Technical field
[0001]
　The present invention, an electromagnetic steel sheet, and to a method for producing a magnetic steel sheet.
Background technique
[0002]
　Generally, when manufacturing the electrical equipment such as motors and transformers using magnetic steel sheet, first, punching the hoop shaped electromagnetic steel plate into a predetermined shape, after laminating electromagnetic steel sheets punched out, fixed, iron to produce the core. After winding the copper wire and the like to the teeth of the iron core, an iron core is impregnated with a varnish, an iron core by spraying such a powder coating, baking and drying is performed. Further, after drying the iron core to for copper connection terminals of the mounting and flange and the bearing, such as motors and transformers by fixing the case it is manufactured.
[0003]
　Here, the surface of the electrical steel sheet, to prevent current from flowing between the laminated steel sheets, in order to improve the magnetic properties by reducing the iron loss, the insulating coating is applied.
[0004]
　Insulating coatings applied to the surface of the electrical steel sheet, the insulating resistance is required, whereas in order to improve the workability in processing the electromagnetic steel sheets, weldability, slipperiness, adhesiveness, heat resistance and coating properties other than insulation property, such as coating properties are also required.
[0005]
　As the insulating coating of such an electromagnetic steel sheet, for example, those based on organic resins, those based on inorganic salts such as chromate or phosphate, and an inorganic acid salt and an organic resin mixtures such as are known as the main component.
[0006]
　In general, those based on the organic resin has a low heat resistance, which the inorganic acid salt as a main component, since it is easy to peel off from the steel sheet during processing, conventionally, the main mixture with an inorganic acid salt and an organic resin that the components were often used as an insulating film.
[0007]
　For example, as a technique relating to insulation coating of electrical steel sheet, old, in JP-B-50-15013, and dichromate, vinyl acetate - acrylic resin copolymer, butadiene - styrene copolymer, or an acrylic resin an organic resin emulsion using the processing solution mainly composed to form an insulating coating techniques such as are disclosed.
[0008]
　Further, JP-A-2002-317276, JP-own the nonionic or anionic surface active agent having a predetermined HLB (Hydrophile-Lipophile Balance) value in the insulating coating solution containing phosphate and chromate quantified compounding discloses a technique regarding an insulating film agent having improved wettability.
[0009]
　In recent years, the increasing awareness of environmental issues, development of a technique for forming an insulating film without using a chromic acid aqueous solution containing hexavalent chromium has been promoted. Such techniques, for example, in JP-A-06-330338 discloses a phosphate having a specific composition, and any one or more of the boric acid and colloidal silica, and emulsion of the organic resin having a specific particle size was blended in a specific ratio, technology baking the steel sheet is disclosed. According to this technique, while using a processing solution containing no chromium compound, it has the same film properties and conventional insulating film containing a chromium compound, and maintains excellent slip properties even after strain relief annealing be able to.
[0010]
　Also, development has been advanced with regard influence on the workability of the electrical steel sheet by an insulating film which does not contain such chromic acid. Electromagnetic example, in JP-A-11-80971 discloses a metal phosphate and an organic resin as a main component, carbon 1s peak and phosphorus 2s peak measured by photoelectron spectroscopy is a processing solution so as to have a certain strength by baking it was applied to a steel sheet, a technique for improving the punching of the electrical steel sheet is disclosed. Furthermore, in JP-A 11-80971 and JP-processing solution mainly composed of a metal phosphate and an organic resin, by boiling or sublimation point is to identify the amount of water-soluble organic compound above 100 ° C., the electromagnetic It discloses that it is possible to further improve the punching property of the steel sheet.
[0011]
　Further, in JP 2002-47576, a first phosphate specific metal ion, an insulating film treatment solution of the electromagnetic steel sheet containing a specific ratio of the phosphonic acid compounds, and, the insulating film treatment solution for technical an electromagnetic steel sheet processing method using are disclosed.
[0012]
　Furthermore, in JP 2008-31245, impart good anti-rust properties to various steel sheets, and are readily removed by alkali degreasing solution, lubricants which can be used as a metal processing oil technology related compositions are disclosed.
[0013]
　Further, in JP 2010-261063, a first phosphate multivalent metal, a chelating agent, a polyamine and, a technique is disclosed an insulated film-forming treatment liquid electrical steel sheet containing a synthetic resin there.
CITATION
Patent Literature
[0014]
Patent Document 1: JP-B 50-15013 Patent Publication
Patent Document 2: JP 2002-317276 Patent Publication
Patent Document 3: JP-A 06-330338 JP
Patent Document 4: JP-A 11-80971 discloses
Patent Document 5: JP 2002-47576 JP
Patent Document 6: JP 2008-31245 JP
Patent Document 7: JP 2010-261063 JP
Summary of the Invention
Problems that the Invention is to Solve
[0015]
　On the other hand, in recent years, with advancements in industrialization in China and Southeast Asia, factories that manufacture such as motor and transformer are constructed many. Therefore, in such areas, although the amount of the electrical steel sheet is greatly increased, the region is relatively high, and, because the humidity is high, rust electromagnetic steel sheet is an issue .
