JP2013075440A - Method for manufacturing laminate, and laminate structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a laminate which can obtain a laminate structure reducing surface roughness of an insulation film subjected to roughening processing, and having insulation properties through the insulation film.SOLUTION: The method for manufacturing the laminate 1 includes: a laminating step of laminating the laminate film 10 on a target laminated material 21 from a surface 11b side of the insulation film 11; a first heating step of heating the insulation film 11 until a gel decomposition after the insulation film 11 is immersed in methyl ethyl ketone at the temperature 23°C for 24 hours becomes 20 w.t.% or more without a substrate film 12 is separated from the insulation film 11; a separation step of separating the substrate film 11 from the insulation film 11A and exposing a surface 11a of the insulation film 11A; and roughening step of roughing the first surface 11a of the insulation film 11C.

Description

  The present invention relates to a method for manufacturing a laminate in which a roughened insulating film is laminated on a member to be laminated, and a laminate structure including a laminate obtained by the method for producing the laminate.

  Conventionally, various thermosetting resin compositions have been used to form multilayer substrates or semiconductor devices.

  For example, the following Patent Document 1 discloses an epoxy resin containing a bisphenol A type epoxy resin, a modified phenol novolac type epoxy resin having a phosphaphenanthrene structure, a phenol novolac curing agent having a triazine ring, and an inorganic filler. A composition is disclosed. Here, after forming a resin insulating layer by heating a prepreg, a resin film or a resin varnish formed of an epoxy resin composition at 100 to 200 ° C. for 1 to 90 minutes, the surface of the resin insulating layer is roughened with a roughening liquid. Roughening treatment is described.

JP 2008-074929 A

  In Patent Document 1, the surface roughness of the surface of the roughened resin insulation layer may not be sufficiently reduced. Furthermore, when a metal layer is formed on the surface of the resin insulation layer by plating, the adhesive strength between the resin insulation layer and the metal layer may be lowered. Furthermore, the insulating property of the resin insulating layer may be low.

  The object of the present invention is to reduce the surface roughness of the roughened insulating film, and further to provide a laminated body production method capable of obtaining a laminated structure excellent in insulation by the insulating film, and the It is providing a laminated structure provided with the laminated body obtained by the manufacturing method of the laminated body.

  The limited objective of this invention is to provide the manufacturing method of a laminated body and laminated structure which can suppress the dimensional change by the heat | fever of an insulating film.

  According to a wide aspect of the present invention, there is provided a method of manufacturing a laminate in which a roughened insulating film is laminated on a lamination target member, the insulating film and a substrate laminated on a first surface of the insulating film. A laminating step of laminating the laminated film on a member to be laminated from a second surface side opposite to the first surface of the insulating film, using the laminated film having a material film; and A first heating step in which the insulating film is heat treated until the gel fraction reaches 20% by weight or more after being immersed in methyl ethyl ketone at 23 ° C. for 24 hours without peeling off the insulating film; A laminate comprising: a peeling step of peeling off the film to expose the first surface of the insulating film; and a roughening step of roughening the first surface of the insulating film. The method of manufacturing is provided.

  In the first heating step, the insulating film is preferably heat-treated until the gel fraction after being immersed in methyl ethyl ketone for 24 hours at 23 ° C. is 60% by weight or more.

  On the specific situation with the manufacturing method of the laminated body which concerns on this invention, the 2nd heating process which heat-processes the said insulating film at 120-220 degreeC after the said peeling process and before the said roughening process further. Provided.

  In the first heating step, the insulating film is preferably heat-treated until the gel fraction after being immersed in methyl ethyl ketone at 23 ° C. for 24 hours is 90% by weight or more.

  In another specific aspect of the method for manufacturing a laminate according to the present invention, the insulating film includes a thermosetting resin and at least one of a fibrous reinforcing material and a filler having an average particle diameter of 1 μm or less.

  In 100% by weight of the component excluding the solvent of the insulating film, the total content of the fibrous reinforcing material and the filler is preferably 50% by weight or more. The thermosetting resin is preferably an epoxy resin. The epoxy resin is preferably a liquid epoxy resin. The insulating film preferably contains a curing agent. The curing agent is preferably at least one selected from the group consisting of a phenol curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine resin, and a cyanate ester resin.

  In another specific aspect of the method for producing a laminate according to the present invention, in the roughening step, the arithmetic average roughness Ra of the first surface subjected to the roughening treatment is 0.4 μm or less, and a ten-point average roughness. The first surface of the insulating film is roughened so that the thickness Rz is 4.0 μm or less.

  In still another specific aspect of the method for manufacturing a laminate according to the present invention, a swelling step of swelling the first surface of the insulating film is further performed after the peeling step and before the roughening step. In the roughening step, the first surface of the swelling insulating film is roughened.

  The laminated structure according to the present invention includes a laminate obtained by the above-described laminate production method, a metal layer laminated on the first surface of the insulating film subjected to the roughening treatment of the laminate, Is provided.

  The adhesive strength between the insulating film and the metal layer is preferably 4.9 N / cm or more.

  The manufacturing method of the laminated body which concerns on this invention uses the laminated | multilayer film which has an insulating film and the base film laminated | stacked on the 1st surface of this insulating film, and uses this laminated film for the 2nd surface of the said insulating film. Laminating step of laminating on the lamination target member from the side, and the gel fraction after immersing the insulating film in methyl ethyl ketone at 23 ° C. for 24 hours without peeling off the base film from the insulating film becomes 20% by weight or more. A first heating step in which the heat treatment is performed, a peeling step in which the base film is peeled from the insulating film to expose the first surface of the insulating film, and the first surface of the insulating film is roughened. Since the roughening process which carries out a roughening process is provided, the surface roughness of the 1st surface of the roughened insulating film can be made small effectively. Furthermore, when a laminated structure is obtained by laminating a metal layer on the first surface of the insulating film, the insulation by the insulating film can be enhanced.

Drawing 1 is a typical partial notch front sectional view for explaining each process of a manufacturing method of a layered product concerning one embodiment of the present invention. FIG. 2 is a schematic partially cutaway front sectional view for explaining each step of the method for manufacturing a laminate according to one embodiment of the present invention. FIG. 3 is a partially cutaway front cross-sectional view schematically showing a laminated structure using a laminated body obtained by the method for manufacturing a laminated body according to an embodiment of the present invention.

  Details of the present invention will be described below.

  The manufacturing method of the laminated body which concerns on this invention is a manufacturing method of the laminated body by which the roughened insulating film is laminated | stacked on the lamination | stacking object member. In the manufacturing method of the laminated body which concerns on this invention, the laminated film which has an insulating film and the base film laminated | stacked on the 1st surface of this insulating film is used. The manufacturing method of the laminated body which concerns on this invention is a layering process which laminates | stacks the said laminated | multilayer film on a lamination | stacking object member from the 2nd surface side opposite to the 1st surface of the said insulating film, and the said base film is insulated. A first heating step in which the insulating film is heat-treated until the gel fraction reaches 20% by weight or more after being immersed in methyl ethyl ketone at 23 ° C. for 24 hours without peeling off the film; And a peeling step for exposing the first surface of the insulating film, and a roughening step for roughening the first surface of the insulating film.

  In the manufacturing method of the laminated body which concerns on this invention, since the structure mentioned above is provided, the surface roughness of the 1st surface of the insulating film by which the roughening process was carried out can be made small. For example, even if the insulating film contains a fibrous reinforcing material or filler, the arithmetic average roughness Ra of the first surface of the roughened insulating film can be 0.4 μm or less, and the ten-point average roughness Rz can be 4.0 μm or less. Furthermore, when a laminated structure is obtained by laminating a metal layer on the first surface of the roughened insulating film, the peel strength between the roughened insulating film and the metal layer can be increased.

  Furthermore, in the manufacturing method of the laminated body which concerns on this invention, since the structure mentioned above is provided, the insulation by an insulating film can be improved in the said laminated structure. Moreover, even if the insulating film contains a fibrous reinforcing material or filler, the insulating properties of the insulating film are sufficiently high.

  Furthermore, in the manufacturing method of the laminated body which concerns on this invention, since the said 1st heating process is performed, without peeling the said base film from the said insulating film, flatness of the 1st surface of the insulating film before a roughening process is carried out. Can increase the sex. In the manufacturing method of the laminated body which concerns on this invention, even if the insulating film contains a fibrous reinforcement and a filler, for example, the flatness of the 1st surface of the insulating film before a roughening process can be improved. As a result, since the flatness of the first surface of the roughened insulating film is also increased, the metal layer can be formed on the first surface of the roughened insulating film with higher accuracy, and further finer Wiring can be formed.

