TW200538583A - Electromagnetic steel sheet having insulating coating - Google Patents

Abstract

An insulating coating for application to an electromagnetic steel sheet, comprises mainly of a Zr compound, an Al compound and a Si compound, optionally further phosphoric acid and/or a phosphate salt, wherein the total content of Zr compound (in terms of ZrO2) and phosphoric acid or the like (in terms of PO4) is regulated so as to range from 45 to 90 mass% on a reduced basis per the total mass of solid contents of the insulating coating. The thus obtained insulating coating despite one whose main components are inorganic substances not containing chromium excels in, after baking at ≤ 300 DEG C but before strain-removing annealing, corrosion resistance, anti-powdering property and appearance and excels in, after strain-removing annealing, scratch resistance. Further application of an upper layer coating containing a resin, etc. is also preferable.

Description

200538583 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to an electromagnetic steel plate having a Cr-free insulating film. [Prior art] Insulating coatings of electromagnetic steel plates used in motors and transformers require not only interlayer resistance, but also various characteristics. For example, convenience in processing and molding, storage, and stability in use are required. In addition, because the electromagnetic steel sheet can be used for a variety of purposes, various insulation coatings can be used in accordance with the application.

For example, if punching, shearing, bending, etc. are performed on an electromagnetic steel sheet, the magnetic characteristics will be deteriorated due to residual strain. Therefore, in order to restore the deteriorated magnetic properties, strain relief annealing is usually performed at about 750 ~ 850 ° C. In this case, the insulating film must be able to withstand strain relief annealing.

Insulation coatings are roughly divided into the following three types: (1) Inorganic coatings that value fusion resistance and heat resistance and can withstand strain relief annealing (in principle, do not contain organic resin); (2) The goal is to consider both punchability and weldability, and Inorganic coatings containing organic resins that are subjected to strain relief annealing; (3) Organic coatings for special purposes that cannot be subjected to strain relief annealing. Among them, those that can withstand the strain-annealing as general purpose products are inorganic-containing coatings of (1) and (2), both of which contain chromium compounds. Special type (2)-Chromate insulation film containing organic resin. Compared with inorganic insulation film, it will be widely used because it will improve the punchability. For example, in Japanese Patent Laid-Open Publication No. 6 0-3 6 4 7 6, 312XP / Invention Specification (Supplement) / 94-07 / 94108335 200538583 is disclosed in a dichromate system containing at least one divalent metal. In the aqueous solution, the ratio of vinyl acetate / Beopa (V e ο V a) (T Μ) is 9 0/1 0 to 4 0 with respect to C r 0 3: 1 0 0 parts by weight of the aqueous solution. The resin emulsion at a ratio of 60/60 is formulated in a ratio of 5 to 120 parts by weight of the solid content of the resin and 10 to 60 parts by weight of the organic reducing agent to form a treatment liquid (c 〇ating 1 iquid). The liquid coating is performed on the surface of a steel substrate (stee 1 sheet), and an electromagnetic steel sheet having an electrically insulating film is formed through a baking step performed by a conventional method.

However, environmental protection awareness is increasing nowadays. In the field of electromagnetic steel sheets, demanders are also eager to have products without a Cr-containing insulating film. Therefore, there have been proposals for an electromagnetic steel sheet having no Cr insulating film. For example, as an insulating film that does not contain Cr and has good punchability, Japanese Patent Laid-Open No. 10-1 3 0 8 5 8 discloses alumina-containing silicon dioxide containing resin and colloidal silicon dioxide. It is an insulating coating of composition. Furthermore, it is disclosed in Japanese Patent Laid-Open Publication No. 10-4 6 3 50 that inorganic compounds composed of one or two or more of colloidal silica, alumina sol, and gadolinium sol are used. An insulating coating formed by adding 100 parts by weight of a colloidal substance to an aqueous solution containing 15 to 400 parts by weight or more of a water-soluble or emulsion resin. In addition, Japanese Patent No. 2 8 1 7 0 2 discloses that in a film composed of an oxide-based polymer composed of at least one of A 1, S i, T i, and Z r, An insulating coating containing 3 to 9 0% by weight of oxide fine particles (particle size 10 to 100 nm) composed of at least one of A1, Si, Ti, and Zr is used. In addition, Japanese Patent No. 2944849 discloses that 6 3I2XP / Invention Specification (Supplement) / 94-07 / 94108335, which mainly contains chromium-free phosphate and contains resin and optionally colloidal silica.

200538583 Insulation coating. In addition, in Japanese Patent Laid-Open No. 9-3 1 6 6 5 5 there are 100 parts by weight of organic resin, and each is compounded with: 5 to 1 0 0 1 Mn, Mg, A 1 and other compounds 20 to 200 parts by weight; among colloids (sols) such as ZrO2, Al2O3, Sn02, and Sb2O5, one or more than 5 parts by weight; a composition for surface treatment of chromium-free electromagnetic steel plates. However, when these electromagnetic steel sheets having an insulating film containing no Cr contain a chromium compound, the bonding between inorganic substances is weak, and there is a problem of poor corrosion resistance. In addition, in the case of tape cutting, selling a drum to wipe the surface of a steel plate to apply back tension (i.e., when a tension pad is used) will cause problems. Moreover, after the strain-relief annealing, the coating will become fragile and the problem of damage will occur. In addition, the baking temperature should be as low as possible from the reduction of energy consumption and manufacturing costs, but the above problems will be more likely to occur when baking is performed at a low temperature of 300 ° C, especially below ° C. The situation will be more obvious. [Summary of the Invention] (Problems to be Solved by the Invention) The present invention was made in order to solve the above-mentioned problems, and is an insulating coating mainly containing no inorganic inorganic material of Cr. After baking at 300 ° C (elimination) Before the strain annealing), the coated electromagnetic steel sheet has excellent corrosion resistance, chalking resistance, and corrosion resistance and damage resistance after the strain annealing is eliminated. 312XP / Invention Specification (Supplement) / 94-07 / 94108335 Reveals: In I: Quantities;, SiO2, ~ 150 weight compared to when it will use the gross condition • Raw flour. It is easy to view Compared with the 200-percent implementation, there is much insulation 7 200538583 (means for solving problems) The present invention provides the following electromagnetic steel sheet with an insulating coating in order to solve the above-mentioned problems. 1. An electromagnetic steel sheet having an insulating coating, comprising an electromagnetic steel sheet having an insulating coating containing Zr compound, A1 compound, and Si compound as main components; wherein the Zr compound is relative to the total solid content of the insulating coating The content is 45 to 90% by mass based on Z r 0 2 conversion.

2. An electromagnetic steel sheet having an insulating coating, which is an electromagnetic steel sheet having an insulating coating containing at least one selected from phosphoric acid and phosphate, a Zr compound, an A1 compound, and a Si compound as a main component; wherein, With respect to the total solid content of the insulating coating, the content ratio converted by P 0 4 of at least one selected from the group consisting of phosphoric acid and phosphate and the content ratio converted by the Z r compound according to Z r 0 2 are 4 5 ~ 90% by mass, and the ratio of the two contents is 0.01 to 0.40 in terms of P04 / Zr02 conversion. 3. The electromagnetic steel sheet having an insulating coating according to the above 1, wherein the insulating coating has M-0-Z r and M-〇 Η-Z r with respect to A 1, S i and F e shown by M. At least one of the bonding states. 4. The electromagnetic steel sheet having an insulation coating as described in the above 2, wherein the insulation coating has M-0-Z r and M-OH-Zr with respect to A 1, S i, P, and F e shown by M. At least one of the bonding states. 5. The electromagnetic steel sheet having an insulating film according to any one of the above 1 to 4, wherein the insulating film does not substantially contain Cr. 6. The electromagnetic steel sheet having an insulating film according to any one of the above 1 to 5, wherein the A 1 compound and the Si compound of the insulating film contain 312XP / Invention Specification (Supplement) / 94-07 / 94108335 200538583 The quantity is calculated according to the ratio of A 1 2 0 3 converted 値 and S i 0 2 converted 値, which is 2 0: 8 0 to 8 0: 2 0. 7. The electromagnetic steel sheet having an insulating coating according to any one of the above 1 to 6, wherein an aqueous treatment solution containing at least A 1 compound, Si compound, and Z r compound in a dissolved or colloidal state is applied to the steel sheet And then baked. 8. The electromagnetic steel sheet having an insulating coating according to the above 7, wherein the Zr compound contained in the aqueous treatment liquid is formed into a solution or a colloidal shape by using at least one of a base, an organic acid, an inorganic acid, and water.

9. The electromagnetic steel sheet with an insulating coating according to the above 8, wherein the Zr compound contained in the aqueous treatment solution is selected from the group consisting of europium acetate, zirconium propionate, europium oxychloride, europium nitrate, ammonium zirconium carbonate, potassium zirconium carbonate, and hydroxyl group. Rhenium chloride, Rhenium sulfate, Zirconium phosphate, Sodium phosphate Rhenium, Potassium hexafluoride, Tetra-n-propoxy zirconium, Tetra-n-butoxyrhenium, Tetraacetonium pyruvate, Tributoxyacetonium pyruvate Among ester zirconium and tributoxystearate hafnium, at least one kind is selected. 10. The electromagnetic steel sheet with an insulating coating according to the above 8, wherein the Zr compound contained in the aqueous treatment liquid is at least one selected from the group consisting of osmium acetate and nitric acid. 1 1. The electromagnetic steel sheet having an insulating coating according to any one of 7 to 10 above, wherein the A 1 compound contained in the above-mentioned aqueous treatment liquid is derived from the A 1 compound composed of a base and an organic acid, and dehydrated therefrom. In the group consisting of the reactants, at least one kind is selected. 12. The electromagnetic steel sheet having an insulating coating according to any one of 7 to 11 above, wherein the silicon compound-based colloidal dioxide contained in the aqueous treatment liquid is used. 9 312XP / Invention Specification (Supplement) / 94-07 / 94108335 200538583 1 3, as in any one of the above 1 to 12, the electromagnetic steel sheet with an insulating coating, wherein at least the first 2 Insulation coating. 14. The electromagnetic steel sheet having an insulating coating according to the above 13, wherein the at least second insulating coating is substantially free of Cr. 15. The electromagnetic steel sheet having an insulating coating according to the above 13 or 14, wherein the second insulating coating comprises an A 1 compound, a Si compound, and a resin.