[0016]
　Specifically, when processing electromagnetic steel plates, laminated electromagnetic steel sheet after stamping to produce an iron core, after fixing the iron cores such as varnish, it has been windings and painting. Here, the end surface of the electromagnetic steel sheets punched out, since the base steel part is exposed, which become very easy to rust.
[0017]
　However, if the punching electromagnetic steel plates, since the punching oil is used in processing, the end surface of the electromagnetic steel sheets punched punching oil adheres. Therefore, usually, the end faces of the magnetic steel sheets are rust by punching oil, it is not immediately rust occurs on the end surface after the punching.
[0018]
　However, from such a difference of step processing capacity of the punching step and the next step, after the stamping process, there are cases where electromagnetic steel sheets punched out is stored over time. Also, depending on the motor and transformers, electrical steel sheets punched, not only the plant, it may be transported between the factory.
[0019]
　Even in such a case, it is necessary that the rust is not generated in the end face portion of the laminated iron core. Therefore, the magnetic steel sheet, not only the corrosion resistance of the steel sheet surface, is also required improvement of the so-called end face corrosion resistance.
[0020]
　Here, the above-mentioned Japanese Patent Publication 50-15013 and JP-2002-317276 Patent insulating film disclosed in Japanese in order to contain a chromium compound, there is a problem in use from the viewpoint of environmental issues. Also, use the above JP-A-06-330338, JP-A No. 11-80971, JP 2002-47576 discloses the technique disclosed in JP-A-2008-31245 and JP 2010-261063 there electromagnetic steel sheet, there is a problem that is not good end face rust resistance after punching.
[0021]
　The present invention has been made in view of the above problems, it is an object of the present invention, even when containing no chromium compound, in addition to insulation, adhesion, corrosion resistance, appearance and end rust resistance after punching is to provide an electromagnetic steel sheet with good insulating coating.
Means for Solving the Problems
[0022]
　Gist of the present invention are the following (1) to (6).
[0023]
　(1) 100 parts by weight of phosphoric acid metal salts, and a binder composed of an organic resin 1 to 50 parts by weight of the average particle size of 0.05 ~ 0.50 .mu.m,
　the content to the solid content 100 parts by mass of the binder but a carboxylic acid compound having 2 to 50 carbon atoms is 0.1 to 10.0 parts by mass
　comprises,
　the organic resin is at least one selected from acrylic resins, epoxy resins and polyester resins,
　an insulating film on the surface of the steel sheet, an electromagnetic steel sheet.
[0024]
　(2) said insulating film contains a polyhydric alcohol of from 0.5 to 10 parts by mass with respect to 100 parts by mass of the solid content of the binder, electrical steel sheet according to (1).
[0025]
　(3) The carboxylic acid compound is an electromagnetic steel sheet according to the number of carbon atoms having a linear or branched alkyl or alkenyl group having 4 to 20 wherein (1) or (2).
[0026]
　(4) and 100 parts by weight of metal phosphate, average particle size was mixed with 1 to 50 parts by weight of the emulsion of the organic resin of 0.05 ~ 0.50 .mu.m in the resin solids, comprising the steps of: preparing a binder solution ,
　the binder solution, the steps of the carboxylic acid compound having 2 to 50 carbon atoms, which mixed 0.1-10.0 parts by mass with respect to 100 parts by mass of the solid content of the binder solution to prepare a treatment solution,
　the treatment liquid is applied to the surface of the electrical steel sheet, comprising the steps of baking and drying,
　wherein the
　said organic resin is at least one selected from acrylic resins, epoxy resins and polyester resins,
　method for manufacturing the electrical steel sheet.
[0027]
　(5) In the step of preparing said processing liquid, wherein the binder solution, a polyhydric alcohol, mixed 0.5 to 10 parts by weight with respect to 100 parts by mass of the solid content of the binder solution, the (4) method for producing a magnetic steel sheet according to.
[0028]
　(6) the carboxylic acid compound has a carbon number having a linear or branched alkyl or alkenyl group having 4 to 20 manufacturing method of an electromagnetic steel sheet according to (4) or (5).
Effect of the invention
[0029]
　As described above, in the present invention, a metal phosphate, an organic resin having a specific average particle diameter, the insulation coating comprising a carboxylic acid compound having 2 to 50 carbon atoms in a specific ratio to the surface of the electrical steel sheet It is formed. Accordingly, the present invention has a good end face rust prevention at the time of the punching laminated, and adhesion, in which corrosion resistance and appearance to provide an electromagnetic steel sheet with good insulating coating.
DESCRIPTION OF THE INVENTION
[0030]
　It will be described in detail preferred embodiments of the present invention.