  Furthermore, in the manufacturing method of the laminated body which concerns on this invention, a fibrous reinforcement and a filler can be mix | blended with sufficient quantity to an insulating film, obtaining the effect mentioned above. For example, the total content of the fibrous reinforcing material and the filler can be 50% by weight or more in 100% by weight of the component excluding the solvent of the insulating film while obtaining the effects described above. Thus, the dimensional change by the heat | fever of an insulating film can be suppressed by increasing the total content of the said fibrous reinforcement and the said filler.

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

  When obtaining a laminated body, first, the laminated film 10 shown to Fig.1 (a) is prepared. The laminated film 10 includes an insulating film 11 and a base film 12 laminated on the first surface 11 a of the insulating film 11. The insulating film 11 has an insulating property. The base film 12 is a support film that supports the insulating film 11. The second surface 11b opposite to the first surface 11a of the insulating film 11 is exposed. A protective film may be laminated on the second surface 11b of the insulating film 11 before use.

  Next, as shown in FIG.1 (b), the laminated | multilayer film 10 is laminated | stacked on the lamination | stacking object member 21 from the 2nd surface 11b side of the insulating film 11 (lamination process). Examples of the lamination target member 21 include a substrate or a metal layer.

  Then, as shown in FIG.1 (c), the gel fraction after immersing the insulating film 11 in methyl ethyl ketone for 24 hours at 23 degreeC, without peeling the base film 12 in the laminated | multilayer film 10 from the insulating film 11 is 20 weight. It heat-processes until it becomes% or more, and obtains the insulating film 11A (1st heating process).

  In the first heating step, with the base film 12 laminated on the first surface 11a of the insulating film 11, the insulating film 11 is heat-treated until the gel fraction reaches 20% by weight or more. The thermosetting reaction can proceed without causing the resin component to flow excessively. The fluidity of the resin component can be reduced after the base film 12 is peeled off by increasing the viscosity of the insulating film by the thermosetting reaction.

  Next, as shown in FIG.1 (d), the base film 12 is peeled from the insulating film 11A, and the 1st surface 11a of the insulating film 11A is exposed (peeling process). By performing the peeling step after the heating step, the flatness of the first surface 11a of the insulating film 11A is increased.

  After the peeling step and before the roughening step described later, the insulating film 11A is heat-treated at 120 to 220 ° C. to obtain the insulating film 11B as shown in FIG. 2 (a) (second heating) Process). Note that the second heating step is not necessarily provided. Without performing the second heating step, a swelling step described later may be performed, or a roughening step described later may be performed.

  Next, after the peeling step and before the roughening step, which will be described later, the first surface 11a of the insulating film 11B is swollen, and as shown in FIG. 2 (b), the swollen insulating film 11C is obtained (swelling step). In the present embodiment, since the second heating step is performed after the peeling step, the swelling step is performed after the second heating step and before the roughening step described later. Yes. In addition, the swelling process does not necessarily need to be provided. The roughening process mentioned later may be performed without performing the said swelling process. When the second heating step is not performed, the first surface 11a of the insulating film 11A is swelled.

  Next, the first surface 11a of the insulating film 11C is roughened to obtain a roughened insulating film 11D as shown in FIG. 2C (roughening step). Here, since the swelling process is performed, the first surface 11a of the insulating film 11C subjected to the swelling treatment is roughened. In the roughening step, the first surface 11a subjected to the roughening treatment has an arithmetic average roughness Ra of 0.4 μm or less and a ten-point average roughness Rz of 4.0 μm or less. 1 surface 11a is preferably roughened. When the swelling process is not performed and the second heating process is not performed, the first surface 11a of the insulating film 11A is roughened. When the swelling process is not performed and the second heating process is performed, the first surface 11a of the insulating film 11B is roughened.

  Thus, the laminated body 1 by which the roughened insulating film 11D shown in FIG. 2C is laminated on the lamination target member 21 can be obtained. In the laminated body 1, the flatness of the first surface 11a of the roughened insulating film 11D is excellent. For this reason, when the insulating layer of a printed wiring board is formed, for example with insulating film 11D of the laminated body 1, the flatness of the surface of an insulating layer can be improved. For this reason, a metal layer can be accurately formed on the surface of the insulating layer, and a fine metal wiring can also be formed.

  In this embodiment, excessive flow of the resin component is suppressed. Hereinafter, problems that occur when the resin component flows excessively will be described.

  For example, when the insulating film contains a fiber reinforcing material and a filler, the total content of the fibrous reinforcing material and the filler in 100% by weight of the component excluding the solvent of the insulating film is 50% by weight or more. By excessively flowing the resin component, the amount of the resin component is reduced near the surface of the insulating film, and the amount of the fibrous reinforcing material and filler is increased. In particular, for example, a fibrous reinforcing material hardly flows together with a resin component, so that so-called resin withering occurs. When resin withering proceeds excessively, the fibrous reinforcing material is exposed on the surface. In particular, when a fibrous reinforcing material such as glass cloth is used, the resin withering phenomenon and the exposure of the fibrous reinforcing material occur remarkably. Moreover, when the abundance of the fibrous reinforcing material and filler in the vicinity of the surface of the insulating film increases, the following first and second problems also occur.

  The first problem is that since the resin component is small during the roughening treatment, it is easily etched excessively, and the surface roughness of the insulating film after the roughening treatment is increased. When the surface roughness is increased, when an insulating layer such as a printed wiring board is formed from an insulating film, for example, fine wiring such as L / S = 13 μm / 13 μm cannot be formed on the surface of the insulating layer. The second problem is that when the amount of fibrous reinforcing material and filler in the vicinity of the surface of the insulating film increases, the insulating film easily absorbs water, resulting in a decrease in insulation due to water absorption. When moisture enters the insulating film through the fiber surface, fatal problems such as migration occur.

  In the method for producing a laminate according to the present invention, by heat-treating the insulating film after being immersed in methyl ethyl ketone at 23 ° C. for 24 hours without peeling off the base film until the gel fraction becomes 20% by weight or more, The thermosetting reaction can proceed without causing the resin component to flow excessively. By increasing the viscosity by the thermosetting reaction of the insulating film, the fluidity of the resin component can be reduced after the base film is peeled off. Therefore, the surface roughness of the roughened first surface can be reduced. Furthermore, when a metal layer such as a copper plating layer is formed on the surface of the insulating film, the insulating properties of the insulating film can be enhanced. Therefore, when an insulating layer such as a printed wiring board is formed from an insulating film, fine wiring can be formed and high insulation can be exhibited. As mentioned above, in the manufacturing method of the laminated body which concerns on this invention, generation | occurrence | production of the above-mentioned 1st problem and a 2nd problem can be suppressed.

  From the viewpoint of further reducing the surface roughness of the first surface of the roughened insulating film, it is preferable that the gel fraction after being immersed in methyl ethyl ketone of the insulating film at 23 ° C. for 24 hours is higher. The gel fraction is preferably 30% by weight or more, more preferably 40% by weight or more, still more preferably 50% by weight or more, still more preferably 60% by weight or more, still more preferably 70% by weight or more, particularly preferably. 80% by weight or more, more particularly preferably 90% by weight or more, and most preferably 95% by weight or more.

  Moreover, the flatness of the insulating film before a roughening process can be improved much more effectively by the said gel fraction being 60 weight% or more. In addition, since the fluidity of the resin component is more effectively lowered after the base film is peeled off, when a metal layer such as a copper plating layer is formed on the first surface of the insulating film, the insulating property by the insulating film Can be further increased.

  Further, the insulating film subjected to the roughening treatment is subjected to the roughening treatment by making the gel fraction after being immersed in methyl ethyl ketone for 24 hours at 23 ° C. for 90% by weight or more, further 95% by weight or more. The surface roughness of the first surface can be further reduced.

  In order to easily peel off the base film from the insulating film, the surface of the base film may be subjected to a release treatment as necessary. For the purpose of facilitating peeling of the base film, the gel fraction may be lowered within the scope of the present invention, and the base film may be peeled off.

  In order to reduce the surface roughness of the roughened cured product, it is also effective to additionally heat after peeling off the base film. In the present invention, such additional heating may be performed.

