JP2013116558A - Polyethylene naphthalate film to which softening agent is adhered, polyethylene naphthalate film which is softened, insulator film with metal foil, method of manufacturing insulator film with metal foil, method of manufacturing laminated structure, and laminated structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyethylene naphthalate film which can obtain a laminated structure with the high peeling strength of an insulator film and a metal foil, and the high adhesion of the insulator film and a thermal conductor, to which a softening agent is adhered.SOLUTION: The polyethylene naphthalate film 31 to which the softening agent is adhered includes: a polyethylene naphthalate film 2 being an insulator film; the softening agent 32 which is adhered to the first main surface 2a side of the polyethylene naphthalate film 2, and softens the first main surface 2a of the polyethylene naphthalate film 2 by heating; and an adhesion enhancing agent 33 which is adhered to the second main surface 2b side of the polyethylene naphthalate film 2. The adhesion enhancing agent 32 adhered to the second main surface 2a side of the polyethylene naphthalate film 2 includes an organic aluminate compound, organic titanate compound, organic zirconate compound, or organic silane compound.

Description

  The present invention relates to a polyethylene naphthalate film to which a softening agent used by being laminated on a metal foil and a thermal conductor having a thermal conductivity of 10 W / m · K or more is attached. The present invention also includes a softened polyethylene naphthalate film using a polyethylene naphthalate film to which the softening agent is attached, an insulating film with a metal foil, a method for producing an insulating film with a metal foil, a method for producing a laminated structure, and The present invention relates to a laminated structure.

  Optical semiconductor elements such as light emitting diode (LED) elements are widely used as light sources for display devices. An optical semiconductor device using an optical semiconductor element has low power consumption and long life. Moreover, the optical semiconductor device can be used even in a harsh environment. Accordingly, optical semiconductor devices are used in a wide range of applications such as mobile phone backlights, liquid crystal television backlights, automobile lamps, lighting fixtures, and signboards.

  When trying to emit light with the necessary brightness in LED lighting equipment and LCD TV backlight applications, the LED element generates more heat, shortening the life of the LED element or reducing the brightness. There is a problem of doing. In order to reduce the problem due to the heat generation, an insulating adhesive capable of effectively dissipating heat is used. In a conventional insulating adhesive, for example, an inorganic filler having a high thermal conductivity is dispersed in a resin.

  As an example of the insulating adhesive, Patent Document 1 below discloses an insulating adhesive containing an epoxy resin, aluminum nitride as an inorganic filler, a curing agent, and a phosphate ester as a dispersant. Yes.

Japanese Patent No. 3751271

  In an insulating film obtained by forming an insulating adhesive as described in Patent Document 1 in a film shape, a metal foil is laminated on one surface, and a thermal conductor having a thermal conductivity of 10 W / m · K or more on the other surface May be stacked. In such an application, the peel strength between the insulating film and the metal foil in the laminate of the metal foil and the insulating film or the laminate of the metal foil, the insulating film and the heat conductor may be low. For this reason, peeling between the insulating film and the metal foil may be a problem.

  Furthermore, the laminate may be used after being folded. Furthermore, when the laminate is used, vibration may be applied to the laminate and the laminate may be bent.

  When the laminate is obtained using a conventional insulating adhesive as described in Patent Document 1, if the laminate is bent or vibration is applied to the laminate, the insulating film is chipped. May occur or may crack. That is, there is a problem that the flexibility of the insulating film is low and the bending characteristics are not sufficient.

  Furthermore, when the said laminated body is obtained using the conventional insulating adhesive as described in patent document 1, the adhesiveness of the insulating film with respect to a heat conductor is low, and a heat conductor peels from an insulating film. There is.

  The object of the present invention is to be used by being laminated on a metal foil and a heat conductor having a thermal conductivity of 10 W / m · K or more, having a high peel strength between the insulating film and the metal foil, and having an insulating film and a heat conduction. The present invention relates to a polyethylene naphthalate film to which a softener capable of obtaining a laminated structure having high adhesion to a body is attached. The present invention also includes a softened polyethylene naphthalate film using a polyethylene naphthalate film to which the softening agent is attached, an insulating film with a metal foil, a method for producing an insulating film with a metal foil, a method for producing a laminated structure, and It is to provide a laminated structure.

  The limited object of the present invention is to provide a softening agent capable of obtaining an insulating film with a metal foil which is hardly bent and cracked and has excellent bending characteristics even when it is bent or given vibration. Of polyethylene naphthalate film to which is attached, softened polyethylene naphthalate film using polyethylene naphthalate film to which the softening agent is attached, insulating film with metal foil, method for producing insulating film with metal foil, and laminated structure It is to provide a manufacturing method and a laminated structure.

  Another limited object of the present invention is a polyethylene naphthalate film to which a softening agent with less surface stickiness is attached, a polyethylene naphthalate film subjected to softening treatment using the polyethylene naphthalate film to which the softening agent is attached, a metal It is providing the manufacturing method of an insulating film with foil, an insulating film with metal foil, a manufacturing method of a laminated structure, and a laminated structure.

  According to a wide aspect of the present invention, there is provided a polyethylene naphthalate film to which a softening agent used by being laminated on a metal foil and a thermal conductor having a thermal conductivity of 10 W / m · K or more is attached. A polyethylene naphthalate film, a softening agent attached to the first main surface side of the polyethylene naphthalate film and softening the first main surface of the polyethylene naphthalate film by heating, and the polyethylene naphthalate film An adhesion improver that adheres to the second principal surface side opposite to the first principal surface side of the phthalate film and improves the adhesion of the polyethylene naphthalate film to the thermal conductor. The adhesion improver attached to the second main surface side of the polyethylene naphthalate film is an organic aluminate compound. , Organic titanate compounds, organic zirconate compound, or an organic silane compound, a polyethylene naphthalate film having a softening agent has adhered is provided.

  In the polyethylene naphthalate film to which the softener according to the present invention is attached, the polyethylene naphthalate film is attached to the second main surface side of the polyethylene naphthalate film, and the second main surface of the polyethylene naphthalate film is softened by heating. It is preferable that a softening agent is further provided. The softener adhering to the second main surface side of the polyethylene naphthalate film preferably contains a thermosetting composition or a compound that dissolves the polyethylene naphthalate film by heating. The softening agent attached to the first main surface side of the polyethylene naphthalate film preferably contains a thermosetting composition or a compound that dissolves the polyethylene naphthalate film by heating. An adhesion improver that is attached to the first main surface side of the polyethylene naphthalate film and that improves the adhesion of the polyethylene naphthalate film to the metal foil is further provided. The adhesion improver adhering to the first main surface side preferably contains an organic aluminate compound, an organic titanate compound, an organic zirconate compound, or an organic silane compound.

  The softened polyethylene naphthalate film according to the present invention is obtained by heating the polyethylene naphthalate film to which the above-mentioned softening agent is attached, and the above-mentioned polyethylene naphthalate film is heated by the softening agent. The main surface of 1 is softened.

  The insulating film with metal foil according to the present invention is an insulating film with metal foil that is used by being laminated on a heat conductor having a thermal conductivity of 10 W / m · K or more, and is a polyethylene film to which the above-mentioned softener is attached. A metal foil is obtained by softening the first main surface of the polyethylene naphthalate film with the softening agent by heating on the first main surface of the phthalate film to which the softening agent of the polyethylene naphthalate film is attached. The polyethylene naphthalate film which is obtained by laminating and is an insulating film, and a metal foil laminated on the first main surface of the polyethylene naphthalate film.

  Further, according to a wide aspect of the present invention, there is provided a method for producing an insulating film with a metal foil used by being laminated on a heat conductor having a thermal conductivity of 10 W / m · K or more, wherein the above-mentioned softener is attached. Using the polyethylene naphthalate film, the first main surface of the polyethylene naphthalate film is heated by the softening agent to the first main surface of the polyethylene naphthalate film to which the softening agent is attached. There is provided a method for producing an insulating film with a metal foil, comprising a step of softening and laminating a metal foil.

  In a specific aspect of the method for producing an insulating film with a metal foil according to the present invention, the polyethylene naphthalate film to which the softening agent is attached is used to increase the peel strength between the polyethylene naphthalate film and the metal foil. It is obtained through a step of attaching a softening agent that softens the first main surface of the polyethylene naphthalate film to the first main surface of the polyethylene naphthalate film before the metal foil is laminated.

  In another specific aspect of the method for producing an insulating film with metal foil according to the present invention, the polyethylene naphthalate film to which the softening agent is attached is the above-mentioned polyethylene naphthalate film before the thermal conductor is laminated. 2 is obtained through a step of attaching an adhesion improver that improves the adhesion of the polyethylene naphthalate film to the thermal conductor.