[0031]
　The present invention, an electromagnetic steel sheet, and to a method for manufacturing electrical steel sheet. Specifically, the present invention provides an electromagnetic steel sheet used as an iron core material, such as electrical equipment, and relates to a manufacturing method of the magnetic steel sheets, in particular, it has good end face rust resistance and containing chromic acid electrical steel sheet having an insulating film which is not, and to a method for manufacturing the electrical steel sheet.
[0032]
　Electromagnetic steel sheet according to the present invention is an electromagnetic steel sheet insulating coating formed on the surface. The insulating coating 100 parts by weight of phosphoric acid metal salts, and a binder composed of an organic resin 1 to 50 parts by weight of the average particle size of 0.05 ~ 0.50 .mu.m, solid content 100 parts by mass of the binder content relative parts are mixed with a carboxylic acid compound having 2 to 50 carbon atoms is 0.1 to 10.0 parts by mass, is distributed film.
[0033]
　First, a description will be given electrical steel sheet insulating coating is formed in this embodiment.
[0034]
　In this embodiment, the electromagnetic steel sheet insulating coating is formed, by mass% Si: 0.1% or more, Al: 0.05% or more, Mn: contains at least 0.01% or more, the balance the non-oriented electrical steel sheet is Fe and impurities can be preferably used. Si, Al and Mn, with increasing content increases the electrical resistance of the electromagnetic steel sheets, improves the magnetic properties, whereas decreasing the workability. Therefore, the content of Si is less than 4.0 wt%, the content of Al is less than 3.0 wt%, the content of Mn is preferably less than 2.0 wt%. The content of any additive elements such as other S, N and C is preferably respectively less than 100 ppm, more preferably less than 20 ppm.
[0035]
　In the present embodiment, for example, a slab having the above steel ingredients were heated to 1150 ~ 1250 ° C., heat rolled in wound into a coil, the temperature range of 1050 ° C. from 800 ° C. in the form of hot-rolled sheet if necessary in after annealing, cold rolled to about 0.15 ~ 0.5 mm, can be further used as an electromagnetic steel sheet which was annealed at 750 ~ 1100 ° C..
[0036]
　The surface of the electrical steel sheet insulating film is formed, before the treatment liquid to be described later is applied, it may be any pre-treatment is performed, for example, such as by degreasing alkali or hydrochloric acid, or sulfuric acid such as pickling treatment with phosphoric acid may be subjected. The surface of the electrical steel sheet before the treatment liquid to be described later is applied is not such pretreatment is performed may be the surface remains after finish annealing.
[0037]
　Further, in this embodiment, the electrical steel sheet insulating coating is formed, it is preferable that the surface roughness (Ra) is 1.0μm or less, more preferably 0.1μm or 0.5μm below. In the case where the Ra less than 0.1 [mu] m, tend to be costly in cold rolling step, if the Ra exceeds 1.0 .mu.m, undesirable because the space factor is lowered. The surface roughness of the magnetic steel (Ra) is the can be measured according to JIS method (JIS B0601).
[0038]
　Will now be described insulation coating in the present embodiment is formed on the surface of the electrical steel sheet.
[0039]
　In this embodiment, the metal phosphate contained in the insulating coating is a solid when dried with an aqueous solution composed mainly of phosphoric acid and metal ions, and functions as a binder in the insulating film . The type of phosphoric acid contained in the phosphoric acid metal salt, is not particularly limited, orthophosphoric acid, metaphosphoric acid, and polyphosphoric acid is preferred. The type of metal ions contained in the phosphoric acid metal salt, is not particularly limited, Al, Mg, Ca, Co, Li, Mn, Ni, Sr, Ti, and Zn etc. are preferred, in particular, Al , Mg, and Zn is more preferable. When preparing a solution of phosphoric acid metal salts, for example, phosphoric acids such as orthophosphoric acid, oxides of the metal ions is preferably prepared by mixing the carbonate or hydroxide.
[0040]
　Further, phosphoric acid metal salts may be used alone or may be used by mixing two or more kinds. It is also possible to use only phosphoric acid metal salts, such as phosphoric acid or boric acid may be further added.
[0041]
　In this embodiment, the organic resin contained in the insulating film functions as a binder in the insulating coating. The organic resin is at least one selected from acrylic resins, epoxy resins and polyester resins. These organic resins generally are commercially available and can be easily obtained. Further, it is possible to obtain the same for each resin emulsion.
[0042]
　The acrylic resin, methyl acrylate, ethyl acrylate, n- butyl acrylate, i- butyl acrylate, n- octyl acrylate, i- octyl acrylate, 2-ethylhexyl acrylate, n- nonyl acrylate, n- decyl acrylate or,, n- use dodecyl acrylate as a monomer, further acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, monomers having a functional group such as crotonic acid or itaconic acid, or 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-Hiro Doxil butyl (meth) acrylate, those obtained by copolymerizing a monomer having a hydroxyl group such as 2-hydroxylethyl (meth) allyl ether and more It can be used to apply.
