 1: 9～9: 1).If be controlled at this scope, then can make coated metal plate have the erosion resistance of expectation and two of processibility concurrently.
By the use of above-mentioned rust-preventive agent, can guarantee the erosion resistance of non-chromate processing metal sheet, but its side effect is that processibility also reduces owing to the interpolation of rust-preventive agent.Therefore as the formation composition of filming, special recommendation is used in combination following: with the vibrin of epoxy sex change polyester based resin and/or phenol (phenol) inductor importing skeleton, and linking agent (preferred isocyanate (isocyanate) is that resin and/or trimeric cyanamide (melamine) are resin, and more preferably both also use).
Wherein, epoxy sex change polyester based resin and phenols body import the polyester based resin (for example, bis-phenol (bisphenol) A being imported the polyester based resin of skeleton) of skeleton, and than polyester based resin, the erosion resistance and the compactness of filming want excellent.
On the other hand, the isocyanate-based linking agent has the effect that improves processibility, thus, also can guarantee excellent processibility even added rust-preventive agent.
Also have, trimeric cyanamide is a linking agent because have excellent erosion resistance, so with aforesaid rust-preventive agent and usefulness, obtain very good anti-corrosion in view of the above.
These isocyanate-based linking agents and trimeric cyanamide are that linking agent also can use separately, but if both and usefulness, the processibility and the erosion resistance that then can make non-chromate handle metal sheet further improve.Specifically, recommend with respect to isocyanate-based resin 100 mass units, containing trimeric cyanamide with the ratio of 5～80 mass units is resin.At trimeric cyanamide is resin when being lower than 5 mass units, can't obtain the erosion resistance of expectation.On the other hand,, the additive effect of isocyanate-based resin is brought into play well if trimeric cyanamide is that resin surpasses 80 mass units, thus the processibility castering action that can't obtain expecting.More preferably, it is with respect to isocyanate-based resin 100 mass units, more than 10 mass units, below 40 mass units, more preferably 15 mass units above, below 30 mass units.
The coated metal plate that is covered by the above-mentioned coating constituent can be preferably uses with coated metal plate as the electromagnetic wave shielding of electronics.At this moment, make the face that covers by the above-mentioned coating constituent within the metal sheet, constitute in the face of the hertzian wave radioactive source.By making the face that containing metal covers the paint composite of ferrite dust that covered, with the hertzian wave radioactive source in opposite directions, thereby the hertzian wave that the hertzian wave radioactive source takes place contacts and is absorbed with metal covering ferrite dust, or is attenuated at least.
For example, the situation of the electronics of dress hertzian wave radioactive source can make the housing of this electronics be made of above-mentioned coated metal plate in the space of sealing, and a whole or subdivision of the inner face of this housing is made of the coverage rate of described paint composite.That is, the face that the above-mentioned coating constituent covered can be constituted towards the hertzian wave radioactive source.This is because electromagnetic wave shielding performance becomes problem in the inboard of electronics.
What can distinguish in a word is, the hertzian wave that takes place from the hertzian wave radioactive source and is compared the ratio one side height of reflection at the ratio that metal sheet absorbed of the housing that constitutes electronics.Consider to think from this viewpoint, if in the coated metal plate of the housing that constitutes electronics, at least inside (constitute the inner side of housing, be called " the inside " in this manual), cover the paint composite of electromagnetic wave absorbability and excellent electric conductivity, at the esoteric hertzian wave meeting of shell multipath reflection, in this process, absorption of electromagnetic wave or decay finally can reduce the hertzian wave that leaks to hull outside from pore etc.
Fig. 1 represents, is used to illustrate the diagrammatic illustration figure based on the principle of the electromagnetic wave absorbability of coated metal plate of the present invention.When hertzian wave radioactive source 2 was housed in housing 1, the hertzian wave of hertzian wave radioactive source 2 emissions from then on shown in the arrow A 1～A5 among the figure, after the inner face multiple reflection of housing 1, leaked into outside (the figure, 4 expression body clearances) from pore 3 grades.At this moment, if the decay that 1 time reflection is produced (former material steel plate than) is when being made as 2dB (decibel), the multipath reflection by 5 times for example is just bring into play the electromagnetic shielding effect that 10dB is arranged.This electromagnetic wave attenuation effect means, if with the independent use of former material steel plate relatively, then strength of electric field becomes 1/3.
