TWI328235B - A heat resistant adhesive insulative coating, and an electrical steel sheet with such coating, a magnetic core using such electrical steel sheet, and a methd of production of the same - Google Patents

Description

[Technical Field] The present invention relates to a heat-resistant adhesive coating film composition and a surface coated with the coating film: a magnetic steel sheet' and the heat-resistant adhesive coating film composition is attached to After lamination, it can be pressurized and heated (in the present invention, unless otherwise specified, it means heat treatment at room temperature or higher and 30 G ° C or lower), and then annealing treatment such as stress removal annealing is performed. In the invention, unless otherwise specified, it means that the heat treatment is more than 300 ° C. Background Art Electromagnetic steel sheets are mainly used for iron cores such as motors and transformers. Usually, the surface of the electromagnetic steel sheet is insulated, and it is generally formed by continuously forming the desired shape, or by means of a layered connection or a method of converging the concave and convex portions. 1 to form a core. The integrated core includes the user and the (10) G° (3) coffee that can be assembled directly into the electrical machine. After the C-Qin Wenlin fire, the ribs are installed in the electrical machine. The latter annealing is called stress-removal annealing, and its purpose is to remove or reduce the shear strain of the guiding steel plate during punching/shearing, the thermal strain caused by the secret of the end face, and even the convergence. The plasticity of the part, such as the plastic strain, is used to implement the magnetic core used in electrical equipment applications requiring high electrical efficiency. . The method of forming the laminated electromagnetic steel sheets by means of welding or tempering has a problem that the iron-to-edge portion is 16-way and the insulation is lowered, or the magnetic properties are deteriorated due to the processing strain. At present, a technique of forming an insulating coating film having an adhesive property on an electromagnetic steel sheet by heat pressing, and laminating and hot pressing after punching or shearing processing has been employed as a disadvantage of avoiding the above fusion or meditation. The method. For example, a method of manufacturing a surface-coated electromagnetic steel sheet (Japanese Patent No. 2613725) has been proposed, and a mixture of a base-modified epoxy resin emulsion containing a latent curing agent as a main component is baked to an incomplete state, or The technique of the present invention is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. These so-called adhesive filming techniques can alleviate the problems caused by the convergence or welding, but the surface of the steel plate is covered with only organic matter, up to 300. (: The above temperature is decomposed, and stress-relieving annealing cannot be performed to maintain the adhesion. Therefore, although an electromagnetic steel sheet which is coated with a film can be used for the core which is not subjected to stress removal annealing, it cannot be used for the purpose of causing iron loss reduction. The stress is removed from the annealed core. On the other hand, the method of stress-removing the electromagnetic steel sheet which has been processed to a desired shape by punching or the like and fixing it by an adhesive is also considered, but since the adhesive must be applied to each small month. There is a resin-free resin-free film disclosed in Japanese Patent Publication No. Sho. In the Japanese Patent Publication No. 42-24519, since there is no function between the steel sheets, the solid core method cannot be applied unless the solidification method such as convergence or welding is performed. In Japanese Laid-Open Patent Publication No. SHO-58-128715 and No. 47-47499, since the inorganic film is composed only of a low-melting glass component, the film is hard and has a bad influence on the punching die. The invention also provides a heat-resistant adhesive insulating coating film and an electromagnetic steel sheet having a heat-adhesive coating film coated with the coating film, and the use of the electromagnetic The iron core of the steel sheet and the method for producing the same can improve the heat resistance of the adhesive insulating coating film coated with the electrically insulating steel sheet with the adhesive insulating film, and can maintain the bonding state and the insulating property even if the stress removal annealing is performed. The present invention uses the following means: (1) A heat-resistant adhesive insulating coating film comprising a resin having a softening point temperature of not less than room temperature and 30 CTC or less and a low melting point inorganic component having a softening point temperature of less than i〇〇〇°c. (2) A heat-resistant adhesive insulating film such as (1), where 25 (TC followed by strength = 10 kg/cm2 or more, 750 °C followed by strength = lkg/cm2 or more. (3) Heat resistance as in (1) Insulating coating film, wherein 3 (TC to 300 °C linear thermal expansion coefficient is 1〇χ1〇-7 (°(:-1) or more, 15(^10-7(.(:-1)). (4) a heat-resistant adhesive insulating coating film as in (1), wherein the aforementioned low melting point is absent The machine component is a low melting point glass frit, water glass, or a mixture of colloidal cerium oxide mixed into a low melting point glass frit or water glass. (5) The heat-resistant adhesive insulating coating film of (4), wherein the aforementioned low melting point inorganic (6) The heat-resistant adhesive insulating coating film according to (4), wherein a mixing ratio of the above-mentioned resin to the low-melting point inorganic component is 2% by mass or more and 500% by mass. (7) The heat-resistant adhesive insulating coating film according to (4), wherein the low-melting point inorganic component is SiO 2 -B 203 - R 20 is a low-melting point glass (skin-based alkali metal). (8) A hybrid insulating coating film of (4), wherein The aforementioned water glass is a soda 5 soda. (9) The adhesive insulating coating film according to (1), wherein the resin contains an epoxy resin, an alkali resin, a phenol resin, and a modified epoxy resin emulsion containing a latent latent hardener as a main component. The mixed solution is baked to an incomplete state of the resin or a mixture of two or more kinds of siloxane polymers. 1〇 〇〇) An electromagnetic steel sheet coated with a heat-resistant adhesive insulating coating film having a coating film such as (丨) on one side of the steel sheet. (11) The electromagnetic steel sheet coated with the heat-resistant adhesive insulating coating film of (1 2 3 4 5 6), wherein the heat-resistant adhesive insulating coating film has a film thickness of 05 μm or more and 20 μm or less. 8 1 (12) A core is made of an electromagnetic steel sheet coated with a heat-resistant adhesive insulating coating such as (1). 3 (13) A method for producing a steel core using an electromagnetic steel sheet coated with a heat-resistant adhesive insulating coating film. The electromagnetic steel sheet of (10) is laminated and pressure-fixed to form an electromagnetic steel sheet laminate, and then 600. ～90 (annealing of TC, the core of 5 20 is integrated. 6 (14) The method of manufacturing the core of the electromagnetic steel sheet coated with the heat-resistant adhesive insulating coating film according to (13), at least the above-mentioned pressure fixing In the stage, heating or fixing is carried out, or it is fixed by a splicing device or a jig, or both of them are used. The present invention combines an insulating coating film of an electromagnetic steel sheet to exhibit two kinds of feeders, specifically, a resin which softens at room temperature or higher and below, and a coating film of a low melting point inorganic knives by a wire analysis method. The resin of the coating film may be formed during heat drying. The core is followed by the function of the body and the low melting point of the inorganic component (4): the stress relief annealing of the heart can have the mechanism of maintaining the integrated state of the core. The simple figure 1 shows the graph of the general differential thermal analysis of the glass. .