16. The electromagnetic steel sheet having an insulating coating according to any one of 1 to 15 above, wherein the second insulating coating further contains a Zr compound. 1 7. A method for manufacturing an electromagnetic steel sheet with an insulating coating, which is a method for manufacturing an electromagnetic steel sheet having an insulating coating that does not substantially contain Cr after applying an aqueous treatment liquid on the electromagnetic steel sheet and baking it; The treatment solution contains: Si compound, A 1 compound, and Zr compound in a dissolved or colloidal state; and the content of the Zr compound in the treatment solution is based on the total solid content of the insulating film after the baking, according to Zr. 2 amount conversion accounts for 45 to 90% by mass. 1 8. A method for manufacturing an electromagnetic steel sheet with an insulating film, which is a method for manufacturing an electromagnetic steel sheet having an insulating film that does not substantially contain Cr after applying an aqueous treatment liquid on the electromagnetic steel sheet and baking it; The treatment liquid contains: at least one selected from phosphoric acid and phosphate, Si compound, A 1 compound, and Z r compound in a dissolved or colloidal state; and the content of at least one selected from phosphoric acid and phosphate in the treatment liquid And the content of the Zr compound in the treatment solution is based on the total solid content of the above-mentioned insulating film after the baking, which is converted into a total amount of 45 to 90% by mass based on the amount of Zr02 and P04; 10 312XP / Invention specification (Supplement) / 94-07 / 94108335 200538583 and the ratio of the amount of Zr〇2 to the amount of P04 PCh / Zr〇2 is 0.01 to 0.40. In the above-mentioned 17 and 18, the above-mentioned requirements of 3 to 16 can also be adopted as the better conditions. [Embodiment] Hereinafter, the present invention will be described in more detail. The present invention is an electromagnetic steel sheet having an insulating coating containing a Zr compound, an A1 compound, a Si compound, and a necessary phosphoric acid and / or phosphate as a main component.

< Electromagnetic steel plate (electric iron plate) > The electromagnetic steel plate (also referred to as "electric iron plate") that can be used in the present invention before forming an insulating coating is to change the resistivity to obtain the required magnetic characteristics, and There is no particular restriction on the adjusted composition steel plate. For example, in terms of increasing iron loss, increasing the resistivity is an effective way, so it is best to add S i,

Among Al, Mn, Cr, P, Ni, Cu, etc., at least one component is selected. The content of these elements can be determined in accordance with the required magnetic characteristics, but generally added separately: S i ·· About 5 mass% or less (including no addition, the same applies hereinafter), A 1: About 3 mass% or less, Mn: about 1.0% by mass or less, Cr: about 5% by mass or less, P: about 0.5% by mass or less, Ni: about 5% by mass or less, and Cu: about 5% by mass or less. A typical electromagnetic steel sheet is Si Additive u 0.1 mass% or more, but a low-grade product may also be Si: 0.05 mass% or more. In addition, in order to improve the magnetic characteristics, an inhibitor-forming element or a segregation element may be added according to the needs. Among Mn, Se, S, Al, N, Bi, B, Sb, Sη, etc., at least Select 1 element. Inhibitor formation 11 312XP / Invention Specification (Supplement) / 94-07 / 94108335 200538583 The addition of elements, etc., usually means that these elements together contain 0.5% by mass or less. The remainder other than the above is iron and minor impurities. Examples of impurities include C, N, 0, and a small amount of S with a small inhibitor effect. The amount of such impurities is as small as possible. If it is a high-quality product, C may contain about 0.02 to 0.05 mass%. The thickness of the electromagnetic steel sheet of the present invention is not particularly limited. Preferably, the thickness is about 0.02 to 1.0 mm.

The surface of the electromagnetic steel sheet forming the insulating coating may be subjected to degreasing treatment with alkali or the like, or pickling treatment with hydrochloric acid, sulfuric acid, or phosphoric acid, etc., and any pretreatment may be performed. Alternatively, it may be an untreated surface in an original manufacturing state. Although the third layer is not required in principle between the insulating coating and the surface of the iron substrate, it is not prohibited. For example, in an ordinary manufacturing method, an oxide film of an iron-based metal may be formed between the insulating film and the surface of the iron substrate. However, the process of removing the same may be omitted. The insulating film according to the present invention is obtained by coating a film material containing the following essential components or other appropriate components on the surface of a steel sheet, followed by drying and / or baking. The coating material to be applied is preferably an aqueous paste or liquid, but it is preferably liquid (aqueous liquid) from the viewpoint of increasing the film thickness (film adhesion amount) to a necessary level or more. In the following description, when it is referred to as a "treatment liquid", a paste is included in principle, and it is easier for the liquid to exhibit an effect in terms of the effect described. < Zr compound > The insulating film adhered to a steel sheet according to the present invention contains a specific amount of a Zr compound. Z r has a maximum of 8 coordination numbers, and generally uses 4 bonds and 12 312χρ / Invention Specification (Supplement) / 94-07 / 94108335 200538583 other substances (especially oxygen) are firmly bonded. Therefore, it can be judged that a strong film can be formed even if a chromium compound is not used by firmly bonding the oxide and hydroxide on the surface of Fe.

However, when only the Zr compound is the main component of the insulating film, the corrosion resistance is slightly deteriorated, and the damage resistance after strain relief annealing tends to increase. This phenomenon is considered to be due to the large number of bonds of the Zr compound, which will prevent the smooth formation of the network, which will result in the formation of a fragile coating. The present inventors have found that when the amount of the Z r compound is limited to a predetermined range and mixed with the A 1 compound and the S i compound, and when phosphoric acid and / or phosphates are mixed more, a significant improvement effect can be obtained. The appropriate content is calculated in terms of Z r 0 2 and is 45 to 90% with respect to the total solid content of the insulating film. It is preferably 50% or more and 80% or less. If it is set within this range, the coating will become strong. This phenomenon can be considered to be due to the formation of a good bonding network between the Zr compound and other substances. In addition, as described later, when phosphoric acid and / or phosphate are further contained, the total with phosphoric acid and the like is set within the above range. Here, the "total solid content" refers to the amount of coating formed on the surface of the electromagnetic steel sheet after drying according to the method described later. The total solids content can be measured by reducing the weight after removing the film from the alkali peeling. The "Z r 0 2 conversion" refers to the calculated content of Z r 0 2 when it is assumed that all the contained Z r form Z r 0 2. Hereinafter, for the sake of simplicity, it is simply referred to as "Z r 0 2 conversion". The conversion of other related compounds is the same. In the present invention, the Zr compound that can be used as a raw material for an insulating film may include, for example, acetic acid, propionic acid, oxygenated acid, sulfonic acid, carbonic acid, 13 312XP / Invention Specification (Supplement) / 94.07 / 94108335 200538583 potassium osmium carbonate, zirconium hydroxy gas, zirconium sulfate, osmium phosphate, sodium phosphate osmium, osmium potassium hexafluoride, tetra-n-propoxyamidine, tetra-n-butoxyammonium, tetraethylammonium pyruvate Ester zirconium, tributoxyacetamidine pyruvate zirconium, zirconium tributoxystearate, etc. These can be used alone or in combination of two or more. These may be in accordance with the present invention, which is an A 1 compound, an Si compound, which is an essential component of the insulating film raw material, or a phosphoric acid and / or phosphate, which is an optional component, other inorganic compounds, organic compounds, and additives described later. For compatibility.

In addition, the Zr compounds listed above may also contain impurities such as Hf, Ti or the oxides of the same family of Zr (Hf〇2, Ti〇2), or even Si〇2, Fe2〇3, totaling 5 About mass% or less. In addition, the main system of impurities

Hf or Hf 02 In the present invention, the Zr compound constituting the raw material of the insulating film is preferably water-soluble compared with the case where it is insoluble in paste water. The reason is because the bond with other substances will be strengthened and a denser film can be formed. The term "water-soluble" refers to a person who dissolves in water or forms a colloid and stably disperses in water. In particular, it is preferable to form the Zr compound into a solution or a colloid through at least any one of a hydroxyl group, an organic acid, an inorganic acid, and water. When the above state is formed, the stability of the treatment liquid will increase, and as a result, the film characteristics will be improved. In addition, the base, organic acid, inorganic acid, and water may exist in the molecule of the Zr compound, or may be supplied from the outside (for example, in a bonded state). Among the Zr compounds listed above, acetic acid, which is more likely to form hydrocolloids or solutions, or thallium nitrate, which is more likely to form solutions, are preferred. 14 312XP / Invention Specification (Supplement) / 94-07 / 94108335 200538583 material. Examples of the form of acetic acid include: (C Η 3 C0 0) n Z r (where n 2 1 to 8, usually 1 or 2), Z r 0 (C Η 3 C0 0) 2 and the like. Examples of the form of europium nitrate include ZrO (N03) 2, ZrO (N03), and the like. < Phosphoric acid, phosphate > In the present invention, phosphoric acid and / or phosphate may be contained in the insulating coating together with the Zr compound. By adding a predetermined amount of phosphoric acid and / or phosphate to the Zr compound, even at a baking temperature of 200 ° C or lower, superior film characteristics can be ensured, and particularly the powder resistance.

