TWI674051B - Laminated body, multilayer circuit board including the same, and method of manufacturing the same - Google Patents

Abstract

An object of the present invention is to provide a method for producing a laminated body which is excellent in heat resistance (for example, soldering heat resistance) and can form a via hole having a small diameter. The present invention provides a method for producing a laminate, comprising: forming a curable resin composition layer composed of a thermosetting resin composition on a support; and obtaining a curable resin composition with a support. Layer step; the above-mentioned hardening resin composition layer with a support is formed on the surface side with the hardening resin composition layer, and is laminated on the base material to obtain a base material and a hardening resin combination with a support material A step of a pre-hardened composite body with a support composed of a material layer; by heating the composite body for the first time, the hardenable resin composition layer is thermally hardened into a hardened resin layer to obtain a base material, and A step of a hardened composite with a support and a hardened resin layer with a support; a step of forming a via hole in the hardened resin layer by making holes from the support side of the hardened composite with the support; ; A step of obtaining a hardened composite composed of a base material and a hardened resin layer by peeling the support from the hardened composite with a support; performing the first step on the hardened composite; (2) a heating step; a step of removing resin residues in the vias of the hardened composite body; and a step of forming a conductor layer on the inner wall surface of the vias of the hardened composite body and the hardened resin layer; The formation of the conductive layer is performed by filling a conductor in the via hole by electroless plating or a combination of electroless plating and electrolytic plating.

Description

Laminated body, multilayer circuit substrate including the laminated body, and manufacturing method of the laminated body

The present invention relates to a method for producing a laminate including a conductor layer and a cured resin layer on a substrate.

With the pursuit of miniaturization, multi-functionalization, and high-speed communication of electronic devices, circuit boards used in electronic devices are required to be further densified. In response to such high-density requirements, multilayer circuit boards have been sought. Such a multilayer circuit board is, for example, an electric insulating layer laminated on an inner layer substrate composed of an electric insulating layer and a conductor layer formed on the surface thereof, and a conductor layer is formed on the electric insulating layer. Further, the electrical insulating layer is laminated and the conductor layer is formed.

A method for manufacturing a multilayer body for forming such a multilayer circuit board, for example, Patent Document 1 discloses a method for manufacturing a multilayer printed circuit board, which must include a support base film having a release layer / release layer and In the pattern processing circuit board, at least the pattern processing portion on one or both sides of the circuit substrate is directly covered with an overlapped state, and the resin composition layer of the adhesive film is heated, pressed, and laminated in a vacuum condition. A step of thermally hardening the resin composition in a state with a supporting base film attached; a step of making a hole with a laser or a drill; a step of peeling the supporting base film; a step of roughening the surface of the resin composition; Next, the roughened surface is plated to form Steps to the conductor layer.

In Patent Document 1, the resin composition is thermally hardened in a state where a support such as a support base film is attached, thereby preventing the resin composition from adhering foreign matter during thermal hardening and causing foreign matter to become disconnected or short-circuited. The bad cause. Further, in Patent Document 1, after the resin composition is thermally cured in a state with a support attached, before the support is peeled off, a hole is formed by a laser or a drill to form a small-diameter via hole.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-196743

However, as in the technique of the above-mentioned Patent Document 1, the resin composition is thermally cured in a state with a support such as a support base film. After the thermal curing, when the support is peeled off, the heating may be insufficient, and the thermal curing may occur. When the heat resistance of the hardened resin is poor.

An object of the present invention is to provide a method for producing a laminated body which is excellent in heat resistance (for example, soldering heat resistance) and can form a via hole having a small diameter.

As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a method for manufacturing a laminated body having a conductive layer and a cured resin layer on a base material adopts a state where a support is attached and a thermosetting resin combination is heated After the material layer is hardened, the hardened resin layer after hardening is perforated from the support side to form a through hole. After the support is peeled off, Removal of the resin residue in the formed via hole can effectively solve the problem of heat resistance that becomes a problem when the curable resin composition layer is thermally cured in a state with a support, and the present invention has been completed. .

That is, according to the present invention, there is provided: [1] A method for producing a laminate, comprising: forming a layer of a curable resin composition composed of a thermosetting resin composition on a support; The first step of the hardening resin composition layer with a support; the hardening resin composition layer with the support described above is formed on the surface side with the hardening resin composition layer, and is laminated on the base material to obtain a base material. And a second step of a pre-cured composite with a support composed of a curable resin composition layer with a support; the first heating of the composite to heat the curable resin composition layer The third step of hardening into a hardened resin layer to obtain a hardened body with a support from a base material and a hardened resin layer with a support; the above-mentioned support from the hardened body with a support The fourth step is to make a hole on the side to form a through hole in the hardened resin layer. By peeling the support from the hardened composite with a support, a hardened composite composed of a base material and a hardened resin layer is obtained. Step 5; Step 6 of performing second heating on the hardened composite body; Step 7 of removing resin residue in the vias of the hardened composite body; and on the inner wall surface of the vias of the hardened composite body and the above The eighth step of forming a conductive layer on the hardened resin layer; in the eighth step, the formation of the conductive layer of the via hole is performed in the via hole by electroless plating or a combination of electroless plating and electrolytic plating. [2] The method for manufacturing a laminated body according to [1], wherein the heating temperature of the second heating in the sixth step is higher than that of the first heating in the third step. Low heating temperature; [3] The method for manufacturing a laminate according to [1] or [2], wherein the formation of the conductor layer on the hardened resin layer, electrolytic electroless plating, or a combination of electroless plating and electrolytic plating [4] A laminated body obtained by the method for manufacturing a laminated body described in any one of the above [1] to [3]; and [5] a multilayer circuit board made of the above [4] The composition of the laminated body.

According to the manufacturing method of the present invention, it is possible to provide a laminated body which is excellent in heat resistance (for example, soldering heat resistance) and can form a via hole having a small aperture, and a multilayer circuit board obtained by using the same.

The manufacturing method of the laminated body of this invention is a method of manufacturing the laminated body which has a conductor layer and a hardened resin layer on a base material, Comprising: (1) Comprising a thermosetting resin composition by forming on a support body The first step of obtaining a curable resin composition layer with a support; (2) forming the above-mentioned curable resin composition layer with a support into a curable resin composition layer The second step of laminating on the substrate to obtain a support-hardened pre-cured composite composed of the substrate and a support-hardening resin composition layer; (3) The first heating is performed on the composite to thermally harden the curable resin composition layer to a cured resin layer to obtain a cured body with a support from a base material and a cured resin layer with a support. The third step of the composite; (4) The fourth step of forming a through hole in the hardened resin layer by making holes from the support side of the hardened composite with the support, and (5) by The fifth step of peeling the support from the hardened composite with a support to obtain a hardened composite composed of a base material and a hardened resin layer; (6) a sixth step of second heating the hardened composite; 7) a seventh step of removing the resin residue in the via hole of the hardened composite body; and (8) an eighth step of forming a conductor layer on the inner wall surface of the via hole of the hardened composite body and the hardened resin layer.

Then, in the method for manufacturing a laminated body of the present invention, in the eighth step, the formation of the conductive layer of the via hole is performed in the via hole by electroless plating, or a combination of electroless plating and electrolytic plating. Filled with conductors.

(Step 1)

The first step of the manufacturing method of the present invention is a step of obtaining a curable resin composition layer with a support by forming a curable resin composition layer composed of a thermosetting resin composition on a support.

The support used in the first step of the production method of the present invention is not particularly limited, and examples thereof include a film-like or plate-like member, and examples thereof include a polyethylene terephthalate film and a polypropylene film. Polymer film, such as polyethylene film, polycarbonate film, polyethylene naphthalate film, polyarylate film, nylon film, polytetrafluoroethylene film, or plate. Film-like glass substrate Wait. As a support, in order to make it easier to peel off from the hardened resin layer in the fifth step to be described later, it is preferable to have a release layer on the surface for release treatment, and a polymer pair having a release layer Ethyl phthalate film is preferred.

The thickness of the support used in the first step of the manufacturing method of the present invention is not particularly limited, but it is preferably 5 to 200 μm, more preferably 10 to 150 μm, and even more preferably 20 to 60 μm. By using a support having a thickness within the above range, the handleability of the curable resin composition layer with the support can be improved.

In addition, a thermosetting resin composition for forming a curable resin composition layer usually contains a curable resin and a curing agent. The curable resin is not particularly limited as long as it can exhibit thermosetting properties in combination with a hardener and has electrical insulation. Examples of the curable resin include epoxy resin, maleimide resin, (meth) acrylic resin, and orthobenzene. Diallyl dicarboxylate resin, triazine resin, alicyclic olefin polymer, aromatic polyether polymer, benzocyclobutene polymer, cyanate ester polymer, polyimide, and the like. These resins can be used individually or in combination of 2 or more types.

Hereinafter, for example, a case where an epoxy resin is used as the curable resin will be described as an example.

The epoxy resin is not particularly limited, and for example, a poly / polyvalent epoxy compound (A) having a biphenyl structure and / or a condensed polycyclic structure can be used. The polyvalent epoxy compound (A) having a biphenyl structure and / or a condensed polycyclic structure [hereinafter, referred to as a polyvalent epoxy compound (A). ) Is a compound having at least two epoxy groups (ethylene oxide rings) in one molecule and having at least one of a biphenyl structure and a condensed polycyclic structure.

