KR20200002637A - Method for producing metal-clad laminate, method for producing and recovering coated press roll - Google Patents

Abstract

The present invention relates to a metal clad laminate in which a polyimide film is filled without irregularities on uneven of a surface of a metal foil, and which has high adhesion between the polyimide film and the metal foil. The metal clad laminate (100) is produced by overlapping the polyimide film (10) and the metal foil (20) as a metal foil and continuously passing between a pair of press rolls (30, 40), and thermally compressing the polyimide film (10) and the metal foil (20). While a press surface of at least one side of the press roll (30) between the pair of press rolls (30, 40) is coated with a coating layer 50 as a film-shaped buffer movable in synchronization with the press roll (30), and thermal compression is performed.

Description

METHODS FOR PRODUCING METAL-CLAD LAMINATE, METHOD FOR PRODUCING AND RECOVERING COATED PRESS ROLL}

TECHNICAL FIELD This invention relates to the manufacturing method of the metal-clad laminated board used for flexible printed circuit boards (FPC) used for electronic products, etc., the manufacturing method of the coating press roll which can be used for the method, and the repair method.

FPC is manufactured by etching the copper layer of the copper clad laminate (CCL; Copper Clad Laminate) which laminated | stacked the resin layer and the copper layer, and carrying out circuit wiring process. As for CCL used for FPC, the single-sided copper clad laminated board (henceforth single sided CCL) by which copper foil is laminated | stacked only on one side of a resin layer, and the double-sided copper clad laminated board (henceforth double-sided CCL) by which copper foil is laminated | stacked on both sides of a resin layer are known.

As a manufacturing method of CCL, the lamination method which thermo-compresses copper foil and a resin film using the metal press roll is known, for example (for example, refer patent document 1, 2).

In addition, in the laminating method, in order to improve the appearance of the laminate when the liquid crystal polymer film and the metal foil are laminated, a resin coating layer of fluorine rubber, silicone rubber or polyimide having a thickness of 0.02 to 5 mm is formed on the surface of the metal press roll. It is proposed to use what was formed (for example, refer patent document 3).

Japanese Patent Laid-Open No. 2001-129918 (patent claims, etc.) Japanese Patent Publication No. 2009-66911 (Fig. 2, etc.) Japanese Patent No. 4398179 (patent claims, etc.)

In recent years, finer wiring has been advanced in FPCs used for connection of the internal parts of the housings of these devices due to high precision and multifunctional display in mobile devices including smart phones. Therefore, in CCL which functions as a connection component by processing laminated copper foil and forming wiring, the required quality with respect to the adhesiveness of copper foil and a resin layer, etc. is becoming more stringent. However, when laminating | stacking a metal foil and a polyimide film by the lamination method, the adhesiveness of a joining surface and the filling of a thermocompression bonding surface are easy to become inadequate, and when a fine wiring process is performed, it causes a peeling of wiring.

Therefore, an object of this invention is to provide the metal-clad laminated board in which a polyimide film is filled unevenly in the unevenness | corrugation of the surface of metal foil, and high adhesiveness of a polyimide film and metal foil.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, when manufacturing a metal-clad laminated board by the lamination method, thermocompression bonding was carried out in the state which covered at least the pressing surface of the pressurization roll of one side of a pair of pressurization rolls with the film-shaped buffer material. By doing this, it was found that the above problems can be solved, and the present invention was completed.

That is, the manufacturing method of the metal-clad laminated board of this invention heat-compresses the said polyimide film and the said metal foil and manufactures a metal-clad laminated board by superimposing a polyimide film and a metal foil and passing a pair of pressure rolls continuously. to be. And the manufacturing method of the metal-clad laminated board of this invention is thermocompression bonding in the state which covered the press surface of at least one side of the press roll among the said pair of press rolls with the film-shaped cushioning material which can move in synchronization with the said press roll. In addition, the said film-like buffer material contains the non-thermoplastic polyimide layer containing a non-thermoplastic polyimide, It is characterized by the above-mentioned.

In the manufacturing method of the metal-clad laminate of this invention, the said film-shaped buffer material may form the coating layer which coat | covers the surface of the said one side press roll in the circumferential direction.

The manufacturing method of the metal-clad laminate of this invention may be the coating press roll which the said one side press roll has the said coating layer, and the other press roll may be a metal roll.

In the manufacturing method of the metal-clad laminate of this invention, you may arrange | position the said metal roll on the said metal foil side.

In the method for producing a metal-clad laminate of the present invention, the film-shaped cushioning material may be formed in an annular shape, or may be rotatably formed by the one-side press roll and a plurality of guide rolls.

In the manufacturing method of the metal-clad laminate of the present invention, the film-shaped cushioning material is formed long and may be conveyed in a roll-to-roll manner.

In the manufacturing method of the metal-clad laminate of this invention, the thickness of the said film-shaped buffer material may be in the range of 1-200 micrometers.

In the method for producing a metal-clad laminate of the present invention, the polyimide film may include a single layer or a plurality of polyimide layers, at least one layer may be a non-thermoplastic polyimide, and at least one of the metal foils is thermally compressed. The surface of the side may be a thermoplastic polyimide layer.

The manufacturing method of the metal-clad laminate of this invention may be a laminated structure in which the said polyimide film contains a base material and the polyimide layer laminated | stacked and formed on this base material.

As for the manufacturing method of the metal-clad laminated board of this invention, the said base material may be copper foil.

The manufacturing method of the coating press roll of this invention is used when heat-compressing the said polyimide film and the said metal foil and manufacturing a metal clad laminated board by making a polyimide film and a metal foil overlap and let them pass continuously between a pair of press rolls. It is a manufacturing method of a coating press roll. And the manufacturing method of the coating press roll of this invention is that the said coating press roll has a metal roll and the coating layer which coat | covers the surface of the said metal roll in the circumferential direction,

Applying a resin solution of a polyimide or polyimide precursor to the surface of the metal roll;

Process of forming the said coating layer by completing the heat processing of the said resin solution on the said metal roll

Characterized in that it comprises a.

The manufacturing method of the coating press roll of this invention may apply the said resin solution to the surface, rotating the said metal roll. In this case, you may apply | coat the said resin solution, moving an application | coating means relatively to the rotating shaft direction of the said metal roll.

The manufacturing method of the coating press roll of this invention may heat-process the said resin solution by heating the said metal roll using the heating mechanism of the said metal roll.

The repairing method of the coating press roll of this invention is used when heat-compressing the said polyimide film and the said metal foil and manufacturing a metal clad laminated board by superimposing a polyimide film and a metal foil and passing a pair of press rolls continuously. It is a repair method of a coating press roll. And the repairing method of the coating press roll of this invention is that the said coating press roll has a metal roll and the coating layer which coat | covers the surface of the said metal roll in the circumferential direction,

Applying a resin solution of a polyimide or polyimide precursor to at least a part of the surface of the coating layer;

Process of completing the heat treatment of the resin solution on the coating pressure roll

Characterized in that it comprises a.

According to the present invention, a polyimide film is filled with irregularities on the surface of the metal foil without unevenness, and a metal-clad laminate in which the polyimide film and the metal foil are firmly adhered can be produced. By using the metal sheet laminate thus produced as a circuit board material such as FPC, a circuit board excellent in adhesion between the micronized wiring and the insulating resin layer can be produced. Therefore, according to this invention, the yield and reliability of an electronic product using a circuit board and a circuit board can be improved.