  When the total content of the fibrous reinforcing material and the filler is 50% by weight or more in 100% by weight of the component excluding the solvent of the insulating film, the effect of reducing the surface roughness and improving the insulating properties Is effectively expressed. When the total content of the fibrous reinforcing material and the filler is 50% by weight or more in 100% by weight of the component excluding the solvent of the insulating film, the resin component is separated from the fibrous reinforcing material and the filler. It becomes easy. However, without removing the base film, the viscosity is increased due to the thermosetting reaction of the resin component by heat treatment until the gel fraction reaches 20% by weight or more after the insulating film is immersed in methyl ethyl ketone at 23 ° C. for 24 hours. The separation of the resin component from the fibrous reinforcing material and the filler can be effectively suppressed.

  The laminated structure according to the present invention includes a laminate obtained by the above-described laminate production method, and a metal layer laminated on the first surface of the insulating film subjected to the roughening treatment of the laminate. Prepare. The adhesive strength between the insulating film and the metal layer is preferably 4.9 N / cm or more.

  In FIG. 3, the laminated structure using the laminated body obtained by the manufacturing method of the laminated body which concerns on one Embodiment of this invention is typically shown with a partial notch front sectional drawing.

  In the laminated structure 51 shown in FIG. 3, a plurality of cured product layers 53 to 56 are laminated on the upper surface 52 a of the circuit board 52. The laminated structure 51 is a multilayer substrate. The cured product layers 53 to 56 are insulating films and are insulating layers. A metal layer 57 is formed in a partial region of the upper surface 52 a of the circuit board 52. Among the plurality of cured product layers 53 to 56, the cured product layers 53 to 55 other than the cured product layer 56 located on the outer surface opposite to the circuit board 52 side include a metal layer in a partial region of the upper surface. 57 is formed. The metal layer 57 is a circuit. Metal layers 57 are arranged between the circuit board 52 and the cured product layer 53 and between the laminated cured product layers 53 to 56, respectively. The lower metal layer 57 and the upper metal layer 57 are connected to each other by at least one of a via hole connection and a through hole connection (not shown).

  In the laminated structure 51, the cured product layers 53 to 56 are formed by curing the insulating film in the laminated body obtained by the method for producing a laminated body according to the present invention. In this embodiment, since the surfaces of the cured product layers 53 to 56 are roughened, fine holes (not shown) are formed on the surfaces of the cured product layers 53 to 56. Further, the metal layer 57 reaches the inside of the fine hole. Moreover, in the laminated structure 51, the width direction dimension (L) of the metal layer 57 and the width direction dimension (S) of the part in which the metal layer 57 is not formed can be reduced. In the laminated structure 51, good insulation reliability is imparted between an upper metal layer and a lower metal layer that are not connected by via-hole connection and through-hole connection (not shown).

  The insulating film preferably includes a thermosetting resin, preferably includes a curing agent, and preferably includes at least one of a fibrous reinforcing material and a filler. Hereinafter, the details of the thermosetting resin, the curing agent, the fibrous reinforcing material, and the filler used for the insulating film will be described.

[Thermosetting resin]
The thermosetting resin is not particularly limited. A conventionally known thermosetting resin can be used as the thermosetting resin. Examples of the thermosetting resin include epoxy resins, cyanate ester resins, phenol resins, bismaleimide-triazine resins, polyimide resins, acrylic resins, and vinylbenzyl resins. As for the said thermosetting resin, only 1 type may be used and 2 or more types may be used together.

  The epoxy resin is not particularly limited. A conventionally well-known epoxy resin can be used as this epoxy resin. The epoxy resin refers to an organic compound having at least one epoxy group. The epoxy resin preferably has two or more epoxy groups. Epoxy resins also include epoxy resin derivatives and epoxy resin hydrogenated products. As for the said epoxy resin, only 1 type may be used and 2 or more types may be used together.

  Examples of the epoxy resin include aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, glycidyl acrylic type epoxy resins, and polyester type epoxy resins. .

  A flexible epoxy resin is preferably used as the epoxy resin. Use of the flexible epoxy resin increases the flexibility of the cured product.

  Examples of the flexible epoxy resin include diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, polyglycidyl ether of long chain polyol, a copolymer of glycidyl (meth) acrylate and a radical polymerizable monomer, and an epoxy group. Polyester resin having a conjugated diene compound as a main component, a compound obtained by epoxidizing a carbon-carbon double bond of a (co) polymer, a carbon-carbon as a partially hydrogenated product of a (co) polymer mainly including a conjugated diene compound Examples thereof include compounds obtained by epoxidizing double bonds, urethane-modified epoxy resins, and polycaprolactone-modified epoxy resins.

  Further, the flexible epoxy resin includes a dimer acid-modified epoxy resin in which an epoxy group is introduced into the molecule of dimer acid or a dimer acid derivative, and a rubber-modified epoxy in which an epoxy group is introduced into the molecule of the rubber component. Examples thereof include resins.

  Examples of the rubber component include NBR, CTBN, polybutadiene, and acrylic rubber.

  The flexible epoxy resin preferably has a butadiene skeleton. Use of a flexible epoxy resin having a butadiene skeleton further increases the flexibility of the cured product. Further, the elongation of the cured product is increased over a wide temperature range from a low temperature range to a high temperature range.

  The epoxy resin includes an adamantane type epoxy resin having an adamantane structure, a naphthalene type epoxy resin having a naphthalene structure, a dicyclopentadiene type epoxy resin having a dicyclopentadiene structure, a biphenyl type epoxy resin having a biphenyl structure, and an anthracene having an anthracene structure Preferably, it is a type epoxy resin, naphthylene ether type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin or bisphenol S type epoxy resin. Among these, bisphenol A type epoxy resin or bisphenol F type epoxy resin is more preferable.

  The epoxy resin is preferably a liquid epoxy resin. The liquid epoxy resin refers to an epoxy resin that is liquid at 25 ° C. Among the liquid epoxy resins, bisphenol A type epoxy resins are preferable. By using the said liquid epoxy resin, even when many below-mentioned fillers are mix | blended, the fluidity | liquidity of the resin varnish obtained can be ensured and favorable handling property can be ensured. In general, the use of a liquid epoxy resin reduces the viscosity of the resulting insulating resin varnish, and when the insulating resin varnish is applied to a base film or the like, the flatness of the insulating film obtained by subsequent heat curing deteriorates. There are things to do. Furthermore, during the heat curing, the insulating resin varnish flows excessively, and as a result, the filler may be exposed on the surface of the obtained insulating film. In such a state, when a roughening process described later is performed, it tends to be difficult to obtain a fine rough surface. In contrast, in the present invention, since the heat treatment is performed without removing the base film from the insulating film, even when a liquid epoxy resin is used, the flatness of the insulating film after subsequent heat curing is suppressed from being deteriorated. Is done. Moreover, since the insulating film is protected by the base film during the heat curing, excessive flow of the insulating resin varnish is suppressed, and the filler is suppressed from being exposed on the surface of the resulting insulating film. As a result, it is easy to obtain a fine rough surface even if a roughening process described later is performed.

[Curing agent]
The said hardening | curing agent is not specifically limited. A conventionally known curing agent can be used as the curing agent. 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 is preferably at least one selected from the group consisting of a phenol curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine resin, and a cyanate ester resin. By using these preferable curing agents, the surface roughness of the surface of the roughened insulating film is further reduced, and the adhesive strength between the cured product and the metal layer is further increased.

  Furthermore, the use of an active ester curing agent, a benzoxazine curing agent or a cyanate ester resin improves the electrical properties of the cured product, in particular the dielectric loss tangent of the cured product is further reduced, and the linear expansion coefficient of the cured product and Water absorption is reduced. Further, the dimensional stability of the cured product when a thermal history is given is further increased.

  Examples of the phenol curing agent include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, phenol aralkyl resin, aminotriazine novolak resin, and the like. These derivatives may be used. As for the said phenol hardening | curing agent, only 1 type may be used and 2 or more types may be used together.

  Examples of the naphthol curing agent include α-naphthol aralkyl resins and β-naphthol aralkyl resins. These derivatives may be used. As for the said naphthol hardening | curing agent, only 1 type may be used and 2 or more types may be used together.

  The active ester curing agent is not particularly limited. A conventionally known active ester curing agent can be used as the active ester curing agent. As for the said active ester hardening | curing agent, only 1 type may be used and 2 or more types may be used together. Specific examples of the active ester curing agent include an active ester curing agent represented by the following formula (1) and an active ester curing agent represented by the following formula (2).