The above-mentioned biphenyl structure refers to a structure in which two benzene rings are connected by a single bond. The biphenyl structure usually forms the main chain of the obtained cured resin, but may also exist in the side chain.

The above-mentioned condensed polycyclic structure refers to a structure obtained by condensing (condensing) two or more monocyclic rings. The ring constituting the condensed polycyclic structure may be an alicyclic ring or an aromatic ring, or may include a hetero atom. The number of condensation rings is not particularly limited. From the viewpoint of improving the heat resistance and mechanical strength of the obtained cured resin layer, two or more rings are preferred. In practice, the upper limit is about 10 rings. Such a condensed polycyclic structure includes, for example, a dicyclopentadiene structure, a naphthalene structure, a fluorene structure, an anthracene structure, a phenanthrene structure, a benzophenanthrene structure, a fluorene structure, an ophthalene structure, and the like. The condensed polycyclic structure is the same as the above-mentioned biphenyl structure, and it is a hardened resin layer obtained. Usually, the main chain constituting the resin contained in the hardened resin layer may exist in the side chain.

The multivalent epoxy compound (A) used in the present invention has a biphenyl structure, a condensed polycyclic structure, or both a biphenyl structure and a condensed polycyclic structure, and improves the heat resistance and mechanical strength of the hardened resin layer obtainable. From the viewpoint, the polyvalent epoxy compound (A) is preferably a biphenyl structure, and more preferably a biphenyl alkyl structure.

In addition, when the polyepoxide compound (A) is used in combination with a biphenyl structure (including a biphenyl structure and a condensed polycyclic structure) and a condensed polycyclic structure, the heat resistance and electrical properties of the cured resin layer are improved. From the viewpoint of sexual characteristics, such a blending ratio is usually 3/7 ~ 7/3 in terms of weight ratio (polyvalent epoxy compound having a biphenyl structure / polyvalent epoxy compound having a condensed polycyclic structure). .

The polyvalent epoxy compound (A) used in the present invention is not limited to its structure as long as it is a compound having at least two epoxy groups in one molecule and having a biphenyl structure and / or a condensed polycyclic structure. From the viewpoint of excellent heat resistance and mechanical strength of the resin layer, a phenolic epoxy compound having a biphenyl structure and / or a condensed polycyclic structure is preferred. Phenolic epoxy compounds, such as phenol Novolac epoxy compounds, cresol novolac epoxy compounds, and the like.

Since the polyvalent epoxy compound (A) can obtain good curing reactivity, its epoxy equivalent is usually 100 to 1500 equivalents, and preferably 150 to 500 equivalents. In addition, in this specification, "epoxy equivalent" means the number of grams (g / eq) of the epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JISK7236.

The polyvalent epoxy compound (A) that can be used in the present invention can be suitably produced in accordance with a conventional method, but can also be obtained from a commercially available product.

An example of a commercially available product of a polyphenylene compound (A) having a biphenyl structure is a phenol-type epoxy compound having a biphenylalkyl structure. For example, the product names are "NC3000-FH, NC3000-H, NC3000, NC3000." -L, NC3100 "(above, manufactured by Nippon Kayaku Co., Ltd.); an epoxy compound having a tetramethylbiphenyl structure, for example, a trade name" YX-4000 "(above, manufactured by Mitsubishi Chemical Corporation).

Examples of commercially available products of the polyvalent epoxy compound (A) having a condensed polycyclic structure are phenolic epoxy compounds having a dicyclopentadiene structure. For example, the product names are "EPICLON HP7200L, EPICLON HP7200, EPICLON." HP7200H, EPICLON HP7200HH, EPICLON HP7200HH "(above, manufactured by DIC Corporation," EPICLON "is a registered trademark), trade names" Tactix556, Tactix756 "(above, manufactured by HUNTSMAN ADVANCED MATERIAL, registered trademark of" Tactix "), trade name [XD -1000-1L, XD-1000-2L "(above, manufactured by Nippon Kayaku Co., Ltd.).

These polyhydric epoxy compounds (A) can be used individually or in mixture of 2 or more types.

In the present invention, a biphenyl structure and / or a polycondensate are used. In the case of a polyvalent epoxy compound (A) having a ring structure, an epoxy compound (B) containing a trivalent or more polyvalent / polyvalent glycidyl group other than the phenol novolac epoxy compound may be used in combination. The epoxy compound (B) containing a trivalent or higher polyvalent glycidyl group can further improve the heat resistance and electrical properties of the obtained cured resin layer.

The epoxy compound (B) containing a trivalent or higher polyvalent glycidyl group other than the phenol novolac epoxy compound is a compound having an epoxy equivalent of 250 or less from the viewpoint of heat resistance and electrical properties of the obtained cured resin layer. Preferably, compounds below 220 are more preferred.

Specifically, the polyhydric phenol type epoxy compound which has the structure which glycidizes the hydroxyl group of a polyvalent phenol of 3 or more, and the glycidation of the amino group of the compound containing a polyvalent amino phenyl group of 2 or more can be exemplified. A glycerylamine type epoxy compound, or a polyglycidyl group-containing compound that glycidizes a trivalent or higher compound having the phenol structure or the aminophenyl structure in the same molecule.

The polyhydric phenol-type epoxy compound which has a structure which glycidizes the hydroxyl group of a trivalent or more polyvalent phenol is not specifically limited, A trivalent or more polyhydric hydroxyphenylalkane type epoxy compound is preferable. Here, the trivalent or higher polyhydric hydroxyphenylalkane type epoxy compound refers to a compound having a structure in which a hydroxyl group of an aliphatic hydrocarbon substituted with a hydroxyphenyl group of 3 or more is glycidized.

The epoxy compound (B) containing a trivalent or higher polyvalent glycidyl group that can be used in the present invention can be suitably produced in accordance with a conventional method, but can also be obtained from a commercially available product.

For example, as a commercially available product of a trihydroxyphenylmethane type epoxy compound, for example, trade names "EPPN-503, EPPN-502H, EPPN-501H" (above, Japanese (Manufactured by Japan Chemical Co., Ltd.), trade names "TACTIX-742" (above, manufactured by Dow Chemical Co., Ltd.), "jER 1032H60" (above, manufactured by Mitsubishi Chemical Co., Ltd.), and the like. Examples of commercially available products of the tetrahydroxyphenylethane type epoxy compound include the trade name "jER 1031S" (above, manufactured by Mitsubishi Chemical Corporation) and the like. Examples of the glycidylamine-type epoxy compound include a tetravalent glycidylamine-type epoxy compound, for example, trade names "YH-434, YH-434L" (above, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and trade names "jER604" "(Above, manufactured by Mitsubishi Chemical Corporation). As a trivalent glycidylamine type epoxy compound, a glycidyl-containing compound having a polyvalent glycidyl group, which is a glycidated trivalent or higher compound having a phenol structure or an aminophenyl structure in the same molecule, may be, for example, a trade name " jER630 "(above, manufactured by Mitsubishi Chemical Corporation).

When the epoxy compound (B) containing a trivalent or higher polyvalent glycidyl group is used in combination, the content ratio of the epoxy compound (B) containing a trivalent or higher polyvalent glycidyl group is not particularly limited. Of the total 100% by weight of the oxygen compound, 0.1 to 40% by weight is preferred, 1 to 30% by weight is more preferred, and 3 to 25% by weight is particularly preferred. In the thermosetting resin composition, the content of the epoxy compound (B) containing a polyvalent glycidyl group having a valence of 3 or more and the relationship between the epoxy compound (B) and the polyvalent epoxy compound (A) fall within the above range, and the obtained cured resin can be further enhanced. The heat resistance and electrical characteristics of the layer, and the adhesion to the conductor layer.

In addition, the thermosetting resin composition used in the present invention, as well as the above-mentioned polyvalent epoxy compound (A) and a trivalent or higher polyvalent glycidyl group-containing epoxy compound (B), may contain these as appropriate. Epoxy compounds other than epoxy compounds. Examples of such other epoxy compounds include epoxy compounds containing phosphorus. An epoxy compound containing phosphorus can favorably be an epoxy compound having a phenanthrene structure, and by using such a phenanthrene junction The structured epoxy compound can further improve the heat resistance, electrical properties, and adhesiveness of the conductor layer of the obtained cured resin layer.

An epoxy compound having a phenanthrene structure may be one having more than one epoxy group in its molecule, but by increasing the bridge density, the mechanical strength and heat resistance of the obtained hardened resin layer can be improved, and the wire can be reduced. From the viewpoint of the expansion ratio and the improvement of electrical characteristics, a polyvalent epoxy compound having at least two epoxy groups in the molecule is preferred.

When the thermosetting resin composition used in the present invention contains an epoxy compound having a phosphaphenanthrene structure as another epoxy compound, the content ratio of the epoxy compound having a phosphaphenanthrene structure is not particularly limited. The thermosetting resin Of the total 100% by weight of the epoxy compound contained in the composition, 20 to 90% by weight is preferable, and 30 to 70% by weight is more preferable.

In addition, as other epoxy compounds, in addition to other epoxy compounds having a phenanthrene structure, alicyclic epoxy compounds, cresol novolac epoxy compounds, and phenol novolac epoxy compounds may be used. , Bisphenol A phenol-type epoxy compound, triphenol-type epoxy compound, tetra (hydroxyphenyl) ethane-type epoxy compound, aliphatic chain epoxy compound, and the like, which can be obtained from appropriate commercially available products.