  In the method for producing a laminated structure according to the present invention, a metal foil is laminated on the first main surface of the polyethylene naphthalate film using the polyethylene naphthalate film to which the softening agent is attached, and the polyethylene A method for manufacturing a laminated structure in which a laminated structure in which the heat conductor is laminated on a second main surface of a naphthalate film is obtained, and a metal foil is provided on the first main surface side of the polyethylene naphthalate film. A heat conductor having a thermal conductivity of 10 W / m · K or more is disposed on the second main surface side of the polyethylene naphthalate film, and the metal foil, the polyethylene naphthalate film, and the heat The conductor is integrated, or a metal foil is disposed on the first main surface side of the polyethylene naphthalate film, and the metal foil and the polyester are disposed. After integrating the lennaphthalate film, a heat conductor having a thermal conductivity of 10 W / m · K or more is disposed on the second main surface side of the polyethylene naphthalate film, and the metal foil and the above Either a polyethylene naphthalate film and the heat conductor are integrated, or a heat conductor having a thermal conductivity of 10 W / m · K or more is disposed on the second main surface side of the polyethylene naphthalate film. Then, after integrating the polyethylene naphthalate film and the heat conductor, a metal foil is disposed on the first main surface side of the polyethylene naphthalate film, and the metal foil and the polyethylene naphthalate film are arranged. And the heat conductor are integrated.

  The laminated structure according to the present invention is laminated on an insulating film with metal foil and a second main surface opposite to the first main surface on which the metal foil in the insulating film with metal foil is laminated. And a thermal conductor having a thermal conductivity of 10 W / m · K or more. In the laminated structure according to the present invention, the insulating film with metal foil is the insulating film with metal foil according to the present invention, or with the metal foil obtained by the method for producing an insulating film with metal foil according to the present invention. It is an insulating film.

  The polyethylene naphthalate film to which the softener according to the present invention is attached is a polyethylene naphthalate film which is an insulating film, and is attached to the first main surface side of the polyethylene naphthalate film, and the polyethylene naphthalate film is heated by heating. A softening agent for softening the first main surface of the polyethylene naphthalate film, and a second main surface opposite to the first main surface side of the polyethylene naphthalate film, and the heat conductor An adhesion improver that improves the adhesion of the polyethylene naphthalate film, and the adhesion improver further includes an organic aluminate compound, an organic titanate compound, an organic zirconate compound, or an organic silane compound, so that polyethylene The peel strength between the naphthalate film and the metal foil can be increased. Furthermore, the adhesion between the polyethylene naphthalate film and the heat conductor can be increased, and the peeling of the heat conductor from the polyethylene naphthalate film can be suppressed.

  In the insulating film with metal foil according to the present invention, the first surface of the polyethylene naphthalate film in the polyethylene naphthalate film to which the above-mentioned softener is attached is heated on the first main surface of the polyethylene naphthalate film by the softener. Since it is obtained by softening the first main surface and laminating the metal foil, the peel strength between the polyethylene naphthalate film and the metal foil can be increased. Moreover, since the said adhesiveness imparting agent is arrange | positioned at the 2nd main surface side of the said polyethylene naphthalate film, the adhesiveness of the said polyethylene naphthalate film with respect to the said heat conductor can be improved.

  In the method for producing an insulating film with metal foil according to the present invention, the polyethylene naphthalate is heated by the softening agent on the first main surface of the polyethylene naphthalate film in the polyethylene naphthalate film to which the softening agent is attached. Since the metal foil is laminated by softening the first main surface of the film, the peel strength between the polyethylene naphthalate film and the metal foil can be increased. Moreover, since the said adhesiveness imparting agent is arrange | positioned at the 2nd main surface side of the said polyethylene naphthalate film, the adhesiveness of the said polyethylene naphthalate film with respect to the said heat conductor can be improved.

FIG. 1 is a partially cutaway front sectional view schematically showing a polyethylene naphthalate film to which a softener according to an embodiment of the present invention is attached. FIG. 2 is a partially cutaway front sectional view schematically showing an insulating film with a metal foil according to an embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing a laminated structure using the insulating film with metal foil shown in FIG. FIG. 4 is a partially cutaway cross-sectional view schematically showing another example of a laminated structure using the insulating film with metal foil shown in FIG. FIG. 5 is a partially cutaway front sectional view schematically showing an insulating film with metal foil according to another embodiment of the present invention.

  Hereinafter, the present invention will be clarified by describing specific embodiments and examples of the present invention with reference to the drawings.

(Polyethylene naphthalate film with softener attached and polyethylene naphthalate film with softened surface)
In FIG. 1, the polyethylene naphthalate film to which the softening agent which concerns on one Embodiment of this invention adheres is typically shown with a partially notched cross-sectional view.

  The polyethylene naphthalate film 31 to which the softening agent shown in FIG. 1 is attached is used by being laminated on a metal foil and a thermal conductor having a thermal conductivity of 10 W / m · K or more. The polyethylene naphthalate film 31 to which the softener is attached includes the polyethylene naphthalate film 2, the first material 32 containing the softener, and the second material 33 containing the adhesion improver. The polyethylene naphthalate film 2 has an insulating property and is an insulating film. A first material 32 containing a softener is attached to the first main surface 2 a side of the polyethylene naphthalate film 2. As a result, the softening agent is adhered to the first main surface 2a side of the polyethylene naphthalate film 2. The first material 32 containing the softening agent is disposed on the first main surface 2 a side of the polyethylene naphthalate film 2. The first main surface 2a of the polyethylene naphthalate film 2 is preferably a surface on which a metal foil is laminated. On the second main surface 2b side opposite to the first main surface 2a side of the polyethylene naphthalate film 2, a second material 33 containing an adhesion improver is attached. As a result, the adhesion improver is attached to the second main surface 2 b side of the polyethylene naphthalate film 2. The first material 32 may contain only a softening agent. The second material 33 may contain only an adhesion improver. The adhesion improver attached to the second main surface 2b side of the polyethylene naphthalate film 2 includes an organic aluminate compound, an organic titanate compound, an organic zirconate compound, or an organic silane compound. The first material 32 containing the softening agent may contain an adhesion improving agent, and the second material 33 containing the adhesion improving agent may contain a softening agent. The first material 32 may be a softening agent, or may be a softening agent and an adhesion-imparting agent. The second material 33 may be an adhesion improver, or may be a softener and an adhesion imparting agent. The composition of the first material 32 containing the softener and the composition of the second material 33 containing the adhesion improver may be the same or different. When the composition of the first material 32 containing the softening agent and the composition of the second material 33 containing the adhesion improver are the same, the production efficiency in obtaining the polyethylene naphthalate film 31 with the softening agent attached is high. Become.

  The second main surface 2b opposite to the first main surface 2a of the polyethylene naphthalate film 2 is preferably a surface on which a heat conductor having a thermal conductivity of 10 W / m · K or more is laminated.

  Since the polyethylene naphthalate film 31 to which the softener according to this embodiment is attached has the above-described configuration, the first material 32 containing the softener is particularly attached to the first main surface 2a side. By peeling the polyethylene naphthalate film 2 from the metal foil by softening the first main surface 2a of the polyethylene naphthalate film 2 by heating and laminating the softened first main surface 2a. Strength can be increased. By attaching the first material 32 containing such a softening agent, the first main surface 2a of the polyethylene naphthalate film 2 can be softened by heating at the time of laminating the metal foil. As a result, polyethylene naphthalate The peel strength between the film 2 and the metal foil can be further increased. That is, the softening agent plays a role of increasing the peel strength between the polyethylene naphthalate film 2 and the metal foil.

  In addition, the 1st material 32 containing the softening agent adhering to the 1st main surface 2a may contain the adhesive improvement agent. The polyethylene naphthalate film 31 to which the softening agent is attached is attached to the first main surface 2a side of the polyethylene naphthalate film 2, and an adhesion improver that improves the adhesion of the polyethylene naphthalate film 2 to the metal foil. May be further provided. The adhesion improver adhering to the first main surface 2a side of the polyethylene naphthalate film 2 preferably contains an organic aluminate compound, an organic titanate compound, an organic zirconate compound, or an organic silane compound. In this case, the peel strength between the polyethylene naphthalate film and the metal foil is further increased.

  Furthermore, in the polyethylene naphthalate film 31 to which the softener according to this embodiment is attached, since the second material 33 containing the adhesion improver is attached to the second main surface 2b side, the polyethylene naphthalate is further added. Since the adhesion improver adhering to the second main surface 2b side of the film 2 contains an organic aluminate compound, an organic titanate compound, an organic zirconate compound, or an organic silane compound, heat is applied to the second main surface 2b. When a conductor is laminated | stacked, the adhesiveness of the polyethylene naphthalate film 2 and a heat conductor can be improved, and peeling from the polyethylene naphthalate film 2 of a heat conductor can be suppressed.

  In addition, the 2nd material 32 containing the adhesive improvement agent adhering to the 2nd main surface 2b side on the opposite side to the 1st main surface 2a of the polyethylene naphthalate film 2 is a polyethylene naphthalate film by heating. The softening agent which softens the 2nd 2nd main surface 2b may be included. That is, the polyethylene naphthalate film 31 to which the softening agent is attached contains a softening agent that softens the second main surface 2b of the polyethylene naphthalate film 2 by heating on the second main surface 2b side of the polyethylene naphthalate film 2. You may go out. In this case, the adhesion between the polyethylene naphthalate film and the heat conductor is further enhanced.

  Furthermore, in the polyethylene naphthalate film 31 to which the softening agent according to the present embodiment is attached, since the insulating film is the polyethylene naphthalate film 2, even if it is bent or given vibration, Cracks can be made difficult to occur.

