JP6234802B2 - Laminate - Google Patents

Description

  The present invention relates to a laminate.

  As a metal-clad laminate used for a flexible wiring board (FPC board) or the like, for example, a laminate of a conductive metal foil on an insulating resin base film such as polyimide or polyethylene terephthalate is used. ing. As a method of laminating a metal foil on such a base film, a method of adhering the base film and the metal foil with an epoxy adhesive or an acrylic adhesive can be mentioned. In addition, as one of the methods for improving the adhesive strength between the base film and the metal foil, a method of adding a silane coupling agent to an epoxy adhesive or an acrylic adhesive, a method of roughening the surface of the metal foil, etc. Is mentioned.

  There is also a method for producing a metal-clad laminate by a technique of laminating a metal on a base film by wet plating. For example, Patent Document 1 discloses a technique using a compound having an azide group or a triazine ring as a method for forming a metal plating film on a polymer substrate.

Japanese Patent No. 4936344

  However, in the technique of bonding the base film and the metal foil with an epoxy adhesive or an acrylic adhesive, the adhesive strength can be improved by adding a silane coupling agent to the adhesive, but more sufficient adhesion can be achieved. In order to secure the force, it is necessary to increase the thickness of the adhesive layer (adhesive layer). Then, since the difference in coefficient of thermal expansion between the adhesive and the base film or the metal foil is large, there is a problem that the laminate is curled when the metal foil is etched and the dimensional stability is poor. In addition, since the adhesive layer is thick, there is a problem that deformation such as a circuit is likely to occur during thermocompression bonding for solder connection or ACF connection using an anisotropic conductive film or the like.

  When roughening the surface of the metal foil in order to increase the adhesive strength, if a laminate using such a metal foil is used for precision electronic parts such as an FPC board, the electrical characteristics are adversely affected. There's a problem. In such a case, there is also a problem that material selection is restricted in that a roughened metal foil must be used to obtain a high adhesive strength. Such a problem becomes prominent particularly when a copper foil is used as the metal foil or when a polyimide film is used as the base film.

  Moreover, the method of laminating a metal on a base film by wet plating is limited in that it has the same composition as the electrolytic metal foil. A laminate using an electrolytic metal foil is inferior in bending resistance to a laminate using a rolled metal foil. For this reason, there is a problem that when mounted on a hinge portion or the like of an electronic device and bent, parts are easily broken or deformed, and the electrical characteristics of the electronic device are adversely affected. And, in order to increase the thickness of the electrolytic metal on the laminate, it is necessary to lengthen the plating time. Therefore, there is a problem that the yield during production is poor and the economy is inferior.

  The present invention has been made in view of the above circumstances, and provides a laminate that has sufficient adhesive strength, is excellent in surface appearance after adhesion, and that can alleviate restrictions on member material selection. Objective.

  As a result of diligent research, the inventors have made a laminate including a resin layer and an adhesive layer containing a silane coupling agent having a specific structure formed on the surface of the resin layer. It has been found that at least the above problems can be solved, and the present invention has been accomplished.

That is, the present invention is as follows.
[1]
A resin layer;
A laminate comprising: an adhesive layer containing a silane coupling agent represented by the following formula (1), formed on the surface of the resin layer.

(R ⁴ O) ₃ Si—R ³ —N—R ² R ¹ (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 24 carbon atoms, a phenyl group, or an aminoalkyl group. R ³ represents 1 to 1 carbon atoms. 6 represents a divalent hydrocarbon group of 6. Each R ⁴ independently represents a monovalent hydrocarbon group having 1 to 24 carbon atoms.)
[2]
The laminate according to [1], further including a metal foil layer or a resin layer formed on the surface of the adhesive layer opposite to the surface on which the resin layer is laminated.
[3]
A metal foil layer;
And an adhesive layer containing a silane coupling agent represented by the following formula (1), formed on the surface of the metal foil layer.

(R ⁴ O) ₃ Si—R ³ —N—R ² R ¹ (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 24 carbon atoms, a phenyl group, or an aminoalkyl group. R ³ represents 1 to 1 carbon atoms. 6 represents a divalent hydrocarbon group of 6. Each R ⁴ independently represents a monovalent hydrocarbon group having 1 to 24 carbon atoms.)
[4]
The laminate according to [3], further including a resin layer formed on the surface of the adhesive layer opposite to the surface on which the metal foil layer is laminated.
[5]
A first metal foil layer;
A first resin layer formed on the surface of the first metal foil layer;
An adhesive layer formed on the surface of the first resin layer;
A second resin layer formed on the surface of the adhesive layer;
A second metal foil layer formed on the surface of the second resin layer in this order,
The said adhesive layer is a laminated body containing the silane coupling agent represented by following formula (1).

(R ⁴ O) ₃ Si—R ³ —N—R ² R ¹ (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 24 carbon atoms, a phenyl group, or an aminoalkyl group. R ³ represents 1 to 1 carbon atoms. 6 represents a divalent hydrocarbon group of 6. Each R ⁴ independently represents a monovalent hydrocarbon group having 1 to 24 carbon atoms.)
[6]
R ³ is a hydrocarbon group having a straight chain of 1 to 3 carbon atoms, laminate according to any one of [1] to [5] of the formula (1).
[7]
The formula (1) is any one selected from the group consisting of the following formula (2), formula (3), and formula (4), according to any one of [1] to [6]. Laminated body.

