JP2023043867A - Method for manufacturing laminated body of soft magnetic alloy ribbon - Google Patents

Abstract

To provide a method for manufacturing a laminate of a soft magnetic alloy material using a thermosetting resin, which can suppress bubble traces remaining on an adhesive surface.SOLUTION: A method for manufacturing a laminate of a soft magnetic alloy ribbon according to the present invention includes a first step of applying a thermosetting resin adhesive to a first soft magnetic alloy ribbon, a second step of heating the first soft magnetic alloy ribbon that has undergone the first step, a third step of obtaining a laminate by bonding the second soft magnetic alloy ribbon and the first soft magnetic alloy ribbon that has undergone the second step together in a heated state via the thermosetting resin adhesive, and a fourth step of curing the thermosetting resin adhesive.SELECTED DRAWING: Figure 4

Description

The present invention relates to a method for manufacturing a laminate of soft magnetic alloy ribbons.

Among soft magnetic alloy materials, amorphous alloys are known to exhibit superior properties in terms of mechanical properties, magnetic properties, corrosion resistance, etc., compared to ordinary crystalline alloys. In particular, Fe-based and Co-based amorphous alloys are known to be soft magnetic materials with small coercive force because grain boundaries are not formed. Amorphous alloys are manufactured as ultra-thin ribbons due to the manufacturing method, so in manufacturing products using amorphous alloy ribbons, amorphous alloy ribbons are laminated to form a laminate. As a result, the development of technology to improve workability and handling is progressing.

In Patent Document 1, as a technique for laminating amorphous alloy ribbons and/or nanocrystalline magnetic alloy ribbons and fixing the interlayers of the laminate, an epoxy resin is applied, laminated, and cured at 150 ° C. for 1 hour. is disclosed. Further, Patent Document 2 discloses a laminate in which amorphous metal ribbons are thermocompression bonded to each other via a polyamideimide resin, wherein the thermocompression bonding temperature is 30° C. or higher, which is the glass transition point of the polyamideimide resin. C. or less (specifically 300 to 360.degree. C.) is disclosed.

JP-A-7-278763 JP 2009-194724 A

However, in the techniques disclosed in Patent Document 1 and Patent Document 2, a laminate of a soft magnetic alloy material in which the layers of the laminate are fixed using a thermosetting adhesive (hereinafter also referred to as a thermosetting resin) is used. During production, air bubbles remain on the adhesive surface, and as a result, there is a problem of deterioration in quality such as a decrease in adhesive strength and variations in the thickness of the laminate.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for manufacturing a laminate of soft magnetic alloy materials using a thermosetting resin, which is capable of suppressing air bubble traces remaining on the bonding surface.

The present invention comprises a first step of applying a thermosetting resin adhesive to a first soft magnetic alloy ribbon, and a second step of heating the first soft magnetic alloy ribbon that has undergone the first step. A step, a second soft magnetic alloy ribbon, and the first soft magnetic alloy ribbon that has undergone the second step are heated and bonded together via the thermosetting resin adhesive to form a laminate and a fourth step of curing the thermosetting resin adhesive.

Further, the present invention includes the step of unwinding the first soft magnetic alloy ribbon and the second soft magnetic alloy ribbon wound into a coil before the first step. and winding the laminate obtained in the fourth step into a coil.

Further, in the present invention, in the third step, when bonding the first soft magnetic alloy ribbon and the second soft magnetic alloy ribbon, the first soft magnetic alloy ribbon and the second soft magnetic alloy ribbon are heated while being heated. It is preferable to apply a pressing force from the bonding direction of the second soft magnetic alloy ribbon.

Further, in the present invention, in the second step, when the glass transition point of the thermosetting resin adhesive is Tg (° C.), the first soft magnetic alloy ribbon and the second soft magnetic alloy It is preferable to hold the ribbon in a temperature range of Tg-150 (° C.) or more and Tg+20 (° C.) or less for 1 second or more and 15 seconds or less.

Further, in the present invention, in the fourth step, the laminate obtained in the third step is Tg-10, where Tg (° C.) is the glass transition point of the thermosetting resin adhesive. (° C.) or more and less than Tg+20 (° C.) for 25 seconds or more and 180 seconds or less.

Further, in the present invention, it is preferable that the soft magnetic alloy ribbon is an amorphous alloy ribbon or a nanocrystalline alloy ribbon, and the thermosetting resin adhesive is an epoxy resin.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the laminated body of the soft magnetic alloy material using a thermosetting resin which can suppress the bubble trace which remains on an adhesive surface can be provided.