  Moreover, the softening process by which the 1st main surface 2a of the polyethylene naphthalate film 2 is softened by the softening agent by heating the polyethylene naphthalate film 31 to which the first material 32 containing the softening agent is attached. A polyethylene naphthalate film is obtained. In the polyethylene naphthalate film subjected to the softening treatment, it is preferable that a component derived from the softening agent after heating is contained in the polyethylene naphthalate film 2 on the first main surface 2a side. That is, the component derived from the softening agent after heating is preferably included in the surface of the polyethylene naphthalate film 2 on the first main surface 2a side. The softened polyethylene naphthalate film may be cured to some extent after the first main surface 2a is once softened.

  In the polyethylene naphthalate film subjected to the softening treatment, it is preferable that the component derived from the adhesion improver after heating is contained in the polyethylene naphthalate film 2 on the second main surface 2b side. That is, it is preferable that a component derived from the adhesion improver after heating is contained in the surface of the polyethylene naphthalate film 2 on the second main surface 2b side. The softened polyethylene naphthalate film may be cured to some extent after the second main surface 2b is once softened.

  From the viewpoint of further increasing the peel strength between the polyethylene naphthalate film and the metal foil, the softener used for the first material and the softener used for the second material are each a thermosetting composition. Or a compound that dissolves the polyethylene naphthalate film by heating. From the viewpoint of further improving the adhesion between the polyethylene naphthalate film and the thermal conductor, the second material includes a thermosetting composition or a compound that dissolves the polyethylene naphthalate film by heating. It is preferable to contain. Each of the first and second materials preferably includes a thermosetting composition. Each of the first and second materials preferably contains both a thermosetting composition and a compound that dissolves the polyethylene naphthalate film by heating.

  From the viewpoint of further increasing the peel strength between the polyethylene naphthalate film and the metal foil, the thermosetting composition preferably contains a thermosetting compound and a curing agent. From the viewpoint of further improving the adhesion between the polyethylene naphthalate film and the thermal conductor, the thermosetting composition preferably includes a thermosetting compound and a curing agent.

  Examples of the thermosetting compound include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenol compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, polyimide compounds, bismaleimide compounds, benzoxazine compounds. And triisocyanurate compounds. The thermosetting compound is preferably an epoxy compound. As for the said thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  The thermosetting compound may be liquid at 23 ° C. or solid at 23 ° C. The thermosetting compound preferably includes a thermosetting compound that is solid at 23 ° C. By using a thermosetting compound that is solid at 23 ° C., stickiness of the surface of the first and second materials (first and second material layers) can be suppressed. As a result, the handleability of the polyethylene naphthalate film to which the softening agent is attached is improved. Further, by suppressing the stickiness of the surfaces of the first and second materials, it is easy to attach a release film to the surfaces of the first and second materials in the polyethylene naphthalate film to which the softening agent is attached. . Furthermore, the polyethylene naphthalate film to which the softening agent is adhered can be peeled well from the release film during use.

  Specific examples of the epoxy compound include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, glycidyl ester type epoxy compound, glycidyl ether type epoxy compound, bixylenol type epoxy compound, biphenol type epoxy compound, Tetraglycidylxylenoylethane compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, chelate type epoxy compound, glyoxal type epoxy compound, amino group-containing epoxy compound, rubber modified epoxy compound, dicyclopentadiene type epoxy compound, silicone modified Epoxy compound, ε-caprolactone modified epoxy compound, triazine type epoxy compound and naphthalene skeleton-containing epoxy compound Etc. The.

  The thermosetting compound preferably contains a bisphenol A type epoxy compound. By using the bisphenol A type epoxy compound, the peel strength between the polyethylene naphthalate film and the metal foil is considerably increased.

  The peel strength between the polyethylene naphthalate film and the metal foil is further increased, the adhesion between the polyethylene naphthalate film and the heat conductor is further increased, and the surfaces of the first and second materials From the viewpoint of effectively suppressing stickiness, the thermosetting compound is preferably an epoxy compound that is solid at 23 ° C.

  From the viewpoint of further increasing the peel strength between the polyethylene naphthalate film and the metal foil, and further enhancing the adhesion between the polyethylene naphthalate film and the thermal conductor, the thermosetting compound is bisphenol A. It is preferable that it is a type epoxy compound or a dicyclopentadiene type epoxy compound.

  Examples of the curing agent include a cyanate ester compound (cyanate ester curing agent), a phenol compound (phenol curing agent), an amine compound (amine curing agent), a thiol compound (thiol curing agent), an imidazole compound, a phosphine compound, and an acid anhydride ( Acid anhydride curing agent), active ester compounds and dicyandiamide. As for the said hardening | curing agent, only 1 type may be used and 2 or more types may be used together.

  The curing agent may be liquid at 23 ° C. or solid at 23 ° C. It is preferable that the said hardening | curing agent contains the hardening | curing agent which is solid at 23 degreeC. By using a curing agent that is solid at 23 ° C., stickiness of the surfaces of the first and second materials can be suppressed. As a result, the handleability of the polyethylene naphthalate film to which the softening agent is attached is improved. Further, by suppressing the stickiness of the surfaces of the first and second materials, it is easy to attach a release film to the surfaces of the first and second materials in the polyethylene naphthalate film to which the softening agent is attached. . Furthermore, the polyethylene naphthalate film to which the softening agent is adhered can be peeled well from the release film during use.

  The curing agent preferably contains an acid anhydride curing agent or a phenol curing agent. By using an acid anhydride curing agent or a phenol curing agent, the peel strength between the polyethylene naphthalate film and the metal foil is considerably increased, and the adhesion between the polyethylene naphthalate film and the thermal conductor is even higher. Become. From the viewpoint of further enhancing the peel strength between the polyethylene naphthalate film and the metal foil, and further enhancing the adhesion between the polyethylene naphthalate film and the thermal conductor, the curing agent is a phenol curing agent. More preferably.

  Heating effectively softens the polyethylene naphthalate film, further increases the peel strength between the polyethylene naphthalate film and the metal foil, and further improves the adhesion between the polyethylene naphthalate film and the heat conductor. From the viewpoint of enhancing, the curing agent is preferably an acid anhydride curing agent, and more preferably an acid anhydride curing agent having an alicyclic skeleton. If the softening effect is high, the pressure required at the time of application to obtain the same peel strength is reduced, and the product area obtained when the same apparatus is used is increased.

  Commercially available acid anhydride curing agents having an alicyclic skeleton include Ricacid HNA and Ricacid HNA-100 (all of which are manufactured by Shin Nippon Chemical Co., Ltd.), YH306, YH307, YH308 and YH309 (and all of which are Mitsubishi). Chemical Co., Ltd.).

  Heating effectively softens the polyethylene naphthalate film, further increases the peel strength between the polyethylene naphthalate film and the metal foil, and further improves the adhesion between the polyethylene naphthalate film and the heat conductor. From the viewpoint of enhancing, the curing agent having an alicyclic skeleton is preferably an acid anhydride curing agent represented by any one of the following formulas (1) to (4), and the following formula (1) Or it is more preferable that it is an acid anhydride hardening | curing agent represented by (4).

  In said formula (4), R1 and R2 show a hydrogen atom, a C1-C5 alkyl group, or a hydroxyl group, respectively.

  When the curing agent is a phenol curing agent, the phenol curing agent is preferably o, o'-diallylbisphenol A. By using o, o′-diallylbisphenol A, the peel strength between the polyethylene naphthalate film and the metal foil is further increased, and the adhesion between the polyethylene naphthalate film and the heat conductor is further enhanced. Become.

  Examples of commercially available o, o'-diallylbisphenol A include "5292B" manufactured by Huntsman.

  When the thermosetting compound and the curing agent are used in combination, the content of the curing agent is preferably 0.01 parts by weight or more, more preferably 0 with respect to 100 parts by weight of the thermosetting compound. .1 part by weight or more, more preferably 1 part by weight or more, preferably 200 parts by weight or less, more preferably 150 parts by weight or less, still more preferably 100 parts by weight or less. When the content of the curing agent is not less than the above lower limit and not more than the above upper limit, the peel strength between the polyethylene naphthalate film and the metal foil is further increased, and the adhesion between the polyethylene naphthalate film and the heat conductor is increased. The nature becomes even higher.

  Examples of the compound that dissolves the polyethylene naphthalate film by heating include polyfunctional phenol novolac, allylphenol novolac, and allylphenol. By using such a compound, the first main surface of the polyethylene naphthalate film can be dissolved and softened by heating during lamination of the metal foil. Preferably, the compound that dissolves the polyethylene naphthalate film softens the first main surface by dissolving the polyethylene naphthalate film by heating during lamination of the metal foil. When the second material contains a softening agent, the second main surface of the polyethylene naphthalate film can be dissolved and softened by heating at the time of laminating the metal foil. The compound that dissolves the polyethylene naphthalate film preferably softens the second main surface by dissolving the polyethylene naphthalate film by heating at the time of laminating the metal foil. Only 1 type may be used for the compound which dissolves the said polyethylene naphthalate film by heating, and 2 or more types may be used together.

