CN101219590B - Conductive clear coated stainless steel sheet - Google Patents
Conductive clear coated stainless steel sheet Download PDFInfo
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- CN101219590B CN101219590B CN2007103009718A CN200710300971A CN101219590B CN 101219590 B CN101219590 B CN 101219590B CN 2007103009718 A CN2007103009718 A CN 2007103009718A CN 200710300971 A CN200710300971 A CN 200710300971A CN 101219590 B CN101219590 B CN 101219590B
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Abstract
The invention provides a conductive clear coated stainless steel sheet comprising a stainless steel sheet main body and a clear coating film formed on at least one surface side of the stainless steel sheet main body, the clear coating film containing a conductive pearl pigment in an amount of 3 to 30 parts by mass based on 100 parts by mass of the solid content of a thermosetting resin composition.
Description
Technical field
The present invention relates to possess the clear-coated stainless steel sheet of transparent coating with electric conductivity.
Background technology
In recent years; Material as the shell of household electrical appliance goods or electronic equipment; Sometimes the surface that is employed in the corrosion resistant plate raw sheet is provided with the clear-coated stainless steel sheet of transparent coating (for example, the spy opens 2001-149860 communique, spy and opens that 2001-316845 communique, spy are opened the 2003-154309 communique, the spy opens the 2003-154309 communique).
On the shell of household electrical appliances or electronic equipment, make it have static electricity resistance sometimes, to prevent adhering to of dust etc.Usually, have static electricity resistance, adopt the method for corrosion resistant plate being given electric conductivity in order to make corrosion resistant plate.
As the method for corrosion resistant plate being given electric conductivity, known to have on the corrosion resistant plate raw sheet method (for example opening the 2006-095709 communique with reference to the spy) that the transparent coating that contains the electroconductive stuffing that is made up of metal dust is set or coating contain conductive agent be the method for the clear dope of material with carbon element with the transparent coating that forms electric conductivity.
The spy opens the high conductivity that conductive coating in the 2006-095709 communique has the degree that can bring into play electromagnetic wave shielding., this conductive coating exist the transparency of transparent coating low, the low problem of visual identification of corrosion resistant plate raw sheet.In addition, when making transparent coating contain material with carbon element, because material with carbon element is black, so transparent coating is by painted and the transparency is descended.So the visual identification of corrosion resistant plate raw sheet reduces, and diminishes the outward appearance of clear-coated stainless steel sheet.The outward appearance of corrosion resistant plate is one of its advantage well.Therefore, if the outward appearance of diminishing then might reduce the availability of corrosion resistant plate.In addition, because transparent coating has or not the judgement difficulty of scuffing, therefore be difficult for carrying out quality management sometimes.
Summary of the invention
The present invention In view of the foregoing accomplishes, and its purpose is to provide a kind of clear-coated stainless steel sheet that has the electric conductivity that can bring into play the static electricity resistance degree and can prevent the visual identification decline of corrosion resistant plate raw sheet.
The present invention comprises following formation.
The 1st mode of the present invention is a kind of conductive clear coated stainless steel sheet, it is characterized in that: have corrosion resistant plate raw sheet and the film forming transparent coating in the side of one side at least of said corrosion resistant plate raw sheet; In said transparent coating,, contain the electric conductivity pearlescent pigment (Pearl Pigment) of 3～30 mass parts with respect to the solids of the compositions of thermosetting resin of 100 mass parts.
The 2nd mode of the present invention is the described conductive clear coated stainless steel sheet of above-mentioned the 1st mode, it is characterized in that:
Between said corrosion resistant plate raw sheet and said transparent coating, having the chemical conversion processing films; This chemical conversion is handled and is filmed that to contain amino silane be that coupling agent and epoxy silane are a side or the both sides in the coupling agent, and it is 2～50mg/m that the adhesion amount of filming is handled in said chemical conversion
2
Said transparent coating be make through blocked isocyanate compounds have bridging property functional group, glass transition point is that 30～90 ℃, number-average molecular weight are 3000～50000 the crosslinked compositions of thermosetting resin that obtains of acrylic resin.
The 3rd mode of the present invention is the described conductive clear coated stainless steel sheet of above-mentioned the 2nd mode; It is characterized in that: in said transparent coating; With respect to the solids of the compositions of thermosetting resin of 100 mass parts, contain the polyolefin wax of 0.25～10 mass parts.
The 4th mode of the present invention is the above-mentioned the 2nd or the 3rd described conductive clear coated stainless steel sheet of mode, it is characterized in that: the acrylic resin in the transparent coating is further through amino resins and crosslinked.