Figure 2 is a diagram showing a ladder-shaped dream oxygenated polymer. t Embodiment J The best form of implementing the invention - ~ people need ten to meet 700. (: to 8 〇〇. (: The degree of the left and right is used as the annealing temperature. As described above, the annealing temperature is divided into the financial assets, so the structure cannot be maintained, and thus the adhesion cannot be maintained. The inventors believe that the beneficial compound is suitable for the WC fine Gt. At the high temperature, the structure can be maintained and the adhesion between the steel sheets can be maintained. Therefore, various inorganic compounds are studied and discussed. As a result, it is found that the low (four) broken blue-group low melting point beneficial machine component, water glass, and colloidal oxide oxide are low. The melting point inorganic component can show a good steel plate joint when the annealing temperature is 7 thieves. (10) If only the low (four) inorganic components are present, the core can not be used before the misfire, so the core cannot be made. It is kept as __ body. Therefore, it is found that by combining the low melting point without subtraction with the resin, it can be fixed before the annealing of the stress relief, and the fixed and subsequent energy can be maintained after the stress removal annealing.

10 15

The iron heart. The following 'first describes the low melting point inorganic component. The inventor of the present invention is inferior to the temperature of the softening point of the inorganic component. Hereinafter, the experimental contents performed to complete the present invention will be described in detail. The inventors of the present invention investigated the subsequent softness in order to confirm the softening point temperature: (4) as a sample. First, prepare a non-oriented electrical steel sheet with a large thickness and a surface without a (four) edge coating. Phase 1 Hai and other electromagnetic steel plates, the average particle size is 5 handsome 'has a low (four) domain material with various softening point temperatures, epoxy resin: resin: expectant resin = 15:3:3 (% by mass) An aqueous emulsion having a solid content of 20% by mass was used as a resin, and the two were mixed and coated by a roll coater. The proportion of the resin to the glass frit is (10)%, that is, the equivalent mass. The amount of coating film is single-sided 8g/m2 ‘one plate temperature 16 generations. The test piece was cut out from the sample prepared by the above method, and then 25 (Γ:: strength and - °c strength). Here, the softening point temperature is measured in the measurement curve of the silk analysis method. The temperature of the fourth observed inflection point temperature after the start, or the lower of the JIS-R3103 1 glass softening point test method (ls〇7884 6 :1, 20 ASTM C338), but the above two methods When it is difficult to measure, it can be replaced by other softening point temperatures. C. The strength is a state in which the sample is 1 cm long in the rolling direction and 3 cm in the direction perpendicular to the rolling direction, and the sample is overlapped at a short side of 1 cm and an area of 3 cm 2 . Next, under the conditions of a pressing pressure·g/3 cm 2 , a heating temperature of 25 〇β (:, 10 1328235, a heating time of 60 seconds, the sheet was stretched at room temperature in the rolling direction, and the strength at the time of peeling was divided by the value of the area of 3 cm 2 . In addition, in the present invention, the value of the pressing force and the strength indicator spring balance is divided by the value of the area, which is expressed as kg/cm2, which is equivalent to 9.8xl04Pa. 5, 750°c and then the strength means more The above low temperature followed by the condition followed by the sample, without adding Under the state, the heating temperature of 750 ° C, the heating time of 2 hours under heating, at room temperature, the tension in the rolling direction, the peel strength values divided by the area of 3cm2. The results are shown in Table 1. 111328235

Strength: kg/cii^~] 750t: Lf3 ao Γ—to 1 c * New Method followed by 250X: <=> CO <3> eo e 〇C^3 <〇«w· ο , softening point Temperature 300*C 35(TC 40(TC 525C 675t: 760t: 88(TC looor 1050Τ: composition (mass %) Ο Ou o LT5 IIII 1 1 1 I deficit c/O 1 <z> ΙΛ III 1 1 1 1 CVI α. 1 s III 1 I 1 1 *〇* mum ca 1 I s II 1 1 1 1 〇CM ! IIII CD 1 1 1 1 II o I 1 o LT3 LT> o ce CO 1 II c=> CO \JS urs i UTS 1 1 ai2o31 1 I I. LT3 u~> 1 io Lf3 C-3 Ο C^3 1 III 1 o _ _ • 1 1 E^J 1 ! ITS c=>C>3<=> c-1o Ln LT5 ; Called c? ° OQ s I LO LT3 CS3 o C^3 e rsa st J mV No. 1 j CV3 cn Inch 卜 rc〇i 〇1 ; 12 1328235

It can be seen from the first table that in the condition number 1 to the condition number 8, when a glass frit having a softening point temperature of 1000 ° C or less is used, the subsequent strength at 250 ° C is l〇kg/cm 2 or more, and the strength is 750 ° C. For lkg/cm2 or above, both values are good. On the other hand, when Condition No. 9 uses a glass frit having a softening point temperature of 1050 eC 5 , the strength at 250 ° C is preferably 10 kg/cm 2 , but the strength at 750 ° C is easily peeled off after annealing. It is known from the above that when the softening point temperature is l〇〇 (the glass frit of TC or less, 250° C., the strength is 10 kg/cm 2 or more, 750° C., and the strength is lkg/cm 2 or more, both of which are The characteristics are all good. 10 Next, for the reason that 75 (TC follows the strength depending on the softening point temperature of the low melting point inorganic component, the inventors considered the following mechanism. The resin is softened by pressing and heating at 25 (rc). When it is coated on both sides, the interface of the coating film disappears and the coating film is followed. However, the temperature stability at this stage is high, and the inorganic component of the low melting point hardly reacts. Then, at 75 〇t plus 15 When it is hot, 'this time it is the softening of the inorganic component of the low melting point, and the smelting is carried out according to the low melting point inorganic component, and the low melting point inorganic component of the contact is combined with each other. As a result, the coating film is formed, and the completion of the steel plate is completed. .therefore, At the heating stage near 75 ° C, the inorganic component of the low melting point softens and even the melting system is extremely heavy.