  The adhesion imparting agent contains the organometallic compound described above. The organometallic compound is an organoaluminate compound, an organotitanate compound, an organozirconate compound, or an organosilane compound. By using these specific organometallic compounds, the adhesion of the polyethylene naphthalate film to the heat conductor is considerably increased. As for the said organometallic compound, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of further improving the adhesion of the polyethylene naphthalate film to the heat conductor, the organometallic compound preferably has an alkoxy group or a chelate structure, and an organic titanate compound having an alkoxy group or a chelate structure, an alkoxy An organic zirconate compound having a group or chelate structure, an organic aluminate compound having an alkoxy group or chelate structure, or an organosilane compound having an alkoxy group or chelate structure is preferred. In addition, from the viewpoint of further improving the adhesion of the polyethylene naphthalate film to the heat conductor, the organometallic compound is preferably an organic aluminate compound, an organic titanate compound, or an organic zirconate compound, An organic zirconate compound is more preferable, and an organic aluminate compound is particularly preferable.

  Preferred organic aluminate compounds include trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum and acetoalkoxyaluminum diisopropylate, and polymers thereof. . Organic aluminate compounds other than these may be used.

  Preferred organic titanate compounds include tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetraisopropoxy titanium, tetra n-butoxy titanium, tetrakis (2-ethylhexyloxy) titanium and titanium-isopropoxy octylene glycolate. And polymers thereof. Organic titanate compounds other than these may be used.

  Preferred examples of the organic zirconate compound include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium tetra n-butoxide, and polymers thereof. Organic zirconate compounds other than these may be used.

  Preferred organic silane compounds include vinyl silane compounds, hexyl silane compounds, and amino silane compounds. Organic silane compounds other than these may be used.

  When the thermosetting compound and the organometallic compound are used in combination, the content of the organometallic compound is preferably 0.001 part by weight or more, more preferably 100 parts by weight of the thermosetting compound. Is 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less. The adhesiveness of the polyethylene naphthalate film with respect to a heat conductor becomes still higher that content of the said organometallic compound is more than the said minimum and below the said upper limit.

(Insulating film with metal foil and manufacturing method of insulating film with metal foil)
In FIG. 2, the insulating film with metal foil which concerns on one Embodiment of this invention is typically shown with a partially notched cross-sectional view.

  The insulating film 1 with metal foil shown in FIG. 2 is used by being laminated on a heat conductor having a thermal conductivity of 10 W / m · K or more. Insulating film 1 with metal foil is a polyethylene naphthalate film 31 to which a softening agent comprising a polyethylene naphthalate film 2, a first material 32 containing a softening agent, and a second material 33 containing an adhesion improver is attached. It is obtained by laminating the metal foil 3. Specifically, using the polyethylene naphthalate film 31 to which the softener is attached, the first main surface 2a to which the first material 32 containing the softener of the polyethylene naphthalate film 2 is attached is softened by heating. It can be obtained by laminating the metal foil 3 by softening the first main surface 2a of the polyethylene naphthalate film 2 with an agent.

  The insulating film 1 with a metal foil includes a polyethylene naphthalate film 2 and a metal foil 3. The polyethylene naphthalate film 2 has an insulating property and is an insulating film. A metal foil 3 is laminated on the first main surface 2 a of the polyethylene naphthalate film 2. The second main surface 2b opposite to the first main surface 2a of the polyethylene naphthalate film 2 is preferably a surface on which a heat conductor having a thermal conductivity of 10 W / m · K or more is laminated. In addition, the metal foil 3 may be laminated | stacked on the whole area | region of the 1st main surface 2a of the polyethylene naphthalate film 2, and may be laminated | stacked on the one part area | region. Moreover, it is preferable that the said metal foil is directly laminated | stacked on the 1st main surface of the said polyethylene naphthalate film.

  The insulating film 1 with a metal foil according to the present embodiment is obtained by laminating the metal foil 3 on the first main surface 2a of the polyethylene naphthalate film 2 in the polyethylene naphthalate film 31 to which the above-described softening agent is attached. Therefore, the peel strength between the polyethylene naphthalate film 2 and the metal foil 3 can be increased.

  Conventionally, in the state of the insulating film with metal foil in which the metal foil is laminated on the first main surface of the polyethylene naphthalate film, the insulating film with metal foil has a thermal conductivity of 10 W / m · K or more. It was not used by being laminated on a certain heat conductor. Conventionally, an insulating film with a metal foil using an insulating film other than a polyethylene naphthalate film is folded in use in the state of a laminate laminated on a heat conductor having a thermal conductivity of 10 W / m · K or more. Have been used. In addition, vibrations may be imparted to the laminate during use, and the laminate may bend.

  Since the insulating film 1 with a metal foil according to the present embodiment has the above-described configuration, since the insulating film is a polyethylene naphthalate film 2 in particular, the insulating film can be bent or vibrated. Chipping and cracking can be made difficult to occur. The insulating film 1 with a metal foil according to the present embodiment has high flexibility and excellent bending characteristics. Therefore, when the insulating film 1 with metal foil is used by being laminated on a heat conductor having a thermal conductivity of 10 W / m · K or more, the insulating film is less likely to be chipped and cracked. It is possible to suppress the appearance failure, peeling, insulation failure, and the like from occurring in the laminated structure using the material.

  In FIG. 2, the first material 32 containing the softening agent is not shown because it penetrates into the polyethylene naphthalate film 2. In addition, you may laminate | stack the metal foil 3 on the 1st main surface 2a of the polyethylene naphthalate film 2 through the 1st material 32 containing a softening agent. Moreover, in FIG. 2, since the 2nd material 33 containing an adhesive improvement agent has osmose | permeated the polyethylene naphthalate film 2, it is not illustrated. The second main surface 2b portion of the polyethylene naphthalate film 2 contains a second material 33 containing an adhesion improver. Specifically, the second main surface 2b portion of the polyethylene naphthalate film 2 contains an organic aluminate compound, an organic titanate compound, an organic zirconate compound, or an organic silane compound. In addition, the adhesiveness improving agent may adhere to the 1st main surface 2a of the polyethylene naphthalate film 2, and the adhesiveness improving agent may be laminated | stacked. The first main surface 2a portion of the polyethylene naphthalate film 2 may contain an adhesion improver.

  In the insulating film with metal foil, it is preferable that the component contained in the first material containing the softening agent penetrates and remains in the polyethylene naphthalate film. In particular, it is preferable that the component contained in the softening agent in the first material penetrates and remains in the polyethylene naphthalate film. In this case, as a result of sufficiently softening the vicinity of the surface of the first main surface of the polyethylene naphthalate film, the peel strength between the polyethylene naphthalate film and the metal foil is further increased. In the insulating film with metal foil, it is preferable that the component contained in the second material containing the adhesion improver penetrates into the polyethylene naphthalate film and remains. In particular, it is preferable that the component contained in the softening agent in the second material permeates and remains in the polyethylene naphthalate film.

  Whether or not the components contained in the first and second materials permeate and remain in the polyethylene naphthalate film is determined by analysis using time-of-flight secondary ion mass spectrometry TOF-SIMS. It is possible to confirm. As a commercial item of the said time-of-flight type secondary ion mass spectrometry TOF-SIMS, "TOF-SIMS type 5" by ION-TOF, etc. are mentioned. In the insulating film with metal foil, the softening agent may be lost by heating or the like. In the insulating film with metal foil, the organic aluminate compound, organic titanate compound, organic zirconate compound, or organic silane compound contained in the adhesion improver is not lost.

  Examples of the polyethylene phthalate film include unstretched polyethylene naphthalate film, uniaxially stretched polyethylene naphthalate film, and biaxially stretched polyethylene naphthalate film. Especially, since the intensity | strength of the said polyethylene naphthalate film becomes still higher, the stretched polyethylene naphthalate film is preferable. Moreover, there exists a tendency which can laminate | stack the said metal foil on the 1st main surface of the said polyethylene naphthalate film at a comparatively low temperature, and can affix by use of the stretched polyethylene naphthalate film. For example, it becomes easy to bond the polyethylene naphthalate film and the metal foil at a temperature lower than the melting point of the polyethylene naphthalate film, and the polyethylene naphthalate film and the metal foil are bonded even at a temperature of 260 ° C. or lower. It becomes easy to match.

  The polyethylene naphthalate film is obtained by reacting 2,6-naphthalenedicarboxylic acid and ethylene glycol using 2,6-naphthalenedicarboxylic acid and ethylene glycol as main components. The ratio of the skeleton derived from 2,6-naphthalenedicarboxylic acid and ethylene glycol is preferably 50% by weight or more, more preferably 80% by weight or more, and still more preferably 90% in 100% by weight of the total skeleton of the polyethylene naphthalate film. % By weight or more.

  In obtaining the polyethylene naphthalate film, other copolymerizable components different from 2,6-naphthalenedicarboxylic acid and ethylene glycol may be used. Examples of other copolymerizable components include terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, biphenyldicarboxylic acid, tetralindicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelain. Acid, sebacic acid, dodecane dicarboxylic acid, cyclohexane dicarboxylic acid, decalin dicarboxylic acid, norbornane dicarboxylic acid, tricyclodecane dicarboxylic acid, pentacyclododecane dicarboxylic acid, isophorone dicarboxylic acid, 3,9-bis (2-carboxyethyl) 2, 4,8,10-tetraoxaspiro [5.5] undecane, trimellitic acid, trimesic acid, pyromellitic acid, tricarballylic acid and esterified products thereof, and diethylene glycol, trimethylene glycol and tetramethylene glycol Lumpur, and the like. Other copolymerizable components other than these may be used. As the other copolymerizable component, only one type may be used, or two or more types may be used in combination.

