KR20130072145A - Both sides metal-clad laminate and method of producing the same - Google Patents

Abstract

PURPOSE: A double-sided metal clad laminate and a manufacturing method thereof are provided to comprise a polyimide resin layer which composes an insulation layer that has high heat resistance and dimensional stability and to suppress generation of micro void between a metal layer and the polyimide resin layer without using a surface shape of the metal layer. CONSTITUTION: A double-sided metal clad laminate (10) comprises metal layers (1) on both sides which integrate a first laminate and a second laminate. The first laminate and the second laminate comprise a metal layer and multiple resin layers respectively which include at least a first polyimide resin layer (2) and a second polyimide resin layers (3,3a). A manufacturing method of a double-sided metal clad laminate comprises the following steps of: the step of forming a first laminate by laminating at least one layer which is composed of a second polyimide resin layer, or a first polyimide resin layer and a second polyimide layer for the second polyimide resin layer to be the most outer layer; the step of forming a second laminate with the same laminating structure as the polyimide resin layer or with the different laminating structure from the polyimide resin layer for the second polyimide resin layer to be the most outer layer like the first laminate in common with the first laminate; and the step of heat-pressing the first laminate and both second polyimide resin layers which are the most outer layers of the second laminate. The step of forming the first and the second polyimide resin layer on a thin metal film includes a process which performs heat treatment for drying or imidization as occasion demands after coating a polyimide precursor resin solution or a polyimide resin solution which becomes the first polyimide resin layer or the second polyimide resin layer.

Description

Double-sided metal sheet laminate and its manufacturing method {BOTH SIDES METAL-CLAD LAMINATE AND METHOD OF PRODUCING THE SAME}

TECHNICAL FIELD The present invention relates to a double-sided metal sheet laminate, and more particularly to a double-sided sheet metal laminate having an insulating layer made of polyimide resin.

In recent years, as high performance, miniaturization and light weight of mobile phones, digital cameras, digital video, PDAs, navigators, hard disks, and other electronic devices, flexible substrates with high degree of freedom of wiring and thinness are easily used as substrate materials for electrical wiring. Is adopted. As for flexible flexible printed circuit boards used for these more advanced electronic devices, demands for smaller high density, multilayer, precision, and high heat resistance are increasing.

 In order to comply with such a requirement, a polyimide resin layer is formed directly by coating (hereinafter abbreviated as coating) on a conductor serving as a circuit wiring in Patent Document 1, and a plurality of polyimide resin layers having different thermal expansion coefficients are formed in multiple layers. It is proposed how to. According to this method, it is possible to provide a flexible printed circuit board having excellent reliability in terms of stability of the dimension against temperature change, adhesive force, planarity after etching, and the like. In addition, the coating method here is a method in which a polyimide precursor resin solution or a polyimide resin solution serving as a polyimide resin layer is applied to a metal layer and then dried, or the metal layer and the polyimide resin layer are bonded by heat treatment for drying and imidization. I shall say.

Moreover, also in the method of forming the flexible printed circuit board which bonds a conductor layer and a resin substrate by heat-compression bonding, the copper foil surface which is a conductor layer is subjected to the roughening process by the plating which consists of copper-cobalt nickel, and adhesiveness improves. The method to make it, ie, the modification by roughening of the copper foil surface, is proposed (patent document 2). Thereafter, the method of bonding the conductor layer and the resin substrate by thermal compression may be abbreviated as "heat compression crimping method".

However, in response to the demand for compact high density, there is a growing need for a so-called double-sided metal sheet laminate in which metal layers serving as conductors are formed on both surfaces of the polyimide resin layer. In the double-sided metal sheet laminated sheet manufactured by the coating method among the said double-sided metal sheet laminated sheets, one metal layer and the polyimide resin layer are formed by the coating method, and since the polyimide resin layer is already hardened by imidization, The metal layer on the side was bonded by a hot pressing method. That is, even in the coating method, in order to manufacture a double-sided metal-clad laminate, at least one metal layer had to be adhered to the polyimide resin layer by a hot pressing method.

On the other hand, since a brazing material having a higher melting temperature than lead soldering due to lead-freeization is used, the polyimide resin layer in contact with the metal layer is highly heat-resistant to cope with an increase in the solder joint temperature. Therefore, when bonding a metal layer and a polyimide resin layer together by the heat-compression method, there exists a problem that a microvoid becomes easy to produce | generate between a metal layer and a polyimide resin layer at the time of heat-compression bonding. When forming a circuit on a flexible printed circuit board by formation of this microvoid, there existed a problem that the adhesive reliability of a metal layer and a polyimide resin layer, such as the peeling of a wiring by the infiltration of an acid wash liquid, falls.

For this problem, for example, Patent Document 3 discloses a method of controlling the plating layer of the copper foil roughening treatment surface which is a metal layer and suppressing the roughening treatment height, that is, the roughening treatment degree. However, this method has a problem that the peel strength between the copper foil and the polyimide resin layer decreases. There remains a problem that both the bonding reliability and the peel strength in such a double-sided metal sheet laminate are achieved.

Japanese Patent Publication Hei 6-93537 Japanese Patent Laid-Open No. 8-335775 WO2010 / 010892 A1

The present invention suppresses the generation of microvoids generated between the metal layer and the polyimide resin layer even though the polyimide resin layer in contact with the roughened metal layer has high heat resistance, and also improves the adhesion reliability between the metal layer and the polyimide resin layer. It aims at providing the double-sided metal sheet laminated board which suppressed the circuit peeling by the infiltration of an acid washing liquid. That is, the subject of this invention is aiming at the coexistence of the adhesive reliability and peeling strength in a double-sided metal sheet laminated board.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors used two single-sided metal sheet laminated sheets formed by the coating method, heat-compression-bonded the polyimide resin layers of each outermost layer of a single-sided metallic sheet laminated board, and double-sided metal. By setting it as a long laminated board, what was able to solve the said subject was found and the present invention was completed. In addition, in this specification below, unless otherwise indicated, a "one side metal lamination board" means that the metal layer adhere | attached on one side of the laminated body which has several polyimide resin layers. In addition, a "double-sided metal sheet laminated board" means that the metal layer adhere | attached on both surfaces of the laminated body which has several polyimide resin layer. In addition, the case where heat-compression bonding of polyimide resin layers is also called heat compression method.

In other words, the double-sided metal sheet laminate of the present invention is a metal sheet laminate having a metal layer on both sides of the first laminate and the second laminate, wherein the first laminate and the second laminate are a metal layer and at least a first polyimide, respectively. It has a several polyimide resin layer containing a resin layer and a 2nd polyimide resin layer, The said 1st polyimide resin layer has a linear humidity expansion coefficient of 20x10 <^-6> /% RH or less, The said 2nd polyimide The resin layer has a glass transition point temperature of 300 ° C. or higher and lower than the glass transition point temperature of the first polyimide resin layer.

