CN1748045A - Flat rolled magnetic steel sheet or strip having its surface coated for bonding - Google Patents

Flat rolled magnetic steel sheet or strip having its surface coated for bonding Download PDF

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Publication number
CN1748045A
CN1748045A CNA2004800034464A CN200480003446A CN1748045A CN 1748045 A CN1748045 A CN 1748045A CN A2004800034464 A CNA2004800034464 A CN A2004800034464A CN 200480003446 A CN200480003446 A CN 200480003446A CN 1748045 A CN1748045 A CN 1748045A
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epoxy
bonding
magnetic steel
steel plate
treatment solution
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CN100476030C (en
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竹田和年
村上明宏
森本当
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Nippon Steel Corp
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Nippon Steel Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/02—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
    • H01F1/18—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets with insulating coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • B05D2202/15—Stainless steel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Power Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Soft Magnetic Materials (AREA)
  • Adhesive Tapes (AREA)

Abstract

The invention provides an electromagnetic steel plate with a surface coating, which can also ensure that the whole surface of a steel plate is bonded and the bonding strength has less decrease even if the coating is thin, and is used to bond by heating and pressurizing, wherein, the surface of the electromagnetic steel plate is provided with an insulating coating which can represent a bonding ability by heating and/or pressurizing. The electromagnetic steel plate is characterized in that: the coating contains an epoxy resin or a modified epoxy resin with a glass transition temperature (Tg) of 80 to 150 DEG C, an epoxy resin curing agent and a mixture which is dispersed in the epoxy resin curing agent and has a particle size of 0.01mu m to 0.5mu m. Also, the Tg of the granular polymer is between 10 and 80 DEG C; in addition, the granular polymer is characterized by acrylic acid series resin.

Description

Flat rolled magnetic steel sheet or strip having its surface coated for bonding
Technical field
The present invention relates to stamping-out or shear the processing back, be used for being undertaken by heating and/or pressurization bonding flat rolled magnetic steel sheet or strip having its surface coated.
Background technology
In general, when using laminated iron core such as electro-magnetic steel plate assembling motor and transformer, adopt shear process or stamping-out carry out after with the electro-magnetic steel plate unit of being processed into iron core stacked, again by means of tight a bolt, methods such as ca(u)lk, welding or bonding are fixed.Then, enter the next processes such as insertion operation of winding coil.
; as the fixing method of laminated iron core following method is arranged also; promptly in advance the surface coated of steel plate by heating and/or pressurization can produce cementability, be called as so-called bonding insulating coating film of filming; stamping-out become the unit iron core and carry out stacked after; pressurized, heated and become secured core just can obtain the laminated iron core that does not have thermal strain and mechanical strain and rigidity good thus.
Though bonding filming requires to have as the effect of the caking agent that is used for fixing iron core with as the effect at the surperficial insulating coating film that forms of electro-magnetic steel plate, but with opposite often, require to have the technology of height as the necessary characteristic of insulating coating film as the necessary characteristic of caking agent.For example, as the characteristic of caking agent, in order to reach uniform adhering state easily, for well, but then, as insulating coating film, when the stamping-out unit of being processed into iron core, hard coat film preferably then is in order to avoid produce defective such as scratch cut on the surface with softness.In addition, as caking agent, should combine securely each other by the unit's of making iron core, the wettability of bonding film coated surface is preferably higher, but as insulating coating film, in order to keep solidity to corrosion, wettability is then preferably low.
For opposite so necessary characteristic is met, Te Kaiping 6-182296 communique discloses following technology: acrylic modified epoxy resin emulsion has cooperated latent curing agent in advance, being coated with equably with this acrylic modified epoxy resin emulsion at surface of steel plate is the mixed solution of main component, under incomplete state, toast then, thereby the good stability, the coating operability that have obtained treatment solution are good, the bonding surface-coated steel plate of using that can prolonged preservation.
But, to open in the technology that flat 6-182296 communique put down in writing above-mentioned spy, the problem of existence is a stacked unit iron core and by pressurized, heated fixedly the time, the whole surface bonding that is difficult to the unit's of making iron core is together.That is to say, in advance the latent curing agent that cooperates by heating with Resins, epoxy generation chemical reaction, making films is solidified and is bonded together, but film each other because of heating mixes mutually, fusion in the bonding of unit iron core surface coated, simultaneously because Resins, epoxy and epoxy hardener generation curing reaction, a part of whole surface bonding that curing reaction takes place in advance and often can not make steel plate together.Can not bond together on the whole surface of steel plate and be under the state of partial fixing, bonding strength between the steel plate produces fluctuation and has the more weak position of bonding strength, so the problem that exists is that iron core decomposes in manufacturing processed, abnormal vibrations in the time of may causing motor etc. to rotate.
So, Te Kaiping 10-343276 communique discloses following technology, promptly in the resin combination that acrylic resin and Resins, epoxy is carried out esterification and obtain, the blending epoxy solidifying agent, the peak temperature with the logarithmic decrement of this resin combination is set at 80～200 ℃ then.After making between bonding the filming of surface of steel plate fusion by this technology and mixing mutually, make the bonding possibility that becomes on whole surface by the curing reaction that carries out resin combination.