  The thickness of the polyethylene naphthalate film is preferably 1 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more, preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 120 μm or less. The insulation property of the said polyethylene naphthalate film becomes it high that thickness is more than the said minimum. When the thickness is not more than the above upper limit, when the insulating film with metal foil is attached to the heat conductor, the heat dissipation becomes even better.

  The polyethylene naphthalate film preferably contains no filler, or the filler content in 100% by volume of the polyethylene naphthalate film is preferably 20% by volume or less. The content of the filler in 100% by volume of the polyethylene naphthalate film is more preferably 10% by volume or less, further preferably 5% by volume or less, and particularly preferably 1% by volume or less. Most preferably, the polyethylene naphthalate film contains no filler.

  The first main surface 2a of the polyethylene naphthalate film 2 before the metal foil 3 is laminated is smooth. In FIG. 5, the insulating film with metal foil which concerns on other embodiment of this invention is shown. The insulating film 21 with metal foil shown in FIG. 5 is used by being laminated on a heat conductor having a thermal conductivity of 10 W / m · K or more. The insulating film with metal foil 21 includes a polyethylene naphthalate film 22 and a metal foil 23. A metal foil 23 is laminated on the first main surface 22 a of the polyethylene naphthalate film 22. The second main surface 22b of the polyethylene naphthalate film 22 is preferably a surface on which a thermal conductor having a thermal conductivity of 10 W / m · K or more is laminated. The first main surface 22a of the polyethylene naphthalate film 22 before the metal foil 23 is laminated is roughened. For this reason, the 1st main surface 22a of the polyethylene naphthalate film 22 is a rough surface which has a convex part. In addition, the surface on which the polyethylene naphthalate film 22 of the metal foil 23 before being laminated on the polyethylene naphthalate film 22 is laminated is smooth.

  Thus, the said 1st main surface of the said polyethylene naphthalate film before the said metal foil is laminated | stacked may be roughened, and the rough surface which has a convex part may be sufficient as it. In this case, since the convex part of the polyethylene naphthalate film can be embedded in the metal foil, and the metal foil can be embedded in the concave part between the convex parts of the polyethylene naphthalate film, the anchor effect As a result, the peel strength between the polyethylene naphthalate film and the metal foil becomes higher. As the roughening treatment method, a conventionally known method can be used. Examples of the roughening treatment method include a sandblast treatment method and a treatment method using a roughening agent.

  The arithmetic mean roughness Ra of the first main surface of the polyethylene naphthalate film before the metal foil is laminated is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.5 μm or more, Preferably it is 20 micrometers or less, More preferably, it is 15 micrometers or less, More preferably, it is 10 micrometers or less. When the arithmetic average roughness Ra is not less than the above lower limit and not more than the above upper limit, the peel strength between the polyethylene naphthalate film and the metal foil becomes higher. The arithmetic average roughness Ra is measured in accordance with JIS B0601-1994.

  Examples of commercially available polyethylene naphthalate films include Teonex series manufactured by Teijin DuPont Films.

  Examples of the material of the metal foil include aluminum, copper, gold, and a graphite sheet. From the viewpoint of further improving the thermal conductivity, the metal foil is preferably a gold foil, a copper foil, or an aluminum foil, and more preferably a copper foil or an aluminum foil. From the viewpoint of further improving the thermal conductivity and facilitating the etching process, the metal foil is more preferably a copper foil.

  Although the thickness of the said metal foil is not specifically limited, Preferably it is 1 micrometer or more, More preferably, it is 5 micrometers or more, More preferably, it is 10 micrometers or more, Preferably it is 500 micrometers or less, More preferably, it is 300 micrometers or less. It becomes easy to handle that the thickness of the metal foil is not less than the above lower limit. When the thickness of the metal foil is not more than the above upper limit, it is possible to further reduce the thickness of the laminated structure using the insulating film with metal foil.

  As shown in FIG. 2, the surface of the metal foil 3 on which the polyethylene naphthalate film 2 is laminated before being laminated on the polyethylene naphthalate film 2 is roughened. For this reason, the surface on which the polyethylene naphthalate film 2 of the metal foil 3 is laminated is a rough surface having convex portions. In addition, the 1st main surface 2a of the polyethylene naphthalate film 2 before the metal foil 3 is laminated | stacked is smooth.

  Thus, it is preferable that the surface on which the polyethylene naphthalate film of the metal foil before being laminated on the polyethylene naphthalate film is laminated is roughened, and it is a rough surface having convex portions. preferable. In this case, since the convex portion of the metal foil can be embedded in the first main surface of the polyethylene naphthalate film, the anchor effect increases the peel strength between the polyethylene naphthalate film and the metal foil. Get higher. As the roughening treatment method, a conventionally known method can be used.

  The ten-point average roughness Rz of the surface of the metal foil before being laminated to the polyethylene naphthalate film is preferably 0.5 μm or more, more preferably 1 μm or more, and still more preferably. It is 5 μm or more, preferably 12 μm or less, more preferably 10 μm or less, and further preferably 10 μm or less. When the ten-point average roughness Rz is not less than the above lower limit and not more than the above upper limit, the peel strength between the polyethylene naphthalate film and the metal foil becomes higher. The ten-point average roughness Rz is measured according to JIS B0601-1994.

  The 90 ° peel strength between the polyethylene naphthalate film and the metal foil is preferably 3 N / cm or more, more preferably 5 N / cm or more, still more preferably 8 N / cm or more, and particularly preferably 10 N / cm or more. The higher the peel strength, the better. When the peel strength is equal to or higher than the lower limit, peeling between the polyethylene naphthalate film and the metal foil is difficult to occur. Moreover, it can suppress effectively that the said polyethylene naphthalate film and the said metal foil peel, when it is bent or a vibration is provided.

  A softening agent that softens the first main surface of the polyethylene naphthalate film is attached to the first main surface of the polyethylene naphthalate film before laminating the metal foil, and then the metal is heated while being heated. By laminating the foil, the peel strength between the polyethylene naphthalate film and the metal foil can be set to the above lower limit or more. Furthermore, as a method of further increasing the peel strength between the polyethylene naphthalate film and the metal foil, the surface of the metal foil before the polyethylene naphthalate film is laminated is roughened. Or a roughening treatment of the first main surface of the polyethylene naphthalate film before being laminated on the metal foil, or a method of forming a plurality of convex portions on the surface. Examples thereof include a method of forming a plurality of convex portions on the main surface and a method of increasing the pressure when the metal foil is pressed and laminated on the first main surface of the polyethylene naphthalate film. Two or more of these methods may be used in combination.

  The 90 ° peel strength is measured in accordance with JIS C6481 (Test condition A) under the conditions of 23 ° C. and humidity of 50%. The 90 ° peel strength can be measured by “TENSILON” manufactured by A & D.

  The insulating film 1 with metal foil can be obtained as follows.

  The manufacturing method of the insulating film 1 with metal foil uses the polyethylene naphthalate film 31 to which the first material 32 containing the softening agent and the second material 33 containing the adhesion improver are attached, and the softening agent is used. The first material 32 containing the softening agent for the polyethylene naphthalate film 2 in the polyethylene naphthalate film 31 to which the second material 33 containing the first material 32 and the adhesion improving agent attached is attached. It is preferable to provide the process (lamination process) of laminating | stacking the metal foil 3 on the main surface 2a. In addition, the first main surface 2a of the polyethylene naphthalate film 2 is softened by heating with the softening agent on the first main surface 2a to which the first material 32 containing the softening agent of the polyethylene naphthalate film 2 is attached. The metal foil 3 is preferably laminated.

  In the laminating step, the metal foil 3 is preferably laminated on the first main surface 2 a of the polyethylene naphthalate film 2 at a temperature lower than the melting point of the polyethylene naphthalate film 2. In this case, thermal deterioration of the polyethylene naphthalate film in the laminating step can be suppressed, good bending characteristics of the polyethylene naphthalate film can be maintained, and further, discoloration of the polyethylene naphthalate film can be suppressed. Furthermore, the peel strength between the polyethylene naphthalate film and the metal foil can be further increased.

  The temperature at which the metal foil 3 is laminated is preferably (the melting point of the polyethylene naphthalate film (° C.) − 5) ° C. or less, more preferably (the melting point of the polyethylene naphthalate film (° C.) − 10) ° C. or less.

  In the laminating step, it is more preferable to laminate the metal foil 3 on the first main surface 2a of the polyethylene naphthalate film 2 at a temperature of 260 ° C. or lower. In this case, thermal degradation of the polyethylene naphthalate film in the laminating step can be effectively suppressed, and good bending characteristics of the polyethylene naphthalate film can be sufficiently maintained. Furthermore, the peel strength between the polyethylene naphthalate film and the metal foil can be further increased. In particular, when the polyethylene naphthalate film is a stretched polyethylene naphthalate film, the metal foil is laminated at a temperature of 260 ° C. or lower on the first main surface of the polyethylene naphthalate film in the laminating step. It is preferable. In this case, the crystal structure of polyethylene naphthalate imparted by stretching is well maintained. As a result, the strength of the polyethylene naphthalate film is further increased, and chipping and cracking are less likely to occur.

  The lower limit of the temperature at which the metal foil 3 is laminated is not particularly limited. Generally the temperature which laminates | stacks the metal foil 3 is 200 degreeC or more, and it is preferable that it is 220 degreeC or more.