Furthermore, after apply | coating the polyimide precursor resin solution or polyimide resin solution which becomes the said 1st polyimide resin layer or the 2nd polyimide resin layer to the said metal layer, it is double-sided by heat processing for the imidation performed by drying and necessity. It is preferable that the said metal layer and the said 1st polyimide resin layer or the 2nd polyimide resin layer adhere | attach, and it is preferable to form the said metal layer using metal foil.

In addition, in the method for producing a double-sided metal sheet laminate of the present invention, the first polyimide resin layer having a linear humidity expansion coefficient of 20 × 10 ⁻⁶ /% RH or less, or the glass transition point temperature is 300 ° C. or more on the metal foil serving as the metal layer. A second polyimide resin layer is formed that is lower than the glass transition point temperature of the first polyimide resin layer, and the first polyimide resin layer and the first agent are formed on the first polyimide resin layer or the second polyimide resin layer. A step of laminating at least one layer of the second polyimide resin layer or the first polyimide resin layer and the second polyimide resin layer so that the second polyimide resin layer becomes the outermost layer, and forming a first laminate Forming a second laminate having the same or different laminate structure of the mid resin layer so that the second polyimide resin layer becomes the outermost layer in the same manner as the first laminate; A step of heat-pressing the second polyimide resin layers of the outermost layer of the first laminate and the second laminate, wherein the first polyimide resin layer or the second polyimide resin layer is formed on the metal foil. The step is a step of applying a polyimide precursor resin solution or a polyimide resin solution to be the first polyimide resin layer or the second polyimide resin layer and then performing a heat treatment for drying and imidization carried out as necessary. It is done.

(Effects of the Invention)

In the double-sided metal-clad laminate of the present invention, the polyimide resin constituting the insulating layer has high heat resistance, exhibits excellent dimensional stability, and the generation of microvoids between the metal layer and the polyimide resin layer that it contacts does not depend on the surface shape of the metal layer. It can be suppressed. In addition, since the double-sided metal sheet laminate of the present invention is excellent in chemical resistance, it is suitable for various applications requiring high precision processing, and its usefulness is very high.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing of the double-sided metal sheet laminated board of 1st Embodiment.
It is sectional drawing of the double-sided metal sheet laminated board of 2nd Embodiment.
3 is a cross-sectional view of another type of double-sided metal sheet laminate.
It is sectional drawing of the single-sided metal sheet laminated board which is an intermediate body for manufacturing the double-sided metal sheet laminated board of 1st Embodiment.
It is a flowchart which shows the manufacturing method of the double-sided metal sheet laminated board of 1st Embodiment.
It is a flowchart which shows the manufacturing method of the double-sided metal sheet laminated board of 2nd Embodiment.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described, referring drawings.

EMBODIMENT OF THE INVENTION The 1st Embodiment of this invention is described using FIG. As shown in FIG. 1, the double-sided metal-clad laminate 10 of the first embodiment includes a plurality of polys having a laminated structure composed of the first polyimide resin layers 2 and 2 and the second polyimide resin layers 3 and 3. The structure provided with the metal layers 1 and 1 on both surfaces of the mid resin layer. The first polyimide resin layers 2 and 2 adhered to the metal layers 1 and 1 are formed by a coating method. Although the 2nd polyimide resin layers 3 and 3 are mentioned later, they are bonded together and the 2nd polyimide bonding layer 3a is formed. The broken line of FIG. 1 shows that it is bonded to the part (FIGS. 2 and 3 are also the same).

In the double-sided metal-clad laminate 11 of the second embodiment of the present invention, the second polyimide resin layers 3, 3 bonded to the metal layers 1, 1 are formed by a coating method. Moreover, as shown in FIG. 2, the 1st polyimide resin layers 2 and 2 and the 2nd polyimide resin layers 3 and 3 are laminated | stacked, and the 2nd polyimide resin layers 3 and 3 of an innermost layer are bonded together. 2nd polyimide resin bonding layer 3a is formed.

In 1st Embodiment and 2nd Embodiment, although the polyimide resin layer formed in the metal layer 1 and 1 by the coating method is a polyimide resin layer of the 1st kind or the polyimide resin layer of a 2nd kind, it may be another form. That is, like the double-sided metal sheet laminate 12 shown in Fig. 3, the first polyimide resin layer is bonded to one metal layer 1, and the second polyimide resin layer is bonded to the other metal layer 1 by a coating method. It can be mentioned. In addition, although the polyimide resin layer of FIGS. 1-3 is 3 layer, 4 layer, and 5 layer (bonding layer is counted as 1 layer) structure, the some polyimide resin layer of this invention is not limited to this, Others It may take a multilayer structure.

In the manufacturing method of the double-sided metal sheet laminated board 10 of 1st Embodiment, as shown in FIG. 5, the polyimide precursor resin solution or polyimide which turns into the 1st polyimide resin layer 2 to the metal layer 1, such as metal foil, first The resin solution is applied (S1). Here, the polyimide precursor resin solution and the polyimide resin solution are collectively referred to as a prepolyimide resin layer. Next, the prepolyimide resin layer corresponding to the second polyimide resin layer 3 is applied and laminated (S2). In FIG. 5, the pre 1st polyimide resin layer and the pre 2nd polyimide resin layer mean the prepolyimide resin layer of the 1st polyimide resin layer 2 and the 2nd polyimide resin layer 3, respectively.

Next, the metal layer 1 and the first polyimide resin layer 2 are bonded together by drying [heat removal of the solvent] (S3) and imidization [heat curing treatment] (S4), and the second polyimide resin layer (3) is also formed. When the polyimide precursor resin solution is applied here, drying and imidization are carried out, and when the polyimide resin solution is applied, only drying is performed. As described above, the single-sided metal sheet laminate 20 having a plurality of polyimide resin layers is formed.

Subsequently, the second polyimide resin layers 3 of the two single-sided metal sheet laminates 20 (20a and 20b) are thermally compressed to form a double-sided metal sheet laminate 10 (S5).

The manufacturing method of the double-sided metal sheet laminated board 11 of 2nd Embodiment is basically the same as that of the double-sided metal sheet laminated board 10 of 1st Embodiment. Another point is that the pre-second polyimide resin layer to be the second polyimide resin layer 3 is applied to the metal layer 1 such as metal foil (S11) as shown in FIG. 6. After step 11 (S11), the coating of the pre-first polyimide resin layer (S12), the coating of the pre-second polyimide layer (S13), the drying [heat removal of the solvent] (S14), and the imidization [heat curing treatment] ] (S15) is performed sequentially. In addition, also in this embodiment, when apply | coating a polyimide resin solution, only drying is performed and there is no step (S15) of imidation.