In recent years, in the understanding of strong request raising to the global environment problem, also strong request realizes the high efficiency of motor and transformer, for improving the efficient of motor and transformer, electro-magnetic steel plate is also required to improve the volume stacking factor, bonding filming also required slimming, and requiring thickness is 3 μ m or following.But distinguished already: the technology that above-mentioned spy opens the record of flat 10-343276 communique does not still solve the whole surface bonding problem together that is difficult to the unit's of making iron core when the bonding thickness of filming of attenuate.
Promptly in general, compare with the situation that the thickness of filming at the organic-inorganic mixing clasp Y insulation Y that is coated with on the non-oriented electromagnetic steel sheet having remains on about 1～2 μ m, be coated with bonding electro-magnetic steel plate of filming and apply thicklyer usually, thickness reaches 3～8 μ m.Trace it to its cause, this is because when thickness is thin, even the small concave-convex surface of rolling defect that produces during rolled sheet material and so on also produces not contacted part on the surface, produces bonding part and the bonding part that does not go up.
That is to say that the surfaceness of surface of steel plate also depends on the setting of roller mill certainly, but the vertex in the predetermined measurement range and the poor (R of lower-most point Max) be about 1～5 μ m, so coating thickness must be greater than this difference.The significant this phenomenon that particularly becomes when thin as thickness when using veneer to measure bonding strength, can be guaranteed relative bonding strength, but when becoming laminated iron core, is pushing the phenomenon that produces strength degradation on the direction of lamination surface open especially.Its result even the bonding strength test of using veneer to carry out is in no problem level, when becoming laminated iron core, also can produce the gap in lamination surface, when serious, generation makes laminated iron core that the problem of decomposing take place because of being subjected to impacting in the operation.
Distinguish in addition: usually the problem of Chan Shenging is, when will have stable on heating bonding film be coated on be coated with common organic-inorganic mixing clasp Y insulation Y film with inorganic be on the electro-magnetic steel plate of insulating coating film the time, usually between insulating coating film and electro-magnetic steel plate, peel off, cause bonding strength to descend.
The technology that is descended as the internal stress that makes Resins, epoxy, up to now openly, pointed out the whole bag of tricks, for example the spy opens clear 62-50361 communique and discloses a kind of technology of using composition epoxy resin, it is characterized in that: exist glass transformation temperature not reach the polymer particles of room temperature in composition system.In order to make bonding the filming can be as the iron core of motor and transformer, bonding filming must have the thermotolerance that can resist the temperature rising that the generation by joule heating causes.The invention that above-mentioned communique is put down in writing is keeping on the stable on heating basis internal stress being descended.
But, it is unusual useful technology that above-mentioned spy opens aspect the effect that the disclosed technology of clear 62-50361 communique descended in the internal stress that makes Resins, epoxy, but not considering to have the two the bonding of characteristic of caking agent and electro-magnetic steel plate insulating coating film films, neither satisfy the technology of all characteristics of bonding film necessary solidity to corrosion and adhesion (blocking) property and so on, so, as bonding many problems of having filmed.
Summary of the invention
The present inventor finds by various experiments: the problem during these thickness of attenuate is, films by coating is bonding that what produce is that so-called internal stress is bigger, finds that these problems can solve by reducing bonding internal stress of filming.
The present inventor has obtained to reducing the necessary knowledge of bonding internal stress of filming, found that a kind of bonding usefulness films, this bonding usefulness is filmed and bonding strength is improved on the direction of the bonding bonding plane of filming when pushing film open, and when not only applying common insulating coating film but also forming bonding filming, can prevent the reduction of bonding strength, thereby finished the present invention.
That is to say that the present invention is with the following main points that constitute.
(1) a kind of flat rolled magnetic steel sheet or strip having its surface coated for bonding, it is to have the electro-magnetic steel plate of insulating coating film that shows cementability by heating and/or pressurization on the surface, it is characterized in that: this is filmed, and to contain by second-order transition temperature (Tg) be 80 ℃ to 150 ℃ Resins, epoxy or epoxy resin modification body, epoxy curing agent and to be dispersed in wherein particle diameter be the mixture that the particle-like polymer of 0.01 μ m to 0.5 μ m constitutes.
(2) according to above-mentioned (1) described flat rolled magnetic steel sheet or strip having its surface coated for bonding, it is characterized in that: the Tg of above-mentioned particle-like polymer is 10 ℃ to 80 ℃.
(3) according to above-mentioned (1) described flat rolled magnetic steel sheet or strip having its surface coated for bonding, it is characterized in that: above-mentioned particle-like polymer is an acrylic resin.
(4) according to above-mentioned (1) described flat rolled magnetic steel sheet or strip having its surface coated for bonding, it is characterized in that:, contain the particle-like polymer of 1～30 weight part with respect to 100 weight part Resins, epoxy.