Moreover, when a metal roll is used as a press roll, the pressure to a press surface tends to become uneven due to the thickness nonuniformity of a polyimide film and the fluctuation of the diameter of the metal roll in the width direction. Under the present circumstances, the problem that a polyimide film is not fully filled in the unevenness | corrugation of the surface of metal foil may arise at the location where pressure is low. In the method of the present invention, by using the film-shaped buffer member, this pressure nonuniformity is made uniform, and the polyimide film is sufficiently filled with the unevenness of the surface of the metal foil over the whole surface, and the manufacture of the metal-clad laminate with which it is firmly adhere | attached is attained.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure explaining the manufacturing method of the metal-clad laminated board of 1st Embodiment of this invention.
It is sectional drawing which shows the structure of a coating press roll.
It is a figure explaining the manufacturing method of a coating press roll.
It is a figure explaining the repair method of a coating press roll.
It is a figure explaining the modification of the manufacturing method of the metal-clad laminated board of 1st Embodiment.
It is a figure explaining the manufacturing method of the metal-clad laminate of 2nd Embodiment of this invention.
It is a figure explaining the modification of the manufacturing method of the metal-clad laminated board of 2nd Embodiment.
It is a figure explaining the manufacturing method of the metal clad laminated board of 3rd embodiment of this invention.
It is a figure explaining the modification of the manufacturing method of the metal-clad laminate of 3rd Embodiment.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described, referring drawings suitably. In the manufacturing method of the metal-clad laminated board of this invention, a polyimide film and a metal foil are thermally crimped | bonded by passing a pair of press rolls continuously and overlapping a polyimide film and a metal foil, and manufacturing a metal-clad laminated board. At this time, thermocompression bonding is performed in the state which covered at least the press surface of the pressurization roll of one side with the film-form buffer material which can move in synchronization with this press roll among a pair of press rolls. Here, the film-form buffer material contains the non-thermoplastic polyimide layer containing a non-thermoplastic polyimide. In addition, although "non-thermoplastic polyimide" is generally a polyimide which does not show softening and adhesiveness even when heated, in this invention, the storage elastic modulus in 30 degreeC measured using the dynamic-viscoelasticity measuring apparatus (DMA) is 1.0. × 10 ⁹ Pa or more, and refers to the storage elastic modulus of the polyimide at 300 ℃ less than 3.0 × 10 ⁸ Pa. In addition, although "thermoplastic polyimide" is generally a polyimide which can clearly confirm the glass transition temperature (Tg), in the present invention, the storage elastic modulus at 30 ° C. measured using a dynamic viscoelasticity measuring device (DMA). The polyimide which is 1.0 * 10 <^9> Pa or more and whose storage elastic modulus in 320 degreeC is less than 3.0 * 10 <^8> Pa.

EMBODIMENT OF THE INVENTION Hereinafter, the 1st-3rd embodiment is given and demonstrated about the preferable aspect of the "film-shaped buffer material" used by the method of this invention.

[First Embodiment]

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing of the manufacturing method of the metal-clad laminated board which concerns on 1st Embodiment of this invention. 2 is an enlarged cross-sectional view of the main portion of the coating press roll used in this method. In this embodiment, the polyimide film 10 and the metal foil 20 are thermally crimped by superimposing the polyimide film 10 and the metal foil 20 and continuously passing them between the pair of pressure rolls 30 and 40. To prepare a metal sheet laminate (100). And the film-form buffer material forms the coating layer 50 which coat | covers the surface of the press roll 30 in the circumferential direction. That is, the one side press roll 30 is a coating press roll which has the coating layer 50. Therefore, in this embodiment, the coating layer 50 as a film-shaped buffer material which can move the press surface of at least one side of the press roll 30 in synchronization with the press roll 30 among the pair of press rolls 30 and 40. The thermocompression bonding is carried out in a state of being coated with Here, the "press surface" of the press roll 30 is the surface of the rotating press roll 30, and makes the polyimide film 10 into the metal foil 20 side (the other press roll 40 side). It means the part to press. The pressing surface is sequentially replaced by the rotation of the pressing roll 30. In addition, the part which the coating layer 50 press-contacts the polyimide film 10 is also replaced one by one in synchronization with the rotation of the press roll 30. In addition, the arrow in FIG. 1 showed the conveyance direction and the rotation direction, and illustration of the unwinding roll, the winding roll, the guide roll, etc. was abbreviate | omitted. In addition, the pair of press rolls 30 and 40 are each equipped with the heating mechanism (not shown).

In FIG. 1, the other press roll 40 is a metal roll which does not have the coating layer 50, but the coating press roll which both the press rolls 30 and 40 have the coating layer 50 may be sufficient. Using both of the press rolls 30 and 40 as a coated press roll is effective for reducing the fluctuation of the pressure at the time of thermal compression in the roll width direction.

On the other hand, it is effective to make one of the press rolls 30 and 40 a coating press roll and the other roll to the metal roll which does not have the coating layer 50 in order to transmit heat efficiently to a crimping | compression-bonding site | part. In this case, it is preferable to make the press roll 40 pressed from the metal foil 20 side into the metal roll which does not have the coating layer 50 like FIG. By arrange | positioning a metal roll on the metal foil 20 side, heat can be transmitted more efficiently to a crimping | compression-bonding site | part. That is, the polyimide film 10 is directly contacted with the metal press roll 40 and the metal foil 20 by the metal foil 20 having high thermal conductivity from the press roll 40 heated by a heating mechanism (not shown). Since heat can be quickly transferred to the crimping section with the adhesive, the efficiency of thermal crimping becomes high, and the adhesion between the polyimide film 10 and the metal foil 20 becomes good.

<Coating press roll>

As shown in FIG. 2, the press roll 30 is made of metal through a metal roll 31 serving as a core, an adhesive layer 33 covering the periphery of the metal roll 31, and an adhesive layer 33. The polyimide coating layer 35 covering the roll 31 is included. The coating layer 50 is comprised by the adhesive bond layer 33 and the polyimide coating layer 35. As shown in FIG. In addition, the adhesive layer 33 does not need to be provided.

It is preferable that the adhesive bond layer 33 contains a polyimide adhesive. The adhesive layer 33 ensures the adhesion between the metal roll 31 and the polyimide coating layer 35. In addition, a polyimide adhesive agent means the adhesive agent which has an imide bond, For example, a siloxane polyimide, a polyether imide, etc. are also included.

On the other hand, it is preferable that the polyimide coating layer 35 contains a non-thermoplastic polyimide. By forming the polyimide coating layer 35 in direct contact with the polyimide film 10 by non-thermoplastic polyimide, wrinkles, stains as the polyimide coating layer 35 is partially thermally fused to the polyimide film 10 It is possible to prevent the occurrence of abnormalities such as appearance.

It is preferable that the polyimide which comprises the polyimide coating layer 35 is a polyimide which has heat resistance whose glass transition temperature (Tg) is 300 degreeC or more, for example. By using the polyimide whose Tg is 300 degreeC or more, the deformation | transformation and damage by the heating at the time of thermocompression bonding are avoided, and the durability of the coating layer 50 can be improved.

In addition, from the same viewpoint, the Tg of the polyimide constituting the polyimide coating layer 35 is, for example, 10 ° C or more higher than the Tg of the thermoplastic polyimide (to be described later) constituting a part of the polyimide film 10. It is preferable.

Moreover, it is preferable that the thermal conductivity of the polyimide coating layer 35 is less than 0.2W / m * K from a viewpoint of alleviating the thermal shock to the polyimide film 10 at the time of thermocompression bonding.

Moreover, in order to suppress the dimensional change by the temperature change at the time of thermocompression bonding, and to ensure the followability with respect to the polyimide film 10 conveyed, the thermal expansion coefficient E of the polyimide coating layer 35 which comprises the coating layer 50 is carried out. It is preferable to make it become the relationship of 0.5 * E <= E1 <= 1.5 * E with respect to the thermal expansion coefficient E1 of the whole polyimide film 10 mentioned later, for example.

Although the thickness of the coating layer 50 (meaning the thickness of the sum total of the adhesive bond layer 33 and the polyimide coating layer 35 in this embodiment) is not specifically limited, For example, it exists in the range of 1-200 micrometers. It is preferable and it is more preferable to exist in the range of 10-100 micrometers. The upper limit of the thickness is preferably 200 µm or less in order to efficiently transfer heat. As described later, when the resin solution of the polyimide or polyimide precursor is applied to the surface of the metal roll 31 and then heat-treated to form the coating layer 50, the formation of the coating layer 50 is easy. In order to make it easy, 100 micrometers or less are more preferable. Moreover, in order to prevent the temperature fluctuation of the width direction of the metal roll 31, it is preferable that the thickness of the coating layer 50 is 25 micrometers or less. 1 micrometer or more is preferable and, as for the minimum of thickness, withstand repeated use, 5 micrometers or more are more preferable.