1 is a schematic diagram of a laminate of soft magnetic alloy ribbons in one embodiment of the present invention. FIG. FIG. 4 is a schematic diagram of a process of bonding (joining) a laminate of soft magnetic alloy ribbons in one embodiment of the present invention. 1 is a schematic diagram of a flexographic printing apparatus in one embodiment of the present invention; FIG. FIG. 4 is a schematic diagram of a laminate manufacturing process using roll to roll in one embodiment of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of a laminated body (test piece) of soft magnetic alloy ribbons used in an example according to the present invention. FIG. 2 is a schematic diagram of a peel strength test jig used in Examples according to the present invention. FIG. 2 is a conceptual diagram of an apparatus for performing second to fourth steps in a drying furnace in which constant temperature control is performed in one embodiment of the present invention. 4 is a graph showing temperature changes of a soft magnetic alloy ribbon in a drying furnace of an apparatus in which second to fourth steps are performed in a drying furnace with constant temperature control in one embodiment of the present invention. . 3 is a schematic diagram showing the configuration of a temperature sensor 15; FIG.

Hereinafter, an embodiment of a method for manufacturing a laminate according to the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments. Also, for clarity of explanation, the following description and drawings have been simplified as appropriate.

Embodiments of the present invention include:
A first step of applying a thermosetting resin adhesive to the first soft magnetic alloy ribbon, a second step of heating the first soft magnetic alloy ribbon that has undergone the first step, and a second The soft magnetic alloy ribbon of 2 and the first soft magnetic alloy ribbon that has undergone the second step are bonded together in a heated state via the thermosetting resin adhesive to obtain a laminate. and a fourth step of curing the thermosetting resin adhesive. In this embodiment, after applying a thermosetting resin adhesive to a plurality of soft magnetic alloy ribbons, before bonding the soft magnetic alloy ribbons, the thermosetting resin adhesive is heated without curing. By doing so, it is possible to suppress air bubble traces remaining on the adhesive surface after bonding.

(First embodiment)
A first embodiment of a method for manufacturing a laminate 11 of soft magnetic alloy ribbons will be described in detail with reference to FIGS. FIG. 1 is a schematic cross-sectional view of a laminate 11 of soft magnetic alloy thin ribbons, and FIG. 2 is a diagram showing a process of bonding (joining) the soft magnetic alloy thin ribbons.
This embodiment includes a first step of applying a thermosetting resin adhesive (hereinafter referred to as a thermosetting resin 2) to the first soft magnetic alloy ribbon 1a, and A second step of heating the soft magnetic alloy ribbon of 1 without curing the thermosetting resin adhesive, the first soft magnetic alloy ribbon 1a that has undergone the second step, and the second 2 soft magnetic alloy thin ribbons 1b are heated and laminated through thermosetting resin 2 to obtain a laminate, and the first and second soft magnetic alloy thin ribbons 1a laminated together. , and a fourth step of heat-treating 1b to cure the thermosetting resin adhesive.

<First step>
First, a thermosetting resin 2 is applied to the first soft magnetic alloy ribbon 1a.
[Soft magnetic alloy ribbon]
As the soft magnetic alloy ribbon according to the present embodiment, an amorphous alloy ribbon (amorphous alloy ribbon), for example, an Fe-based amorphous alloy ribbon such as 2605HB1M material manufactured by Metglas can be used. "2605HB1M" is a registered trademark of Hitachi Metals, Ltd.
As the soft magnetic alloy ribbon, a nanocrystalline alloy ribbon in which nanocrystals are crystallized by applying a heat treatment to an amorphous alloy ribbon can also be used. For example, it is preferable to use a nanocrystalline alloy ribbon having a saturation magnetic flux density of 1.6 T or more. Although the thickness of these soft magnetic alloy thin ribbons 1a is not particularly limited, it is, for example, 10 to 100 μm, preferably 10 to 30 μm.

[Thermosetting resin]
The thermosetting resin 2 used for adhesion (bonding) includes epoxy resin, polyimide resin, polyimideamide resin, and the like. Each of them can be selected according to the environment to which the laminate 11 is exposed and the intended use. In particular, epoxy resins are preferable from the viewpoint of high heat resistance and relatively high glass transition point (Tg). There are also a one-liquid type in which water is added to a solvent and a two-liquid type in which a liquid agent and a curing agent are mixed and stirred in a predetermined ratio before use. For example, in the case of a one-liquid epoxy resin, it is relatively inexpensive and does not use a solvent such as an organic solvent, so it is easy to manage the working environment and safety, and the manufacturing cost can be reduced.