Finally, the second polyimide resin layers 3 of the two single-sided metal sheet laminates formed in the same manner as in the first embodiment are heat-pressed to form a double-sided metal sheet laminate 11 (S16). S13 to S16 correspond to S2 to S5 of the first embodiment.

In addition, in order to make it the same form as the double-sided metal sheet laminated board 12 of FIG. 3, the laminated structure of the polyimide resin layer of two single-sided metal sheet laminated boards 20a and 20b may differ. However, the polyimide resin layer of the outermost layer which heat-presses is 2nd polyimide resin layer 3 whose glass transition point temperature is 300 degreeC or more.

The reason why the second polyimide resin layer 3 is heat-compressed when bonding two single-sided metal sheet laminates is that the glass transition point temperature is lower than that of the first polyimide resin layer 2. It is because it can suppress low and defects, such as deterioration of a metal-clad laminated board by high temperature heat-pressing, can be suppressed.

FIG. 4 shows an example of a cross-sectional view of the single-sided metal sheet laminate 20 formed as described above, and as shown in FIG. 4, the second polyimide resin layer 3 of the two single-sided metal sheet laminates 20a and 20b. 3) Prepare to be heat compressed. Although FIG. 4 is an illustration in the case of forming the double-sided metal sheet laminated board 10 of FIG. 1, as mentioned above, this invention is not limited to the said embodiment.

In the above process, although the method of forming the several polyimide resin layer 2 and 3 collectively was illustrated above, the preimide resin layer was apply | coated, dried, and imidized (heat-hardened) sequentially, and polyimide was carried out one by one. You may form the resin layers 2 and 3. Alternatively, the drying may be carried out sequentially, and the imidization (heat curing) treatment may be performed at the same time. Each of these treatments can be arbitrarily combined before forming a plurality of polyimide resin layers. In addition, a detailed manufacturing method is mentioned later.

In the metal layer 1 of the present invention, it is preferable to use metal foil from the viewpoint of adhesion, and as the metal of the metal foil, copper, aluminum, stainless steel, iron, silver, palladium, nickel, chromium, molybdenum, tungsten, zirconium, gold, And metals selected from cobalt, titanium, tantalum, zinc, lead, tin, silicon, bismuth, indium or these alloys. Copper foil is especially preferable at the point of electroconductivity. Moreover, it is preferable to apply to the metal foil of the film thickness of 5-30 micrometers, and, as for the manufacturing method of the double-sided metal sheet laminated board of this invention, the film thickness of 7-20 micrometers is more preferable. If the film thickness of the metal foil is less than 5 mu m, it is likely to cause wrinkles or the like in the production process, and if it exceeds 30 mu m, it is disadvantageous to respond to the recent fine wiring pattern.

Moreover, in these metal layers 1, it aims at the improvement of the adhesive force with a polyimide resin, etc., and the surface is sizing, chromium plating, nickel plating, chromium- nickel plating, copper- zinc alloy plating, copper oxide precipitation, or aluminum alcohol. Such as chemical or surface roughening treatments by rate, aluminum chelate, silane coupling agent, triazine thiols, benzotriazoles, acetylene alcohols, acetylacetones, catechols, o-benzoquinones, tannins, quinolinols, and the like. Mechanical surface treatment may be performed.

Here, it is preferable that the surface roughness of the surface which contact | connects the polyimide resin layer 2 or 3 of the metal layer 1 is 0.5-3 micrometers in Rz. It is because adhesive force (adhesive strength) with a polyimide resin layer becomes more favorable in it being this range. It is more preferable that it is 1-2.5 micrometers, since both the preferable adhesive force and the favorable etching property at the time of fine wiring pattern formation can be aimed at. Rz represents the 10-point average roughness prescribed | regulated by JIS B 0601 (1994) here.

The polyimide resin of this invention means resin which consists of a polymer which has an imide group in structures, such as a polyimide, polyamideimide, polyetherimide, polyesterimide, polysiloxane imide, and polybenzimidazole imide.

The polyimide resin which comprises the 1st polyimide resin layer 2 of this invention has the characteristic that the linear humidity expansion coefficient is 20x10 <^-6> /% RH or less. It is because the curl of the single-sided and double-sided metallic sheet laminate due to the humidity change at the time of hot pressing can be suppressed very much. This is because the dimensional stability due to the change in the humidity environment of the double-sided metal sheet laminate as a product can be maintained. Preferably it is 15 * 10 <^-6> /% RH or less from a point of curl suppression and dimensional stability.

Here, the linear humidity expansion coefficient is a measured value obtained by measuring the length (L ₂₅ and L ₈₀ ) in the major axis direction at 25% and 80% relative humidity (RH) of a resin film having a size of 1.5 cm x 3 mm at 25 ° C. Is obtained by the following equation from the difference L (cm) = L ₈₀ -L ₂₅ .

L (cm) × 1 / 1.5 (cm) × 1 / (80-25) (% RH)

Specific measurement conditions were used in combination with a thermomechanical analyzer (manufactured by Seiko Instruments Co., Ltd.) and a humidifier for the thermomechanical analyzer (manufactured by Seiko Instruments Co., Ltd.), and the resin film of the sample under the control of measurement temperature of 25 ° C. The dimensional change in the major axis direction at 25% and 80% relative humidity is measured, and the rate of dimensional change per 1% RH is calculated as the linear humidity expansion coefficient. Here, when a sample is a resin layer formed on a conductor, what used the removal of a conductor layer by etching etc. as a single layer resin film can be used.

Moreover, the polyimide resin which comprises the 1st polyimide resin layer 2 is a tetra amino compound containing 50 mol% or more of 4,4'- diamino-2,2'- dimethyl biphenyl (m-TB). It is preferable that it is obtained by making it react with a carboxylic acid compound. This is because a preferable linear humidity expansion coefficient can be achieved. It is more preferable to use the diamino compound containing 70 mol% or more of m-TB. 100 mol% may be sufficient as m-TB, but 80-98 mol% is more preferable.

Moreover, as polyimide resin which comprises the 1st polyimide resin layer 2, it is more preferable to contain 50 mol% or more of either or both of the structural units represented by following General formula (1) and (2). In addition, when both are included, the total amount is a range of the said content.

A diamino compound of the examples of the other m-TB, may be mentioned an aromatic diamino compound represented by NH ₂ -Ar ₁ -NH ₂ as desired. Ar ₁ here is selected from the group represented by following formula (3), Substitution position of an amino group is arbitrary, but p, p'-position is preferable. Ar ₁ may have a substituent but preferably does not have or is a lower alkyl or lower alkoxy group having 1 to 6 carbon atoms. You may use 1 or more types of these aromatic diamino compounds.