[0043]
　As the epoxy resin, for example, it can be used those obtained by reacting a carboxylic anhydride to the amine-modified epoxy resin. Specifically, bisphenol A- diglycidyl ether, caprolactone ring-opening adduct of bisphenol A- diglycidyl ether, bisphenol F- diglycidyl ether, bisphenol S- diglycidyl ether, novolac glycidyl ethers, and the like dimer acid glycidyl ether the epoxy resin, isopropanolamine, monopropanolamine, mono-butanol, monoethanolamine, diethylenetriamine, ethylenediamine, Butaruamin, propylamine, isophoronediamine, tetrahydrofurfurylamine, xylenediamine, hexylamine, nonylamine, triethylenetetramine, tetramethylene pentamine, and denatured by the action of an amine such as diaminodiphenyl sulfone, no Succinic acid, itaconic anhydride, maleic anhydride, citraconic anhydride, phthalic anhydride, and can be suitably used those obtained by reacting a carboxylic anhydride such as trimellitic anhydride.
[0044]
　The polyester resin, for example, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, succinic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, and citraconic acid and dicarboxylic acids such as, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl, 1,6-hexanediol, triethylene glycol, dipropylene glycol, and can be suitably used a polyester resin and a glycol are reacted, such as polyethylene glycol. Further, the polyester resin described above, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, or the like methacrylic anhydride may be used those obtained by graft polymerization.
[0045]
　Each organic resin described above may be an emulsion, or may be a water-soluble resin. When the organic resin is an emulsion, the organic resin may be a one or a mixture of two or more of the organic resin described above. Further, when the organic resin is an emulsion, the average particle size of the organic resin is preferably 0.05 ~ 0.50 .mu.m. When the average particle size of the organic resin is less than 0.05 .mu.m, an organic resin tends to aggregate in the processing liquid, the uniformity of the insulating coating is reduced. Further, when the average particle diameter of the organic resin is 0.50μm greater, stability of the solution is lowered. Further, the average particle size of the organic resin in the case where the organic resin is an emulsion is preferably 0.10μm or more, and preferably not more than 0.30 .mu.m.
[0046]
　Incidentally, the average particle diameter of the organic resin, a number average diameter in the case of approximating the primary particles of organic resin and spherical (i.e., number average particle diameter of primary particles of the organic resin), for example, a laser it can be determined by the diffraction and scattering method (a method in accordance with JIS Z8825-1).
[0047]
　Mixing ratio of the phosphoric acid metal salt and an organic resin, relative to 100 parts by weight of phosphoric acid metal salts, the total of the organic resin is 1 to 50 parts by weight. When the mixing ratio of the organic resin is less than 1 part by mass, because of excessively low concentration of the organic resin, easy aggregation occurs, resulting in stability of the coating solution is lowered. On the other hand, when the mixing ratio of the organic resin is 50 parts by mass, the heat resistance of the formed insulating film is not appropriate to decrease.
[0048]
　Incidentally, phosphoric acid metal salt and an organic resin, and functions as a binder of the insulating coating. The film thickness of the insulating coating is preferably about 0.3 ~ 5.0 .mu.m, more preferably 0.5 ~ 2.0 .mu.m.
[0049]
　Here, in this embodiment, contained in the insulating film, a carboxylic acid compound having 2 to 50 carbon atoms is used as antirust components, it is contained in the binder. The above-mentioned carboxylic acid compounds, carboxylic acid compounds having at least one carboxy group, the carboxylic acid compound and a carboxylic acid salt compound is a salt of a metal, or, that a mixture of a carboxylic acid compound and a carboxylic acid salt compound the say. These components, upon punching electromagnetic steel plates, for easy dissolution in punching oil, it is possible to improve the rust prevention of punching oil adhering to the end surface of the electromagnetic steel sheets punched out. Therefore, according to the present invention, it is possible to improve the end face rust resistance after punching electromagnetic steel plates.
[0050]
　The carboxylic acid compound having 2 to 50 carbon atoms, the monocarboxylic acid, lauric acid, linear fatty acids such as stearic acid, and unsaturated carboxylic acids, and aromatic carboxylic acid derivatives such as benzoic acid can be mentioned having a naphthene nucleus It is. Further, the dicarboxylic acid, succinic acid, alkyl succinic acids, alkyl succinic acid half ester, alkenyl succinic acids, alkenyl succinic acid half ester, succinic acid derivatives, such as succinic acid imide, hydroxy fatty acids, mercapto fatty acid, sarcosine derivatives, such as phthalic acid aromatic carboxylic acid derivatives, and, like oxidized wax, including wax or petrolatum oxides.
[0051]
　The carboxylate compounds having 2 to 50 carbon atoms, and salts with the above-mentioned carboxylic acid compound and a metal. As the aforementioned metal, cobalt, manganese, zinc, aluminum, calcium, barium, lithium, magnesium, and copper and the like.