When phosphoric acid and / or phosphate are contained, the Z r 0 2 conversion content rate of the Z r compound relative to the total solid content of the insulating film and the P 0 4 conversion content rate of phosphoric acid and / or phosphate are set in total. It is 4 5 to 90% by mass, and the ratio of the content is based on the conversion 値 described above, and P04 / Zr〇2 値 is set to 0 · 0 1 to 0 · 4 0 〇 In other words, in the Zr compound When the Zr 0 2 conversion content rate and the P Ch conversion content rate of phosphoric acid and / or phosphate are less than 90% by mass, a significant improvement effect can be obtained. Conversely, when the total amount is less than 4 5 mass ° / ◦, it is best to avoid it because the effect is too small. In addition, if the Z r 0 2 conversion content ratio of the Z r compound and the P 0 4 conversion content ratio with respect to phosphoric acid and / or phosphate are set to 0 0 1 to 0 according to P 0 4 / Z r 0 2. If it is 40, even if the film is formed at a low temperature of about 200 ° C, problems such as powdering will not occur. Specifically, when it is less than 0.01, the effect of improving powdering resistance during low-temperature baking using phosphoric acid and / or phosphate is small. If it exceeds 0.4, the Zr compound in the treatment solution will react with phosphoric acid, which tends to cause the coating to become rough. In addition to reducing the powdering resistance improvement effect, the Zr compound 15 312XP / Invention Specification (Supplement) / 94-07 / 9410833 5 200538583 The effect of improving the corrosion resistance and damage resistance after strain relief annealing will also decrease to some extent.

It has been known from practice that Zr compounds and phosphoric acid will form Zr phosphate and produce a water-insoluble Shen Dianwu. However, the inventors have found that in the above-mentioned ratio range of the present invention, the treatment liquid is stable, and has a property that it is superior in coating if the moisture disappears and a strong film is formed quickly. The stable mechanism of this treatment solution can be considered as follows: (1) Because of the strong bonding force of plutonium to water, water will gather around the Zr compound in the treatment solution as a blocking agent against phosphoric acid; ( 2) Under the coexistence of water, the Z r compound is coordinated to a state surrounding the acid (salt) to form a more stable complex. In any case, it can be considered that if the water disappears, Zr phosphorylation will proceed rapidly. Furthermore, because of the high reactivity of phosphoric acid and / or phosphate with Zr, when phosphoric acid and / or phosphate is contained, the total of phosphoric acid and / or salt filling and Zr compound is regulated. the amount. In addition, when phosphoric acid and / or phosphate are added, if there is little water, it will be cured early and workability will be affected. Therefore, when using a film material with less moisture for reasons such as obtaining a thick film, it is best not to add phosphoric acid and / or phosphate or to suppress the amount of addition. In the present invention, the phosphoric acid system that can be contained in the treatment liquid is only required to be commercially available, and the rest is not particularly limited. It is best to use, for example, orthophosphoric acid, phosphoric anhydride, linear polyphosphoric acid, and cyclic amidinophosphoric acid. In addition, as the phosphate, water-soluble salts such as Mg phosphate, A1 phosphate, Ca phosphate, and Zn phosphate are preferably used. These phosphoric acid and phosphate can be used alone or in combination. 2 16 312XP / Invention Manual (Supplement) / 94-07 / 94108335

200538583 or more. &lt; S i compound> The insulating film system of the present invention contains a S i compound. S i compounds, which are thermally stable and stable compounds, react with Z r to form complexes such as zirconia (Z r (S i)), which have the effect of improving the coating properties. It is easy to use colloidal silicon dioxide. Colloidal silicon dioxide is an inorganic colloid with S i 0 2 as the main component. It is large crystalline. The particle diameter is preferably 20 nm or less, and more preferably 10 nm or less. The smaller the particle size, the better the film can be formed. Therefore, the lower limit is not limited. If it is set to ultrafine particles, even if the same content is added to the overall surface area, the interaction with other components will improve the strength of the film. In addition, when the particle size is small, it is easy to reduce the colloidal silica concentration because the silica particles will easily cause agglomeration between them and other components. Conversely, it is also possible to set a practically appropriate particle size. The average particle size can be measured by the BET method (specific surface area using an adsorption method. In addition, the actual diameter (converted spherical diameter) from an electron microscope photograph can be used instead.) <A 1 compound> The insulating film system of the present invention contains A 1 compound. The A 1 compound and the Zr compound form a complex with high heat resistance and stability, and have improved properties. The A 1 compound contained in the treatment liquid is preferably an A 1 compound formed from a hydroxyl group and an organic compound and / or dehydrated therewith. Reactants, such as alumina sol 312XP / Invention Specification (Supplements) / 94-07 / 94108335, are the wrong results. Most of them are not good, they can also be increased due to special restrictions. In the second case, the concentration t conversion is required. ) The average is constructed by the coating acid. If it is considered that the coating and baking of the steel sheet is performed by using an aqueous treatment solution, the A 1 compound is preferably soluble in water, or dispersed in a colloidal or suspended state. In addition, as long as there is no characteristic problem in the shape, any shape such as a feather shape or a spherical shape may be used. The A1, S i compounds preferably do not contain other metal elements above the impurity level. &lt; Ratio of S i compound to A 1 compound &gt;

The insulating coating of the present invention is the above-mentioned A 1 compound and the above-mentioned Si compound, and is converted into S i 0 2 according to A 1 2 0 3 conversion, and preferably contains a range of 2 0: 8 0 to 8 0: 2 0 (mass ratio). . This ratio is particularly preferably in the range of 3 0: 7 0 to 7 0: 3 0 (mass ratio), and more preferably in the range of 3 5: 6 5 to 6 5: 3 5 (mass ratio). If the A 1 compound and the S i compound are contained in the insulating film in such a mass ratio, the effect of improving the corrosion resistance, chalking resistance, and damage resistance of the strain relief annealing plate to a high level can be achieved. In addition, the total of the A 1 compound and the S i compound converted from A 1 2 0 3 and S i 0 2 should preferably contain more than 10% by mass of the total solid content of the insulating film. According to the study by the inventors, it is considered that the bonding morphology of the Zr compound and other substances in the insulating film of the present invention is relative to A 1, Si, P (if contained) and Fe, and if these are in accordance with M This means that it has at least one of the bonding states of M-0-Zr · and M-OH-Zr. Specifically, Zr-0-Fe, Zr-〇H-Fe 'A1 — 0 — Zr — 0 — A1, Si — 0 — Zr_0 — Si, P — 0 — Zr — Ο — P Bonding state. Among them, 0 or 0H is supplied from surrounding water molecules, or oxygen or hydroxyl contained in any compound. 18 312XP / Invention Specification (Supplement) / 94-07 / 94108335

200538583 In other words, the insulating film of the present invention can be considered to be composed of an amorphous composite oxide (which contains many impurities) containing z r, S i ′ p (if contained), and F e. The present invention is, as described above, an electromagnetic steel sheet having an insulating coating comprising the Zr compound, the compound, the Si compound, and phosphoric acid and / or phosphate. Here, the "main component" refers to the content of each component after conversion, Al2O3 conversion, Si02 conversion, and P04 conversion, which accounts for about 80% by mass or more of the total solid content of the insulating film. The total amount is preferably 90% by mass or more. In addition, from the viewpoint of ensuring an improvement effect, the present invention is an electromagnetic steel having an insulating coating composed of the Z r compound, the A 1 compound, the S i compound, and phosphoric acid and / or phosphate. good. Among them, if the amount is below the predetermined amount, the following additives are most contained in addition to the four components. <Tianlikou agent> In order to further improve the film performance and uniformity, the insulating film of the present invention should preferably contain: surfactant (non-ionic, cation, anionic surfactant; silicone interfacial activity) Agents: acetylene glycol: rust inhibitors (amine-based, non-amine-based rust inhibitors, etc.), boric acid, silane coupling agents (silane, epoxy silane, etc.), lubricants (wax, etc.), organic and inorganic additives such as these additives Known materials suitable for chromate-based coatings or non-chromate-based insulating coatings, which have been proposed so far, can be used. When using these additives, in order to maintain sufficient coating characteristics, 312XP / Invention Specification (Supplements) / 94-07 / 94108335 A Bu contains the combination of \ 1 and ZrO2. The above mentioned are only the pre-ion ions that are particularly good.) 'Amine-based agent. Insulation cycle is preferably 19,2005,38583, which is about 10% by mass or less with respect to the total solid content of the insulating film of the present invention. &lt; Other inorganic compounds and organic compounds &gt; The insulating film of the present invention may contain other inorganic compounds and / or organic compounds as long as the effects of the present invention are not impaired.

