TW515851B - Non-oriented electromagnetic steel sheet having insulating film excellent in film properties, method for producing same, and insulating film-forming agent used for producing the same - Google Patents

Abstract

The present invention provides a film-forming agent for an insulating film-coated non-oriented electromagnetic steel sheet showing a high space factor, and excellent in blanking quality, adhesion of the film and slip characteristics subsequent to stress relief annealing, a non-oriented electromagnetic steel sheet having the insulating film and a method for producing the same. The present invention provides a non-oriented electromagnetic steel sheet having an insulating film excellent in film properties, the insulating film comprising a metal phosphate and an organic resin as the principal components, the 1s peak intensity of C being from 4 to 20 times as much as the 2s peak intensity of P when the insulating film is measured by photoelectron spectral analysis.

Description

^ 851 V. Description of the invention (1) A7 β · 7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This invention is about an insulating film-forming agent for high space factor # Non-directional electromagnetic steel sheet, which Presents excellent adhesion of insulating film and excellent stamping quality, and has excellent lubrication characteristics after stress relief annealing, adhesion and corrosion resistance of insulating film, and coating the bottom of steel sheet with insulating film-forming agent Method for manufacturing a non-oriented electromagnetic steel sheet. When manufacturing laminated cores for motors, transformers, etc. from non-oriented electromagnetic steel sheets, the unit cores are usually cut or die punched from non-oriented electromagnetic steel sheets, stacked, and stacked. It is prepared by bolting, plugging, brazing, bonding or similar steps. The thus obtained laminated iron core is subjected to a coil bonding 'or the like, and finally assembled into a motor or a transformer. An insulating film is usually formed on a non-oriented electromagnetic steel sheet. Because the various properties of steel sheets, such as soldering quality, stamping quality, and corrosion resistance, depend heavily on the properties of the insulating film, it is not only important to give insulation performance, but also to have excellent film properties of the insulation film. It has hitherto been known that inorganic, organic, and inorganic-organic hybrid insulating films can be used as an insulating film for non-oriented electromagnetic steel sheets. However, steel sheets having inorganic insulating films exhibit poor stamping quality, which Compared with an organic insulating film or an inorganic-organic hybrid insulating film. Compared with a steel sheet with an organic insulating film, when the stress is relieved and annealed, it exhibits poor film adhesion and poor corrosion resistance. This is compared with an inorganic insulating film or an inorganic-organic hybrid insulating film. For this reason, inorganic insulating films and films are not suitable. Inorganic-organic hybrid insulating films have been studied in depth to solve the problems between inorganic and organic insulating films. Japanese Examined patent This paper standard is applicable to Chinese National Standard (CNS) Λ4 specification (2 丨 0 × 297) 漦 Please read the precautions before reading

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4 515851 A7 B7 i. Description of the invention (2 Kokoku published by Kokoku, the Shell Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, proposes a method of forming an insulating film on a non-oriented electromagnetic steel sheet to make the result Thin steel sheet exhibits thin film properties, such as high space factor, excellent adhesion of the film and excellent stamping quality. The method includes forming a dielectric film with a treatment solution, the solution containing a dichromate and a resin Organic resin emulsion, the main component of the resin is a resin such as a vinyl acetate resin, a butadiene-styrene copolymer, or acrylic acid. However, when using a dichromate, it is common in inorganic-organic hybrid insulating films. In the directional electromagnetic steel sheet, a Cr compound is used as a component of the film. In this case, in the process of manufacturing a non-directional electromagnetic steel sheet, or a customer using such a non-directional electromagnetic steel sheet, a serious problem is faced. Environmental issues, so it is hoped to develop a technology for treating an insulating film with a compound containing no chromium. Early Unexamined Patent Publication No. 6-330338 The following treatment methods are disclosed. A treatment method comprises mixing a phosphate with a specific composition and an organic resin emulsion with a specific particle size in a specific ratio, and coating a steel sheet with the resulting treatment solution to The steel sheet is baked. The treatment solution used in this method does not contain chromium compounds, and the steel sheet obtained by this method exhibits film properties comparable to those of conventional insulating film steel sheets containing chromium compounds, and is relieved of stress. After annealing, excellent lubricating properties are maintained. However, the following problems have been found in the technique disclosed in Japanese Unexamined Patent Publication No. 3333338. The organic resin emulsion in the treatment solution often coagulates, or when applied In the coating and baking steps. As a result, the 'non-organic resin' part and the organic resin's part in the insulating film are mixed, resulting in the paper size of the steel paper conforming to the Chinese National Standard (CNS) Λ4 specification (210X297) Note on the back then fill in this page] * Clothing-fill in this order