[0052]
　Carboxylic acid-based compound is 2 to 50 carbon atoms. Less than 2 carbon atoms, i.e., formic acid and its salts 1 carbon atoms has a high volatility, not only the effect can not be expected due to containing, toxic. On the other hand, when the number of carbon atoms exceeds 50, since the viscosity of the carboxylic acid compound is high, the less area to adhere to the end surface, as a result, corrosion protection is poor. Carboxylic acid-based compound preferably has a carbon number of 5 or more and 30 or less.
[0053]
　Carboxylic acid-based compound is preferably carbon atoms having a linear or branched alkyl or alkenyl group having 4 to 20 and more preferably has an alkyl or alkenyl group of a straight chain of carbon atoms 8 to 14 . The carboxylic acid compound having a C linear or branched alkyl or alkenyl group having 4 to 20 alkyl succinic acids, alkyl succinic acid half ester, alkenyl succinic acids, alkenyl succinic acid half esters, alkyl benzoate, alkenyl acid, alkyl salicylic acids, alkenyl salicylic acid, alkyl phthalates, and alkenyl phthalic acid, and salts thereof, and the like.
[0054]
　The content of the carboxylic acid compound, based on 100 parts by weight of the solid content of the binder is 0.1 to 10.0 parts by mass. Note that when the content is less than 0.1 part by weight, it is impossible to obtain the effect as anticorrosive ingredients. On the other hand, if the content is 10.0 parts by mass, stickiness may occur. Further, the content of the mixture of these anticorrosive ingredients, relative to 100 parts by weight of the solid content of the binder is preferably at least 0.3 part by weight, preferably not more than 3.0 parts by mass.
[0055]
　In the present embodiment, the case of adding a carboxylic acid compound in the coating solution, using various surfactants, may be the above-mentioned carboxylic acid compound are mixed after emulsification. The surfactant used for emulsification of the carboxylic acid compound is not particularly limited, for example, a suitable nonionic surfactant, specifically, polyoxyethylene alkyl ethers, poly polyoxyethylene alkyl phenyl ethers, or polyoxyethylene alkyl esters are more preferable.
[0056]
　In the present invention, in order to improve the corrosion resistance and appearance, it is also possible to add a phosphonic acid compound in the insulating coating as necessary. The phosphonic acid compounds, phosphonic acid, phosphonate, amino trimethylene phosphonic acid, amino trimethylene phosphonate, hydroxyethane phosphonic acid, and can be suitably used hydroxyethane phosphonates and derivatives thereof, in particular , can be used 1-1-hydroxy-1,1-diphosphonic acid are more preferable.
[0057]
　The content of the phosphonic acid compound, relative to 100 parts by weight of the solid content of the phosphoric acid metal salt is preferably 5 to 50 parts by weight. When the content of the phosphonic acid compound is less than 5 parts by weight, the effect due to containing it can not be confirmed, undesirably. On the other hand, if the content of the phosphonic acid compound is 50 parts by mass is not preferable because the resulting stickiness. Further, the content of the phosphonic acid compound, relative to 100 parts by weight of the solid content of the phosphoric acid metal salt, more preferably at 8 parts by mass or more, more preferably 25 parts by mass or less.
[0058]
　Further, in the present invention may be added further polyhydric alcohol insulating coating. The polyhydric alcohol used in the present invention has two or more groups hydroxyl groups in the molecule, and represent those sufficiently dissolved in the coating solution for insulation coating according to the present invention. Specific examples of such polyhydric alcohols, such as diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, 2-methyl-2,4-pentanediol, 2 - ethyl-2,4-hexanediol, glycerin and the like.
[0059]
　The content with respect to the insulating film of the polyhydric alcohol with respect to 100 parts by weight of the solid content of the phosphoric acid metal salt is preferably 0.5 to 10 parts by weight. When the content of the polyhydric alcohol is less than 0.5 part by mass is not preferable because the appearance of the magnetic steel sheets forming the insulating film is degraded. On the other hand, if the content of the polyhydric alcohol is 10 parts by mass is not preferable because the resulting stickiness. Further, the content of the polyhydric alcohol with respect to 100 parts by weight of the solid content of the phosphoric acid metal salt, more preferably 1 part by mass or more, and more preferably 5 parts by mass or less.
[0060]
　Furthermore, in the present invention, the coating solution for forming the insulating film, for the purpose of improving such 耐疵 with resistance, may be used to further contain a water-soluble inorganic materials such as silicates and alumina sol, various surface active agents such as it may be used a surface tension lowering agent comprising further blended. Further, the coating solution for forming an insulating film, color pigments or extender pigments such as titanium oxide and calcium carbonate, rust inhibitors such as zinc phosphate and calcium phosphate, thickeners, dispersing agents, Narumakusukezai, defoamers , organic solvents, and it may be used by further addition of an antiseptic agent.