The resin (especially the resin contained in the second insulating film described later) may be contained in a small amount, preferably less than 5% by mass, and more preferably about 3% by mass or less. However, if it is contained excessively, the resin will form defects and deteriorate the corrosion resistance, so it is best not to add strength. In addition, the present invention aims to obtain good film characteristics without adding a chromium compound. Therefore, it is preferable that the insulating coating of the present invention does not substantially contain Cr from the viewpoint of preventing environmental pollution caused by manufacturing steps and products. The amount of chromium that can be regarded as an impurity is based on the total solid content of the insulating film, and is preferably 0.1% by mass or less based on the amount of C r 0 3 conversion. &lt; Manufacturing method of insulation film &gt; A method for manufacturing the above-mentioned insulation film of the present invention on the surface of an electromagnetic steel sheet will be described. The starting material of the present invention is an electromagnetic steel plate (electric iron plate). The steel sheet of the present invention is not particularly required to be previously processed. It is suitable to use untreated or degreased treatment such as alkali, or pickling treatment performed in accordance with hydrochloric acid, sulfuric acid, or phosphoric acid. Then, the electromagnetic steel sheet is coated with: the Z r compound, the A 1 compound, the S i compound, and the above-mentioned erucic acid and / or phosphate necessary to be compounded, and the above-mentioned additive necessary, etc .; Treatment solution. 20 312XP / Invention Specification (Supplement) / 94-07 / 94108335

200538583 Then, an electromagnetic coating can be formed on the electromagnetic steel sheet coated with the above-mentioned treatment solution in accordance with the baking treatment. The coating method of the insulating film can be adopted by the general industry, such as a coating machine, a spray coater, a sprayer, a knife coater, and other equipment. In addition, the baking method can also be implemented by commonly used methods such as Hot air, wire heating, induction heating and other methods. The baking temperature is not unusual. When no phosphoric acid and / or salt is added, the temperature reached is preferably set to above 150 ° C, and below 350 ° C. The upper limit is preferably 300 ° C. When phosphoric acid and / or phosphate are added, especially at 200 ° C baking, superior coating characteristics will be obtained. Even if the lower limit is 50 ° C baking temperature, it will still have good coating characteristics, but it is best to set it above. Especially preferably above 100 ° C. &lt; Strain Relief Annealing &gt; The electromagnetic steel sheet with an insulating coating according to the present invention is subjected to a fire relief. For example, a punching process can be performed to remove the strain. The better environment for eliminating fire is N 2 environment, D X gas environment, etc. Iron is also less oxidized. However, some slight oxidation still has advantages. In the above-mentioned environment, the dewpoint is increased, for example, it is set to D p: 5 ~ 60 ° C. By oxidizing the cutting end surface to some extent, the corrosion resistance can be further improved. The preferred strain relief annealing temperature is above 60 ° C, and preferably below ° C. The preferred lower limit temperature is 65 ° C, more preferably above 700 ° C or even around 750 ° C or above 750 ° C. In addition, the temperature is preferably above 8 50 ° C. The longer the holding time during strain relief annealing is, the longer the 312XP / Invention Specification (Supplement) / 94 · 07/94108335 roll baking method. Infrared phosphoric acid is best below 900 ° C with a dew point of 900 ° C. Temperature limit is good, 21 200538583 is better than 2 hours. &lt; Amount of Insulation Coating Adhesion &gt; The amount of insulation coating adhesion is not particularly specified, and the total of the average single side is preferably 0.05 g / m2 or more. The adhesion amount is preferably 5 g / m2 or less. The amount of adhesion, that is, the measurement of the total solid content of the insulating film of the present invention, can be measured from the weight reduction after the film is removed by peeling off the alkali. In addition, when the amount of adhesion is small, the fluorescence X-ray can also be used for measurement. In this case, the amount of adhesion can be calculated from the calibration curve prepared by the alkali peeling method.

If the adhesion amount is less than 0.05 g / m2, there is a possibility of insufficient corrosion resistance or insulation. On the other hand, if the adhesion amount exceeds 5 g / m2, the coating workability may be reduced. The preferred upper or lower limit is above 0 · 1 g / m2 or below 3.0 g / m2. A more preferable upper or lower limit is 0.2 g / m2 or more, or 1.5 g / m2 or less. The insulating coating of the present invention is preferably formed on both sides of the steel sheet, but may be formed on only one side depending on the purpose. In other words, depending on the purpose, it can be applied to only one side, and another insulating film can be formed on the other side, or an insulating coating can not be applied on the other side. &lt; Second insulating film (upper film) &gt; In the present invention, an insulating film (hereinafter referred to as a "base film") containing the Zr compound, the A1 compound, the Si compound, and phosphoric acid and / or phosphates required for blending ") On the surface, it is preferable to have at least a second insulating film (hereinafter referred to as an" upper film ") having a composition different from that of the base film. Here, the upper-layer coating system only needs to form at least one layer on the surface of the base coating film, and it may be two or more layers. The composition of each upper layer is not necessary. 22 312XP / Invention Specification (Supplement) / 94-07 / 94108335 200538583 Do not restrict, but for the same reason as the base film, it is best not to contain C r 〇 or less substantially. For the base film In the case where only one upper layer film is formed on the surface, a preferred example of the composition of the upper layer film will be described. On the surface of the base coating film of the present invention, it is preferable that an insulating coating containing an A 1 compound, a Si compound, and a resin is used as an upper coating layer to obtain more excellent corrosion resistance, damage resistance, and appearance. It is preferable that the upper layer film further contains a Zr compound.

&lt; A 1 compound, Si compound> The A 1 compound and the Si compound contained in the treatment liquid for forming the upper layer film of the present invention are not particularly required, and the same treatment liquid for the base film of the present invention can be used. The aforementioned A 1 compound and the aforementioned Si compound are contained. <Resin> The resin component contained in the upper layer film of the present invention is not particularly specified, and it is preferable to use, for example, acrylic resin, alkyd resin, polyolefin resin, polyethylene resin, polypropylene resin, ethylene- One or two or more types of water-based resins (emulsions, acrylic resins, styrene resins, vinyl acetate resins, epoxy resins, phenol resins, polyester resins, amino ethyl acetate resins, and melamine resins) Dispersant, water-soluble). &lt; Z r compound, phosphoric acid and / or phosphate &gt; The upper layer film of the present invention may further contain a Z r compound. It may also contain Zr compounds, and phosphoric acid and / or phosphate. Zr compound and phosphoric acid contained in the treatment solution for forming an insulating film, and / 23 312XP / Invention Specification (Supplement) / 94-07 / 94] 08335

200538583 or phosphate does not need to be specified, and the above-mentioned Zr compounds, phosphoric acid, and salts contained in the above-mentioned treatment solution for base film can be used. &lt; Additives, etc. &gt; The upper film system of the present invention may contain the same components as the above-mentioned base film, or additives. The content rate is also the same as that contained in the above-mentioned substrate. For example, the total solid content of the additive with respect to the insulating film of the present invention is preferably about 10% by mass or less. &lt; Addition amount of each compound and the like &gt; The content of each main component of the upper layer film does not need to be specified, but it is preferably within the following range. The content ratio of the A 1 compound contained in the upper layer film of the present invention is 10% by mass or more relative to the total solid content of the upper layer film in terms of A 1 2 0 3 conversion. The upper limit is preferably set to 90% by mass or less. In particular, the upper limit is preferably 15 mass% or more, and more preferably 20 mass% or more. In particular, the upper limit is preferably 85 mass% or less, and more preferably 80 mass%. Furthermore, the above S i compound ratio contained in the upper layer film of the present invention is calculated based on S i 0 2 and is better than 10 mass% relative to the total solid content of the upper layer film. The upper limit is preferably set to 90% by mass, and the lower limit is preferably set to 15% by mass or more, and more preferably 20% by mass / °. In addition, the upper limit is particularly preferably 85% by mass or less, and more preferably less than the mass. In addition, the above-mentioned resin content rate contained in the upper layer film of the present invention is 312XP / Explanation of the Invention_ Supplement) / 94-07 / 94108335 The quality of other phosphoric acid membranes is the best. The content is as follows: under. The upper limit is 80% and the best 24 200538583 is above 0.1% by mass. The upper limit is preferably set to 50% by mass or less. The lower limit is particularly preferably set to 1 mass% or more, and more preferably 5 mass% or more. In addition, the upper limit is particularly preferably 45 mass% or less, and more preferably 40 mass% or less.

In addition, the content rate 'when the Zr compound is contained in the upper film of the present invention is calculated in terms of ZrO2, and is preferably set to 90% by mass or less of the total solid content of the upper film. The upper limit is particularly preferably set to 80% by mass or less, and more preferably 70% by mass or less. The lower limit is not specifically set, but the effect of adding more than 20% by mass will be greater. It is preferably at least 30 mass%. When the Zr compound and phosphoric acid and / or phosphate are contained in the upper film of the present invention, based on the total of Zr〇2 conversion and P04 conversion 値, it is better than the above-mentioned preferred Zr addition amount when Zr is added alone ( Z r 0 2 conversion). In addition, the existence ratio of tartaric acid and the like to the Zr compound is converted in terms of P 0 4 / Z r 0 2 and is preferably set to 0.01 to 0.40, and more preferably 0.3 or less. When Zr compound, or Zr compound and phosphoric acid and / or phosphate are contained, the ratio of A 1 compound to S i compound is calculated based on A 1 2 0 3 conversion and S i 0 2 conversion, preferably 2 0: 8 0 to 8 0: 2 0 (mass ratio). When the content ratios of the A 1 compound, the Si compound, and the resin contained in the upper film of the present invention are within the above ranges, the properties of the compound, the resistance to chalking, and the resistance to damage after strain relief annealing will be reduced. To achieve a particularly superior equilibrium, it is a better state. In addition, if the Zr compound is further contained within the above-mentioned content range, the film will be further strengthened and the above-mentioned characteristics will be improved. The so-called "total solid content of the upper film" refers to the case of the above-mentioned base film, and refers to the dried adhesion of the film made on the surface of the electromagnetic steel plate. the amount. The total solid content of the upper coating is determined by measuring the weight loss after the coating has been removed by peeling off the alkali, and it can be obtained by subtracting the total solid content of the base coating determined in advance. &lt; Manufacturing method of upper film &gt;