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 515851 A7 --------- ___137 V. Description of the Invention (3)-The die punching performance of the sheet is reduced. When an insulating film is to be formed on a non-oriented electromagnetic steel sheet, the steel sheet is usually coated with an insulating film treatment solution and baked, and then continuously annealed. Therefore, it is important in the industry that an insulating film with excellent film properties can be formed stably over a long period of time without the aggregation of organic resins. Furthermore, because many motors and transformers have complex shapes, such as a clearance mold Shock conditions sometimes deviate from the optimal values. In the case of applying the technique disclosed in Japanese Unexamined Patent Early Publication No. 6-330338, it was found that the stamping quality was lowered. As a result of in-depth study of these problems, the inventors of the present invention have found the best method for manufacturing a non-directional electromagnetic steel sheet with an insulating film. The main components of the film are a phosphate and an organic resin. The quality of die punching is not good. Even when the die punching conditions are not good, such as a complex die punching shape, the die punching quality is improved. In addition to being used to add organic resin to the film composition, it is also added to the inorganic component of phosphate. Dispersing an organic compound increases the amount of organic carbon contained on the surface of the insulating film. The present invention is based on the findings as described above. The gist of the present invention is described in the following. The first object of the present invention is to provide a non-oriented electromagnetic steel sheet having an insulating film with excellent film properties. The main components of the insulating film are A metal phosphate and an organic resin. When the insulating film is measured by photoelectron spectroscopy, the Is peak intensity of C (carbon) is 4 to 20 times that of the 2s peak intensity of P (phosphorus). This paper is applicable to China National Standard (CNS) Λ4 specification (210 X 297 public)

丄 5851 Printed A7 B7 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (4) ^ The second object of the present invention is to provide a method for manufacturing non-oriented electromagnetic steel sheet, which is one of the insulating films with excellent film properties. It includes coating a non-directional electromagnetic steel sheet substrate with an insulating film-forming agent. The film-forming agent is a processing solution. The main component is a metal salt and an organic resin, and further contains from 5 to 50 parts by weight of a water-soluble organic compound having a melting point or sublimation point of at least loot: based on 100 parts by weight of metal phosphate, and baking the coated steel sheet at 200 to 400 c. A third object of the present invention is to provide an insulating film-forming agent, which is a non-directional electromagnetic steel sheet used for producing an insulating film with excellent film properties. The agent is a treatment solution containing a main component of A metal phosphate and an organic resin, and further containing from 5 to 50 parts by weight of a water-soluble organic compound having a melting point or sublimation point of at least 100 ° C. based on 100 parts by weight of the metal phosphate. The present invention will be described in detail below. It is well-known that the stamping quality of a non-oriented electromagnetic steel sheet is greatly affected by the composition of the insulating film. Non-directional electromagnetic steel sheet with an organic insulating film shows good stamping quality, and non-directional electromagnetic steel sheet with an organic-inorganic hybrid insulating film mixed with a chromate and an organic resin also shows Good punching quality. Therefore, it can be estimated that the stamping quality of non-oriented electromagnetic steel sheet is improved by the lubrication effect of organic resin. However, the non-directional electromagnetic steel sheet with an insulating film composed of a mixture of phosphate and an organic resin has not improved the stamping quality of the image with a chromium 6 undersalt and an organic resin mixture composition. Non-directional electromagnetic steel sheets of insulating films have the same degree. This paper is suitable for ---_