(5) according to above-mentioned (1) described flat rolled magnetic steel sheet or strip having its surface coated for bonding, it is characterized in that: above-mentioned Resins, epoxy is in advance by being able to modification with acrylic resin generation esterification.
(6) according to each described flat rolled magnetic steel sheet or strip having its surface coated for bonding of above-mentioned (1) to (5), it is characterized in that: be formed with on the surface that organic and inorganic mix insulation is filmed or inorganic be on the electro-magnetic steel plate of insulating coating film, be formed with and comprise Resins, epoxy or epoxy resin modification body, epoxy curing agent and be dispersed in particle-like polymer wherein and have the insulating coating film of cementability.
Description of drawings
Fig. 1 adopts the condition of surface of sem observation fracture bonding plane and the photo that obtains, and the bonding plane that wherein ruptures is at 200 ℃ * 10kgf/cm 2Make under * 30 minutes the heating and pressurizing condition sample panel that stamping-out is processed into 2cm * 3cm shape be able to bonding after, under normal temperature, press off test, reclaim sample separately then and its fracture obtained.Figure 1A is the photo of breaking state of the bonding plane of prior art, and Figure 1B is the photo of the breaking state of bonding plane of the present invention.
Fig. 2 represents is the synoptic diagram of the stripping test method used of one of the measuring method as bonding strength and implements the newly-designed synoptic diagram that presses off test method(s) when of the present invention.The both is the stripping strength assay method that peels by caking agent or the bonding steel plate that fits together of filming, but in the stripping test method, steel plate produces big distortion, so the characteristic by steel plate itself produces very large influence, in contrast, in pressing off test method(s), owing to stackedly fixing many steel plates, the influence of steel plate can be suppressed at bottom line, can carefully estimate the characteristic of adhesive member.
Embodiment
Just implementing concrete scheme of the present invention below describes.
Of the present inventionly film that need to disperse epoxy curing agent and particle diameter in Resins, epoxy or epoxy resin modification body be the specific organic resin particle of 0.01 to 0.5 mu m range.
The Resins, epoxy that uses among so-called the present invention, be that second-order transition temperature (Tg) after solidifying is at 80 ℃ of resins to 150 ℃ of scopes, so long as before the curing reaction at normal temperatures for liquid, be preferably the solid resin and in monomer, on average have 1 or above epoxy group(ing), the restriction that just has nothing special, but suitable epoxy equivalent (weight) is 100～5000.
Specifically, dihydroxyphenyl propane, F, AD type are arranged, phenol lacquer resin type, ortho-cresol lacquer resin type, phenol compound modified version etc., the resin that has aromatic ring structure in the monomer is suitable.
Of the present invention filming not only can be used Resins, epoxy, and can use the modification body of Resins, epoxy.Resins, epoxy is made not special qualification of method of modification body, but on main chain, use specific substituting group, all cpds is combined on the hydroxyl of the epoxy group(ing) of Resins, epoxy end or side chain.Particularly film, because preferably carry out the curing reaction of Resins, epoxy after the resinous principle fusion, so as the modification body, it is suitable making acrylic resin carry out the resulting acrylic modified epoxy resin of esterification in Resins, epoxy as bonding.
As the acrylic resin that uses in above-mentioned epoxy resin modification body, the polymkeric substance that comprises the polymerizable monomer of the vinyl polymer that contains carboxyl is suitable.Specifically, be by being selected from α, 1 kind of monomer among the alkyl ester of β-ethylenic unsaturated carboxylic acid, hydroxyalkyl acrylate and the N-hydroxyalkylamides and have the α of carboxyl, β-ethylenically unsaturated monomers and styrenic vinyl monomer constitute, and can these mixture copolymerization be obtained by use common radical polymerization initiator in organic solvent.
α as the present invention's use, the alkyl ester of β-ethylenic unsaturated carboxylic acid for example has: esters of acrylic acid (methyl acrylate, ethyl propenoate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, the vinylformic acid n-pentyl ester, the just own ester of vinylformic acid, Isooctyl acrylate monomer, the vinylformic acid n-octyl, vinylformic acid methoxyl group ethyl ester, the vinylformic acid ethoxy ethyl ester, the acrylic acid-2-ethyl butyl ester, ethyl acrylate, decyl acrylate etc.), methyl acrylic ester (methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, n-BMA, the methacrylic acid n-pentyl ester, the just own ester of methacrylic acid, lauryl methacrylate(LMA), the methacrylic acid stearyl ester, n octyl methacrylate, methacrylic acid decyl monooctyl ester, methacrylic acid-2-ethylhexyl, decyl-octyl methacrylate etc.).
As α, the hydroxyalkyl acrylate of β-ethylenic unsaturated carboxylic acid, for example have: 2-Hydroxy ethyl acrylate, vinylformic acid hydroxy propyl ester, vinylformic acid 3-hydroxyl butyl ester, vinylformic acid-2, two (methylol) ethyl esters of 2-, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-3-hydroxyl butyl ester, methacrylic acid hydroxyl propyl ester, methacrylic acid-2,3-dihydroxyl propyl ester etc.