The upper-layer film system of the present invention can be manufactured in the same manner as the above-mentioned base film. That is, on the surface of the base film obtained by the above method, an upper layer film can be obtained by the same method. In addition, when the strain relief annealing is performed on the electromagnetic steel sheet on which the upper film of the present invention has been formed, it is the same as the annealing method when only the above-mentioned base film is formed. &lt; The adhesion amount of the base film and the upper film &gt; The film adhesion amount when forming the upper film is also arbitrary, and the adhesion amount of the base film is set to 0. 0 01 ~ 1.0 g / m2, and the upper film adhesion amount is preferably set to 0.04 to 4.0 g / m2. If it is within this range, an insulating film having a thin base film will be formed, and cracking which is a cause of deterioration of corrosion resistance will not be particularly likely to occur. The adhesion amount of the base film is particularly preferably 0.005 g / m2 or more, and more preferably 0.01 g / m or more. In addition, it is particularly preferably 0. 2 g / m2 or less. In addition, the addition of an upper layer film is very useful for ensuring the insulation. In order to prevent damage or defects of the base film, the thickness is preferably set to 0.2 g / m2. In addition, it can also be improved by forming a thinner substrate. The effect of appearance. When the upper layer is applied after the substrate is applied, the dissolution of the steel sheet Fe, which is liable to occur due to the aqueous treatment solution, is suppressed, and the appearance can be judged to be improved. &lt; Insulating film with more than 3 layers &gt; In the present invention, even if no other insulating film is formed on the above-mentioned upper layer film 26 312XP / Invention Manual (Supplement) / 94-07 / 94108335 200538583 film layer, it will still have excellent advantages The characteristics of the coating are not particularly limited in terms of forming other layers. For example in more force. For the purpose of enhancing corrosion resistance, etc., it is possible to further form a film composed of only a resin. In this case, the resin may be the same as that contained in the upper film. In addition, methods such as coating and baking can also be based on the method of using the base film or the above-mentioned upper film. [Examples] Hereinafter, the effects related to the present invention will be specifically described based on the examples, but the present invention is not limited to these examples.

(Example 1) According to the following method, electromagnetic steel sheets each having an insulating coating shown in Tables 1 to 5 were manufactured. In addition, Table 1 shows an example of an electromagnetic steel sheet having a single-layer insulating film, and Table 2 shows an example of an electromagnetic steel sheet having a two-layer insulating film having a predetermined upper film. In addition, Tables 3 and 4 show examples of electromagnetic steel sheets having two layers of insulating coatings having various upper coatings. Table 5 shows the coating characteristics. The Zr compound, the A1 compound, and the Si compound are respectively added to the deionized water to form an insulating coating composition (Table 1) or a base coating composition (Tables 2 to 4) shown in Table 4 and Table 4, respectively. Each treatment liquid for the first layer (single-layer film or basement film). In this system, it is adjusted to the amount of deionized water, and a total of 50 g / 1 of the treatment liquid is added in terms of Z r 0 2, A 1 2 0 3, and S i 0 2 in total. This% • each treatment liquid was applied to an electromagnetic steel plate (S i: 0.25% by mass) with a thickness of 0.5 mm by a newspaper coater, and cut into a width of 150 mm and a length of 300 mm. The surface of the test piece of small size is directly burned with propane gas. After baking at a temperature of 230 ° C, it is left to cool at normal temperature to form an insulating coating. 27 312XP / Invention Manual (Supplement) / 94-07 / 94108335 200538583 In addition, the particle size of colloidal silica is about 3 to 8 nm. Then, in the examples and comparative examples shown in Tables 2 to 4, the A 1 compound, the Si compound, the resin, the Z r compound, and the acid blocking agent and / or the tank acid salt were formed according to the composition of the upper film shown in each table. This method is added to deionized water to prepare each treatment liquid for the second layer (upper film). Among them, Al2O3, Si02, Zr02, and P04 conversion amounts and the solid content of the resin are adjusted so that the amount of deionized water is 50 g / 1 of the treatment liquid. Using each of these treatment solutions,

An upper layer film is formed on the layer (base film) under the conditions shown in Tables 2 to 4. Conditions other than those shown in the tables are the same as in the first layer. The results are summarized as shown in Tables 1 to 6 and Figs. In addition, FIG. 1 and FIG. 2 are related to the invention examples 1 to 6 and comparative examples 1 to 6 of the related table 1. The corrosion resistance after baking (before strain relief annealing) and the damage resistance after strain relief annealing are shown. , And the relationship between the Z r compound content (Z r 0 2 converted mass (%) relative to the total solids mass in the film). It is obvious from Tables 1, 2, 5 and Figs. 1 and 2 that any of the present inventions are superior in appearance, corrosion resistance, chalking resistance, and damage resistance of strain relief annealing plates. Each film characteristic evaluation method is as follows. &lt; Appearance &gt; Visually observe and judge the surface after painting and baking. (Judgment criteria) A: Uniform appearance B: Extent of some rainbow patterns, approximately uniform C: Moderate degree of rainbow patterns, unevenness D: Large discoloration, unevenness 28 312XP / Invention Manual (Supplement) / 94 -07/94108335 200538583 &lt; Corrosion resistance after baking and after strain relief annealing &gt; Each test piece coated with each treatment liquid to form an insulating film was subjected to constant humidity at 98% relative humidity and constant temperature at 50 ° C It was kept in the tank for 2 days, and the area ratio of occurrence of rust on the surface of the test piece was determined, and the corrosion resistance was evaluated according to the following judgment criteria. In addition, the "rust generation area ratio" refers to the total percentage of the rust generation area relative to the total observed area, and is visually judged.

Furthermore, the same test was also performed on the surface of the sample subjected to strain relief annealing after being held in a N 2 environment at 7 5 (TC for 2 hours), and the corrosion resistance was evaluated. 0 (judgment criterion) A: Area ratio of occurrence of rust = 0% or more, less than 5% B: Area ratio of rust occurrence = 5% or more, less than 20% C: Area ratio of rust occurrence = 20% or more, less than 50% D: Area ratio of rust occurrence = 50% or more &lt; Dusting resistance after baking &gt; Test conditions: The test piece is reciprocated under the condition that the felt on one side of the test piece forming the insulating film is pressed against the felt, and the test result is observed. Scratches to evaluate the peeling and powdering state of the film. The felt contact surface is 20x10mm wide, the crimping load is 3.8kg / cm2 (0.4MPa), and the reciprocating motion is simply equivalent to 400m. ) A: Hardly found any marks B: Some scratches and some degree of chalking C: Film peeling, obvious scratches and degree of chalking 29 312XP / Invention Manual (Supplement) / 94-07 / 94 】 08335 200538583 D: Exposed degree of exfoliated iron substrate, a lot of dust &lt; After strain relief annealing Damage resistance &gt; Test conditions: The surface of the annealed sample held in an N 2 environment at 750 ° C for 2 hours was scraped with an edge portion obtained by cutting the same steel plate, and then the damage, Degree of chalking (Judgment Criteria) A: Hardness and chalking are not found B: Severe scratches and chalking are found

C: The degree of scratches and chalking is clearly found D: The degree of peeling of the iron substrate is exposed, and there is a lot of dust

30 312XP / Invention Specification (Supplement) / 94-07 / 94108335 200538583 Table 1

Insulation coating film characteristics Zr compound Zr compound content "[%] The remaining inorganic component adhesion amount [g / m2] Appearance after baking and inch 1 insect resistance after corrosion resistance Powder resistance after baking resistance comparison after annealing Example 1 No 0 alumina sol (60) + colloidal silica (40) 0. 7 BDBAA Comparative Example 2 Acetic acid Zr 20 // // BCBAA Comparative Example 3 // 30 // // BCBAA Comparative Example 4 // 40 // // BCBAA Invention Example 1 // 45 // // BBBAA Invention Example 2 // 50 // // BABAA Invention Example 3 // 60 // // BABAA Invention Example 4 // 70 II // BABAA Invention Example 5 // 80 II // BABAA Invention Example 6 // 90 II // BBBAB Comparative Example 5 // 95 // // BBCAC Example of car delivery 6 // 100 None 0.7 BBDAD Invention Example 7 // 60 Alumina sol (60) + Colloidal Silicon Dioxide (40) 0.01 BBBAA Invention Example 8 // // // 0.05 BBBAA Invention Example 9 // // // 0.1 BBBAA Invention Example 10 // // &quot; 0.2 BABAA Invention Example 11 / / // II 1.0 BABAA Invention Example 12 // // II 1.5 BABBB Invention Example 13 II // // 3.0 BBBBB Comparative Example 7 // // Alumina Gel 0.7 BBCAB Invention Example 14 // // Alumina Sol (80) + Colloidal Silicon Dioxide (20) // BBBAA Invention Example 15 // // Alumina Sol (40) + Colloidal Silicon Dioxide (60) // BABAA 1 spring example 16 // // alumina sol (20) + colloidal silicon dioxide (80) // BBBAA comparative example 8 // // colloidal silicon dioxide 11 BBCAB invention example 17 propionic acid Zr // alumina sol (60) + Colloidal Silicon Dioxide (40) 11 BABAA Invention Example 18 Nitric Acid Zr II // // BABAA Invention Example 19 // 80 // // BABAA Invention Example 20 Acetic acid Zr + Zr nitrate (mass ratio 1: 1) 60 // // The Zr〇2 conversion mass percentage of the BABAA relative to the total solid content of the insulating film * 2: the main component of the insulating film other than the Zr compound. () Mass ratio of internal A1 compound to Si compound (Al2〇3 conversion, Si0 2 conversion) 31 312XP / Invention specification (Supplement) / 94-07 / 94108335 200538583