  In the laminating step, it is preferable to pressurize the surface of the metal foil 3 opposite to the polyethylene naphthalate film 2 side. The pressure of pressurization is, for example, about 0.1 MPa or more and 50 MPa or less. When the pressurization pressure is not less than the above lower limit and not more than the above upper limit, the peel strength between the polyethylene naphthalate film and the metal foil is further increased, and the deformation of the polyethylene naphthalate film can be suppressed.

  In order to increase the peel strength between the polyethylene naphthalate film 2 and the metal foil 3, the manufacturing method of the insulating film 1 with the metal foil includes the first main surface 2a of the polyethylene naphthalate film 2 before the metal foil 3 is laminated. Furthermore, it is preferable to further include a step of attaching a first material 32 containing a softening agent that softens the first main surface 2a of the polyethylene naphthalate film 2 by heating. It is preferable to use the polyethylene naphthalate film 31 to which the softening agent obtained through the process of making this 1st material 32 adhere is used for the manufacturing method of the insulating film 1 with metal foil. In this case, the polyethylene naphthalate film 2 and the metal are laminated by laminating the metal foil 3 while heating the first main surface 2a on which the first material 32 containing the softening agent of the polyethylene naphthalate film 2 is disposed. It is preferable to obtain the insulating film 1 with metal foil whose peel strength with the foil 3 is 3 N / cm or more.

  The manufacturing method of the insulating film 1 with metal foil is the adhesion which improves the adhesiveness of the polyethylene naphthalate film 2 to the heat conductor on the second main surface 2b of the polyethylene naphthalate film 2 before the heat conductor is laminated. It is preferable to further include a step of attaching the second material 33 containing the property improving agent. It is preferable to use the polyethylene naphthalate film 31 to which the softening agent obtained through the process of attaching this adhesive improvement agent is used for the manufacturing method of the insulating film 1 with metal foil. By adhering the second material 33 containing such an adhesion improver, a heat conductor is applied to the second main surface 2b on which the second material 33 containing the adhesion improver of the polyethylene naphthalate film 2 is disposed. When laminated, the adhesion between the polyethylene naphthalate film 2 and the heat conductor is increased. The step of attaching the second material 33 containing the adhesion improver may be performed simultaneously with the step of attaching the first material 32 containing the softening agent, or may be performed separately. The step of attaching the first material 32 containing the softening agent may be performed before the metal foil 3 is laminated on the polyethylene naphthalate film 2 or after the lamination.

(Laminated structure)
The insulating film 1 with a metal foil according to one embodiment of the present invention shown in FIG. 2 is used by being laminated on a thermal conductor having a thermal conductivity of 10 W / m · K or more. In FIG. 3, an example of the laminated structure using the insulating film 1 with metal foil shown in FIG. 2 is shown with sectional drawing.

  A laminated structure 11 shown in FIG. 3 includes an insulating film 1 with a metal foil, a heat conductor 12, and an optical semiconductor device 13.

  The thermal conductivity of the thermal conductor 12 is 10 W / m · K or more. The heat conductor 12 is laminated on the second main surface 2b opposite to the first main surface 2a on which the metal foil 3 of the polyethylene naphthalate film 2 in the insulating film 1 with metal foil is laminated. An optical semiconductor device 13 is laminated on the surface of the metal foil 3 opposite to the polyethylene naphthalate film 2 side. In addition, in FIG. 3, illustration of the convex part of the surface of the metal foil 3 is abbreviate | omitted.

  In the laminated structure 11, the amount of heat generated in the optical semiconductor device 13 is easily transmitted to the heat conductor 12 via the metal foil 3 and the polyethylene naphthalate film 2. In the laminated structure 11, heat can be efficiently dissipated by the heat conductor 12.

  The heat conductor whose heat conductivity is 10 W / m · K or more is not particularly limited. Examples of the heat conductor having a thermal conductivity of 10 W / m · K or more include aluminum, copper, alumina, beryllia, silicon carbide, silicon nitride, aluminum nitride, and graphite sheet. Especially, it is preferable that the heat conductor whose said heat conductivity is 10 W / m * K or more is a metal, and it is more preferable that it is copper or aluminum. Copper or aluminum is excellent in heat dissipation.

  FIG. 4 is a partially cutaway sectional view showing another example of a laminated structure using the insulating film 1 with a metal foil shown in FIG. A laminated structure 11 </ b> A shown in FIG. 4 includes an insulating film 1 with a metal foil and a heat conductor 12. The thermal conductivity of the thermal conductor 12 is 10 W / m · K or more. The heat conductor 12 is laminated on the second main surface 2b opposite to the first main surface 2a on which the metal foil 3 of the polyethylene naphthalate film 2 in the insulating film 1 with metal foil is laminated.

  Thus, the laminated structure according to the present invention includes a laminated structure in which the metal foil, the polyethylene naphthalate film, and the heat conductor are laminated, and the optical semiconductor device is not mounted.

  Moreover, when obtaining the said laminated structure, you may integrate the said metal foil, the polyethylene naphthalate film to which the said softening agent adhered, and the said heat conductor 3 layers simultaneously. Further, after the two of these three layers are integrated in advance, the remaining one layer may be further integrated. That is, you may obtain a laminated structure, without obtaining the insulating film with metal foil beforehand. Specifically, a metal foil is laminated on the first main surface of the polyethylene naphthalate film using the polyethylene naphthalate film to which the softening agent is attached, and the second surface of the polyethylene naphthalate film. When obtaining a laminated structure in which the heat conductor is laminated on the main surface, (1) a metal foil is disposed on the first main surface side of the polyethylene naphthalate film, and the polyethylene naphthalate film is A thermal conductor having a thermal conductivity of 10 W / m · K or more is disposed on the second main surface side, and the metal foil, the polyethylene naphthalate film, and the thermal conductor are integrated, or (2 ) A metal foil is arranged on the first main surface side of the polyethylene naphthalate film, and the metal foil and the polyethylene naphthalate film are integrated. Then, a thermal conductor having a thermal conductivity of 10 W / m · K or more is disposed on the second main surface side of the polyethylene naphthalate film, and the metal foil, the polyethylene naphthalate film, and the thermal conductivity are arranged. Or (3) arranging a thermal conductor having a thermal conductivity of 10 W / m · K or more on the second main surface side of the polyethylene naphthalate film, and After integrating the phthalate film and the heat conductor, a metal foil is disposed on the first main surface side of the polyethylene naphthalate film, and the metal foil, the polyethylene naphthalate film, and the heat conductor are arranged. And the above laminated structure may be obtained.

  By disposing the polyethylene naphthalate film so as to be in contact with the metal foil on the first main surface side and in contact with the heat conductor on the second main surface side, between the metal foil and the heat conductor, Heat dissipation of the laminated structure in which the metal foil, the polyethylene naphthalate film, and the heat conductor are integrated as a result of the absence of a thick layer other than the polyethylene naphthalate film and the proximity of the metal foil and the heat conductor. Performance can be increased.

  Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention. The present invention is not limited to the following examples.

  In the examples and comparative examples, the following materials were used as the polyethylene naphthalate film and the softening agent.

(Insulating film (polyethylene naphthalate film))
(1) Polyethylene naphthalate film 1 (biaxially stretched polyethylene naphthalate film, thickness 50 μm, melting point 272 ° C., Teonex manufactured by Teijin DuPont Films)
(2) Polyethylene naphthalate film 2 (biaxially stretched polyethylene naphthalate film, thickness 38 μm, melting point 272 ° C., Teonex manufactured by Teijin DuPont Films)
(3) Polyethylene naphthalate film 3 (biaxially stretched polyethylene naphthalate film, thickness 25 μm, melting point 272 ° C., Teonex manufactured by Teijin DuPont Films)

(Surface treatment solution)
Thermosetting compound:
(1) Bisphenol A type epoxy resin (“YD127” manufactured by Nippon Steel Chemical Co., Ltd., liquid at 23 ° C.)
(2) Solid bisphenol A type epoxy resin (“YD011” manufactured by Mitsubishi Chemical Corporation, dimer, solid at 23 ° C.)
(3) Triazine type epoxy resin (“TEPIC SP” manufactured by Nippon Steel Chemical Co., Ltd., solid at 23 ° C.)
(4) Biphenyl type epoxy resin (“YX4000H” manufactured by Mitsubishi Chemical Corporation, solid at 23 ° C.)
(5) Dicyclopentadiene type epoxy resin 1 (“HP7200L” manufactured by DIC, solid at 23 ° C.)
(6) Dicyclopentadiene type epoxy resin 2 (“EXA7200HH” manufactured by DIC, solid at 23 ° C.)
(7) Naphthalene skeleton-containing high heat resistant epoxy resin (“EPICLON HP4710” manufactured by DIC, solid at 23 ° C.)
(8) Alicyclic epoxy resin (“Celoxide 2021P” manufactured by Daicel Chemical Industries, Ltd., liquid at 23 ° C.)
(9) Bismaleimide resin (“BMI-2300” manufactured by Daiwa Kasei Co., Ltd., solid at 23 ° C.)
(10) Benzoxazine resin (“pd-type” manufactured by Shikoku Kasei Co., Ltd., solid at 23 ° C.)
(11) Oxetane resin (“OXBP” manufactured by Ube Industries, Ltd., liquid at 23 ° C.)
(12) Modified epoxy acrylate ("EBECRYL3700" manufactured by Daicel Cytec, solid at 23 ° C)
(13) Cresol novolac type epoxy resin (“YDCN-704” manufactured by Nippon Steel Chemical Co., Ltd., solid at 23 ° C.)