Ik condition 9 reading point, the low melting point of the temperature, the non-inorganic components are in contact with each other, and the contact area in the temperature zone of 75 :: this: the inorganic components of the melting point cannot be fully combined, and the result is (4)结结结13 1328235 On the other hand, the low melting point inorganic component of the softening point temperature of condition number 1 to 8 of the first table, due to the contact between the low melting point inorganic components, can be at 75 ° C The temperature zone softens, so a certain contact area is obtained between the inorganic components of the low melting point. Therefore, a junction between the inorganic components of the low melting point can be formed, and as a result, the bonding strength can be obtained. In addition, even if it is a low melting point inorganic component having a softening point temperature of 1000 C higher than the heating temperature of 750 ° C, a certain 750 乞 乞 强度 强度 强度 强度 未 未 未 未 未 未 未 未 未 未 软化 软化 软化 软化 软化 软化 软化 软化 软化 软化 软化 软化For the low melting point inorganic component of 880 C or 1000 C in the temperature range of 750 ° C, 10 will have a softening reaction, and the low melting point inorganic components will be combined with each other to integrate the coating film and then the steel sheet. The 250C adhesive strength is set to l〇kg/cm2 or more, which is the standard subsequent strength which can be handled without peeling in the manufacturing process from the low temperature to the "final fixing" to the final fixing. Further, the force of the (10) force is set to lkg/cm2 to 15, which is the standard adhesion strength which does not peel after being assembled into an electric machine. • The low melting point inorganic component of the present invention may be a low melting point glass frit, water glass, or a colloidal cerium oxide mixed into a low melting point glass frit or water glass. When the low melting point inorganic component used is an inorganic powder, the particle diameter is also important. If the particle size is too large, coarsening of the surface of the coating film will occur, which will hinder the contact between the coating films. In order to have sufficient contact between the coating films or between the powders, it is preferred that the inorganic particles having a low melting point have an average particle diameter of 2 μm or less. In particular, the average particle diameter is preferably 4 μm or less, or even 3 μηι or less. Next, the inventors conducted research and discussion on the mixing ratio of the inorganic component of the low melting point and the resin of 14 1328235. First, a non-oriented electrical steel sheet having a thickness of 0 35 mm and having an insulating coating film mainly composed of magnesium chromate on the surface was prepared. With respect to the electromagnetic steel sheets, a low melting point glass material having an average particle diameter of 3 μm and a softening point temperature of 55 (rc (B2〇3=30%, Si〇2=20%, BaO=30%, Na20=l) was used. 〇%, ZnO=10%) As a low melting point inorganic component, the resin composition is epoxy resin: alkali resin: phenol resin = 20: 5: 3 (% by mass) 'Aqueous emulsion having a solid content fraction of 2% by mass The two were mixed and coated by a roll coater. At this time, the mixing ratio of the resin to the glass frit was adjusted to various values. The amount of the coating film was set to 5 g/m 2 on one side, and dried at a temperature of 15 ° C. The test piece prepared by the method was cut out, and then the strength was measured at 250 ° C and the strength was 75 (TC followed by the strength. The results are shown in Table 2. Table 2 Condition No. resin / frit mixing ratio (% by mass) Then strength: Kg/cm2 250. 750〇C 1 ~To 5 0 5 2 ~~2〇~ 10 2 3 50 20 5 4 100 40 6 5 300 50 4 6 5〇〇~ 40 1 7 ~700 40 0.5 by the second It can be seen from the table that when Condition No. 2 to Condition No. 6, that is, when the resin/glass 15 glass material mixing ratio is 20% or more and 500% or less, the 25 CTC bonding strength is 10 kg/cm 2 or more, and 750 ° C is strong. The degree is lkg/cm2 or more, and the values of both are good. On the other hand, under the condition that the resin/glass frit mixing ratio of condition number 丨 is 10%, the 250C bonding strength is 5kg/cm2, 750〇c, and then the strength is 0.5kg/cm2 'both are lower. Also, under the condition that the resin/glass 15 of condition number 7 is 7GG%, the strength at 25G °C is good. kg/Cm 'but 75 (rC followed by strength) It is a lower value of .5kg/cm2. When the mixing ratio of the above eucalyptus/slope material is 20% or more and 500% or less, both the 25G°C strength and the 75th generation strength are good. Further, the reason for the ratio of the strength-dependent resin to the low-melting inorganic component ratio is as follows. The inventors considered the following mechanism. The resin and the low-melting point inorganic component each share 25 (Γ (: heating function and 75 G ° C heating) Therefore, it is estimated that the ratio of the resin/low melting point inorganic component ratio to the (four) degree is determined by the respective heating temperatures to investigate whether the two are in a functional state. When considering the strength, 2 thieves will play the next function when they are heated. Listening to the state, and considering the 75 (the surface occupied state of the inorganic component of the low melting point which functions as the next function when the rc is heated, when the rc is heated, when the ratio of the resin is small, for example, when the ratio of the resin is small, for example, Condition No. 1 of Table 2, the inorganic component of the low melting point accounts for most of the surface, and the resin is hardly visible on the surface. In this state, the state in which the respective coating films are pressed is superimposed, and even if heated at 250 C, there is no sufficient contact area between the resins. Therefore, the resin which exhibits the adhesive property between the coating films cannot fully exhibit the function. Therefore, 25 (rc followed by a small value (in the case of condition number 1, 25 〇 °c followed by a strong yield = 5 kg / cm 2 ). For the wot: heating can not fully follow the state of 75 ° ° heating, Even if the inorganic component of the low melting point is softened and melted, 25 (the 251 does not have sufficient contact between the coating films when heated by rc), the inorganic components of the low melting point are not sufficiently contacted and bonded. As a result, the ratio of 75 is lower. The value (in the case of condition number 1 '750 ° C followed by the strength = 0.5 kg / cm 2 ). According to this mechanism, the ratio of 1328235 β intensity, the resin relative to the low melting point inorganic component is too small, 250 ° c followed by 750 ° C followed by the strength Both show a lower value. On the other hand, when the ratio of the resin to the low-melting inorganic component is too large, 'there is a sufficient resin on the surface of the coating film at 25 〇. Therefore, a larger bonding strength can be obtained (in the case of condition number 7, 250 ° C followed by intensity = 40 kg / cm 2 ). However, when 75 ° ° C is heated

Since the inorganic component which can exert the lower melting point of the function is not sufficiently present on the surface of the coating film, 75 (the subsequent strength of TC is a small value (in the case of the condition bat number $, 75 〇 ° C, then the strength = 〇. 5 kg / Cm2). 10 In addition, the core can be prevented by lowering the inorganic component of the low melting point to 30°C to 300° (the line thermal expansion coefficient is set to 1〇χ1〇Ί) or more, 150X10-YC·1) or less. The characteristics of the magnetic gas during the forming are uneven.

Further, the inventors produced a steel sheet coated with a coating film and a core made of the steel sheet as the material under the following conditions, and investigated the magnetic characteristics. First, a plurality of non-directional electromagnetic steel sheets having a thickness of 0.5 mm and an insulating coating film on the surface were prepared. For these electromagnetic steel sheets, a low melting point glass frit having an average particle diameter of 5 μϊη and various thermal expansion coefficients is used as the low melting point inorganic component, and the resin composition is an epoxy resin: alkali resin: phenol resin = 1 〇: 4: 5 ( Mass %), an aqueous emulsion containing 1 part by mass of 20% by mass, mixed both, and coated with 2 rolls using a roll coater. The mixing ratio of the resin to the glass frit is a solid content ratio of 200%. The coating film was placed on one side l〇g/m2, and dried at a plate temperature. A ring-shaped sample having an inner diameter of 1 〇 16 cm (4 inches) and an outer diameter of U 吋) was prepared from the samples, and the pressure was 1 〇 kg/cm 2 / liter of 25 于 in the state of the layer 2 〇. (: heating for 4 hours, making a coating film followed by a core. Then, the core was pressed at a temperature of 750 ° C for 2 hours without pressurizing the core at 17 1328235. Finally, the iron loss value was measured at a frequency of 50 Hz and a magnetic flux density of 1.5 tesla. The results are shown in Table 3.