As α, the N-hydroxyalkylamides of β-ethylenic unsaturated carboxylic acid for example has the N substituted propenyl class monomer of N hydroxymethyl acrylamide, N-methylol methacrylamide, N-butoxymethyl acrylamide, N-butoxymethyl Methacrylamide etc.
The present invention preferably contains and is selected from above-mentioned α, at least a kind or multiple monomer among β-ethylenic unsaturated carboxylic acid monomer.
Secondly, as the α with carboxyl, β-ethylenically unsaturated monomers for example can list vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid, Ba Dousuan, methylene-succinic acid, citraconic acid, styracin etc.
As the styrenic vinyl monomer, for example can enumerate vinylbenzene, Vinyl toluene, t-butyl styrene etc.
About the above-mentioned manufacture method that contains the vinyl polymer of carboxyl, not special the qualification can be carried out under the following conditions, with respect to whole monomers, the α that will contain carboxyl, β-ethylenically unsaturated monomers are set at 10～60 quality %, are preferably set to 15～30 quality % especially; Copolymerization temperature is 50～150 ℃, is preferably 60～90 ℃ especially.
With the Tg of Resins, epoxy after solidifying or epoxy resin modification body be limited to 80 ℃ to 150 ℃ reason be because: during 80 ℃ of less thaies, the poor heat resistance after bonding, the heating in the time of can not tolerating motor or transformer and drive; And when surpassing 150 ℃, it is really up to the mark to film, and bonding strength descends, when perhaps using as motor or transformer, because of caused degenerations such as vibration are exceedingly carried out.Be preferably 90 ℃～120 ℃ scope especially, more preferably 110 ℃～120 ℃.Disperse particles shaped polymer in the Resins, epoxy in Tg is in this scope makes internal stress be minimized by this.
Secondly, so-called particle-like polymer used in the present invention, operable is particle diameter at 0.01 μ m to 0.5 mu m range and can be with the polymkeric substance of dispersion state stable existence in Resins, epoxy.As the kind of the operable microparticle polymer of the present invention, suitable have acrylic resin, vinyl acetate between to for plastic, polyester, urethane, polyethylene, polypropylene, a polycarbonate etc.
Specifically, as acrylic resin, be with esters of acrylic acid (methyl acrylate, ethyl propenoate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, the vinylformic acid n-pentyl ester, the just own ester of vinylformic acid, Isooctyl acrylate monomer, the vinylformic acid n-octyl, vinylformic acid methoxyl group ethyl ester, the vinylformic acid ethoxy ethyl ester, the acrylic acid-2-ethyl butyl ester, ethyl acrylate, decyl acrylate etc.), methyl acrylic ester (methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, n-BMA, the methacrylic acid n-pentyl ester, the just own ester of methacrylic acid, lauryl methacrylate(LMA), the methacrylic acid stearyl ester, n octyl methacrylate, methacrylic acid decyl monooctyl ester, methacrylic acid-2-ethylhexyl, decyl-octyl methacrylate etc.), vinylformic acid-2-hydroxyl ethyl ester, Propylene glycol monoacrylate, vinylformic acid 3 hydroxy butyl esters, vinylformic acid-2, two (hydroxymethyl) ethyl esters of 2-, 2-hydroxyethyl methacrylate, methacrylic acid-3-hydroxy butyl ester, Rocryl 410, methacrylic acid-2,3-dihydroxyl propyl ester, N hydroxymethyl acrylamide, the N-methylol methacrylamide, N-butoxymethyl acrylamide, N-butoxymethyl Methacrylamide, vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid, Ba Dousuan, methylene-succinic acid, citraconic acid, styracin, vinylbenzene, Vinyl toluene, monomers such as t-butyl styrene are in 1 step, 2 steps or more make it the product of emulsion polymerization in the operation of multistep.
As vinyl acetate between to for plastic, be the multipolymer of vinyl acetate between to for plastic, vinyl acetate between to for plastic and Veova, vinyl acetate-ethylene copolymer etc.
As urethane, what can use is the material that has ammonia ester bond and mainly obtained by chemical reaction by isocyanate compound and polyalcohols or polyethers in monomer, be that toluene is supportted vulcabond, ditane-4, polyalcohols, the polyethers chemical combination of isocyanate compounds such as 4-vulcabond, hexamethylene diisocyanate, trimethyl propane-1-methyl-2-isocyanato--4-carbamate, polymethylene polyphenyl isocyanate, an xylylene vulcabond and polyoxyethylene glycol, polypropylene glycol, polyether triol etc. form.
As polyester, that can use generally obtains the acid of 2-base with 2 yuan of alcohol reactions, specifically, as the acid of 2-base, can use maleic anhydride, fumaric acid, hexanodioic acid, Tetra hydro Phthalic anhydride, m-phthalic acid, as 2 yuan of alcohol, can make spent glycol, propylene glycol, glycol ether, 1,3 butylene glycol, dipropylene glycol, season pentanediol, bis-phenol dihydroxyethyl ether etc.
