JP2013206902A - Manufacturing method of component for power semiconductor module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a component for a power semiconductor module which uses a laminated body inhibiting oxidation discoloration of a copper plate and improving abrasion resistance of the copper plate.SOLUTION: In a manufacturing method of a component 11 for a power semiconductor module according to this invention, a laminated body 1, including a copper plate 2, a first silicon oxide film 4 laminated on a first surface of the copper plate 2, and an insulation layer 3 disposed on the second surface side of the copper plate 2 that is opposite to the first surface, is used. The manufacturing method of the component 11 for the power semiconductor module according to this invention includes the steps of: laminating a conductive layer 12 on a surface of the insulation layer 3 which is opposite to the copper plate 2 side; curing the insulation layer 3; and embedding the first silicon oxide film 4, the copper plate 2, the insulation layer 3, and the conductive layer 12 in a mold resin 13.

Description

  The present invention relates to a laminate including a copper plate and an insulating layer. The present invention also relates to a cut laminate using the laminate. Moreover, this invention relates to the manufacturing method of the components for power semiconductor modules using this laminated body.

  In recent years, miniaturization and high performance of electric devices have been advanced. Along with this, the mounting density of electronic components is increasing, and the need to dissipate heat generated from electronic components is increasing. As a method of dissipating heat, a method of adhering a heat conductor having high heat dissipation and a thermal conductivity of 10 W / m · K or more to a heat generation source is widely adopted. In addition, an insulating adhesive material having an insulating property is used to bond the heat conductor to a heat source.

  An example of an electrical device using the insulating adhesive material is disclosed in Patent Document 1 below. In Patent Document 1, an insulating resin layer having a thermal conductivity of 1.0 to 7.5 W / (m · K) and a thickness of 50 to 150 μm is provided on one main surface of a plate-shaped metal heat sink. There is disclosed a circuit board for a semiconductor power module having a metal insulating plate provided and configured, and a lead frame provided on the insulating resin layer of the metal insulating plate. The lead frame has a stepped bent portion. The bent portion is located 2 mm or more inward from the end of the main surface of the heat sink, and is bent so that the floating dimension of the lead frame at the end of the heat sink is 1 mm or more. The metal insulating plate and the lead frame are press-bonded via an adhesive resin layer having a thickness of 10 to 50 μm.

  In Patent Document 1, a copper plate and an aluminum plate are exemplified as the heat sink.

Japanese Patent No. 3846699

  As described above, in recent years, downsizing and high performance of electric devices have been advanced. Along with this, the mounting density of electronic components is increasing, and the need to dissipate heat generated from electronic components is increasing. In particular, in the power semiconductor module described in Patent Document 1, a considerably large amount of heat is likely to be generated from the heat source.

  Moreover, since a copper plate has higher thermal conductivity than an aluminum plate, it is preferable to use a copper plate for the heat sink. However, there is a problem that the copper plate is easily discolored by oxidation. Furthermore, there is a problem that the surface of the copper plate is easily damaged during handling, and as a result, the appearance of the electronic component is deteriorated and the physical properties of the electronic component are lowered.

  The objective of this invention is providing the laminated body which can suppress the oxidation discoloration of a copper plate, and can improve the abrasion resistance of a copper plate, and the cutting | disconnection laminated body using this laminated body.

  Moreover, the objective of this invention is providing the manufacturing method of the components for power semiconductor modules using the laminated body which can suppress the oxidation discoloration of a copper plate and can improve the abrasion resistance of a copper plate.

  According to a wide aspect of the present invention, there is provided a laminated body used for an electronic component, which is a copper plate, a first silicon oxide film laminated on a first surface of the copper plate, and the first of the copper plate. A laminate comprising an insulating layer disposed on a second surface side opposite to the surface is provided.

  Moreover, according to the wide situation of this invention, the manufacturing method of the components for power semiconductor modules using the laminated body mentioned above is provided.

  That is, according to the wide aspect of the present invention, the copper plate, the first silicon oxide film laminated on the first surface of the copper plate, and the second surface opposite to the first surface of the copper plate A step of laminating a conductive layer on a surface of the insulating layer opposite to the copper plate side, a step of curing the insulating layer, and There is provided a method for manufacturing a component for a power semiconductor module, comprising a step of embedding the silicon oxide film, the copper plate, the insulating layer, and the conductive layer in a mold resin.

  In this specification, both the invention relating to the above-described laminate and the invention relating to the above-described method for manufacturing a module component for a power semiconductor device are disclosed.

  The insulating layer preferably contains an inorganic filler having a thermal conductivity of 10 W / m · K or more. The insulating layer is preferably formed using a curable composition containing a curable compound, a curing agent, and an inorganic filler having a thermal conductivity of 10 W / m · K or more.

  The thickness of the first silicon oxide film is preferably 10 nm or more and 1 μm or less.

  It is preferable that the hardening rate of the surface of the insulating layer on the copper plate side is larger than the hardening rate of the surface of the insulating layer opposite to the copper plate side.

  It is preferable that the first silicon oxide film is formed of a hydrolysis condensate of tetrafunctional alkoxysilane, a reaction product of polysilazane, or an active hydrogen reaction product of isocyanate silane.

  It is preferable that the thickness of the copper plate is 100 μm or more and 5 mm or less.

  The insulating layer preferably contains 70 wt% or more and less than 95 wt% of an inorganic filler having a thermal conductivity of 10 W / m · K or more in 100 wt% of the insulating layer. The content of the inorganic filler in the insulating layer portion located on the surface of the insulating layer on the copper plate side is larger than the content of the inorganic filler in the insulating layer portion located on the surface opposite to the copper plate side of the insulating layer. It is preferable.

  The insulating layer is laminated on the second surface of the copper plate, or further comprising a second silicon oxide film laminated on the second surface of the copper plate, and the second silicon oxide film It is preferable that the insulating layer is laminated on the surface opposite to the copper plate side.

  According to a wide aspect of the present invention, a cut laminate obtained by cutting the laminate described above is provided.

  The cut laminate according to the present invention is preferably obtained by cutting the above-described laminate by press punching.

In a specific aspect of the method for manufacturing a power semiconductor module component according to the present invention, a cut laminate obtained by cutting the laminate is used to conduct electricity on the surface opposite to the copper plate side of the insulating layer. Laminate the layers. In this case, it is preferable to cut the laminate by press punching.

  The laminate according to the present invention is disposed on a copper plate, a first silicon oxide film laminated on the first surface of the copper plate, and a second surface side opposite to the first surface of the copper plate. Therefore, the oxidative discoloration of the copper plate can be suppressed, and the scratch resistance of the copper plate can be improved.

  In the method for manufacturing a power semiconductor module according to the present invention, since the laminate is used, it is possible to suppress oxidative discoloration of the copper plate and improve the scratch resistance of the copper plate.

FIG. 1 is a cross-sectional view schematically showing a laminate according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing a power semiconductor module component obtained using the laminate according to the embodiment of the present invention.

  The laminate according to the present invention is a laminate used for an electronic component. The laminate according to the present invention is arranged on a copper plate, a first silicon oxide film laminated on the first surface of the copper plate, and a second surface side opposite to the first surface of the copper plate. And an insulating layer. The insulating layer may be laminated on the second surface of the copper plate, and a second silicon oxide film or the like may be sandwiched between the insulating layer and the copper plate. Note that the second silicon oxide film may be omitted.

  By adopting the above-described configuration in the laminate according to the present invention, it is possible to suppress oxidation discoloration of the copper plate and to improve the scratch resistance of the copper plate. Although the copper plate has high thermal conductivity, there is a problem that the surface of the copper plate is easily oxidized and discolored. On the other hand, oxidation discoloration of the copper plate can be suppressed by laminating the first silicon oxide film on the first surface of the copper plate. Furthermore, since the film laminated on the first surface of the copper plate is a silicon oxide film, the scratch resistance is considerably increased.

  In the method for manufacturing a power semiconductor module component according to the present invention, the above-described laminate is used. The manufacturing method of the component for power semiconductor modules which concerns on this invention uses the laminated body mentioned above, the process of laminating | stacking a conductive layer on the surface opposite to the said copper plate side of the said insulating layer, and the process of hardening the said insulating layer And a step of embedding the first silicon oxide film, the copper plate, the insulating layer, and the conductive layer in a mold resin.

  By adopting the above-described configuration in the method for manufacturing a power semiconductor module component according to the present invention, it is possible to suppress oxidation discoloration of the copper plate and to improve the scratch resistance of the copper plate.