18 1328235

19 1328235 From condition (4) 2 to condition 9 of Table 3, it can be seen that the core composition of the low melting point inorganic component is 30 ° C to 300 ° C and the thermal expansion coefficient is above 15 〇 xlO-YC · 1) The iron loss can be smaller than 3 grass / (four). On the other hand, condition number 1 uses a linear thermal expansion coefficient of 160xl0-7rc 5, and the frit is a larger 3.27 (job), and condition number U) uses a linear thermal expansion coefficient (four)-busy! When the glass frit is used, the iron loss value is also 3.26 (W/kg). From the above, it can be seen that when the coefficient of thermal expansion of the low melting point is from the thief to 300 ° C, the thermal expansion coefficient is less than or equal to or less than 5 〇χΐ〇 7 (^ 丨), the iron loss at the time of formation of the core after annealing can be relatively good. The reason why the iron loss in the iron core state after annealing depends on the linear thermal expansion coefficient of the inorganic component of the low melting point, the inventors considered the following mechanism. With . (: pressurization, heating, and then the resin in the coating film softens and melts. On both sides, when applied, the interface of the coating film disappears and the coating film is followed. However, the temperature stability at this stage is high, The low melting point inorganic component can hardly be reversed. Then, at 750C heating, the inorganic component of the low melting point is softened, and the inorganic component is melted according to the low melting point inorganic component, and the inorganic components of the point contact are combined with each other. As a result, the film is integrated with the film, and then the steel plate is followed by the steel. Then, after cooling to room temperature, the iron loss value is measured. Here, it can be studied: at 75 (the temperature of the TC is high, the surface of the steel plate is fully followed) 2, when cooling to room temperature, the stress problem occurs in the forming core. Generally speaking, once the stress is applied to the core, the magnetic properties will deteriorate. Here, firstly, the relationship between the thermal expansion coefficient of the material and the stress is explained. Generally, a substance with a large coefficient of thermal expansion and a substance with a small thermal expansion coefficient are next to each other at a high temperature. When cooled to room temperature, a material having a large coefficient of thermal expansion may have a tensile modulus of 1, 20 1328235 and a coefficient of thermal expansion. The team #雷—“ The shells will have compressive stresses, each of which has a role. In the electromagnetic steel sheet, the direction weight + the pressure 玍 effect expansion coefficient is about i..: steel (= no other direction ^ low melting point Inorganic into eight (C). Another aspect, used in the experiment ιο-Yc]). Therefore, the 1,., expansion coefficient is 5x 1G.7rc, when the hemp powder, it will produce more than the steel plate When the inorganic powder with a small coefficient is small, the tensile stress is “when the thermal expansion system with a steel plate is used.

For this real _ stress each acts on the forming core. Ίο Thinking about bamboo, it can be presumed that under the condition number 1 and there is the maximum line heat machine powder (4), the maximum compression force of the core forming material will be obtained, and the inorganic powder with the minimum line thermal expansion system under condition number 10 In the case of the case, the maximum tensile stress is generated for the formed core, and each produces; t / Λ * t action. The difference in thermal expansion coefficient from the steel sheet is the largest, since the condition No. 1 and the condition number 10 which are expected to generate the maximum stress are large, and the iron loss value is large due to the stress. Another-side,

In the case of Condition No. 2 to Condition No. 9, the thermal expansion coefficient of the inorganic powder used is different from the thermal expansion coefficient of the steel sheet, but the difference is small, so that even if the tensile stress or compressive stress of the formed core acts, The value will also be small, and as a result, it is presumed that it will not have a large influence on the iron loss value. The low melting point inorganic component of the present invention exhibits a low melting point glass having a softening point of a normal stress removal annealing temperature of 750 C or less. The low-melting glass is softened and melted in the stress-relieving annealing, and then solidified by cooling, and can be subjected to stress removal annealing followed by two plates. The composition of the low melting point glass can be exemplified by: Si〇2_B2〇3_R2〇 (R system metallurgy) system, p2〇5-R2〇 (R system metal) system, S1〇2-Pb〇-B203 system, 21 1328235

Si〇2-B2〇3-Zn〇, Sn〇-p2〇5, Si〇2-B2CVZr〇2, etc. Among them, Si〇2_B2〇3-R2〇 (RS alkali metal) is the best because of In addition to lead-free, - the stress after the removal of the chasing fire is also higher. The low-melting inorganic component may also be added with a liquid such as water glass, and the water-breaking glass 5 is particularly preferably a soda sulphate. The advantage of using water glass is that, for example, since powder particles are not contained, unevenness due to particles is not generated on the coated surface, and a smooth surface can be easily obtained. In particular, in the case of using soda sulphate, a high-strength household having a strength of 1.0 MPa or more after stress-relieving annealing can be obtained. Further, in the case of using potassium citrate, a high strength of about 10 to 4.0 MPa before the stress-removal annealing can be obtained. As the low melting point inorganic component of the present invention, it is possible to use a mixture of colloidal cerium oxide and the above inorganic component. By mixing colloidal cerium oxide or the like, the viscosity can be adjusted to remove the softening viscosity of the annealed inorganic component. Further, when the colloidal oxide oxide does not soften and remains in the stress-relieving annealing, it can also function as the aggregate 15 in the film to improve the adhesion strength after stress-relieving annealing. When the resin to be used in the present invention is pressed and heated by a phenol resin or an epoxy resin, and then the steel sheet is adhered to, the thermosetting resin which is hardened may be suitably used, such as an alkali resin or a mercapto acrylic resin. Heating does not occur. • Thermoplastic resins for hardening reactions are also suitable. Thermoplasticity and thermosetting properties - 20 resins are applicable, but are preferred for use. The resin of the present invention is softened at room temperature or higher and 30 (TC or less, but it is preferably 5 〇 ° C or more and 80 Å in consideration of the forging property, etc. (: above, l 〇〇 ° C or more is preferable, particularly 120 30 or more (30 or less TC or less is softened to exhibit fluidity. The softening viscosity which exhibits fluidity is 1 x 10 〇 8 dPa · s or less is 22 1328 235. The hardened resin is a thermoplastic resin, and When the temperature at which the thermoplasticity is expressed is 120T: or more and 300 °C or less, the resin which is hardened by baking on the surface of the steel sheet is softened by heating at a temperature of TC or less. 5 When it is heated to a higher temperature than the glass transition temperature and softened to a rubber state or a flowing state, it is a softening mechanism when the resin is thermosetting. In particular, a short time of 20 seconds or less is performed at a low temperature of TC or less. When the resin is treated to cure the resin, even if a crosslinking reaction for forming a three-dimensional skeleton by heating is carried out, it can be temporarily softened by glass transfer and then heated to a temperature of 咼, and then the crosslinking reaction can be further carried out to be hardened. The alkali-modified epoxy tree 6 emulsion of the inventive resin previously mixed with the latent hardener is based on the mixing of the latent hardener in the epoxy resin, and it is difficult to chemically react, and the mixture of the epoxy contact and the latent hardener The epoxy resin herein refers to a resin having two or more epoxy groups in the monomer, which are: double-type eight-type, double-aged (four), double-seeking type, art-type type, varnish type,胄 秘 秘 清 varnish type, glycidyl vinegar type, alicyclic type, etc., and latent hardeners such as: dicyandiamide, melamine, organic acid biguanide, guanamine, ketimine, third amine salt , imidazolium salt, 3-fluorinated salt, microcapsule-type hardener, molecular sieve type hardener, etc. The combination of the above 20% oxygen resin and epoxy resin hardener is used to deteriorate the resin. The surface of the oxygen resin and the epoxy resin hardener mixture is combined with the resin. As a test for the above-mentioned deterioration, the resin is isopropyl acrylate & methacrylate, acrylic acid, acrylic acid vinegar, benzene One of dilute acetic acid, etc., or two or more of polymerization or copolymerization Although the mixing ratio of the epoxy resin hardener in the ring 23 varies greatly depending on the type of the epoxy resin or the hardener, it is usually read as 5 to 2 parts by mass of the hardener. Preferably, the ready-to-use liquid containing the pre-mixed latent agent epoxy resin emulsion as the main component is applied to the steel 2 surface and must be baked to an incomplete state, and the incomplete state means no adhesion or agglomeration. And after pressing h, it is connected by pressure heating