The coating layer 50 as a film-shaped buffer material has the effect | action which alleviates the bias of the pressure at the time of thermocompression bonding, and distributes pressure equally, and has an effect which adhere | attaches the polyimide film 10 and the metal foil 20 uniformly. Therefore, the polyimide film 10 is unevenly filled in the unevenness of the surface of the metal foil 20, and the polyimide film 10 and the metal foil laminate 20 can be manufactured to which the metal foil 20 is firmly bonded. Can be.

Although the coating layer 50 can use preferably the film containing at least a non-thermoplastic polyimide, the film containing only a non-thermoplastic polyimide may be sufficient, and may contain another component as needed. Specific examples of other components include resins other than non-thermoplastic polyimide, various additives for improving various properties as the coating layer 50, and the like. In addition, a plurality of non-thermoplastic polyimides may be used in combination. Moreover, you may also contain a filler.

<Method of manufacturing coating press roll>

The press roll 30 which has the metal roll 31 and the coating layer 50 which coat | covers the surface of this metal roll 31 in the circumferential direction is the following process a and process b;

a) the process of apply | coating the resin solution of a polyimide or a polyimide precursor to the surface of the metal roll 31,

b) A step of forming the coating layer 50 by completing the heat treatment of the resin solution on the metal roll 31.

It can be prepared by a method comprising a.

In process a, it is preferable to apply | coat a resin solution to the surface, rotating the metal roll 31. As shown in FIG. As a method of apply | coating a resin solution on the metal roll 31, you may use coating means, such as a coater and a spray, for example, and after immersing the metal roll 31 in resin solution, the metal roll 31 is pulled up. The dipping method may be used. When applying a resin solution to the surface of the metal roll 31 using coating means, such as a coater and a spray, it is more preferable to apply a resin solution, moving a coating means relatively to the rotation axis direction of the metal roll 31. FIG. desirable. For example, as shown in FIG. 3, the discharge port of the application means 61 is brought into close proximity or contact with the surface of the metal roll 31, and the discharge port is further made into the metal roll 31 while rotating the metal roll 31. As shown in FIG. It is preferable to continuously supply the resin solution 63 to the surface of the metal roll 31 from the discharge port while relatively moving in the rotation axis direction. Here, "releasing the discharge port relatively in the rotation axis direction of the metal roll 31" means moving from one end of the rotating metal roll 31 to the other end. Therefore, the resin solution 63 is applied to the surface of the metal roll 31 in spiral form. Moreover, after apply | coating the resin solution 63 to the surface of the metal roll 31, you may rotate the metal roll 31 before a heat processing start for the purpose of equalizing the thickness of the resin solution 63, and the like.

In the process b, heat processing is completed by heating on the metal roll 31, and the coating layer 50 is formed. Heating may put the metal roll 31 in oven, and may heat the whole, and may heat the surface of the metal roll 31 with a hot air by a heater. In addition, you may heat from the inside of the metal roll 31 using the heating mechanism (not shown) of the metal roll 31 itself.

The heat treatment conditions vary depending on the chemical structure, thickness, area of the polyimide constituting the coating layer 50, the solvent species of the resin solution 63, and the like, but the maximum temperature is preferably in the range of 300 ° C or more and 500 ° C or less. Do. Moreover, when heated rapidly, outgas at the time of temperature rising may generate | occur | produce a bubble, and it is preferable to heat up to the maximum temperature for 30 minutes or more, for example.

In the case where the coating layer 50 is composed of a plurality of polyimide layers, the steps a and b may be repeated, or the steps b may be collectively performed after the steps a are repeated a predetermined number of times.

<Repair method of coating press roll>

When the coating layer 50 forms the coating layer 50 on the surface of the metal roll 31, defects, such as air bubbles, surface roughness, and foreign material adhesion, may arise. In addition, the same defect may occur in the use of the press roll 30 which has the coating layer 50, ie, manufacture of the metal-clad laminated board 100. FIG. When a defect arises in the coating layer 50 of the press roll 30, the defect location can be repaired. Repair of the press roll 30 which has the coating layer 50 is the following process c and process d;

c) applying a resin solution of a polyimide or polyimide precursor to at least a part of the surface of the coating layer 50 (for example, the defect portion and its surroundings),

d) process of completing the heat treatment of the resin solution on the press roll 30 having the coating layer 50;

It may include.

In the process c, for example, as shown in FIG. 4, the discharge port of the application means 61 such as a syringe is brought into proximity or contact with the surface of the metal roll 31, and the resin is applied to the surface of the metal roll 31 from the discharge port. The solution 63 is applied topically.

The heat treatment of the step d can be performed in the same manner as the step b in the method for producing the coated press roll.

In addition, before the process c, you may perform a process c after removing a defect, a defect, and the surrounding coating layer 50 from the surface of the metal roll 31. FIG. In addition, after the heat treatment of step d is completed, a treatment for smoothing the surface of the coating layer 50, for example, polishing with an abrasive may be performed.

<Polyimide film>

The polyimide film 10 thermocompression-bonded with the metal foil 20 contains the polyimide layer of a single layer or multiple layers, and may further contain arbitrary layers other than a polyimide layer. In this case, it is preferable that at least one layer is a non-thermoplastic polyimide layer, and at least the surface of the side which is heat-compressed with the metal foil 20 is a thermoplastic polyimide layer. In this case, in order to ensure adhesiveness with the metal foil 20, it is preferable that the glass transition temperature (Tg) of a thermoplastic polyimide exists in the range of 200-350 degreeC, and the inside of the range of 280-320 degreeC is more preferable.

The thickness of the polyimide film 10 is preferably in the range of 1 to 150 μm, for example, from the viewpoint of realizing thinning of a circuit board such as FPC obtained by processing the metal-clad laminate 100, and 2 to 100 μm. The range of I is more preferable. If the thickness of the polyimide film 10 is less than 1 µm, there is a concern that functions such as electrical insulation may be impaired. When the thickness of the polyimide film 10 exceeds 150 micrometers, thickness reduction of circuit boards, such as FPC, becomes difficult.

It is preferable that the thermal expansion coefficient of the whole polyimide film 10 is approximated to the thermal expansion coefficient of the metal foil 20 as much as possible. By making the thermal expansion coefficient of the polyimide film 10 close to the thermal expansion coefficient of the metal foil 20, generation | occurrence | production of the curvature in the FPC process, etc. can be suppressed. From this viewpoint, in the metal-clad laminate 100, the coefficient of thermal expansion E1 of the entire polyimide film 10 and the coefficient of thermal expansion E2 of the metal foil 20 are, for example, 0.7 × E1 ≦ E2 ≦ 1.1 × E1. It is preferable to

Moreover, the form of the laminated structure containing arbitrary layers other than a polyimide layer may be sufficient as the polyimide film 10. As arbitrary layers, a base material, a peeling film, etc. are mentioned, for example. As a preferable embodiment of the polyimide film 10, as shown in FIG. 5, a polyimide film 10A having a laminated structure including a base 71 and a polyimide layer 73 laminated on the base 71. ). Here, as base material 71, metal foil, such as copper foil, is mentioned, for example. When the base material 71 is copper foil, the polyimide film 10A is single sided CCL. By using single-sided CCL as the polyimide film 10A, double-sided CCL (double-sided copper clad laminate) used for double-sided circuit boards capable of high-density wiring can be manufactured, which is particularly advantageous. In addition, when using single-sided CCL as 10A of polyimide films, it is preferable to arrange | position so that the press roll 30 which has the coating layer 50 on the copper foil layer side of single-sided CCL may be press-contacted. Since the coating layer 50 of the press roll 30 is interposed, it can avoid that an excess heat history is added to the copper foil as the base material 71. Moreover, by arrange | positioning so that the press roll 30 which has the coating layer 50 on the copper foil layer side of single-sided CCL may contact-contact with copper foil as the base material 71, and maintains conveyability It can be able to prevent the micro size defect of copper foil.