The 5th mode of the present invention is the described conductive clear coated stainless steel sheet of either party formula in above-mentioned the 2nd～the 4th mode; It is characterized in that: in said transparent coating; With respect to the solids of the compositions of thermosetting resin of 100 mass parts, contain the Ludox of 2～10 mass parts.
The 6th mode of the present invention is the described conductive clear coated stainless steel sheet of either party formula in the 1st～the 5th mode, it is characterized in that: the shell that is used for hard drive.
Conductive clear coated stainless steel sheet of the present invention has the electric conductivity that can bring into play the static electricity resistance degree, and can prevent that the visual identification of corrosion resistant plate raw sheet from descending.
Description of drawings
Fig. 1 is the cutaway view of an embodiment of expression conductive clear coated stainless steel sheet of the present invention.
The specific embodiment
Below, an embodiment example of conductive clear coated stainless steel sheet of the present invention is described.
Fig. 1 representes the conductive clear coated stainless steel sheet of this embodiment example.The conductive clear coated stainless steel sheet 10 of this embodiment example has: corrosion resistant plate raw sheet 11, film forming in the chemical conversion of the single face side of corrosion resistant plate raw sheet 11 handle film 12 and film forming handle 12 the lip-deep transparent coating 13 of filming in chemical conversion.
Corrosion resistant plate raw sheet 11 as in the above-mentioned conductive clear coated stainless steel sheet 10 can use the steel plate that is formed by known stainless steel.
[chemical conversion is handled and is filmed]
Handle as chemical conversion and to film 12, be preferably that to contain amino silane be that coupling agent and epoxy silane are filming of a side or both sides in the coupling agent.Film 12 if between corrosion resistant plate raw sheet 11 and transparent coating 13, have the chemical conversion processing that contains these silane couplers; Then can become non-harmful chromate-free (chromate-free), can also improve the adaptation between corrosion resistant plate raw sheet 11 and the transparent coating 13.
Here, be coupling agent as amino silane, for example, can enumerate out N-2 (aminoethyl) 3-aminopropyl methyl dimethoxysilane, N-2 (aminoethyl) 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane etc.
As epoxy silane is coupling agent, for example, can enumerate out 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane etc.
Chemical conversion is handled 12 the adhesion amount of filming and is preferably 2～50mg/m
2If handling 12 the adhesion amount of filming, chemical conversion is lower than 2mg/m
2, then gloss and corrosion resistance descend easily, if adhesion amount surpasses 50mg/m
2, then the film coated surface after the boiled water test produces bubble sometimes.The preferred upper limit that 12 the adhesion amount of filming is handled in chemical conversion is 30mg/m
2, 10mg/m more preferably
2
12 the adhesion amount of filming is handled in chemical conversion, can be through measuring SiO with fluorescent x-ary analysis
2Amount is obtained.
[transparent coating]
The electric conductivity pearlescent pigment
In order to prevent static, the specific insulation of known materials (being the specific insulation of whole laminations in the material of laminated construction) must be 10
7Ω cm following (10
4～10
7Ω cm) (synthetic resin, 28 (2), 14 pages, nineteen eighty-two).
The electric conductivity pearlescent pigment that is contained in the transparent coating 13 is that electric conductivity and all excellent metal oxide of the transparency cover the pearlescent pigment that forms on the mica (mica).Pearlescent pigment generally is to be the structure of mica (being made up of aluminium oxide, magnesia, silica, fluorine compounds etc.) with metal oxide cover sheet shape mica particle.The transparency of such pearlescent pigment is high, and has electric conductivity.
Above-mentioned metal oxide is not limited especially.As above-mentioned metal oxide, be preferably the metal oxide more than a kind or 2 kinds that is selected from tin-oxide, sb oxide, indium oxide, the zinc oxide.Under the situation that adopts above-mentioned metal oxide, can access the high electric conductivity and the transparency.
The content of the metal oxide in the electric conductivity pearlescent pigment is preferably more than 40 quality %.If above-mentioned metal oxide is lower than 40 quality %, then be difficult to guarantee electric conductivity.
The content of the metal oxide in the electric conductivity pearlescent pigment is preferably below 60 quality %.If above-mentioned metal oxide surpasses 60 quality %, then the coverage rate of mica is saturated, and it is unfavorable therefore to consider from the cost aspect.
The content of the metal oxide in the electric conductivity pearlescent pigment also can be 100 quality %.When the content of metal oxide is 100 quality %, mean it is conductive metal oxide itself.
As such electric conductivity pearlescent pigment, can adopt commercially available electric conductivity pearlescent pigment.The for example commercially available electric conductivity pearlescent pigment that ミ Na テ Star Network 40CM (Merk Japanese firm system) etc. is arranged.In addition, as the high electroconductive oxide of the transparency, for example commercially available to have as tin-antimony be TWU-1 (Mitsubshi Materials Corp's system) of oxide etc.