(C ₂ H ₆ O) ₃ SiC ₃ H ₆ NH ₂ (2)

(CH ₃ O) ₃ SiC ₃ H ₆ NH ₂ (3)

(CH ₃ O) SiC ₃ H ₆ NHC ₂ H ₄ NH ₂ (4)
[8]
The laminated body according to any one of [1], [2], and [4] to [7], wherein the resin layer is a polyimide layer.
[9]
The laminate according to any one of [2] to [8], wherein the metal foil layer is a copper foil layer.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the laminated body which has sufficient adhesive strength, is excellent also in the surface external appearance after adhesion | attachment, and can ease the restriction | limiting of the material selection of a member.

It is a schematic sectional drawing of the 1st aspect of the laminated body of this embodiment. It is a schematic sectional drawing of the 2nd aspect of the laminated body of this embodiment. It is a schematic sectional drawing of the application example of the 2nd aspect of the laminated body of this embodiment. It is a schematic sectional drawing of the 3rd aspect of the laminated body of this embodiment. It is a schematic sectional drawing of the 4th aspect of the laminated body of this embodiment. It is a schematic sectional drawing of the 5th aspect of the laminated body of this embodiment. It is a schematic sectional drawing of the 6th aspect of the laminated body of this embodiment. It is a schematic sectional drawing of the 7th aspect of the laminated body of this embodiment. It is the upper surface schematic of the sample used by evaluation of the peeling strength of an Example.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof. In the drawings, positional relationships such as up, down, left and right are based on the positional relationships shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. Furthermore, in the drawings, overlapping description of common elements is omitted.

(Laminate)
FIG. 1 represents a schematic cross-sectional view of a first aspect of the laminate of the present embodiment. The first aspect of the laminate of the present embodiment includes a resin layer 11 and an adhesive layer 12 formed on the surface of the resin layer 11 and containing a silane coupling agent represented by the following formula (1); It is the laminated body 1 containing. The adhesive layer 12 contains a silane coupling agent represented by the above-described formula (1). The laminate 1 can be bonded to other members via the adhesive layer 12. Examples of other members include other metal foils and resins. Furthermore, the laminated body of this embodiment can also take the form of what is called a polymer film etc. in which the contact bonding layer 12 was formed on the resin layer 11 of a film (it may be called a sheet | seat) form.

(R ⁴ O) ₃ Si—R ³ —N—R ² R ¹ (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 24 carbon atoms, a phenyl group, or an aminoalkyl group. R ³ represents 1 to 1 carbon atoms. 6 represents a divalent hydrocarbon group of 6. Each R ⁴ independently represents a monovalent hydrocarbon group having 1 to 24 carbon atoms.)

From the viewpoint of reactivity, R ¹ and R ² are preferably each independently a linear hydrocarbon group having 2 or 3 carbon atoms.

Specific examples of R ¹ and R ² include, for example, hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-hexyl group, i-hexyl. Group, amino group, aminomethyl group, aminoethyl group, phenyl group and the like. Among these, a hydrogen atom, an amino group, and an aminomethyl group are preferable from the viewpoint of reactivity. From the viewpoint of adhesive strength and the like, it is preferable that at least one of R ¹ and R ² is a hydrogen atom.

From the viewpoints of solubility and reactivity, R ³ is preferably a linear hydrocarbon group having 1 to 3 carbon atoms.

Specific examples of R ³ include, for example, methylene group, ethylene group, n-propylene group, i-propylene group, n-butylene group, i-butylene group, n-hexylene group, i-hexylene group, phenyl group and the like. Can be mentioned. Among these, methylene group, ethylene group, n-propylene group, i-propylene group, n-butylene group, i-butylene group are preferable from the viewpoint of solubility and reactivity, and methylene group, ethylene group, n-propylene. Group and n-butylene group are more preferable, and ethylene group is still more preferable.

From the viewpoint of solubility and reactivity, R ⁴ is preferably a linear hydrocarbon group having 1 to 4 carbon atoms.

Specific examples of R ⁴ include, for example, ethyl group, methyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and the like. Among these, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group are preferable from the viewpoint of reactivity. Furthermore, from the viewpoint of solubility and reactivity, an ethyl group, a methyl group, and an n-propyl group are more preferable, and an n-propyl group is still more preferable.

Specific examples of the silane coupling agent represented by the formula (1) are selected from the group consisting of the following formula (2), formula (3), and formula (4) having an amino group from the viewpoint of reactivity. The compound represented by any one is preferable.

(C ₂ H ₆ O) ₃ SiC ₃ H ₆ NH ₂ (2)

(CH ₃ O) ₃ SiC ₃ H ₆ NH ₂ (3)

(CH ₃ O) SiC ₃ H ₆ NHC ₂ H ₄ NH ₂ (4)

In addition, the —C ₃ H ₆ — group bonded to the Si atom in the formulas (2), (3), and (4) may be an n-propylene group or an i-propylene group. From the viewpoint of properties, it is more preferably an n-propylene group.

  The thickness of the adhesive layer 12 is not particularly limited, but is preferably 1 nm to 500 nm, more preferably 1 nm to 400 nm, and still more preferably 5 nm to 300 nm.

  In the present embodiment, the adhesiveness of the adhesive layer can be expressed by including the silane coupling agent represented by the formula (1), but by using the silane coupling agent, a monomolecular layer (or to it) A close thin layer adhesive layer 12 can be formed. Thereby, the intermolecular force between the silane coupling agent represented by the formula (1) and the molecule on the surface of the resin layer and the molecule on the surface of the metal foil layer efficiently interacts and can be bonded more firmly. (However, the operation of the present embodiment is not limited to these).