  By the way, a laminated body may be cut | disconnected and used. Specifically, the laminate may be used after being cut into a predetermined size by press punching. At the time of cutting by press punching or the like, the film laminated on the surface of the copper plate is easily broken, and the film is easily peeled off from the copper plate. Furthermore, the surface of the copper plate is easily damaged. On the other hand, since the film laminated on the first surface of the copper plate is a silicon oxide film, the silicon oxide film is hardly broken, the silicon oxide film is hardly peeled off from the copper plate, and the surface of the copper plate is scratched. It can suppress sticking. As a result, a good electronic component such as a power semiconductor module component can be obtained.

  In the laminate, the surface of the insulating layer opposite to the copper plate side is preferably a surface laminated on the conductive layer. The laminate is preferably a laminate used by laminating a conductive layer on the surface of the insulating layer opposite to the copper plate side.

  The laminate is preferably a laminate used by cutting. The laminated body is preferably a laminated body that is cut and used in a state where the first silicon oxide film, the copper plate, and the insulating layer are laminated. The laminate is preferably a laminate used by being cut by press punching.

  The cut laminate according to the present invention is obtained by cutting the laminate. At this time, the laminate is cut into a predetermined size. The cut laminate according to the present invention is preferably obtained by cutting the laminate by press punching. Even if such cutting is performed, the first silicon oxide film is difficult to break, and the surface of the copper plate can be further prevented from being damaged.

  Moreover, in the manufacturing method of the component for power semiconductor modules which concerns on this invention, a conductive layer is laminated | stacked on the surface opposite to the said copper plate side of the said insulating layer using the cutting laminated body obtained by cut | disconnecting the said laminated body. It is preferable to do. In this case, it is preferable to cut the laminate by press punching.

  The laminated body may include a second silicon oxide film laminated on the second surface of the copper plate. In this case, oxidation discoloration of the copper plate is further suppressed. Even without the second silicon oxide film, it is possible to suppress the oxidative discoloration of the copper plate and to improve the scratch resistance of the copper plate on the first surface of the copper plate. When there is a second silicon oxide film, it is possible to suppress the oxidative discoloration of the copper plate and to improve the scratch resistance of the copper plate on both the first surface and the second surface of the copper plate.

  When the laminated body includes the second silicon oxide film, it is preferable that an insulating layer is laminated on the surface of the second silicon oxide film opposite to the copper plate side. The laminated body further includes a second silicon oxide film laminated on the second surface of the copper plate, and the insulating layer is laminated on a surface opposite to the copper plate side of the second silicon oxide film. It is preferable that the insulating layer is laminated on the second surface of the copper plate.

  The thicknesses of the first silicon oxide film and the second silicon oxide film are each preferably 1 nm or more, more preferably 10 nm or more, still more preferably 50 nm or more, preferably 10 μm or less, more preferably 5 μm or less, still more preferably Is 1 μm or less. The thicknesses of the first silicon oxide film and the second silicon oxide film are particularly preferably 50 nm or more and 1 μm or less, respectively. When the thickness of the silicon oxide film is not less than the above lower limit and not more than the above upper limit, the oxidative discoloration of the copper plate is further suppressed, and the scratch resistance of the copper plate is further enhanced.

The main component of the first and second silicon oxide films is preferably SiO ₂ . The first and second silicon oxide films are preferably glass (amorphous solid). The first and second silicon oxide films are preferably in a glass state.

  The material for forming the first and second silicon oxide films is not particularly limited as long as the material is a silicon oxide film. Examples of the material for forming the first and second silicon oxide films include a hydrolysis-condensation product of tetrafunctional alkoxysilane, a reaction product of polysilazane, and an active hydrogen reaction product of isocyanate silane. The first and second silicon oxide films are formed by a hydrolytic condensate of tetrafunctional alkoxysilane, a reaction product of polysilazane, or an active hydrogen reaction product of isocyanate silane. Is preferred. By forming the first and second silicon oxide films using such materials, the oxidative discoloration of the copper plate is further suppressed, and the scratch resistance of the copper plate is further enhanced. In addition, since such a material forms a silicon oxide film at a relatively low temperature, the discoloration of copper can be effectively prevented during the formation of the silicon oxide film.

The thickness of the copper plate is not particularly limited. The thickness of the copper plate is preferably 1 μm or more, more preferably 10 μm or more, further preferably 100 μm or more, preferably 1 cm or less, more preferably 5 mm or less. When the thickness of the copper plate is not less than the above lower limit and not more than the above upper limit, the heat dissipation and handling properties of the electronic component using the laminate are further enhanced.

  The insulating layer has a plurality of layers with different curing rates, and is preferably a multilayer. However, the insulating layer may be a single layer. The insulating layer preferably includes a first insulating layer disposed on the copper plate side and a second insulating layer disposed on the side opposite to the copper plate side. The laminate includes the first silicon oxide film laminated on the first surface of the copper plate, the copper plate, a first insulating layer disposed on the second surface side of the copper plate, and the first It is preferable to provide the 2nd insulating layer laminated | stacked on the surface on the opposite side to the said copper plate side of 1 insulating layer. In this manner, by making the insulating layer into a multilayer, it is possible to impart partially different properties to the insulating layer.

  The curing rate of the surface of the insulating layer opposite to the copper plate side is preferably 1% or more, and may be 10% or more. The curing rate of the second insulating layer is preferably 1% or more, and may be 10% or more.

  The curing rate of the surface of the insulating layer on the copper plate side is preferably larger than the curing rate of the surface of the insulating layer opposite to the copper plate side. It is preferable that the curing rate of the first insulating layer is larger than the curing rate of the second insulating layer. In this case, the adhesion between the insulating layer and the conductive layer can be further effectively improved.

  From the viewpoint of improving both the thermal conductivity of the entire insulating layer and the adhesion between the insulating layer and the conductive layer in a balanced manner, the curing rate of the surface of the insulating layer on the copper plate side is determined by the copper plate of the insulating layer. 1% or more, preferably 5% or more, more preferably 10% or more, more preferably 20% or more, or 30% or more larger than the cure rate of the surface opposite to the side. Also good. From the viewpoint of improving both the thermal conductivity of the entire insulating layer and the adhesion between the insulating layer and the conductive layer in a balanced manner, the curing rate of the first insulating layer is the curing rate of the second insulating layer. Is preferably 1% or more, more preferably 5% or more, still more preferably 10% or more, and may be 20% or more, or 30% or more.

  It is preferable that the curing rate of the surface opposite to the copper plate side of the insulating layer is 20% or more and 80% or less. It is preferable that the curing rate of the surface laminated | stacked on the conductive layer of the said insulating layer is 20% or more and 80% or less. It is preferable that the curing rate of the second insulating layer is 20% or more and 80% or less. In this case, the adhesion between the insulating layer and the conductive layer can be effectively increased.

  The curing rate of the surface opposite to the copper plate side of the insulating layer may be less than 70%, less than 60%, or less than 50%. The curing rate of the second insulating layer is preferably 1% or more, may be less than 70%, may be less than 60%, or may be less than 50%.

  The curing rate of the surface of the insulating layer on the copper plate side is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, may be 80% or more, and may be 90% or more. It may be 95% or more, or 100%. The curing rate of the first insulating layer is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, may be 80% or more, and may be 90% or more. 95% or more, or 100%.

The second insulating layer is preferably an uncured product or a semi-cured product. The second insulating layer may be an uncured material that is not cured at all and can be cured, or may be a semi-cured material that has been cured and can be further cured. The first insulating layer is preferably a semi-cured product or a cured product. The first insulating layer may be a semi-cured product that has been cured and can be further cured, or a cured product that has been cured.

  The curing rate of the insulating layer is determined by measuring the heat of curing when the uncured insulating layer is heated. When measuring the curing rate, for example, a differential scanning calorimetry (DSC) apparatus (“DSC7020” manufactured by SII Nanotechnology) or the like is used. Specifically, the curing rate of the insulating layer is measured as follows.

  At a measurement start temperature of 30 ° C. and a temperature increase rate of 3 ° C./min, the insulating layer (such as the first insulating layer or the second insulating layer) is heated to 300 ° C. and held for 1 hour. The amount of heat generated when the insulating layer is cured at this temperature rise (hereinafter referred to as heat amount A) is measured. In addition, a curable composition for forming an insulating layer was applied to a release PET (polyethylene terephthalate) sheet having a thickness of 50 μm so as to have a thickness of 80 μm, and 1 ° C. under a room temperature vacuum of 23 ° C. and 0.01 atm. An uncured insulating layer dried without heating is prepared in the same manner as the insulating layer in the above laminate except that it is dried for a period of time. Using this insulating layer, the amount of heat (hereinafter, referred to as the amount of heat B) generated when the temperature is hardened is measured in the same manner as the measurement of the amount of heat A described above. From the obtained heat quantity A and heat quantity B, the curing rates of the first and second insulating layers are obtained by the following formula.