The thermosetting resin composition used in the present invention may also contain a phenol resin (C) containing a triazine structure. The phenol resin (C) containing a triazine structure is an aromatic hydroxy compound such as phenol, cresol, naphthyl alcohol, a compound having a triazine ring such as melamine or benzomelamine, and a condensation polymer of formaldehyde. The phenol resin (C) containing a triazine structure usually has a structure represented by the following general formula (1).

(In formula (1), R ¹ and R ² are hydrogen atoms or methyl groups, and p is an integer from 1 to 30. In addition, R ¹ and R ² may be the same or different from each other, and p is 2 or more. , the plural R ^2, may be the same or different from each other. Further, in formula (1), on at least one amine, can also be another group (e.g., alkyl group) substituted with an amine group contained in the Hydrogen atom.)

A phenol resin (C) containing a triazine structure is a hardener that acts as an epoxy compound due to the presence of a phenolic reactive hydroxyl group. In particular, a phenol resin (C) containing a triazine structure is used to obtain a hardened resin. Layer, which exhibits excellent adhesion to a substrate.

The phenol resin (C) containing a triazine structure can be produced according to a conventional method, but it can also be obtained from a commercially available product. Examples of such commercially available products include, for example, trade names "LA7052, LA7054, LA3018, and LA1356" (above, manufactured by DIC Corporation).

The above triazine-containing phenol resins (C) can be used alone or in combination of two or more kinds.

The blending amount of the phenol resin (C) containing a triazine structure in the thermosetting resin composition used in the present invention is preferably 1 to 60 parts by weight relative to 100 parts by weight of the total amount of the epoxy compound used, and 2 to 60 parts by weight is preferred. It is more preferably 50 parts by weight, more preferably 3 to 40 parts by weight, and particularly preferably in a range of 4 to 20 parts by weight.

In addition, in the thermosetting resin composition of the present invention, Equivalent ratio of the epoxy compound used to the phenol resin (C) containing a triazine structure [total number of active hydroxyl groups of the phenol resin (C) containing a triazine structure, relative to the total epoxy group of the epoxy compound used The ratio (number of active hydroxyl groups / epoxy group)] is preferably 0.01 to 0.6, more preferably 0.05 to 0.4, and further preferably 0.1 to 0.3. When the blending amount of the phenol resin (C) containing a triazine structure is within the above range, the electrical properties and heat resistance of the obtained cured resin layer can be further improved. In addition, the equivalent ratio of the epoxy compound used to the phenol resin (C) containing a triazine structure can be calculated from the total epoxy equivalent of the epoxy compound used and the total active hydroxyl group of the phenol resin (C) containing a triazine structure. Find the equivalent.

In addition, the thermosetting resin composition used in the present invention preferably contains an active ester compound (D) in addition to the above components. The active ester compound (D) may be any compound having an active ester group. In the present invention, a compound having at least two active ester groups in the molecule is preferred. The active ester compound (D) reacts an ester site with an epoxy group by heating, and acts as a curing agent for the epoxy compound of the present invention in the same manner as the phenol resin (C) containing the triazine structure.

The active ester compound (D) is an active ester compound obtained by reacting a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound from the viewpoint of improving the heat resistance of the obtained cured resin layer. Preferably, an active ester compound obtained by reacting one or two or more kinds selected from the group consisting of a carboxylic acid compound, a phenol compound, a naphthyl alcohol compound, and a thiol compound is more preferable, so as to have a carboxylic acid compound and phenolic properties. An aromatic compound obtained by the reaction of a hydroxy group, and an aromatic compound having at least two active ester groups in the molecule is particularly preferred. The active ester compound (D) may be linear or branched. The active ester compound (D) is exemplified in the case of a compound derived from a compound having at least two carboxylic acids in the molecule. A compound having at least two carboxylic acids therein can improve compatibility with an epoxy compound when it contains an aliphatic chain, and can improve heat resistance when it has an aromatic ring.

Specific examples of the carboxylic acid compound used to form the active ester compound (D) include benzoic acid / benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and Phthalic acid, pyromellitic acid, etc. Among these, from the viewpoint of improving the heat resistance of the obtained cured resin layer, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like are preferred. Phthalic acid, isophthalic acid and terephthalic acid are more preferred, and isophthalic acid and terephthalic acid are more preferred.

Specific examples of the thiocarboxylic acid compound used to form the active ester compound (D) include thioacetic acid and thiobenzoic acid.

Specific examples of the hydroxy compound used to form the active ester compound (D) include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, and methylated bisphenol. Phenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol, benzene Triphenol, dicyclopentadienyl diphenol, phenol novolac and the like. Among them, from the viewpoint of improving the solubility of the active ester compound (D) and improving the heat resistance of the obtained cured resin layer, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6- Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac are preferred. Dihydroxybenzophenone and trihydroxydibenzophenone Benzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol and phenol novolac are more preferred, and dicyclopentadienyl diphenol and phenol novolac are more preferred.

Specific examples of the thiol compound used to form the active ester compound (D) include benzenedithiol and triazinedithiol.

The manufacturing method of an active ester compound (D) is not specifically limited, It can manufacture by a conventional method. For example, it can be obtained by the condensation reaction of the said carboxylic acid compound and / or a thiocarboxylic acid compound, and a hydroxyl compound and / or a thiol compound.

The active ester compound (D) can be, for example, an aromatic compound having an active ester group disclosed in Japanese Patent Application Laid-Open No. 2002-12650 and a polyfunctional polyester disclosed in Japanese Patent Application Laid-Open No. 2004-277460. Sale. Commercially available products include, for example, the product name "EXB9451, EXB9460, EXB9460S, EPICLON HPC-8000-65T" (above, manufactured by DIC Corporation, "EPICLON" is a registered trademark), and the product name is "DC808" (Japanese Epoxy Resin Company) (Manufactured by Japan Epoxy Co., Ltd.) under the trade name "YLH1026".

In the thermosetting resin composition used in the present invention, the blending amount of the active ester compound (D) is preferably 10 to 150 parts by weight, and 15 to 130 parts by weight based on 100 parts by weight of the total epoxy compound used. More preferably, it is more preferably in a range of 20 to 120 parts by weight.

In addition, in the thermosetting resin composition used in the present invention, the equivalent ratio of the epoxy compound used to the active ester compound (D) [the total number of reactive groups of the active ester compound (D) is relative to that of the epoxy compound used. The ratio of the total number of epoxy groups (the amount of active ester groups / the amount of epoxy groups)] is preferably 0.5 to 1.2, more preferably 0.6 to 0.9, and further preferably a range of 0.65 to 0.85.

In addition, in the thermosetting resin composition used in the present invention, the equivalent ratio of the epoxy compound used to the phenol resin (C) and the active ester compound (D) containing a triazine structure is {the epoxy group of the epoxy compound used Total pair contains three The ratio of the total number of active hydroxyl groups of the phenol resin (C) and the active ester group of the active ester compound (D) in the azine structure [epoxy group amount / (active hydroxyl group amount + active ester group amount)]}, usually less than 1.2 , Preferably from 0.6 to 0.99, and more preferably from 0.65 to 0.95. By making the said equivalent ratio into the said range, favorable electrical characteristics can be exhibited in the hardened resin layer obtained. In addition, the equivalent ratio of the epoxy compound used to the phenol resin (C) and the active ester compound (D) containing a triazine structure can be a phenol resin containing a triazine structure from the total epoxy equivalent of the epoxy compound used. The total active hydroxyl equivalent of (C) and the total active ester equivalent of the active ester compound (D) were calculated.

The thermosetting resin composition used in the present invention may further contain other components described below in addition to the above components.

By blending a filler with the thermosetting resin composition, the resulting cured resin layer can be made with low linear expansion. As the filler, any of conventional inorganic fillers and organic fillers can be used, but an inorganic filler is preferred. Specific examples of the inorganic filler include, for example, calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, water and aluminum oxide, magnesium hydroxide, and hydrogen. Alumina, barium sulfate, silicon dioxide, talc, clay, etc. Furthermore, the filler used may be a surface treated in advance with a silane coupling agent or the like. The content of the filler used in the thermosetting resin composition of the present invention is not particularly limited, and it is usually 30 to 90% by weight in terms of solid content.

In addition, the thermosetting resin composition may be formulated with an alicyclic olefin polymer having a polar group. Examples of the polar group include a group having a structure capable of reacting with an epoxy group to form a covalent bond, and a group containing a hetero atom and having no reactivity to the epoxy group, so as to contain a hetero atom and to the epoxy group. Non-reactive groups are preferred. Such alicyclic olefin polymers are not reactive to epoxy groups. Or, therefore, it is substantially free of a functional group having reactivity with an epoxy group. Here, the "substantially free of a functional group having reactivity to an epoxy group" refers to an alicyclic olefin polymer, and to the extent that it does not prevent the effect of the present invention from being exhibited, it does not contain a reactive group to an epoxy group. The meaning of the functional group. The functional group having an epoxy group reactivity may be, for example, a group having a structure capable of reacting with an epoxy group to form a covalent bond. A functional group such as a carboxylic acid anhydride group, a hydroxyl group, and an epoxy group, which contains a hetero atom that reacts with the epoxy group to form a covalent bond.