  The adhesive layer 12 may further contain various solvents, additives and the like in addition to the silane coupling agent represented by the formula (1). In addition, it does not specifically limit as a method of forming the contact bonding layer 12 on the surface of the resin layer 11, A various method is employable. For example, a solution of the silane coupling agent represented by the formula (1) using a solvent is used, and this is applied to the resin layer 11 by a known method. Examples of the application means include a spray and a roller coater.

  When using a solvent as the solution of the silane coupling agent, the content of the silane coupling agent represented by the formula (1) in the solution is preferably 0.01 to 10% by mass, More preferably, it is -5 mass%, and it is still more preferable that it is 0.1-2 mass%. By setting the content of the silane coupling agent in the above range, a much thinner coating film can be formed.

  Examples of the solvent include water, alcohol (eg, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, cellosolve, carbitol, etc.), ketone (eg, acetone, methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbon (eg, Benzene, toluene, xylene, etc.), aliphatic hydrocarbons (eg, hexane, octane, decane, dodencan, octadecane, etc.), esters (eg, ethyl acetate, methyl propionate, methyl phthalate, etc.), ethers (eg, tetrahydrofuran, Ethyl butyl ether, anisole, etc.). Among these, water, alcohol and the like are preferable from the viewpoint of storage stability. These may be used alone or in combination of two or more.

  The laminated body 1 of this embodiment can further laminate | stack another member through the contact bonding layer 12, and can be set as the laminated body of a various structure. Hereinafter, various aspects that this embodiment can take will be further illustrated.

  FIG. 2 represents a schematic cross-sectional view of the second aspect of the laminate of the present embodiment. The 2nd aspect of the laminated body of this embodiment is the laminated body 2 which further contains the metal foil layer 23 formed on the surface of the contact bonding layer 12 on the opposite side to the surface where the resin layer 11 of the laminated body 1 was laminated | stacked. It is. That is, the laminated body 2 is the laminated body 2 including the metal foil layer 23, the adhesive layer 12, and the resin layer 11 in this order, and is a single area layer body in which one metal foil layer 23 is formed. The laminate 2 can be obtained by further laminating the metal foil layer 23 on the laminate 1. Alternatively, the laminate 2 can also be obtained by bonding the resin layer 11 and the metal foil layer 23 via the adhesive layer 12.

  As a manufacturing method of the laminated body 2, the method of integrating by the thermocompression bonding which the surface of the contact bonding layer 12 of the laminated body 1 and the surface of the metal foil layer 23 are piled up, etc. are mentioned, for example. The conditions for thermocompression bonding are not particularly limited, and suitable conditions can be adopted as appropriate. The heating temperature is preferably 30 to 400 ° C, more preferably 100 to 400 ° C, and still more preferably 150 to 300 ° C. Further, the pressure may be reduced during the thermocompression bonding. This facilitates the removal of gas or the like that has entered between the layers during thermocompression bonding.

  In addition, although the aspect which has the layer structure of metal foil layer 23 / adhesion layer 12 / resin layer 11 was illustrated in FIG. 2, although not shown in figure, the aspect which has a layer structure of resin layer / adhesion layer 12 / resin layer 11 is also this. In the embodiment, it can be adopted. This is an embodiment in which a resin layer is used instead of the metal foil layer 23. That is, a laminate in which another resin layer is formed on the surface of the adhesive layer 12 opposite to the surface on which the resin layer 11 of the laminate 1 is laminated can also be used. Such a laminate can be used as a reinforcing film (or reinforcing plate) or the like by bonding a film having a thin resin layer with the adhesive layer 12, for example.

  FIG. 3 is a schematic cross-sectional view of an application example of the second aspect of the present embodiment. That is, the laminated body 2 a is a laminated body in which the metal foil layer 24 is further formed on the laminated body 2. The laminate 2a is a double-sided laminate in which two metal foil layers 23 and 24 are formed. In addition, the laminated body 2a does not necessarily have to be based on the structure of the laminated body 1 or the laminated body 2. For example, in the laminated body 25 including the adhesive layer 12, the resin layer 11, and the metal foil layer 24 in this order, The aspect in which the metal foil layer 23 was further formed may be sufficient. This laminated body 25 is a one-area layered body in which one metal foil layer 24 is formed.

  As a manufacturing method of the laminated body 25, the solution containing the silane coupling agent represented by Formula (1) on the surface of the resin layer 11 of the copper foil laminated body which has the metal foil layer 24 and the resin layer 11, for example. Examples of the method include forming the adhesive layer 12 on the surface of the resin layer 11 by applying and drying. Such a laminate 25 can be firmly bonded to other members including a metal foil layer and a resin layer with the adhesive layer 12 as an adhesive surface. Therefore, the laminate 2a can also be suitably used as a member of a multilayer metal-clad laminate.

  Although not shown, another resin layer may be formed instead of the metal foil layer 23 on the surface of the adhesive layer 12 opposite to the surface on which the resin layer 11 of the laminate 1 is laminated. In this case, another metal foil layer can be further laminated on the surface of the resin layer.

  FIG. 4 shows a schematic cross-sectional view of the third aspect of the laminate of the present embodiment. The 3rd aspect of the laminated body of this embodiment is the adhesive layer 32 containing the silane coupling agent represented by following formula (1) formed on the surface of the metal foil layer 31 and the metal foil layer 31. FIG. And a laminated body 3 including: Since the adhesive layer 32 contains the silane coupling agent represented by the above formula (1), the laminate 3 and other members can be bonded via the adhesive layer 32. Examples of other members include resin.