Base film upper layer film + 3 t film Special powder baking resistance after baking, scorch resistance after annealing, Zr compound, Zr compound blessing amount, remaining inorganic component, adhesion amount 2 [g / m J [g / ηΐΊ Appearance baking Post-corrosion resistance Comparative example of tapeworm resistance after annealing 9 Zr 60 acetate Alumina sol (60) + _ Colloidal silica (40) 0.000 5 0.6 CCCAAA D A Invention example 21 // // // 0.001 // BBBAA Invention Example 22 // // // 0.002 // BBBAAA Invention Example 23 // // 0.005 // AAAAAA Invention Example 24 // // 0.01 // AAAAA Invention Example 25 // // // 0 02 // AAAAAA Invention Example 26 // // // 0.05 // AAAAA Invention Example 27 // // // 0.1 // AAAAA Invention Example 28 // 11 // 0.5 // AAAAA Invention Example 29 11 // / / 0.7 // AAAAA _ 明 例 30 // // 1.0 1.0 AAAAA 1 Example 31 // // II ί. 5 // BBBAA Invention Example 32 // // // 3.0 // BBBAA Comparative Example 10 None 0 // 0.1 // ADBAA Comparative Example 11 Acetate Zr 20 // // // ACBAA Comparative Example 12 // 30 // // // ACBAA Comparative Example 13 // 40 // // // ACBAA Invention Example 33 // 45 // // // ABAAA Invention Example 34 // 50 // // // AAAAA Invention Example 35 // 70 // // // AAAAA Invention Example 36 // 80 // // // AAAAA Invention Example 37 // 90 // // // AABAB Comparative Example 14 // 95 II // II ABCAC Comparative Example 15 // 100 None // ACDAD Invention Example 38 // 60 Alumina Sol (60) + Colloidal Silicon Dioxide (40) // L5 AAAAA // // // 3.0 AAAAA Invention Example 40 // // // 4.0 AAAAB Invention Example 41 Propionate Zr // // 0.6 AAAAA Invention Example 42 Nitric Acid Zr // // // // AAAAA Invention Example 43 // 80 // // // AAAAA Invention Example 44 Acetic acid Zr + Nitrate Zr (mass ratio 1: 1) 60 // // // AAAAA * 2: constitutes the first layer (basement film ) Other than Zr compounds. () Mass ratio of internal A1 compound to Si compound (AhO3 conversion, si〇2 conversion) * 3: Composition: tree finger (polyester) (solid content is divided into 30% of the total solid content of the upper film) ', ^ The rest of the tritiated chain sol and colloidal silica (AhCkSiO2 conversion ratio = 6〇: 4〇) 312XP / Invention Specification (Supplement) / 94-07 / 94108335 32 200538583 Table 3

* 1: Zr〇2 conversion quality relative to the total solid content of the insulating film (base film) ^ * 2: Main components other than the Zr compound constituting the first layer (base film). () Mass ratio of internal A1 compound to Si compound (Ah03 conversion, Si02 conversion) * 3: Main component other than resin constituting the second layer (base film). () Mass ratio of internal system A1 compound to Si compound (AΙΛ conversion, Si〇2 conversion) The percentage of gold ^ with respect to the mass of the total solid content of the insulating coating (upper coating) 312XP / Invention Specification (Supplement) / 94-07 / 94] 08335 33 200538583 Table 4 Basement membrane

Zr compound

Zr compound content ”Adhesion, [g / m2] Inorganic main component of the upper film * Tree and grease type Invention Example 57 Zr 60 acetate Alumina sol (50) + silica M (50) 0.1 Alumina soluble (42 ) + Colloidal Silicon Dioxide (28) + Acetic Acid Zr (30) Resin Solid Content Mass Enzyme 30 0.6 Invention Example 58 Alumina Sol (24) + Colloidal Silicon Dioxide (16) + Zr (60) Acetate Invention Example 59 Alumina sol (12) + colloidal silica (8) + acetic acid-ZK80) Alumina sol invention example 60 nitrate Zr (24) + colloidal silica (16) + Zr (60)

Invention Example 64 Alumina sol (21) + colloidal silica (14) + acetate Zr (5b + acid filling (10) 0.1 polyester 30) Invention Example 65 Alumina sol (20) + colloidal silica (14) + acetic acid Zr (51) + phosphoric acid (15) ----—_- ____Q 丄 b) * ι · Relative to the insulation film (the total solid content of the substrate is Zr〇2, the amount is 100% $ * 2: constitute the first layer (Base film) Main component other than Zr compound () Mass ratio of internal A1 compound to Si compound (A1Λ conversion, Si02 conversion) 3: Main component other than resin constituting the second layer (upper layer coating) The mass ratio of A1 compound (A1Λ3 conversion), si compound (Si〇2 conversion), zr compound (Zr〇2 conversion), and phosphoric acid (salt) (P04 conversion) in 〇 *: relative to the insulation coating ( Upper film) Percentage of total solids mass J12XP / Invention Manual (Supplement) / 94-07 / 94108335 34 200538583

table 5

Coating Characteristics Appearance Corrosion Resistance after Baking Annealing Resistance after Baking Annealing Resistance after Baking Powder Damage Resistance After Annealing Comparative Example 16 ABCAB Invention Example 45 ABAAA Invention Example 46 AAAAA Invention Example 47 ABAAA Comparative Example 17 ABCAB Invention Example 48 AAAAA Invention Example 49 AAAAA Invention Example 50 AAAAA Invention Example 51 AAAAA Invention Example 52 AAAAA Invention Example 53 AAAAA Invention Example 54 AAAAA Invention Example 55 AAAAA Invention Example 56 AAAAA Invention Example 57 AAAAA Invention Example 58 AAAAA Invention Example 59 AAAAA Invention Example 60 AAAAA Invention Example 61 AAAAA Invention Example 62 AAAAA Invention Example 63 AAAAA Invention Example 64 AAAAA Invention Example 65 AAAAA 312XP / Invention Specification (Supplement) / 94-07 / 94 丨 08335 35

200538583 (Example 2) An electromagnetic steel sheet having the respective coatings shown in Tables 6 to 11 was manufactured according to the following method. In addition, Tables 6 and 7 show examples of electromagnetic steel sheets having a single-layer insulation, and Tables 8 and 9 show examples of electromagnetic steel sheets having a predetermined upper-layer insulating film. In addition, Table 10 shows an example of an electromagnetic steel sheet having a two-layer insulating film with an upper film, and Table 11 shows film characteristics. Z r compounds, phosphoric acid and / or phosphates, A 1 compounds, and S i compounds were formed in the manner shown in Tables 6 to 10 (Table 6, Base coating composition (Tables 8 to 10)). , Added to the deionized water to make each treatment liquid for the first layer (single-layer film or bottom film). Here, it is adjusted according to the amount of deionized water according to Z r 0 2, P 0 4, A 1 2 0 3, S i 0 2 was changed to a total of 50 g / 1 of the treatment liquid. Each of these treatment liquids was applied to a steel plate (Si: 0.25% by mass) having a thickness of 0.5 mm by a roll coater, and cut into The surface of a large test piece with a width of 150 mm and a length of 300 mm was directly burned with propane gas, and after baking was performed at the baking temperature (reach temperature) shown in the table, it was released at normal temperature to form an insulating coating. Then, in Table 8 In the examples and comparative examples shown in ~ 10, A 1 is compounded with a Si compound, a resin, a Zr compound, and an acid filling agent and / or a structuric acid salt to be added to the deionized water in the composition manner of the upper layer film shown in each table. Each treatment liquid used for the second layer (upper layer film), among which Al2O3, Si02, ZP04 equivalent amount, and resin The mass of the form is adjusted so that the treatment liquid is added with 50 g / 1 relative to the amount of detachment. 312XP / Invention Manual (Supplement) / 94-07 / 94108335 2 of the insulation coating, each of which is compounded 7) or The adjustment system has a small electromagnetic quantity of 6 to 1 0. Set the cold object and adjust it according to the shape of r 0 2. Sub-water 36 200538583 Use each of these treatment liquids on the first layer (basement film) according to Table 8 ~ 1 0 Under the conditions shown, an upper layer film was formed. Conditions other than those shown in the tables are the same as in the first layer.

The results are summarized as shown in Tables 6 to 11 and Figures 3 and 4. In addition, as shown in FIG. 3, related to Invention Examples 6 to 7 of Table 9 and Comparative Examples 1 to 7 and 20, the powder resistance after baking (before strain relief annealing), and phosphoric acid (salt) and The relationship diagram between Z r compound existence ratio (P 0 4 equivalent mass / Z r 0 2 equivalent mass). In addition, FIG. 4 is related to invention examples 7 to 1 of Table 6 (phosphoric acid and / or phosphate addition: Black dots) and Invention Example 1 4 to 2 0 (no addition: blank triangle), the relationship between powdering resistance after baking and baking temperature. It is obvious from Tables 6 to 9, Tables 1 and 1, and 3 and 4 that any of the present inventions have good film properties, especially the first layer of steel plates containing phosphoric acid, etc., which are implemented even at low temperatures. Baking still has superior appearance, corrosion resistance, powder resistance and damage resistance after strain relief annealing.