The content of the electric conductivity pearlescent pigment in the transparent coating 13 is 3～30 mass parts with respect to the solids of the compositions of thermosetting resin of 100 mass parts, more preferably 5～15 mass parts.If the content of electric conductivity pearlescent pigment is lower than 3 mass parts, then the mutual contact of electric conductivity pearly-lustre particle is insufficient, so electric conductivity can not improve.If the content of electric conductivity pearlescent pigment surpasses 30 mass parts, then the conductance of transparent coating 13 is saturated, and coating descends simultaneously, and the visual identification of conductive clear coated stainless steel sheet 10 is also descended.
Compositions of thermosetting resin
Compositions of thermosetting resin preferably carries out the crosslinked resin that obtains through blocked isocyanate compounds to the acrylic resin (being designated hereinafter simply as acrylic resin) with bridging property functional group.Compositions of thermosetting resin so long as above-mentioned resin just can make conductive clear coated stainless steel sheet 10 become chromate-free, and can improve scratch resistance, against weather, reagent resistance.
Here, bridging property functional group is the functional group more than a kind or 2 kinds that is selected from hydroxyl, carboxyl, the alkoxysilane group etc.Preferred each acrylic resin molecule has the bridging property functional group more than 2.
Acrylic resin is at least a kind of non-functionality acrylic monomers and at least a kind of functional monomer's a copolymer.
As non-functionality acrylic monomers; For example, can enumerate out aliphatic acrylate or ring type acrylic acid ester such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-EHA, methyl methacrylate, EMA, isopropyl methacrylate, n-BMA, the own ester of methacrylic acid normal-butyl, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl methacrylate.
As the functional monomer, can enumerate out monomer, monomer, have the monomer of alkoxysilane group etc. with carboxyl with hydroxyl.
As monomer with hydroxyl; For example; Can enumerate out hydroxy alkyl esters such as acrylic acid 2-ethoxy, methacrylic acid 2-ethoxy, acrylic acid hydroxypropyl, methacrylic acid hydroxypropyl, contain the acrylic monomers (for example, trade name プ ラ Network セ Le FM1～5, FA-1～5 of Daicel chemical industry system) of lactone modified hydroxyl.
As monomer, for example, can enumerate out acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid etc. with carboxyl.
As monomer, for example, can enumerate out vinyltrimethoxy silane, VTES, methacryl propyl trimethoxy silicane etc. with alkoxysilane group.
In acrylic resin, also can make other monomer copolymerization beyond non-functionality acrylic monomers and the functional monomer.As other monomer, for example, can enumerate out methyl vinyl ether, ethyl vinyl ether, normal-butyl propyl vinyl ether, n-butyl vinyl ether class; Phenylethylene such as styrene, AMS; Acrylamide monomers such as acrylamide, N hydroxymethyl acrylamide, DAAM etc.
The glass transition point of preferred acrylic resins is 30～90 ℃, more preferably 50～90 ℃.When continuous this conductive clear coated stainless steel sheet 10 of punching press, because of friction, processing heating make the temperature on surface rise to 80～100 ℃.If the glass transition point of acrylic resin is lower than 30 ℃, then transparent coating 13 is softening, sometimes attached on the mould.In addition, if the glass transition point of acrylic resin surpasses 90 ℃, the tendency that produces pin hole, levelability deficiency etc. is arranged then.
The glass transition temperature that makes acrylic resin is in above-mentioned scope, as long as the suitable composition of selecting acrylic resin.
The number-average molecular weight of acrylic resin is preferably 3000～50000, and more preferably 4000～10000.If the number-average molecular weight of acrylic resin is lower than 3000, then the reactivity with blocked isocyanate compounds reduces, and is difficult to form transparent coating 13, if surpass 50000, then the dissolubility in solvent reduces, and is difficult to obtain clear dope.
The number-average molecular weight of acrylic resin can the condition (for example, the kind of polymerization temperature, polymerization initiator or amount etc.) when making acrylic resin be adjusted.
Making acrylic resin carry out crosslinked crosslinking agent is that blocked isocyanate compounds is the compound that in 1 molecule, has the NCO more than 2.Specifically, be aromatic diisocyanates such as toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, XDI, naphthalene diisocyanate; Aliphatic diisocyanates such as hexamethylene diisocyanate, dimer acids vulcabond, alicyclic diisocyanates such as IPDI, cyclohexane diisocyanate; The addition product of the biuret formula of this PIC, isocyanide urea ring type addition product etc. can be enumerated out with end-capping reagents such as phenol, oximes, active methylene class, epsilon-caprolactams class, triazole type, azoles quinoline classes and carry out end-blocking.Can use the dissociate promoter of organotin catalysts such as dibutyltin dilaurate as end-capping reagent.