[0061]
　In the present embodiment, for electromagnetic steel sheet having a composition as described above, after coating the coating liquid by mixing the components described above, by baking and drying by heating, to produce a magnetic steel sheet forming an insulating film on the surface be able to.
[0062]
　In the case of applying the coating solution to the surface of the electrical steel sheet, the coating method is not particularly limited. For example, may be formed by coating a coating solution using a roll coater method on the surface of the electrical steel sheet, a spray method, a coating liquid using a coating method such as dipping method may be applied to the surface of the electrical steel sheet.
[0063]
　The heating system for causing the baking and drying the coating solution is not particularly limited, it is possible to use such conventional radiant furnace or a hot air furnace, also use the method by electrical heating including induction heating method it may be.
[0064]
　Here, baking and drying conditions of the coating solution, for example, preferably in the range of 0.99 ~ 400 ° C. for the heating temperature is preferably 5 to 30 seconds for baking time. The heating temperature is more preferably in the range of 260 ~ 380 ° C.. If the heating temperature is less than 0.99 ° C., undesirable because it may moisture remaining in the insulating film after baking. On the other hand, when the heating temperature exceeds 400 ° C., since the added organic resin is likely to be oxidized, it is not preferred. Further, if the baking time is less than 5 seconds is not preferable because it may baking is uneven. On the other hand, if the baking time exceeds 30 seconds, the proportion of the added corrosion inhibitor remains in the insulation coating may be lowered, which is undesirable.
Example
[0065]
　First, Si: 3.0 wt%, Al: 0.8 wt%, Mn: contained 0.5 wt%, balance being Fe and impurities, a plate thickness of 0.30 mm, surface roughness It was prepared non-oriented electrical steel sheet is 0.28μm in terms of ra (center-line average roughness).
[0066]
　Then, orthophosphoric acid, Al (OH) 3 , Mg (OH) 2 each metal hydroxides such as, oxides, or a carbonate in water to a concentration of phosphoric acid metal salt is 40 wt% lysed, by mixing stirring, to prepare an aqueous solution of metal phosphate.
[0067]
　Subsequently, by combining the six organic resin shown below, were each 30 mass% emulsion solution. For comparison, a commercially available urethane resin, prepared polyethylene resins were each 30 mass% emulsion solution. Further, an aqueous solution of phosphoric acid metal salt in the proportions shown in Table 1, a 30 wt% emulsion solution of an organic resin are mixed to prepare a binder treatment solution having a composition shown in Table 1.
[0068]
　Incidentally, the binder treatment liquid shown in Table 1 No. 11 is an aqueous solution of magnesium chromic acid, was adjusted by mixing 30 wt% emulsion solution of an acrylic resin 3. Aqueous solution of said magnesium chromic acid, after dissolving chromic acid anhydride in pure water at a predetermined amount, was adjusted by dissolving gradually while stirring the magnesium oxide equivalents.
[0069]
　(1) acrylic resin 1
　methyl methacrylate 40 wt%, styrene monomer 30 wt%, 2-hydroxyethyl methacrylate 10 mass%, obtained by copolymerizing 20 mass% of ethylene glycol methacrylate was synthesized acryl resin 1.
[0070]
　(2) acrylic resin 2
　methyl acrylate 20 wt% of styrene monomer 30 mass%, isobutyl acrylate 25 wt%, 4-hydroxybutyl acrylate 20 mass%, obtained by copolymerizing 5 wt% of ethylene glycol dimethacrylate, acrylic resin 2 synthesized.
[0071]
　(3) Acrylic resin 3
　methyl acrylate 40 wt%, ethyl acrylate 40 wt%, obtained by copolymerizing 20 mass% of styrene monomer were synthesized acrylic resin 3.
[0072]
　(4) acrylic resin 4
　acrylate 40 wt%, dimethyl acrylate 40 mass%, obtained by copolymerizing 20 mass% of styrene monomer were synthesized acryl resin 4.
[0073]
　(5) Epoxy resin (carboxyl group-containing epoxy resin)
　after the bisphenol A epoxy resin modified with monoethanolamine, succinic anhydride is graft polymerized to synthesize a carboxyl group-containing epoxy resin.
[0074]
　(6) Polyester resins (carboxyl group-containing polyester resin)
　After copolymerizing 40 mass% of dimethyl terephthalate and 40 wt% neopentyl glycol, 10% by weight of fumaric acid and 10% by weight of trimellitic anhydride is graft polymerized, It was synthesized carboxyl group-containing polyester resin.
[0075]
[Table 1]

[0076]
　In Table 1, "-" means that does not contain the additive. The proportion in Table 1 is the ratio in terms solids.