37 312XP / Invention Specification (Supplement) / 94-07 / 94108335 200538583 Table 6

Zr compound acid, phosphoric acid salt (zirconium salt) / Zr chemical compound ratio W Zr, P compound content, / ◦] The rest of the ingredients are selected 3 Baking temperature [° c &quot; ——. ^ — · — Adhesion [gfm2 ] Appearance: Corrosion resistance after baking: Corrosion resistance after annealing: Corrosion resistance after annealing: Comparative example of post-pulverization resistance and damage resistance after annealing Annealing-0-Vaporized aluminum sol (60) + colloidal silica (40) 150 0.7 BDBDA Comparative Example 2 Zr Acetic Acid 0.2 20 // // ——. // // BCBDA Comparative Example 3 // // 30 // // CB c A Comparative Example 4 // // // 40 // // // JL / B c BBA Invention Example 1 η // // 45 // // BBBAA Invention Example 2 // // // 50 // // // BABAA Invention Example 3 η / / // 60 // // II BABAA Invention Example 4 // // // 70 // // // BABAA Invention Example 5 // II // 80 // // // BABAA Invention Example 6 // // // 90 // // // BBBAB Comparative Example 5 // II // 95 // // // BBCAC _ Comparative Example 6 // // // 100 None // // BBDAD Invention Example 7 // // // 60 oxide sol (60) + colloidal silicon dioxide (40) 200 // BABAA Invention Example 8 // // // // II 17 5 // BABAA Invention Example 9 // // // // II 150 // BABAA Invention Example 10 // // II &quot; // 125 // BABAA Invention Example 11 // // // // // 100 // BABAA ^^ 12 12 // // // // 75 — // BABAA Invention Example 13 // II // // // 60 // BABBA Invention Example 14 // None 0 // // 200 // BABBA Invention Example 15 // // // // // 175 // BABCA Invention Example 16 // // // // // 150 // BABDA Invention Example 17 // II // // // 125 // BABDA Invention Example 18 // // // 11 // 100 // BABDA Invention Example 19 // // // II // 75 // BABDA Invention Example 20 // // // // // 60 // BABDA Business Example 21 // Phosphoric Acid 0.2 // // 150 0.01 BBBAA _ Business Example 22 // // // // // // 0. 05 BBBAA Invention Example 23 // // // // // // 0.1 _ BBBAA Invention Example 24 // // // // // // 0.2 BABAA Invention Example 25 // // // // // // 1.0 BABAA Invention Example 26 // // // II // // 1.5 BABBB invention queue 27 // // // // // // 3.0. BBBBB ^ J \ &gt; \ Heart 丄 fL / 4 / Zil L / 2 目】 目 * 2: Relative to Insulation film total solids mass (&amp; 〇2 converted mass + Mass conversion percentage) * 3: Mass ratio of A1 compound to Si compound in the main component () other than &amp; compound, phosphoric acid, phosphate constituting the first layer (base film) (Al2O3 conversion, Si. 2 conversion) 38 312XP / Invention Specification (Supplement) / 94 · 07/94108335 200538583 Table 7

Zr compound Phosphoric acid, phosphate Phosphate (salt) / Zr compound ratio 31: 1

Zr, P compound nm

The remaining I5 ginseng inorganic baking a degree [c] [adhesion amount g / m2] Comparative Example 7 Comparative Example 8 Invention Example 28 Invention Example 29 Invention 30 Splash ^ Ming Example 31 Invention Example 32 Comparative Example 9 'Invention Example 33 Invention Example 34 Inventive Example 35 Inventive Example 36 Inventive Example 37 Inventive Example 38 Inventive Example 39 Inventive Example 40 Intensive Service Example 41 Inventive Example 42 Inventive Example 43 Inventive Example 44 Inventive Example 45 Inventive Example 46 Inventive Example 47 * 1 * 2 * 3 mnr C Acid Zr Acetic acid Zr Nitric acid Zr Acetic acid Zr + Nitric acid Zr * 4 Phosphoric acid without phosphoric acid 4 Acid A1 Phosphate Mg Phosphoric acid Ca W Acid + Phosphoric acid AΓ Phosphate A1 + Phosphorus S ^ Mg * 4 Phosphoric acid phosphate A1 Phosphoric acid Oxidation short: | (60) + Glue: ^ Silicon dioxide (you,

0.2 alumina sol (80) + colloidal silica (2 must alumina sol (40) + colloidal silica (6 must

Alumina sol (20) + colloidal silica (group

Alumina sol (60) + colloidal silica (volume

100 150 The percentage of P〇4 / Zr〇2 値 converted from P04 and Zr〇2 to the total solids mass of the insulation film (Zra-equivalent mass and B04-equivalent mass) constitutes the first layer (base film) Except for Zr compound, phosphoric acid, and phosphate, the main component () is the mass ratio of A1 compound to Si compound (AI2O3 conversion, Sift conversion) * 4: mass ratio 1: 1 312XP / Invention Specification (Supplement) / 94 -07/94108335

B T B B B

39 200538583 Table 8

Coating characteristics

Alumina sol (60) + colloidal silica (40)

Alumina sol (60) + colloid two gasified fossil mm

* 1: P〇4 / Zr〇2 converted from P04 and Zr〇2 値 * 2 ·· One hundred eight with respect to the total solid content of the insulation film (Zr〇2 converted mass · 4 converted mass) * 3 : The main [() internal mass ratio of A1 compound to Si compound (AI2O3 conversion, si02 conversion) knife other than Zr compound, phosphoric acid, and dishate that constitute the first layer (base film). * 4: Composition · Resin (polyester) (solid content is divided into the total solid content of the upper layer by 300 / 〇) 'The rest of the oxide sol and colloidal silica (AlUiO2 conversion ratio = 60:' 4〇 ); Hong roasted temperature coffee. 3 ΠχΡ / Invention Specification (Supplement) / 94-07 / 94108335

40 200538583 Table 9 Basement membrane

Zr compound phosphoric acid, phosphate phosphate (salt) / Zr compound ratio wood 1

Zr, P compound contains [%]

Invention Example 74 Invention Example 75 Alumina sol (60) + colloidal silica (40)

Alumina solvent (80) + colloidal silica (20) Invention Example 76 Propionate Zr Invention Example 77 Acetic acid Zr Fill S ^ Al Invention Example 78 Fill S 観 g

P〇4 / Zr〇2 converted from P〇4 and Zr〇2

Baking temperature [° c &quot; 75 The rest of the body composition alumina sol (40) + colloidal silicon dioxide (60) alumina sol (20) + colloidal gasification (80) alumina to (60) + Colloid II [彳 b 硅 urn

The percentage of the baking-resistant post-bake corrosion ABAAA relative to the total solids mass of the insulating film (Zr〇2 converted mass + P04 converted mass) constitutes the main layer (the Zr compound, phosphoric acid, and phosphate) of the first layer (base film) except ) Mass ratio of internal system A1 compound to Si compound (Ah03 conversion, si02 conversion) Knife * 4: Composition: tree finger (poly vinegar) (solid content is divided into the upper solid film and the total solid content of the upper layer and its remaining mass Scores &amp; Huana knee and victorious stone dioxide (then 3: Sia conversion ratio = 60: 40); Although chess 312XP / Invention Manual (Supplement) / 94-07 / 94108335

After-annealing resistance DCBBB

Powder resistance after baking D c B A A

Damage property after annealing D c B A A

A

A

A

A

A

A

A

A

A

A

A

A

A

A

A 41 200538583 Table ίο Zr Compound Wall Acid, Phosphate Phosphate (Salt) / Zr Compound Ratio * 1 Zr, P Compound Content * 2 [° / 〇] Peach-free composition in other parts * 3 Baking temperature [° c] Attached [gfm2] Inorganic main component * 4 Resin type Resin solid content% Amount ° / 〇5 Baking ', Tian / JHL Degree [° c] Attached [g% 2] Invention Example 81 Acetic acid Zr phosphoric acid 0.2 60 alumina sol (60) + colloidal silica (40) 75 0 · 1 alumina sol (60) + colloidal silica (40) acrylic 30 230 0.6 Invention Example 82 // // // // / / // // // melamine // // // Invention Example 83 // // // // // // // 11 11 Aminoethyl ethyl acetate // // // Invention Example 84 // / / // // // // // &quot; epoxy // // // Mingle Arm, 85 // // // // // // // II Polyethylene 5 // 11 Invention Example 86 // // // // // // // // 20 // // Inventive Example 87 // // II // // // // // Polyester 10 // // Inventive Example 88 // // II // // // // // // 20 // // Invention Example 89 // // 11 // // // // Oxidized sol (42) + colloidal silica (28) + Acetate Zr (30) // 30 // // Invention Example 90 II // // // // // // Alumina Sol (24) + Colloidal Silicon Dioxide (16) + Acetic Acid Zr (60) // // // Lu Ming Example 91 // // // // // // // Emulsification solution (12) + colloidal silica (8) + acetic acid Zr (80) // // // Invention Example 92 Nitric acid Zr // // // // // // alumina sol (24) + colloidal silicon dioxide (16) + nitric acid Zr (60) // // // // invention of L 93 acetic acid Zr // // // // // 0.01 oxide dissolved (24) + colloidal silicon dioxide (16) + acetic acid Zr (60) polyethylene 8 // 11 Invention Example 94 II // // // // // 0.1 alumina sol (21) + colloidal silicon dioxide (14) + acetic acid Zr (55) + phosphoric acid (10) polyester 30 // // 312XP / Invention Specification (Supplement) / 94-07 / 9410833 5 42 200538583 Invention Example 96 711 1 // // /; // // // 0.1 alumina sol (20) + colloidal silicon dioxide (14) + acetic acid Zr (51) + phosphoric acid Al (15) poly 6 purpose 30 // // invention Example 97 // Phosphoric acid A1 // // // // // // // // // * 1: P〇4 / Zr〇2 値 * 2 converted from P〇4 and Zr〇2 : Percentage of the total solid content of the insulation film (converted mass +? 〇4converted mass) * 3: constitute the first layer (base Bottom film), except for compounds, linoleic acid, and osmic acid salts. (1) The mass ratio of the internal A1 compound to the Si compound (AhOa conversion, Si02 conversion) * 4: The second layer (upper film) Main ingredients other than resin. () The mass ratio of the internal A1 compound (equivalent to Al2O3), &amp; compound (equivalent to Si02), Zr compound (equivalent to Zr02), and phosphoric acid (salt) (equivalent to P4) relative to the insulation film (Upper film) Percentage of total solid content Table 11