In addition, the single-sided CCL as the polyimide film 10A is coated with a resin solution of a polyimide or polyimide precursor on the substrate 71, dried, and then subjected to heat treatment to form the polyimide layer 73. It is preferable that it is single-sided CCL manufactured by the casting method. In addition, although the polyimide layer 73 may be formed only from a single layer, when the adhesiveness and dimensional stability of the polyimide layer 73 and copper foil are considered, it is preferable to consist of multiple layers. In the case where the polyimide layer 73 is provided in plural layers, the resin solution of another polyimide or polyimide precursor containing different constituent components can be formed sequentially on the resin solution of the polyimide or polyimide precursor. When the polyimide layer 73 consists of multiple layers, you may use the resin solution of the same structure twice or more. In addition, the one-sided CCL manufactured by the casting method is an advantageous embodiment which is excellent in dimensional stability, and by arranging the coating layer 50 only on the copper foil layer side of the single-sided CCL, the rate of dimensional change at the time of thermocompression bonding can be suppressed low. . In addition, when single-sided CCL is used as the polyimide film 10A, the metal-clad laminate 100A obtained is a double-sided CCL (double-sided copper clad laminate).

When the polyimide layer 73 in the single-sided CCL is a laminated structure of a non-thermoplastic polyimide layer and a thermoplastic polyimide layer, preferably the thickness ratio (non-thermoplastic polyimide layer) of the non-thermoplastic polyimide layer and the thermoplastic polyimide layer / Thermoplastic polyimide layer) is preferably in the range of 1.5 to 10.0. If the value of this ratio is not 1.5, the non-thermoplastic polyimide layer with respect to the entire polyimide layer 73 becomes thin, so that the rate of dimensional change when the copper foil is etched tends to be large, and if it exceeds 10.0, the thermoplastic polyimide layer Since it becomes thin, the adhesive reliability of the polyimide layer 73 and copper foil falls easily.

<Metal foil>

As the metal of the metal foil 20, for example, copper, aluminum, stainless steel, iron, silver, palladium, nickel, chromium, molybdenum, tungsten, zirconium, gold, cobalt, titanium, tantalum, zinc, lead, tin, silicon, bismuth , Metal selected from indium, alloys thereof, and the like. Particularly preferred from the viewpoint of conductivity is metal foil of copper or copper alloy. In order to continuously produce the metal-clad laminates 100 and 100A, an elongated metal foil 20 in which a roll having a predetermined thickness is wound in a roll shape is used.

It is preferable that the surface roughness of the surface which directly contacts the polyimide film 10 of the metal foil 20 is 0.1-7 micrometers, for example in Rz. It is because adhesive force with the polyimide film 10 becomes it favorable enough that it is this range. Furthermore, it is more preferable if Rz is 0.3-3.0 micrometers. Here, Rz represents the 10-point average roughness prescribed | regulated to JIS B 0601 (1994).

<Thermal crimping conditions>

The heating method of the heating rolls 30 and 40 will not be specifically limited if it can heat at predetermined temperature, For example, a heat medium circulation system, a hot air heating system, a dielectric heating system, etc. are mentioned. It will not specifically limit, if it can apply a predetermined pressure also about a pressurization system, For example, a hydraulic system, a pneumatic system, a gap-gap pressure system etc. are mentioned.

Although the pressure at the time of the thermocompression bonding of the polyimide film 10 and the metal foil 20 by the press rolls 30 and 40 is not specifically limited, For example, the inside of the range of 0.1-50 MPa is preferable.

Moreover, as for the temperature at the time of thermocompression bonding, 280 degreeC or more is preferable, for example, More preferably, it exists in the range of 300-400 degreeC.

Second Embodiment

FIG. 6: is explanatory drawing of the manufacturing method of the metal clad laminated board which concerns on 2nd Embodiment of this invention. In this embodiment, the film-like buffer material is formed in ring shape. That is, in this embodiment, 50 A of annular polyimide films are arrange | positioned in the outer periphery of 40 A of pressurized rolls of at least one side among a pair of metal press rolls 40A, 40B, and this is made into a film-shaped buffer material. do. Here, a "cylindrical shape" also includes a cylindrical shape. In FIG. 6, although the film-form cushioning material is not arrange | positioned at the side of the other press roll 40B, you may thermocompress in the state which covered both the press rolls 40A and 40B with the film-form buffer.

The inner diameter of 50 A of annular polyimide films is formed larger than the outer diameter of 40 A of press rolls, and is rotatably formed by the press roll 40A of one side, and guide rolls 80A, 80B. By rotating the annular polyimide film 50A in the same direction as the rotational direction of the pressure roll 40A, the annular polyimide film capable of moving the pressing surface of the pressure roll 40A in synchronism with the pressure roll 40A. Thermocompression bonding can be performed in a state covered by 50A. In addition, the guide roll is not limited to two, You may arrange | position one or three or more.

As mentioned above, since the inner diameter of 50 A of annular polyimide films is larger than the outer diameter of 40 A of press rolls, 50 A of annular polyimide films are not being fixed to 40 A of press rolls. The polyimide has hygroscopic properties, and moisture contained in the annular polyimide film 50A rapidly volatilizes upon thermal compression, which may cause a poor appearance of the metal-clad laminate 100. When the inner diameter of the annular polyimide film 50A is sufficiently larger than the outer diameter of the pressure roll 40A, a part of the pressure roll 40A is covered before the annular polyimide film 50A reaches the thermocompression bonding surface. Since it becomes possible to contact and preheat so that the water contained in 50 A of annular polyimide films can be reduced. It is preferable to make time for the annular polyimide film 50A to contact the pressure roll 40A to 1 second or more.

Although the thickness of the cyclic polyimide film 50A is not specifically limited, For example, it is preferable to exist in the range of 1-200 micrometers, and it is more preferable to exist in the range of 10-100. The upper limit of the thickness is preferably 200 µm or less in order to efficiently transfer heat, and 25 µm or less is preferable in order to prevent temperature fluctuations in the width direction of the pressure roll 40A. 1 micrometer or more is preferable and, as for the minimum of thickness, withstand repeated use, 5 micrometers or more are more preferable.

The ring-shaped polyimide film 50A is, for example, after applying a resin solution of a polyimide or polyimide precursor to the surface of a cylindrical or cylindrical release material, and completing the heat treatment of the resin solution on the release material, the release material It can manufacture by peeling from. The coating method and heat treatment conditions of the resin solution to a mold release material can be performed according to the process a and b in the manufacturing method of a coating press roll.

The cyclic polyimide film 50A may include a single layer or a plurality of polyimide layers. In this case, it is preferable that at least 1 layer is a non-thermoplastic polyimide, and the surface (inner peripheral surface) of the side which contact | connects 40 A of pressure rolls at least is a thermoplastic polyimide layer. That is, 50 A of annular polyimide films may make it easy to contact with the surface of the metal press roll 40A using the thermoplastic polyimide layer with high adhesiveness.

On the other hand, in 50 A of annular polyimide films, it is preferable that the surface (outer peripheral surface) of the side which makes direct contact with the polyimide film 10 contains a non-thermoplastic polyimide. By forming a surface in direct contact with the polyimide film 10 by the non-thermoplastic polyimide layer, wrinkles, stains, and the like, as the annular polyimide film 50A is partially thermally fused to the polyimide film 10 Occurrence of abnormalities can be prevented. It is preferable that the polyimide which comprises the non-thermoplastic polyimide layer in 50 A of cyclic polyimide films is a polyimide which has heat resistance whose glass transition temperature (Tg) is 300 degreeC or more, for example. By using the polyimide whose Tg is 300 degreeC or more, the deformation | transformation and damage by the heating at the time of thermocompression bonding are avoided, and the durability of the cyclic polyimide film 50A can be improved.

In addition, from the same viewpoint, the Tg of the non-thermoplastic polyimide layer in the ring-shaped polyimide film 50A is, for example, more than the Tg of the thermoplastic polyimide (to be described later) constituting a part of the polyimide film 10. For example, it is preferable that it is 10 degreeC or more high.