Examples of the tetracarboxylic acid reacted with the diamino compound include aromatic tetracarboxylic acids, acid anhydrides, esterified compounds, and halides thereof, but aromatic tetracarboxylic acid compounds are preferable, and polyamides that are precursors of polyimide resins are preferred. Since the synthesis | combination of an acid (polyamic acid) is easy, the acid anhydride is preferable. In addition, there may be mentioned as the aromatic tetracarboxylic acid compounds include O (CO) is the compound represented by ₂ Ar ₂ (CO) ₂ O is preferred.

Wherein Ar ₂ is a tetravalent aromatic group may be represented by the following formula (4), it is the substitution position of an acid anhydride group [(CO) ₂ O] is preferably in a random but symmetric position. Ar ₂ may have a substituent but is preferably not or a lower alkyl group having 1 to 6 carbon atoms. Preferred aromatic tetracarboxylic acid compounds are biphenyltetracarboxylic anhydride (BPDA), 4,4'-oxydiphthalic anhydride (ODPA), pyromellitic anhydride (PMDA) or combinations thereof. More preferred aromatic tetracarboxylic acid compounds are BPDA, PMDA, or both, and it is appropriate to adjust the balance of production performance by using BPDA and PMDA in a molar ratio of 0:10 to 8: 2.

The polyimide resin constituting the first polyimide resin layer 2 may be reacted with, for example, a mole of the above-described tetracarboxylic acid compound in a solvent that is substantially equivalent to a diamino compound containing 50 mol% or more of the m-TB described above. It can manufacture by the two steps of the synthesis | combination and imidation reaction of polyamic acid (polyamic acid) which is a precursor of a polyimide resin.

Until the synthesis | combination of the polyamic acid which is a precursor of a polyimide resin, it is performed in a reaction container etc. before application | coating to the metal layer 1. Alternatively, the process may be carried out until imidization to form a polyimide resin solution. And the polyamic-acid solution or polyimide resin solution which is a precursor is apply | coated to a metal layer, and it is set as a prepolyimide resin layer. Naturally, it is apply | coated also on the prepolyimide resin layer or polyimide resin layer which has already been apply | coated.

Next, the glass transition point temperature of the polyimide resin which comprises the 2nd polyimide resin layer 3 of this invention is 300 degreeC or more, and comprises the 1st polyimide resin layer 2 Lower characteristics. Preferably it is the range of 300-330 degreeC. By doing in this way, while maintaining the heat resistance of the whole insulating layer, the balance of adhesiveness with a metal layer can be aimed at. Moreover, it is preferable that it is 50 degreeC or more higher than the glass transition point temperature of a 2nd polyimide resin layer, and, as for the same reason, it is more preferable that it is 50-120 degreeC higher.

Moreover, the polyimide resin which comprises the 2nd polyimide resin layer 3 is a diamino compound and tetracarboxyl containing 50 mol% or more of 2, 2-bis [4- (aminophenoxy) phenyl] propane (BAPP). It is preferable that it is obtained by reaction with an acid compound. It is because a preferable glass transition point temperature can be achieved. It is more preferable to use the diamino compound containing 70 mol% or more of BAPP. The structure of BAPP is shown by following General formula (5).

As a non BAPP of the diamino compound it may be mentioned first as in the polyimide for the polyimide resin constituting the resin layer (2) an aromatic diamino compound represented by the NH ₂ -Ar ₁ -NH ₂ as the preferred . 1,3-bis (4-aminophenoxy) benzene (1,3-BAB) and 1,4-bis (4-aminophenoxy) benzene (1,4-BAB) can also be preferably used.

As a tetracarboxylic-acid compound made to react with a diamino compound, it is preferable to use a compound similarly to the case of the polyimide resin which comprises said 1st polyimide resin layer. 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride (DSDA) and 3,3', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA) can also be used. .

The polyimide resin which comprises the 1st polyimide resin layer 2 and the 2nd polyimide resin layer 3 can be manufactured by the following method, for example. That is, the said diamino compound and tetracarboxylic dianhydride are mixed in a solvent in the ratio of substantially equivalent molar ratio, and it makes it react in the range of reaction temperature O-200 degreeC, Preferably it is the range of 0-100 degreeC, and a polyimide precursor resin. There is a method of obtaining a solution and further obtaining a polyimide resin by imidating it.

As a solvent, N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), dimethyl sulfate, sulfolane, butyrolactone, cresol, phenol, halogenated phenol And cyclohexanone, dioxane, tetrahydrofuran, diglyme, and triglyme.

As mentioned above, imidation may be performed after apply | coating the polyimide precursor (polyamic acid) resin solution to the metal layer 1.

The prepolyimide resin layer to be applied to the metal layer 1 may be either a polyimide precursor resin solution or a polyimide resin solution in which imidization is terminated, but when the polyimide is not solvent soluble, it is polyimide from the viewpoint of viscosity adjustment. Precursor resin solutions are preferred.

Next, the manufacturing method of the double-sided metal sheet laminated board of this invention is demonstrated in detail with reference to FIG. In order to manufacture the double-sided metal sheet laminate of the present invention, a prepolyimide resin layer is first applied to the metal layer 1 (S1, S11). In the case of manufacturing a double-sided metal sheet laminate in which the polyimide resin layer is a laminated structure of three or more layers, at least one single-sided sheet metal laminate is further coated with another prepolyimide resin layer to form a plurality of polyimide resin layers. Let it be a laminated body (S2, S12). At this time, as shown in FIG. 5 or FIG. 6, when the prepolyimide resin layer applied to a metal layer becomes the 1st polyimide resin layer 2, any of the cases where it becomes the 2nd polyimide resin layer 3 may be sufficient. good. In addition, the coating method for forming a polyimide resin layer of multiple layers can select arbitrary methods, Preferably the following three methods are preferable by the point of coating precision.

1) 2 or more types of prepolyimide resin layers are apply | coated simultaneously on a conductor with a multilayer die.

2) After apply | coating a prepolyimide resin layer by arbitrary methods, another prepolyimide resin layer is further apply | coated by the knife coat system, the die system, etc. on the undried application surface.

3) Application | coating a prepolyimide resin layer by arbitrary methods After drying, another prepolyimide resin layer is further apply | coated to the dry coating surface by arbitrary methods.

The knife coat method used here is a method of uniformly applying a resin solution with a bar, a squeegee, a knife or the like.