Curing agent:
(1) Acid anhydride curing agent 1 (“YH307” manufactured by Mitsubishi Chemical Corporation, liquid at 23 ° C.)
(2) Acid anhydride curing agent 2 (“YH306” manufactured by Mitsubishi Chemical Corporation, liquid at 23 ° C.)
(3) Acid anhydride curing agent 3 (“YH309” manufactured by Mitsubishi Chemical Corporation, solid at 23 ° C.)
(4) Phenol curing agent 1 (Phenol novolac curing agent, “Resitop PSM4326” manufactured by Gunei Chemical Co., Ltd., solid at 23 ° C.)
(5) Phenol curing agent 2 (“5292B” manufactured by Huntsman, liquid at 23 ° C. (viscous liquid))

Organometallic compounds:
(1) Organic aluminate compound (acetoalkoxyaluminum diisopropylate, “Plenact AL-M” manufactured by Ajinomoto Fine Techno Co., Ltd.)
(2) Organic titanate compound ("Plenact KR55" manufactured by Ajinomoto Fine Techno Co., Ltd.)
(3) Organic zirconate compound ("Orgatics ZA-45" manufactured by Matsumono Fine Chemical Co., Ltd.)
(4) Organosilane compound (vinyltrimethoxysilane, “KBM-1003” manufactured by Shin-Etsu Chemical Co., Ltd.)

Other ingredients:
(1) Cresol novolac resin (DIC Corporation "KA-1160")
(2) Solvent (Methyl ethyl ketone (MEK))

Example 1
A polyethylene naphthalate film 3 (biaxially stretched polyethylene naphthalate film, thickness 25 μm, melting point 272 ° C., Teonex manufactured by Teijin DuPont Films Ltd.) was prepared as an insulating film.

  In addition, a copper foil (thickness: 38 μm) having a roughened surface on which the insulating film was laminated and having a plurality of convex portions was prepared. The ten-point average roughness Rz of the roughened copper foil surface was 7 μm.

  In addition, 7.4 parts by weight of solid bisphenol A type epoxy resin (“YD011” manufactured by Mitsubishi Chemical Corporation, dimer, solid at 23 ° C.) and phenol curing agent 1 (phenol novolac curing agent, “registry” manufactured by Gunei Chemical Co., Ltd. 4 parts by weight of “Top PSM 4326”, solid at 23 ° C.), 0.3 part by weight of phenol curing agent 2 (“5292B” manufactured by Huntsman, liquid at 23 ° C. (viscous liquid)), and organic aluminate compound (acetoalkoxyaluminum) A surface treatment solution was obtained by blending 0.3 part by weight of diisopropylate, “Plenact AL-M” manufactured by Ajinomoto Fine Techno Co., Ltd., and 190 parts by weight of methyl ethyl ketone as a solvent. The surface treatment solution is a first material containing a softening agent and a second material containing an adhesion improver.

  After the first main surface of the insulating film was immersed in the surface treatment solution and the second main surface of the insulating film was immersed in the surface treatment solution, the solvent was removed by drying. Thus, the 1st material containing a softening agent was made to adhere to the 1st main surface side of the above-mentioned insulating film, and the softening agent was arranged on the 1st main surface side of the above-mentioned insulating film. Furthermore, the 2nd material containing an adhesive improvement agent was made to adhere to the 2nd main surface side of the said insulating film, and the adhesiveness improvement agent was arrange | positioned to the 2nd main surface side of the said insulating film.

  Next, an insulating film with a copper foil is obtained by laminating and pasting the copper foil on the first main surface of the insulating film from the roughened surface side at a temperature of 240 ° C. and a pressure of 8 MPa. It was. In the obtained insulating film with copper foil, a plurality of convex portions of the copper foil were embedded in the polyethylene naphthalate film.

(Examples 2 to 43)
The following are the process conditions when laminating and sticking the copper foil from the roughened surface side to the first main surface of the insulating film, and the types and amounts of the ingredients used in the surface treatment solution, the kind of the insulating film The insulating film with copper foil was obtained like Example 1 except having set up as shown in Tables 1-4. In all of the insulating films with copper foil obtained in Examples 2 to 43, a plurality of convex portions of the copper foil were embedded in the polyethylene naphthalate film.

(Comparative Example 1)
5 parts by weight of bisphenol A liquid epoxy resin 2 (“828U” manufactured by Mitsubishi Chemical Corporation), 2 parts by weight of hexahydrophthalic acid skeleton liquid epoxy resin (“AK-601” manufactured by Nippon Kayaku Co., Ltd.), and epoxy group-containing acrylic 5 parts by weight of a resin (Mafuru “G-1030S” manufactured by NOF Corporation), 4 parts by weight of an alicyclic skeleton acid water (“MH-700” manufactured by Shin Nippon Rika Co., Ltd.), and isocyanuric modified solid dispersion type imidazole ( 1 part by weight of "2MZA-PW" manufactured by Shikoku Kasei Co., Ltd., 1 part by weight of surface hydrophobized fumed silica ("MT-10" manufactured by Tokuyama Corporation), and 80 parts by weight of spherical alumina ("DAM-10" manufactured by Denka) An insulating material was obtained by mixing and kneading the part.

  The obtained insulating material was applied onto a release PET (polyethylene terephthalate) film and dried at 90 ° C. for 30 minutes to obtain an insulating film (thickness: 38 μm).

  After laminating the copper foil used in Example 1 on the first main surface of the obtained insulating film, the insulating film was cured at 120 ° C. for 1 hour and further at 200 ° C. for 1 hour to obtain an insulating film with copper foil. Got. When using this insulating film with copper foil, the release PET film was peeled off.

(Comparative Examples 2 and 3)
The following are the process conditions when laminating and sticking the copper foil from the roughened surface side to the first main surface of the insulating film, and the types and amounts of the ingredients used in the surface treatment solution, the kind of the insulating film An insulating film with a copper foil was obtained in the same manner as in Example 1 except that the setting was made as shown in Table 4.

(Reference Example 1)
A polyethylene naphthalate film 2 (biaxially stretched polyethylene naphthalate film, thickness 38 μm, melting point 272 ° C., Teonex manufactured by Teijin DuPont Films Ltd.) was prepared as an insulating film. The first material containing the softening agent was not attached to the first main surface side of the insulating film, and the second material containing the adhesion improver was not attached to the second main surface side. Moreover, the copper foil used in Example 1 was prepared.

  Next, an insulating film with a copper foil is obtained by laminating and pasting the copper foil on the first main surface of the insulating film at a temperature of 240 ° C. and a pressure of 30 MPa from the roughened surface side. It was. In the obtained insulating film with copper foil, a plurality of convex portions of the copper foil were embedded in the polyethylene naphthalate film.

(Evaluation)
(1) Bending characteristics 1
The obtained insulating film with copper foil was cut into a size of 1 cm in width and 10 cm in length. An aluminum plate (width 1 cm, length 10 cm, thickness 0.5 mm) as a support was laminated on the surface of the insulation film with copper foil opposite to the insulation film side of the copper foil to obtain a laminate. In this state, the laminate was folded in a U-shape so that the insulating film was on the outside and the aluminum plate was on the inside, so that the distance between the ends was 4 mm in the 180 ° direction at the center. It was evaluated whether or not the insulating film after bending was cracked or chipped.

[Criteria for bending property 1]
○○: No cracks or chipping occurred in the folded insulating film ○: No cracks occurred in the folded insulating film, but small cracks occurred ×: The entire surface of the folded insulating film across the width direction There are cracks or large chips that can be visually observed

(2) Bending characteristics 2
The aluminum plate (thickness 0.5 mm) was laminated | stacked on the 2nd main surface opposite to the 1st main surface where the metal foil in the obtained insulating film with copper foil was laminated | stacked. Next, after removing the copper foil by etching, the insulating film with an aluminum plate was cut into a size of 1 cm in width and 10 cm in length. In this state, the laminate was folded in a U-shape so that the insulating film was on the outside and the aluminum plate was on the inside, so that the distance between the ends was 4 mm in the 180 ° direction at the center. It was evaluated whether or not the insulating film after bending was cracked or chipped.

[Criteria for bending property 2]
○○: No cracks or chipping occurred in the folded insulating film ○: No cracks occurred in the folded insulating film, but small cracks occurred ×: The entire surface of the folded insulating film across the width direction There are cracks or large chips that can be visually observed

(3) 90 ° peeling strength (peeling strength)
Using “TENSILON” manufactured by A & D, the 90 ° peel strength between the insulating film and the copper foil was measured in accordance with JIS C6481 (Test condition A) under conditions of 23 ° C. and 50% humidity. .

(4) Surface stickiness A release film was attached to each surface of the first material and the second material of the polyethylene naphthalate film to which the softening agent was adhered. Then, the stickiness of the surface was determined according to the following criteria from the state when the release film was peeled off.