Moreover, in order to suppress the dimensional change by the temperature change at the time of thermocompression bonding, and to ensure the precise followability with respect to the polyimide film 10 conveyed, the thermal expansion coefficient E3 of the whole of the cyclic polyimide film 50A is It is preferable to make it become the relationship of 0.5xE3 <= E1 <= 1.5 * E3, for example with respect to the thermal expansion coefficient E1 of the whole polyimide film 10 mentioned later.

As the annular polyimide film 50A, a cyclic metal sheet laminate such as annular CCL may be used. By using the annular metal sheet laminate as the annular polyimide film 50A, handling properties are improved and durability can be increased. As an annular metal sheet laminated board used as 50 A of annular polyimide films, it is preferable that it is an annular metal sheet laminated board manufactured by the casting method from a viewpoint of durability.

The annular polyimide film 50A as the film-like cushioning material has the effect of alleviating pressure at the time of thermocompression bonding and evenly distributing, and having an effect of uniformly adhering the polyimide film 10 and the metal foil 20 to each other. have.

The other structure and effect in this embodiment are the same as that of 1st embodiment. In addition, also in this embodiment, as a modified example, instead of the polyimide film 10 as shown in FIG. 7, the metal-clad laminated board 100A is manufactured by using the polyimide film 10A which has a laminated structure. can do.

It is preferable that 50 A of annular polyimide films are heated before thermocompression bonding, and water content is reduced. For example, the polyimide constituting the cyclic polyimide film 50A has a hygroscopic property, and the water contained therein volatilizes upon thermal compression, and in particular, in the case of the polyimide film 10A, the one-sided CCL side There exists a possibility of causing the external appearance defect of the copper foil in. In the case of using the annular polyimide film 50A at the time of thermocompression bonding, by increasing the insertion angle and ensuring time for contact with the heating roll 40A before reaching the thermocompression surface, the annular polyimide 50 A of films are contacted so that a part of heating roll 40A may be covered, and 50 A of annular polyimide films can be heated beforehand. At this time, it is preferable to make time for the annular polyimide film 50A to contact 40 A of heating rolls to 1 second or more.

[Third Embodiment]

FIG. 8: is explanatory drawing of the manufacturing method of the metal clad laminated board which concerns on 3rd Embodiment of this invention. In this embodiment, the film-like buffer material is formed long and it is set as the structure conveyed by a roll-to-roll type. That is, in this embodiment, the elongate polyimide film 50B is arrange | positioned between at least one side press roll 40A and the polyimide film 10 among a pair of metal press rolls 40A, 40B. Let this be a film-shaped buffer material. In FIG. 8, although the film-form buffer material is not arrange | positioned at the side of the other press roll 40B, you may thermocompress in the state which covered both the press rolls 40A and 40B with the film-form buffer material.

The elongate polyimide film 50B is formed so as to be able to be conveyed by the pressure roll 40A, the unwinding roll 90A, and the winding roll 90B. By carrying out elongate polyimide film 50B in the same direction as the rotation direction of 40 A of press rolls, the elongate polyimide film which can move the press surface of 40 A of press rolls in synchronism with 40 A of press rolls. Thermocompression bonding can be performed in a state covered by 50B. In addition, in order to adjust the angle at the time of contact with the press roll 40A, and the angle at the time of separation, you may provide one or more guide rolls arbitrarily.

As described above, the elongate polyimide film 50B is not fixed to the pressure roll 40A. In the same manner as in the case of the annular polyimide film 50A in the second embodiment, the elongated polyimide film 50B conveyed at the same speed as the pressure roll 40A is pressurized before reaching the thermocompression bonding surface. Since it becomes possible to preheat by making a part of roll 40A contact and coat | cover it, the water contained in elongate polyimide film 50B can be reduced. It is preferable to make time for the elongate polyimide film 50B to contact the pressure roll 40A to 1 second or more.

Although the thickness of elongate polyimide film 50B is not specifically limited, For example, it is preferable to exist in the range of 1-200 micrometers, and it is more preferable to exist in the range of 10-100. The upper limit of the thickness is preferably 200 µm or less in order to efficiently transfer heat, and 25 µm or less is preferable in order to prevent temperature fluctuations in the width direction of the pressure roll 40A. 1 micrometer or more is preferable and, as for the minimum of thickness, withstand repeated use, 5 micrometers or more are more preferable.

The elongate polyimide film 50B may contain the single layer or the polyimide layer of multiple layers. In this case, it is preferable that at least one layer is a non-thermoplastic polyimide, and at least the surface of the side which contacts 40A of pressure rolls is a thermoplastic polyimide layer. That is, the elongate polyimide film 50B may be made to adhere to the surface of the metal press roll 40A easily using the thermoplastic polyimide layer with high adhesiveness.

On the other hand, in the elongate polyimide film 50B, it is preferable that the surface of the side which makes direct contact with the polyimide film 10 contains a non-thermoplastic polyimide. By forming the surface in direct contact with the polyimide film 10 by the non-thermoplastic polyimide layer, the appearance of wrinkles, stains, and the like caused by the elongate polyimide film 50B partially fused to the polyimide film 10 It can prevent occurrence. It is preferable that the polyimide which comprises the non-thermoplastic polyimide layer in elongate polyimide film 50B is a polyimide which has heat resistance whose glass transition temperature (Tg) is 300 degreeC or more, for example. By using the polyimide whose Tg is 300 degreeC or more, the deformation | transformation and damage by the heating at the time of thermocompression bonding are avoided, and the durability of elongate polyimide film 50B can be improved.

In addition, from the same viewpoint, the Tg of the non-thermoplastic polyimide layer in the elongate polyimide film 50B is, for example, more than the Tg of the thermoplastic polyimide (to be described later) constituting a part of the polyimide film 10. For example, it is preferable that it is 10 degreeC or more high.

Moreover, in order to suppress the dimensional change by the temperature change at the time of thermocompression bonding, and to ensure the precise followability with respect to the polyimide film 10 conveyed, the thermal expansion coefficient E4 of the whole elongate polyimide film 50B is It is preferable to make it become the relationship of 0.5xE4 <= E1 <= 1.3 * E4, for example with respect to the thermal expansion coefficient E1 of the whole polyimide film 10 mentioned later.

As elongate polyimide film 50B, you may use commercially available polyimide films, such as Kapton V (brand name) by Toray Dupont Corporation, Euphilex S (brand name) by Ube Koyama Co., Ltd., for example.

As the elongate polyimide film 50B, a metal-clad laminate such as CCL having an elongated shape may be used. By using a metal-clad laminate as elongate polyimide film 50B, while handling property is improved, durability can be improved. As a metal sheet laminated board used as elongate polyimide film 50B, it is preferable that it is a metal sheet laminated board manufactured by the casting method from a viewpoint of durability and thickness uniformity.

The elongate polyimide film 50B as the film-like cushioning material has the effect of alleviating the pressure at the time of thermocompression bonding and evenly distributing, and having the effect of uniformly adhering the polyimide film 10 and the metal foil 20 to each other. have.

The other structure and effect in this embodiment are the same as that of 1st and 2nd embodiment. In addition, also in this embodiment, as a modified example, instead of the polyimide film 10, as shown in FIG. 9, the metal-clad laminated board 100A is manufactured by using the polyimide film 10A which has a laminated structure. can do.

It is preferable that the elongate polyimide film 50B is heated before a thermocompression bonding to reduce moisture. For example, the polyimide constituting the elongated polyimide film 50B has a hygroscopic property, and the moisture contained therein is volatilized at the time of thermal compression, especially in the case of the polyimide film 10A, the one-sided CCL side There exists a possibility of causing the external appearance defect of the copper foil in. When using the elongate polyimide film 50B at the time of thermocompression bonding, elongate polyimide is made by increasing the insertion angle and making time to contact with the heating roll 40A before reaching the thermocompression surface. The film 50B is contacted so that a part of 40 A of heating rolls may be covered, and it becomes possible to heat the elongate polyimide film 50B beforehand. At this time, it is preferable to make time for the elongate polyimide film 50B to contact 40 A of heating rolls to 1 second or more.