As the drying and imidization (heat curing) treatment method, any method may be utilized, but after applying the prepolyimide resin layer, the laminate including the pre-dried uncured prepolyimide resin layer may be set to a predetermined temperature. A plurality of layers of polyimide resin layers are formed by a method of performing a heat treatment at a high temperature (200 ° C. or more) by allowing a fixed time to stand in a hot air drying furnace or continuously moving within an area of the drying furnace to secure a predetermined dry curing time. The single-sided metal sheet laminate 20 having the same is formed.

In addition, in consideration of the efficiency of work, product ratio and the like, after applying the prepolyimide resin layer, a pre-dried uncured laminate is wound in a roll shape, and a batch processing method of drying at a high temperature and performing heat curing is also possible. . In order to prevent the oxidation of the metal layer 1 which is a conductor in this batch treatment method, it is preferable to perform heat treatment at high temperature (200 degreeC or more) under reducing gas atmosphere or reducing gas atmosphere pressure reduction under reduced pressure.

In the drying and imidization (heat curing) treatment step, the prepolyimide resin layer is further imide-opened when the solvent is removed by heat treatment and a polyimide precursor resin solution is used. At this time, when the heat treatment is rapidly performed at a high temperature, a skin layer is formed on the surface of the resin, which makes it difficult to evaporate the solvent or foams. Therefore, the heat treatment is preferably performed while gradually increasing the temperature from a low temperature to a high temperature. Moreover, 300-400 degreeC is preferable as a final heat processing temperature for making into the imidated (cured) polyimide resin layer.

Although the resin solution concentration at the time of using a polyimide precursor resin solution as a prepolyimide resin layer depends on the polymerization degree of the polyimide precursor which is a polymer, it is 5-30 weight% normally, Preferably it is 10-20 weight%. This is because when the polymer concentration is higher than 5% by weight, a sufficient film thickness is obtained by one application, and when the polymer concentration is lower than 30% by weight, the viscosity of the resin solution does not become too high so that the coating can be satisfactorily applied in terms of uniformity and smoothness. .

The film thickness of the polyimide resin layer formed on the metal layer 1 is the dimensional stability control by maintaining the heat resistance of the entire polyimide layer in which the first polyimide resin layer 2 is an insulating layer, and controlling the linear expansion coefficient or the humidity expansion coefficient. From a viewpoint of 3-30 micrometers is preferable and 5-25 micrometers is more preferable. In addition, the second polyimide resin layer 3 is basically not required to be so thick in terms of good adhesiveness due to thermocompression, and is preferably 0.5 to 5 µm, more preferably 1 to 3 µm. Do. It is preferable to make the 2nd polyimide resin layer 3 into a film thickness thinner than the 1st polyimide resin layer 2 here. Moreover, 7-80 micrometers is preferable, as for the thickness of the whole polyimide resin layer of a laminated structure, 10-60 micrometers is more preferable, 20-30 micrometers is the most preferable.

As for the single-sided metal sheet laminated board 20 formed as mentioned above, the laminated structure of the 1st polyimide resin layer 2 and the 2nd polyimide resin layer 3 is the 1st polyimide resin layer 2 comrades, and the 2nd There may be a part in which the polyimide resin layers 3 are laminated. However, it is better to laminate | stack alternately from a viewpoint of curl control at the time of manufacture of a single-side metal sheet laminated board. Either one layer may be sufficient.

By the above process, the single-sided metal sheet laminated board 20 illustrated in FIG. 4 can be formed. Subsequently, the second polyimide resin layers 3 and 3 of the two single-sided metal sheet laminates 20a and 20b are heat-pressed to form a double-sided metal sheet laminate 10 or 11 illustrated in FIGS. 1 and 2. At this time, the laminated structure of the polyimide resin layer of the two single-sided metal sheet laminated sheets 20 may be different, and the example is the double-sided metal sheet laminated sheet 12 of FIG. Moreover, the 1st polyimide resin layer 2 may be one of the polyimide resin layers heated and crimped.

Therefore, at least one of the single-sided metal-clad laminates 20 to be bonded needs to be the second polyimide resin layer 3 of the outermost polyimide resin layer. Since sufficient strength is obtained in the adhesiveness of the polyimide resin layers heat-squeezed, it is preferable to bond together the two single-sided metal sheet laminated boards 20 whose outermost layer is the 2nd polyimide resin layer 3.

When bonding the polyimide resin layers of the two single-sided metal sheet laminates 20 together, the heat-compression bonding can take the following method, for example. That is, a hydro press, a vacuum hydropress, an autoclave pressurized vacuum press, a continuous thermal laminator, or the like can be used. Among them, vacuum hydropress is a preferred method for heat pressing in that sufficient press pressure is obtained, residual volatilization can be easily removed, and oxidation of conductors such as metal foil can be prevented.

Although it does not specifically limit about the hot press temperature at the time of this hot pressing, It is preferable that it is more than the glass transition point temperature of the polyimide resin used. In addition, about hot press pressure, although it depends also on the kind of press apparatus to be used, 0.1-50 Mpa (1-500 kg / cm <2>) is suitable. If the press temperature at the time of hot pressing is too high, there is a possibility that defects such as deterioration of the metal layer and the polyimide resin layer may occur, so that the second polyimide resin layers 3 having the lower glass transition point temperatures are also used. It is more preferable to bond together.

The double-sided metal sheet laminate produced as described above has excellent adhesion and adhesive strength between the metal layer 1 and the polyimide resin layer in contact with the metal layer 1 on both sides. Therefore, it is a highly acid-resistant double-sided metal sheet laminate that does not produce microvoids and does not peel off the circuit due to the penetration of the acid cleaning liquid. Moreover, the glass transition point temperature of all the some polyimide resin layers is 300 degreeC or more, and the compatibility with high heat resistance is aimed at. Moreover, since it has the polyimide resin layer whose linear humidity expansion coefficient is 20x10 <^-6> /% RH or less, generation | occurrence | production of a curl and dimensional change by a humidity change can be suppressed.

That is, the double-sided metal-clad laminate of the present invention forms the adhesion between the metal layer and the polyimide resin layer by a coating method, so that (1) both surfaces have very good adhesion and adhesive strength, and are excellent in acid resistance and the like. Moreover, since the 1st polyimide resin layer 2 whose linear humidity expansion coefficient is 20x10 <^-6> /% RH or less is used, (2) the dimensional stability as a double-sided metal sheet laminated board is favorable, and it is characterized by the curl also being suppressed. Moreover, since the glass transition point temperature is lower than the 1st polyimide resin layer 2, and the 2nd polyimide resin layer 3 which rigidity falls and becomes a glass state at 330 degrees C or less is used, (3) double-sided metal sheet laminated board As a result, the adhesiveness of all the laminated parts is very good. In summary, the outstanding effect that the outstanding properties of said (1)-(3) can be achieved simultaneously is exhibited.