  Curing rate (%) = [1- (heat amount A / heat amount B)] × 100

  The ratio of the thickness of the second insulating layer to the thickness of the first insulating layer (the thickness of the second insulating layer / the thickness of the first insulating layer) is preferably 0.03 or more, more preferably 0.00. 1 or more, more preferably 0.3 or more, preferably 10 or less, more preferably 3 or less, still more preferably 1 or less.

  From the viewpoint of improving both the thermal conductivity of the entire insulating layer and the adhesion between the second insulating layer, which is a cured product, and the conductive layer in a well-balanced manner, the thickness of the first insulating layer is the first thickness. The ratio of the insulating layer to the thickness is particularly preferably 0.3 or more and 1 or less.

  The thickness of the insulating layer (the entire insulating layer) is not particularly limited. The thickness of the insulating layer is preferably 80 μm or more, more preferably 100 μm or more, preferably 200 μm or less, more preferably 170 μm or less. When the thickness of the insulating layer is equal to or more than the above lower limit, heat dissipation in the entire insulating layer, adhesion between the insulating layer and the conductive layer, which is a cured product, and voltage resistance in the entire insulating layer are improved in a well-balanced manner.

  The insulating layer is preferably formed using a curable compound (A) and a curing agent (B). The first insulating layer is preferably formed using a first curable composition containing a curable compound (A) and a curing agent (B). It is preferable that the said 2nd insulating layer is formed using the 2nd curable composition containing a sclerosing | hardenable compound (A) and a hardening | curing agent (B). From the viewpoint of forming an insulating layer with good curability, the insulating layer is preferably formed using a curable compound (A1) having a cyclic ether group and a curing agent (B). It is preferable that the said insulating layer and the said curable composition contain an inorganic filler (C). Each of the first insulating layer and the first curable composition preferably contains an inorganic filler (C). Each of the second insulating layer and the second curable composition preferably contains an inorganic filler (C). The inorganic filler (C) is preferably an inorganic filler having a thermal conductivity of 10 W / m · K or more.

  The insulating layer preferably includes an inorganic filler having a thermal conductivity of 10 W / m · K or more. In this case, the thermal conductivity of the insulating layer is increased and the heat dissipation is increased. However, each of the insulating layer, the first insulating layer, and the second insulating layer may include an inorganic filler having a thermal conductivity of less than 10 W / m · K.

  Hereinafter, first, details of each component used for the insulating layer will be described.

(Curable compound (A))
The insulating layer is preferably formed using a curable compound (A). The said curable composition contains a sclerosing | hardenable compound (A). The curable compound (A) is preferably a thermosetting compound. The curable compound (A) is preferably a curable compound (A1) having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The curable compound (A1) having a cyclic ether group is preferably a curable compound having an epoxy group or an oxetanyl group. The curable compound (A) is cured by the action of the curing agent (B). As for the curable compound (A) used for an insulating layer, only 1 type may be used and 2 or more types may be used together. The curable compound (A) used for the first insulating layer and the curable compound (A) used for the second insulating layer may be the same or different.

  The curable compound (A1) may contain an epoxy compound (A1a) having an epoxy group, or may contain an oxetane compound (A1b) having an oxetanyl group.

  From the viewpoint of further improving the heat resistance and voltage resistance of an insulating layer that is a cured product (hereinafter sometimes simply referred to as a cured product), the curable compound (A) preferably has an aromatic skeleton. From the viewpoint of further improving the thermal conductivity and voltage resistance of the cured product, the curable compound (A) preferably includes a curable compound having a polycyclic aromatic skeleton, and includes a cyclic ether group and a polycyclic ring. It is more preferable to include a curable compound having a formula aromatic skeleton. Examples of the polycyclic aromatic skeleton include a naphthalene skeleton, an anthracene skeleton, a xanthene skeleton, a fluorene skeleton, and a biphenyl skeleton. From the viewpoint of further improving the thermal conductivity and voltage resistance of the cured product, the polycyclic aromatic skeleton is preferably a biphenyl skeleton.

  The content of the curable compound having a polycyclic aromatic skeleton in the total 100% by weight of the curable compound (A) is preferably 30% by weight or more, more preferably 50% by weight or more, and further preferably 60% by weight. That's it. The total amount of the curable compound (A) may be a curable compound having a polycyclic aromatic skeleton.

  Specific examples of the epoxy compound (A1a) having an epoxy group include an epoxy monomer having a bisphenol skeleton, an epoxy monomer having a dicyclopentadiene skeleton, an epoxy monomer having a naphthalene skeleton, an epoxy monomer having an adamantane skeleton, and an epoxy having a fluorene skeleton. Examples of the monomer include an epoxy monomer having a biphenyl skeleton, an epoxy monomer having a bi (glycidyloxyphenyl) methane skeleton, an epoxy monomer having a xanthene skeleton, an epoxy monomer having an anthracene skeleton, and an epoxy monomer having a pyrene skeleton. These hydrogenated products or modified products may be used. As for an epoxy compound (A1a), only 1 type may be used and 2 or more types may be used together.

  Examples of the epoxy monomer having a bisphenol skeleton include an epoxy monomer having a bisphenol A type, bisphenol F type, or bisphenol S type bisphenol skeleton.

  Examples of the epoxy monomer having a dicyclopentadiene skeleton include dicyclopentadiene dioxide and a phenol novolac epoxy monomer having a dicyclopentadiene skeleton.

Examples of the epoxy monomer having a naphthalene skeleton include 1-glycidylnaphthalene,
2-glycidylnaphthalene, 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, 1,7-diglycidylnaphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene, and 1,2,5,6-tetraglycidylnaphthalene and the like.

  Examples of the epoxy monomer having an adamantane skeleton include 1,3-bis (4-glycidyloxyphenyl) adamantane and 2,2-bis (4-glycidyloxyphenyl) adamantane.

  Examples of the epoxy monomer having a fluorene skeleton include 9,9-bis (4-glycidyloxyphenyl) fluorene, 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene, and 9,9-bis (4- Glycidyloxy-3-chlorophenyl) fluorene, 9,9-bis (4-glycidyloxy-3-bromophenyl) fluorene, 9,9-bis (4-glycidyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-Glycidyloxy-3-methoxyphenyl) fluorene, 9,9-bis (4-glycidyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-glycidyloxy-3,5-dichlorophenyl) Fluorene and 9,9-bis (4-glycidyloxy-3,5-dibromophenyl) Fluorene, and the like.

  Examples of the epoxy monomer having a biphenyl skeleton include 4,4'-diglycidylbiphenyl and 4,4'-diglycidyl-3,3 ', 5,5'-tetramethylbiphenyl.

  Examples of the epoxy monomer having a bi (glycidyloxyphenyl) methane skeleton include 1,1′-bi (2,7-glycidyloxynaphthyl) methane, 1,8′-bi (2,7-glycidyloxynaphthyl) methane, 1,1′-bi (3,7-glycidyloxynaphthyl) methane, 1,8′-bi (3,7-glycidyloxynaphthyl) methane, 1,1′-bi (3,5-glycidyloxynaphthyl) methane 1,8'-bi (3,5-glycidyloxynaphthyl) methane, 1,2'-bi (2,7-glycidyloxynaphthyl) methane, 1,2'-bi (3,7-glycidyloxynaphthyl) Examples include methane and 1,2′-bi (3,5-glycidyloxynaphthyl) methane.

  Examples of the epoxy monomer having a xanthene skeleton include 1,3,4,5,6,8-hexamethyl-2,7-bis-oxiranylmethoxy-9-phenyl-9H-xanthene.

  Specific examples of the oxetane compound (A1b) having an oxetanyl group include, for example, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 1,4-benzenedicarboxylate bis [(3- Ethyl-3-oxetanyl) methyl] ester, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, and oxetane-modified phenol novolac. As for an oxetane compound (A1b), only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of further improving the heat resistance of the insulating layer that is a cured product, the curable compound (A) preferably has two or more cyclic ether groups.

From the viewpoint of further improving the heat resistance of the cured product, the content of the curable compound having two or more cyclic ether groups in the total 100% by weight of the curable compound (A) is preferably 70% by weight or more. More preferably, it is 80% by weight or more and 100% by weight or less. The content of the curable compound having two or more cyclic ether groups in the total 100% by weight of the curable compound (A) may be 10% by weight or more and 100% by weight or less. Further, the entire curable compound (A) may be a curable compound having two or more cyclic ether groups.

  The molecular weight of the curable compound (A) is preferably less than 10,000. The molecular weight of the curable compound (A) is preferably 200 or more, more preferably 1200 or less, still more preferably 600 or less, and particularly preferably 550 or less. When the molecular weight of the curable compound (A) is not less than the above lower limit, the adhesiveness of the surface of the insulating layer is lowered, and the handleability of the laminate is further enhanced. When the molecular weight of the curable compound (A) is not more than the above upper limit, the adhesiveness of the cured product is further enhanced. Furthermore, the cured product is hard and hard to be brittle, and the adhesiveness of the cured product is further enhanced.