Also have, so-called electronics in the present invention means except that electronics, also comprises as the equipment that the hertzian wave generation is arranged of electrical equipment and opticinstrument etc. and near the electronic apparatus optical device of the use electromagnetic equipment of generation.
As these electronics, can list: for example, the information storage goods of CD and LD, DVD, CD-ROM, CD-RAM, PDP, LCD etc.; The PC correlated product of communicating by letter with the electric appliance and electronic of bus location, vehicle-mounted AV etc.; The AV equipment of projector and TV, video recorder, game machine etc.; The manifolder of duplicating machine and printer etc.; The power supply box shell of air-conditioner outdoor unit etc., controlling box shell, vending machine, refrigerator chamber etc.
Next, the method for making coated metal plate of the present invention is described.Coated metal plate of the present invention can be used known coating process, and the above-mentioned coating constituent is coated the surface of metal sheet, makes it dry and makes.
Coating process is not specially limited, but can elect as inferior method: for example, make cleaning surfacesization, as required at the long-bar metal belt surface of implementing coating pre-treatment (for example phosphatizing, chromate treating etc.), water the method for washing applying coatings such as (curtainflow coater) by rolling method (roll coater), gunite (spray), curtain formula, make it pass through hot-air drying stove exsiccant method etc.Comprehensively examine or check by the homogeneity of film thickness and processing cost, coating efficient etc. rolling method preferably in practicality.
Also have,, also might as well implement phosphatizing or chromate treating as the coating pre-treatment in order to improve compactness and the erosion resistance with resin coating.But, in the chromate treating material, the viewpoint of the chromium wash-out from resin-coated metal sheet uses, the Cr adhesion amount during preferably with chromate treating is suppressed at 35mg/m
2Below.This is because if in this scope, then can suppress to separate out from the chromium dissolving of basic chromium processing layer.Also have, in existing chromate treating material, the water-fast adaptation of set as required last one deck application, because the dissolving of 6 valency chromium is separated out, the tendency that reduction is arranged under wet environment, the water-fast adaptation of last one deck tunicle but, is suppressed, so also can not worsen because in above-mentioned metal sheet, dissolve to separate out.Perhaps, if, implement aforesaid chromium based process freely, then can obtain the coated-body of non-chromate type by rolling method, gunite, impregnating process etc.
[embodiment]
Illustrate in greater detail the present invention by the following examples, but following embodiment does not limit character of the present invention, can suitably change enforcement yet in the scope of following in preceding aim described later, its any all be contained in technical scope of the present invention.
To contain paint composite, be covered in the one side of metal sheet,, investigate its electromagnetic wave absorbability, electroconductibility and processibility this coated metal plate by the soft magnetism ferrite dust of conductive metal covering.
As the soft magnetism ferrite dust, adopting Ni-Zn is ferrite dust (Toda Kogyo Corp.'s system, " BSN-125 (trade(brand)name) ", median size 13 μ m), with this soft magnetism ferrite dust, impregnated in hydrochloric acid and be adjusted in the tart palladium chloride aqueous solution, the surface of soft magnetism ferrite dust is applied the processing of palladium catalyst.
After the processing, be that ferrite dust is scattered in the plating bath with Ni-Zn, carry out electroless plating, obtaining by the Ni-Zn that covers as the Ni of conductive metal is ferrite dust (below, be called Ni and cover ferrite dust).
Contain single nickel salt 225g/L, sodium hypophosphite 225g/L, Trisodium Citrate 20g/L in the plating bath, it is adjusted to pH4～6.Make plating bath carry out pneumatic blending.If plating temperature is 70 ℃, the plating time is 30～120 minutes.Plating temperature and time are represented in following table 1.
Cover ferrite dust for the Ni that obtains, adopt the ICPS-1000 of society of Shimadzu Seisakusho Ltd. system, measure Ni adhesion amount (plating adhesion amount) by the ICP method.Measurement result is represented in following table 1.Also have, the plating adhesion amount is the value when establishing Ni covering ferrite dust as 100 quality %.
The Ni that obtains covers the median size of ferrite dust and measures with following order.Make Ni cover ferrite and be scattered in the pure water, adopt Leeds ﹠amp; The Microtrac 9220FRA irradiating laser of Northrup society system is measured the median size that Ni covers ferrite dust according to the intensity map of the scattering that produces.Measurement result is represented in following table 1.