7 515851 Μ 5. Description of the invention (5) ---- On the other hand, the C content on the surface of the insulating film, which is mainly composed of a phosphate and an organic resin, can be measured by photoelectron spectroscopy. The inventors of the present invention found that when the ls peak strength of 0 is as strong as 4 to 20 times that of the 25 peak strength of P, the punching quality of the non-oriented electromagnetic steel sheet is good. Furthermore, the inventors of the present invention have found that by using insulation film formation, it is a mixture of a processing solution, and its main components are a phosphate and an organic resin, plus a water-soluble organic compound, Then c's. The ratio of the peak intensity to the 2s peak intensity of P can be increased, so the stamping quality of non-oriented steel sheets is also significantly improved. Although the function of the water-soluble organic compound has not been clearly stated, it is estimated that this compound increases the stability of the organic resin molecules in the processing solution and remains in the film after baking to enhance the lubricating effect of the film. Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs. The inorganic compounds used in the present invention are explained. Examples of metal phosphates used in the present invention include aluminum phosphate, calcium phosphate, zinc phosphate, and magnesium phosphate. Metal phosphate acts as a binder. The metal salt is usually the reaction product of a metal oxide and acid breaking. The properties of the thin film thus formed will vary depending on the molecular ratio of metal oxide to phosphoric acid. When A1 is used as the metal of the present invention, the molecular ratio of A1203 / Q3P04 is used in a range of 0.3 to 0.20. When the molecular ratio is less than 0.13, the free phosphoric acid increases, which undesirably increases the moisture absorption of the insulating film. On the other hand, when the molecular ratio exceeds 0.20, the stability of the phosphate itself decreases, and the filling of aluminum acid in the solution will not be ideal. Similarly, when calcium phosphate, zinc phosphate, magnesium phosphate is used, the molecular ratio of metal oxide / phosphoric acid is limited to 0.40 to 0.60. ； In the present invention, if necessary, it can be selected from colloidal silica and boric acid. __ This paper size is applicable to Chinese National Standards (CNS) Λ4 specifications (210X297 ^^ 7 ~ 515851 A7 ______ B7) Printed by the Industrial and Consumer Cooperatives 5. Invention Description (6) and one or two substances in borate. When these substances are added, the film can be improved, for example, the film is thickened, the film surface gloss is improved, or the like. Second, the following will be Explain the organic resin used in the present invention. Examples of the organic resin used in the present invention include acrylic resin, polystyrene, vinegar resin, epoxy resin, polyurethane, vinegar, polyamine, and benzoic acid. Resin, melamine, polysiloxane, polypropylene, and polyethylene. One or at least two such resins can be used in the present invention. There is no particular limitation on the particle size of the organic resin emulsion. However, when considering the stability of the treatment solution The ideal particle size is from South to 1.0 V m. The ideal mixing ratio of organic resin to phosphate is from 5 to 300 parts by weight. The organic resin component is 100 parts by weight of phosphorus. Salt. When the organic resin component is less than 5 parts by weight, the film becomes white and loses its gloss. When the organic resin component exceeds 300 parts by weight, the film may peel off after stress relief annealing. Water-soluble for use in the present invention An organic compound is a water-soluble organic substance such as an alcohol, an ester, a ketone, an ether, a carboxylic acid, or a sugar, and it is soluble in a solution of an inorganic substance such as a phosphate. When a non-directional electromagnetic steel sheet The material is coated with a mixture. The mixture is obtained by mixing a treatment solution. The treatment solution contains a phosphate and an organic resin and has a water-soluble organic compound. After drying, the water-soluble organic compound is contained in a compound such as Among the inorganic components of monophosphate. Furthermore, the water-soluble organic compound in the present invention naturally represents that it is an organic compound that is infinitely soluble in water, but an organic compound that has a relatively high solubility in water also satisfies Compounds referred to herein. Specific examples of water-soluble organic compounds that can be used include alcohols, such as those on this paper.