The particle diameter of particle-like polymer used in the present invention must be in the scope of 0.01 μ m to 0.5 μ m.This be because: during particle diameter less than 0.01 μ m, even when thickness of the present invention is thin, the effect of the bonding strength that can not be improved even particle diameter surpasses 0.5 μ m, also hinders the fusion between the Resins, epoxy, causes bonding strength to descend.
The present inventor finds: in bonding filming, the particle diameter when particle-like polymer disperses is brought into play more important role, uses the very microparticle polymer of narrow range that is in of 0.01 μ m to 0.5 μ m, and can satisfy the bonding desired various characteristics of filming.
As its reason, because bonding thickness of filming is extremely thin, even be the thick tens μ m only of a few μ m, so for particulate is evenly dispersed in the Resins, epoxy, so its size limited, for example, when adding the also big particulate of particle diameter ratio thickness, because coating the only fine-grained zone of constituent occurs when dry, thereby can not form " island-Hai structure ", can not get effect of the present invention so can infer.Therefore, the particle diameter that can obtain the microparticle polymer of effect is limited in the very narrow scope, the result that the present inventor studies, preferably 0.05 μ m or more than, further preferably 0.1 μ m or more than, particularly preferably be in the scope that is in 0.2 μ m to 0.4 μ m.
The particle-like polymer that uses among the present invention, its second-order transition temperature is suitable is 10 ℃ to 80 ℃ scope.Under the situation of 10 ℃ of second-order transition temperature less thaies, add man-hour in the joint-cutting operation with stamping-out, have the tendency of damage easily of filming, and surpassing under 80 ℃ the situation, probably filming albefaction occurs.Second-order transition temperature more suitably, its lower limit be 25 ℃ or above, 35 ℃ or above, 45 ℃ or above so that be 55 ℃ or more than, in addition, its upper limit be 70 ℃ or following, 65 ℃ or following.
About in Resins, epoxy, making particle-like polymer dispersive method of the present invention, not what special qualification, can mechanically mix each resin, perhaps make emulsion respectively and mix later on, perhaps also can in acrylic modified epoxy resin solution, acrylic resin be made particle-like polymer by means of emulsion polymerization.
As the form of particle-like polymer, be preferably spherically usually, but also can be hollow type and special-shaped or inner different so-called mixed type such as egg shape with the composition of outside.In addition, according to the intermiscibility of Resins, epoxy, can not present clear and definite outward appearance sometimes yet.Apply the possibility of excessive pressure if consider the part man-hour that adds carrying out joint-cutting etc., and then the interface adhesivity of Resins, epoxy and particle-like polymer is high more, and processibility is good more, so also harmless even do not present clear and definite outward appearance.
As the addition of particle-like polymer, with respect to 100 parts by weight of epoxy resin, 1～30 weight part is suitable.During less than 1 weight part, effect of the present invention can not occur, when surpassing 30 weight parts, aggegation and precipitation take place easily between the particle-like polymer, thereby aspect processing, produce obstacle.
So-called epoxy curing agent used in the present invention is the material that can make epoxy resin cure, generally begins curing reaction by being heated to preset temperature.Specifically, can list acid anhydride type curing agent (Tetra hydro Phthalic anhydride, hexahydro phthalic anhydride, tetrahydronaphthalic anhydride, pyromellitic acid dianhydride, 1,2,4,5-pyromellitic anhydride etc.), fatty amine (diethylenetriamine, Triethylenetetramine (TETA), polymeric amide, 2-ethyl-4-methylimidazole etc.), mphenylenediamine, Dyhard RU 100, organic acid dihydrazide, aminimide, ketoimine, tertiary ammonium salt, the boron trifluoride amine salt, polyamide fibre, melamine resin, resol, xylene resin, NBR, polysulphide, aniline resin, blocked isocyanate, acrylic resin etc.Characteristic shows to such an extent that good especially material is melamine resin, soluble phenolic resin type resol, blocked isocyanate, acrylic resin etc.
The weight ratio of epoxy curing agent is with respect to carrying out resultant 100 weight parts of esterification, preferred 1～30 weight part with Resins, epoxy.During epoxy curing agent less than 1 weight part, the thermotolerance of filming after bonding has the tendency of degeneration, when surpassing 30 weight parts, is coated with dry after fixing agent and has tendency concentrated, albefaction nearby in film coated surface.
In addition, as the amount of filming, be preferably 1～6g/m 2, be preferably 1～3g/m especially 2Not enough 1g/m 2The time, bonding strength has the tendency of decline, surpasses 6g/m 2The time, the tendency of stacking factor variation is arranged.
Secondly, form on electro-magnetic steel plate that the baking condition of setting when filming is not special to be limited, be set in 150～800 ℃ the drying oven, preferably the plate temperature is set at 100～300 ℃ and carries out short baking current.