Then, (thickness of slab is 0.8mm, and the Zn adhesion amount is 20g/m to adopt electrogalvanizing steel plate as former material metal sheet
2), in its one side, cover by filming that the paint composite (base resin is an epoxy sex change vibrin, and linking agent is an isocyanic ester) that contains above-mentioned Ni covering ferrite dust is formed, and obtain coated metal plate.The thickness that is formed at the paint composite of metal sheet surface is represented in following table 1.Also have, in the content that the content and the Ni of the shared soft magnetism ferrite dust of paint composite cover ferrite dust, expression in following table 1 respectively.
Also have, in No.7, use soft magnetism ferrite dust (no Ni covers) like this, cover the surrogate of ferrite dust as above-mentioned Ni.
And, in No.8,, except that Ni covers ferrite dust, also be coated with in one side on the surface of above-mentioned electrogalvanizing steel plate, by containing filming that paint composite as the carbon black of thermal diffusivity additive constitutes, thereby obtain coated metal plate.The content of carbon black is represented in following table 1.
In No.8, measure infrared rays integration emissivity with above-mentioned method, estimate thermal diffusivity.Judgement criteria, ◎ be infrared rays integration emissivity more than 0.7, the expression thermal diffusivity is good, * be lower than 0.7 for infrared rays integration emissivity, represent that thermal diffusivity is bad.The result represents in following table 2.
Then, electromagnetic wave absorbability, electroconductibility and the processibility of resulting each coated metal plate have been estimated.Follow the evaluation of orientations of following (1)～(3), estimate each characteristic respectively.Evaluation result is represented in following table 2.
(1) electromagnetic wave absorbability evaluation
Fig. 2 is the figure of method that is used to illustrate the absorption of electromagnetic wave performance of coated metal plate.In the housing 1 of square shape, high frequency tours antenna 5 is set, make it to combine with magnetic field and constitute.This high frequency tours antenna 5 is connected in an end of concentric cable 6 by junctor (not shown), and the other end of concentric cable 6 is connected to network analyser 7.In network analyser 7, on one side sweep rate hertzian wave takes place on one side,, be transfused to (high frequency incoming wave: arrow B) in the housing 1 via concentric cable 6, high frequency tours antenna 5.In the resonant frequency of housing 1 because the input hertzian wave put aside, so observe the characteristic (with reference to Fig. 3) that volume reflection tails off.Therefore, this high frequency reflection wave is transfused to (high frequency reflection wave: arrow C) in network analyser 7 as observed value.
At this moment, if the Q value of trying to achieve with following formula (1) of metering housing 1, the size of accumulative energy in housing 1 as can be known.Also have, the Q value of trying to achieve according to following formula (1), it is the condition that satisfies according to admittance (admittance) track, (for example calculate by difference on the frequency Δ f that tries to achieve and resonant frequency fr, middle island is with the light work, " gloomy NORTEL gas engineering book series 3 microwave engineering basis and principles " gloomy north is published Co., Ltd. and is taken place the 159th～163 page).
Q value=fr/ Δ f ... (1)
The Q value of trying to achieve from above-mentioned formula (1) becomes more little, means that the accumulative energy reduces in housing 1.Therefore, the Q value becomes more little, also reduces from the electromagnetic field level of housing 1 to external reflection.During actual mensuration, use 106 * 156 * 200 (mm) size housing 1 and carry out.
The form of this moment is by mode chart 4 expressions, and but, this figure is that the electromagnetic field that is shown in the resonance mode of the minimum like this frequency of Ez=0, TE011 distributes, and among the figure, expression respectively: E is a high frequency magnetic field, and F is a high-frequency electric field.The above-mentioned Ez meaning is the strength of electric field of z direction, and TE011 represents the attitude that the electromagnetic field of resonance mode distributes.This TE meaning is in the propelling of z direction, laterally to have electric field at it as ripple.Back asyllabia " 011 " expression for x, y, z direction, has 1 in the intensity distribution of y and z direction electric field, does not change (for example, with reference to 141～144 pages in above-mentioned special routine document) in the intensity distribution of x direction electric field.
Also have, electromagnetic field shown in Figure 4 distributes, by following formulate.
Hz＝H011·cos(ky·y)·sin(kz·z)
Hy＝(-kz·ky/kc2)·H011·sin(ky·y)·cos(kz·z)
Ex＝(-jωμky/kc2)·H011·sin(ky·y)·sin(kz·z)
At this, ky=π/b, kz=π/c, kc=ky.The y of the rectangular parallelepiped (housing 1) of b, c difference presentation graphs 4, the length of z direction, j is an imaginary number, and ω is each frequency, and μ is the permeability of air.