  In said formula (2), X is a benzene ring or a naphthalene ring, k represents 0 or 1, and n is 0.25-1.5 on the average of a repeating unit.

  As a commercial item of the said active ester hardening | curing agent, EXB9451, EXB9460, EXB9460S-65T, HPC-8000-65T (The diphthalate esterified product of dicyclopentadiene frame | skeleton, the product of DIC, the active ester group equivalent about 223), DC808, for example (Phenyl novolac acetylated product, Mitsubishi Chemical Corporation, active ester group equivalent of about 149), YLH1026 (phenol novolak benzoylated product, Mitsubishi Chemical Corporation, active ester group equivalent of about 200), YLH1030 (Mitsubishi Chemical Corporation, active ester) Group equivalent of about 201), YLH1048 (manufactured by Mitsubishi Chemical Corporation, active ester group equivalent of about 245), and the like.

  The active ester curing agent is not limited to the active ester curing agent specifically exemplified above.

  Specific examples of the benzoxazine resin include a resin in which a substituent having an aryl group skeleton such as a methyl group, an ethyl group, a phenyl group, a biphenyl group, or a cyclohexyl group is bonded to nitrogen of the oxazine ring, and a methylene group or an ethylene group. And a resin in which a substituent having an arylene skeleton such as a phenylene group, a biphenylene group, a naphthalene group, or a cyclohexylene group is bonded between nitrogen atoms of two oxazine rings. As for the said benzoxazine resin, only 1 type may be used and 2 or more types may be used together. By reacting the benzoxazine resin with the epoxy resin, the heat resistance of the cured product is further increased, and the water absorption and linear expansion coefficient of the cured product are further decreased.

  The benzoxazine monomer, the benzoxazine oligomer, and the resin in which the benzoxazine monomer or the benzoxazine oligomer is polymerized by ring-opening polymerization of the oxazine ring are included in the benzoxazine resin.

  Examples of the cyanate ester resin include novolak-type cyanate ester resins, bisphenol-type cyanate ester resins, and prepolymers obtained by partially triazine. As for the said cyanate ester resin, only 1 type may be used and 2 or more types may be used together. By using the cyanate ester resin, the linear expansion coefficient of the cured product is further reduced.

  A curing agent other than the curing agent may be added to the insulating film. Examples of the other curing agent include dicyandiamide, amine compounds, amine compound derivatives, hydrazide compounds, melamine compounds, acid anhydrides, thermal latent cationic polymerization catalysts, and photolatent cationic polymerization initiators. Derivatives of these curing agents may be used. In addition to a curing agent, a curing catalyst such as acetylacetone iron may be used.

  Examples of the amine compound include a chain aliphatic amine compound, a cyclic aliphatic amine compound, and an aromatic amine compound.

  Examples of the chain aliphatic amine compound include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, and polyoxypropylenetriamine.

  Examples of the cycloaliphatic amine compound include mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane and N-aminoethylpiperazine. Can be mentioned.

  Examples of the aromatic amine compound include m-xylenediamine, α- (m / p-aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, and α, α-bis (4-aminophenyl) -p-diisopropyl. Examples include benzene.

  A tertiary amine compound may be used as the amine compound. Examples of the tertiary amine compound include N, N-dimethylpiperazine, pyridine, picoline, benzyldimethylamine, 2- (dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol. .

  Specific examples of the derivative of the amine compound include a polyaminoamide compound, a polyaminoimide compound, and a ketimine compound.

  Examples of the polyaminoamide compound include compounds synthesized from the amine compounds and carboxylic acids. Examples of the carboxylic acid include succinic acid, adipic acid, isophthalic acid, terephthalic acid, dihydroisophthalic acid, tetrahydroisophthalic acid, and hexahydroisophthalic acid.

  Examples of the polyaminoimide compound include compounds synthesized from the amine compound and maleimide compound. Examples of the maleimide compound include diaminodiphenylmethane bismaleimide.

  Other specific examples of the compound synthesized from the amine compound include compounds synthesized from the amine compound and an epoxy compound, a urea compound, a thiourea compound, an aldehyde compound, a phenol compound, and an acrylic compound.

  Examples of the hydrazide compound include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 7,11-octadecadien-1,18-dicarbohydrazide, eicosane diacid dihydrazide, and adipic acid dihydrazide. Is mentioned.

  Examples of the melamine compound include 2,4-diamino-6-vinyl-1,3,5-triazine.

  Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride. Hexahydrophthalic anhydride and methylhexahydrophthalic anhydride.

  The content of the curing agent is preferably 1 part by weight or more, more preferably 30 parts by weight or more, preferably 200 parts by weight or less, more preferably 140 parts by weight or less with respect to 100 parts by weight of the thermosetting resin. . An insulating film fully hardens | cures that content of the said hardening | curing agent is more than the said minimum. When the content of the curing agent is not more than the above upper limit, it is difficult for an excessive curing agent to remain in the cured product.

[Curing accelerator]
The insulating film preferably contains a curing accelerator. The curing accelerator is not particularly limited. Conventionally known curing accelerators can be used as the curing accelerator. As for the said hardening accelerator, only 1 type may be used and 2 or more types may be used together.

  The curing accelerator is preferably an imidazole curing accelerator. The imidazole curing accelerator is 2-undecylimidazole, 2-heptadecylimidazole, 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 Imidazolyl- (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-triazi 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, It is preferably at least one selected from the group consisting of 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole.

  Examples of the curing accelerator include phosphine compounds such as triphenorphosphine, diazabicycloundecene (DBU), diazabicyclononene (DBN), DBU phenol salt, DBN phenol salt, octylate, p- Examples include toluene sulfonate, formate, orthophthalate, and phenol novolac resin salt.

  The content of the curing accelerator is preferably 0.01 parts by weight or more, more preferably 0.5 parts by weight or more, preferably 3 parts by weight or less, more preferably 2 parts by weight with respect to 100 parts by weight of the thermosetting resin. Less than parts by weight. An insulating film fully hardens | cures that content of the said hardening accelerator is more than the said minimum. When the content of the curing accelerator is not more than the above upper limit, the cross-linking in the cured product becomes uniform, the storage stability of the insulating film is further increased, and the surface roughness of the surface of the roughened cured product is more Even smaller.

[Filler]
The insulating film preferably contains at least one of a fibrous filler and a filler.

  Examples of the filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, and strontium titanate. , Calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, smectite clay mineral, swellable mica, vermiculite, and organic layered layered silicates such as halloysite Examples include silicates. As for the said filler, only 1 type may be used and 2 or more types may be used together.

  The filler is preferably silica, and the filler is preferably surface-treated with a silane coupling agent. As for the said silica, only 1 type may be used and 2 or more types may be used together.

  The hygroscopicity of silica surface-treated with a silane coupling agent is relatively low. Moreover, aggregation of the silica in an insulating film is suppressed by use of the silica surface-treated with the silane coupling agent. When silica that has not been surface-treated with a silane coupling agent is used, the silica tends to absorb moisture or the silica tends to aggregate in the insulating film.

  Further, by using silica surface-treated with a silane coupling agent, appropriate adhesiveness is developed at the interface between the silica and the resin component, so that the silica can be appropriately removed during the roughening treatment. When silica that has not been surface-treated with a silane coupling agent is used, the adhesion at the interface between the silica and the resin component is low, and therefore silica tends to be excessively detached during the roughening treatment. When the roughening solution penetrates into the interface between the resin component and the resin component, the resin component is scraped, and the surface roughness of the roughened cured product tends to increase.

  As the average particle diameter of the silica, a median diameter (d50) value of 50% is adopted. The average particle diameter can be measured using a laser diffraction / scattering particle size distribution measuring apparatus.

  A plurality of types of silica having different average particle diameters may be used. In consideration of fine packing, it is preferable to use a plurality of types of silica having different particle size distributions. In this case, the said insulating film can be used conveniently for the use as which fluidity | liquidity is requested | required like a component built-in board | substrate, for example.

  The average particle diameter of the silica is preferably 1 μm or less. When the average particle size is 1 μm or less, the silica is more easily detached at the time of the roughening treatment. Furthermore, it is difficult to form relatively large holes on the surface of the cured product, and uniform and fine irregularities can be formed.

  In the case where a fine wiring having an L / S of 15 μm / 15 μm or less is formed on the surface of the cured product, the insulating property can be improved, and therefore the maximum particle diameter of silica is preferably 2 μm or less. Note that “L / S” indicates the dimension (L) in the width direction of the wiring / the dimension (S) in the width direction of the portion where the wiring is not formed.