The viscosity of the thermosetting resin 2 is not particularly limited, but, for example, if an epoxy resin with a high heat resistance temperature is selected, the viscosity tends to increase.

[Method of applying adhesive]
Methods for applying the thermosetting resin to the surface of the soft magnetic alloy ribbon 1a include flexographic printing (method) and coater method. With flexographic printing, it is possible to control the coating film thickness.
The range of high viscosity referred to in the present embodiment specifically means 2.0 Pa·s or more.
Here, if the viscosity of the thermosetting resin 2 is high, for example, even if it is applied to the surface of the soft magnetic alloy thin ribbon 1a being conveyed, it is difficult to wet and spread. This is effective when manufacturing a laminate of alloy ribbons.

Application by flexographic printing using a flexographic printing apparatus will be described with reference to FIG.
In flexographic printing, the liquid agent 3b to be applied to the material to be printed 3a is accumulated in the concave portions of the anilox roll 3c having an uneven outer peripheral surface, and the liquid agent 3b accumulated in the concave portions is transferred to the transfer roll 3d (see FIG. 3). ) to transfer the liquid material 3b transferred to the transfer roll 3d to the printing material 3a. Also, a jig called a doctor blade 3e is used to scrape off a constant amount of the liquid material 3b accumulated in the concave portions of the outer peripheral surface of the anilox roll 3c, thereby making the coating thickness constant.

In this embodiment, the soft magnetic alloy ribbon 1a or the soft magnetic alloy ribbon 1b can be used as the material to be printed 3a, and the thermosetting resin 2 can be used as the liquid agent 3b. Also, the anilox roll 3c and the transfer roll 3d may be made of resin, metal, or ceramics.

The coating thickness when applied to the surfaces of the soft magnetic alloy ribbons 1a and 1b may be about 2 to 10 μm. When the height in the stacking direction is restricted, the thickness of the coating is preferably thin in order to stack more soft magnetic alloy ribbons 1a and 1b. For example, 2-8 μm is more preferred.

[Glass transition point]
Glass transition temperature (Tg) is the temperature at which a glass transition occurs in an amorphous solid. That is, it becomes a rubbery state above the glass transition point, and becomes a glassy state below the glass transition point. In general, the glass transition point (Tg) varies depending on the type of resin, but is about 150° C. to 180° C. for epoxy resins.

<Second step>
After the first step, the first soft magnetic alloy ribbon 1a is heated. By heating the first soft magnetic alloy ribbon 1a before being superimposed in the third step, it is possible to prevent the gas volatilized when heating the thermosetting resin from remaining in the bonding surface. , it is possible to prevent air bubbles from remaining on the adhesive surface. As the heating condition, for example, it is desirable to hold the temperature in the temperature range of Tg-150 (° C.) or more and Tg+20 (° C.) or less for 1 second or more and 15 seconds or less.
Moreover, it is preferable to heat both the first soft magnetic alloy ribbon 1a and the second soft magnetic alloy ribbon 2a. By heating both the first soft magnetic alloy ribbon 1a and the second soft magnetic alloy ribbon 2a, the first soft magnetic alloy ribbon 1a and the second soft magnetic alloy ribbon are heated in the third step. This is because the thin strip 2a can be adhered to the adhesion surface without being affected by a temperature gradient.

[Heating method]
As a method for heating the soft magnetic alloy ribbons 1a and 1b, induction heating is used to raise the temperature of the soft magnetic alloy ribbons 1a and 1b themselves, and a gas heater or an electric heater is used to raise the temperature of the atmosphere. The soft magnetic alloy ribbons 1a and 1b may be heated under the atmosphere, or placed on a hot plate and heated.