[0077]
　Was measured by laser scattering and diffraction, an average particle size of the acrylic resin 1 is 0.15 [mu] m, an average particle size of the acrylic resin 2 is 0.14 .mu.m, the average particle size of the acrylic resin 3 a 0.16 [mu] m, an average particle size of the acrylic resin 4 is 0.35 .mu.m, the average particle size of the epoxy resin is 0.20 [mu] m, an average particle size of the polyester resin was 0.11 .mu.m.
[0078]
　Further, the binder treatment solutions shown in Table 1, anti-corrosion agents of the carboxylic acid-based compound shown in Table 2, or other rust preventive is contained a predetermined amount, to prepare a coating solution.
[0079]
[Table 2]

[0080]
　The content of the rust inhibitor in the 2 tables is the ratio of the case where the solid content of the binder treatment solution is 100 parts by mass. In Table 2, "-" means that does not contain a rust inhibitor.
[0081]
　The application of the treatment liquid to the surface of the electromagnetic steel sheet, using a roll coater method, as a binder thickness of about 0.5 [mu] m, was adjusted roll rolling reduction and the like. Drying was carried out using a hot-air furnace, and baked dry. Evaluation measurement results of Examples and Comparative Examples were shown in Table 3.
[0082]
　Hereinafter, the evaluation methods of the respective Examples and Comparative Examples prepared in the above, will be described in detail.
[0083]
　Insulating, based on the inter-layer resistance was measured according to JIS method (JIS C2550), 3 [Omega] · cm 2 less than / sheets as "×", 3 [Omega] · cm 2 / sheet or more 10 [Omega · cm 2 less than / sheets " △ and ", 10Omu · Cm 2 / or more sheets · Cm 30Omu 2 less than / sheet as" ○ ", · Cm 30Omu 2 was evaluated / sheet or more as" ◎ ". In addition, insulating properties, evaluation was as acceptable sample of "◎" or "○".
[0084]
　Adhesion was evaluated 10 mm, 20 mm, wound steel sample pasted adhesive tape each metal rod 30mm in diameter, in peeling off the traces of the insulating coating after peeled off the adhesive tape from the steel samples. Insulating coating in the bending of 10mmφ is what was not peeled off and a "10mmφOK", and those insulating coating in the bending of 20mmφ was not peeled off as "20mmφOK", those in the bending of 30mmφ insulating coating was not peeled off " and 30mmφOK "insulation coating in the bending of 30mmφ was what was peeled as" 30mmφOUT ". In addition, adhesion, evaluation is "10mmφOK", was passing a sample of the "20mmφOK" or "30mmφOK".
[0085]
　Corrosion resistance, carried out according to the salt spray test of JIS method (JIS Z2371), was carried out at 10 points evaluated for samples after 4 hours aging. The evaluation criteria are as follows. In addition, corrosion resistance, evaluation was as acceptable sample of more than 7 points.
　　10: rust was not
　　　9: amount rust is very small (less area ratio
　　　0.1%) 8: rust occurred area ratio of = 0.1% excess 0.25% or less
　　　7: occurred area ratio of rust = 0.25% exceeds 0.50% or less
　　　6: rust occurred area ratio of = 0.50% excess of 1% or less
　　　5: rust occurred area ratio of = 1% excess 2.5%
　　　4: rust occurrence the area ratio = 2.5% excess 5%
　　　3: rust occurred area ratio of = 5% excess of 10% or less
　　　2: rust occurred area ratio of = 10% excess of 25% or less
　　　1: occurred area ratio of rust = 25% excess of 50% or less
[0086]
　End face corrosion resistance by using the cutting machine which is not 10% of the coating oil clearance, cutting the magnetic steel sheets coated with the insulating coating was evaluated as an evaluation plane by aligning the end face after cutting. Temperature 50 ° C. The electromagnetic steel sheet after cutting, in a thermo-hygrostat of 90% humidity was 48 hours aging were evaluated rust area ratio of subsequent evaluation plane similar to the corrosion resistance. The evaluation criteria are as follows. The end face rust resistance, the evaluation was evaluated as acceptable samples of more than 7 points.
　　10: rust was not
　　　9: amount rust is very small (less area ratio
　　　0.1%) 8: rust occurred area ratio of = 0.1% excess 0.25% or less
　　　7: occurred area ratio of rust = 0.25% exceeds 0.50% or less
　　　6: rust occurred area ratio of = 0.50% excess of 1% or less
　　　5: rust occurred area ratio of = 1% excess 2.5%
　　　4: rust occurrence the area ratio = 2.5% excess 5%
　　　3: rust occurred area ratio of = 5% excess of 10% or less
　　　2: rust occurred area ratio of = 10% excess of 25% or less
　　　1: occurred area ratio of rust = 25% excess of 50% or less
[0087]
　The appearance was evaluated film thickness uniformity of the insulating coating, shiny insulating film, those which are uniformly smooth and "5", the gloss is but a slightly poor uniformity and "4", slightly shiny there some smooth Although inferior in uniformity to "3", the gloss is low, the inferior slightly inferior uniformity in smoothness is "2", gloss, uniformity, the inferior smoothness It was evaluated as "1". It should be noted that the appearance was as acceptable sample is rated a "4" or more.