  The shape of the silica is not particularly limited. Examples of the shape of silica include a spherical shape and an indefinite shape. In the roughening treatment, silica is more easily detached, so that the silica is preferably spherical and more preferably true spherical.

The specific surface area of the silica is preferably 3 m ² / g or more. When the specific surface area is 3 m ² / g or more, the mechanical properties of the cured product are increased, and the adhesion between the cured product and the metal layer is further increased. The specific surface area is determined by the BET method.

  As the silica, crystalline silica obtained by pulverizing natural silica raw material, crushed fused silica obtained by flame melting and pulverizing natural silica raw material, and natural silica raw material obtained by flame melting, pulverizing and flame melting Examples include spherical fused silica, fumed silica (Aerosil), and synthetic silica such as sol-gel silica.

  Because of its high purity, fused silica is preferably used as the silica. The silica may be used as a silica slurry in a state dispersed in a solvent. When silica slurry is used, workability and productivity increase when an insulating film is produced.

  As the silane coupling agent, a conventionally known silane compound can be used. The silane coupling agent is at least one selected from the group consisting of epoxy silane, amino silane, isocyanate silane, acryloxy silane, methacryloxy silane, vinyl silane, styryl silane, ureido silane, sulfide silane and imidazole silane. Preferably there is. Alternatively, silica surface-treated with an alkoxysilane such as silazane may be used. As for the said silane coupling agent, only 1 type may be used and 2 or more types may be used together.

  By adding the silica surface-treated with the silane coupling agent to the insulating film, the dispersibility of the silica is further enhanced. The dispersibility of silica has a great influence on reducing the surface roughness. When silica is agglomerated, the surface of the insulating film is partially deeply shaved by the roughening treatment, and the rough surface tends to be uneven or the surface roughness tends to be partially increased.

  Examples of methods for obtaining silica surface-treated with a silane coupling agent include the following first to third methods.

  The first method includes a dry method. Examples of the dry method include a method of directly attaching a silane coupling agent to silica. In the dry method, silica is charged into a mixer, and an alcohol solution or an aqueous solution of a silane coupling agent is added dropwise or sprayed with stirring, followed by further stirring and classification with a sieve. Then, the surface-treated silica is obtained by dehydrating and condensing the silane coupling agent and silica by heating.

  The second method includes a wet method. In the wet method, a silane coupling agent is added while stirring a silica slurry containing silica, and after stirring, classification is performed by filtration, drying, and sieving. Next, the surface-treated silica is obtained by dehydrating and condensing the silane compound and silica by heating.

  As a third method, there is a method in which dehydration condensation is performed by heating and refluxing after adding a silane coupling agent while stirring a silica slurry containing silica.

  In 100% by weight of the component excluding the solvent of the insulating film, the total content of the fibrous reinforcing material and the filler is preferably 50% by weight or more, preferably 85% by weight or less, more preferably 80% by weight or less. It is. Further, in 100% by weight of the component excluding the solvent of the insulating film, the content of the filler is preferably 50% by weight or more, preferably 85% by weight or less, more preferably 80% by weight or less. When the total content of the fibrous reinforcing material and the filler and the content of the filler are equal to or higher than the lower limit, the total surface area of the holes formed by the detachment of the filler is increased during the roughening treatment. Furthermore, the adhesive strength between the cured product and the metal layer is sufficiently high. When the total content of the fibrous reinforcing material and the filler and the content of the filler are not more than the upper limit, the cured product is not easily brittle and the adhesive strength between the cured product and the metal layer is further increased. . Note that the insulating film may not contain a solvent. The content of 100% by weight of the component excluding the solvent of the insulating film means 100% by weight of the insulating film when the insulating film contains no solvent.

[Phenoxy resin]
The insulating film preferably contains a phenoxy resin. By using the phenoxy resin, the surface roughness of the roughened cured product can be kept small, and the adhesive strength between the cured product and the metal layer can be increased. Moreover, since the said phenoxy resin acts as a stress relaxation component, the impact resistance of hardened | cured material also becomes high. As for the said phenoxy resin, only 1 type may be used and 2 or more types may be used together.

  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 preferably has a weight average molecular weight of 30,000 or more. When the weight average molecular weight of the phenoxy resin is smaller than 30,000, the surface roughness of the surface of the roughened cured product tends to increase. The said weight average molecular weight shows the weight average molecular weight in polystyrene conversion.

  In 100% by weight of the component excluding the solvent of the insulating film, the content of the phenoxy resin is preferably 1% by weight or more, and preferably 15% by weight or less. When the content of the phenoxy resin is not less than the above lower limit and not more than the above upper limit, the surface roughness of the roughened cured product is further reduced, and the adhesive strength between the cured product and the metal layer is further increased. Get higher.

[Other ingredients]
In addition to the thermosetting resin, the insulating film may contain a resin copolymerizable with the thermosetting resin, if necessary. The copolymerizable resin is not particularly limited. Examples of the copolymerizable resin include thermosetting modified polyphenylene ether resin.

  Specific examples of the thermosetting modified polyphenylene ether resin include resins in which the polyphenylene ether resin is modified with a functional group such as an epoxy group, an isocyanate group, or an amino group.

  As a commercial item of the curable modified polyphenylene ether resin in which the polyphenylene ether resin is modified with an epoxy group, for example, trade name “OPE-2Gly” manufactured by Mitsubishi Gas Chemical Co., Ltd. may be mentioned.

  If necessary, the insulating film may be a thermoplastic resin, a thermoplastic elastomer, a crosslinked rubber, an oligomer, an inorganic compound, a nucleating agent, an antioxidant, an anti-aging agent, a thermal stabilizer, a light stabilizer, or an ultraviolet absorber. Agents, lubricants, flame retardant aids, antistatic agents, antifogging agents, fillers, softeners, plasticizers, colorants and the like may be included.

  Specific examples of the thermoplastic resin include a polysulfone resin, a polyether sulfone resin, a polyimide resin, a polyetherimide resin, a polycarbonate resin, a polyether ether ketone resin, and a polyester resin.

  Examples of the colorant include phthalocyanine / blue, phthalocyanine / green, iodin / green, disazo yellow, and carbon black.

[Other details of insulating film, laminated sheet, and method for producing laminate]
The manufacturing method of the said insulating film is not specifically limited. For example, the insulating film can be obtained by coating a thermosetting resin composition (resin varnish) containing an organic solvent on a base film (base film) and drying the solvent by heating with hot air or the like.

  Examples of the base film include polyolefin such as polypropylene and polyvinyl chloride, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and polycarbonate. In order to improve the peelability, the base film is preferably subjected to a mold release treatment. The base film may be subjected to mat treatment or corona treatment. The thickness of the base film is not particularly limited. The thickness of the base film is usually 10 to 150 μm, preferably 20 μm or more, and preferably 60 μm or less.

  Before being laminated on the lamination target member, a protective film may be laminated on the second surface of the insulating film. When the insulating film is used, the protective film is peeled off. By using the protective film, it is possible to suppress dust or the like from being attached to the insulating film or scratching the insulating film. In addition, the insulating film can be rolled and stored in a state where the protective film is laminated. In consideration of gas barrier properties, a multilayer film may be used as the protective film.

  The thermosetting resin composition for obtaining the insulating film may contain an organic solvent. Examples of the organic solvent include ketones, acetate esters, cellosolves, carbitols, aromatic hydrocarbons, dimethylformamide, and dimethylacetamide. Examples of the ketones include acetone, methyl ethyl ketone, and cyclohexanone. Examples of the acetates include ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and the like. Examples of the cellosolves include cellosolve and butyl cellosolve. Examples of the carbitols include carbitol and butyl carbitol. Examples of the aromatic hydrocarbon include toluene and xylene. As for the said organic solvent, only 1 type may be used and 2 or more types may be used together. In the insulating film, the residual amount of the high boiling point solvent is preferably small. By using a plurality of types of organic solvents having different boiling points, it is possible to control the handling properties of the insulating film and the fluidity of the insulating film at the time of lamination on a member to be laminated such as a substrate.

  In 100% by weight of the component excluding the solvent of the insulating film, the content of the organic solvent is preferably 1% by weight or more, and preferably 5% by weight or less. When the content of the organic solvent is equal to or higher than the lower limit, the fluidity of the insulating film becomes appropriate when laminating on a lamination target member such as a substrate. When the content of the organic solvent is not more than the above upper limit, the glass transition temperature of the cured product becomes high, and problems such as the occurrence of blister (swelling) during reflow hardly occur.