It is contemplated that mechanism of the present invention is the reduction of internal stress, but details is not still understood, open in the disclosed technology of clear 62-50361 communique above-mentioned spy, subambient second-order transition temperature is effective, but in bonding filming, the second-order transition temperature of particle-like polymer it would be better to that 10 ℃ to 80 ℃ scope is good, moreover it is still indeterminate that the particle diameter of particle-like polymer greatly influences the detailed reason of bonding strength.But, under bonding situation of filming, compare with organic resin, thermal expansivity is very little, the surface of steel plate big in rigidity used with the form that forms extremely thin epoxy resin layer, the internal stress of the organic resin that what is called is general reduces mechanism, can be estimated as different reasons and play a role.
Fig. 1 adopts the adhesive portion section of sem observation sample and the photo that obtains, and wherein sample (No.2) is at 200 ℃ * 10kgf/cm 2Carry out bonding forming with bonding with the surface electrical magnetic steel plate under * 30 minutes the condition, described bonding with surface electrical magnetic steel plate coating based on resin combination of the present invention and toast and obtain, and sample (No.1) carries out bonding obtaining with the sample based on the prior art example.In the sample Figure 1A based on the prior art example, breaking portion is even surface as can be seen, and the propagation of be full of cracks takes place rapidly.
In contrast, in based on sample Figure 1B of the present invention, produce small concavo-convexly in breaking portion, the propagation path of be full of cracks is together entangled to each other.
Can infer from these observationss: under situation based on resin combination of the present invention, the acrylic resin particulate is dispersed in and forms so-called " island-Hai structure " in the Resins, epoxy external phase, postponed the propagation of be full of cracks by this, thereby bonding strength is improved.
Moreover the bonding strength of implementing among shear bond strength and the present invention that presses off test shows different movements.That is to say, in shear strength test,, there is not the effect of power in vertical direction with respect to the bonding plane of steel plate, in contrast, in pressing off test, with respect to bonding plane, at the strong action component of vertical direction, certainly, variation has taken place in the bonding movement of peeling off of filming, but considers the electromagnetic force on the laminated iron cores such as motor that act in the reality, it is contemplated that: press off test and reflected the necessary intensity of actual laminated iron core more accurately.
Usually, as the strength detection method that presses off direction, generally be the stripping strength assay method.But, the result that the present inventor studies, crooked because sample produces when using electro-magnetic steel plate to measure stripping strength, be difficult to make between the bonding sample and peel off swimmingly, fluctuation becomes very big, causes measuring difficulty.
In addition, in the modulation stripping strength is measured with the steel-sheet method, having different condition of surface because add the electro-magnetic steel plate of various composition of steel, so, probably will show and the actual different movement of laminated iron core.
So the present inventor finds: as the strength detection method that presses off direction, fill in chock in stacked bonding iron core sample, can measure the bonding strength that presses off direction by this.Open the measuring method of the bonding strength in the clear 62-50361 communique as above-mentioned spy, use stripping test method (ASTM D1876), the present invention has initiated electro-magnetic steel plate with pushing test method open, and compares with the prior art example.Fig. 2 represents as the test method(s) of measuring among the stripping test method of previous method and the present invention that presses off.
Embodiment
The coil of the non-oriented electromagnetic steel sheet having (thickness of slab 0.5mm, silicon amount 0.5%) after the annealing that will handle with known method, smart is not coated with common insulating coating film and tries material with its original state as confession.Then particle-like polymer shown in the epoxy resin latex shown in the mixture table 1 and epoxy curing agent and the table 2 is in turn produced the treatment solution shown in the table 3.After adopting the apparatus for coating separate application treatment solution of rubber rollers mode, under 160 ℃ plate temperature, carry out baking processing, so that make the glue spread of filming reach record amount in the table.
Cut sample from this coil, estimate the various characteristics of filming.Its result is as shown in table 4.As supplying the examination material, it is 1g/m that the magnesium chromate that this coil is coated with on common electro-magnetic steel plate, crylic acid resin organic-inorganic mix the glue spread of filming to a kind of situation with the coil of following coating baking down 2, its result is as shown in table 5.In addition,, for example need to change conversion formula according to the different situation of the few situation of glue spread many situation, glue spread and steel surface roughness etc. for glue spread is converted into thickness, but when adopting the present invention to be coated with, 1g/m 2Shi Dayue is 0.6 μ m～1 μ m.
About in the bonding strength of pushing open on the direction of bonding plane,, fix with unit clamp behind stacked 40 such samples, at 200 ℃ * 10kgf/cm from being coated with the sample that the coil that toasts each solution cuts 2cm * 3cm size with predetermined amount 2Produce bonding laminated iron core under * 30 minutes the heating and pressurizing condition, after this clamp-on wedge type and press son, the load when measuring the laminated iron core separation at the central part of lamination surface.