<Third step>
After the second step, one surface of the first soft magnetic alloy ribbon 1a and one surface of the second soft magnetic alloy ribbon 1b are bonded together. Here, furthermore, when bonding one surface of the first soft magnetic alloy thin ribbon 1a and one surface of the second soft magnetic alloy thin ribbon 1b together, heating may be performed, or positively The heated state obtained by the heating in the second step may be maintained even without heating. It is preferable to press the alloy ribbon 1b from a direction perpendicular to the main surface of the ribbon using a pressure device. As a pressure device, for example, there is a roller, and the roller is pressed from the vertical direction perpendicular to the plane of the laminate 10 (the direction perpendicular to the main surface of the soft magnetic alloy ribbon, the bonding direction). can be done. The pressing force can be, for example, 1 MPa or more and 100 MPa or less, or 1 MPa or more and 50 MPa or less.
Here, when one surface of the first soft magnetic alloy thin ribbon 1a and one surface of the second soft magnetic alloy thin ribbon 1b are bonded while being heated, a heated pressure device, for example, a heated A roller may be used.
Further, when the temperature of the first soft magnetic alloy ribbon 1a and the second soft magnetic alloy ribbon 1b heated in the second step is lowered before they are bonded together in the third step, adhesion Air bubbles may remain on the surface. Therefore, for example, as shown in FIG. 4, it is desirable to perform the second to third steps in the same heating furnace to prevent temperature drop.

[Heating method]
As a method for heating one side of the soft magnetic alloy ribbons 1a and 1b or, for example, the roller of the pressure device, induction heating is used to raise the temperature of the soft magnetic alloy ribbon or the roller itself. A gas heater or an electric heater may be used to raise the temperature of the atmosphere and heat the soft magnetic alloy ribbon or the roller in the atmosphere.

<Fourth step>
After the second step, the first and second soft magnetic alloy ribbons are heated at a temperature not exceeding 10°C to the low temperature side (Tg-10°C or higher) with respect to the glass transition point of the thermosetting resin. Heat treatment is performed for 180 seconds or less.
[Heating/holding conditions (heat treatment conditions)]
The bonded first and second soft magnetic alloy ribbons are further heated and held to harden the thermosetting resin, thereby bonding them. A laminate 10 in which the soft magnetic alloy ribbons 1a and 1b are bonded together is heated in a temperature range suitable for the glass transition point (Tg) of the thermosetting resin 2 used as an adhesive (joining) agent, and Hold for a very short time.
The specific heating temperature and holding time are as follows: (a) When the glass transition point is Tg, it can be 60 seconds or more and 180 seconds or less in the temperature range of Tg−10 (° C.) or more and Tg+5 (° C.) or less. (b) where Tg is the glass transition point, in the temperature range of Tg+5 (° C.) or more and Tg+20 (° C.) or less, the time can be 40 seconds or more and 180 seconds or less; In the temperature range of Tg+20 (° C.) or more and Tg+40 (° C.) or less, it can be 25 seconds or more and 180 seconds or less. In the temperature range of , it can be 25 seconds or more and 180 seconds or less, and (e) when the glass transition point (Tg) is 40 ° C. (Tg + 40 ° C.) or more, and the glass transition point is Tg, at Tg + 40 (° C.) or more, It can be 15 seconds or more and 180 seconds or less. When the heating temperature becomes high, control for an extremely short time is required, and the time control becomes complicated. The following are more preferred.
Note that the term "maintenance" as used herein includes not only the case where a constant heating temperature is maintained, but also the case where the temperature changes continuously or stepwise in the target temperature range.
By heating and holding the laminate 10 of the soft magnetic alloy ribbons under such heating and holding conditions, it is possible to manufacture the laminate 11 of the soft magnetic alloy ribbons with reduced air bubble traces generated on the bonding surface. can. This is because excess gas generated when the thermosetting resin is heated vaporizes in advance if the heating and holding are performed under the conditions described above.

[Heating method]
As a method for heating the laminate 10, induction heating may be used to raise the temperature of the laminate 10 itself. Alternatively, a gas heater or an electric heater may be used to raise the temperature of the atmosphere, and the laminate 10 may be heated in the atmosphere. It may be heated or placed on a hot plate for heating.

Here, in the embodiment according to the present invention, the number of laminated soft magnetic alloy ribbons need not be limited to two. For example, when the soft magnetic alloy ribbon 1c is newly prepared and the soft magnetic alloy ribbons 1a, 1b and 1c are laminated in this order, one surface of the soft magnetic alloy ribbon 1a and one side of the soft magnetic alloy ribbon 1c The thermosetting resin 2 may be applied to the surfaces, one surface of the soft magnetic alloy ribbon 1a and one surface of the soft magnetic alloy ribbon 1b, or both surfaces of the soft magnetic alloy ribbon 1b. That is, the soft magnetic alloy thin ribbons may be laminated in such a manner that the thermosetting resin is present between them. In this case, the soft magnetic alloy ribbon coated with the thermosetting resin is the first soft magnetic alloy ribbon, and the soft magnetic alloy ribbon not coated with the thermosetting resin is the second soft magnetic alloy ribbon. becomes.