The resonant frequency of the resonance mode of this moment is about 1220MHz.When estimating, be made as Q0 value (measurement result: 1740) as benchmark with 6 of rectangular parallelepiped during for stainless-steel sheet, then, 1 (face of 106mm * 156mm) with the bottom surface, with 3 of the totals of lateral 2 (2 faces of 106mm * 200mm), change to the test sample of test, with the Q value measured as the Q1 value, by calculating the ratio (rate of fall-off) of Q1/Q0, the absorption of electromagnetic wave effect [electromagnetic wave absorbability] of validation test sample.
In the present invention, the ratio (rate of fall-off) of the Q1/Q0 that calculates according to aforesaid method is that conduct " example of the present invention " below 0.970 is estimated.
(2) evaluation of electroconductibility
Use Mitsubishi Chemical's society's system " lorestaEP " as the electroconductibility determinator, and probe use Mitsubishi Chemical society system 4 probe (the ESP probe: MCP-TPO8P), the resistivity of working sample.In the present invention, according to following judgement criteria, be estimating of ◎ or zero as " example of the present invention " with the result.
[judgement criteria]
◎: be lower than 0.1m Ω
Zero: more than the 0.1m Ω, but be lower than 1 Ω
△: more than 1 Ω, but be lower than 106 Ω
*: more than 106 Ω
(3) evaluation of processibility
Carry out the resistance to bending test (180 ° are adjacent to pliability test) according to JIS K 5400, the crackle (crack) of the paint composite epithelium after the visual observations test and the extent of exfoliation of the paint composite epithelium after the winding (taping) are with following standard evaluation.In the present invention, according to the result of following judgement criteria be ◎ or ● conduct " example of the present invention " and estimate.
[judgement criteria]
◎: not unusual
●: the crack is arranged a little, peel off
Zero: the crack is arranged, peel off
*: the crack, peel off comprehensive generation
[table 1]
| No. | The soft magnetism ferrite dust | Cover | Metal covers ferrite dust | The thermal diffusivity additive | Average film thickness (μ m) | ||||||
| Kind | Median size (μ m) | Content (quality %) | The kind of plating | Plating temperature (℃) | The plating time (branch) | Plating adhesion amount (quality %) | Median size (μ m) | Content (quality %) | Content (quality %) | ||
| 1 | Ni-Zn system | 13 | 36 | Ni | 70 | 30 | 9.8 | 13.2 | 40 | - | 10 |
| 2 | Ni-Zn system | 13 | 34 | Ni | 70 | 45 | 15.5 | 13.5 | 40 | - | 10 |
| 3 | Ni-Zn system | 13 | 25 | Ni | 70 | 45 | 15.5 | 13.5 | 30 | - | 10 |
| 4 | Ni-Zn system | 13 | 42 | Ni | 70 | 45 | 15.5 | 13.6 | 50 | - | 10 |
| 5 | Ni-Zn system | 13 | 51 | Ni | 70 | 45 | 15.5 | 13.5 | 60 | - | 10 |
| 6 | Ni-Zn system | 13 | 22 | Ni | 70 | 120 | 44.8 | 16.8 | 40 | - | 10 |
| 7 | Ni-Zn system | 13 | 40 | - | - | - | 0 | 13 | 40 | - | 10 |
| 8 | Ni-Zn system | 13 | 25 | Ni | 70 | 45 | 15.5 | 13.5 | 30 | 10 | 10 |
[table 2]
| No. | Electromagnetic wave absorbability | Electroconductibility | Processibility | Thermal diffusivity | ||
| Q1 | Q0 | Rate of fall-off (Q1/Q0) | ||||
| 1 | 1610 | 1750 | 0.92 | ○ | ● | - |
| 2 | 1630 | 1750 | 0.93 | ◎ | ● | - |
| 3 | 1660 | 1750 | 0.95 | ○ | ◎ | - |
| 4 | 1700 | 1750 | 0.97 | ○ | ◎ | - |
| 5 | 1580 | 1750 | 0.9 | ◎ | ● | - |
| 6 | 1540 | 1750 | 0.88 | ◎ | ○ | - |
| 7 | 1680 | 1750 | 0.96 | △ | × | - |
| 8 | 1600 | 1750 | 0.91 | × | ● | - |
| 9 | 1665 | 1750 | 0.95 | ○ | ○ | ◎ |
Can carry out following investigation from table 1 and table 2.No.1～5, the 8th are covered in the paint composite that satisfies the prerequisite of the present invention regulation the example of metal sheet surface.Coated metal plate, electromagnetic wave absorbability and surface conductivity excellence.And these examples are because the coating thickness suitably controlled, so be the also excellent coated metal plate of processibility.In addition, in No.8, because by the surface of the paint composite covered metal plate that contains the thermal diffusivity additive, so be the also excellent coated metal plate of thermal diffusivity.