Table 1
The solution title Resins, epoxy Epoxy curing agent Second-order transition temperature (℃)
Epoxy 1 BPA AR 85
Epoxy 2 Acrylic acid modified BPA PR 110
Epoxy 3 Acrylic acid modified BPA - * 125
Epoxy 4 NR PR 150
Epoxy 5 BPA AR 30
Epoxy 6 BPA AR 55
Epoxy 7 NR AR 165
*: for epoxy 3, because acrylic resin modifiedly play a role, so do not add solidifying agent as solidifying agent.
Table 2
The solution title Resin is formed Particle diameter (μ m) Second-order transition temperature (℃)
Particulate 1 EA+PVA+BA 0.2 10
Particulate 2 MMA+St+BA+HPMA 0.4 80
Particulate 3 MMA+EA+St 0.35 60
Particulate 4 PVA+PU 0.1 75
Particulate 5 PVA+EA+MA 0.3 40
Particulate 6 PU+PVA+EHMA 0.008 45
Particulate 7 PVA+PU 0.8 87
Particulate 8 PVA+MMA 0.23 -15
Particulate 9 St+MMA 0.15 130
*: the explanation of the shortenings in the table 1,2
BPA: bisphenol type epoxy
NR: lacquer resins type epoxy
PR: the solvable type phenolic resin type of phenol solidifying agent
AR: amino resin curing agents
EA: ethyl propenoate
MMA: methyl methacrylate
St: vinylbenzene
BA: butyl acrylate
PVA: vinyl acetate between to for plastic
PA: polyethylene
PU: urethane
HPMA: Rocryl 410
MA: vinylformic acid
EHMA: methacrylic acid-2-ethylhexyl
*: the part in the table is converted with the resin solid composition, is weight part
Table 3
The solution title Resins, epoxy (100 weight part) Particle-like polymer Remarks
Treatment solution 1 Epoxy 2 Particulate 1 10 weight parts The present invention
Treatment solution 2 Epoxy 2 Particulate 15 weight parts The present invention
Treatment solution 3 Epoxy 2 Particulate 2 20 weight parts The present invention
Treatment solution 4 Epoxy 1 Particulate 18 weight parts The present invention
Treatment solution 5 Epoxy 1 Particulate 2 10 weight parts The present invention
Treatment solution 6 Epoxy 1 Particulate 3 10 weight parts The present invention
Treatment solution 7 Epoxy 2 Particulate 35 weight parts The present invention
Treatment solution 8 Epoxy 4 Particulate 45 weight parts The present invention
Treatment solution 9 Epoxy 4 Particulate 17 weight parts The present invention
Treatment solution 10 Epoxy 3 Particulate 35 weight parts The present invention
Treatment solution 11 Epoxy 2 Particulate 6 30 weight parts The super scope of particulate small particle size
Treatment solution 12 Epoxy 1 Particulate 3 0.5 weight parts The super scope of particulate addition
Treatment solution 13 Epoxy 1 Particulate 1 50 weight parts The super scope of particulate addition
Treatment solution 14 Epoxy 3 Particulate 7 15 weight parts The super scope of the big particle diameter of particulate
Treatment solution 15 Epoxy 2 Particulate 88 weight parts The super scope of particulate Tg point
Treatment solution 16 Epoxy 3 Particulate 9 20 weight parts The super scope of particulate Tg point
Treatment solution 17 Epoxy 5 Particulate 3 15 weight parts The super scope of epoxy Tg point
Treatment solution 18 Epoxy 6 Particulate 5 20 weight parts The super scope of epoxy Tg point
Treatment solution 19 Epoxy 7 Particulate 3 10 weight parts The super scope of epoxy Tg point
Treatment solution 20 Epoxy 2 Do not add particulate Do not add particulate (prior art)
Table 4
Treatment solution Glue spread (g/m 2) Bonding strength (kgf/cm 2) Press off (kgf) c Adhesion d
During normal temperature a During high temperature b
Embodiment 1 Treatment solution 1 2.0 160 75 866 ○
Embodiment 2 Treatment solution 2 2.2 155 50 671 ○
Embodiment 3 Treatment solution 3 2.8 154 82 755 ◎
Embodiment 4 Treatment solution 4 1.9 142 55 748 ○
Embodiment 5 Treatment solution 5 2.3 134 80 841 ◎
Embodiment 6 Treatment solution 6 2.1 147 49 633 ○
Embodiment 7 Treatment solution 7 2.7 144 57 533 ◎
Embodiment 8 Treatment solution 8 2.4 152 63 583 ○
Embodiment 9 Treatment solution 9 1.6 154 69 775 ○
Embodiment 10 Treatment solution 10 1.5 108 52 480 ◎
Reference examples 1 Treatment solution 11 2.1 136 49 124 ○
Reference examples 2 Treatment solution 12 2.9 141 41 231 ○
Reference examples 3 Treatment solution 13 3.4 131 38 614 ×
Reference examples 4 Treatment solution 14 1.9 87 23 364 ◎
Reference examples 5 Treatment solution 15 3.1 143 10 450 △
Reference examples 6 Treatment solution 16 1.9 128 52 264 ○
Reference examples 7 Treatment solution 17 3.1 163 16 735 ×
Reference examples 8 Treatment solution 18 1.8 133 26 636 △
Reference examples 9 Treatment solution 19 2.1 96 86 112 ◎
Prior art example 1 Treatment solution 20 1.6 147 58 214 ◎
(notes) a: at pressure is 10kg/cm 2, temperature is that crimping was measured shear bond power at normal temperature after 60 seconds under 200 ℃ the condition.