(Second embodiment)
<Method for manufacturing laminate by continuous production method>
A second embodiment of the method for manufacturing the laminate 11 of soft magnetic alloy ribbons will be described in detail with reference to FIG. This embodiment corresponds to a case where a continuous production method such as roll-to-roll is applied.
FIG. 4 shows the manufacturing process of the laminate 11 when a continuous production method such as roll-to-roll is applied to the lamination of the three soft magnetic alloy ribbons 1a, 1b, and 1c. The arrows in FIG. 4 indicate the rotation direction of the coil body and the rotation direction when coiled.

As shown in FIG. 4, for example, the soft magnetic alloy ribbon 1a, the soft magnetic alloy ribbon 1b, and the soft magnetic alloy ribbon 1c wound around the coil are unwound (unwinding step in FIG. 4). ), the thermosetting resin 2 is applied to one surface of the soft magnetic alloy thin ribbon 1a and one surface of the soft magnetic alloy thin ribbon 1b by the flexographic printing device 3 (first step, coating step in FIG. 4). ). Here, the soft magnetic alloy ribbon 1a and the soft magnetic alloy ribbon 1b coated with the thermosetting resin 2 serve as the first soft magnetic alloy ribbon, and the soft magnetic alloy ribbon 1c serves as the second soft magnetic alloy. It becomes an alloy ribbon. Next, the soft magnetic alloy ribbons 1a, 1b, and 1c are laminated while being heated by the heating device 5a (second step; preheating step in FIG. 4), and then in the vertical direction ( From the direction perpendicular to the main surface of the soft magnetic alloy ribbon, the bonding direction), that is, from the vertical direction perpendicular to the unwinding and winding direction, the pressure device 4a (for example, the heating device 5b to a predetermined temperature) The laminated body 10 is obtained by pressing a roller heated in (a third step, a bonding step in FIG. 4). Then, the laminated body 10 is heat-treated in the heating device 5c having a region heated to a predetermined temperature (fourth step: heating and holding (heat treatment) step in FIG. 4), and the laminated body 11 obtained after the heat treatment is It can be manufactured by a process of winding into a coil (winding process in FIG. 4).

Here, the laminate of the soft magnetic alloy thin ribbons obtained by the process of winding into a coil by roll-to-roll (the winding process in FIG. 4) has a certain peel strength or holding power. Additional heating in a constant temperature bath (additional heating step after winding the laminate) accelerates the progress of curing of the adhesive, and can be expected to assist the insufficient heating and increase the adhesive strength. In addition, by shortening the heating process of the roll-to-roll and taking time to completely harden by additional heating after winding, it is expected that the heating equipment will be simplified, the cost will be reduced, and the process will be faster. Heating conditions are preferably 40° C. to 130° C. for 1 hour or more.

Moreover, in the present embodiment, it is preferable to perform the second to fourth steps in a drying furnace in which constant temperature control is performed. By carrying out multiple processes in a drying furnace with constant temperature control, the soft magnetic alloy ribbon can be processed without being exposed to the outside air, and the adhesive is not affected by the outside temperature. It is possible to proceed with the process. Here, the number of drying ovens is not limited to one, and a plurality of drying ovens may be continuously connected as long as constant temperature control is possible.

FIG. 7 shows a conceptual diagram of an apparatus in which the second to fourth steps are performed in a drying furnace with constant temperature control. This apparatus is, for example, an apparatus for arranging four drying furnaces 9a, 9b, 9c, and 9d as drying furnaces and bonding three sheets of soft magnetic alloy ribbons 1a, 1b, and 1c. The arrows in FIG. 7 indicate the rotation direction of the coil body and the rotation direction when coiled.