  The use of the laminate is not particularly limited. The insulating film is, for example, a substrate material for forming a core layer or a build-up layer of a multilayer substrate, an adhesive sheet, a laminate, a resin-coated copper foil, a copper-clad laminate, a TAB tape, a printed board, a prepreg, or It is suitably used for varnishes and the like.

  The laminate is suitably used for applications that require insulation, such as a resin-coated copper foil, a copper-clad laminate, a printed board, a prepreg, an adhesive sheet, or a TAB tape.

  Multiple layers of insulating layers and conductive plating layers cured by an additive method or semi-additive method that forms a circuit after forming a conductive plating layer on the surface of the insulating layer cured with the above insulating film The laminate is more preferably used for a build-up substrate or the like. In this case, the bonding reliability between the insulating layer obtained by curing the insulating film and the conductive plating layer is increased. When the hole through which silica or the like is formed on the surface of the insulating layer obtained by curing the insulating film is small, the insulation reliability between patterns is increased. Further, when the depth of the hole through which the silica is removed is shallow, the insulation reliability between the layers is increased. By using the laminated body, for example, fine wiring with L / S of 13 μm / 13 μm can be formed, and the reliability of the wiring is increased.

  The laminate can also be used as a sealing material or a solder resist. In addition, the high-speed signal transmission performance of the wiring formed on the surface of the insulating layer obtained by curing the insulating film can be enhanced, so that a high-frequency characteristic is required. In addition, the above laminate can be used.

  The insulating film may be a prepreg in which a fibrous reinforcing material is impregnated with the thermosetting resin composition. The fibrous reinforcing material is generally porous.

  The fibrous reinforcing material is not particularly limited as long as it can be impregnated with the thermosetting resin composition. Examples of the fibrous reinforcing material include organic fibers and glass fibers. Examples of the organic fiber include carbon fiber, polyamide fiber, polyaramid fiber, and polyester fiber. In addition, examples of the form of the fibrous reinforcing material include a form of a woven fabric such as a plain weave or a twill weave, and a form of a concave nonwoven fabric. The fibrous reinforcing material is preferably a glass fiber nonwoven fabric.

  In 100% by weight of the component excluding the solvent of the insulating film, the content of the fibrous reinforcing material is preferably 50% by weight or more, preferably 85% by weight or less, more preferably 80% by weight or less. When the content of the fibrous reinforcing material is not less than the above lower limit, the adhesive strength between the cured product and the metal layer is sufficiently high. When the content of the fibrous reinforcing material is not more than the above upper limit, the cured product is not easily brittle, and the adhesive strength between the cured product and the metal layer is further increased.

  A prepreg can be obtained by impregnating the thermosetting resin composition with, for example, a fibrous reinforcing material by a hot melt method or a solvent method and semi-curing by heating. That is, a prepreg in a state where the thermosetting resin composition is impregnated in the fibrous reinforcing material is obtained.

  In the above hot melt method, without dissolving the resin in an organic solvent, the resin is once coated on the resin and the coated paper having good releasability, and then laminated on a sheet-like reinforcing material or directly applied by a die coater. Thus, a prepreg is obtained. The solvent method is a method in which a fibrous reinforcing material is immersed in a resin varnish in which a resin is dissolved in an organic solvent, the resin varnish is impregnated in the fibrous reinforcing material, and then dried.

  In the first heating step, the heating temperature of the insulating film is preferably in the range of 120 to 220 ° C. In the second heating step, the heating temperature of the insulating film is preferably in the range of 120 to 220 ° C. When the heating temperature is less than 120 ° C., the insulating film is not sufficiently cured, and as a result, the unevenness of the surface of the cured product after the roughening treatment tends to increase. When the heating temperature exceeds 220 ° C., the curing reaction of the insulating film is likely to proceed rapidly. For this reason, the degree of curing tends to be partially different, and a rough portion and a dense portion are likely to be formed. As a result, the unevenness of the surface of the cured product becomes large.

  There is no particular limitation on the heating time when the insulating film is heat-cured. In the first heating step, the insulating film is heated and cured until the gel fraction after being immersed in methyl ethyl ketone at 23 ° C. for 24 hours becomes 20% by weight or more. If the base film is peeled off in a state where the gel fraction is less than 20% by weight, since the insulating film is not sufficiently cured, the flatness of the insulating film before the roughening treatment is increased, or after the roughening treatment The unevenness of the surface of the cured product becomes large.

  In the first heating step, the gel fraction after being immersed in methyl ethyl ketone of the insulating film at 23 ° C. for 24 hours is preferably 90% by weight or more, and more preferably 95% by weight or more. When the gel fraction is 90% by weight or more, the surface roughness of the roughened insulation film is further reduced, and when the gel fraction is 95% by weight or more, the roughened insulation film. The surface roughness of the surface is further reduced.

  In order to form fine irregularities on the surface of the cured product, the insulating film is roughened. The insulating film is preferably subjected to a swelling treatment before the roughening treatment. However, the insulating film is not necessarily subjected to the swelling treatment.

  As the swelling treatment method, for example, a method of treating the reaction product with an aqueous solution or an organic solvent dispersion solution of a compound mainly composed of ethylene glycol or the like is used. For the swelling treatment, a 40% by weight ethylene glycol aqueous solution is suitably used.

  For the roughening treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfuric acid compound is used. These chemical oxidizers are used as an aqueous solution or an organic solvent dispersion after water or an organic solvent is added.

  Examples of the manganese compound include potassium permanganate and sodium permanganate. Examples of the chromium compound include potassium dichromate and anhydrous potassium chromate. Examples of the persulfate compound include sodium persulfate, potassium persulfate, and ammonium persulfate.

  The roughening treatment method is not particularly limited. For the roughening treatment, for example, 30 to 90 g / L permanganic acid or permanganate solution or 30 to 90 g / L sodium hydroxide solution is preferably used.

  When the number of roughening treatments is large, the roughening effect is large. However, if the number of roughening treatments exceeds 3, the roughening effect may be saturated, or the resin component on the surface of the cured product may be scraped more than necessary, and silica or the like may be detached from the surface of the cured product. It becomes difficult to form holes having the shape. For this reason, it is preferable that a roughening process is performed once or twice.

  The insulating film is preferably roughened at 50 to 80 ° C. for 5 to 30 minutes. When the insulating film is subjected to a swelling treatment, the insulating film is preferably subjected to a swelling treatment at 50 to 80 ° C. for 5 to 30 minutes. When the roughening treatment or the swelling treatment is performed a plurality of times, the time for the roughening treatment or the swelling treatment indicates the total time. By roughening or swelling the insulating film, the surface roughness of the roughened insulating film surface is further reduced. Specifically, an insulating film having an arithmetic average roughness Ra of 0.4 μm or less and a ten-point average roughness Rz of 4.0 μm or less can be obtained more easily.

  If the arithmetic average roughness Ra is too large, when a wiring is formed on the surface of the insulating layer, the transmission speed of the electrical signal in the wiring may not be increased. If the ten-point average roughness Rz is too large, when the wiring is formed on the surface of the insulating layer, the transmission speed of the electrical signal in the wiring may not be increased. The arithmetic average roughness Ra and the ten-point average roughness Rz are determined by a measuring method based on JIS B0601-1994.

  The average diameter of the plurality of holes formed on the surface of the insulating layer is preferably 4 μm or less. If the average diameter of the plurality of holes is larger than 4 μm, it may be difficult to form a wiring having a small L / S on the surface of the cured product, and the formed wirings are likely to be short-circuited.

  If necessary, electrolytic plating can be performed after applying a known plating catalyst or electroless plating. By plating the surface of the insulating layer, a laminate including the insulating layer and the metal layer is obtained.

  When wiring such as copper having a small L / S is formed in the insulating layer, the signal processing speed of the wiring is increased. For example, even if the signal is a high frequency of 5 GHz or more, if the surface roughness of the insulating layer is small, the loss of the electric signal at the interface between the wiring and the insulating layer is small.

  By using the laminate obtained by the method for producing a laminate according to the present invention, for example, fine wiring with an L / S of about 13 μm / 13 μm can be formed on the surface of the insulating layer with high accuracy. In addition, a fine wiring having an L / S of 10 μm / 10 μm or less can be formed on the surface of the insulating layer without causing a short circuit between the wirings. In the insulating layer in which such wiring is formed, an electric signal can be transmitted stably and with a small loss.