Commercially available article as blocked isocyanate compounds; For example, can enumerate out デ ス モ ジ ユ one Le (desmodur) BL1100, BL1265MPA/X, VPLS2253, BL3475BS/SN, BL3272MPA, BL3370MPA, BL4265SN, デ ス モ-サ system 2170, Sumidur 3175 (above), デ ユ ラ ネ-ト 17B-60PX, TPA-B80X, MF-B60X, MF-K60X (above is Asahi Chemical Corp's system), バ-ノ Star Network DB-980K, D-550, B3-867, B7-887-60 (above is Dainippon Ink. & Chemicals Inc's system), コ ロ ネ-ト 2515,2507,2513 (above is Nippon Polyurethane Industry Co., Ltd.'s system) etc. for firmly changing Bayer polyurethane Co., Ltd. system.These blocked isocyanate compounds can be used a kind separately, also can and use.
For acrylic resin, consider with the aspect of further raising scratch resistance from making transparent coating 13 hardening, as crosslinking agent, preferably not only adopt above-mentioned blocked isocyanate compounds, also adopt amino resins (melmac) to carry out crosslinked.
Amino resins be make amino-compound (melamine, guanamines, urea) and formaldehyde (formalin) take place addition reaction and with ethanol carry out modification the general name of resin.As concrete example, can enumerate out melmac, benzoguanamine resin, urea resin, butylation urea resin, butylation urea melamine, glycoluril resin, acetylguanamine resin, cyclohexyl guanamine resin etc.Wherein, consider, be preferably melmac from anti-fingerprint contaminative, scratch resistance, reagent resistance aspect.
According to the kind of the ethanol that carries out modification, melmac for example can be categorized as methylated melamine resin, normal-butyl melmac, isobutyl melmac, mixed alkyl melmac etc.
Specifically; As the methylated melamine resin, can enumerate out サ イ メ Le 300,301,303,350,370,771,325,327,703,712,715,701,267,285,232,235,236,238,211,254,204,212,202,207 (above is Mitsui サ イ テ Star Network Co., Ltd. system), LUWIPAL 063,066,068,069,072,073 (above is the BASF system), ス one パ one ベ Star カ ミ Application L-105 (above is Dainippon Ink. & Chemicals Inc's system), メ ラ Application 522,523,620,622,623 (above is Hitachi Chemical Co., Ltd.'s system) etc.
As the normal-butyl melmac, can enumerate out マ イ コ-ト 506,508 (above for Mitsui サ イ テ Star Network Co., Ltd. system), ユ-バ Application 20SB, 20SE, 21R, 22R, 122,125,128,220,225,228,28-60,20HS, 2020,2021,2028,120 (above be Mitsui Chemicals, Inc's system), PLASTOPAL EBS 100A, 100B, 400B, 600B, CB (above be BASF system), ス one パ one ベ Star カ ミ Application J-820, L-109, L-117, L-127, L-164 (above be Dainippon Ink. & Chemicals Inc's system), メ ラ Application 21A, 22,220,2000,8000 (above be Hitachi Chemical Co., Ltd.'s system), テ ス ア ジ Application 3020,3021,3036 (above change into polymer Co., Ltd. system for Hitachi) etc.
As the isobutyl melmac, can enumerate out ユ-バ Application 60R, 62,62E, 360,361,165,166-60,169,2061 (above be Mitsui Chemicals, Inc's system), ス one パ one ベ Star カ ミ Application G-821, L-145, L-110, L-125 (above be Dainippon Ink. & Chemicals Inc's system), PLASTOPAL EBS 4001, FIB, H731B, LR8824 (above be BASF system), メ ラ Application 27,28,28D, 245,265,269,289 (above be Hitachi Chemical Co., Ltd.'s system), テ ス ア ジ Application 3027,3028,3029,3030,3037 (above change into polymer Co., Ltd. system for Hitachi) etc.
As the mixed alkyl melmac, can enumerate out サ イ メ Le 267,285,232,235,236,238,211,254,204,212,202,207 (above is Mitsui サ イ テ Star Network Co., Ltd. system) etc.
Amino resins can use a kind separately, also can be also with more than 2 kinds.
Lubricating wax
As polyolefin wax, for example, can enumerate out hydrocarbon system waxes such as paraffin, microwax, polyethylene, polyethylene-fluorine etc.
When processing electrically conductive clear-coated stainless steel sheet 10, be coated with film temperature and rise because of processing heating and frictional heat make.Therefore, preferred polyolefm is that the fusing point of wax is 70～160 ℃.If the fusing point of polyolefin wax is lower than 70 ℃, then add softening, fusing in man-hour, can not bring into play superperformance sometimes as solid lubrication additive.If the fusing point of polyolefin wax surpasses 160 ℃, then hard particle is present in the surface, and frictional behaviour is reduced, and therefore can not get high processability sometimes.