On the other hand, No.7 is the example of the prerequisite of discontented unabridged version invention regulation, because, will contain not the paint composite of the soft magnetism ferrite dust that is covered by conductive metal, be covered in the surface of metal sheet, so surface conductivity is poor.
Also have, No.6 is a reference example, because the plating adhesion amount is many, thus aggegation between the soft magnetism ferrite dust in plating process, the processibility deterioration.
Claims (11)
1, a kind of paint composite is characterized in that, contains:
Resin; Soft magnetism ferrite dust, this soft magnetism ferrite dust account for 20～60 quality % of described paint composite, and its surface is covered by conductive metal.
2, according to the paint composite of claim 1 record, it is characterized in that described soft magnetism ferrite dust is that Ni-Zn is a ferrite dust.
3, according to the paint composite of claim 1 record, it is characterized in that the median size of described soft magnetism ferrite dust is below the 20 μ m.
4, according to the paint composite of claim 1 record, it is characterized in that described conductive metal is Ni.
5, the paint composite of putting down in writing according to claim 1, it is characterized in that, the adhesion amount of described conductive metal on described soft magnetism ferrite dust, with the particle of the described soft magnetism ferrite dust that covered by described conductive metal each as benchmark, be 8～40 quality %.
According to the paint composite of claim 1 record, it is characterized in that 6, the median size of the described soft magnetism ferrite dust that is covered by described conductive metal is below the 20 μ m.
7, according to the paint composite of claim 1 record, it is characterized in that described resin is vibrin or sex change vibrin.
8, according to the paint composite of claim 1 record, it is characterized in that described paint composite also contains the thermal diffusivity additive.
9, the paint composite of putting down in writing according to Claim 8 is characterized in that described thermal diffusivity additive is a carbon black.
10, a kind of coated metal plate is characterized in that, the one side at least of described coated metal plate, and the paint composite of being put down in writing by claim 1 covers.
According to the coated metal plate of claim 10 record, it is characterized in that 11, described paint composite is that 3～50 μ m cover with thickness.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005101672 | 2005-03-31 | ||
| JP2005101672A JP2006286729A (en) | 2005-03-31 | 2005-03-31 | Paint composition excellent in electromagnetic wave absorbency and conductivity, and coated metal plate coated therewith |
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| CN1840589A true CN1840589A (en) | 2006-10-04 |
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| CNA2006100683649A Pending CN1840589A (en) | 2005-03-31 | 2006-03-30 | Paint composition with excellent electromagnetic absorption and electro-conductivity and metal plate coated with the same |
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| Country | Link |
|---|---|
| JP (1) | JP2006286729A (en) |
| KR (1) | KR100741616B1 (en) |
| CN (1) | CN1840589A (en) |
| TW (1) | TW200641077A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103555102A (en) * | 2013-10-14 | 2014-02-05 | 苏州富莱希涂料有限公司 | Reflective thermal-insulation exterior wall coating |
| WO2018000798A1 (en) * | 2016-06-28 | 2018-01-04 | 王强 | Heat-curable magnetic epoxy resin powder and method for encapsulating an inductor using same |
| CN111033646A (en) * | 2017-08-03 | 2020-04-17 | 保德科技股份有限公司 | Composite particle, powder, resin composition, and molded body |
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| KR100745692B1 (en) * | 2006-02-28 | 2007-08-03 | 한국전자통신연구원 | Composition for complex sheet with thermal dissipation, emi shielding and absorption, and products manufactured therefrom |
| CN101945566A (en) * | 2007-03-23 | 2011-01-12 | 株式会社神户制钢所 | Conductive resin coating metal panel |