  As a material for forming the metal layer, a metal foil or metal plating used for shielding or circuit formation, and a plating material used for circuit protection can be used.

  Examples of the plating material include gold, silver, copper, rhodium, palladium, nickel, and tin. Two or more kinds of these alloys may be used, and a plurality of metal layers may be formed of two or more kinds of plating materials. Furthermore, depending on the purpose, the plating material may contain other metals and substances other than the above metals. The metal layer is preferably a copper plating layer formed by a copper plating process. From the viewpoint of suppressing peeling of the metal layer, the adhesive strength between the insulating layer and the metal layer is preferably 4.9 N / cm or more.

  Hereinafter, the present invention will be specifically described by giving examples and comparative examples. The present invention is not limited to the following examples.

  In the examples and comparative examples, the following materials were used.

[Thermosetting resin]
Bisphenol A type liquid epoxy resin (1) (“RE-410S” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 178)

[Curing agent]
Biphenyl type phenol curing agent (1) (“MEH7851-4H” manufactured by Meiwa Kasei Co., Ltd., OH equivalent 243, softening point 130 ° C.)
Naphthol curing agent (2) (“SN485” manufactured by Tohto Kasei Co., Ltd., OH equivalent 213, softening point 86 ° C.)
Active ester curing agent (3) (manufactured by DIC "HPC-8000-65T", solid content 65% by weight toluene solution, active group equivalent 223, softening point 152 ° C)
Cyanate ester resin (4) ("PRIMASET BA-230S" manufactured by Lonza, methyl ethyl ketone solution having a solid content of 75% by weight, specific gravity of the solution: 1.09, specific gravity of the cyanate ester resin alone: 1.18)

[Curing accelerator]
Curing accelerator (1) (“2MAOK-PW” manufactured by Shikoku Kasei Co., Ltd.)

[Silica slurry]
100 parts by weight of silica (“SOC1” manufactured by Admatechs) and 70% by weight of silica (specific gravity 2.20) surface-treated with 2 parts by weight of aminosilane (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.), and DMF (N , N-dimethylformamide) and a slurry containing 70% by weight of silica (1)

[solvent]
N, N-dimethylformamide (DMF, special grade, manufactured by Wako Pure Chemical Industries, Ltd.)

Example 1
(1) Preparation of thermosetting resin composition 15.78 g of bisphenol A type liquid epoxy resin (1), 0.17 g of curing accelerator (1), 47.39 g of a slurry containing 70% by weight of silica (1), 19.43 g of N, N-dimethylformamide was stirred at room temperature (23 ° C.) for 2 hours until a uniform solution was obtained.

  Next, 17.23 g of a biphenyl type phenol curing agent (1) was further added and stirred for 1 hour at room temperature (23 ° C.) to prepare a thermosetting resin composition.

(2) Production of Laminated Film A release-treated transparent polyethylene terephthalate (PET) film (“PET5011 550” manufactured by Lintec Corporation, thickness 50 μm) was prepared as a base film. The obtained thermosetting resin composition was applied onto the surface of the PET film subjected to the mold release treatment using an applicator so that the thickness after drying was 50 μm. Next, by drying in a gear oven at 100 ° C. for 12 minutes, an insulating film in a B stage state (length 200 mm × width 200 mm × thickness 50 μm, uncured sheet-like thermosetting resin composition) is produced. did. In this way, a laminated film in which a PET film was laminated on the first surface of the insulating film was obtained.

(3) Lamination process and 1st heat processing The obtained lamination sheet was vacuum-laminated on the glass epoxy board | substrate (FR-4, Risho Kogyo "CS-3665") from the 2nd surface side of an insulating film. (Laminating step), the insulating film was heat-treated at 170 ° C. for 60 minutes (heating conditions of the first heat treatment) (first heat treatment). Thereafter, the PET film as the base film was peeled off to obtain a laminated sample. After performing the following swelling process, the following roughening process was performed.

(4) Swelling step The laminated sample was placed in a swelling solution at 80 ° C. (“Swelling Dip Securigant P” manufactured by Atotech) and rocked at a swelling temperature of 80 ° C. for 15 minutes. Thereafter, it was washed with pure water. In this manner, an insulating film subjected to swelling treatment was formed on the glass epoxy substrate.

(5) Roughening process:
The above laminated sample subjected to swelling treatment was put into a roughened aqueous solution of potassium permanganate (“Concentrate Compact CP” manufactured by Atotech Co., Ltd.) at 80 ° C. and rocked for 15 minutes at a roughening temperature of 80 ° C. Thereafter, the plate was washed for 2 minutes with a 25 ° C. cleaning solution (“Reduction Securigant P” manufactured by Atotech), and further washed with pure water. In this way, a roughened insulating film was formed on the glass epoxy substrate.

(6) Production of laminated structure After the roughening step, the following copper plating treatment was performed.

  The roughened insulating film on the glass epoxy substrate was subjected to electroless copper plating and electrolytic copper plating in the following procedure.

  The surface of the roughened insulating film was treated with a 60 ° C. alkaline cleaner (“Cleaner Securigant 902” manufactured by Atotech) for 5 minutes and degreased and washed. After washing, the roughened insulating film was treated with a predip solution at 25 ° C. (“Predip Neogant B” manufactured by Atotech) for 2 minutes. Thereafter, the roughened insulating film was treated with an activator solution at 40 ° C. (“Activator Neogant 834” manufactured by Atotech) for 5 minutes, and a palladium catalyst was attached. Next, the roughened insulating film was treated for 5 minutes with a reducing solution at 30 ° C. (“Reducer Neogant WA” manufactured by Atotech).

  Next, the roughened insulating film is placed in a chemical copper solution (“Basic Print Gantt MSK-DK” manufactured by Atotech, “Kappa Print Gantt MSK” manufactured by Atotech, “Stabilizer Print Gantt MSK” manufactured by Atotech) Electroless plating was performed until the plating thickness reached about 0.5 μm. After the electroless plating, annealing was performed at a temperature of 120 ° C. for 30 minutes in order to remove the remaining hydrogen gas. All the processes up to the electroless plating process were performed while the treatment liquid was 1 L on a beaker scale and the insulating film subjected to the roughening treatment was swung.

Next, electroplating was performed on the insulating film that had been electrolessly plated and roughened until the plating thickness reached 25 μm. An electric current of 0.6 A / cm ² was passed using copper sulfate (“Reducer Cu” manufactured by Atotech Co., Ltd.) as the electrolytic copper plating. After the copper plating treatment, the roughened insulating film was heated at 180 ° C. for 1 hour and cured to form a cured product (insulating film). Thus, the laminated body in which the copper plating layer was formed on the hardened | cured material was produced.

(Examples 2 to 7 and Comparative Examples 1 and 2)
The types and amounts of the blending components, the heating conditions of the first heating step, the presence or absence of peeling of the base film before the first heating step were set as shown in Table 1 below, and Examples In Examples 6 and 7, a thermosetting resin composition was prepared in the same manner as in Example 1 except that the second heating step was performed, and a laminated film and a laminated structure were produced.

  In Example 6, after the peeling step and before the swelling step, the insulating film was heat-treated at 170 ° C. for 45 minutes (heating conditions for the second heat treatment) (second heat treatment). In Example 7, after the peeling step and before the swelling step, the insulating film was heat-treated at 170 ° C. for 55 minutes (heating conditions for the second heat treatment) (second heat treatment).

  In Comparative Examples 1 and 2, before the first heat treatment, the base film was peeled off from the insulating film, and after the base film was peeled off from the insulating film, the first heat treatment was performed.

(Examples 8 and 9 and Comparative Examples 3 and 4)
Bisphenol A type liquid epoxy resin (1) 15.78 g, curing accelerator (1) 0.17 g, silica (1) 70 wt% slurry 47.39 g, N, N-dimethylformamide 19.43 g, The mixture was stirred at room temperature (23 ° C.) for 2 hours until a uniform solution was obtained.

  Next, 17.23 g of a biphenyl type phenol curing agent (1) was further added and stirred for 1 hour at room temperature (23 ° C.) to prepare a thermosetting resin composition.

  The obtained thermosetting resin composition (resin varnish) was impregnated into a glass cloth (Asahi Kasei E-Materials, thickness 20 μm), dried at 140 ° C. for 12 minutes, and an insulating film (prepreg) having a thickness of 0.1 mm. Got. The obtained insulating film contains 70% by weight of glass cloth and 30% by weight of the thermosetting resin composition. A transparent polyethylene terephthalate (PET) film ("PET5011 550" manufactured by Lintec Co., Ltd., thickness 50 µm) that had been subjected to release treatment was laminated on the first surface of the obtained insulating film to obtain a laminated film.