The alicyclic olefin polymer may be suitably combined with, for example, an alicyclic olefin monomer (a) containing no hetero atom and containing an aromatic ring; and an alicyclic olefin monomer (b) containing no aromatic ring and containing a hetero atom. ); An alicyclic olefin monomer (c) containing both an aromatic ring and a heteroatom; and an aromatic ring and a heteroatom that do not contain an aromatic ring and a heteroatom, and can be copolymerized with the above alicyclic olefin monomers (a) to (c) The body (d) can be easily obtained by polymerization in accordance with a conventional method. The obtained polymer may be further hydrogenated.

The blending amount of the alicyclic olefin polymer having a polar group used in the thermosetting resin composition of the present invention is not particularly limited, and it is usually 50 parts by weight or less based on 100 parts by weight of the total amount of the epoxy compound used. It is preferably 35 parts by weight or less.

The thermosetting resin composition may contain a hardening accelerator, if necessary. The hardening accelerator is not particularly limited, and examples thereof include aliphatic polyamines, aromatic polyamines, secondary amines, tertiary amines, acid anhydrides, imidazole derivatives, organic acid hydrazines, cyanodiamines and derivatives thereof, Urea derivatives, etc. Among them, imidazole derivatives are particularly preferred.

The imidazole derivative is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include 2-ethylimidazole and 2-ethyl-4-methylimidazole. Azole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-heptylimidazole, etc. Alkyl-substituted imidazole compounds; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl- 2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2'-cyanoethyl) imidazole, and the like containing a aryl group or an aralkyl group and substituted with a hydrocarbon group Imidazole compounds. These can be used individually or in combination of 2 or more types.

In the thermosetting resin composition used in the present invention, the blending amount of the hardening accelerator is usually 0.1 to 10 parts by weight and preferably 0.5 to 8 parts by weight based on 100 parts by weight of the total amount of the epoxy compound used.

In addition, the thermosetting resin composition may be suitably blended for the purpose of improving the flame retardancy of the obtained cured resin layer. For example, a halogen blend flame retardant or a phosphoric acid ester flame retardant is generally blended in an electrically insulating film. Flame retardant for the resin composition used.

In addition, the thermosetting resin composition used in the present invention may further be suitably blended with a flame retardant auxiliary, a heat stabilizer, a weather stabilizer, an anti-aging agent, an ultraviolet absorber (laser processability improver), and the like, as desired. Leveling agent, antistatic agent, slip agent, antiblocking agent, anti-fog agent, slip agent, dye, natural oil, synthetic oil, wax, emulsion, magnetic material, dielectric properties Conventional ingredients such as regulators and tougheners.

The method for preparing the thermosetting resin composition used in the present invention is not particularly limited, and the above-mentioned components may be directly mixed, or may be mixed in a state of being dissolved or dispersed in an organic solvent, and a part of the above-mentioned components may be dissolved or dissolved. The composition is prepared in a state dispersed in an organic solvent, and the remaining components are mixed in the composition.

In the first step of the manufacturing method of the present invention, the curable resin composition layer composed of the thermosetting resin composition is formed on a support using the thermosetting resin composition described above, and the curability of the support is obtained. Resin composition layer.

The method for forming a curable resin composition layer composed of a thermosetting resin composition on a support is not particularly limited. The thermosetting resin composition is coated with an organic solvent as desired, and is coated, sprayed, or cast on the support. A method of drying is preferred.

The thickness of the curable resin composition layer is not particularly limited, but it is usually from 5 to 50 μm, preferably from 7 to 40 μm, preferably from 10 to 35 μm, and from 10 to 30 μm from the viewpoint of handleability and the like.

Examples of the method for applying the thermosetting resin composition include a dipping method, a roll coating method, a curtain coating method, a die coating method, a slit coating method, and a gravure coating method.

The curable resin composition layer may be in a semi-hardened state in addition to the case where the thermosetting resin composition is not cured. Here, the term "uncured" refers to a case where the curable resin composition layer is immersed in a solvent capable of dissolving a curable resin (for example, an epoxy resin) used to prepare a thermosetting resin composition, so that substantially all the curable resin is dissolved. status. In addition, the so-called semi-hardening is a state where it can be hardened by further heating, and it is hardened to a halfway point. A part of the hardening resin (specifically, an amount of 7% by weight or more and a part of the remaining amount) is dissolved in the soluble use The state of the solvent of the curable resin of the thermosetting resin composition is prepared, or the volume of the molded body after immersion in the solvent for 24 hours is changed to a state of 200% or more (expansion rate) of the volume before immersion.

Moreover, after applying a thermosetting resin composition to a support body, you may dry it as needed. The drying temperature is preferably a temperature at which the curable resin composition does not harden, and may be set in accordance with the type of the curable resin used, and is usually 20 to 300 ° C, and preferably 30 to 200 ° C. If the drying temperature is too high, the curing reaction proceeds excessively, and the resulting curable resin composition layer may not be in an uncured or semi-cured state. The drying time is usually 30 seconds to 1 hour, and preferably 1 minute to 30 minutes.

In addition, in the first step of the production method of the present invention, the curable resin composition layer may be formed into a structure having two or more layers. For example, a resin layer (hereinafter, this resin layer is referred to as a "first resin layer") formed using the above-mentioned thermosetting resin composition (hereinafter, this thermosetting resin composition is referred to as a "first thermosetting resin composition"). .), On the support, a second thermosetting resin composition different from the first thermosetting resin composition was used to form a second resin layer different from the first resin layer, and a first thermosetting resin combination was used thereon. By forming the first resin layer, the curable resin composition layer is formed into a two-layer structure. In this case, for example, the second resin layer may be used as a coating layer for forming a conductor layer by electroless plating or the like, and the first resin layer may be used as an adhesive layer to be adhered to a substrate. .

The second thermosetting resin composition for forming the second resin fat layer is not particularly limited. Generally, a hardening resin different from the first thermosetting resin composition and a hardening agent may be used to improve the hardening resin composition. From the viewpoint of the electrical properties and heat resistance of the layer, the curable resin is preferably one containing an alicyclic olefin polymer having a polar group.

The alicyclic olefin polymer having a polar group is not particularly limited The alicyclic structure includes, for example, a cycloalkane structure or a cycloolefin structure. Since mechanical strength and heat resistance are excellent, those having a naphthenic structure are preferred. Examples of the polar group contained in the alicyclic olefin polymer include alcoholic hydroxyl group, phenolic hydroxyl group, carboxyl group, alkoxy group, epoxy group, glycidyl group, oxycarbonyl group, carbonyl group, amine group, and carboxylic anhydride group. , Sulfonic group, phosphate group, etc. Among them, a carboxyl group, a carboxylic acid anhydride group, and a phenolic hydroxyl group are preferable, and a carboxylic acid anhydride group is more preferable.

In addition, the hardener contained in the second thermosetting resin composition is not particularly limited as long as it can form a bridge structure by heating the alicyclic olefin polymer having a polar group, and it can be generally formulated in electrical properties. A hardener for a resin composition for forming an insulating film. The hardener is preferably a compound having two or more functional groups which can react with the polar group of the alicyclic olefin polymer having a polar group to be used to form a bond.

For example, when an alicyclic olefin polymer having a carboxyl group, a carboxylic acid anhydride group, and a phenolic hydroxyl group is used as the alicyclic olefin polymer having a polar group, a curing agent that can be suitably used includes, for example, a polyvalent epoxy compound, a polyvalent Isocyanate compounds, polyamine compounds, polyhydrazine compounds, aziridine compounds, basic metal oxides, organic metal halides, and the like. These can be used alone or in combination of two or more. In addition, these compounds may be used in combination with a peroxide as a hardener.

Among them, as the curing agent, the reactivity with the polar group of the alicyclic olefin polymer having a polar group is eased, and the operation of the second thermosetting resin composition is facilitated. Therefore, a polyvalent epoxy compound is preferred. It is particularly preferable to use a glycidyl ether type epoxy compound or an alicyclic polyvalent epoxy compound.

In the second thermosetting resin composition, the blending amount of the hardener is, With respect to 100 parts by weight of the alicyclic olefin polymer having a polar group, it is preferably 1 to 100 parts by weight, more preferably 5 to 80 parts by weight, and further preferably a range of 10 to 50 parts by weight. By making the compounding quantity of a hardening | curing agent into the said range, the mechanical strength and electrical characteristics of a hardened resin layer can be made favorable.

In addition, the second thermosetting resin composition may contain a hindered phenol compound and a hindered amine compound in addition to the above components.

The compounding amount of the hindered phenol compound in the second thermosetting resin composition is not particularly limited, and it is preferably 0.04 to 10 parts by weight, and 0.3 to 5 parts by weight relative to 100 parts by weight of the alicyclic olefin polymer having a polar group. The weight part is more preferable, and the range of 0.5 to 3 weight part is more preferable. By making the compounding quantity of a hindered phenol compound into the said range, the mechanical strength of a hardened resin layer can be made favorable.