  In the present specification, the molecular weight in the curable compound (A) means a molecular weight that can be calculated from the structural formula when it is not a polymer and when the structural formula can be specified. Means weight average molecular weight.

  The curable compound (A) in a total of 100% by weight of the total resin components (hereinafter, may be abbreviated as the total resin component X) contained in the curable composition (the entire curable composition used for the insulating layer). ) Is preferably 50% by weight or more, more preferably 60% by weight or more, preferably 99.5% by weight or less, more preferably 99% by weight or less, and still more preferably 98% by weight or less. The content of the curable compound (A) is preferably 50% in a total of 100% by weight of the total resin components (hereinafter sometimes abbreviated as “total resin component X1”) contained in the first curable composition. % Or more, more preferably 60% by weight or more, preferably 99.5% by weight or less, more preferably 99% by weight or less, and still more preferably 98% by weight or less. The content of the curable compound (A) is preferably 50% in a total of 100% by weight of the total resin components (hereinafter sometimes abbreviated as “total resin component X2”) contained in the second curable composition. % Or more, more preferably 60% by weight or more, preferably 99.5% by weight or less, more preferably 99% by weight or less, and still more preferably 98% by weight or less. When the content of the curable compound (A) is not less than the above lower limit, the adhesiveness and heat resistance of the cured product are further enhanced. When the content of the curable compound (A) is not more than the above upper limit, the coating property of the curable composition is further enhanced. In addition, all the resin components X, X1, and X2 refer to the sum total of the curable compound (A), the curing agent (B), and other resin components added as necessary. The inorganic filler (C) is not included in all the resin components X, X1, and X2.

(Curing agent (B))
The insulating layer is preferably formed using a curing agent (B). Each of the first and second curable compositions preferably contains a curing agent (B). The curing agent (B) is not particularly limited as long as the curable composition can be cured. The curing agent (B) is preferably a thermosetting agent. As for the hardening | curing agent (B) used for an insulating layer, only 1 type may be used and 2 or more types may be used together. The curing agent (B) used for the first insulating layer and the curing agent (B) used for the second insulating layer may be the same or different.

  From the viewpoint of further improving the heat resistance of the cured product, the curing agent (B) preferably has an aromatic skeleton or an alicyclic skeleton. The curing agent (B) preferably includes an amine curing agent (amine compound), an imidazole curing agent, a phenol curing agent (phenol compound) or an acid anhydride curing agent (acid anhydride), and includes an amine curing agent. More preferred. The acid anhydride curing agent includes an acid anhydride having an aromatic skeleton, a water additive of the acid anhydride or a modified product of the acid anhydride, or an acid anhydride having an alicyclic skeleton, It is preferable to include a water additive of an acid anhydride or a modified product of the acid anhydride.

From the viewpoint of improving the dispersibility of the inorganic filler (C) and further enhancing the voltage resistance and thermal conductivity of the cured product, the curing agent (B) preferably contains a basic curing agent. Further, from the viewpoint of further improving the dispersibility of the inorganic filler (C) and further increasing the voltage resistance and thermal conductivity of the cured product, the curing agent (B) is an amine curing agent or an imidazole curing agent. More preferably, it includes an amine curing agent, and particularly preferably includes dicyandiamide. Moreover, it is also preferable that a hardening | curing agent (B) contains both a dicyandiamide and an imidazole hardening | curing agent. By using these preferable curing agents, the dispersibility of the inorganic filler (C) in the curable composition is increased, and a cured product having an excellent balance of heat resistance, moisture resistance and electrical properties can be obtained. As a result, even if there is much content of an inorganic filler (C), thermal conductivity becomes quite high. In particular, when dicyandiamide is used, the adhesiveness between the cured product, the copper plate and the conductive layer is considerably increased.

  Examples of the amine curing agent include dicyandiamide, an imidazole compound, diaminodiphenylmethane, and diaminodiphenylsulfone. From the viewpoint of further improving the adhesion between the cured product, the copper plate and the conductive layer, the amine curing agent more preferably contains a dicyandiamide or an imidazole compound. From the viewpoint of further enhancing the storage stability of the insulating layer before curing, the curing agent (B) preferably contains a curing agent having a melting point of 180 ° C. or higher, and an amine curing agent having a melting point of 180 ° C. or higher. It is more preferable to contain.

  Examples of the imidazole curing agent include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl. 2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2 '-Methyl Midazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6 [2′-Ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole Can be mentioned.

  Examples of the phenol curing agent include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, polyparavinylphenol, bisphenol A type novolak, xylylene modified novolak, decalin modified novolak, poly ( And di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, and poly (di-p-hydroxyphenyl) methane. From the viewpoint of further enhancing the flexibility of the cured product and the flame retardancy of the cured product, a phenol resin having a melamine skeleton, a phenol resin having a triazine skeleton, or a phenol resin having an allyl group is preferable.

  Commercially available products of the phenol curing agent include MEH-8005, MEH-8010, and MEH-8015 (all of which are manufactured by Meiwa Kasei Co., Ltd.), YLH903 (manufactured by Mitsubishi Chemical Corporation), LA-7052, LA-7054, and LA-7751. LA-1356 and LA-3018-50P (all of which are manufactured by DIC Corporation), PS6313 and PS6492 (all of which are manufactured by Gunei Chemical Co., Ltd.), and the like.

Examples of the acid anhydride having an aromatic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride include, for example, a styrene / maleic anhydride copolymer, a benzophenone tetracarboxylic acid anhydride, and a pyromellitic acid anhydride. , Trimellitic anhydride, 4,4'-oxydiphthalic anhydride, phenylethynyl phthalic anhydride, glycerol bis (anhydrotrimellitate) monoacetate, ethylene glycol bis (anhydrotrimellitate), methyltetrahydroanhydride Examples include phthalic acid, methylhexahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride.

  Examples of commercially available acid anhydrides having an aromatic skeleton, water additives of the acid anhydrides, or modified products of the acid anhydrides include SMA Resin EF30, SMA Resin EF40, SMA Resin EF60, and SMA Resin EF80 (any of the above Also manufactured by Sartomer Japan), ODPA-M and PEPA (all manufactured by Manac), Ricacid MTA-10, Ricacid MTA-15, Ricacid TMTA, Ricacid TMEG-100, Ricacid TMEG-200, Ricacid TMEG-300, Ricacid TMEG-500, Ricacid TMEG-S, Ricacid TH, Ricacid HT-1A, Ricacid HH, Ricacid MH-700, Ricacid MT-500, Ricacid DSDA and Ricacid TDA-100 (all of which are manufactured by Shin Nippon Rika Co., Ltd.) PICLON B4400, EPICLON B650, and EPICLON B570 (all manufactured by both DIC Corporation).

  The acid anhydride having an alicyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride is an acid anhydride having a polyalicyclic skeleton, a water additive of the acid anhydride, or the A modified product of an acid anhydride, or an acid anhydride having an alicyclic skeleton obtained by addition reaction of a terpene compound and maleic anhydride, a water additive of the acid anhydride, or a modified product of the acid anhydride It is preferable. By using these curing agents, the flexibility of the cured product and the moisture resistance and adhesion of the cured product are further increased.

  Examples of the acid anhydride having an alicyclic skeleton, a water addition of the acid anhydride, or a modified product of the acid anhydride include methyl nadic acid anhydride, acid anhydride having a dicyclopentadiene skeleton, and the acid anhydride And the like.

  Examples of commercially available acid anhydrides having the alicyclic skeleton, water additions of the acid anhydrides, or modified products of the acid anhydrides include Ricacid HNA and Ricacid HNA-100 (all of which are manufactured by Shin Nippon Rika Co., Ltd.) , And EpiCure YH306, EpiCure YH307, EpiCure YH308H, EpiCure YH309 (all of which are manufactured by Mitsubishi Chemical Corporation) and the like.

  The curing agent (B) is preferably methyl nadic acid anhydride or trialkyltetrahydrophthalic anhydride. Use of methyl nadic anhydride or trialkyltetrahydrophthalic anhydride increases the water resistance of the cured product.