State. Usually, it is dried at 1~5G seconds in the temperature of the furnace of ~3GGI, and can be transferred to an incomplete state. 10 浐 In addition, a stone-oxygenated polymer can be used as a resin which softens by heating. The siloxane polymer is a polymer which constitutes a main skeleton by inorganic bonding of Si_〇_Si. Since Si and C can be chemically bonded directly to an organic group or a ruthenium like Si-CH3, Si-C6H5, or Si-H, a siloxane polymer having a skeleton modified with an organic group or η can be obtained.

Si's 4 combined hands,! The formation of Si_R (R is an organic group or a ruthenium junction 15 and the remaining three Si-Ο bonds are called T cores. The number of nucleus and Si nucleus in the T core is three, that is, RSi (-0-Si) 3' is called T3 core. Si nucleus can be investigated by NMR. In general, as the nucleus forming the siloxane polymer, in addition to the T nucleus, there are also nucleus and Q nucleus. In the four bonding hands of Si, two of them form Si-R (R-based organic group or H), and the other two form Si-O bond 20. The Q-core system is composed of four combinations of Si and four. The Si-Ο bond is formed. When the Si of the T3 core is repeatedly combined according to a certain rule, a ladder-shaped molecule as shown in Fig. 2 is formed. The polymer composed of the ladder-shaped molecule generates a ladder-like molecule by coating and baking. The entanglement of the chain gives the surface state of the surface which is hardened by sticking or agglomeration. When lGGt: above, the entangled molecular chain will unravel and show fluidity. Right is the range showing fluidity. In addition to the methyl group bonded to the Si core, the ring gas group may also be included in combination with the Si core. The heptane polymer of the present invention may be in an organic trialkyl decane or an organic three gas system. One or both of them are raw materials, and are hydrolyzed under a hydrochloric acid catalyst to know that the organic-alkoxy group can be exemplified by triethoxy zephyr, trimethoxy zea, methyl trimethoxy wei, methyl triethyl ethane. Oxyl, ethyltrimethoxy decane, ethyl diethoxy decane, propyl trimethoxy oxime, propyl triethoxy decane, isopropyl trimethoxy decane, isopropyl triethoxy夕夕元笨基~methoxy cerules, phenyl triethoxy zebra, methyl propyl methoxy propyl tridecyloxy decane, methacryloxypropyl triethoxy fluorene, Epoxyoxypropyl propyl tri-foxy money, glycidoxypropyl trioxonium aminopropyl dimethyl decyl decane, aminopropyl triethoxy decane, etc., and organic three gas (four) For example, methyl trigas, ethyl trioxane, phenyl trioxane, etc. It is also possible to disperse one or two of the organic tri-Oxide or the organic gas to the organic solvent. Post-hydrolysis. Various alcohols such as methanol, ethanol, propanol, and alcohol, or propane, toluene, dioxane, etc. can be used as a solvent. The mass ratio of the organic solvent of the oxyl money is higher than the above: ~ Η 2 is preferred. The hydrolysis is carried out with respect to the water of the original oxy-propyl group, and hydrochloric acid is added as a catalyst for hydrolysis. When organic trihydrate is used as a raw material, by adding water, a by-product gp is formed so that water 1328235 can be dissolved under a hydrochloric acid catalyzing agent without adding it, so that hydrochloric acid may not be added.

The sol of the secret is usually produced by a process such as concentration to promote the polycondensation reaction to produce a sulphur-oxygenated polymer. In the concentrating system, the organic solvent or the alcohol of the product is removed by a rotary evaporator or the like, and the mass of the concentrate is about 15 to 60% of the amount of the solution before the shrinking, and the softening property is exhibited by heating. It is better to look at the contraction. A method other than the shrinkage method, such as adding K〇H and the like, and refluxing under a rat atmosphere to promote the polycondensation reaction, can also obtain a compound of Shixia oxygen. The obtained aspartic acid-fired polymer was diluted to about 1.5 to 1 G times in an organic solvent or water to obtain a coating liquid. In general, by encouraging. The c to 200 ° C for 15 to 12 G seconds can be obtained by pressurization heating. Further, in the resin or the low-melting point inorganic component of the present invention, it may appear in the coating film of the present invention at least in the appearance of the coating film of the present invention, and the visible particles are not visible. The state of the state remains, but if the function of the bonding is exhibited by appropriate heating and annealing, there is no problem in the present invention.

As long as it is an electromagnetic steel sheet manufactured by general rolling or annealing, the present invention is applicable to both types of directional electromagnetic steel sheets and non-directional electric boards, and is particularly useful for non-oriented electrical steel sheets for motor cores. , can best exert its effect. For the general manufacturing method of the grain-oriented electrical steel sheet or the non-oriented electrical steel sheet, a surface coating film is formed on the surface of both steel sheets upon completion of annealing. A surface of the grain-oriented electrical steel sheet is formed with a sulphate-based coating film containing a oxidizing component and a chromate-based coating film is formed on the surface of the non-oriented electrical steel sheet. In particular, in the case of a grain-oriented electrical steel sheet, there is a method of forming a coating film of the H+ body in the case of completing the annealing, and a method of forming a coating film for the H+ body, a method of not forming a coating method, and a bx pickling generation. (4) The method of removing the stone coating film from the town, etc. The invention can be applied regardless of whether or not it is used. Μ 2 Τ Τ Τ Τ 耐热 耐热 耐热 耐热 耐热 耐热 耐热 耐热 耐热 耐热 耐热 耐热 耐热 耐热 耐热 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘 缘The coating liquid C of the coating film composition is immersed in an electromagnetic steel sheet. The coating amount is lg/m or more and 30 g/m2 or less.

Du is particularly good for 2 〆 or more, 10 g/m 2 or less is preferably 0 10 m, and then & € 缘 涂 验 m m 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及The two layers can be separated and coated. The inorganic component having a low melting point may be dispersed in a matrix such as a dot or a strip in a matrix of each organic component, and the organic component may be dispersed in a dot shape or a strip shape in an inorganic matrix such as Weizhuan. The film thickness is one-side 〇.5μιη or more, and 2G qing is below the film thickness.