  FIG. 5 represents a schematic cross-sectional view of the fourth aspect of the laminate of the present embodiment. The fourth aspect of the laminate of the present embodiment includes, for example, a laminate further including a resin layer 43 formed on the surface of the adhesive layer 32 opposite to the surface on which the metal foil layer 31 of the laminate 3 is laminated. Body 4. The laminate 4 can be used as a laminate in which the resin layer 43 and the metal foil layer 31 are bonded via the adhesive layer 32. In addition, the laminated body 4 does not necessarily need to assume the structure of the laminated body 1 and includes, for example, a resin layer 43, an adhesive layer 32, and a metal foil layer 31 in this order. The structure containing the silane coupling agent represented by this may be sufficient. In this case, the laminate 3 is a laminate having a configuration of resin layer 43 / adhesive layer 32 / metal foil layer 31. Such a laminated body 3 is a single area layer body in which one metal foil layer 31 is formed.

  FIG. 6 represents a schematic cross-sectional view of the fifth aspect of the laminate of the present embodiment. The laminate 5 is a laminate in which the metal foil layer 531 / adhesive layer 521 / resin layer 51 / adhesive layer 522 / metal foil layer 532 are laminated in this order, and two metal foil layers 531 and 532 are formed. It is a double-sided laminate.

  The laminate 5 can be manufactured, for example, by the following method. First, the adhesive layers 521 and 522 are formed on both surfaces of the resin layer 51 by applying a solution containing the silane coupling agent represented by the formula (1) on both surfaces of the resin layer 51 and drying the solution. In addition, a method in which the adhesive layer 521 and the metal foil layer 531 are overlaid, and the adhesive layer 522 and the metal foil layer 532 are overlaid so that they are integrated by thermocompression bonding. Or the method of forming the contact bonding layer containing Formula (1) on the surface of the resin layer 11 of the laminated body 2 (refer FIG. 2), and thermocompression-bonding it and the other metal foil layer etc. are mentioned (not shown).

  FIG. 7 shows a schematic cross-sectional view of the sixth aspect of the laminate of the present embodiment. The laminated body 6 includes a first metal foil layer 631, a first resin layer 611 formed on the surface of the first metal foil layer 631, and an adhesive formed on the surface of the first resin layer 611. A layer 62, a second resin layer 612 formed on the surface of the adhesive layer 62, and a second metal foil layer 632 formed on the surface of the second resin layer 612 in this order, The adhesive layer 62 is a laminate containing a silane coupling agent represented by the formula (1). That is, the laminate 6 is a laminate in which the metal foil layer 631 / resin layer 611 / adhesive layer 62 / resin layer 612 / metal foil layer 632 are laminated in this order, and two metal foil layers 631 and 632 are formed. It is a double-sided laminate.

  Examples of a method for producing the stacked body 6 include the following methods. First, a copper foil laminate having a metal foil layer 631 and a resin layer 611 and a copper foil laminate having a metal foil layer 632 and a resin layer 612 are prepared. As these copper foil laminates, commercially available products such as copper foil laminate resin films and single-sided copper clad laminates can also be used. An adhesive layer 62 is formed on the surface of the resin layer 611 by applying a solution containing the silane coupling agent represented by the formula (1) to the surface of the resin layer 611 of the copper foil laminate and drying it. And the method of carrying out the thermocompression bonding of the two copper foil laminated bodies so that the contact bonding layer 62 and the resin layer 612 may be piled up is mentioned.

  Or the laminated body 25 (refer FIG. 3) which is the layer structure of the adhesive layer 12 / resin layer 11 / metal foil layer 24 is prepared, and the copper foil laminated body which has the metal foil layer 631 and the resin layer 611 mentioned above, and thermocompression bonding The method of doing is also mentioned. In this case, thermocompression bonding is performed so that the adhesive layer 12 and the resin layer 611 are overlapped (not shown).

  FIG. 8 shows a schematic cross-sectional view of the seventh aspect of the laminate of this embodiment. Laminate 7 is a laminate in which metal foil layer 73 / adhesive layer 12 / resin layer 11 / metal foil layer 24 are laminated in this order, and is a double-sided laminate in which two metal foil layers 73 and 24 are formed. is there.

  As a manufacturing method of the laminated body 7, for example, a laminated body 25 (see FIG. 3) having a layer configuration of adhesive layer 12 / resin layer 11 / metal foil layer 24 is prepared, and the adhesive layer 12 and the metal foil layer 73 are prepared. For example, a method of superimposing them by thermocompression bonding.

Each laminated body of this embodiment mentioned above contains various resin including polyimide etc., copper etc. by including the silane coupling agent represented by Formula (1) in the adhesive layer. Adhesive strength can be exerted on various metals. Although it is not certain as a reason which can exhibit adhesive force with respect to metals, such as copper, it estimates as follows. First, a hydroxy group (OH) present on the surface of a metal such as copper, and a silanol group (—Si (OH) ₃ ) generated by hydrolysis of the —Si (OR ⁴ ) ₃ group of the formula (1), It is presumed to be bound by a condensation reaction.

Furthermore, when at least one of R ¹ and R ² bonded to the nitrogen atom is a hydrogen atom, it is presumed that the adhesive force to a resin such as polyimide is improved for the following reason. Bonding by a condensation reaction between a hydroxy group and a silanol group present on the resin surface as well as a metal surface such as copper or a carbonyl group (for example, -CO It may be due to a hydrogen bond generated between the hydrogen of (-N-bond etc.).

  As described above, since the silane coupling agent represented by the formula (1) can form a new bond with both the resin and the metal in one molecule, the adhesive layer has a sufficient adhesive force. At the same time, even a monomolecular film can exhibit a sufficient adhesive force. That is, the monomolecular adhesive layer can adhere a resin or metal while being a thin adhesive layer.