Similarly to FIG. 4, for example, the soft magnetic alloy ribbon 1a, the soft magnetic alloy ribbon 1b, and the soft magnetic alloy ribbon 1c wound around the coil body are each unwound (the unwinding step in FIG. 4 ), the thermosetting resin 2 is applied to one surface of the soft magnetic alloy thin ribbon 1a and one surface of the soft magnetic alloy thin ribbon 1b by the flexographic printing device 3 (first step, coating step in FIG. 4). ). Here, the soft magnetic alloy ribbon 1a and the soft magnetic alloy ribbon 1b coated with the thermosetting resin 2 serve as the first soft magnetic alloy ribbon, and the soft magnetic alloy ribbon 1c serves as the second soft magnetic alloy. It becomes an alloy ribbon. Next, the soft magnetic alloy ribbons 1a, 1b, and 1c enter the drying furnace 9a and proceed while being heated (second step; preheating step in FIG. 4). Lamination by pressing a roller 4b heated in a drying furnace 9a from the direction perpendicular to the main surface of the magnetic alloy ribbon, the bonding direction), that is, the vertical direction perpendicular to the unwinding and winding direction A body 11 is obtained (third step: bonding step in FIG. 4). After that, the laminate 11 is heat-treated in drying furnaces 9a, 9b, 9c, and 9d having regions heated to a predetermined temperature (fourth step: heating and holding (heat treatment) step in FIG. 4). The laminate 11 thus obtained is wound into a coil (winding step in FIG. 4).

(Laminate for peel strength evaluation)
FIG. 5 shows a schematic diagram of a laminate 12 (laminate for peel strength evaluation) used for the peel strength test.
As shown in FIG. 5, the laminated body 12 is a laminated body in which a part of one surface of the soft magnetic alloy ribbon 1a and a part of one surface of the soft magnetic alloy ribbon 1b are bonded together. That is, the laminated body is a laminated body in which one end side of the laminated body in the longitudinal direction is not bonded (bonded).

(Peel strength measurement method)
The peel strength of the laminate 12 is the force required to separate the laminated soft magnetic alloy thin ribbons 1a and soft magnetic alloy thin ribbons 1b, that is, peel strength or holding force.
Methods for measuring peel strength include, for example, the 90° or 180° peel test method (JISZ023:2009).
As a specific example of the 180° peel test method, the peel strength can be measured using a peel strength measuring device 6 as shown in FIG.
First, the other surface of the soft magnetic alloy ribbon constituting the laminate 12 (the surface not coated with the thermosetting resin), for example, the other surface of the soft magnetic alloy ribbon 1a, the metal base 6d, and both surfaces Fix with tape 6e. Next, one end side of the laminate 12 that is not bonded is gripped by a clip 6a, and the grip 4a is pulled by a force gauge 6b fixed via a linear guide 6c. The peel strength of body 12 can be measured.

As described above, in the method for manufacturing a laminate of soft magnetic alloy ribbons according to the present embodiment, when the thermosetting resin used as an adhesive is heated and cured, the gas volatilized from the thermosetting resin causes the adhesion surface to It becomes possible to remove the generated bubble traces, and a manufacturing method with excellent workability and handleability and high productivity is realized. In particular, by a production method using a continuous production method such as roll-to-roll, the laminate of soft magnetic alloy ribbons can be produced with higher productivity. In addition, since the heat treatment time of the laminate 10 can be shortened, energy-saving manufacturing is possible, and a reduction in the length of the heating zone (furnace length) can be expected.

Examples based on the second embodiment will be described in detail below.
First, a long laminate was produced by a roll-to-roll apparatus using the production method of the second embodiment, and then cut to 150 mm to produce a laminate for evaluation.
Fe-based amorphous alloy ribbon HB1M material manufactured by Metglas with an average thickness of 25 μm and a width of 30 mm was used as the soft magnetic alloy ribbon. E-530 (viscosity 2.26 Pa·s/25° C., glass transition point (Tg): 180° C.) manufactured by Somar Co., Ltd., which is a one-liquid type epoxy resin, was used as the thermosetting resin used as the adhesive. .
As a flexographic printer, Esiproof manufactured by RK PrintCoat Instruments was used.