The acid value of polyolefin wax is preferably 0～30.If the acid value of polyolefin wax surpasses 30, then the intermiscibility with compositions of thermosetting resin increases, and polyolefin wax floats to film coated surface on being difficult to equably, so the processability of conductive clear coated stainless steel sheet 10 is insufficient sometimes.
The content of the polyolefin wax in the transparent coating 13, the solids with respect to the compositions of thermosetting resin of 100 mass parts is preferably 0.25～10 mass parts.If the content of polyolefin wax is lower than 0.25 mass parts, then processability is not enough sometimes, if surpass 10 mass parts, at film coated surface generation speckle, diminishes the outward appearance of conductive clear coated stainless steel sheet 10 sometimes.
Ludox
In addition, transparent coating 13 can contain the Ludox that the particle diameter of silicon oxide particle is nanometer (nm) level.If transparent coating 13 contains Ludox, the hardness of then filming, scratch resistance, anti-fingerprint contaminative improve.
The content of Ludox is preferably 2.0～10 mass parts with respect to the compositions of thermosetting resin of 100 mass parts by the solid component, more preferably 3.0～8.0 mass parts.If the content of Ludox is lower than 2.0 mass parts, then scratch resistance or hardness are not enough, if surpass 10 mass parts, and the tendency that then has processability to descend.
In transparent coating 13, also can further contain levelling agent, antifoaming agent, anti-oxidant, ultra-violet absorber, delustering agent, silane coupler etc. as additive.In addition, also can contain epoxy resin, silicone resin, fluororesin, polyester etc.
The thickness of transparent coating 13 is preferably 1～10 μ m.If the thickness of transparent coating 13 is lower than 1 μ m, then can not give full play to the lubricating function of transparent coating 13, the processability of conductive clear coated stainless steel sheet 10 is descended.In addition, can not improve electric conductivity sometimes.If the thickness of transparent coating 13 surpasses 10 μ m, then the lubricating function of transparent coating 13 is saturated, and the difficult sometimes transparent coating that forms.
[manufacturing approach]
Below, an example of the manufacturing approach of above-mentioned conductive clear coated stainless steel sheet is described.In addition, the manufacturing approach of conductive clear coated stainless steel sheet 10 is not limited to following example.
In this routine manufacturing approach, at first, corrosion resistant plate raw sheet 11 is implemented alkali degreasing or utilized known preliminary treatment such as corrosion sour, alkali.
Then, to contain amino silane be that coupling agent and epoxy silane are a side or both sides' the chemical conversion treatment solution in the coupling agent in coating on corrosion resistant plate raw sheet 11, after drying, forms chemical conversion and handle and film 12.
Can adopt commercially available article as above-mentioned chemical conversion treatment solution.As commercially available chemical conversion treatment solution; For example, can enumerate out パ Le コ one ト E305,3750,3751,3753,3756,3757,3970 (Japanese パ one カ ラ イ ジ Application グ (phosphatization processing) Co., Ltd.'s system), ア Le サ one Off 440 (Nippon Paint Co., Ltd.'s system) etc.
As the coating process of chemical conversion treatment solution, for example, can adopt that spraying, roller coat, rod are coated with, curtain coating, electrostatic applications etc.
The baking temperature of chemical conversion treatment solution (surface temperature) is preferably 60～140 ℃.
Then, handle on 12 the surface of filming to be coated with clear dope in chemical conversion, and dry (roasting).When this was dry, acrylic resin carried out crosslinked through blocked isocyanate compounds, formed compositions of thermosetting resin.Thus, form the transparent coating 13 that contains electric conductivity pearlescent pigment and compositions of thermosetting resin.Obtain conductive clear coated stainless steel sheet 10.
Here; So-called clear dope is to contain electric conductivity pearlescent pigment, acrylic resin, blocked isocyanate compounds and solvent as must composition, and the curing catalysts, amino resins, polyolefin wax, Ludox etc. that contain blocked isocyanate compounds are as the coating of composition arbitrarily.
The acrylic resin in the clear dope and the ratio of blocked isocyanate are: preferably with respect to the bridging property functional group of 1 mol propylene acid resin; NCO is 0.1～2.0 mole a ratio; More preferably with respect to the bridging property functional group of 1 mol propylene acid resin; NCO is 0.1～1.0 mole a ratio, and especially preferably with respect to the bridging property functional group of 1 mol propylene acid resin, NCO is 0.2～0.8 mole a ratio.
In order to shorten the formation time of transparent coating 13, clear dope can contain the curing catalysts of blocked isocyanate compounds.