15 0.5 handsome' is difficult to fully cover the entire surface of the steel sheet, and sufficient joint strength cannot be obtained. On the other hand, if the film thickness is more than 2 〇μπι, the occupancy rate is greatly lowered during pressurization and heating. Therefore, the film thickness is preferably 〇5 qing or more and 2 〇 以下 or less. After the coating film composition of the present invention is applied to the surface of the electromagnetic steel sheet, it is first baked to harden it so as not to cause sticking or agglomeration. After coating, an electromagnetic steel sheet coated with a heat-resistant adhesive insulating coating film can be produced by baking at 5 Torr to 2 °C. This project can be carried out before iron core punching or iron core lamination, but it is applied first when the steel sheet is manufactured. The so-called pre-applied electromagnetic steel sheet makes it easier to make iron and make engineering easier. When the steel sheet is formed into a desired steel sheet having a shape of 27 1328235 and is forged, it is heated at a high temperature at the above-mentioned baking temperature to soften the resin. When the electromagnetic steel sheets having the coating film of the present invention are laminated on both sides and subjected to hot rolling, the resin which is softened by heating during hot rolling is integrated, and the electromagnetic steel sheets can be attached to the case of cooling. Further, when the electromagnetic steel sheet having only one side of the present invention is laminated in the same direction, the surface of the electromagnetic steel sheet without the coating layer of the present invention can uniformly diffuse the resin component softened by heating, so that it can be cooled. Then continue. Since the high-temperature hot rolling increases the cost, the hot rolling temperature is preferably 3 Torr or less, and the 10 hot rolling pressure is preferably 0.1 MPa or more and 50 MPa or less, more preferably 1 MPa or more and 20 MPa or less. Since the pressure of hot rolling is too low, sufficient adhesion cannot be obtained and it is difficult to integrate the core; and when the pressure of hot rolling is too high, the subsequent layer may flow and flow out from the layers. After the electromagnetic steel sheet of the present invention is punched into a desired shape, 15 layers of pressure and heat are applied after lamination, which can be used as an integrated core. Then, even if stress relief annealing is performed as needed, the adhesion between the laminated steel sheets can be maintained. The temperature of the stress-removal annealing is usually 650 ° C or more and 85 (TC or less, and more preferably 700 ° C or more and 80 (TC or less). In addition, since the coating film of the present invention does not undergo stress relief annealing, etc. It has the ability to be used, so it can be used for cores that do not undergo stress-relieving annealing. That is, it can be used for both the stress-removal annealing and the non-stress-removal annealing, and it can be used in the case of stress-removal annealing. When it is fixed by pressurization or heating, it can also be fixed by a splicing device or a jig. 28 Example 1 The solid content ratio of the alkali resin: epoxy resin: phenol resin = 10:4:3 (% by mass) is In a 20% by mass aqueous resin dispersion, the mixing softening point/dish degree is 450. (: and a glass frit having various particle diameters. The resin/glace mixing ratio of the liquid of the mixed glass frit is 2% by weight. The coating liquid was applied onto a non-oriented electrical steel sheet having a thickness of 55 mm and having an insulating coating film on the surface of the steel sheet, and the coating film amount was 6 g/m 2 on one side, followed by drying temperature. 15〇t after drying, then proceed The thickness of the coating film on one side is ΙΟμιη. From the sample prepared by this method, a test piece having a length of 1 〇 cm in the rolling direction and a length of 3 cm in the direction perpendicular to the direction of the phase 10 is cut out. Then, in the short side portion Two test pieces were stacked with a stacking length of 1 cm and an overlap area of 3 cm2, and were heated to 250 ° C under a pressure of 1 〇 kg/cm 2 and kept for 60 seconds, and then a test piece for measuring the strength of 25 Å was prepared. The test piece for the strength measurement was prepared at 750 ° C and then cooled to 75 ° C for 2 hours and 15 after cooling in a portion of the test for strength measurement. The tensile strength of the test piece prepared by the above method was measured by a tensile tester, and the results are shown in Table 4. The fourth table and the first part of the article describe the average particle diameter of the resin/destructive material: um, then the strength: kg/cn^ Preparation 250 〇C 750〇C 1 2 40 7 Example 2 -3 5 ~ ~~--~~ 35 8 Example 10 40 6 Example 4 15 30 4 Example 5 20 20 5 Example 6 25 5 Before the stripping comparison, the average size of the glass frit in Condition No. 4 to Condition No. 5 is 29 13 28235 2μιη to 20μιη of the sample group, 250 ° C and subsequent strength of 10kg / cm2 or more, and 750 C bonding strength is also good ikg / cm2 or more, in contrast, the condition - number 6 glass frit average particle size is 25μπι For the sample, the 25CTC has a strength of 5 kg/cm2, and the 750° 〇 is too small to be measured, which is not good. 5 Therefore, the comparative example in which the glass frit average particle diameter is 20 μm or less is smaller than the average particle size of 25 μm. More excellent. Example 2 Φ Modulation for resin inspection: Epoxy resin: phenol resin = 11 : 3 : 4 (% by mass) of a resin aqueous dispersion having a solid content ratio of 2 〇 mass %, mixed 10 composition was 1 〇 Liquid of glass frit (Example) of 3=25 mass%, Si〇2=65 mass%, Na2〇=1〇 mass% and muscle to 3〇〇°C having a coefficient of thermal linear expansion of ^xlO-YC·1) And the composition of the mixture with the aqueous resin dispersion is B2〇3_50% by mass, Si〇2=25% by mass, Κ2〇=25% by mass, and the linear thermal expansion coefficient of 3〇艽 to 3(8) °C is (4)Zhejiang) Glass 15 (Comparative Example) liquid 15 body. Both glass frits use an average particle size of 10 grams. Further, in the mixed glass-frequency liquid, the resin and the glass frit mixing ratio are both 100%. The coating was applied to a non-oriented electrical steel sheet having a chrome-magnesium-based insulation and a coated film which was annealed using a pro-coating machine with a thickness of 0.5 mm and a steel sheet surface. The coating film was made of a single-sided 8 coffee. After drying at a drying temperature of 140 ° C, the coating thickness of the cold W ° single side was 6 μm. The lio 16 cm (4 inches) and the outer diameter mm of the sample prepared by the method were obtained. The ring-shaped sample of 5 inches was heated at a pressure of 10 kg/cm 2 and a temperature of 250 C for 4 hours in a state of 2 layers, thereby producing a coated film-type core. Then, the core was not pressurized. In the state, 1 temperature shoe is annealed for 2 hours. Finally, the temperature is 30, and the magnetic flux density is I.5 to extract the axis value. The result is shown in Table 5, Table 5, condition, number, line, thermal expansion coefficient, CC1, iron core loss. (W/kg) Preparation 1 40xl〇-7 3.05 Example 2 170X107 3.27 The iron loss of the iron produced by the comparative glassy soil is a good 3 Q5 (w/kg). In contrast, condition number 2 uses linear thermal expansion. The iron core produced by the glass crucible with a coefficient of 17〇χ1〇—Yc is a large 3 27 (w/kg) and cannot be called good. The examples of the present invention are superior to those of the comparative examples. Example 3 The following four kinds of coating liquids 10 were prepared. The coating liquid a was added to the mixture of 100 parts by mass of water, and the amount of the alkali-modified epoxy resin emulsion of the mixed latent curing agent was added. 5 parts by mass of methyl ethyl ketone. The glass obtained by coating and baking the coating liquid has a glass transition temperature of 1 〇 4 and softens at 12 Å or more.