The hindered amine compound is a compound having at least one 2,2,6,6-tetraalkylpyridyl group having a secondary amine or a tertiary amine in the fourth position in the molecule. The carbon number of the alkyl group is usually 1 to 50. The hindered amine compound is preferably a compound having at least one 2,2,6,6-tetraalkylpyridyl group having a secondary amine or a tertiary amine in the fourth position. In addition, in the present invention, it is preferable to use a hindered phenol compound and a hindered amine compound in combination. By using these in combination, an aqueous solution of a permanganate is used for the hardened resin layer to perform surface roughening treatment, even if the surface is roughened. When the processing conditions are changed, the surface roughness of the cured product after the surface roughening treatment can be kept low.

The amount of the hindered amine compound is not particularly limited. It is usually 0.02 to 10 parts by weight, preferably 0.2 to 5 parts by weight, and more preferably 0.25 to 3 parts by weight relative to 100 parts by weight of the alicyclic olefin polymer having a polar group. Part by weight is preferred. By making the compounding quantity of a hindered amine compound into the said range, the mechanical strength of a hardened resin layer can be made favorable.

The second thermosetting resin composition may contain a hardening accelerator in addition to the above components. The hardening accelerator may be a hardening accelerator generally formulated in a resin composition for forming an electrical insulating film. For example, a hardening accelerator similar to that of the first thermosetting resin composition can be used. The blending amount of the hardening accelerator in the second thermosetting resin composition may be appropriately selected according to the purpose of use, and is preferably 0.001 to 30 parts by weight relative to 100 parts by weight of the alicyclic olefin polymer having a polar group. It is preferably 0.01 to 10 parts by weight, and more preferably 0.03 to 5 parts by weight.

The second thermosetting resin composition may contain a filler in addition to the above components. As the filler, the same fillers as those used for the first thermosetting resin composition can be used. In the second thermosetting resin composition, the blending amount of the filler is, in terms of solid content, usually 1 to 50% by weight, preferably 2 to 45% by weight, and more preferably 3 to 35% by weight.

In addition, the second thermosetting resin composition, in addition to the above components, may be blended with a hardening accelerator, a flame retardant, a flame retardant aid, a heat stabilizer, a weather stabilizer, and anti-aging as well as the first thermosetting resin composition. Agent, ultraviolet absorber (laser processability improver), leveling agent, antistatic agent, slip agent, anti-adhesive agent, anti-fog agent, slip agent, dye, natural oil, synthetic oil, wax, emulsion, magnetic Materials, conventional properties of dielectric property modifiers, toughness agents, etc.

The method for producing the second thermosetting resin composition is not particularly limited, and the above-mentioned components may be directly mixed, or may be mixed in a state of being dissolved or dispersed in an organic solvent, and a part of the above-mentioned components may be dissolved or dispersed in an organic material. The state of the solvent prepares a composition, and the remaining components are mixed in the composition.

In the first step of the manufacturing method of the present invention, a first resin layer is used. When constituting a curable resin composition layer with two layers of the second resin layer, for example, the following two methods may be used. That is, (1) the second thermosetting resin composition is coated, sprayed, or cast on a support, dried as desired to form a second resin layer, and then the first thermosetting resin is further combined thereon A method for manufacturing or coating a substrate and drying it as desired to form a first resin layer; and (2) a second thermosetting resin composition which is applied, sprayed, or cast on a support according to The second resin layer with a support is desirably dried, and the first thermosetting resin composition coated, sprayed, or cast on another support is dried as desired. A method of laminating the first resin layer, integrating the formed bodies, and peeling off the support on the first resin layer side, and manufacturing the method. Among these manufacturing methods, the manufacturing method described in (1) above is preferred because it is an easy process and has excellent productivity.

In the manufacturing method of the above (1), when the second thermosetting resin composition is applied, sprayed, or cast on a support, and the second resin layer formed using the second thermosetting resin composition is applied, sprayed or sprayed, When spraying or casting the first curable resin composition, or using the second thermosetting resin composition and the first thermosetting resin composition in the manufacturing method of (2) above, a second resin layer with a support and a second resin layer are obtained. When there is a first resin layer having a support, an organic solvent is preferably added to the second thermosetting resin composition or the first thermosetting resin composition, and the support is preferably coated, sprayed or cast.

In the above-mentioned manufacturing methods (1) and (2), the thickness of the second resin layer and the first resin layer is not particularly limited. The thickness of the second resin layer is preferably 1 to 10 μm, and 1.5 to 8 μm. The thickness of the first resin layer is preferably 4 to 45 μm, more preferably 7 to 40 μm, and more preferably 2 to 5 μm. The thickness is preferably 9 to 29 μm. If the thickness of the second resin layer is too small, when the second resin layer is used as a layer to be plated, and the conductive layer is formed by electroless plating, the formability of the conductive layer may be reduced. On the other hand, if the thickness of the second resin layer is too thick, the linear expansion of the cured resin layer may increase. In addition, if the thickness of the first resin layer is too thin, the embeddability of the wiring may be reduced.

Examples of the method for applying the second thermosetting resin composition and the first thermosetting resin composition include a dipping method, a roll coating method, a curtain coating method, a mold coating method, a slit coating method, and a gravure coating method. Law, etc.

The drying temperature is preferably a temperature at which the second thermosetting resin composition and the first thermosetting resin composition do not harden, and is usually 20 to 300 ° C and preferably 30 to 200 ° C. The drying time is usually 30 seconds to 1 hour, and preferably 1 minute to 30 minutes.

(Step 2)

In the second step of the manufacturing method of the present invention, the hardened resin composition layer with a support obtained in the first step is laminated on the substrate at the formation surface side of the hardened resin composition layer to obtain A step of a pre-cured composite with a support composed of a base material and a layer of a curable resin composition with a support.

The substrate is not particularly limited, and examples thereof include a substrate having a conductive layer on the surface. A substrate having a conductive layer on the surface and a conductive layer on the surface of the electrically insulating substrate. The electrically insulating substrate may include, for example, a conventional electrically insulating material (for example, an alicyclic olefin polymer, epoxy Compounds, maleimide resins, (meth) acrylic resins, diallyl phthalate resins, triazine resins, polyphenylene ethers, glass, etc.) are hardened and formed. In addition, the conductor layer is not particularly limited, and is usually a conductor including a conductive metal or the like. The formed wiring layer may further contain various circuits. The structure and thickness of wiring and circuits are not particularly limited. Specific examples of the substrate having a conductive layer on the surface include a printed circuit board, a silicon wafer substrate, and the like. The thickness of the substrate having the conductive layer on the surface is usually 10 μm to 10 mm, preferably 20 μm to 5 mm, and more preferably 30 μm to 2 mm. In addition, the height (thickness) of the wiring of the substrate having the conductive layer on the surface is usually 3 to 35 μm. In addition, when the hardened resin layer is formed, the difference between the thickness of the hardenable resin composition and the height (thickness) of the wiring of a substrate having a conductor layer on the surface is "hardened" from the viewpoint of improving wiring embedding and insulation reliability. The thickness of the flexible resin composition-the height (thickness) of the wiring "is preferably 35 μm or less, and more preferably 3 to 30 μm.

In addition, the substrate used in the present invention having a conductive layer on the surface is preferably treated beforehand on the surface of the conductive layer in order to improve the adhesion with the curable resin composition layer. The method of the pretreatment is not particularly limited, and a known technique can be used. For example, if the conductor layer is made of copper, then the surface of the conductor layer is brought into contact with a strongly alkaline oxidizing solution, and an oxidation treatment method for roughening the surface of the conductor by forming a layer of copper oxide; A method of reducing with sodium borohydride, formalin, etc .; a method of roughening plating chromatography on a conductor layer; a method of making a conductor layer in contact with an organic acid to dissolve copper grain boundaries to roughen it; and The conductive layer is a method of forming a primer layer using a thiol compound, a silane compound, or the like. Among these, from the viewpoint of the ease of maintaining the shape of the fine wiring pattern, a method for roughening the grain boundary of copper by contacting the conductive layer with an organic acid and dissolving the grain boundary of the copper, and using a thiol compound or a silane compound for the conductive layer A method of forming the primer layer is preferred.

In the second step of the manufacturing method of the present invention, a support will be attached The method of laminating the curable resin composition layer on the substrate side by forming the curable resin composition layer on the substrate includes, for example, a thermosetting resin composition layer with a support and a curable resin composition layer. A method of forming a surface-side thermocompression bond on a substrate, and the like.

The method of thermocompression bonding is to superimpose a molded body or a composite molded body with a support body in contact with the conductor layer of the substrate, and use pressure lamination, pressing, vacuum lamination, vacuum pressing, and roll lamination. A method such as thermocompression bonding (lamination) is performed with a press such as this. By heating and pressing, the interface between the conductor layer on the surface of the substrate and the molded body or the composite molded body can be combined with substantially no voids present. The molded article or composite molded article is usually laminated on a conductor layer of a substrate in an unhardened or semi-hardened state.

The operating temperature of thermocompression bonding is usually 30 ~ 250 ° C, preferably 70 ~ 200 ° C. The applied pressure is usually 10kPa ~ 20MPa, preferably 100kPa ~ 10MPa, and the time is usually 30 seconds ~ 5 hours in 1 minute. ~ 3 hours is better. In addition, thermocompression bonding is preferably performed under reduced pressure in order to improve the embedding of the wiring pattern and suppress the occurrence of bubbles. The pressure for thermocompression bonding under reduced pressure is usually 100 kPa to 1 Pa, and preferably 40 kPa to 10 Pa.