  Even when the thickness is larger than the thickness of the monomolecular film (when there are a plurality of molecules), sufficient adhesive force is expressed. Specifically, when a plurality of silane coupling agents represented by the formula (1) are present between the adherends, a hydrogen bond or a silanol group between amino groups that do not contribute directly to a bond with a functional group present on the substrate surface. It is considered that the adhesive force can be exerted even by an adhesive layer having a thickness of a monomolecular film or more due to the coupling by a condensation reaction between them (however, the action of this embodiment is not limited to these).

(Resin layer)
It does not specifically limit as a material used for the resin layer of this embodiment, Various resin can be used. Examples thereof include polyamide imide and polyether imide. Among these, polyimide is preferable from the viewpoint of improving adhesive strength and functionality as a laminate. Since the imide skeleton can be firmly bonded to the silane coupling agent represented by the formula (1), it is possible to bond more strongly.

  The polyimide is not particularly limited as long as it has an imide skeleton. For example, a condensation polymer of an aromatic diamine and an aromatic tetracarboxylic acid, a bismaleimide resin that is an addition polymer of an aromatic diamine and bismaleimide, or a polyaminobis that is an addition polymer of an aminobenzoic acid hydrazide and a bismaleimide. Examples thereof include thermosetting polyimides such as a maleimide resin and a bismaleimide triazine resin composed of a dicyanate compound and a bismaleimide resin.

  In the conventional polyimide-based copper-clad laminate, for example, a thermoplastic polyimide (TPI) having a low glass transition point (Tg) is interposed on the bonding surface in order to bond the metal foil layer and the polyimide layer. It was necessary to let them. However, since thermoplastic polyimide has a low Tg and a high coefficient of thermal expansion (CTE), there is a problem that it is inferior in heat resistance and dimensional stability as compared with thermosetting polyimide, which causes problems when thermocompression bonding. Cheap. In this regard, the polyimide film of the present embodiment can exhibit excellent adhesive force even if it is various polyimides by blending the silane coupling agent represented by the formula (1) into the adhesive layer, and adhesion. Excellent surface appearance afterwards. Therefore, the type of polyimide is not restricted.

  From the above viewpoint, the polyimide used in this embodiment is preferably a non-thermoplastic polyimide or a thermosetting polyimide. As used herein, the non-thermoplastic polyimide refers to a material whose elastic modulus gradually decreases with increasing temperature at a certain temperature (for example, 200 ° C.) or higher, but does not have fluidity. This means that the elastic modulus hardly decreases even when the temperature rises above a certain temperature.

  By blending the silane coupling agent represented by the formula (1) into the adhesive layer, even a non-thermoplastic polyimide or a thermosetting polyimide can be adhered to the metal foil layer. Non-thermoplastic polyimide and thermosetting polyimide have a high Tg of 300 ° C. or higher and a low CTE, so that they are further excellent in heat resistance and dimensional stability. Therefore, in the case of an electronic component, the pattern accuracy is high and excellent electrical characteristics can be stably exhibited. Therefore, it is possible to meet demands such as formation of a fine pattern circuit.

  The surface of the resin layer may be subjected to plasma treatment or corona treatment.

  The thickness of the resin layer is not particularly limited, and a suitable thickness can be selected as appropriate. The thickness of the resin layer is preferably 5 to 125 μm, more preferably 5 to 75 μm, and still more preferably 5 to 50 μm. In this embodiment, since the strong adhesive force can be exhibited by mix | blending the silane coupling agent represented by Formula (1) with an adhesive layer, there is no restriction | limiting of the thickness of a resin layer.

(Metal foil layer)
The metal foil layer is not particularly limited, and various materials can be used. In this embodiment, the restriction | limiting on the material regarding a metal foil layer can be eased. For example, conventionally, surface treatment such as surface roughening has been performed on the metal foil layer from the viewpoint of improving the adhesive force with the resin layer. However, when such surface roughening is performed, the electrical characteristics of the electronic component may not be stable. Moreover, since the electrical activity of the metal foil layer is higher when the surface treatment such as surface roughening is not performed, it is desired not to roughen the surface as much as possible. In this respect, by blending the silane coupling agent represented by the formula (1) into the adhesive layer, even if it is a metal foil layer (flat metal foil layer) having a low surface roughness, Can be glued.

  In the present embodiment, a metal foil layer subjected to surface roughening can be used, but a metal foil layer not subjected to surface roughening is preferable. Furthermore, the metal foil layer is preferably subjected to pickling treatment. When using a metal foil layer that has been subjected to surface roughening in the present embodiment, it is preferable to remove the excess copper component in advance using an acid, an etching solution, or the like to reduce the surface roughness. It does not specifically limit as an acid or an etching liquid, For example, a well-known thing can be used.

  From the viewpoint described above, the metal foil layer preferably has a ten-point average roughness (Rz) of 2.0 μm or less, more preferably 1.5 μm or less, and further 1.0 μm or less. preferable. The ten-point average roughness can be measured by the method described in Examples described later.

  Moreover, it does not specifically limit as a material of a metal foil layer, A various metal can be used. For example, aluminum, stainless steel, etc. are mentioned. Among these, it is preferable that it is a copper foil layer from a viewpoint of the functional improvement as a laminated body. By being a copper foil layer, as described above, a bond can be formed with the silane coupling agent represented by the formula (1), and bonding can be performed. A laminate that is a copper foil layer can be suitably used as a copper clad laminate (CCL) or the like used for an FPC board or the like.