Example

Embodiments of the present invention will be described in more detail with reference to the following Examples. Moreover, the superiority of this embodiment is revealed by showing a comparative example.

1. Metal foil

As metal foil used as a metal layer, the copper foil of 1.6 micrometers used the surface roughness (Rz) of the side which contact | connects 12 micrometers and a polyimide resin layer.

2. Measurement of various physical properties and performance test method

[Line Humidity Expansion Coefficient]

The polyimide resin which etched the copper foil which is a metal layer, and became the film state was used for the thermomechanical analyzer (made by Seiko Instruments Co., Ltd.) in combination with the humidity device for thermomechanical analyzer (made by Seiko Instruments Co., Ltd.), and the said method was used. Saved by.

[Linear thermal expansion coefficient]

The polyimide resin which etched copper foil and became the film state was heated up to 255 degreeC using a thermomechanical analyzer (made by Seiko Instruments Co., Ltd.), and it hold | maintained at that temperature for 10 minutes, and then cooled at the speed of 5 degreeC / min. The average thermal expansion coefficient (linear thermal expansion coefficient) from 240 degreeC to 100 degreeC was calculated | required.

[Measurement of Glass Transition Temperature]

Using a dynamic viscoelasticity measuring device (RSA-III) manufactured by SAI Eye Nano Technology Co., Ltd. It was set as glass transition point temperature.

[Measurement of Acid Resistance]

The evaluation of acid resistance was performed on a flexible single-sided copper clad laminate (single-sided metal laminate) by circuit processing with a line width of 1 mm, and then immersed in an aqueous solution of 18 wt% hydrochloric acid for 50 ° C. for 60 minutes, and then at the end of the circuit from the insulation layer side (polyimide resin layer side). The discoloration part by percolation of hydrochloric acid was measured using the 200 times optical microscope, and it was set as the index of acid resistance as percolation width (micrometer).

[Measurement of Adhesive Force]

The adhesive force between the copper foil and the polyimide resin layer was subjected to circuit processing with a line width of 1 mm to the flexible single-sided copper clad laminate, and the copper foil was peeled off in a 180 ° direction using a tensile tester (Stograph-M1) manufactured by Toyo Seiki Co., Ltd. Initial peel strength was measured. Moreover, the peeling strength after the said acid resistance measurement was measured (post-acid peeling strength / initial peeling strength) x100 was made into the peeling strength retention (%).

Hygroscopic Soldering Heat Test

A commercially available photoresist film is laminated on a laminate composed of a conductor / resin layer / conductor, and is exposed to a predetermined pattern forming mask (365 nm, exposure amount of about 500 J / m 2) so that the copper foil layer is circular in shape of 1 mm in front and back. The resist layer was cured and formed on the pattern. Then, the cured resist part is developed (developing solution is a 1% NaOH aqueous solution), and the copper foil layer which is not necessary for the formation of a predetermined pattern is etched away using a ferric chloride aqueous solution, and the lead is further removed by removing the cured resist layer with an alkaline liquid. A sample (a laminate in which a circular pattern having a diameter of 1 mm was formed on the front and back of a conductor layer of a laminate composed of a conductor, an insulating resin layer, and a conductor) with a pattern for evaluating heat resistance corresponding to presoldering was obtained.

After leaving a sample for 192 hours in 40 degreeC 90% RH environment, it immersed for 10 second in the molten soldering bath with different temperature, and observed the presence or absence of the deformation and swelling in the copper foil layer location. Deformation and swelling did not occur in the copper foil layer, so the maximum temperature of the solder bath was taken as the soldering heat resistance temperature.

3. Synthesis of Polyimide Precursor Resin

Synthesis Example 1 Precursor for Second Polyimide Resin Layer

302 g of N, N-dimethylacetamide was placed in a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen. 30.99 g (0.076 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was dissolved in the reaction vessel while stirring in the vessel. Then 16.96 g (0.078 mol) of pyromellitic dianhydride was added. After that, stirring was continued for 3 hours to obtain a polyamic acid (polyamic acid) resin solution a having a solution viscosity of 2,960 mPa · s. In addition, a solution viscosity is a value of the apparent viscosity in 25 degreeC by an E-type viscosity meter (it is the same below).

The linear expansion coefficient of the polyimide resin obtained from this polyamic acid was 55 × 10 ⁻⁶ (1 / K), and the linear humidity expansion coefficient was 7.0 × 10 ⁻⁶ /% RH.

Synthesis Example 2: Precursor for Second Polyimide Resin Layer

334 g of N, N-dimethylacetamide was placed in a vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen. 2,2-bis [4- (4-aminophenoxy) phenyl] propane 29.24 g (0.072 mol) and 3.81 g (0.018 mol) of 4,4-diamino-2,2-dimethylbiphenyl were added to the reaction vessel. Was dissolved with stirring in a vessel. Then 20.00 g (0.092 mol) of pyromellitic dianhydride were added. After that, stirring was continued for 3 hours to obtain a resin solution b of polyamic acid. The solution viscosity of the resin solution b of polyamic acid was 3,140 mPa * s.

The linear expansion coefficient of the polyamide resin obtained from this polyamic acid was 56x10 <^-6> (1 / K).

Synthesis Example 3: Precursor for Control Polyimide Resin Layer

630 g of N, N-dimethylacetamide was placed in a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen. 26.83 g (0.134 mol) of 4,4'-diaminodiphenyl ether was dissolved in the reaction vessel while stirring in the vessel. Then, dianhydride was added to 42.96 g (0.133 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic acid. After that, stirring was continued for 2 hours to obtain a resin solution c of polyamic acid having a solution viscosity of 2,850 mPa · s.

The linear expansion coefficient of the polyimide obtained from this polyamic acid was 53x10 <^-6> (1 / K).

Synthesis Example 4 Precursor for Control Polyimide Resin Layer

255 g of N, N-dimethylacetamide was placed in a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen. 22.13 g (0.076 mol) of 1,3-bis (4-aminophenoxy) benzene was dissolved in the reaction vessel while stirring in the vessel. Then 16.71 g (0.047 mol) of diphenylsulfontetracarboxylic dianhydride and 6.78 g (0.031 mol) of pyromellitic dianhydride were added. After that, stirring was continued for 2 hours to obtain a resin solution d of polyamic acid having a solution viscosity of 2,640 mPa · s.

The linear expansion coefficient of the polyimide obtained from this polyamic acid was 61x10 <^-6> (1 / K).