[Criteria for surface stickiness]
◯: There was no stickiness on each surface of the first material and the second material, and the release film could be peeled well without the first material and the second material moving to the release film. Although the surfaces of the first material and the second material were somewhat sticky, the release film could be peeled off with almost no migration of the first material and the second material to the release film. Each surface of the material of 2 was considerably sticky, and the first material and the second material were largely transferred to the release film, or the release film was poorly peeled.

(5) Adhesiveness An aluminum plate (thickness 0.5 mm) is laminated on the second main surface opposite to the first main surface on which the metal foil in the obtained insulating film with copper foil is laminated, and a laminated structure Got.

  The copper foil and polyethylene naphthalate film of the obtained laminated structure were cut using a cutter to form a rectangular copper foil pattern (length 10 cm × width 1 cm). Adhesion of polyethylene naphthalate film to aluminum plate by observing the presence or absence of float and peeling of aluminum plate laminated on the opposite side of copper foil of polyethylene naphthalate film when copper foil is peeled off from the end Evaluated. Adhesion was determined according to the following criteria.

[Adhesion criteria]
○○: No floating or peeling on the aluminum plate at a position corresponding to the widthwise end and center of the peeled copper foil ○: Aluminum at a position corresponding to the widthwise end of the peeled copper foil In the position corresponding to the central part in the width direction of the peeled copper foil where the maximum length is less than 1 mm on the plate, no peeling on the aluminum plate. Δ: Corresponding to the widthwise end of the peeled copper foil At the position where the aluminum plate floats up to a maximum length of 1 mm and corresponds to the central portion of the peeled copper foil in the width direction, and no peeling on the aluminum plate ×: width direction of the peeled copper foil There is peeling on the aluminum plate at a position corresponding to the center of

  The results are shown in Tables 1 to 4 below. In Tables 1 to 4 below, “O” was given to the insulating film used. In Table 4 below, “-” indicates that evaluation is not performed, and “* 1” indicates “120 ° C. for 1 hour, and 200 ° C. for 1 hour”.

  In addition, as a result of analysis using time-of-flight secondary ion mass spectrometry TOF-SIMS (“TOF-SIMS type 5” manufactured by ION-TOF), each of the insulating films with copper foil obtained in Examples 1 to 43 On the first main surface side of the polyethylene naphthalate film, the component contained in the softener penetrated into the polyethylene naphthalate film and remained. Further, in the insulating films with copper foils obtained in Examples 1 to 43, the components contained in the second material on the second main surface side of the polyethylene naphthalate film are polyethylene naphthalate films. It penetrated and remained. Moreover, by the cross-sectional observation, it confirmed that the said metal foil was directly laminated | stacked on the said 1st main surface of the said polyethylene naphthalate film in the insulating film with a copper foil of Examples 1-43.

  Moreover, regarding evaluation of adhesiveness, the result of the laminated structure using the aluminum plate as a heat conductor was shown to Tables 1-4. About the insulating film with copper foil of Examples 1-43, the adhesion evaluation of the laminated structure which used the SUS board as a heat conductor is so good that the evaluation result of the adhesiveness of the laminated structure which used the aluminum plate as a heat conductor is good. It was confirmed that the evaluation result of sex tends to improve.

DESCRIPTION OF SYMBOLS 1 ... Insulating film with metal foil 2 ... Polyethylene naphthalate film 2a ... 1st main surface 2b ... 2nd main surface 3 ... Metal foil 11 ... Laminated structure 11A ... Laminated structure 12 ... Thermal conductor 13 ... Optical semiconductor Apparatus 21 ... Insulating film with metal foil 22 ... Polyethylene naphthalate film 22a ... First main surface 22b ... Second main surface 23 ... Metal foil 31 ... Polyethylene naphthalate film with softener attached 32 ... First containing softener 1 material 33 ... 2nd material containing adhesion improver

Claims (13)

A polyethylene naphthalate film to which a softening agent used by being laminated to a metal foil and a thermal conductor having a thermal conductivity of 10 W / m · K or more is attached,
A polyethylene naphthalate film which is an insulating film;
A softener that is attached to the first main surface side of the polyethylene naphthalate film and softens the first main surface of the polyethylene naphthalate film by heating;
An adhesion improver that adheres to the second main surface side opposite to the first main surface side of the polyethylene naphthalate film and improves the adhesion of the polyethylene naphthalate film to the thermal conductor. And
The adhesion improver adhering to the second main surface side of the polyethylene naphthalate film includes an organic aluminate compound, an organic titanate compound, an organic zirconate compound, or an organic silane compound, and a softening agent adhered. Polyethylene naphthalate film.   The softening agent according to claim 1, further comprising a softening agent that is attached to the second main surface side of the polyethylene naphthalate film and that softens the second main surface of the polyethylene naphthalate film by heating. Polyethylene naphthalate film with a stick.   The softener adhering to the second main surface side of the polyethylene naphthalate film contains a thermosetting composition or a compound that dissolves the polyethylene naphthalate film by heating. A polyethylene naphthalate film to which the softening agent according to 2 is attached.   The softener adhering to the first main surface side of the polyethylene naphthalate film contains a thermosetting composition or a compound that dissolves the polyethylene naphthalate film by heating. A polyethylene naphthalate film to which the softening agent according to any one of 1 to 3 is attached. An adhesion improver that adheres to the first main surface side of the polyethylene naphthalate film and improves the adhesion of the polyethylene naphthalate film to the metal foil;
The adhesion improver adhering to the first main surface side of the polyethylene naphthalate film contains an organic aluminate compound, an organic titanate compound, an organic zirconate compound, or an organic silane compound. A polyethylene naphthalate film to which the softener according to any one of the preceding items is attached. It is obtained by heating the polyethylene naphthalate film to which the softener according to any one of claims 1 to 5 is attached,
A softened polyethylene naphthalate film in which the first main surface of the polyethylene naphthalate film is softened by heating with the softening agent. An insulating film with a metal foil used by being laminated on a heat conductor having a thermal conductivity of 10 W / m · K or more,
The softening agent by heating on the first main surface of the polyethylene naphthalate film to which the softening agent of the polyethylene naphthalate film is attached. By softening the first main surface of the polyethylene naphthalate film and laminating a metal foil,
The polyethylene naphthalate film which is an insulating film;
An insulating film with a metal foil, comprising: a metal foil laminated on the first main surface of the polyethylene naphthalate film. A method for producing an insulating film with a metal foil used by being laminated on a heat conductor having a thermal conductivity of 10 W / m · K or more,
By using the polyethylene naphthalate film to which the softener according to any one of claims 1 to 5 is attached, the first main surface of the polyethylene naphthalate film to which the softener is attached is heated. The manufacturing method of the insulating film with metal foil provided with the process of softening the said 1st main surface of the said polyethylene naphthalate film with the said softening agent, and laminating | stacking metal foil.   The polyethylene naphthalate film to which the softening agent is attached is the first main body of the polyethylene naphthalate film before the metal foil is laminated in order to increase the peel strength between the polyethylene naphthalate film and the metal foil. The manufacturing method of the insulating film with metal foil of Claim 8 obtained through the process of attaching the softener which softens the said 1st main surface of the said polyethylene naphthalate film to a surface by heating.   The polyethylene naphthalate film to which the softening agent is attached has adhesion of the polyethylene naphthalate film to the heat conductor on the second main surface of the polyethylene naphthalate film before the heat conductor is laminated. The manufacturing method of the insulating film with metal foil of Claim 8 or 9 obtained through the process of attaching the adhesive improvement agent to improve. A metal foil is laminated on a first main surface of the polyethylene naphthalate film using the polyethylene naphthalate film to which the softening agent according to any one of claims 1 to 5 is attached, and the polyethylene naphthalate film is laminated. A method for producing a laminated structure for obtaining a laminated structure in which the heat conductor is laminated on a second main surface of a phthalate film,
A metal foil is disposed on the first main surface side of the polyethylene naphthalate film, and a heat conductor having a thermal conductivity of 10 W / m · K or more is disposed on the second main surface side of the polyethylene naphthalate film. Arrange and integrate the metal foil, the polyethylene naphthalate film and the thermal conductor,
After disposing a metal foil on the first main surface side of the polyethylene naphthalate film and integrating the metal foil and the polyethylene naphthalate film, the second main surface of the polyethylene naphthalate film A thermal conductor having a thermal conductivity of 10 W / m · K or more on the side, and integrating the metal foil, the polyethylene naphthalate film, and the thermal conductor, or
A thermal conductor having a thermal conductivity of 10 W / m · K or more is disposed on the second main surface side of the polyethylene naphthalate film, and the polyethylene naphthalate film and the thermal conductor are integrated. Then, the manufacturing method of a laminated structure which arrange | positions metal foil in the said 1st main surface side of the said polyethylene naphthalate film, and integrates the said metal foil, the said polyethylene naphthalate film, and the said heat conductor. Insulating film with metal foil according to claim 7,
Heat conduction that is laminated on the second main surface opposite to the first main surface on which the metal foil is laminated in the insulating film with metal foil and has a thermal conductivity of 10 W / m · K or more. A laminated structure comprising the body. An insulating film with a metal foil obtained by the method for producing an insulating film with a metal foil according to any one of claims 8 to 10,
Heat conduction that is laminated on the second main surface opposite to the first main surface on which the metal foil is laminated in the insulating film with metal foil and has a thermal conductivity of 10 W / m · K or more. A laminated structure comprising the body.

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