  The thickness of the metal foil layer is not particularly limited, and a suitable thickness can be selected as appropriate. In this embodiment, since the strong adhesive force can be exhibited by mix | blending the silane coupling agent represented by Formula (1) with an adhesive layer, there is no restriction | limiting of the thickness of a metal foil layer. The thickness of the metal foil layer is preferably 2 to 400 μm, more preferably 2 to 70 μm, and still more preferably 2 to 35 μm.

  The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples.

<Preparation of copper foil layer / (adhesive layer) / polyimide layer single-area layered body (Examples 1 to 9, Comparative Example 1), see FIG. 2>

Example 1
A corona-treated polyimide film (non-thermoplastic polyimide, manufactured by Kaneka Corporation, “Apical 50NPI”, thickness 50 μm) was immersed in an acetone solvent, and then dried with a dryer set at 80 ° C. 1 mL of a 2% aqueous solution of 3-aminopropyltrimethoxysilane, “KBM-903” (manufactured by Shin-Etsu Chemical Co., Ltd .; a silane coupling agent represented by formula (2)) is dropped on this polyimide film, and a glass rod is used. Uniformly stretched throughout the film. And this was preserve | saved for 10 minutes in the dryer set to 60 degreeC, and the polyimide film 1 was obtained.
Also, a 10 cm x 12 cm electrolytic copper foil (Fukuda Metal Foil Powder Co., Ltd., “CF-T9DA-SV”, thickness 18 μm) subjected to rust prevention treatment with acetone and a dryer set at 60 ° C. And the copper foil surface was dried to obtain an electrolytic copper foil 1.
And the polyimide film 1 and the electrolytic copper foil 1 were thermocompression-bonded on the conditions of 180 degreeC * 9MPa * 10min (Hot-Hot) and the vacuum degree 0.1MPa using the press. After thermocompression bonding, it was allowed to cool at room temperature to obtain a single-sided copper-clad laminate 1 (copper foil layer / (adhesive layer) / polyimide layer).

(Example 2)
A polyimide film 2 was obtained in the same manner as in Example 1, except that the 2% aqueous solution of “KBM-903” was changed to the 0.5% aqueous solution of “KBM-903”.
Moreover, the electrolytic copper foil 1 produced in Example 1 was used as the electrolytic copper foil.
And by the method similar to Example 1, the single-sided copper clad laminated body 2 (copper foil layer / (adhesion layer) / polyimide layer) was obtained from the polyimide film 2 and the electrolytic copper foil 1.

(Example 3)
A polyimide film (manufactured by Kaneka Corporation, “Apical 50NPI”, thickness 50 μm) was immersed in an acetone solvent, and then dried in a dryer set at 80 ° C. to obtain polyimide film 3.
In addition, after immersing an electrolytic copper foil (Fukuda Metal Foil Industry Co., Ltd., “CF-T9DA-SV”, thickness 18 μm) subjected to rust prevention treatment in an acetone solvent, a dryer set at 80 ° C. And dried. 1 mL of a 0.5% aqueous solution of “KBM-903” was dropped on this electrolytic copper foil, and uniformly spread over the entire copper foil using a glass rod. And this was preserve | saved for 10 minutes in the dryer set to 60 degreeC, and the electrolytic copper foil 3 was obtained.
And the single-sided copper clad laminated body 3 (copper foil layer / (adhesion layer) / polyimide layer) was obtained from the polyimide film 3 and the electrolytic copper foil 3 by the method similar to Example 1. FIG.

Example 4
An untreated polyimide film (manufactured by Toray DuPont, “Kapton 200EN”, thickness 50 μm) was immersed in an acetone solvent, and then dried with a dryer set at 80 ° C. to obtain polyimide film 4.
Moreover, the electrolytic copper foil 3 produced in Example 3 was used as the electrolytic copper foil.
And by the method similar to Example 3, the single-sided copper clad laminated body 4 (copper foil layer / (adhesion layer) / polyimide layer) was obtained from the polyimide film 4 and the electrolytic copper foil 3.

(Example 5)
A polyimide film 5 (made by Toray DuPont, “Kapton 200EN”, thickness 50 μm) subjected to plasma treatment was immersed in an acetone solvent and then dried with a dryer set at 80 ° C. to obtain polyimide film 5. .
Moreover, the electrolytic copper foil 3 produced in Example 3 was used as the electrolytic copper foil.
And the single-sided copper clad laminated body 5 (copper foil layer / (adhesion layer) / polyimide layer) was obtained from the polyimide film 5 and the electrolytic copper foil 3 by the same method as in Example 3.

(Example 6)
The polyimide film 3 produced in Example 3 was used as the polyimide film.
A rolled copper foil (JX Nikko Co., Ltd., “GHSN”, thickness 12 μm) subjected to corona treatment was immersed in an acetone solvent and then dried with a dryer set at 80 ° C. 1 mL of a 0.5% aqueous solution of “KBM-903” was dropped on this rolled copper foil, and uniformly spread over the entire copper foil using a glass rod. And this was preserve | saved for 10 minutes in the dryer set to 60 degreeC, and the rolled copper foil 6 was obtained.
And the single-sided copper clad laminated body 6 (copper foil layer / (adhesion layer) / polyimide layer) was obtained from the polyimide film 3 and the rolled copper foil 6 by the same method as in Example 3.