  In the total 100% by weight of the total resin component X, the content of the curing agent (B) is preferably 0.5% by weight or more, more preferably 1% by weight or more, preferably 50% by weight or less, more preferably 40% by weight. % Or less. In the total 100% by weight of all the resin components X1, the content of the curing agent (B) is preferably 0.5% by weight or more, more preferably 1% by weight or more, preferably 50% by weight or less, more preferably 40% by weight. % Or less. The content of the curing agent (B) is preferably 0.5% by weight or more, more preferably 1% by weight or more, preferably 50% by weight or less, more preferably 40% by weight in the total 100% by weight of the total resin component X2. % Or less. It is easy to fully harden the whole curable composition as content of a hardening | curing agent (B) is more than the said minimum. When the content of the curing agent (B) is not more than the above upper limit, it is difficult to generate an excessive curing agent (B) that does not participate in curing. For this reason, the heat resistance and adhesiveness of hardened | cured material become still higher.

(Inorganic filler (C))
The insulating layer preferably contains an inorganic filler (C). The first and second insulating layers preferably include an inorganic filler having a thermal conductivity of 10 W / m · K or more. The curable composition preferably contains an inorganic filler (C). Each of the first and second curable compositions preferably contains an inorganic filler (C). The use of the inorganic filler (C) increases the thermal conductivity of the cured product. As a result, the thermal conductivity of the cured product is increased. As for the said inorganic filler (C), only 1 type may be used and 2 or more types may be used together. The inorganic filler (C) used for the first insulating layer and the inorganic filler (C) used for the second insulating layer may be the same or different.

  From the viewpoint of further increasing the thermal conductivity of the cured product, the thermal conductivity of the inorganic filler (C) is preferably 10 W / m · K or more, more preferably 15 W / m · K or more, and even more preferably 20 W / m. -K or more. The upper limit of the thermal conductivity of the inorganic filler (C) is not particularly limited. Inorganic fillers having a thermal conductivity of about 300 W / m · K are widely known, and inorganic fillers having a thermal conductivity of about 200 W / m · K are easily available.

  The inorganic filler (C) is preferably at least one selected from the group consisting of alumina, synthetic magnesite, crystalline silica, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide and magnesium oxide, More preferably, it is at least one selected from the group consisting of alumina, crystalline silica, boron nitride and aluminum nitride. Use of these preferable inorganic fillers further increases the thermal conductivity of the cured product.

  The inorganic filler (C) is more preferably at least one selected from the group consisting of spherical alumina, crushed alumina, crystalline silica, boron nitride, aggregated particles, and spherical aluminum nitride. Use of these preferable fillers further increases the thermal conductivity of the cured product. The boron nitride and the aggregated particles are preferably boron nitride and boron nitride aggregated particles that are not aggregated particles.

  The inorganic filler (C) preferably contains an inorganic filler having a new Mohs hardness of 12 or less. The new Mohs hardness of the inorganic filler having the new Mohs hardness of 12 or less is more preferably 9 or less. Use of an inorganic filler having a new Mohs hardness of not more than the above upper limit further increases the workability of the cured product.

  From the viewpoint of further improving the workability of the cured product, the inorganic filler (C) is preferably at least one selected from the group consisting of synthetic magnesite, crystalline silica, zinc oxide, and magnesium oxide. The new Mohs hardness of these inorganic fillers is 9 or less.

  The inorganic filler (C) may contain a spherical filler (spherical filler), may contain a crushed filler (crushed filler), or may contain a plate-like filler (plate-like filler). Good. It is particularly preferable that the inorganic filler (C) includes a spherical filler. Since spherical fillers can be filled at high density, the use of spherical fillers further increases the thermal conductivity of the cured product.

  Examples of the crushed filler include crushed alumina. The crushing filler is obtained, for example, by crushing a lump-like inorganic substance using a uniaxial crusher, a biaxial crusher, a hammer crusher, a ball mill, or the like. By using the crushed filler, the filler in the insulating layer tends to be bridged or have a structure in which the filler is effectively brought into close proximity. Therefore, the thermal conductivity of the cured product is further increased. Moreover, generally the crushing filler is cheap compared with a normal filler. For this reason, the cost of a laminated body becomes low by use of a crushing filler.

The average particle size of the crushed filler is preferably 12 μm or less, more preferably 10 μm.
Hereinafter, it is preferably 1 μm or more. When the average particle size of the crushed filler is not more than the above upper limit, the crushed filler can be dispersed with high density in the curable composition, and the withstand voltage of the cured product is further enhanced. When the average particle diameter of the crushed filler is not less than the above lower limit, it becomes easy to fill the crushed filler with high density.

  The aspect ratio of the crushing filler is not particularly limited. The aspect ratio of the crushed filler is preferably 1.5 or more, and preferably 20 or less. Fillers with an aspect ratio of less than 1.5 are relatively expensive and increase the cost of the laminate. When the aspect ratio is 20 or less, filling of the crushed filler is easy.

  The aspect ratio of the crushed filler can be determined, for example, by measuring the crushed surface of the filler using a digital image analysis particle size distribution measuring apparatus (“FPA” manufactured by Nippon Luft).

  When the inorganic filler (C) is a spherical filler, the average particle diameter of the spherical filler is preferably 0.1 μm or more, and preferably 40 μm or less. When the average particle size is 0.1 μm or more, the inorganic filler (C) can be easily filled at a high density. When the average particle size is 40 μm or less, the voltage resistance of the cured product is further enhanced.

  The “average particle diameter” is an average particle diameter obtained from a volume average particle size distribution measurement result measured by a laser diffraction particle size distribution measuring apparatus.

  From the viewpoint of suppressing thickness variation of the cured product and effectively increasing the thermal conductivity of the cured product, the maximum particle size of the inorganic filler (C) is preferably 70 μm or less, more preferably 50 μm or less. In addition, the maximum particle diameter of the said crushing filler and the said plate-shaped filler means the major axis of the largest particle.

  The content of the inorganic filler (C) in 100% by weight of the insulating layer is preferably 70% by weight or more, more preferably 75% by weight or more, still more preferably 80% by weight or more, particularly preferably 85% by weight or more, and most preferably 86 wt% or more, preferably less than 97 wt%, more preferably less than 95 wt%. In 100% by weight of the curable composition (the whole curable composition used for the insulating layer), the content of the inorganic filler (C) is preferably 70% by weight or more, more preferably 75% by weight or more, and still more preferably 80% by weight. % Or more, particularly preferably 85% by weight or more, most preferably 86% by weight or more, preferably less than 97% by weight, more preferably less than 95% by weight. When the content of the inorganic filler (C) in the insulating layer and the curable composition is not less than the above lower limit and not more than the above upper limit, the cured state of the insulating layer, which is a cured product, becomes good and the thermal conductivity becomes considerably high. .

  In 100% by weight of the first insulating layer and in 100% by weight of the first curable composition, the content of the inorganic filler (C) is preferably 85% by weight or more, more preferably 86% by weight or more, preferably 97% by weight. %, More preferably less than 95% by weight. When the content of the inorganic filler (C) in the first insulating layer and the first curable composition is not less than the above lower limit and not more than the above upper limit, the cured state of the first insulating layer that is a cured product is favorable. And the thermal conductivity is considerably high.

In 100% by weight of the second insulating layer and 100% by weight of the second curable composition, the content of the inorganic filler (C) is preferably 67% by weight or more, preferably less than 97% by weight, more preferably 95% by weight. %. When the content of the inorganic filler (C) in the second insulating layer and the second curable composition is not less than the above lower limit and not more than the above upper limit, the cured state of the second insulating layer that is a cured product is favorable. And the adhesion between the second insulating layer, which is a cured product, and the conductive layer is considerably increased.

  From the viewpoint of improving both the thermal conductivity of the entire insulating layer and the adhesion between the second insulating layer, which is a cured product, and the conductive layer in a well-balanced manner, the insulation located on the surface of the insulating layer on the copper plate side The content of the inorganic filler in the layer portion is preferably larger than the content of the inorganic filler in the insulating layer portion located on the surface opposite to the copper plate side of the insulating layer, more preferably 1% by weight or more. More preferably 5% by weight or more, and more preferably 10% by weight or more. From the viewpoint of improving both the thermal conductivity of the entire insulating layer and the adhesion between the second insulating layer, which is a cured product, and the conductive layer in a balanced manner, an inorganic filler (100 wt% of the first insulating layer) The content of C) is preferably greater than the content of the inorganic filler (C) in 100% by weight of the second insulating layer, more preferably 1% by weight or more, and more preferably 5% by weight or more. Preferably, it is more than 10% by weight.

  From the viewpoint of improving both the thermal conductivity of the entire insulating layer and the adhesion between the second insulating layer, which is a cured product, and the conductive layer in a well-balanced manner, an inorganic filler (100% by weight of the second insulating layer) Ratio of content of C) to content of inorganic filler (C) in 100% by weight of first insulating layer (content of inorganic filler (C) in 100% by weight of second insulating layer / first The content of the inorganic filler (C) in 100% by weight of the insulating layer) is preferably 0.7 or more, and preferably 0.95 or less.