[0088]
　Space factor was measured according to JIS method (JIS C2550). Incidentally, the space factor was evaluated as acceptable samples is not less than 99.4%.
[0089]
　They are summarized in Table 3 The evaluation results of the above electrical steel sheet.
[0090]
[table 3]

[0091]
　By referring to the results shown in Table 3, the effect of the present invention was revealed.
[0092]
　According to the results of Table 3, Examples 1-7 according to the present invention, a good end face rust resistance, it was found that rusting after punching is small. Further, Examples 1-7 according to the present invention, insulation, adhesion, corrosion resistance, both appearance and space factor were found to be good. Specifically, Examples 1-7, has for Reference Example comprising an insulating film containing chromium compound, approximately equal insulation, adhesion, corrosion resistance, an end face rust resistance, appearance and lamination factor I understand.
[0093]
　On the other hand, Comparative Examples 1 to 9, insulation, adhesion, corrosion resistance, an end face rust resistance, or appearance and space factor is, that is inferior to Examples 1-7 according to the present invention all right. Specifically, Comparative Examples 1 and 2, since the content of the organic resin is outside the scope of the present invention, the end face rust resistance deteriorated. In Comparative Example 3, since the content of the rust inhibitor is larger than the range of the present invention, adhesion and lamination factor is lowered, and the appearance is deteriorated. Comparative Example 4, since the content of the rust inhibitor is less than the range of the present invention, have reduced the end face rust resistance, Comparative Example 9, because it does not include rust inhibitors, the end face rust resistance There has been lowered. Furthermore, Comparative Example 5, since the type of the anticorrosive agent is different from the anti-rust agent as defined in the present invention, have reduced the end face rust resistance, Comparative Examples 6 and 7, the type of the organic resin in the present invention because different from a prescribed organic resin, it reduces the end face rust resistance, and appearance is deteriorated. Comparative Example 8, since the number of carbon atoms of the rust preventive exceeds 50, insulation and lamination factor is lowered, and the appearance is deteriorated.
[0094]
　As described above, the electromagnetic steel sheet according to the embodiment of the present invention, since superior end face rust resistance, insulating property, adhesiveness, it is possible to improve the corrosion resistance, appearance and lamination factor, motor and it is possible to improve the transformer manufacturing efficiency.
[0095]
　Having described in detail preferred embodiments of the present invention, the present invention is not limited to such an example. It would be appreciated by those skilled in the relevant field of technology of the present invention, within the scope of the technical idea described in the claims, it is intended to cover various modifications, combinations, for even such modifications are intended to fall within the technical scope of the present invention.

claims
[Claim 1]
　100 parts by weight of phosphoric acid metal salts, and a binder composed of an organic resin 1 to 50 parts by weight of the average particle size of 0.05 ~ 0.50 .mu.m,
　the content to the solid content 100 parts by mass of the binder 0. a carboxylic acid compound having 2 to 50 carbon atoms is 1 to 10.0 parts by mass,
　wherein the
　said organic resin is at least one selected from acrylic resins, epoxy resins and polyester resins,
　insulating coatings a surface of the steel sheet, an electromagnetic steel sheet.
[Claim 2]
　The insulating film contains a polyhydric alcohol of from 0.5 to 10 parts by mass with respect to 100 parts by mass of the solid content of the binder, electrical steel sheet according to claim 1.
[Claim 3]
　The carboxylic acid-based compound, carbon atoms having a linear or branched alkyl or alkenyl group having 4 to 20 electrical steel sheet according to claim 1 or 2.
[Claim 4]
　100 parts by mass phosphoric acid metal salt, a step of average particle size of the emulsion of the organic resin of 0.05 ~ 0.50 .mu.m were mixed with 1 to 50 parts by weight of resin solids, to prepare a binder solution,
　the binder a liquid, comprising: a carboxylic acid compound having 2 to 50 carbon atoms, which mixed 0.1-10.0 parts by mass with respect to 100 parts by mass of the solid content of the binder solution to prepare a treatment liquid,
　the treatment liquid It was applied to the surface of the electrical steel sheet, comprising the steps of baking and drying,
　wherein the
　said organic resin is at least one selected from acrylic resins, epoxy resins and polyester resins,
　method for manufacturing the electrical steel sheet.
[Claim 5]
　In the step of preparing said processing liquid, wherein the binder solution, a polyhydric alcohol, mixed 0.5 to 10 parts by weight with respect to 100 parts by mass of the solid content of the binder solution, an electromagnetic of claim 4 method of manufacturing a steel plate.
[Claim 6]
　The carboxylic acid-based compound, carbon atoms having a linear or branched alkyl or alkenyl group having 4 to 20 manufacturing method of an electromagnetic steel sheet according to claim 4 or 5.