As described above, in the metal-clad laminates 100 and 100A obtained in the first to third embodiments, the polyimide films 10 and 10A are filled without irregularities in the irregularities of the surface of the metal foil 20, and the polyimide films (10, 10A) and the metal foil 20 are firmly adhere | attached. The adhesive strength (peel strength) of the polyimide films 10 and 10A and the metal foil 20 can be controlled according to the kind and ratio of the raw material monomers of the polyimide constituting the polyimide films 10 and 10A, heat treatment conditions, and the like. Can be.

[Polyimide]

Subsequently, in the first to third embodiments, a part or the whole of the polyimide films 10 and 10A, the coating layer 50, the annular polyimide film 50A or the elongated polyimide film 50B is constituted. The polyimide to be described will be described. Since a polyimide is made by imidating the polyamic acid which is a precursor, and is manufactured by making a specific acid anhydride and a diamine compound react, the specific example of a polyimide is understood by demonstrating an acid anhydride and a diamine compound. In the present invention, the polyimide includes a polymer having an imide group in a molecular structure, such as polyamideimide, polyetherimide, polyesterimide, polysiloxaneimide, polybenzimidazoleimide, etc. in addition to polyimide. Means resin.

As the diamine compound used as a raw material of the polyimide, can be used in the aromatic diamine compound include aliphatic diamine compounds such as, for example, there may be mentioned aromatic diamine compounds represented by NH ₂ -Ar1-NH ₂ as appropriate. Here, Ar1 is selected from the group represented by a following formula, The substitution position of an amino group is arbitrary, but p and p 'positions are preferable. Ar1 may have a substituent, but preferably does not have or, when it has, the substituent is preferably a lower alkyl or lower alkoxy group having 1 to 6 carbon atoms. These aromatic diamine compounds may use only 1 type, and may use 2 or more types together.

As the acid anhydride to be reacted with the diamine compound, an aromatic tetracarboxylic anhydride is preferable in view of the ease of synthesis of the polyamic acid. The aromatic tetracarboxylic acid anhydrides can be given as is not particularly limited, for example, _{O (CO) 2 Ar2 (CO} ) suitable for the compound represented by O _2. Here, Ar2 is preferably a tetravalent aromatic group represented by the following formula, and the substitution position of the acid anhydride group [(CO) ₂ O] is arbitrary, but the position of symmetry is preferable. Although Ar <2> may have a substituent, it is preferable not to have it, or, when it has, it is preferable that the substituent is a C1-C6 lower alkyl group.

The polyimide films 10 and 10A, the coating layer 50, the annular polyimide film 50A, and the elongate polyimide film 50B may have a multilayer structure including a thermoplastic polyimide layer and a non-thermoplastic polyimide layer. Therefore, the preferable example of the acid anhydride and diamine compound used for each of thermoplastic polyimide and non-thermoplastic polyimide is demonstrated.

Thermoplastic Polyimide:

When the polyimide is a thermoplastic polyimide, the polyimide is not particularly limited. Examples of the polyimide include, for example, 3,4'-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) benzene, Using diamine compound containing 50 mol% or more of 1 or more types chosen from 1, 4-bis (4-amino phenoxy) benzene and 2, 2-bis [4- (4-amino phenoxy) phenyl] propane It is preferable. Moreover, although it is not specifically limited, As an acid anhydride component of a raw material, for example, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride Using an acid anhydride containing at least 50 mol% of at least one selected from water, 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride and 4,4'-oxydiphthalic anhydride desirable. By using a predetermined amount of these diamine compounds and acid anhydrides, the adhesiveness by a thermoplastic polyimide is fully exhibited, and thermocompression property becomes high.

Non-thermoplastic Polyimide:

When the polyimide is a non-thermoplastic polyimide, the polyimide is not particularly limited. Examples of the polyimide include 1,3-phenylenediamine, 2,2'-dimethyl-4,4'-diaminobiphenyl as the diamino component of the raw material. It is preferable to use the diamine compound which contains 60 mol% or more of 1 or more types chosen from 2,2'-bis (trifluoromethyl) benzidine and 3,4'- diamino diphenyl ether. Moreover, although it is not specifically limited, As an acid anhydride component of a raw material, 60 or more types chosen from pyromellitic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride are 60, for example. It is preferable to use the acid anhydride containing mol% or more. By using a predetermined amount of these diamine compounds and acid anhydrides, characteristics, such as heat resistance and dimensional stability by non-thermoplastic polyimide, are exhibited.

In the thermoplastic polyimide and the non-thermoplastic polyimide, the thermal expansion coefficient, the storage modulus, the glass transition temperature, and the like can be controlled by selecting the kind of the diamine compound and the acid anhydride and the molar ratios thereof.

Moreover, in the said thermoplastic polyimide and non-thermoplastic polyimide, when it has two or more structural units of a polyimide, although it exists as a block or may exist at random, it is preferable to exist at random.

The polyimide is, for example, in a solvent, the above-mentioned diamine compound and an acid anhydride are mixed in a substantially equimolar ratio, and reacted in a range of a reaction temperature of 0 to 200 ° C, preferably in a range of 0 to 100 ° C, and a polyamide It can obtain by obtaining the resin solution of an acid and imidating it. As a solvent, for example, N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), dimethyl sulfate, sulfolane, butyrolactone, cresol, phenol And halogenated phenol, cyclohexanone, dioxane, tetrahydrofuran, diglyme, triglyme and the like.

Usually, the synthesis of polyamic acid is carried out in a reaction vessel or the like. For example, a polyimide layer can be obtained by applying a resin solution of polyamic acid on an arbitrary substrate, drying to form a polyamic acid layer, and imidating the polyamic acid layer by subsequent heat treatment. Overlapping, you may repeat application | coating on the polyamic-acid layer or polyimide layer already formed. Or you may form the polyimide layer by apply | coating in the form of the solution which melt | dissolved the polyimide previously imidized in the solvent, and drying it on the surface of arbitrary base materials. When the polyimide films 10 and 10A, the coating layer 50, the cyclic polyimide film 50A, and the elongate polyimide film 50B have a multilayer structure, a plurality of polyamic acids are sequentially formed on any substrate. Although the method of carrying out imidization collectively after apply | coating and drying a resin solution of is preferable, it is not limited to this. That is, you may form a some polyimide layer by apply | coating collectively the resin solution of several polyamic acid with a multilayer die etc. to an arbitrary base material, and carrying out the imidation by heat processing collectively after drying this. Moreover, you may form a polyimide layer one by one by performing application drying of the resin solution of several polyamic acid from imidation one by one sequentially. When forming a some polyimide layer, each of these processes can be combined arbitrarily.

The method of applying the polyimide solution or the resin solution of the polyamic acid on any substrate is not particularly limited, and may be applied by application means represented by a coater such as a comma, die, knife, or lip. . At the time of formation of a multilayer polyimide layer, the method of repeating the operation which apply | coats a polyimide solution (or the resin solution of polyamic acid) to a base material, and dries is preferable.

As a method of drying and heat | fever imidation treatment, arbitrary methods, such as a batch processing system and a continuous processing system, can be selected, for example. In the batch treatment method, after applying a resin solution of polyamic acid to an elongated metal foil, the laminate is wound in a roll shape without being imidized, and a predetermined time is set in a hot air drying furnace that can be set at a predetermined temperature. It is a method of completing imidation by standing still and finally heat-processing at high temperature 200 degreeC or more. In the continuous treatment method, after the resin solution of polyamic acid is applied to an elongated metal foil, the inside of the drying furnace is continuously moved to secure a predetermined heat treatment time, and finally, the heat treatment is performed at a high temperature of 200 ° C or higher. to be. Although these may select either method from a viewpoint of productivity, a yield, etc., it is preferable to perform heat processing in high temperature of 200 degreeC or more in a reduced pressure environment, a reducing gas atmosphere, or a reducing gas atmosphere, and under reduced pressure environment. In addition, the solvent of the polyamic acid resin is removed and imidized by heating in the drying and imidization treatment process. At this time, if the heat treatment is performed rapidly at a high temperature, a skin layer is formed on the surface of the resin, making it difficult to evaporate the solvent. Since foaming occurs, it is preferable to heat-process while raising from low temperature to high temperature step by step. Moreover, in a heat | fever imidation process, it is preferable to heat-process at the temperature of 300-400 degreeC finally.