(Example 7)
The polyimide film 3 produced in Example 3 was used as the polyimide film.
A rolled copper foil (JB Nikko Co., Ltd., “BHY”, thickness 12 μm) subjected to the roughening treatment was immersed in an acetone solvent, and then dried with a drier set at 80 ° C. 1 mL of a 0.5% aqueous solution of “KBM-903” was dropped on this rolled copper foil, and uniformly spread over the entire copper foil using a glass rod. And this was preserve | saved for 10 minutes in the dryer set to 60 degreeC, and the rolled copper foil 7 was obtained.
And the single-sided copper clad laminated body 7 (copper foil layer / (adhesion layer) / polyimide layer) was obtained from the polyimide film 3 and the rolled copper foil 7 by the same method as in Example 3.

(Example 8)
The polyimide film 3 produced in Example 3 was used as the polyimide film.
From a 0.5% aqueous solution of “KBM-903” to a 2% aqueous solution of 3-aminopropyltriethoxysilane, “KBE-903” (manufactured by Shin-Etsu Chemical Co., Ltd .; a silane coupling agent represented by formula (3)) Except for the changed points, an electrolytic copper foil 8 was obtained in the same manner as in Example 3.
And the single-sided copper clad laminated body 8 (copper foil layer / (adhesion layer) / polyimide layer) was obtained from the polyimide film 3 and the electrolytic copper foil 8 by the same method as in Example 3.

Example 9
The polyimide film 3 produced in Example 3 was used as the polyimide film.
Example 3 except that a 0.5% aqueous solution of “KBM-903” was changed to a 2% aqueous solution of “KBM-603” (manufactured by Shin-Etsu Chemical Co., Ltd .; a silane coupling agent represented by formula (4)). In the same manner as above, an electrolytic copper foil 9 was obtained.
A single-sided copper-clad laminate 9 (copper foil layer / (adhesive layer) / polyimide layer) was obtained from the polyimide film 3 and the electrolytic copper foil 9 by the same method as in Example 3.

(Comparative Example 1)
The polyimide film 3 produced in Example 3 was used as the polyimide film.
In the same manner as in Example 3, except that 1 mL of a 2% aqueous solution of 3-glycidoxypropyltrimethoxysilane, “KBM-403” (manufactured by Shin-Etsu Chemical Co., Ltd.) was hung on the electrolytic copper foil, the electrolytic copper foil a Got.
And by the method similar to Example 3, the single-sided copper clad laminated body a was obtained from the polyimide film 3 and the electrolytic copper foil a.

<Copper foil layer / (adhesive layer) / polyimide layer / (adhesive layer) / preparation of double-sided laminate of copper foil layers (Examples 10 to 12), see FIG. 6>
(Example 10)
A corona-treated polyimide film (non-thermoplastic polyimide, manufactured by Kaneka Corporation, “Apical 50NPI”, thickness 50 μm) was immersed in an acetone solvent, and then dried with a dryer set at 80 ° C. 1 mL of a 0.5% aqueous solution of “KBM-903” was dropped on one side of this polyimide film, and the film was uniformly spread over the entire film using a glass rod. And this was preserve | saved for 10 minutes in the dryer set to 60 degreeC. After taking out from the dryer, 1 mL of a 0.5% aqueous solution of “KBM-903” was dropped on the other surface of the polyimide film, and uniformly spread over the entire film using a glass rod. And this was preserve | saved for 10 minutes in the dryer set to 60 degreeC, and the polyimide film 10 was obtained.
Moreover, the electrolytic copper foil 1 produced in Example 1 was used as the electrolytic copper foil.
And using the press machine, the electrolytic copper foil 1 was each thermocompression-bonded on both surfaces of the polyimide film 10 on the conditions of 180 degreeC * 3MPa * 10min (Hot-Hot) and the vacuum degree 0.1MPa. After thermocompression bonding, it was allowed to cool at room temperature to obtain a double-sided copper-clad laminate 10 (copper foil layer / (adhesive layer) / polyimide layer / (adhesive layer) / copper foil layer).

(Example 11)
A polyimide film 3 was used as the polyimide film.
Two electrolytic copper foils 3 produced in Example 3 were used as the electrolytic copper foil.
And the electrolytic copper foil 11 was each thermocompression-bonded on both surfaces of the polyimide film 3 on the conditions of 180 degreeC * 9MPa * 10min (Hot-Hot) and the vacuum degree 0.1MPa using the press machine. After thermocompression bonding, it was allowed to cool at room temperature to obtain a double-sided copper-clad laminate 11 (copper foil layer / (adhesive layer) / polyimide layer / (adhesive layer) / copper foil layer).

(Example 12)
Double-sided copper clad laminate 12 (copper foil layer) in the same manner as in Example 11, except that 1 mL of 0.5% aqueous solution of “KBM-903” was changed to 1 mL of 0.5% aqueous solution of “KBM-603”. / (Adhesive layer) / polyimide layer / (adhesive layer) / copper foil layer).

<Copper foil polyimide laminate / (adhesive layer) / preparation of double-sided laminate of copper foil polyimide laminate (Examples 13 to 14), see FIG. 7>
(Example 13)
Two pieces of a 10 cm × 12 cm polyimide layer / copper foil layer single-area layered body (manufactured by Arisawa Manufacturing Co., Ltd., “PNS H1035RA”) were prepared, dipped in an acetone solvent, and then dried in a dryer set at 80 ° C. I let you. 1 mL of a 2% aqueous solution of “KBM-903” was hung on one of the single-area layers, and the whole film was uniformly spread using a glass rod. These were stored in a dryer set at 60 ° C. for 10 minutes.
Using a press machine, the polyimide layers of the two single-area layers were bonded and thermocompression bonded under the conditions of 180 ° C. × 9 MPa × 10 minutes (Hot-Hot) and a degree of vacuum of −0.1 MPa. And it stood to cool at room temperature, and obtained the double-sided copper clad laminated body 13 (copper foil polyimide laminated body / (adhesion layer) / copper foil polyimide laminated body).