9. Description of the invention (butanol and propanol, polyhydric alcohols, such as hydrazone, and diL glycerol, ethylene glycol, and glycerol, substances having a metal acid structure: ethyl carboxylic acids, such as acetic acid and propionic sugar, soluble Fibrillants, ΓΓΓ, such as sodium maleate, cools, such as difluoride and butyl cellosolve, carbitols, methyl -1 and diethylene glycol diethyl, _, such as tetraethylene glycol di T ether and 1,4-dihumor enthalpy, phase-like sugar alcohols or charcoal. 8 kinds of 'such as ethylene glycol-formamidine vinegar and sorbus,' because the water-soluble organic compounds in the fortune After drying, keep it in a film towel. The boiling point of liquid water-soluble organic compounds or solid α compounds must be higher than the boiling point of water. C is higher. Usually the Buddha or sublimation point is ideally at least 200 ° C. The mixing amount of the water-soluble organic compound is limited to 5 to 50 parts by weight, based on 100 parts by weight of phosphate, and the reason is described below. When the amount is less than 5 parts by weight, 'the effect of the water-soluble organic compound is not obtained in this way ; When the equivalent is at least 50 reset parts, the film becomes cloudy white, and a glossy film cannot be obtained Surface economy, printed by the Consumer Standards Cooperative of the Central Bureau of Standards. In the present invention, the Is peak intensity of C measured by photoelectron spectroscopy is defined to be 4 to 20 times the intensity of the 2s peak of P. The reason is as follows. When the displayed Is peak intensity of C is less than 4 times the 2s peak intensity of P, it is impossible to ensure that the non-directional electromagnetic steel sheet has sufficient stamping quality; when the Is peak intensity of C displayed by the film is greater than the 2s peak intensity of P 20 times that of the film, the film shows very poor gloss. Photoelectron spectroscopy is used here because it can be used to measure the element content appearing on the surface of the insulating film. Example 10 This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297) (Public dream) 515851 A7 B · 7 V. Description of the invention (8) One coil of a non-directional electromagnetic steel sheet with a thickness of 0.5mm, which is treated by conventional methods and then annealed, is coated with a rubber roller coating instrument such as A treatment solution shown in Table 1, and dried at 300 ° C (steel sheet temperature), with a coating amount of 1.2g / m2. Some samples were cut from the coil, and a part of the sample was under a nitrogen stream. At 750 ° C Annealed under stress for 2 hours. Then the film properties were evaluated and the results obtained are shown in Table 2. Table 1 • · _ — (Please read the precautions before completing this page) Inorganic component (parts by weight) of organic solution (parts by weight) Organic resin component (parts by weight) Water-soluble organic matter Example 1 Aluminum phosphate (100) Styrene-acrylic acid (50) Glycerin (10) Example 2 Aluminum phosphate (100) Styrene -Acrylic acid (30) Sorbitol (6) Example 3 Aluminum phosphate (100) Acrylic acid-epoxy (25) Glycerin (40) Example 4 Magnesium phosphate (100) Acrylic acid-phenol (30) Ethylene glycol (20) Example 5 Aluminum phosphate (100) Acrylic acid-epoxide (75) 1,4 Dihumane (15) Example 6 Magnesium phosphate (100) Acrylic acid-vinyl acetate 1 (30) Butyl cellosolve (20) Example 7 Magnesium phosphate ( 100) Acrylic acid-phenol (30) Diethylene glycol-Saga 40) Comparative example 1 Aluminum phosphate (100) Styrene-acrylic acid (30) Ethylene glycol ⑴ Comparative example 2 Aluminum phosphate (100) Epoxy (30) B Diol (80) Comparative Example 3 Magnesium Phosphate (100) Styrene-Acrylic (30) Ethanol (10) Conventional Example 1 Aluminum Phosphate (100) Styrene (30) No Conventional Example 2 * Magnesium Chromate (100) Boric acid (20) Acrylic-styrene-ethyl acetate Ethylene glycol (2) Note: * The conventional example is an example of a common insulating film of an electromagnetic steel sheet, which contains magnesium chromate as the main component. 、 1 'This paper size applies to Chinese national standard (CNS) Λ4 specification (210X 297 male f) 515851 A7 --------- B.7 V. Description of invention (9) Table 2 Photoelectron spectrum analysis peak of processing solution Strength proportional space factor (%) —---— Adhesive lubricating characteristics \%) Stamping quality • C (lX104 times) Example 1 5.16 99.6 ㊉ 1 f \ r \ Example 2 6.57 99.5 ㊉ 1 υο — 100 Example 3 7.59 99.6 ㊉ 1 υυ 100 > 100 cases 4 7.20 99.7-> 100 ㊉ 100 > 100 > 100 > 1 00 cases 5 8.80 99.6 ㊉ I ~~ '——— 100 -----— 100 Example 6 11.00 99.5 ~~ Θ ~ Example 7 6.19 99.6 Θ 100 〆1 V / V / ^ 1 00 Comparative Example 1 2.13 99.6 ㊉ 100 〆1 UU 1 9 Comparative Example 2 21.63 99.5 Δ 100 1 JL 1 〇〇 Comparative Example 3 2.95 99.4 ㊉ 100 1 \ J \ J Case 1 Case 2 # 1.30 99.4 ㊉ 100 δ 99.6 Θ 20 > 100 Note: * a: Peel resistance is evaluated by a match tape. ㊉ ·· No adhesion, 0: Some degree of adhesion, △: Strong adhesion, X: Peeling. : Acceptance ratio in lubrication test. • C: Use an EI core type 66mm wide steel die, and count the die punch until the height of the round opening of the steel sheet is 6 ^ m. ": The conventional chromic acid-containing film does not contain phosphorus. In addition, it was measured by photoelectron spectroscopy, and ESCA-KI (trade name)

, Manufactured by Shimazu Corporation), the 2S peak of p is close to I89ev, and the Is peak of C is close to 285en. The measured sample was washed with distilled water and acetone and then measured. Furthermore, a commercially available surface lubricity tester was used to measure the lubricating properties. The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (2 丨 〇 > < 297 public j).