  Using the obtained laminated film, the heating conditions of the first heating step, the presence or absence of peeling of the base film before the first heating step were set as shown in Table 2 below, and the implementation In Example 9, a laminated body and a laminated structure were produced in the same manner as in Example 1 except that the second heating step was performed.

  In Example 9, after the peeling step and before the swelling step, the insulating film was heat-treated at 170 ° C. for 45 minutes (heating conditions for the second heat treatment) (second heat treatment).

  In Comparative Examples 3 and 4, the first heat treatment was performed after the base film was peeled off from the insulating film and the base film was peeled off from the insulating film before the first heat treatment.

(Evaluation)
(1) Average linear expansion coefficient The base film was peeled off from the insulating film using the obtained laminated film. The insulating film was heated at 170 ° C. for 60 minutes and further cured by heating at 180 ° C. for 1 hour to obtain a cured product. The obtained cured product was cut into a size of 3 mm × 25 mm. Using a linear expansion meter (“TMA / SS120C” manufactured by Seiko Instruments Inc.), the average of the cured product at 23 to 100 ° C. under the conditions of tensile load 2.94 × 10 ⁻² N and heating rate 5 ° C./min. The linear expansion coefficient (α1) and the average linear expansion coefficient (α2) at 150 to 260 ° C. were measured.

(2) Evaluation of gel fraction The obtained insulating film was subjected to a heat history until immediately before the PET film as the base film was peeled off, to obtain a semi-cured product A as an insulating film. Moreover, the semi-hardened material B which is an insulating film was obtained over the heat history just before a roughening process.

  The obtained semi-cured product A and semi-cured product B were each cut into a size of 50 mm × 50 mm to prepare test samples. The initial weight (W1) of this test sample was measured. Next, the test sample was immersed in methyl ethyl ketone at 23 ° C. for 24 hours. Thereafter, the test piece in methyl ethyl ketone was filtered using a # 400 metal mesh that had been previously weighed to obtain a test sample residue on the metal mesh. The residue was dried with a metal mesh at 23 ° C. for 72 hours. The total weight of the metal mesh and the residue after drying was measured, and the weight of the metal mesh was subtracted to obtain the weight (W2) of the residue after drying. From the measured value, the gel fraction was calculated by the following formula (X). The average value measured five times was taken as the gel fraction.

  Gel fraction (% by weight) = W2 / W1 × 100 Formula (X)

  The gel fraction immediately before peeling off the base film was evaluated using the semi-cured product A. The gel fraction immediately before the roughening treatment was evaluated using the semi-cured product B.

(3) Evaluation of flatness Instead of a glass epoxy substrate (FR-4, “CS-3665” manufactured by Risho Kogyo Co., Ltd.), a copper pattern with a spacing of 75 μm (one copper pattern: 40 μm long × 40 μm wide × 1 cm thick) is used. Using the laminated films of Examples 1 to 7 and Comparative Examples 1 and 2 in the same manner except that the substrate having the upper surface was used, the respective steps of Examples 1 to 7 and Comparative Examples 1 and 2 were laminated. A structure was obtained.

  When obtaining this laminated structure, the flatness of the first surface of the insulating film before the roughening treatment was evaluated.

  Using a contact-type surface roughness meter (“Mitutoyo SJ-301” manufactured by Mitutoyo Corporation), the height A of the first surface of the insulating film located at the portion where the copper pattern was formed was measured at 50 locations. Moreover, 50 height B of the 1st surface of the insulating film located in the part in which the said copper pattern is not formed adjacent to 50 measurement points of height A was measured. The difference between the average value of height A and the average value of height B was determined, and the obtained value was shown as the flatness value. The smaller this value, the better the flatness.

(4) Adhesive strength Notches were cut into a width of 10 mm on the surface of the copper plating layer of the obtained laminated structure. Then, the adhesive strength of hardened | cured material (insulation film) and a copper plating layer was measured on the conditions of the crosshead speed | rate of 5 mm / min using the tensile tester (Shimadzu Corporation "autograph").

(5) Surface roughness (arithmetic average roughness Ra and ten-point average roughness Rz)
Arithmetic average roughness Ra and ten points of the first surface of the insulating film subjected to the roughening treatment in accordance with JIS B0601-1994 using a non-contact type surface roughness meter ("WYKO" manufactured by Beco). The average roughness Rz was measured.

(6) Insulation reliability test The copper plating layer of the obtained laminated structure was made into a copper wiring pattern of L / S = 10 μm / 10 μm, and the laminated structure on which this copper wiring pattern was formed was used at 135 ° C., 85 %, DC5V, and 200 hours were used for the insulation reliability test. The insulation reliability test was judged with “O” when the insulation resistance was 1.0 × 10 ⁶ Ω or more and “X” when the insulation resistance was less than 1.0 × 10 ⁶ Ω. The cross section of the wiring was still observed after the test, and the presence or absence of copper migration was also confirmed.

  The results are shown in Tables 1 and 2 below.

DESCRIPTION OF SYMBOLS 1 ... Laminated body 10 ... Laminated film 11 ... Insulating film 11A-11D ... Insulating film 11a ... 1st surface 11b ... 2nd surface 12 ... Base film 21 ... Lamination target member 51 ... Laminated structure 52 ... Circuit board 52a ... Upper surface 53-56 ... Hardened material layer (insulating film)
57 ... Metal layer

Claims (14)

A method for producing a laminate in which a roughened insulating film is laminated on a lamination target member,
Using a laminated film having an insulating film and a base film laminated on the first surface of the insulating film, the laminated film is moved from the second surface side opposite to the first surface of the insulating film. A laminating step of laminating on a lamination target member;
A first heating step in which the base film is not peeled off from the insulating film, and the insulating film is heat-treated until the gel fraction reaches 20% by weight or more after being immersed in methyl ethyl ketone at 23 ° C. for 24 hours;
A peeling step of peeling the base film from the insulating film to expose the first surface of the insulating film;
And a roughening step of roughening the first surface of the insulating film.   The manufacturing method of the laminated body of Claim 1 which heat-processes in the said 1st heating process until the gel fraction after immersing the said insulating film in methyl ethyl ketone at 23 degreeC for 24 hours becomes 60 weight% or more.   The manufacturing method of the laminated body of Claim 1 or 2 further equipped with the 2nd heating process which heat-processes the said insulating film at 120-220 degreeC after the said peeling process and before the said roughening process.   The lamination according to any one of claims 1 to 3, wherein in the first heating step, the insulating film is heat-treated until the gel fraction after being immersed in methyl ethyl ketone at 23 ° C for 24 hours is 90% by weight or more. Body manufacturing method.   The manufacturing method of the laminated body in any one of Claims 1-4 in which the said insulating film contains a thermosetting resin and at least one of a fibrous reinforcement and an average particle diameter of 1 micrometer or less.   The manufacturing method of the laminated body of Claim 5 whose total content of the said fibrous reinforcing material and the said filler is 50 weight% or more in 100 weight% of components except the solvent of the said insulating film.   The manufacturing method of the laminated body of Claim 5 or 6 whose said thermosetting resin is an epoxy resin.   The manufacturing method of the laminated body of Claim 7 whose said epoxy resin is a liquid epoxy resin.   The manufacturing method of the laminated body of any one of Claims 1-8 in which the said insulating film contains a hardening | curing agent.   The method for producing a laminate according to claim 9, wherein the curing agent is at least one selected from the group consisting of a phenol curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine resin, and a cyanate ester resin.   In the roughening step, the arithmetic average roughness Ra of the roughened first surface is 0.4 μm or less and the ten-point average roughness Rz is 4.0 μm or less. The manufacturing method of the laminated body in any one of Claims 1-10 which roughens the surface of 1. After the peeling step and before the roughening step, further comprising a swelling step of swelling the first surface of the insulating film;
The manufacturing method of the laminated body of any one of Claims 1-11 which roughens the said 1st surface of the said insulating film by which the roughening process was carried out in the said roughening process. A laminate obtained by the laminate production method according to any one of claims 1 to 12,
A laminated structure comprising: a metal layer laminated on the first surface of the insulating film subjected to the roughening treatment of the laminated body.   The laminated structure according to claim 13, wherein an adhesive strength between the insulating film and the metal layer is 4.9 N / cm or more.

Images