(Other ingredients)
The insulating layer and the curable composition may include a polymer having a weight average molecular weight of 10,000 or more. As for this polymer, only 1 type may be used and 2 or more types may be used together.

  As the polymer, a curable resin such as a thermoplastic resin and a thermosetting resin can be used. The polymer is preferably a curable resin.

  The thermoplastic resin and thermosetting resin are not particularly limited. The thermoplastic resin is not particularly limited, and examples thereof include styrene resin, phenoxy resin, phthalate resin, thermoplastic urethane resin, polyamide resin, thermoplastic polyimide resin, ketone resin, and norbornene resin. The thermosetting resin is not particularly limited, and examples thereof include amino resins, phenol resins, thermosetting urethane resins, epoxy resins, thermosetting polyimide resins, and amino alkyd resins. Examples of the amino resin include urea resin and melamine resin.

  From the viewpoint of suppressing the oxidative degradation of the cured product, further improving the heat cycle resistance and heat resistance of the cured product, and further reducing the water absorption rate of the cured product, the polymer is a styrene resin, phenoxy resin or epoxy resin. It is preferable that it is a phenoxy resin or an epoxy resin, more preferably a phenoxy resin. In particular, use of a phenoxy resin or an epoxy resin further increases the heat resistance of the cured product. Moreover, use of a phenoxy resin further lowers the elastic modulus of the cured product and further improves the cold-heat cycle characteristics of the cured product. The polymer may not have a cyclic ether group such as an epoxy group.

  As the styrene resin, specifically, a homopolymer of a styrene monomer, a copolymer of a styrene monomer and an acrylic monomer, or the like can be used. Among these, a styrene polymer having a styrene-glycidyl methacrylate structure is preferable.

Examples of the styrene monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-
Chlorostyrene, p-ethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, Examples thereof include pn-dodecylstyrene, 2,4-dimethylstyrene, 3,4-dichlorostyrene, and the like.

  Specifically, the phenoxy resin is, for example, a resin obtained by reacting an epihalohydrin with a divalent phenol compound, or a resin obtained by reacting a divalent epoxy compound with a divalent phenol compound.

  The phenoxy resin comprises a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol A / F mixed skeleton, a naphthalene skeleton, a fluorene skeleton, a biphenyl skeleton, an anthracene skeleton, a pyrene skeleton, a xanthene skeleton, an adamantane skeleton, and a dicyclopentadiene skeleton. It is preferred to have at least one skeleton selected from the group. Among these, the phenoxy resin preferably has at least one skeleton selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol A / F mixed skeleton, a naphthalene skeleton, a fluorene skeleton, and a biphenyl skeleton. Preferably, it has at least one skeleton of a fluorene skeleton and a biphenyl skeleton. Use of the phenoxy resin having these preferable skeletons further increases the heat resistance of the cured product.

  The epoxy resin is an epoxy resin other than the phenoxy resin. Examples of the epoxy resins include styrene skeleton-containing epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, biphenol type epoxy resins, naphthalene type epoxy resins, and fluorene type epoxy resins. , Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, epoxy resin having adamantane skeleton, epoxy resin having tricyclodecane skeleton, and epoxy resin having triazine nucleus in skeleton Etc.

  In the total 100% by weight of the total resin component X, the total 100% by weight of the total resin component X1, and the total 100% by weight of the total resin component X2, the content of the polymer is preferably 20% by weight or more. Preferably it is 30 weight% or more, Preferably it is 60 weight% or less, More preferably, it is 50 weight% or less. When the content of the polymer is not less than the above lower limit, the handleability of the curable composition is improved. When the polymer content is not more than the above upper limit, dispersion of the inorganic filler (C) becomes easy. The all resin components X, X1, and X2 include a polymer.

  The insulating layer and the curable composition may contain rubber particles. Use of the rubber particles increases the stress relaxation property and flexibility of the cured product. The insulating layer and the curable composition may contain a dispersant. Use of the dispersant further increases the thermal conductivity and voltage resistance of the cured product.

  The insulating layer and the curable composition may contain a base material such as glass cloth, glass nonwoven fabric, and aramid nonwoven fabric. The insulating layer and the curable composition preferably do not contain a base material, and particularly preferably do not contain glass cloth. When the insulating layer and the curable composition do not contain the base material, the thickness of the entire insulating layer is reduced, and the thermal conductivity of the cured product is further increased. Various processing such as laser processing or drilling can be easily performed. The insulating layer may not be a prepreg.

Furthermore, the insulating layer and the curable composition may be a silane coupling agent, an antioxidant, an ion scavenger, a tackifier, a plasticizer, a thixotropic agent, a photosensitizer, and a color as necessary. An agent or the like may be included. The all resin components X, X1, and X2 contain a silane coupling agent.

(Details of laminate)
The method for forming the first and second silicon oxide films is not particularly limited. As this formation method, for example, there is a method in which a silicon oxide film is formed by placing a material to be a silicon oxide film on the surface of a copper plate and then heating the material. As a method of arranging a material to be a silicon oxide film on the surface of the copper plate, a material to be a silicon oxide film or a material solution obtained by diluting the material with a solvent or the like is spin-coated, roll coating, spray coating, curtain coating, Examples of the method include coating by various printing methods such as dip coating, flexographic printing, and offset printing. The method for forming the first and second silicon oxide films is not limited to this method.

  The manufacturing method of the said laminated body is not specifically limited. As this manufacturing method, for example, the curable composition is applied by a solvent casting method or the like on a copper plate on which a first silicon oxide film is laminated, and the curable composition is cured as necessary. And a method of forming an insulating layer. Curing of the curable composition may be performed before the insulating layer is laminated on the copper plate, may be performed after being laminated, or may be performed before the protective film is laminated on the insulating layer. It may be performed after being laminated. Moreover, the manufacturing method of the said laminated body is not limited to this method. Further, the first silicon oxide film may be formed after the insulating layer is formed.

  In addition, when the insulating layer is a multilayer, the method for manufacturing the laminate is not particularly limited. As this manufacturing method, for example, the above-mentioned curable composition is applied by a solvent casting method or the like on a copper plate on which a first silicon oxide film is laminated, and the curing of the first curable composition is allowed to proceed. After forming the first insulating layer, the second curable composition described above is applied onto the first insulating layer by a solvent cast method or the like, and the second curable composition is applied as necessary. A method of forming a second insulating layer by advancing the curing of the product, and the above-mentioned curable composition sheet by coating the first curable composition described above on a release film by a solvent casting method or the like. After the formation, the curable composition sheet is laminated on the copper plate on which the first silicon oxide film is laminated, and then the curable composition is cured as necessary to form an insulating layer. After the curing of the curable composition 1 is advanced to form the first insulating layer, the first insulating layer is formed on the first insulating layer. The second curable composition sheet formed in the same manner is laminated on the first insulating layer, and the second curable composition is cured as necessary to form the second insulating layer. Etc. Moreover, hardening of a 1st curable composition may be performed after the lamination and application | coating of a 2nd curable composition. Curing of the first curable composition may be performed before or after the first insulating layer is laminated on the copper plate. In addition, the first and second insulating layers may be formed by an extrusion method. Moreover, the manufacturing method of the said laminated body is not limited to these methods.

  The thermal conductivity of the insulating layer (the entire insulating layer) is preferably 2 W / m · K or more, more preferably 3 W / m · K or more, still more preferably 4 W / m · K or more, and particularly preferably 5 W / m · K. That's it. The higher the thermal conductivity of the insulating layer, the higher the thermal conductivity of the entire insulating layer.

  The dielectric breakdown voltage of the cured insulating layer (the entire insulating layer) is preferably 30 kV or higher, more preferably 40 kV or higher, still more preferably 50 kV or higher, particularly preferably 80 kV or higher, and most preferably 100 kV or higher. The higher the dielectric breakdown voltage, the more sufficient insulation can be ensured when the laminate is used for large current applications such as for power devices.

  In FIG. 1, an example of the laminated body which concerns on one Embodiment of this invention is shown with sectional drawing.

A laminate 1 shown in FIG. 1 includes a copper plate 2, an insulating layer 3, a first silicon oxide film 4, and a second silicon oxide film 5. Note that the second silicon oxide film 5 may be omitted. The insulating layer 3 includes a first insulating layer 3A and a second insulating layer 3B.

  The first silicon oxide film 4 is laminated on the first surface of the copper plate 2. The second silicon oxide film 5 is laminated on the second surface opposite to the first surface of the copper plate 2. The insulating layer 3 is disposed on the second surface side of the copper plate 2. The insulating layer 3 is laminated on the surface opposite to the copper plate 3 side of the second silicon oxide film 5. The first insulating layer 3 </ b> A is disposed on the second surface side of the copper plate 2. The first insulating layer 3A is laminated on the surface of the second silicon oxide film 5 opposite to the copper plate 3 side. The second insulating layer 3B is laminated on the surface opposite to the copper plate 2 side of the first insulating layer 3A.