First, a coating roll of a flexographic printing device incorporated in a roll-to-roll device is vertically pressed against the unwound amorphous alloy ribbon, and the epoxy resin is transferred onto one plane of the amorphous alloy ribbon with a width of 30 mm. applied (first step).
Next, the amorphous alloy ribbon coated with the epoxy resin is passed through a metal plate heated to 170° C. incorporated in a roll-to-roll device and heated for about 1 second (second step). , overlapping another amorphous alloy ribbon. At this time, the surface of the amorphous alloy ribbon (the surface opposite to the surface coated with the thermosetting resin) is pressed from above and below by a pressure device 4a (metal roller) incorporated in the roll-to-roll device. They were laminated while being pressure-bonded (third step).
The laminate obtained by bonding was heated and held at 180° C. for 60 seconds in a drying oven (fourth step), and then wound up. A length of 150 mm is cut from the wound long laminate, and then one of the laminated amorphous alloy ribbons is peeled off from the end of the laminate by about 30 mm in the longitudinal direction to obtain the laminate ( Example 1) was produced. Furthermore, a laminate was prepared in the same manner as in Example 1 except that the laminate was not heated before bonding, and was prepared as a comparative example.
For evaluation of the peel strength of the laminate, the peel strength measuring device shown in FIG. 5 was used to peel off one ribbon of the laminate, and the maximum load was evaluated as the peel strength (gf/mm).

(Experimental result)
Ten sets were prepared for each of Example 1 and Comparative Example, and the peel strength was measured. The average peel strength was 5.6 gf/mm when no heating was applied before bonding, whereas the average peel strength was 7.0 gf/mm when heating was performed before bonding. , confirmed that the peel strength increased by about 20%.

Table 1 shows the thickness measurement results of the laminate for evaluation (Example 1). For comparison, the thickness measurement results of a comparative example produced without heating before bonding are also shown. Nine sets of laminates for evaluation of peel strength were produced under each condition, and the thickness was measured.
As shown in Table 1, the thickness variation 3σ was 62.2 mm when no heating was performed before bonding, whereas the thickness variation 3σ was 5.5 mm when heating was performed before bonding. , confirmed that the thickness of the laminate for evaluation was dramatically improved.

The reason for these experimental results regarding peel strength and thickness is that the gas generated from the epoxy resin volatilizes by heating before bonding, which reduces the number of air bubbles remaining on the bonding surface, increases the bonding area, and increases the bonding strength. This is considered to be due to the improvement and suppression of variations in the thickness of the adhesive within the bonding surface.

Next, in the second embodiment, a long laminate is manufactured using the manufacturing method in which the second to fourth steps are performed in a drying oven in which a constant temperature is controlled, and the manufactured long Example 2 was obtained by cutting out a laminate for evaluation from the laminate of .

First, the apparatus used in the fabrication of Example 2, in which the second to fourth steps are carried out in a drying oven controlled at a constant temperature, will be described. Here, four drying ovens (hereinafter referred to as units) were arranged continuously as units 1 to 4 as drying ovens with constant temperature control. As the unit, a K248M930 model drying furnace manufactured by Himeji Rika Co., Ltd. was used, and the size of each unit was about 1250 mm in length, about 600 mm in height, and about 1000 m in width. The heating method of the unit is a hot air drying method using a heater and a blower, and the hot air circulates in the furnace, and the temperature inside the furnace (furnace temperature) can be controlled up to 280°C. Further, the unit 1 was provided with rollers 4 for pressing the soft magnetic alloy thin ribbons transported into the drying furnace from above and below to bond them together while crimping them.
Here, the roller 4b used in this apparatus was a rubber roller obtained by lining a cylindrical SUS304 seamless tube with a diameter of 76.3 mm, a length of 300 mm and a thickness of 7.0 mm with silicon rubber.

FIG. 8 shows the temperature change of the soft magnetic alloy ribbon when the soft magnetic alloy ribbon was transported at a speed of 3 m/min in this apparatus. This data is the result of carrying the soft magnetic alloy ribbon with the thermocouple 7 attached thereto as the temperature sensor 15 into the apparatus and measuring it.

A configuration of the temperature sensor 15 will be described with reference to FIG. As a soft magnetic alloy ribbon, a Fe-based amorphous alloy ribbon HB1M made by Metglas with a width of 70 mm was prepared, and as shown in FIG. A thermocouple 7 was sandwiched, and the amorphous alloy ribbons 16a and 16d were fixed with a Kapton tape 8. As shown in FIG. Here, the thermocouple used was model number TH-8162-20 manufactured by Three High Co., Ltd.

Looking at the temperature change in FIG. 8, the temperature starts to rise from about 30°C at the entrance of the furnace, and after passing the point where the roller is installed, it rises from about 130°C to a maximum of 183°C, and then drops to 130°C. It can be seen that the gas is discharged from the furnace outlet.