EXAMPLE

An Example is shown below and the characteristic of this invention is demonstrated more concretely. However, the scope of the present invention is not limited to the Example. In addition, in the following Examples, unless otherwise indicated, various measurements and evaluation are based on the following.

[Coefficient of Thermal Expansion (CTE)]

The polyimide film of the size of 3mm x 20mm was heated up from 30 degreeC to 265 degreeC at a constant temperature increase rate, applying the load of 5.0g using a thermomechanical analyzer (Bruker company make, brand name; 4000SA), and also at this temperature After hold | maintaining for 10 minutes, it cooled at the speed | rate of 5 degreeC / min, and calculated | required the average thermal expansion coefficient (linear thermal expansion coefficient) from 240 degreeC to 100 degreeC.

[Glass Transition Temperature (Tg)]

The glass transition temperature is a polyimide film having a size of 5 mm x 20 mm, using a dynamic viscoelasticity measuring device (DMA: U.B., Inc., trade name; E4000F), and the temperature increase rate is 4 ° C / min from 30 ° C to 400 ° C. The measurement was performed at a frequency of 11 Hz, and the temperature at which the elastic modulus change (tan δ) becomes the maximum was taken as the glass transition temperature.

[Measurement of viscosity]

The measurement of the viscosity measured the viscosity in 25 degreeC using the E-type viscosity meter (the Brookfield company make, brand name; DV-II + Pro). The rotation speed was set so that torque might be 10%-90%, and the value when the viscosity stabilized after 2 minutes after starting a measurement was read.

[Peel Strength]

Peel strength is a double-sided tape on the resin layer side of the metal-clad laminate in which the metal on the conductor layer side is processed by wiring having a width of 1 mm using a tensilon tester (trade name: Straw Graph VE-1D manufactured by Toyo Seiki Seisakusho). It fixed to the SUS board and calculated | required the force at the time of peeling a metal wiring from a resin layer at the speed | rate of 50 mm / min in 180 degree direction.

[Thermal pressing surface charge state]

After etching the copper foil of the copper clad laminated board after thermocompression bonding over the whole width | variety, the surface of a polyimide film is visually observed and observed that the whole surface is a uniform color tone, and it is defective that there exists a part from which a color tone differs. It was made.

The symbol used in the Example etc. shows the following compounds.

BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane

m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl

PMDA: pyromellitic dianhydride

BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride

DMAc: N, N-dimethylacetamide

Synthesis of Polyamic Acid Solution

Synthesis Example 1

87.5 kg of DMAc was put into a reaction vessel equipped with a thermocouple and a stirrer, and nitrogen was introduced, and 8.11 kg of BAPP was added to the reaction vessel and dissolved while stirring in the vessel. Subsequently, 4.10 kg of PMDA was added. Then, stirring was continued for 3 hours and polymerization reaction was performed and the resin solution 1 of polyamic acid a was obtained. The viscosity of the resin solution 1 (solid content: 12.5%) was 1,300 cps. In addition, the polyimide obtained by imidating polyamic acid a is thermoplastic, and the thermal expansion coefficient (CTE) of the polyimide film of thickness 25micrometer formed with polyamic acid a is 55x10 <^-6> / K, and glass transition temperature is It was 320 degreeC.

Synthesis Example 2

212.5 kg DMAc was put into the reaction container which can be introduce | transduced with a thermocouple and a stirrer, and 17.9 kg m-TB was added to this reaction container, and it melt | dissolved in stirring in a container. Then 4.94 kg BPDA and 14.7 kg PMDA were added. Thereafter, stirring was continued for 3 hours to conduct a polymerization reaction, to obtain a resin solution 2 of polyamic acid b. The viscosity of the resin solution 2 (solid content: 15%) was 26,500 cps. In addition, the polyimide obtained by imidating the polyamic acid b was non-thermoplastic, and the thermal expansion coefficient (CTE) of the 25-micrometer-thick polyimide film formed from the polyamic acid b was 22x10 <^-6> / K.

[Production of Polyimide Coating Roll]

After rotating the metal roll provided with the heater inside, the resin solution 2 produced in the synthesis example 2 was apply | coated to the surface of the metal roll using a coater, and the metal roll was heated by a heater for 1 hour from room temperature to 360 degreeC. It heated up over and obtained the polyimide coating roll which has a polyimide coating layer of predetermined thickness on the surface.

(Example 1)

The resin solution 1 manufactured by the synthesis example 1 was hardened using the die-coater on the rough surface of copper foil 1 based on elongate copper foil 1 (rolled copper foil, thickness; 12 micrometers, width: 500 mm). After apply | coating uniformly so that the thickness might be set to 2.5 micrometers, it heat-dried at 130 degreeC and removed the solvent. Subsequently, the resin solution 2 produced in the synthesis example 2 was apply | coated uniformly so that the thickness after hardening might be set to 20 micrometers on this application | coating surface side, it heat-dried at 120 degreeC, and the solvent was removed. Further, the same resin solution 1 as applied to the first layer on the coated surface side was uniformly applied so that the thickness after curing was 2.5 μm, heated and dried at 130 ° C. to remove the solvent, and heat-treated stepwise to 360 ° C. And the single-side copper clad laminated board 1a which has a polyimide film whose thickness is 25 micrometers was obtained.

The polyimide coating roll 1 (thickness of a polyimide coating layer; 50 micrometers) is arrange | positioned at the copper foil 1 side of single-sided copper clad laminated board 1a using the heating pressurization apparatus which has a pair of pressure rolls, and the poly of the single-sided copper clad laminated board 1a The long copper foil 2 (electrolytic copper foil, thickness; 12 micrometers, width | variety width; 540 mm) was arrange | positioned at the mid layer side, and the metal roll was arrange | positioned on the opposite side to the thermocompression bonding surface of copper foil 2. Roll surface temperature in nitrogen atmosphere, conveying these via a guide roll; 300 to 400 ° C., linear pressure of the press roll; Conveying speed, in the range of 38.6 to 115.8 kgf / cm; On the conditions of 4.0 m / min, it thermally crimped continuously and the double-sided copper clad laminated board 1b was obtained. The external appearance of the copper foil surface on the coating surface side of the obtained double-sided copper clad laminated board 1b was favorable in the whole surface, and the peeling strength of the copper foil on the crimping side was 1.6 kN / m.

(Comparative Example 1)

Except having made both the press rolls into the metal roll, it carried out similarly to Example 1, and obtained double-sided copper clad laminated board 1b '. The external appearance of the copper foil surface on the coating surface side of the obtained double-sided copper clad laminated board 1b 'was partially defective, and the peel strength of the copper foil on the crimping side was 1.2 kN / m.

Table 1 shows the results of Example 1 and Comparative Example 1.

(Example 2)

Except having used polyimide coating roll 2 (thickness of a polyimide coating layer; 75 micrometers), it carried out similarly to Example 1, and obtained double-sided copper clad laminated board 2b. The external appearance of the copper foil surface of the coated surface side of the obtained double-sided copper clad laminated board 2b was favorable for the whole surface, and the peeling strength of the copper foil of the crimping | compression-bonding side was 1.6 kN / m.

(Example 3)

Except having used polyimide coating roll 3 (thickness of a polyimide coating layer; 25 micrometers), it carried out similarly to Example 1, and obtained double-sided copper clad laminated board 3b. The external appearance of the copper foil surface of the application surface side of the obtained double-sided copper clad laminated board 3b was favorable for the whole surface, and the peeling strength of the copper foil of the crimping | compression-bonding side was 1.6 kN / m.

(Example 4)

Except having used polyimide coating roll 4 (thickness of a polyimide coating layer; 20 micrometers), it carried out similarly to Example 1, and obtained double-sided copper clad laminated board 4b. The external appearance of the copper foil surface of the coated surface side of the obtained double-sided copper clad laminated board 4b was favorable for the whole surface, and the peeling strength of the copper foil of the crimping | compression-bonding side was 1.6 kN / m.