(Step 3)

The third step of the manufacturing method of the present invention is performed by using a support-cured pre-hardened composite composed of a base material and a hardened resin composition layer with a support obtained in the second step described above. The first heating is a step of thermally curing the curable resin composition layer to constitute a cured resin layer.

The heating temperature for the first heating in the third step is suitable according to the curing temperature of the curable resin composition layer or the type of support used. It can be set, preferably from 100 to 250 ° C, preferably from 120 to 220 ° C, and even more preferably from 150 to 210 ° C. The heating time of the first heating in the third step is usually 0.1 to 3 hours, and preferably 0.25 to 1.5 hours. The heating method is not particularly limited, and for example, it may be performed using an electric furnace or the like. In addition, heat curing is preferably carried out in air from the viewpoint of productivity.

Step 4)

The fourth step of the manufacturing method of the present invention is a step of forming a through hole on the support side of the hardened composite body with a support obtained in the third step, and forming a through hole in the hardened resin layer.

In the fourth step, the method for forming the via hole is not particularly limited, and it can be formed by performing a physical treatment such as a drill, a laser, and a plasma etching method on the support side. Among these methods, since a laser method (a carbon dioxide laser, an excimer laser, a UV-YAG laser, etc.), that is, a method of forming a via hole by irradiating a laser from a support side, Since finer via holes can be formed without deteriorating the characteristics of the hardened resin layer, it is preferable. In the manufacturing method of the present invention, a through hole is formed in the hardened resin layer by making a hole from the support side, so that a small hole (for example, a top diameter (diameter) ), Preferably 15 to 65 μm, and more preferably 15 to 55 μm).

(Step 5)

The fifth step of the manufacturing method of the present invention is a step of obtaining a hardened composite composed of a base material and a hardened resin layer by peeling the support from the hardened composite with the support attached. The method for peeling the support is not particularly limited.

(Step 6)

The sixth step of the manufacturing method of the present invention is the curing after peeling the support. The composite is subjected to a second heating step.

In the manufacturing method of the present invention, the hardening resin composition layer is thermally hardened while the support is attached to form a hardened resin layer, and then a via hole is formed in the hardened resin layer. Then, the hardened resin layer is peeled off After the support is further subjected to a second heating, in addition to sufficiently curing the hardened resin layer, the volatile components contained in the hardened resin layer (for example, used to prepare the first thermosetting resin composition or the second thermosetting resin combination By properly removing organic solvents such as organic solvents), the heat resistance (for example, soldering heat resistance) of the cured resin layer can be improved. In particular, when the thermosetting is performed while the support is attached without peeling off the support, the volatile components may not be properly removed due to the influence of the support (especially, there may be cases where In the case of a volatile component in a region, etc.), due to the influence of such a volatile component, the resulting cured resin layer may have insufficient heat resistance. In contrast, in the manufacturing method of the present invention, the support is heat-cured in a state where the support is attached without peeling (first heating). On the other hand, after the support is peeled off, the second heating is performed again, which may be appropriate. The volatile components, etc., which cannot be removed due to the influence of the support during the first heating, can be sufficiently removed to thereby sufficiently improve heat resistance (for example, soldering heat resistance).

In the sixth step, the heating temperature for the second heating is not particularly limited. From the viewpoint of good adhesion between the hardened resin layer after heating and the conductor layer formed on the hardened resin layer, it is higher than the first The temperature of the first heating in the third step is preferably a lower temperature, more preferably a temperature lower than the heating temperature of the first heating by 10 ° C or higher, and further preferably a temperature lower than the heating temperature of the first heating by 30 ° C or higher. In addition, the heating temperature of the second heating can be adjusted with the boiling temperature of the organic solvent used to prepare the first thermosetting resin composition or the second thermosetting resin composition. The point relationship is preferably set at a temperature that is 5 ° C or higher than the boiling point of the organic solvent used, and more preferably at a temperature that is 10 ° C or higher than the boiling point of the organic solvent used. Specifically, the heating temperature for the second heating is preferably in the range of 130 to 170 ° C, and more preferably in the range of 140 to 160 ° C. By setting the heating temperature of the second heating to the above range, the heat resistance of the hardened resin layer can be improved, and at the same time, the resin residue in the via hole can be more appropriately removed when the seventh step described later is performed, thereby making the via hole Continuity reliability is better.

The heating time for the second heating in the sixth step is usually 0.1 to 3 hours, and preferably 0.25 to 1.5 hours. The heating method is not particularly limited, and it may be performed using, for example, an electric furnace. In addition, from the viewpoint of productivity, heat curing is preferably performed in air.

(Step 7)

The seventh step of the manufacturing method of the present invention is a step of removing the resin residue in the via hole from the cured composite after the second heating.

The method of removing the resin residue in the via hole is not particularly limited, and examples thereof include a method of desmearing the cured composite after the support is peeled off. The method of removing the dross is not particularly limited, and for example, a method of contacting a solution (a dross removing solution) of an oxidizing compound such as permanganate. Specifically, the laminated body forming the via hole can be immersed in a 60-80 ° C aqueous solution at a concentration of 60 g / L of sodium permanganate and 28 g / L of sodium hydroxide, and immersed by shaking for 1 to 50 minutes. , For slag removal.

Furthermore, in the manufacturing method of the present invention, the surface roughening treatment for roughening the surface of the hardened resin layer may be performed before or after the slag removing treatment for removing the resin residue in the via hole. . Surface roughening treatment In order to improve the adhesion between the hardened resin layer and the conductor layer.

The method for the surface roughening treatment is not particularly limited, and examples thereof include a method of bringing the surface of the cured resin layer into contact with an oxidizing compound. Examples of the oxidizing compound include a conventional compound having an oxidizing ability such as an inorganic oxidizing compound or an organic oxidizing compound. Since it is easy to control the average surface roughness of the hardened resin layer, it is particularly preferable to use an inorganic oxidizing compound or an organic oxidizing compound. Examples of the inorganic oxidizing compound include permanganate, anhydrous chromic acid, dichromate, chromate, persulfate, active manganese dioxide, osmium tetroxide, hydrogen peroxide, and periodate. Examples of organic oxidizing compounds include dicumyl peroxide, octanoyl peroxide, m-chloroperoxybenzoic acid, peracetic acid, Ozone, etc.

In addition, in the manufacturing method of the present invention, the surface roughening treatment of the hardened resin layer may be performed at the same time as the slag removal treatment for removing the resin residue in the via hole.

(Step 8)

The eighth step of the manufacturing method of the present invention is a step of forming a conductor layer on the inner wall surface of the via hole of the cured composite and the cured resin layer after removing the resin residue in the via hole in the eighth step.

In the eighth step of the manufacturing method of the present invention, a conductor is filled in the via hole by electroless plating or a combination of electroless plating and electrolytic plating, and a conductor layer is formed at least on the inner wall surface of the via hole. It is possible to form a conductive layer with excellent adhesion in a via hole with high production efficiency.

In addition, the method of forming the conductor layer on the hardened resin layer is not particularly limited. From the viewpoint that a conductive layer having excellent adhesion can be similarly formed, it is preferable to perform it by electroless plating or a combination of electroless plating and electrolytic plating.

When forming a conductor layer by electroless plating, first, a metal film layer is formed on the inner wall surface of the via hole and the surface of the electrical insulating layer, and generally, catalyst cores such as silver, palladium, zinc, and cobalt are attached to the via. The inner wall surface of the hole and the electrical insulation layer. The method for attaching the catalyst core to the inner wall surface of the via hole and the electrical insulating layer is not particularly limited, and examples thereof include immersion in a metal compound such as silver, palladium, zinc, cobalt, and the like or a salt thereof. A method for reducing the metal at a concentration of 0.001 to 10% by weight in a solution of an organic solvent such as water, alcohol, or chloroform (including an acid, an alkali, a complexing agent, and a reducing agent as necessary). Wait.

The electroless plating solution used in the electroless plating method may be a conventional self-catalytic type electroless plating solution. The types of metals, reducing agents, complexing agents, hydrogen ion concentration, and dissolved oxygen concentration included in the plating solution may be used. It is not particularly limited. For example, an electroless copper plating solution using ammonium hypophosphite, hypophosphite, ammonium borohydride, hydrazine, formalin, etc. as a reducing agent; an electroless nickel-phosphorus liquid using sodium hypophosphite as a reducing agent; Electroless nickel-boron solution with methylamine borane as reducing agent; electroless palladium solution; electroless palladium-phosphorus solution with sodium hypophosphite as reducing agent; electroless gold liquid; electroless silver liquid; An electroless plating solution, such as an electroless nickel-cobalt-phosphorus solution, using sodium phosphate as a reducing agent.

After the metal thin film is formed, the surface of the substrate is brought into contact with a rust preventive agent and subjected to a rust preventive treatment. In addition, after forming the metal thin film, the metal thin film may be heated in order to improve adhesion and the like. The heating temperature is usually 50 to 350 ° C, preferably 80 to 250 ° C. The heating at this time may be performed under a pressure condition. The pressing method at this time may be, for example, a physical method using a hot press, a pressurized heating roll, or the like. Method of pressure means. The applied pressure is usually 0.1 to 20 MPa, and more preferably 0.5 to 10 MPa. Within this range, high adhesion between the metal thin film and the electrical insulating layer can be ensured.