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, = ". (Please read the notes on the back before filling this page}

12 515851 A7 ----------- B7 V. Description of the invention (10). A 10 mm diameter steel ball 'was moved at a speed of 20 mrn / seC and measured at a load of 100 gf. After 10 times of back and forth rubbing, the evaluation of the lubricating characteristics is as follows: · Samples with defects and peeling are acceptable; defects formed on the samples or the balls are stuck are excluded. It can be known from Table 2 that the non-directional electromagnetic steel sheet forming the insulating film in the examples shows a south space factor, excellent stamping quality, excellent adhesion of the film, and excellent lubrication characteristics. According to the present invention, a non-directional electromagnetic steel sheet can be obtained, which has an insulating film formed of an insulating film treatment agent, the treatment agent does not contain chromium compounds, and it exhibits two spatial factors, and has excellent die punching quality. , Excellent adhesion of the film and excellent lubricating properties. (Please read the notes on the back first

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Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

Claims (1)

^ A ^ A Members are kindly requested to indicate whether the revision of JL · · mentioned on February 20, 2007 has been changed, and whether the substance of the revision is intentionally revised. In the patent reexamination case No. 87119467, the scope of the patent is amended. Date of revision: 9) Zhuo February 1. A non-directional electromagnetic steel sheet with excellent thin film characteristics-a thin film, a thin film, and an insulating film containing a Quanli Cao, 3 metal phosphate and an organic resin as the main damage -Step comprising 5 to 50 parts by weight of a water-soluble organic compound based on 100 parts by weight of a metal phosphate, the water-soluble organic compound is selected from one or more of the following compounds: butanol, propanol Glycerol, glycerol, ethylene glycol, triethylene glycol, ethyl ethyl ketone, diethyl ketone, acetic acid, propionic acid, sodium maleate, sucrose, fluorenyl cellosolve, monoethylene glycol ether, monoethylene glycol diethylene glycol Ethyl bond, tetraethylene glycol dimethyl bond, i, xinyihane, ethylene glycol-fluorenyl ether ester, sorbitol or pyrogallol; when the insulating film is analyzed by photoelectron spectroscopy, (: 13 peak intensity is strong Up to 4 times to 20 times the intensity of the 23 peaks of 1 > 2 · —A kind of insulation with excellent film properties A method for a non-directional electromagnetic steel sheet of a thin film, comprising coating the non-directional electromagnetic steel sheet substrate with an insulating film-forming agent, the film-forming agent is one containing a metal phosphate and a resin as main components And a treatment solution further comprising 5 to 50 parts by weight of a water-soluble organic compound based on 100 parts by weight of a metal phosphate, the water-soluble organic compound being selected from one or more of the following compounds : Butanol, propanol, propylene glycol, glycerol, ethylene glycol, triethylene glycol, methyl ethyl ketone, diethyl ketone, acetic acid, propionic acid, sodium maleate, sucrose, fluorenyl cellosolve, diethylene glycol monomethyl ether, Diethylene glycol diethyl ether, tetraethylene glycol diethyl ether, 1,4-dioxane, ethylene glycol-fluorenyl ether esters of sorbitol or pyrophosphate, and their melting point or sublimation point is at least 10 (TC , This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) 14 515851 A8 B8 C8 D8__ VI. Application for patent scope, and baking the coated steel sheet at 200 to 400 ° C. 3 · —Insulating film forming agent for non-directional electromagnetic steel sheet used for manufacturing insulating film with excellent thin film performance. The agent is a treatment containing a metal salt and an organic resin as main components. A solution, and further comprising 5 to 50 parts by weight of a water-soluble organic compound based on 100 parts by weight of a metal phosphate, the water-soluble organic compound being selected from one or more of the following compounds: butanol, Propanol, propylene glycol, glycerol, ethylene glycol, triethylene glycol, acetophenone, diethyl ketone, acetic acid, propionic acid, sodium maleate, sucrose, methyl cellosolve, diethylene glycol scale, diethylene glycol Drunk'—B-bond, tetraglycan®? • bi-bond, -di-u-yaki, ethylene glycol-methyl etherate, sorbitol or pyrogallol, and its melting point or sublimation point is at least 100 ° C. ....., ri -------- • Ref ..... (Please read the notes on the back before filling this page) Order — This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 15