  FIG. 2 is a cross-sectional view showing an example of a power semiconductor module component obtained using the laminate according to one embodiment of the present invention.

  A power semiconductor module component 11 shown in FIG. 2 is formed using the above-described laminate 1. However, the insulating layer 3 in the laminate 1 is cured.

  The power semiconductor module component 11 includes a first silicon oxide film 4, a copper plate 2, an insulating layer 3 that is a cured product, a second silicon oxide film 5, a conductive layer 12, and a mold resin 13. . The insulating layer 3 that is a cured product includes a first insulating layer 3A that is a cured product, and a second insulating layer 3B that is a cured product.

  The conductive layer 12 is laminated on the surface of the insulating layer 3 opposite to the copper plate 2 side. The conductive layer 12 is laminated on the surface of the second insulating layer 3B opposite to the first insulating layer 3A side. The first silicon oxide film 4, the copper plate 2, the second silicon oxide film 5, the insulating layer 3, and the conductive layer 12 are embedded in the mold resin 13. Part of the conductive layer 12 is preferably exposed from the mold resin 13.

  In the power semiconductor module component 11, the conductive layer 12 is laminated on the surface of the insulating layer 3 in the laminate 1, and then the insulating layer 3 is cured, and the copper plate 2, the insulating layer 3, and the conductive layer 12 are molded resin 13. It is obtained by embedding in. At this time, the first silicon oxide film 4, the copper plate 2, the second silicon oxide film 5, the insulating layer 3, and the conductive layer 12 are embedded in the mold resin 13 so that a part of the conductive layer 12 is exposed. Is preferred. Alternatively, the insulating layer 3 may be cured after the first silicon oxide film 4, the copper plate 2, the second silicon oxide film 5, the insulating layer 3, and the conductive layer 12 are embedded in the mold resin 13. For example, the insulating layer 3 may be cured when the mold resin 13 is cured.

  It is preferable that the laminated body which concerns on this invention is a laminated body used for components for power semiconductor modules. Moreover, the use of the laminate is not limited to the power semiconductor module component described above. Using the above laminated body, for example, a metal body is bonded to each conductive layer such as a laminated board or a multilayer wiring board provided with copper circuits on both sides, a copper foil, a copper plate, a semiconductor element or a semiconductor package via an insulating layer. Various electronic components that are used may be obtained. The laminate is suitably used for bonding a copper plate to a conductive layer of a semiconductor device in which a semiconductor element is mounted on a substrate. Furthermore, the laminate is also preferably used for bonding a copper plate to a conductive layer of an electronic component device in which electronic component elements other than semiconductor elements are mounted on a substrate.

The laminate is used by arranging the laminate on a surface opposite to the lead frame, a semiconductor element mounted on the surface of the lead frame, and a surface of the lead frame on which the semiconductor element is mounted. It is preferred that The laminate includes a lead frame, a semiconductor element mounted on a surface of the lead frame, an insulating layer disposed on a surface side of the lead frame opposite to the surface on which the semiconductor element is mounted, It is preferably used for obtaining a semiconductor device having a copper plate disposed on the surface side opposite to the lead frame side of the insulating layer. The laminate is suitably used to obtain a semiconductor device sealed with a mold resin by transfer molding so that the surface opposite to the surface in contact with the insulating layer of the copper plate is exposed. The laminate was sealed with mold resin by transfer molding so that the surface of the first silicon oxide film opposite to the surface where the insulating layer is laminated is exposed via the copper plate. It is suitably used for obtaining a semiconductor device.

  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 order to form the insulating layer, the following materials were prepared.

[polymer]
(1) Bisphenol A type phenoxy resin (“E1256” manufactured by Mitsubishi Chemical Corporation, Mw = 51000)
(2) Polystyrene (“HRM26” manufactured by Toyo Styrene Co., Ltd., Mw = 300,000)

[Curable compound (A)]
(1) Bisphenol A liquid epoxy resin ("Epicoat 828US" manufactured by Mitsubishi Chemical Corporation, Mw = 370)
(2) Bisphenol F type liquid epoxy resin (“Epicoat 806L” manufactured by Mitsubishi Chemical Corporation, Mw = 370)
(3) Naphthalene skeleton liquid epoxy resin (“EPICLON HP-4032D” manufactured by DIC, Mw = 304)
(4) Biphenyl skeleton epoxy resin (“Epicoat YX4000” manufactured by Mitsubishi Chemical Corporation, Mw = 368)

[Curing agent (B)]
(1) Alicyclic skeleton acid anhydride (“MH-700” manufactured by Shin Nippon Rika Co., Ltd.)
(2) Biphenyl skeleton phenolic resin (“MEH-7851-S” manufactured by Meiwa Kasei Co., Ltd.)
(3) Diaminodiphenylmethane (melting point 90 ° C)
(4) Dicyandiamide (melting point 208 ° C)
(5) Isocyanur-modified solid dispersion type imidazole (“2MZA-PW” manufactured by Shikoku Kasei Co., Ltd., melting point 253 ° C.)

[Inorganic filler (C)]
(1) 5 μm crushed alumina (crushed filler, “LT300C” manufactured by Nippon Light Metal Co., Ltd., average particle diameter 5 μm, maximum particle diameter 15 μm, thermal conductivity 36 W / m · K, new Mohs hardness 12)
(2) Spherical alumina (“DAM-10” manufactured by Denka Co., Ltd., average particle size 10 μm, maximum particle size 30 μm, thermal conductivity 36 W / m · K, new Mohs hardness 12)
(3) Aluminum nitride (“TOYALNITE-FLX” manufactured by Toyo Aluminum Co., Ltd., average particle size 14 μm, maximum particle size 30 μm, thermal conductivity 200 W / m · K, new Mohs hardness 11)
(4) Crystalline silica (“Crystallite CMC-12” manufactured by Tatsumori Co., Ltd., average particle size 5 μm, maximum particle size 20 μm, thermal conductivity 10 W / m · K, new Mohs hardness 9)
(5) Boron nitride agglomerated particles (“TPX25” manufactured by Momentive, average particle diameter 25 μm, maximum particle diameter 100 μm, thermal conductivity 60 W / m · K, new Mohs hardness 2)

[Additive]
(1) Epoxysilane coupling agent (“KBE402” manufactured by Shin-Etsu Chemical Co., Ltd.)

[solvent]
(1) Methyl ethyl ketone In order to form a surface treatment film on the surface of a copper plate, the following materials were prepared.

[Silicon surface treatment agent for forming a silicon oxide film on the surface of a copper plate]
(1) Type 1: Surface treatment agent 1 (2 wt% solution of tetrafunctional ethyl silicate hydrolyzate)
(2) Type 2: Surface treatment agent 2 (perhydropolysilazane solution (“NP-110” manufactured by Clariant))
(3) Type 3: Surface treatment agent 3 (tetraisocyanate silane (“Orgatics SI-400” manufactured by Matsumoto Fine Chemical Co., Ltd.))

[Surface treatment agent for forming a film other than a silicon oxide film on the surface of a copper plate]
(1) Type A: Surface treatment agent A (epoxysilane coupling agent (“KBE403” manufactured by Shin-Etsu Chemical Co., Ltd.))
(2) Type B: Surface treatment agent B (acrylic hard coat agent)

Example 1
A copper plate having a thickness of 0.5 μm was prepared. A 2% by weight solution of tetrafunctional ethyl silicate hydrolyzate was spray-coated on the first surface of the copper plate so that the thickness of the resulting surface treatment film (first silicon oxide film) was 100 nm. After the application, it was dried at 130 ° C. for 10 minutes to obtain a copper plate on which the surface treatment film was laminated.

  Next, an alumina ceramic layer (insulating layer) having a thickness of 100 μm was laminated on the second surface of the copper plate to obtain a laminate.

(Example 2)
A copper plate having a thickness of 0.5 μm was prepared. A 2% by weight solution of a tetrafunctional alkoxysilane hydrolyzate was spray-applied to the first surface of the copper plate so that the thickness of the resulting surface treatment film (first silicon oxide film) was 100 nm. After the application, it was dried at 130 ° C. for 10 minutes to obtain a copper plate on which the surface treatment film was laminated.

  A first curable composition for forming a first insulating layer, using a homodisper type stirrer, blending and kneading each component in the proportions shown in Table 1 below (the blending unit is parts by weight), and A second curable composition for forming a second insulating layer was prepared.