As the curing catalysts of blocked isocyanate compounds, can enumerate out di-n-butyl tin-oxide, di-n-butyl tin chloride, di-n-butyl tin dilaurate, di-n-butyl tin diacetate, di-n-butyl tin octylate oxide, normal-butyl dioctyl tin dilaurate, tetra-n-butyl tin etc.
When except blocked isocyanate compounds, also containing amino resins as crosslinking agent in the clear dope; The content of the amino resins in the clear dope is 10～40 mass parts with respect to the acrylic resin solids of 100 mass parts preferably, more preferably 15～30 mass parts.If the content of the amino resins in the clear dope is lower than 10 mass parts, then can not fully improve scratch resistance, if surpass 40 mass parts, the difficult sometimes transparent coating 13 that forms.
In addition, contain at clear dope under the situation of amino resins, the tendency of prolongation hardening time (roasting time) of acrylic resin is arranged, therefore can contain the curing catalysts of amino resins.If clear dope contains the curing catalysts of amino resins, then hardening time can be shortened.
As the curing catalysts of amino resins, for example, can use sulfonic acid series catalysts or amine series catalysts etc., but consider from the angle that can bring into play effect to the shortening of roasting time especially, be preferably the p-methyl benzenesulfonic acid series catalysts.
When the total gauge with acrylic resin and blocked isocyanate compounds and amino resins was decided to be 100 mass parts, the amount of the curing catalysts of amino resins was preferably 0.5～5 mass parts, more preferably 1～2 mass parts.
If when the total gauge with acrylic resin, blocked isocyanate compounds and amino resins is decided to be 100 mass parts; The amount of the curing catalysts of amino resins is lower than 0.5 mass parts; Then hardening time can not be shortened sometimes; If surpass 5 mass parts, the tendency of the processability decline of the conductive clear coated stainless steel sheet 10 that obtains is arranged then.
In clear dope, contain under the situation of polyolefin wax, preferred polyolefm is that the average grain diameter of wax is 0.1～7.0 μ m.If the average grain diameter of polyolefin wax surpasses 7.0 μ m, then the dispersiveness of the polyolefin wax in the transparent coating 13 descends.If the average grain diameter of polyolefin wax is lower than 0.1 μ m, the processability of the conductive clear coated stainless steel sheet 10 that then obtains descends.
In clear dope, contain under the situation of Ludox, can modulate clear dope through adding organic silicon sol.
So-called organic silicon sol is the colloidal solution that in organic solution, stably is dispersed with the colloidal silica of nano-scale.
As organic silicon sol, can enumerate out MA-ST-M, IPA-ST, EG-ST, EG-ZL, NPC-ST, DMAC-ST, DMAC-ST-ZL, XBA-ST, MIBK-ST (above is Nissan Chemical Ind Ltd's system) etc.Organic silicon sol can use a kind separately, also can be also with more than 2 kinds.
As the coating process of clear dope, can adopt the method identical with the coating process of chemical conversion treatment solution.
In the conductive clear coated stainless steel sheet 10 of above explanation, owing to have the electric conductivity that can bring into play the static electricity resistance degree, thereby abundant release electrostatic, can prevent that dust from adhering to.In addition, because transparent coating 13 is the films that contain the electric conductivity pearlescent pigment of specified quantitative, thereby the transparency is excellent, can prevent that the visual identification of corrosion resistant plate raw sheet 11 from descending.Therefore, the aesthetic property of this conductive clear coated stainless steel sheet 10 is excellent.
Such conductive clear coated stainless steel sheet 10 is suitable for adhering to sometimes the shell that dust can become the electronic equipment of failure cause.Especially be more suitable for being used for the shell of hard disk drive.
In addition, the present invention is not limited to above-mentioned embodiment example.For example, in above-mentioned embodiment, there is chemical conversion to handle in the single face film forming of corrosion resistant plate raw sheet and films and transparent coating, film and transparent coating but also can have chemical conversion to handle in the two sides of corrosion resistant plate raw sheet film forming.
In addition, in above-mentioned embodiment, between corrosion resistant plate raw sheet and transparent coating, have the chemical conversion processing and film, film but also can not have the chemical conversion processing.
Embodiment
(embodiment 1)
In the four-hole boiling flask that possesses thermometer, reflux condenser, agitator, addition funnel, nitrogen conduit; Press the combined amount shown in the table 1; Pack into toluene, butyl acetate; Be warmed up to 110 ℃, stir, with the mixture that dripped methyl methacrylate, styrene, n-BMA, methacrylic acid 2-hydroxyl ethyl ester, methyl acrylate, azodiisobutyronitrile (AIBN) in 3 hours while be blown into nitrogen.After drip finishing, append AIBN again, it was reacted 3 hours again, obtain nonvolatile component and be the solution of 50% acrylic resin in identical temperature.