B: after bonding under the condition of above-mentioned a, measure bonding strength down in the state that is heated to 150 ℃.
C: stacked 40 samples that cut into 2cm * 3cm, with 200 ℃ * 10kgf/cm 2After * 30 minutes condition is bonding, fill in chock (7 ° of drill point angles), measure the maximum load of this moment at the central part of lamination surface.
D: at normal temperature, with 20kg/cm 2Exert pressure after 72 hours, estimate bonding degree.Bonding fully be not designated as ◎, bonding slightly be designated as zero, bonding but with hand peel off do not need power be designated as △, more than zero for qualified.
Table 5
Treatment solution Glue spread (g/m 2) Bonding strength (kgf/cm 2) Press off (kgf) c Adhesion d
During normal temperature a During high temperature b
Embodiment 1 Treatment solution 1 1.4 113 36 461 ◎
Embodiment 2 Treatment solution 2 1.3 102 44 270 ◎
Embodiment 3 Treatment solution 3 1.5 104 31 344 ◎
Embodiment 4 Treatment solution 4 1.6 127 33 416 ○
Embodiment 5 Treatment solution 5 1.4 98 41 462 ○
Embodiment 6 Treatment solution 6 1.3 119 40 311 ◎
Embodiment 7 Treatment solution 7 1.3 112 38 217 ◎
Embodiment 8 Treatment solution 8 1.6 102 31 238 ◎
Embodiment 9 Treatment solution 9 1.1 137 43 357 ◎
Embodiment 10 Treatment solution 10 1.3 121 38 360 ○
Reference examples 1 Treatment solution 11 1.7 81 43 98 ◎
Reference examples 2 Treatment solution 12 1.6 73 38 125 ○
Reference examples 3 Treatment solution 13 1.5 67 29 166 △
Reference examples 4 Treatment solution 14 1.4 88 31 155 ○
Reference examples 5 Treatment solution 15 1.2 104 13 162 △
Reference examples 6 Treatment solution 16 1.1 101 34 132 ○
Reference examples 7 Treatment solution 17 1.3 105 10 241 △
Reference examples 8 Treatment solution 18 1.5 89 23 155 △
Reference examples 9 Treatment solution 19 1.6 34 39 93 ◎
Prior art example 1 Treatment solution 20 1.4 87 31 134 ◎
According to the present invention, by using by second-order transition temperature (Tg) is the mixture that particle-like polymer that 80 ℃ to 150 ℃ Resins, epoxy or epoxy resin modification body, epoxy curing agent and particle diameter are 0.01 to 0.5 μ m disperses to form, even scumbling also can reduce the reduction of bonding strength, also can fully guarantee in the bonding strength of pushing open on the direction of bonding plane, and then can reduce the reduction of the bonding strength when on common insulating coating film, being coated with.

Claims (6)

1. flat rolled magnetic steel sheet or strip having its surface coated for bonding, its surface at electro-magnetic steel plate has by heating and/or pressurization and shows the insulating coating film of cementability, and this electro-magnetic steel plate is characterised in that: describedly film that to contain by second-order transition temperature Tg be 80 ℃ to 150 ℃ Resins, epoxy or epoxy resin modification body, epoxy curing agent and to be dispersed in wherein particle diameter be the mixture that the particle-like polymer of 0.01 μ m to 0.5 μ m constitutes.
2. flat rolled magnetic steel sheet or strip having its surface coated for bonding according to claim 1 is characterized in that: the Tg of described particle-like polymer is 10 ℃ to 80 ℃.
3. flat rolled magnetic steel sheet or strip having its surface coated for bonding according to claim 1 is characterized in that: described particle-like polymer is an acrylic resin.
4. flat rolled magnetic steel sheet or strip having its surface coated for bonding according to claim 1 is characterized in that: with respect to 100 weight part Resins, epoxy, contain the particle-like polymer of 1～30 weight part.
5. flat rolled magnetic steel sheet or strip having its surface coated for bonding according to claim 1 is characterized in that: described Resins, epoxy is in advance by being able to modification with acrylic resin generation esterification.
6. according to each described flat rolled magnetic steel sheet or strip having its surface coated for bonding of claim 1 to 5, it is characterized in that: be formed with on the surface that organic and inorganic mix insulation is filmed or inorganic be on the electro-magnetic steel plate of insulating coating film, be formed with and comprise Resins, epoxy or epoxy resin modification body, epoxy curing agent and be dispersed in particle-like polymer wherein and have the insulating coating film of cementability.
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