Synthesis Example 5 Precursor for First Polyimide Resin Layer

3.076 kg of N, N-dimethylacetamide was placed in a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen. In this reaction vessel, 225.73 g (1.063 mol) of 4,4'-diamino-2,2'-dimethylbiphenyl was dissolved in the vessel while stirring. 61.96 g (0.211 mole) of 3,3'-4,4'-biphenyltetracarboxylic dianhydride and 183.73 g (0.842 mole) of pyromellitic dianhydride (PMDA) were then added. After that, stirring was continued for 3 hours to obtain a resin solution e of polyamic acid having a solution viscosity of 20,000 mPa · s.

The polyimide resin obtained from this polyamic acid showed a low linear expansion coefficient of ^7x10-6 (1 / K) and ^20x10-6 (1 / K) or less, and had non-thermoplastic properties. The linear humidity expansion coefficient was 9.0 × 10 ⁻⁶ /% RH.

Synthesis Example 6 Precursor for Control Polyimide Resin Layer

1.11 kg of N, N-dimethylacetamide was placed in a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen. In this reaction vessel, 66.51 g (0.259 mol) of 4,4'-diamino-2'-methoxybenzanilide and 34.51 g (0.172 mol) of 4,4'-diaminodiphenyl ether were dissolved in the vessel while stirring. Then 92.62 g (0.425 mol) of pyromellitic dianhydride was added. After that, stirring was continued for 3 hours to obtain a resin solution f of 24,000 mPa · s polyamic acid.

The polyimide resin obtained from this polyamide exhibited a low linear expansion coefficient of 19 × 10 ⁻⁶ (1 / K) and 20 × 10 ⁻⁶ (1 / K) or less, and had non-thermoplastic properties. The linear humidity expansion coefficient was 27.0 × 10 ⁻⁶ /% RH.

The synthetic | combination conditions of each synthesis example, and each resin physical property at the time of imidating each obtained polyimide acid and making it as a polyimide resin are put together in Table 1, and are shown. In addition, in the item of "role" of Table 1, "base" shows what plays the role of dimensional stability control of a double-sided metal sheet laminated board, and "TPI" shows that it plays the role of adhesiveness by thermocompression bonding. Therefore, "base" is a polyimide resin used for a 1st polyimide resin layer or its equivalent layer (for comparative example), and "TPI" is a polyimide used for a 2nd polyimide resin layer or its equivalent layer (for comparative example). It is a mid resin.

Example 1

Resin solution a of polyamic acid prepared in Synthesis Example 1 and polyamide prepared in Synthesis Example 5 on a copper foil having a surface roughness (Rz) of 1.6 μm (Furugawa Denki Kogyo Co., Ltd., film thickness 12 μm, electrolyzed product) The resin solution e of the acid was applied sequentially, and then the resin solution a was applied thereon, and dried and finally subjected to heat treatment at 300 ° C. or more for about 2 minutes, so that the total film thickness of the polyimide resin layer was 25 μm (layer structure: a / e A flexible single-sided copper clad laminate (single-sided metal sheet laminated sheet) having a / a = 2.5 μm / 20 μm / 2.5 μm) was obtained. In addition, the layer obtained from the resin solution a is a 2nd polyimide resin layer, and the layer obtained from the resin solution e is a 1st polyimide resin layer.

These two single-sided copper clad laminates were bonded together to the polyimide resin surfaces, and were simultaneously supplied at a rate of 1 m / min between a pair of heating rolls and thermo-compressed, thereby providing a flexible double-sided copper clad laminate having a total film thickness of 50 μm. (Double-sided metal sheet laminate) was obtained. At this time, the roll surface temperature was 390 degreeC, and the linear pressure between rolls was 134 kN / m. Moreover, the ratio of the layer obtained from the resin solution e of polyamic acid and the layer obtained from the resin solution a of polyamic acid in the polyimide resin layer was 4: 1.

The 1 mm peel of this double-sided copper clad laminate had an initial adhesive force of 0.98 kN / m. In addition, the permeation width by the acid resistance test of this circuit was 69 micrometers, and the retention of peeling strength was 89%. The results are shown in Table 2. The results of Examples 2 and 3 and Comparative Examples 1 to 3 are also shown in Table 2 below.

Example 2

In the same manner as in Example 1, the flexible double-sided copper-clad laminate of 50 µm was obtained by bonding the polyimide resin surfaces of the single-sided copper-clad laminate to each other.

The resin solution coated on the copper foil was a resin solution b / resin solution e / resin solution b (layer structure: b / e / b = 2.5 μm / 20 μm / 2.5 μm) in order, and the polyamide in the obtained polyimide resin layer The ratio of the layer obtained from the resin solution e of the acid, and the layer obtained from the resin solution b of the polyamic acid was 4: 1. In addition, the layer obtained from the resin solution b is a 2nd polyimide resin layer.

Example 3

In the same manner as in Example 1, the flexible double-sided copper-clad laminate of 50 µm was obtained by bonding the polyimide resin surfaces of the single-sided copper-clad laminate to each other.

The resin solution apply | coated on copper foil is resin solution e / resin solution a (layer structure: e / a = 22.5 / 2.5 micrometers) in order, and the layer and poly obtained from resin solution e of polyamic acid in the obtained polyimide resin layer The ratio of the layer obtained from the resin solution a of amic acid was 9: 1.

Comparative Example 1

In the same manner as in Example 1, the resin solution a / resin solution e / resin solution a was sequentially applied and dried on the copper foil, and finally subjected to a heat treatment at 300 ° C. or more for about 2 minutes, and the thickness of the polyimide resin layer was 25 μm (layer Structure: The flexible single-sided copper clad laminated board of a / e / a = 2.5 micrometer / 20 micrometer / 2.5 micrometers) was obtained. The ratio of the layer obtained from the resin solution e of polyamic acid and the layer obtained from the resin solution a of polyamic acid in the obtained polyimide resin layer was 4: 1. A copper foil having a surface roughness (Rz) of 1.6 µm was bonded to the polyimide resin surface of this single-sided copper clad laminate (Furugawa Denki Kogyo Co., Ltd., film thickness of 12 µm, electrolytic product), and thermally compressed in the same manner as in Example 1 A flexible double-sided copper clad laminate was obtained.

Comparative Example 2

In the same manner as in Example 1, the flexible double-sided copper-clad laminate of 50 µm was obtained by bonding the polyimide resin surfaces of the single-sided copper-clad laminate to each other.

The resin solution apply | coated on copper foil is resin solution a / resin solution e (layer structure: a / e = 2.5 micrometer / 22.5 micrometer) in order, and the layer obtained from the resin solution e of polyamic acid in the obtained polyimide resin layer, The ratio of the layer obtained from the resin solution a of polyamic acid was 9: 1.