15 coating liquid B 100 parts by mass of mixed water, 40 parts by mass of an alkali resin emulsion, 40 parts by mass of an epoxy resin emulsion, and 4 parts by mass of an amine epoxy curing agent. The resin obtained by coating and baking the coating liquid is softened at 150 ° C or higher.

The coating liquid C 20 was hydrolyzed by dropping an aqueous solution of 35.3 g of mixed water and 4 g of 35% hydrochloric acid in 4 g of a mixture of 178 g of decyltriethoxydecane and 138 g of ethanol. The hydrolyzed liquid was concentrated at 58 °c using a rotary evaporator until no solvent appeared in 31 1328235. The mass of the concentrate is 30% of the mass of the solution prior to concentration. The concentrate had a mass average molecular weight of 10,000. Since the concentrate table showed a stringiness, it was presumed that methyltriethoxysilane was polymerized into a chain polymer-shape. The concentrate was subjected to 70. (:, 15 minutes of heat treatment, curing occurs, 5 but softening starts from about 180 ° C. 200 parts by mass of ethanol is mixed with 100 parts by mass of the concentrate.

Coating liquid D • 178 g of methyltriethoxydecane and 152 g of tetramethoxynonane were dispersed in 270.3 g of 2-ethoxyethanol. The coating liquid was prepared by adding 4.8 g of acetic acid as a catalyst and hydrolyzing by adding 36 g of 10 water. The alkane polymer cannot be softened by heating. _ In the sixth table, the glass in the middle of the coating liquid is composed of the temperature in the back bracket and the softening temperature of the glass. The glass described in the sixth table is a powder having an average particle size of from 2 μm. In the examples and comparative examples, the coating liquid 15 was applied to both sides of a non-oriented electromagnetic steel sheet having a thickness of about 5 minutes by a coater, and baked in a furnace set to 70 C for 15 minutes. The coating amount was 7 g/m2. The surface of the film after baking is not sticky. A test piece of 3 cm in length and a length of i 〇 cm was used, and a part of the test piece was overlapped. • (4) of the following part was 6em2' and the field was further performed. Cut off the film outside the next part before hot rolling. The test piece of 20 (rc, 丨min' i〇MPa was followed by two test pieces. 75 (rc, 2 hour stress removal annealing was performed in nitrogen. The tensile strength of the horizontal direction was used to cut the tensile strength. The adhesion strength before and after stress relief annealing was evaluated. Comparative Example 1 is a glass having a softening temperature higher than that of the stress removal annealing temperature, so that there is no adhesion after annealing in 32 1328235. In Comparative Example 2, the resin cannot be softened by heating, so it cannot be used. Hot rolling was followed by Comparative Example 3. Since the low-point glass was not contained, the adhesion after stress-relieving annealing could not be obtained. Table 6 1 i 1-coating liquid non-directional electrical inlet steel sheet surface quite " MPa) After annealing before annealing S Example 1 Your cloth A 1 运 mass transport has 2.0 2.3 ^L〇cMrNa, 0 series botanical powder (54〇r) 25®ft water '---- ISO Piers S Example 2 Coating solution A. 100 parts have 2.5 1.7 ο-κ, 0*F is Banban powder (360t:) 25 parts s---- 1500«© Example 3 Coating liquid Β 100 The quality S has 1.9 1. i ΜίΓίη〇-Βϊ, 0, the glass powder is not 6岔r) 25 single servings 200 quality id: part of the example 4 ΐΦϊδο H HJ quality precious parts without 2.3 2.0 _Si〇r"&, 〇,-Na.n series glass powder (540 Ό 30 quality & part ethoxy ethoxyethanol (10) quality turtle parts Comparative Example 1 coating liquid 7 100 quality book has 2. 1 0.0 Glass powder is not {16900 25 quality a part water 150 quality 比较 part comparison example 2 coating liquid B 100 expensive parts are available 0.0 can not be implemented _Si0j-B, 0,-Na, 0 series glass powder (54 〇Π 25 quality迓 水 150 150 150 150 150 150 比较 M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M M

5 Example 4 # The following three coating liquids were produced.

The coating liquid A was added to 40 parts by mass of the water-containing latent curing agent, 40 parts by mass of the modified epoxy resin emulsion, and 5 parts by mass of methyl ethyl ketone. Coating, baking 1〇 The glass transition temperature of the resin obtained by the coating liquid was 1〇4. (:, and at 120. (: above softening.

The coating liquid B was mixed with 100 parts by mass of water, 40 parts by mass of an alkali resin emulsion, and 40 parts by mass of an epoxy resin emulsion, and 4 parts by mass of an amine-based epoxy curing agent. Coating and baking the coating 33