Then, the metal thin film formed by the electroless plating method is further subjected to electrolytic plating to grow the plated film. Thereby, a conductor can be filled in a via hole by electroless plating and electrolytic plating, and a thickened coating can be performed on a hardened resin layer. The electrolytic plating is performed on the hardened resin layer. When the plating film is thickened, a resist pattern for plating can be formed on the metal thin film formed by the electroless plating method, and further electrolytic plating can be performed thereon. The plating film is grown, the resist is removed, and the metal thin film is etched into a pattern by etching to form a conductor layer. Then, the conductor layer formed by this method is generally composed of a patterned metal thin film and a plating layer grown thereon.

Since the laminated body obtained by the manufacturing method of the present invention is obtained through the above-mentioned first to eighth steps, it has excellent heat resistance (for example, soldering heat resistance), and can form via holes with small apertures. Such characteristics are suitably used as a multilayer circuit board.

In addition, the layered body obtained by the manufacturing method of the present invention is used as the base material used in the second step of the manufacturing method of the present invention, and the above-mentioned third to eighth steps can be repeatedly performed to further multi-layer. In this way, the required multilayer circuit substrate can be obtained.

[Example]

Hereinafter, the present invention will be described more specifically with examples and comparative examples. In addition, the "part" and "%" in each case are based on weight unless specifically mentioned. Various physical properties are evaluated in accordance with the following methods.

(1) Formability of small-aperture vias

After the via hole is formed, the slag removal treatment and the second heated hardened composite are performed. The via hole after the slag removal treatment is observed with an electron microscope (magnification: 1000 times), and the opening diameter of the via hole is measured to make a small aperture. The formation of vias was evaluated on the following basis.

A: The opening diameter of the via hole is less than 55 μm

B: The opening diameter of the via hole is 55 μm or more and 65 μm or less

C: The opening diameter of the via hole exceeds 65 μm

(2) Deslagging

After the via hole is formed, the slag removal treatment and the second heated hardened composite are performed. The via hole after the slag removal treatment is observed with an electron microscope (magnification: 5000 times), and the resin residue (smear in the via hole) )) The observations were evaluated on the following basis.

A: In the via hole, the area where the rubber residue exists is less than 3% of the measurement area

B: In the via hole, the area where the slag exists is 3% or more of the measurement area, and less than 10%

C: The area where the rubber slag exists in the via hole is 10% or more of the measurement area.

(3) Welding heat resistance

The obtained multilayer printed wiring board was floated on a solder bath at 260 ° C. for 60 seconds, and then the appearance of the floating multilayer printed wiring board was observed and evaluated in accordance with the following criteria.

(Evaluation criteria)

A: No swelling was confirmed

C: Swelling was observed at one or more places.

Synthesis Example 1

As the first stage polymerization, 35 moles of 5-ethylene-bicyclo [2.2.1] hept-2-ene, 0.9 moles of 1-hexene, 340 moles of anisole, and 0.005 moles of 4-Ethyloxybenzylidene (dichloro) (4,5-diol-1,3-dimethyl-4-imidazolin-2-ylidene (4,5-dibromo-1,3-dimesityl -4-imidazolin-2-ylidene)) (tricyclohexylphosphine) ruthenium (C1063, manufactured by Wako Pure Chemical Industries, Ltd.) as a ruthenium-based catalyst, put in a nitrogen-substituted pressure-resistant glass reactor, and polymerize under stirring at 80 ° C. The reaction was performed for 30 minutes to obtain a solution of a norbornene-based ring-opening polymer.

Next, as the second stage polymerization, the first stage polymerization of the resulting solution was added 45 mole portion tetracyclo [6.5.0.1 ^2,5 .0 ^8,13] tridec -3,8,10,12- tetraene 20 moles of bicyclic [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, 250 moles of anisole and 0.01 moles of C1063 were obtained by stirring at 80 ° C for 1.5 hours under stirring A solution of a norbornene-based ring-opening polymer. As a result of measuring gas chromatography on this solution, it was confirmed that substantially no monomer remained, and the polymerization conversion rate was 99% or more.

Next, the solution of the obtained ring-opened polymer was placed in an autoclave equipped with a nitrogen-substituted stirrer, 0.03 mole portion C1063 was added, and the hydrogenation reaction was performed at 150 ° C. and a hydrogen pressure of 7 MPa for 5 hours. A solution of an alicyclic olefin polymer (1) of a hydride of a norbornene-based ring-opened polymer. The alicyclic olefin polymer (1) had a weight average molecular weight of 60,000, a number average molecular weight of 30,000, and a molecular weight distribution of 2. The hydrogenation rate was 95%, and the content of the repeating unit having a carboxylic acid anhydride group was 20 mol%. The solid content concentration of the alicyclic olefin polymer (1) solution was 22%.

Example 1 (Preparation of the first thermosetting resin composition)

50 parts of a biphenylmethylene skeleton phenolic epoxy resin (trade name "NC-3000L", manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269) as a multivalent epoxy compound (A) having a biphenyl structure; 50 parts of a tetrahydroxyphenylethane type epoxy compound (trade name "jER 1031S") which is a polyglycidyl group-containing epoxy compound (B) having a trivalent or higher valence (trade name "jER 1031S", manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 200, softening point 90 ° C); 30 parts of a triazine structure-containing cresol novolac resin (trade name "Phenolite LA-3018-50P") as a phenol resin (C) containing a triazine structure; 50% non-volatile propylene glycol methyl ether solution, Active hydroxyl equivalent 154 (manufactured by DIC) (15 parts based on cresol novolac resin containing triazine structure); 115.3 parts of active ester compound (trade name "EPICLON HPC-8000-65T") as active ester compound (D) , 65% toluene solution with non-volatile content, manufactured by DIC Corporation, active ester equivalent (223) (75 parts in terms of active ester compounds); 350 parts of silica (filler name "SC2500-SXJ") , Manufactured by Admatechs); 1 part of a hindered phenol antioxidant (trade name) as an anti-aging agent Of Irganox (registered trademark) 3114 ", manufactured by BASF Corporation) and 110 parts of anisole (boiling point 154 deg.] C) were mixed in a planetary mixer with stirring for 3 minutes. Further, 8.3 parts of a solution of 1-benzyl-2-phenylimidazole as a hardening accelerator was dissolved in anisole at 30% (2.5 parts in terms of 1-benzyl-2-phenylimidazole), The varnish of the first thermosetting resin composition was obtained by stirring with a planetary mixer for 5 minutes. The content of the filler in the varnish was 64% in terms of solid content.

(Second thermosetting resin composition)

454 parts of the alicyclic olefin polymer (1) solution [100 parts converted from the alicyclic olefin polymer (1)] obtained in Synthesis Example 1; 36 parts of a multi-component having a dicyclopentadiene skeleton as a hardener Epoxy compound (trade name `` EPICLON "HP7200L", manufactured by DIC, "EPICLON" is a registered trademark); 24.5 parts of silicide as an inorganic filler (trade name "ADMAFINE SO-C1", manufactured by Admatechs, with an average particle diameter of 0.25 μm, and "ADMAFINE" is a registered trademark ); 1 part of tris (3,5-di-tertiarybutyl-4-hydroxybenzyl) isocyanurate (trade name "Irganox (registered trademark) 3114", manufactured by BASF Corporation) as an anti-aging agent; 0.5 Parts of 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole as a UV absorber; and 0.5 parts of 1- as a hardening accelerator Benzyl-2-phenylimidazole was mixed with anisole, and the concentration of the formulation was 16% to obtain a varnish of the second thermosetting resin composition.

(Production of hardened composites)

The varnish of the second thermosetting resin composition obtained above was coated with a polyethylene terephthalate film layer (support, 50 μm thickness) having a release layer on the surface using a wire bar. Next, it was dried at 80 ° C. for 5 minutes in a nitrogen atmosphere to obtain a support-attached film layer on which a second resin layer (plated layer) having a thickness of 3 μm, which was composed of an uncured second thermosetting resin composition, was formed. .

Next, the varnish of the first thermosetting resin composition obtained above was applied using a doctor blade (manufactured by TESTER Industries) and an automatic film applicator (manufactured by TESTER Industries). The formation surface of the second resin layer composed of the second thermosetting resin composition of the film layer of the support was then dried under a nitrogen atmosphere at 80 ° C. for 5 minutes to obtain a second resin layer having a total thickness of 30 μm and The first resin layer (adhesive layer) is a curable resin composition layer with a support. This hardened resin composition layer with a support is a second thermosetting resin composition composed of a second support, depending on the support. The resin layer and the first resin layer composed of the first thermosetting resin composition are formed in this order.

Next, in addition to the above, the surface of a core material obtained by impregnating a glass fiber and a halogen-free epoxy compound-containing glass fiber with a core material was adhered to a copper having a thickness of 18 μm and a thickness of 0.8 mm. 160mm square (length 160mm, width 160mm) on both sides of the copper substrate surface, the surface is in contact with the organic acid for micro etching treatment to form a conductor layer with a wiring width and wiring pitch of 50 μm and a thickness of 18 μm to obtain an inner layer Substrate.