(Example 5)

Except having used polyimide coating roll 5 (thickness of polyimide coating layer; 15 micrometers), it carried out similarly to Example 1, and obtained double-sided copper clad laminated board 5b. The external appearance of the copper foil surface of the coated surface side of the obtained double-sided copper clad laminated board 5b was favorable for the whole surface, and the peeling strength of the copper foil of the crimping | compression-bonding side was 1.6 kN / m.

(Example 6)

Except having used polyimide coating roll 6 (thickness of a polyimide coating layer; 12 micrometers), it carried out similarly to Example 1, and obtained double-sided copper clad laminated board 6b. The external appearance of the copper foil surface of the coated surface side of the obtained double-sided copper clad laminated board 6b was favorable for the whole surface, and the peeling strength of the copper foil of the crimping | compression-bonding side was 1.6 kN / m.

(Example 7)

Except having used polyimide coating roll 7 (thickness of polyimide coating layer; 10 micrometers), it carried out similarly to Example 1, and obtained double-sided copper clad laminated board 7b. The external appearance of the copper foil surface of the coated surface side of the obtained double-sided copper clad laminated board 7b was favorable for the whole surface, and the peeling strength of the copper foil of the crimping | compression-bonding side was 1.6 kN / m.

(Example 8)

Except having used polyimide coating roll 8 (thickness of polyimide coating layer; 8 micrometers), it carried out similarly to Example 1, and obtained double-sided copper clad laminated board 8b. The external appearance of the copper foil surface of the coated surface side of the obtained double-sided copper clad laminated board 8b was favorable for the whole surface, and the peeling strength of the copper foil of the crimping | compression-bonding side was 1.6 kN / m.

(Example 9)

Except having used the polyimide coating roll 9 (thickness of a polyimide coating layer; 100 micrometers), it carried out similarly to Example 1, and obtained double-sided copper clad laminated board 9b. The external appearance of the copper foil surface of the coated surface side of the obtained double-sided copper clad laminated board 9b was favorable for the whole surface, and the peeling strength of the copper foil of the crimping | compression-bonding side was 1.6 kN / m.

(Example 10)

Instead of arranging the polyimide coating roll 1 on the copper foil 1 side of the single-sided copper clad laminate 1a in Example 1, the polyimide belt 10 (thickness; 20 µm, tensile strength; 400 MPa, tensile) from which moisture was removed by preheating A double-sided copper clad laminate 10b was obtained in the same manner as in Example 1 except that the elastic modulus; 9 GPa, seamless type). The external appearance of the copper foil surface of the coated surface side of the obtained double-sided copper clad laminated board 10b was favorable for the whole surface, and the peeling strength of the copper foil of the crimping | compression-bonding side was 1.6 kN / m. In addition, the contact time with the press roll of the polyimide belt 10 was 2 seconds.

(Example 11)

Instead of placing the polyimide coating roll 1 on the copper foil 1 side of the single-sided copper clad laminated board 1a in Example 1, the commercially available polyimide film 11 (thickness; 25 micrometers) which removed water by preheating was arrange | positioned. A double-sided copper clad laminate 11b was obtained in the same manner as in Example 1 except for the above. The external appearance of the copper foil surface of the coated surface side of the obtained double-sided copper clad laminated board 11b was favorable for the whole surface, and the peeling strength of the copper foil of the crimping | compression-bonding side was 1.6 kN / m. In addition, the insertion angle with respect to the pressure roll of the polyimide film 11 was 70 degrees.

As described above, as described in detail, according to the manufacturing method of the metal-clad laminate of the present embodiment, the metal-clad laminate in which the polyimide film is filled unevenly on the unevenness of the surface of the metal foil, and the polyimide film and the metal foil are firmly adhered to each other. Is obtained. By using the metal sheet laminate thus produced as a circuit board material such as FPC, a circuit board excellent in adhesion between the micronized wiring and the insulating resin layer can be produced. Therefore, according to this invention, the yield and reliability of an electronic product using a circuit board and a circuit board can be improved.

As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not restrict | limited to the said embodiment.

10, 10A... Polyimide film
20... Metal foil
30... Pressurized roll (coating pressurized roll)
31... Metal roll
33.. Adhesive layer
35... Polyimide coating layer
40... Pressurized roll
50... Coating layer
50A... Annular polyimide film
50B... Long shape polyimide film
61... Application means
63... Resin solution
71... materials
73... Polyimide layer
80A, 80B... Guide roll
90A... Unwinding roll
90B... Winding roll
100, 100A... Metal sheet laminate

Claims (15)

As a method of manufacturing a metal-clad laminate by thermally compressing the polyimide film and the metal foil by superimposing a polyimide film and a metal foil and passing a pair of pressure rolls continuously,
Among the pair of press rolls, at least one press face of the press roll on the one side is thermally crimped in a state of being covered with a film-shaped buffer member movable in synchronism with the press roll, and the film-shaped buffer member is non-thermoplastic. A non-thermoplastic polyimide layer containing a polyimide is included. The manufacturing method of the metal clad laminated board of Claim 1 in which the said film-form buffer material forms the coating layer which coat | covers the surface of the said pressurized roll of the one side in the circumferential direction. The said one side press roll is a coating press roll which has the said coating layer, and the other press roll is a metal roll, The manufacturing method of the metal-clad laminated board of Claim 2 characterized by the above-mentioned. The said metal roll is arrange | positioned at the said metal foil side, The manufacturing method of the metal-clad laminated board of Claim 3 characterized by the above-mentioned. The manufacturing method of the metal clad laminated board of Claim 1 in which the said film-shaped buffer material is formed in ring shape, and is formed rotatably by the said one side press roll and the some guide roll. The said film-shaped shock absorbing material is long formed, and the manufacturing method of the metal clad laminated board of Claim 1 conveyed by roll-to-roll type. The thickness of the said film-shaped buffer material exists in the range of 1-200 micrometers, The manufacturing method of the metal-clad laminated board of any one of Claims 1-6 characterized by the above-mentioned. The side according to any one of claims 1 to 6, wherein the polyimide film comprises a single layer or a plurality of layers of polyimide layers, and at least one layer is a non-thermoplastic polyimide, and is at least thermally compressed with the metal foil. The manufacturing method of the metal sheet laminated board whose surface is a thermoplastic polyimide layer. The method for producing a metal-clad laminate according to any one of claims 1 to 6, wherein the polyimide film is a laminate structure comprising a substrate and a polyimide layer laminated on the substrate. The manufacturing method of the metal sheet laminated board of Claim 9 whose said base material is copper foil. As a manufacturing method of the coating press roll used when a polyimide film and a metal foil are overlapped and continuously passed between a pair of press rolls, the said polyimide film and the said metal foil are thermo-compressed and a metal sheet laminated board is manufactured,
The said coating press roll has a metal roll and the coating layer which coat | covers the surface of this metal roll in a circumferential direction,
Applying a resin solution of a polyimide or polyimide precursor to the surface of the metal roll;
Process of forming the said coating layer by completing the heat processing of the said resin solution on the said metal roll
Method of producing a coating press roll comprising a. The manufacturing method of the coating press roll of Claim 11 which apply | coats the said resin solution to the surface, rotating the said metal roll. The manufacturing method of the coating press roll of Claim 12 which apply | coats the said resin solution, moving an application | coating means relatively to the rotation axis direction of the said metal roll. The manufacturing method of the coating press roll as described in any one of Claims 11-13 which heat-processes the said resin solution by heating the said metal roll using the heating mechanism of the said metal roll. A method for repairing a coated pressure roll used when a polyimide film and a metal foil are overlapped and continuously passed through a pair of pressure rolls to thermally compress the polyimide film and the metal foil to produce a metal-clad laminate.
The said coating press roll has a metal roll and the coating layer which coat | covers the surface of this metal roll in a circumferential direction,
Applying a resin solution of a polyimide or polyimide precursor to at least a part of the surface of the coating layer;
Process of completing the heat treatment of the resin solution on the coating pressure roll
The repair method of the coating press roll characterized by including the.

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