Comparative Example 3

In the same manner as in Example 1, the flexible double-sided copper-clad laminate of 50 µm was obtained by bonding the polyimide resin surfaces of the single-sided copper-clad laminate to each other.

The resin solution coated on the copper foil was a resin solution c / resin solution f / resin solution d (layer structure: c / f / d = 2 μm / 21 μm / 2 μm) in order, and the polyamide in the obtained polyimide resin layer The ratio of the layer obtained from the resin solution c of the acid, the layer obtained from the resin solution f, and the layer obtained from the resin solution d was almost 1: 10: 1. In addition, the layer obtained from the resin solutions c and d is a 2nd polyimide resin layer, and the layer obtained from the resin solution f is a 1st polyimide resin layer.

In Table 2, "fill strength" indicates initial peel strength. "Peel strength retention" and "sew width" are as described above.

As is clear from Table 2, each of the Examples exhibits superior performances to the Comparative Examples in terms of initial peel strength, peel strength retention, permeation width, and solder heat resistance and humidity. In addition, in Comparative Example 3, the resin d of the bonded portion was equivalent to the second polyimide resin layer, but the glass transition point temperature was less than 300 ° C., so that the performance of soldering heat and humidity was insufficient.

1 metal layer (metal foil) 2nd polyimide resin layer
3, 3a 2nd polyimide resin layer 10, 11, 12 double-sided metal sheet laminated board
20, 20a, 20b single sided metal sheet laminate

Claims (14)

As a metal sheet laminate which has a metal layer on both surfaces which integrated the 1st laminated body and the 2nd laminated body:
The first laminate and the second laminate each have a metal layer and a plurality of polyimide resin layers including at least a first polyimide resin layer and a second polyimide resin layer,
The first polyimide resin layer has a linear humidity expansion coefficient of 20 × 10 ⁻⁶ /% RH or less,
The second polyimide resin layer has a glass transition point temperature of 300 ° C. or higher and lower than the glass transition point temperature of the first polyimide resin layer. The method of claim 1,
The glass transition point temperature of the said 1st polyimide resin layer is 50-120 degreeC higher than the glass transition point temperature of the said 2nd polyimide resin layer, The double-sided metal sheet laminated board characterized by the above-mentioned. 3. The method according to claim 1 or 2,
Both the first laminate and the second laminate have the second polyimide resin layer as the outermost layer,
The said metal sheet laminated body bonded together the said 2nd polyimide resin layer of the said outermost layer by heat-pressing, The double-sided metal sheet laminated board characterized by the above-mentioned. The method according to any one of claims 1 to 3,
The metal-clad laminate includes a polyimide resin layer in which the polyimide resin layer in contact with the metal layer of the first polyimide resin layer or the second polyimide resin layer becomes the first polyimide resin layer or the second polyimide resin layer in the metal layer. A double-sided metal sheet laminate, wherein a mid precursor resin solution or a polyimide resin solution is applied to the metal layer by drying after application and heat treatment for imidization performed as necessary. The method according to any one of claims 1 to 4,
The surface roughness Rz of the surface which contact | connects the said 1st polyimide resin layer or the 2nd polyimide resin layer of the said metal layer exists in the range of 0.5-3 micrometers. 6. The method according to any one of claims 1 to 5,
The second polyimide resin layer reacts a diamino compound and a tetracarboxylic acid compound containing 50 mol% or more of 2,2-bis [4- (4-aminophenoxy) phenyl] propane to react the polyimide precursor resin. It is obtained by passing, The double-sided metal sheet laminated board characterized by the above-mentioned. 7. The method according to any one of claims 1 to 6,
The first polyimide resin layer reacts a diamino compound and tetracarboxylic acid compound containing 50 mol% or more of 4,4'-diamino-2,2'-dimethylbiphenyl, via a polyimide precursor resin A double-sided metal sheet laminate is obtained. The first polyimide resin layer having a linear humidity expansion coefficient of 20 × 10 ⁻⁶ /% RH or less, or the glass transition point temperature of 300 ° C. or more, and the glass transition point temperature of the first polyimide resin layer on the metal foil serving as the metal layer. A lower second polyimide resin layer is formed, and the first polyimide resin layer, the second polyimide resin layer, or the first polyimide on the first polyimide resin layer or the second polyimide resin layer. A step of laminating at least one layer of the resin layer and the second polyimide resin layer so that the second polyimide resin layer becomes the outermost layer, and forming a first laminate;
Forming a second laminating agent having the same or different lamination structure of the polyimide resin layer so as to make the second polyimide resin layer become the outermost layer in the same manner as in the first laminate;
It has a process of heat-pressing the said 2nd polyimide resin layers of the outermost layer of a said 1st laminated body and a said 2nd laminated body,
The step of forming the first polyimide resin layer or the second polyimide resin layer on the metal foil includes a polyimide precursor resin solution or a polyimide resin solution which becomes the first polyimide resin layer or the second polyimide resin layer. A method for producing a double-sided metal sheet laminate, characterized in that it is a step of performing a heat treatment for drying after application and for imidization performed as necessary. The method of claim 8,
The said 2nd laminated body does not make a polyimide resin layer into a laminated structure, and forms only one layer of the said 2nd polyimide resin layers on the said metal foil, The manufacturing method of the double-sided metal sheet laminated board characterized by the above-mentioned. The method of claim 8,
Both the first laminate and the second laminate are formed by alternately laminating the first polyimide resin layer or the second polyimide resin layer. 11. The method according to any one of claims 8 to 10,
A glass transition point temperature 50-120 degreeC higher than said 2nd polyimide resin layer is formed as said 1st polyimide resin layer, The manufacturing method of the double-sided metal sheet laminated board characterized by the above-mentioned. The method according to any one of claims 8 to 11,
The surface roughness (Rz) of the surface which contact | connects the said 1st polyimide resin layer or the 2nd polyimide resin layer as said metal foil uses the metal foil of 0.5-3 micrometers, The manufacturing method of the double-sided metal sheet laminated board characterized by the above-mentioned. 13. The method according to any one of claims 8 to 12,
The second polyimide resin layer reacts a diamino compound and a tetracarboxylic acid compound containing 50 mol% or more of 2,2-bis [4- (4-aminophenoxy) phenyl] propane to react the polyimide precursor resin. A method of producing a double-sided metal sheet laminate, characterized in that it is formed via. 14. The method according to any one of claims 8 to 13,
The first polyimide resin layer reacts a diamino compound and tetracarboxylic acid compound containing 50 mol% or more of 4,4'-diamino-2,2'-dimethylbiphenyl, via a polyimide precursor resin Method for producing a double-sided metal sheet laminate, characterized in that formed.

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