The liquid obtained resin softens at 150 ° C or higher. Coating liquid C In an aqueous solution of 178 g of methyltriethoxydecane and 138 g of ethanol, an aqueous solution of 35.3 g of mixed water and 1.04 g of 35% hydrochloric acid was dropped to carry out hydrolysis. The hydrolyzed liquid was concentrated at 58 r with a rotary evaporator until solvent appeared. The mass of the concentrate is the mass of the solution before concentration @ 30%. The concentrate had a mass average molecular weight of 10,000. Since the concentrate exhibits a stringiness, it is presumed that methyltriethoxysilane is polymerized into a chain polymer. The concentrate was heat-treated at 70 ° C for 15 minutes, but softened from about 180 ° C. 200 parts by mass of ethanol was mixed with 1 part by mass of the concentrate. In the examples, the coating liquids A to C were diluted with water, and various water glasses were added to prepare a coating liquid. In the examples and the comparative examples, the coating liquid was applied to both sides of a non-oriented electrical steel sheet having a thickness of 5 mm by a roll coater, and baked in a furnace set at 70 ° C for 15 minutes. The coating amount was l〇g/m2. The surface of the film after baking is not sticky. A test piece of 3 cm in length and 1 cm in length was used, and a part of the test piece was overlapped so that the area of the succeeding portion was 6 cm 2 ', and hot rolling was performed. The film coated on the outside of the succeeding portion was removed before hot rolling. The test piece was subjected to hot rolling at 20 CTC, 1 minute, and 1 MPa. 75 (TC, 2 hour stress removal annealing was performed in nitrogen. The tensile strength before and after stress removal annealing was evaluated using the shear tensile strength of the horizontal strength of the bonding surface. 1328235 No. 7 coating liquid non-directional 窀 panel Surface coating film U followed by strength (MPa) Annealing solution before annealing A 1 (30 mass fraction 嗑 Example 1 citrate soda 1 < SiO: / Nai 〇 = 2 · 1 false ear ratio 50 mass S There are 2.4 1 1.0 water iso-quality most) coated mi〇〇sm part B example 2 citrate soda 1 (S _3 material 1 · molar ratio) 100 quality S shares 1.1 2.1 water 150 mass distribution coating gallery 100 Halo part Example 3 Sodium citrate No. 3 (S丨OjAa: 0=3·2 angil ratio)) 40 liters of 2.1.1 water 200 parts by mass of coating liquid C 100 mass S part 4 矽Soda soda 1 <Si0j/Na; 0=l 1® ear ratio U 50«g parts no 2.3 2.0 2 - ethoxyethanol 100 parts by mass mm 100 parts by mass Example 5 Potassium citrate A (Si02A2 〇 = 3 50 quality Dongfen has 4.1 0.9 water 1S0 parts by mass and 100 parts by weight. Example 6 Potassium citrate 2K (SiOs/Na^i 5 ear ratio) 7S parts by mass 3.9 1. 1 Water 1S0 quality children's allowance 1 mm · 100 quality 1 1 Example 7 Lithium niobate 35 iSifVLhOA 5 丨 Mo Er than 50 parts by mass LI 0.9 Water 200 quality children's coating liquid A 00 quality S Η Example 8 Sodium Citrate No. 1 (Si〇z/Na2〇: 2.1 angil ratio)> 10 g parts have 2.1 0.8 colloidal cerium oxide (pulling diameter 300 ιω) 2 S mass parts water 100 mass _s serving 1 }Application and baking of inorganic-organic mixed treatment liquid containing chromic acid and alkali resin as main components / coating and insulating film on the surface -

Example 5 The coating liquid D described in Example 3 was produced. The polyester 5 spherical particles having a mixed average particle diameter of 4 μm and a softening temperature of 200X were mixed with 10 parts by mass of the coating liquid D1〇〇. After application to a non-oriented electrical steel sheet coated with a surface film of an inorganic-organic mixed treatment liquid by a roll coater, it was baked in a furnace set to 1 〇〇 for 2 minutes. The coating amount was i〇g/m2, and a test piece having a thickness of 3 cm and a length of i〇cm was used, and a part of the test piece was placed so that the area of the succeeding portion was 6 cm 2 , and hot rolling was performed. The crucible coated on the outside of the succeeding portion was removed before hot rolling. The test piece was immersed by hot rolling at 230 ° C for 1 minute and 1 MPa. Into the nitrogen, 35 1328235, 750 ° C, 2 hours of stress removal annealing. The tensile strength before and after stress relief annealing was evaluated using the tensile strength of the shear strength of the horizontal direction of the adjoining surface. The subsequent strengths before and after stress removal annealing were 1. 〇 MPa and 2.1 MPa, respectively. Industrial Applicability 5 According to the present invention, after the punching or shearing process, the integrated core can be obtained by pressurization and heating, and then the subsequent energy can be maintained even if the stress removal annealing is performed. An electromagnetic steel sheet coated with a heat-resistant adhesive insulating coating film. The iron core can be integrated without welding or splicing, so that the iron loss due to welding or splicing can be prevented from deteriorating, and the bonding state and the insulating property can be maintained after the stress removal 10 annealing, so that it can be produced. Core with excellent magnetic properties. [Simple description of the diagram] Figure 1 shows the general differential thermal analysis curve of glass. Figure 2 is a diagram showing a ladder-like siloxane polymer. 15 [Key component symbol description] None 36

Claims (1)

Patent Application No. 94,136,171, Patent Application Revision, Revision / / Period: ^/, Year 2, Patent Application Range: 1. A heat-resistant adhesive insulating coating film containing: softening point temperature above room temperature, 3〇 Hey. 〇 the following resin; and the low-melting point inorganic component' is a mixture of different inorganic mixtures, and the softening point temperature of the mixture is below 1 〇〇〇〇c; and the heat-resistant adhesive insulating film is removed even under stress In the large case, in the case of heating below the stress-removal annealing temperature, there is still a function of allowing the steel sheets to be adjacent to each other, and it can be used for the surface of the heat-resistant adhesive insulating steel sheet. 2. The heat-resistant adhesive insulating coating film according to item 1 of the patent application, wherein 250 ° 〇 is next strength = 10 kg / cm 2 or more, 750 〇 C and then strength = 1 kg / cm 2 or more. 3. For example, the heat-resistant adhesive insulating coating film of the first application of the patent range, 30 ° (: to 300 ° (: line thermal expansion coefficient is above, 150 x io Vc-1). 4. If the patent application scope 1 The heat-resistant adhesive insulating coating film, wherein the low-melting point inorganic component is a low-melting point glass frit, water glass, or a pulverized oxidized granule mixed into a low-melting glass frit or water glass. The heat-resistant adhesive insulating coating film, wherein the low-melting-point inorganic component is an average particle diameter of 2 μm or less. 6. The heat-resistant adhesive insulating coating film of claim 4, wherein the resin has a low-melting inorganic component The mixing ratio is 20% by mass or more and 500% or less by mass. 7. The heat-resistant adhesive insulating coating film according to item 4 of the patent application scope, wherein the first inorganic component of the low-refining point is Si〇2-B2〇3_R2 Low-focus glass (R-based metal inspection) 8. A heat-resistant adhesive insulating coating film according to item 4 of the patent application, wherein the water glass is sodium citrate. 5 9. The heat resistance of the first item of the patent application is Sexual insulation coating, The resin is selected from the group consisting of an epoxy resin, an alkali resin, a phenol resin, and a resin obtained by baking a mixture of a base-modified epoxy resin emulsion containing a latent latent curing agent as an essential component to an incomplete state, or a helium oxygen. One or two or more kinds of alkane. 1〇1〇· An electromagnetic steel sheet coated with a heat-resistant adhesive insulating coating film, which has a coating film as described in the third paragraph of the patent application on at least one side of the steel sheet. 11. The electromagnetic steel sheet coated with a heat-resistant adhesive insulating coating material according to claim 10, wherein the heat-resistant adhesive insulating coating film has a thickness of 15 0.5 μm or more and 20 μm or less. A core of an electromagnetic steel sheet coated with a heat-resistant adhesive insulating coating film as in the first aspect of the patent application. 13' A method of manufacturing a core using an electromagnetic steel sheet coated with a heat-resistant adhesive insulating coating film, as claimed in the patent application The electromagnetic steel sheet of the first item is entangled and pressure-fixed, and is formed into an electromagnetic steel sheet laminate, and then annealed at 6 〇〇 to 900 ° C to obtain an integrated structure. 14. A method for producing a core of an electromagnetic steel sheet coated with a heat-resistant adhesive insulating coating film according to claim 13 of the patent application, at least at the stage of pressurization and fixing, heating, fixing, or arranging The device or the cooling device 38 1328235 is fixed or used in combination. 39