Then, mix blocked isocyanate " デ ス モ ジ ユ one Le VPLS2253 " (firmly change Bayer polyurethane Co., Ltd. system, the NCO containing ratio is 10.5 quality %), obtain clear dope as curing agent.
Then, be the solids of the compositions of thermosetting resin of 100 mass parts with respect to the total solid composition, the electric conductivity pearlescent pigment that mixes 5.0 mass parts is that (Merk Japanese firm system, (principal component is SiO to ミ Na テ Star Network 40CM with laminar mica
2) cover and the pigment that obtains with tin-oxide and sb oxide; The content of tin-oxide and sb oxide add up to be approximately 43 quality %) and the polyolefin wax of 2.0 mass parts (fusing point is that 120 ℃, particle diameter are the Tissuemat E of 2 μ m), it is contained in the clear dope.
Table 1
At the single face of corrosion resistant plate raw sheet (the No.4 attrition process article of SUS304), utilize the rolling method coating to contain the chemical conversion treatment solution that amino silane is a coupling agent, the mode that reaches 100 ℃ with surface temperature makes its drying, and film forming is that adhesion amount is 10mg/m
2Chemical conversion handle and to film.
Then, handle on the surface of filming in chemical conversion, utilize rod to be coated with method coating clear dope, the mode that reaches 193 ℃ with surface temperature is carried out roasting, and making thickness is the transparent coating film forming of 3 μ m, obtains clear-coated stainless steel sheet.
To the clear-coated stainless steel sheet that obtains, utilize dicyclo method (double リ Application グ method) under the environment of 23 ℃ of temperature, relative humidity 50%, to measure resistance, obtain surface resistivity based on formula (1), obtain specific insulation based on formula (2).About specific insulation, only obtain the specific insulation of clear-coated stainless steel sheet integral body and transparent coating.In addition, the whole specific insulation of clear-coated stainless steel sheet is to be the value that 0.4mm calculates with thickness.Only the specific insulation of transparent coating is that the resistivity with the corrosion resistant plate raw sheet is 0, is the value that 5 μ m calculate with the thickness of transparent coating.Its result is as shown in table 2.
Surface resistivity and specific insulation adopt that (Kawaguchi's motor is made made P-616, and the main electrode diameter is that the area of 50mm, main electrode is 19.63cm by tester (Adventest system numeral multiple-position measurement device R6441D) and electrode
2, lateral electrode internal diameter be that the external diameter of 70mm, medial electrode is 50mm) determinator that constitutes measures.But the surface resistivity of comparative example 1 is the value that adopts superinsulation appearance (Kawaguchi's motor is made made R-503) to obtain.
Formula (1) (surface resistivity)={ π (D+d)/(D-d) } * R
Formula (2) (specific insulation)=(R * A)/t
(D: lateral electrode internal diameter, d: medial electrode external diameter, R: the measured value of resistance, A: main electrode area, t: sample thickness)
Table 2
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | ? |
| The content of electric conductivity pearlescent pigment (mass parts) in the transparent coating | 5 | 10 | 20 | 0 | 2 | ?40 | ? |
| Surface resistivity (Ω) | 1.09×10 6 | 6.22×10 5 | 2.12×10 5 | ＞1.9×10 8 | 1.51×10 6 | ?- | ? |
| Specific insulation (Ω cm) | Steel plate is whole | 6.13×10 6 | 5.64×10 6 | 4.55×10 6 | 1.27×10 8 | 1.28×10 7 | ?- |
| Transparent coating only | 4.91×10 8 | 4.52×10 8 | 3.64×10 8 | 1.02×10 10 | 1.02×10 9 | ?- | ? |
"-" expression undetermined in the table.
(embodiment 2,3, comparative example 1～3)
Except in clear dope, press beyond the content of the electric conductivity pearlescent pigment in the transparent coating of regulation shown in the table 2, likewise obtain clear-coated stainless steel sheet with embodiment 1.Then, surface resistivity and specific insulation have likewise been measured with embodiment 1.Its result is as shown in table 2.
The clear-coated stainless steel sheet of embodiment 1～3 that in clear dope, contains the electric conductivity pearlescent pigment of specified quantitative, excellent electric conductivity.In addition, the transparency of transparent coating is high, and the visual identification of corrosion resistant plate raw sheet is also good.
On the contrary, to be lower than the electric conductivity of clear-coated stainless steel sheet of comparative example 1,2 of 3 mass parts low for the electric conductivity pearlescent pigment content in the clear dope.
Electric conductivity pearlescent pigment content in clear dope is in the comparative example 3 of 40 mass parts, because of coating is low, can not evenly be coated with, and produces speckle, thereby has ended experiment.