| JP4932586B2 (en) * | 2007-05-07 | 2012-05-16 | 新日本製鐵株式会社 | Surface-treated metal plate and casing for electronic equipment |
| KR101237001B1 (en) * | 2010-08-20 | 2013-02-25 | 동현전자 주식회사 | Composition for complex sheet, complex sheet comprising the same, and preparation method of the complex sheet |
| CN104217834B (en) * | 2013-06-03 | 2018-01-23 | 株式会社田村制作所 | Soft magnetic powder composition, core, reactor |
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| WO2019146661A1 (en) * | 2018-01-23 | 2019-08-01 | パウダーテック株式会社 | Composite particle, powder, resin composition, and molded article |
| CN111712464B (en) | 2018-02-13 | 2023-04-18 | 保德科技股份有限公司 | Mn ferrite powder, resin composition, electromagnetic wave shielding material, electronic material, and electronic component |
| JPWO2019159800A1 (en) * | 2018-02-13 | 2021-02-12 | パウダーテック株式会社 | Composite particles, powders, resin compositions and moldings |
| KR102212258B1 (en) * | 2018-10-31 | 2021-02-04 | 엔트리움 주식회사 | EMI protection composition, method of fabricating the same and electronic device including EMI protection layer |
| JP7240011B2 (en) * | 2019-01-29 | 2023-03-15 | パウダーテック株式会社 | ELECTRODE-FORMING MATERIAL, ELECTRODE MANUFACTURING METHOD, AND ELECTRODE |
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| US5171937A (en) * | 1991-07-22 | 1992-12-15 | Champlain Cable Corporation | Metal-coated shielding materials and articles fabricated therefrom |
| JP2951487B2 (en) * | 1992-09-11 | 1999-09-20 | ユニデン株式会社 | Electromagnetic wave shielding method |
| JP3209456B2 (en) * | 1992-10-27 | 2001-09-17 | 関西ペイント株式会社 | Radio wave antireflective body and radio wave antireflection method |
| JPH07183110A (en) * | 1993-12-22 | 1995-07-21 | Mitsubishi Materials Corp | Electromagnetic wave shielding powder piece |
| KR970004601B1 (en) * | 1993-12-30 | 1997-03-29 | 고려화학 주식회사 | Coating composition |
| JP2843288B2 (en) * | 1995-12-07 | 1999-01-06 | 本田技研工業株式会社 | Electronic device sealing material |
| JPH1126982A (en) * | 1997-07-03 | 1999-01-29 | Otsuka Chem Co Ltd | Magnetic seal agent and manufacture of radio wave absorber |
| JP3875860B2 (en) * | 2001-07-16 | 2007-01-31 | Ｊｆｅスチール株式会社 | Pre-coated steel sheet with excellent environmental harmony, processed part corrosion resistance and processed part adhesion |
| JP3796257B2 (en) * | 2001-07-25 | 2006-07-12 | 株式会社神戸製鋼所 | Coated body for electronic device members having excellent heat dissipation and self-cooling properties, and electronic device parts |
| JP4484405B2 (en) * | 2001-08-20 | 2010-06-16 | 住友軽金属工業株式会社 | Electromagnetic wave-absorbing precoated aluminum plate with excellent press workability |
| JP2004027064A (en) * | 2002-06-26 | 2004-01-29 | Nippon Steel Corp | Coating material excellent in heat radiation and electromagnetic wave absorbability and coated metal plate |
| JP2004216276A (en) * | 2003-01-15 | 2004-08-05 | Mitsubishi Rayon Co Ltd | Method for producing pseudo sheet-like material of hollow fiber membrane bundle, pseudo sheet-like material of hollow fiber membrane bundle, and hollow fiber membrane module |
-
2005
- 2005-03-31 JP JP2005101672A patent/JP2006286729A/en active Pending
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2006
- 2006-02-07 KR KR1020060011466A patent/KR100741616B1/en not_active IP Right Cessation
- 2006-02-14 TW TW095104930A patent/TW200641077A/en not_active IP Right Cessation
- 2006-03-30 CN CNA2006100683649A patent/CN1840589A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555102A (en) * | 2013-10-14 | 2014-02-05 | 苏州富莱希涂料有限公司 | Reflective thermal-insulation exterior wall coating |
| WO2018000798A1 (en) * | 2016-06-28 | 2018-01-04 | 王强 | Heat-curable magnetic epoxy resin powder and method for encapsulating an inductor using same |
| CN111033646A (en) * | 2017-08-03 | 2020-04-17 | 保德科技股份有限公司 | Composite particle, powder, resin composition, and molded body |
Also Published As
| Publication number | Publication date |
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| KR20060106638A (en) | 2006-10-12 |
| JP2006286729A (en) | 2006-10-19 |
| TWI320798B (en) | 2010-02-21 |
| TW200641077A (en) | 2006-12-01 |
| KR100741616B1 (en) | 2007-07-23 |
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