The hardened resin composition layer with a support obtained as described above was cut into a square of 150 mm, and the surface on the side of the hardened resin composition layer was placed inside with the support attached, and adhered to both sides of the inner substrate. Then, a vacuum laminator equipped with a heat-resistant rubber platen was used to reduce the pressure to 200 Pa, and heat-press and laminate at a temperature of 110 ° C. and a pressure of 0.1 MPa for 60 seconds. Next, after standing still at room temperature for 30 minutes, the curable resin composition layer was cured by heating (first heating) at 180 ° C. for 30 minutes to form a cured resin layer (electrical insulating layer).

Next, a carbon dioxide laser processing machine (product name "LUC-2K21", manufactured by Hitachi Via Mechanics) was used for the hardened resin layers formed on both sides of the inner substrate to maintain the state of the support with a pulse. ) At a condition of 6 μs width, 2000 Hz frequency, twice, a carbon dioxide laser is irradiated from the support side, and a via hole with an opening diameter of 49 μm is formed in the hardened resin layer. Then, the support is peeled from the hardened resin layer forming the via hole.

(2nd heating step)

Next, the cured composite after peeling the support was heated at 200 ° C. for 30 minutes (second heating).

(Slag removal step)

Next, the second heated hardened composite was prepared into a swelling liquid ("Swelling Dip Securiganth P", manufactured by Atotech Corporation, "Securiganth" is a registered trademark) at 500 mL / L and 3 g / L sodium hydroxide at 60 ° C. After shaking for 15 minutes, it was washed with water.

Next, 640 mL / L of an aqueous solution of permanganate ("Concentrate Compact CP", manufactured by Atotech) and an 80 ° C aqueous solution with a sodium hydroxide concentration of 40 g / L were shaken and immersed for 15 minutes, and then washed with water.

Next, the hardened composite was immersed in a 40 ° C aqueous solution prepared with an aqueous hydroxylamine sulfate solution ("Reduction Securiganth P500", manufactured by Atotech, "Securiganth") for 5 minutes, and neutralized for 5 minutes, and neutralized. After the reduction treatment, it was washed with water. Then, the thus obtained slag removal treatment and the second heated hardened composite were evaluated for the formation of small-pore vias and the slag removal properties in accordance with the method described above. The results are shown in Table 1.

(Cleaner.conditioner)

Next, the slag-removed hardened composite will be cleaned. The concentration of the aqueous solution ("Alcup MCC-6-A", manufactured by Uemura Industrial Co., Ltd., "Alcup" is a registered trademark) was adjusted to 50 ml / L of a 50 ° C aqueous solution for 5 minutes for cleaning. Adjustment processing. Next, the hardened composite was immersed in washing water at 40 ° C for 1 minute, and then washed with water.

(Soft etching process step)

Next, the hardened composite was immersed in an aqueous solution prepared with a sulfuric acid concentration of 100 g / L and a sodium persulfate 100 g / L for 2 minutes to perform a soft etching treatment, and then washed with water.

(Pickling treatment step)

Next, the hardened composite was prepared into an aqueous solution having a sulfuric acid concentration of 100 g / L. After immersing for 1 minute for pickling, it was washed with water.

(Catalyst attaching step)

Next, the hardened composite was prepared into Alcup Activator MAT-1-A (trade name, manufactured by Uemura Industrial Co., Ltd., "Alcup" is a registered trademark) 200 mL / L, Alcup Activator MAT-1-B (trade name, Uemura Industrial Co., Ltd.) ("Alcup" is a registered trademark), 30 mL / L, 0.35 g / L sodium hydroxide, 60 ° C Pd salt-containing plating catalyst aqueous solution was immersed for 5 minutes, and then washed with water.

(Activation step)

Next, the hardened composite was prepared into Alcup Reducer MAB-4-A (trade name, manufactured by Uemura Industrial Co., Ltd., "Alcup" is a registered trademark) 20 mL / L, Alcup Reducer MAB-4-B (trade name, Uemura Industrial Co., Ltd.) ("Alcup" is a registered trademark), a 200 mL / L aqueous solution was immersed at 35 ° C for 3 minutes, and the plating catalyst was reduced, and then washed with water.

(Accelerated processing steps)

Next, the hardened composite was immersed in a 50 mL / L aqueous solution of Alcup Accelerator MEL-3-A (trade name, manufactured by Uemura Industrial Co., Ltd., registered trademark) at 25 ° C for 1 minute.

(Electroless plating step)

Prepared as Thru-cup PEA-6-A (trade name, manufactured by Uemura Industrial Co., Ltd., "Thru-cup" is a registered trademark) 100mL / L, Thru-cup PEA-6-B-2X (trade name, Uemura Industrial Co., Ltd.) (Manufactured) 50 mL / L, Thru-cup PEA-6-C (trade name, manufactured by Uemura Industrial Co., Ltd.) 14 mL / L, Thru-cup PEA-6-D (trade name, manufactured by Uemura Industrial Co., Ltd.) 15 mL / L, Thru- cup PEA-6-E (trade name, manufactured by Uemura Industrial Co., Ltd.) 50 mL / L, 37% formalin aqueous solution 5 mL / L electroless copper plating solution, impregnated with 36 ^c C for 20 minutes while blowing in air An electroless copper plating process is performed to form a metal thin film on the inner wall surface of the via hole of the cured composite and the surface of the cured resin layer (the surface of the cured second resin layer composed of the second thermosetting resin composition).

Next, the hardened composite forming the metal thin film was immersed at room temperature in a rust-prevention solution prepared at 10 mL / L of AT-21 (trade name, manufactured by Uemura Industries, Ltd.) for 1 minute, and then washed with water. Furthermore, a rust-proof hardened composite was produced by drying. The hardened composite subjected to the rust prevention treatment was subjected to an annealing treatment at 150 ° C. for 30 minutes in an air atmosphere.

An electrolytically plated copper film having a thickness of 30 μm was formed on the hardened composite body subjected to the annealing treatment by copper electrolytic plating. Next, the hardened composite was heat-treated at 180 ° C. for 60 minutes to obtain a via hole of the hardened composite, which was filled with a conductor composed of a metal thin film layer and electrolytic copper plating, and the hardened resin layer of the hardened composite. (Electrical insulation layer) A multilayer printed circuit board with two layers on both sides of a conductor layer composed of a metal thin film layer and an electrolytic plated copper film is formed on the (electrical insulation layer). Then, using the obtained multilayer printed wiring board, evaluation of soldering heat resistance was performed. The results are shown in Table 1.

Example 2

A cured composite and a multilayer printed wiring board were obtained in the same manner as in Example 1 except that the heating temperature was changed from 200 ° C to 160 ° C in the second heating step, and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 1

A cured composite and a multilayer printed wiring board were obtained in the same manner as in Example 1 except that the heating in the second heating step was not performed, and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 2

After the hardening resin composition layer with the support is adhered to both sides of the inner substrate, the support is peeled off, the first heating and the via hole are formed while the support is peeled, and the second heating is performed at the same time. In the procedure, the heating temperature was changed from 200 ° C to other than 160 ° C, and a cured composite and a multilayer printed wiring board were obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

As shown in Table 1, according to the manufacturing method of the present invention, as a result, a laminated body capable of forming a via hole having a small aperture and having excellent soldering heat resistance was obtained (Examples 1 and 2).

On the other hand, when the second heating (the formation of via holes and heating after peeling of the support) was not performed, the solder heat resistance was inferior (Comparative Example 1).

In addition, in the state where the support was peeled off, when the first heating was performed and the via hole was formed, a via hole with a small pore size could not be formed (Comparative Example 2).

Claims (5)

A method for producing a laminate, comprising: forming a layer of a curable resin composition composed of a thermosetting resin composition on a support; and obtaining a layer of a curable resin composition layer with a support. 1 step; the above-mentioned hardening resin composition layer with a support is formed on the surface side with the hardening resin composition layer, and is laminated on the substrate to obtain a base material and a hardening resin composition with a support A second step of a pre-hardened composite with a support composed of layers; the first heating of the composite to thermally harden the hardenable resin composition layer into a hardened resin layer to obtain a base material, and The third step of the support-attached hardened composite with the support-attached hardened resin layer; openings are made from the support side of the above-mentioned support-attached hardened composite to form conduction in the above-mentioned hardened resin layer. 4th step of holes; 5th step of peeling the support from the hardened composite with a support to obtain a hardened composite composed of a base material and a hardened resin layer; The sixth step of the second heating; the seventh step of removing the resin residue in the via hole of the hardened composite body; and the first step of forming the conductor layer on the inner wall surface of the via hole of the hardened composite body and the hardened resin layer. 8 steps; in the 8th step, the formation of the conductive layer of the via is performed by filling the conductor in the via with electroless plating or a combination of electroless plating and electrolytic plating. The method for manufacturing a laminated body according to item 1 of the scope of patent application, wherein the heating temperature of the second heating in the sixth step is lower than the heating temperature of the first heating in the third step. The method for manufacturing a laminated body according to item 1 or 2 of the scope of patent application, wherein the formation of the conductor layer on the hardened resin layer is performed by electroless plating, or a combination of electroless plating and electrolytic plating. A laminated body is obtained by the method for manufacturing a laminated body according to any one of items 1 to 3 of the scope of patent application. A multilayer circuit substrate is composed of a laminated body as described in item 4 of the scope of patent application.