Film properties Appearance After baking Resistance to touch After annealing Annealing Resistance To powder after baking Resistance to damage after annealing Anneal Example 81 AAAAA Invention Example 82 AAAAA Invention Example 83 AAAAA Invention Example 84 AAAAA Invention Example 85 AAAAA Invention Example 86 AAAAA Invention Example 87 AAAAA Invention Example 88 AAAAA Invention Example 89 AAAAA Invention Example 90 AAAAA Invention Example 91 AAAAA &gt; Invention Example 92 AAAAA Invention Example 93 AAAAA Invention Example 94 AAAAA Invention Example 95 AAAAA Invention Example 96 AAAAA Invention Example 97 AAAAA

(Industrial Applicability) According to the present invention, it is possible to provide an insulating film mainly composed of an inorganic substance that does not substantially contain chromium, even at a temperature lower than 300 ° C, or lower than 200 ° C. In the following, when manufacturing is performed by coating and baking, the corrosion resistance and powder resistance after baking (before strain relief annealing), appearance, and 43 312XP / Invention Specification (Supplement) / 94-〇 after strain relief annealing are performed. 7/94108335 200538583 Electromagnetic steel sheet with insulation coating and excellent damage. [Brief description of the figure] FIG. 1 is a graph showing the effect of the amount of Zr compound added on the insulating film (horizontal axis: mass%) on the corrosion resistance (vertical axis) after baking (before strain relief annealing). Fig. 2 is a graph showing the effect of the amount of Zr compound added on the insulating film (horizontal axis: mass%) on the damage resistance (vertical axis) after strain relief annealing. Figure 3 is a graph showing the effect of P 0 4 / Z r 0 2 (mass%) on the chalking resistance (longitudinal axis) of the insulation coating baked at 75 ° C.

Figure 4 shows the baking temperature (horizontal axis: ° C) of the powdering resistance (vertical axis) of the insulating film (black dots) containing phosphoric acid and / or phosphate, and the insulating film (blank triangle) not included. Impact diagram.

44 312XP / Invention Specification (Supplement) / 94-07 / 94108335

Claims (1)

200538583 X. The scope of patent application: 1. An electromagnetic steel sheet with an insulating coating, which contains the Zr pseudonym A 1 compound and Si compound as the main component; characterized by Zr relative to the total solid content of the insulating coating The compound contains 4 5 to 90 mass ° / 〇 in terms of Z r 0 2. 2. An electromagnetic steel sheet with an insulating coating, which contains at least one selected from the group consisting of phosphates, Zr compounds, A1 compounds, and Si as the main components; characterized in that, relative to the total thickness of the insulating coating For the solid content, the content ratio converted by P04 and at least one selected from the above-mentioned phosphoric acid and phosphorus, and the content ratio converted by the above-mentioned Zr conversion according to Zr 0 2 are 4 5-9 0 mass! , And the ratio of the two containing: is calculated according to P 0 4 / Z r 0 2 as 0. 0 0 0 0 4 0. 3. For example, the electromagnetic steel with an insulation film in the scope of the patent application, wherein the insulation coating j has M-0-Z r and M-0 相对 with respect to A 1, S i and F e shown by M. -At least one of the bonding states in Z r. 4. For the electromagnetic steel with an insulation coating, as described in the second item of the patent application, the insulation system has M-0-Z r and M-0 with respect to A 1, S i, P, and F e indicated by M. Η-At least any bonding state in Z r. 5. The electric board with an insulating film according to item 1 or 2 of the scope of patent application, wherein the insulating film does not substantially contain Cr. 6. The electric board with an insulating film according to item 1 or 2 of the scope of the patent application, wherein the content of the A1 compound and the S i substance in the insulating film is converted according to A 1 2 0 3 値 and S i 0 2 converted 0 The ratio is 2 0 8 0: 2 0 〇312XP / Invention Specification (Supplement) / 9 ^ 07/94108335 ', the rate of depletion, the rate of depletion with the phosphate compound, the Chinese board, the magnetic coating Steel magnetic steel compound: 80 ~ 45 200538583 7. For example, the electromagnetic steel sheet with an insulating coating in the scope of application for patents 1 or 2 will contain at least A 1 compound, Si compound, and Z r compound in a dissolved or colloidal state. The aqueous treatment solution is coated on a steel plate and then baked. 8. The electromagnetic steel sheet with an insulating coating according to item 7 of the scope of patent application, wherein the Zr compound contained in the above-mentioned aqueous treatment liquid is formed into a solution or a colloid by using at least any one of a hydroxyl group, an organic acid, an inorganic acid, and water. shape. 9. The electromagnetic steel sheet with an insulating coating according to item 7 of the scope of the patent application, wherein the Zr compound contained in the above-mentioned aqueous treatment solution is selected from the group consisting of gadolinium acetate, gadolinium propionate, gadolinium oxygenate, zirconium nitrate, ammonium zirconium carbonate, and carbonic acid. Potassium hydroxide, zirconium hydroxide gas, zirconium sulfate, zirconium phosphate, zirconium sodium phosphate, potassium hafnium hexafluoride, tetra-n-propoxy hafnium, tetra-n-butoxy zirconium, tetraethylpyrene pyruvate, tributoxy At least one kind of zirconium acetamate pyruvate and zirconium tributoxystearate is selected. 10. The electromagnetic steel plate with an insulating coating according to item 8 of the scope of patent application, wherein the Zr compound contained in the aqueous treatment liquid is at least one selected from zirconium acetate and hafnium nitrate. 1 1. The electromagnetic steel sheet with an insulating coating according to item 7 of the scope of patent application, wherein the A 1 compound contained in the above-mentioned aqueous treatment solution is composed of the A 1 compound composed of a hydroxyl group and an organic acid and a dehydration reaction product thereof. In the group, select at least one. 12. The electromagnetic steel plate with an insulating coating according to item 7 of the scope of the patent application, wherein the silicon compound-based colloidal silica contained in the above-mentioned aqueous treatment liquid. 1 3. If the electromagnetic field with an insulation coating 46 or 312χρ / Invention Specification (Supplement) / 94-07 / 941 〇8335 200538583 steel sheet, as described in item 1 or 2 of the scope of patent application, the surface of the above insulation coating has at least more The second insulating coating. 14. The electromagnetic steel sheet with an insulating coating according to item 13 of the scope of patent application, wherein the at least second insulating coating is substantially free of C r. 15. The electromagnetic steel sheet with an insulating coating according to item 13 of the scope of the patent application, wherein the second insulating coating contains an A1 compound, a Si compound, and a resin. 16. The electromagnetic steel plate with an insulating coating according to item 15 of the scope of patent application, wherein the second insulating coating further contains a Zr compound. 1 7. —A method for manufacturing an electromagnetic steel sheet having an insulating coating, which is a method for manufacturing an electromagnetic steel sheet having an insulating coating that does not substantially contain Cr after applying an aqueous treatment liquid on the electromagnetic steel sheet and baking it; The above-mentioned treatment solution contains: Si compound, A1 compound, and Zr compound in a dissolved or colloidal state; and the content of the Zr compound in the treatment solution is based on the total solid content of the insulating film after the baking, according to ZrO2 amount conversion accounts for 45 to 90% by mass. 1 8. A method for manufacturing an electromagnetic steel sheet with an insulating coating, which is a method of manufacturing an electromagnetic steel sheet having an insulating coating substantially free of Cr after applying an aqueous treatment solution on the electromagnetic steel sheet and baking it; The above treatment solution contains: at least one selected from phosphoric acid and phosphate, a Si compound, an A 1 compound, and a Zr compound in a dissolved or colloidal state; and at least one selected from phosphoric acid and phosphate in the above treatment solution. The content of Zr and the Zr compound content in the treatment solution are based on the total solid content of the insulating coating after the baking described above. Based on the amount of ZrO2 and P (h amount, the total accounts for 47 312XP / Invention Specification (Supplement Pieces) / 94-07 / 94108335 200538583 45 to 90% by mass; and the ratio P4 / Zr〇2 of the above-mentioned amount of Zr〇2 to the above-mentioned amount of P04 is 0 · 0 1 to 0 · 40. 312XP / Invention Specification (Supplement) / 94-07 / 94108335 48