Using this apparatus, two soft magnetic alloy ribbons were laminated and bonded together to produce a laminate for evaluation. As a soft magnetic alloy ribbon, an Fe-based amorphous alloy ribbon HB1M material manufactured by Metglas with a width of 70 mm, and an epoxy resin (E-530 manufactured by Somar Co.) as a thermosetting resin used as an adhesive were prepared. Before conveying the amorphous alloy ribbon into the device, the application roll of the flexographic printing device is pressed vertically against the unwound amorphous alloy ribbon to spread the epoxy resin on one plane of the amorphous alloy ribbon. Transfer coated at 30 mm (first step).

After that, the amorphous alloy ribbon coated with the epoxy resin and another unwound amorphous alloy ribbon were conveyed together into the apparatus, and the temperature was changed from 30° C. to 130° C. as shown in the temperature change in FIG. After heat treatment for 15 seconds (second step), the two amorphous alloy ribbons were bonded together while pressing rubber rollers from above and below to bond them together (third step). As shown in FIG. 7, the bonded amorphous alloy ribbons are subjected to heat treatment at 130° C. to 183° C. at maximum for 80 seconds (fourth step) to form a long laminated body, which is removed from the furnace. Transported and rolled up. A length of 150 mm was cut from the wound long laminate, and then one of the laminated amorphous alloy ribbons was peeled off from the end of the laminate by about 30 mm in the longitudinal direction. and

Regarding Example 2, the peel strength (gf/mm) was measured using the peel strength measuring device shown in FIG. A result similar to that of 1 was obtained.

1a: Soft magnetic alloy ribbon 1b: Soft magnetic alloy ribbon 1c: Soft magnetic alloy ribbon 2: Thermosetting resin 3: Flexo printing device 3a: To-be-printed material 3b: Liquid agent (thermosetting resin)
3c: Anilox roll 3d: Transfer roll 3e: Doctor blade 4a: Pressure device 4b: Rollers 5a, 5b, 5c: Heating device 6: Peel strength measuring device 6a: Clip 6b: Force gauge 6c: Linear guide 6d: Metal base 6e : Double-sided tape 7: Thermocouple 8: Kapton tape 9a: Drying furnace (unit 1)
9b: Drying oven (unit 2)
9c: Drying oven (unit 3)
9d: Drying oven (unit 4)
10: Laminated body 11: Laminated body 12: Laminated body 13: Feed roller 14: Guide roller 15: Temperature sensor 16a: Amorphous alloy ribbon 16b: Amorphous alloy ribbon

Claims (6)

A first step of applying a thermosetting resin adhesive to the first soft magnetic alloy ribbon;
a second step of heating the first soft magnetic alloy ribbon that has undergone the first step;
The second soft magnetic alloy ribbon and the first soft magnetic alloy ribbon that has undergone the second step are bonded together in a heated state via the thermosetting resin adhesive to obtain a laminate. 3 steps;
and a fourth step of curing the thermosetting resin adhesive. Before the first step,
A step of unwinding the first soft magnetic alloy ribbon and the second soft magnetic alloy ribbon wound in a coil shape,
2. The method for manufacturing a laminate of soft magnetic alloy ribbons according to claim 1, further comprising the step of winding the laminate obtained in the fourth step into a coil. In the third step,
When bonding the first soft magnetic alloy ribbon and the second soft magnetic alloy ribbon, the bonding direction of the first soft magnetic alloy ribbon and the second soft magnetic alloy ribbon is heated while heating. 2. The method for producing a laminate of soft magnetic alloy thin strips according to claim 1, wherein the pressing force is applied from the beginning. In the second step, when the glass transition point of the thermosetting resin adhesive is Tg (°C),
Holding the first soft magnetic alloy ribbon and the second soft magnetic alloy ribbon in a temperature range of Tg-150 (° C.) or more and Tg+20 (° C.) or less for 1 second or more and 15 seconds or less. A method for manufacturing a laminate of soft magnetic alloy ribbons according to claim 1. In the fourth step,
When the glass transition point of the thermosetting resin adhesive is Tg (°C),
The laminate obtained in the third step,
2. The method for producing a laminate of soft magnetic alloy ribbons according to claim 1, wherein the temperature is maintained in a temperature range of Tg-50 (° C.) or more and Tg+20 (° C.) or less for 25 seconds or more and 180 seconds or less. The soft magnetic alloy ribbon is an amorphous alloy ribbon or a nanocrystalline alloy ribbon,
6. The method for manufacturing a laminate of soft magnetic alloy ribbons according to claim 1, wherein the thermosetting resin adhesive is an epoxy resin.

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