(Example 14)
Double-sided copper clad laminate 14 (copper foil polyimide laminate / (), except that 2% aqueous solution of “KBM-903” was changed to 0.5% aqueous solution of “KBM-903”. Adhesive layer) / copper foil polyimide laminate) was obtained.

<Copper foil / (adhesive layer) / preparation of double-sided laminate of copper foil polyimide laminate (Example 15), see FIG. 8>
(Example 15)
The electrolytic copper foil 3 produced in Example 3 was used as the electrolytic copper foil.
One piece of a 10 cm × 12 cm polyimide layer / copper foil layer (Arisawa Seisakusho Co., Ltd., “PNS H1035RA”) was prepared, dipped in an acetone solvent, and then dried in a dryer set at 80 ° C. The obtained single area layered body 15 was obtained.
And using a press machine, it bonded so that the electrolytic copper foil 3 and the polyimide layer of the one area layer body 15 may overlap on the conditions of 180 degreeC * 9MPa * 10 minutes (Hot-Hot), and a vacuum degree -0.1MPa. And thermocompression bonded. And it stood to cool at room temperature, and obtained the double-sided copper clad laminated body 15 (copper foil / (adhesion layer) / copper foil polyimide laminated body).

(Evaluation of peel strength)
Evaluation of the peeling strength of the laminated body produced in each Example and each comparative example was performed based on JISC6471. After patterning an etching resist R having a width of 10 mm on the copper foil surface of the produced laminate, a sample obtained by removing the remaining copper foil by etching was used as a sample. FIG. 7 shows a schematic top view of the sample used in the evaluation of the peel strength in the example. This sample was fixed to the reinforcing plate with double-sided tape, the sample was peeled off from the reinforcing plate in the direction of 180 °, and the adhesive strength at that time was measured. And it evaluated based on the following references | standards.
If it is 5N or more: ◎
When less than 5N to 3N or more: ○
If less than 3N: △
When it cannot be measured without bonding: ×

(Surface roughness of laminated body; Rz)
The ten-point average roughness (Rz) of the surface of the laminate was measured in accordance with JIS B0601-1976, and the value was defined as the surface roughness.

  The structures and evaluation results of the examples and comparative examples are shown in Tables 1 to 4 below.

* 1: “◎” 5N or more, “O” less than 5N to 3N or more, “△” less than 3N, “x” not adhered and measurement not possible

* 1: The peel strength indicates the result of (front side) / (back side).
“◎” 5N or more, “O” less than 5N to 3N or more, “△” less than 3N, “x” not adhered and measurement not possible

* 1: “◎” 5N or more, “O” less than 5N to 3N or more, “△” less than 3N, “x” not adhered and measurement not possible

* 1: “◎” 5N or more, “O” less than 5N to 3N or more, “△” less than 3N, “x” not adhered and measurement not possible

  From the above, it was at least confirmed that each of the laminates of each example had sufficient adhesive strength, and the restriction on the selection of materials to be bonded could be relaxed. Furthermore, it was also confirmed that there was no structural limitation when the laminate was formed.

  The laminate according to the present invention can be used in a wide range of fields as a material for various electronic components such as a flexible printed laminate.

1, 2, 2a, 25, 3, 4, 5, 6, 7 ... laminate, 11, 43, 51, 611, 612 ... resin layer, 12, 32, 521, 522, 62 ... adhesive layer, 23, 24 , 31, 531, 532, 631, 632, 73 ... metal foil layer, R ... etching resist

Claims (5)

A first metal foil layer;
A first resin layer formed on the surface of the first metal foil layer;
An adhesive layer formed on the surface of the first resin layer (provided that the adhesive layer does not include a resin);
A second resin layer formed on the surface of the adhesive layer;
A second metal foil layer formed on the surface of the second resin layer in this order,
The adhesive layer is a laminate containing a silane coupling agent represented by the following formula (1),
The ten-point average roughness (Rz) of the first and second metal foil layers is 1.0 μm or less,
2. The peel strength between the first resin layer and the first metal foil layer and the peel strength between the second resin layer and the second metal foil layer are respectively 3. A laminated body of 8 N / cm or more (however, the first and second resin layers are not treated with alkali).

(R ⁴ O) ₃ Si—R ³ —N—R ² R ¹ (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 24 carbon atoms, a phenyl group, or an aminoalkyl group. R ³ represents 1 to 1 carbon atoms. 6 represents a divalent hydrocarbon group of 6. Each R ⁴ independently represents a monovalent hydrocarbon group having 1 to 24 carbon atoms.) The laminate according to claim 1, wherein R ^{3 in the} formula (1) is a linear hydrocarbon group having 1 to 3 carbon atoms. The laminate according to claim 1 or 2 , wherein the formula (1) is any one selected from the group consisting of the following formula (2), formula (3), and formula (4).

(C ₂ H ₆ O) ₃ SiC ₃ H ₆ NH ₂ (2)

(CH ₃ O) ₃ SiC ₃ H ₆ NH ₂ (3)

(CH ₃ O) SiC ₃ H ₆ NHC ₂ H ₄ NH ₂ (4) The laminate according to any one of claims 1 to 3 , wherein the resin layer is a polyimide layer. The laminate according to any one of claims 1 to 4 , wherein the metal foil layer is a copper foil layer.