  The first curable composition was applied onto a release PET sheet having a thickness of 50 μm and dried in an oven at 90 ° C. for 30 minutes to produce a first insulating layer having a thickness of 80 μm on the PET sheet. In addition, the second curable composition was coated on a release PET sheet having a thickness of 50 μm and dried in an oven at 90 ° C. for 30 minutes to produce a second insulating layer having a thickness of 80 μm on the PET sheet. .

  The obtained first insulating layer was bonded on the second surface of the copper plate on which the surface treatment film was laminated using a thermal laminator, and then at 200 ° C. for 1 hour (of the first curable composition). Curing conditions) Cured. Thereafter, the second insulating layer is bonded onto the first insulating layer using a thermal laminator, and then cured at 130 ° C. for 3 minutes (curing conditions for the second curable composition) to produce a laminate. did.

(Examples 3 to 30 and Comparative Examples 1 and 2)
The types of materials used to form the surface treatment film, the thickness of the surface treatment film, the thickness of the copper plate, the types and amounts of each component used in the first and second curable compositions are shown in Tables 1 to 3 below. A surface treatment film was formed in the same manner as in Example 2 except that it was as shown in FIG. 4, and a curable composition was prepared to obtain a laminate. In Comparative Examples 1 and 2, a film other than the silicon oxide film was formed on the first surface of the copper plate.

(Comparative Example 3)
A curable composition was prepared in the same manner as in Example 2 except that the surface treatment film was not formed on the surface of the copper plate without subjecting the copper plate to a surface treatment, and a laminate was obtained.

(Evaluation)
(1) Processability of laminated body The obtained laminated body was cut by press punching into a size of 5 cm x 5 cm with a 45 ton press to obtain an evaluation sample. The surface treatment film of the obtained evaluation sample was observed with a magnifying glass having a magnification of 10 times. The processability of the 10 laminates was determined according to the following criteria.

[Judgment criteria for laminate workability]
○: No cracking of the surface treatment film and peeling of the surface treatment film from the copper plate in 10 laminates. Δ: No cracking of the surface treatment film or peeling of the surface treatment film from the copper plate in 10 laminates. The number of generated laminates is 1 to 3 ×: in 10 laminates, the number of laminates in which the surface treatment film is cracked or the surface treatment film is peeled off from the copper plate is 4 or more

(2) Oxidation-resistant discoloration of copper plate The obtained laminate was cut by press punching into a size of 5 cm × 5 cm with a 45 ton press to obtain an evaluation sample. The obtained evaluation sample was heat-treated in an oven at 170 ° C. for 10 hours. The degree of discoloration due to oxidation of the copper plate was observed from the brightness of the surface of the laminate before and after the heat treatment on the surface treatment film side (in Comparative Example 3, the surface on the copper plate side). The oxidation resistance change of the copper plate was determined according to the following criteria.

[Criteria for oxidation resistance change of copper plate]
○: The luminance after heat treatment is 70% or more of the luminance before heat treatment Δ: The luminance after heat treatment is 50% or more and less than 70% of the luminance before heat treatment ×: The luminance after heat treatment is less than 50% of the luminance before heat treatment

(3) Scratch resistance of copper plate The laminate was placed on a stainless steel plate (surface treatment finish No. 6) with the surface treatment film side (copper plate side in Comparative Example 3) facing down. Furthermore, after the roller was reciprocated 5 times at a distance of 5 cm with a load of 1 kg on the surface of the laminate on the stainless steel plate, scratches on the surface of the copper plate after this reciprocation treatment were observed. The scratch resistance of the copper plate was determined according to the following criteria.

[Criteria for scratch resistance of copper plate]
○: 3 or less scratches with a depth of 10 μm or more and a length of 3 cm or more Δ: 4 to 10 scratches with a depth of 10 μm or more and a length of 3 cm or more ×: 11 scratches with a depth of 10 μm or more and a length of 3 cm or more More than books

(4) Dielectric breakdown voltage (withstand voltage)
The obtained laminate was cut into a size of 5 cm × 5 cm by press punching with a 45 ton press. Thereafter, an insulating layer having a size of 5 cm × 5 cm (entire insulating layer) was taken out to obtain an evaluation sample. The obtained evaluation sample was cured in an oven at 200 ° C. for 1 hour to obtain an insulating layer as a cured product. Using a withstand voltage tester (“MODEL7473” manufactured by EXTECH Electronics), an AC voltage was applied between the insulating layers so that the voltage increased at a rate of 1 kV / sec. The voltage at which the insulating layer was broken was taken as the breakdown voltage.

(5) Heat dissipation The obtained laminate was cut into a size of 5 cm × 5 cm by press punching with a 45 ton press to obtain an evaluation sample. Using the obtained evaluation sample, the surface of the insulating layer was pressed at a pressure of 196 N / cm ² against a heating element with a smooth surface controlled to 60 ° C. of the same size. The surface temperature of the copper plate was measured by a thermocouple. The heat dissipation was determined according to the following criteria.

[Criteria for heat dissipation]
○: Temperature difference between the heating element and the surface of the copper plate exceeds 3 ° C. and within 6 ° C. Δ: Temperature difference between the heating element and the surface of the copper plate exceeds 6 ° C. and within 10 ° C. ×: Temperature of the heating element on the surface of the copper plate The difference exceeds 10 ° C

(6) Adhesiveness Using the obtained laminated body, it heated at 200 degreeC for 1 hour, pressing the electrolytic copper foil of thickness 35 micrometers on the surface of an insulating layer with the pressure of 1 MPa. Thereafter, the peel strength between the insulating layer, which is a cured product, and the copper foil was measured by a 90 ° peel test.

  The blending components and results are shown in Tables 1 to 4 below.

DESCRIPTION OF SYMBOLS 1 ... Laminated body 2 ... Copper plate 3 ... Insulating layer 3A ... 1st insulating layer 3B ... 2nd insulating layer 4 ... 1st silicon oxide film 5 ... 2nd silicon oxide film 11 ... Power semiconductor module components 12 ... Conductive layer 13 ... Mold resin

Claims (12)

A copper plate, a first silicon oxide film laminated on the first surface of the copper plate, and an insulating layer disposed on the second surface side opposite to the first surface of the copper plate. Using the laminate,
Laminating a conductive layer on the surface of the insulating layer opposite to the copper plate side;
Curing the insulating layer;
A method for manufacturing a component for a power semiconductor module, comprising: embedding the first silicon oxide film, the copper plate, the insulating layer, and the conductive layer in a mold resin.   The method for manufacturing a power semiconductor module component according to claim 1, wherein the insulating layer includes an inorganic filler having a thermal conductivity of 10 W / m · K or more.   The said insulating layer is formed using the curable composition containing the sclerosing | hardenable compound, the hardening | curing agent, and the inorganic filler whose heat conductivity is 10 W / m * K or more. A method for manufacturing power semiconductor module components.   The manufacturing method of the components for power semiconductor modules of any one of Claims 1-3 whose thickness of a said 1st silicon oxide film is 10 nm or more and 1 micrometer or less.   5. The power semiconductor module according to claim 1, wherein a curing rate of the surface of the insulating layer on the copper plate side is larger than a curing rate of the surface of the insulating layer opposite to the copper plate side. A manufacturing method for parts.   The first silicon oxide film according to any one of claims 1 to 5, wherein the first silicon oxide film is formed by a hydrolytic condensate of tetrafunctional alkoxysilane, a reaction product of polysilazane, or an active hydrogen reaction product of isocyanate silane. A method for manufacturing power semiconductor module components.   The manufacturing method of the components for power semiconductor modules of any one of Claims 1-6 whose thickness of the said copper plate is 100 micrometers or more and 5 mm or less.   8. The insulating layer according to claim 1, wherein the insulating layer contains an inorganic filler having a thermal conductivity of 10 W / m · K or more in an amount of 70 wt% or more and less than 95 wt% in 100 wt% of the insulating layer. The manufacturing method of the components for power semiconductor modules as described in 2 ..   The content of the inorganic filler in the insulating layer portion located on the surface of the insulating layer on the copper plate side is larger than the content of the inorganic filler in the insulating layer portion located on the surface opposite to the copper plate side of the insulating layer. The manufacturing method of the components for power semiconductor modules of any one of Claims 1-8.   The insulating layer is laminated on the second surface of the copper plate, or further comprising a second silicon oxide film laminated on the second surface of the copper plate, and the second silicon oxide film The manufacturing method of the components for power semiconductor modules of any one of Claims 1-9 by which the said insulating layer is laminated | stacked on the surface opposite to the said copper plate side.   The power according to any one of claims 1 to 10, wherein a conductive layer is laminated on a surface of the insulating layer opposite to the copper plate side, using a cut laminate obtained by cutting the laminate. Manufacturing method of semiconductor module components.   The manufacturing method of the components for power semiconductor modules of Claim 11 which cut | disconnect the said laminated body by press punching.

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