More than, preferred embodiment of the present invention has been described, but the present invention is not limited to these embodiment.In the scope that does not break away from aim of the present invention, can carry out structure additional, omit, displacement, and other change.The present invention is not limited by above explanation, and limited by the scope of accompanying claims.
Claims (8)
1. conductive clear coated stainless steel sheet is characterized in that:
Has corrosion resistant plate raw sheet and film forming transparent coating in the side of one side at least of said corrosion resistant plate raw sheet;
In said transparent coating, with respect to the solids of the compositions of thermosetting resin of 100 mass parts, contain the electric conductivity pearlescent pigment of 3～30 mass parts,
Between said corrosion resistant plate raw sheet and said transparent coating, having the chemical conversion processing films; This chemical conversion is handled and is filmed that to contain amino silane be that coupling agent and epoxy silane are a side or the both sides in the coupling agent, and it is 2～50mg/m that the adhesion amount of filming is handled in said chemical conversion
2
Said transparent coating be make through blocked isocyanate compounds have bridging property functional group, glass transition point is that 30～90 ℃, number-average molecular weight are 3000～50000 the crosslinked compositions of thermosetting resin that obtains of acrylic resin.
2. conductive clear coated stainless steel sheet as claimed in claim 1 is characterized in that:
In said transparent coating,, contain the polyolefin wax of 0.25～10 mass parts with respect to the solids of the compositions of thermosetting resin of 100 mass parts.
3. according to claim 1 or claim 2 conductive clear coated stainless steel sheet is characterized in that: the acrylic resin in the transparent coating is further through amino resins and crosslinked.
4. according to claim 1 or claim 2 conductive clear coated stainless steel sheet is characterized in that: in said transparent coating, with respect to the solids of the compositions of thermosetting resin of 100 mass parts, contain the Ludox of 2～10 mass parts.
5. according to claim 1 or claim 2 conductive clear coated stainless steel sheet is characterized in that: the shell that is used for hard drive.
6. conductive clear coated stainless steel sheet as claimed in claim 3 is characterized in that: in said transparent coating, with respect to the solids of the compositions of thermosetting resin of 100 mass parts, contain the Ludox of 2～10 mass parts.
7. conductive clear coated stainless steel sheet as claimed in claim 3 is characterized in that: the shell that is used for hard drive.
8. conductive clear coated stainless steel sheet as claimed in claim 4 is characterized in that: the shell that is used for hard drive.
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| JP2006341312 | 2006-12-19 | ||
| JP341312/2006 | 2006-12-19 | ||
| JP289796/2007 | 2007-11-07 | ||
| JP2007289796A JP5276829B2 (en) | 2006-12-19 | 2007-11-07 | Conductive clear coated stainless steel sheet |
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| CN101219590A CN101219590A (en) | 2008-07-16 |
| CN101219590B true CN101219590B (en) | 2012-02-29 |
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| KR101069950B1 (en) | 2008-12-26 | 2011-10-04 | 주식회사 포스코 | Steel Sheet Having Superior Electro-Conductivity and Resin Composition Therefor |
| JP5290888B2 (en) * | 2009-07-10 | 2013-09-18 | 古河スカイ株式会社 | Acrylic resin pre-coated metal plate |
| CN102993378B (en) * | 2012-11-19 | 2014-12-10 | 江苏三木化工股份有限公司 | Terpene resin modified acrylic resin for polypropylene plastics and preparation method of terpene resin modified acrylic resin |
| WO2016054427A1 (en) | 2014-10-03 | 2016-04-07 | 3M Innovative Properties Company | Methods for managing the scattering of incident light and articles created therefrom |
| JP6821399B2 (en) | 2016-11-10 | 2021-01-27 | 関西ペイント株式会社 | Matte clear paint composition for aluminum parts |
| CN108047782A (en) * | 2017-12-13 | 2018-05-18 | 天津宝兴威科技股份有限公司 | A kind of protective coating formula of nano-silver conductive film |
| CN111978779A (en) * | 2019-05-05 | 2020-11-24 | 贝内克-长顺汽车内饰材料（张家港）有限公司 | Pearlescent powder, pearlescent paint and TPO product coated with pearlescent paint |
| CN112175463A (en) * | 2020-08-25 | 2021-01-05 | 嘉美食品包装(滁州)股份有限公司 | Multicolor transparent coating, multicolor three-piece can and preparation method thereof |
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| CN1282308A (en) * | 1997-12-17 | 2001-01-31 | 默克专利股份有限公司 | Transparent medium with angular-selective transmitting or reflecting properties |
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| JP5276829B2 (en) | 2013-08-28 |
| JP2008173627A (en) | 2008-07-31 |
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