TW201729660A - Method for manufacturing laminate manufacturing a laminate which is superior in heat resistance and enables the formation of a via-hole of a small diameter - Google Patents

Abstract

The object of the present invention is to provide a method for manufacturing a laminate which is superior in heat resistance (e.g. welding heat resistance) and enables the formation of a via-hole of a small diameter. This invention provides a method for manufacturing a laminate, which comprises: a step of forming, on a support, a curable resin composition layer composed of thermosetting resin compositions, thereby obtaining a support-attached curable resin composition layer; a step of laminating the support-attached curable resin composition layer on a substrate by a curable resin composition layer formation side, thereby obtaining a support-attached pre-curing complex composed of the substrate and the support-attached curable resin composition layer; a step of performing first heating on the support-attached pre-curing complex and heat curing the curable resin composition layer to form a cured resin layer, thereby obtaining a support-attached cured complex composed of the substrate and the support-attached cured resin layer; a via-hole formation step of boring the support-attached cured complex from the side of the support; a step of peeling the support from the support-attached cured complex, thereby obtaining a cured complex composed of the substrate and the cured resin layer; a step of performing second heating of the cured complex; a step of removing a resin residue in the via-hole of the cured complex; and a step of forming a conductor layer on the inner wall face of the via-hole of the cured complex and the cured resin layer. The formation of the conductor layer on the via-hole is performed by electroless plating or a combination of electroless plating and electrolytic plating on the conductors filled in the via hole.

Description

Method for manufacturing laminate

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

In order to reduce the size of the electronic device, increase the number of functions, and increase the speed of the communication, the circuit board used in the electronic device is required to be further increased in density. In order to achieve such a high density, the circuit board is required to be multilayered. In such a multilayer circuit substrate, for example, an electrically insulating layer is laminated on an inner layer substrate composed of an electrically insulating layer and a conductor layer formed on a surface thereof, and a conductor layer is formed on the electrically insulating layer. Further, the formation of the electrical insulating layer and the formation of the conductor layer are repeated.

A method for producing a laminate for forming such a multilayer circuit substrate, for example, Patent Document 1, discloses a method of manufacturing a multilayer printed wiring board, which must include: a support base film having a release layer/release layer and At least the pattern processing portion on one or both sides of the circuit-processed circuit substrate, the resin composition layer of the adhesive film is directly covered and overlapped, and the steps of heating, pressurizing, and laminating under vacuum conditions a step of thermally hardening the resin composition in a state in which a base film is supported; a step of opening a hole by a laser or a drill; a step of peeling off the base film; and a step of roughening the surface of the resin composition; Next, the roughened surface is plated to form a conductor layer.

In Patent Document 1, the resin composition is thermally cured in a state in which a support such as a support base film is attached, thereby preventing the resin composition from adhering to foreign matter during thermal curing, and the foreign matter is broken or short-circuited. Bad cause. Further, in Patent Document 1, after the resin composition is thermally cured in a state in which the support is attached, a hole having a small aperture can be formed by opening a hole by a laser or a drill before peeling off the support.

[Previous Technical Literature]

[Patent Literature]

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

However, as in the technique of Patent Document 1, the resin composition is thermally cured in a state in which a support such as a support base film is attached, and after the heat is cured, when the support is peeled off, the heat is insufficient and the heat is hardened. The hardened resin has a poor heat resistance.

An object of the present invention is to provide a method for producing a laminate having excellent heat resistance (for example, solder heat resistance) and capable of forming via holes having a small aperture.

As a result of intensive studies to achieve the above object, the present inventors have found a method for producing a laminate having a conductor layer and a cured resin layer on a substrate, and a combination of a heat-curable resin composition in a state in which a support is attached. After the layer is hardened, the hardened resin layer after hardening is opened from the support side to form a via hole, and after the support is peeled off, the step of heating is performed again, and thereafter By removing the resin residue in the via hole formed, it is possible to effectively solve the problem of heat resistance which is a problem when the curable resin composition layer is thermally cured in a state in which the support is attached, and the present invention has been completed. .

In other words, according to the present invention, there is provided a method for producing a laminate comprising: a layer of a curable resin composition comprising a thermosetting resin composition formed on a support; The first step of the curable resin composition layer having a support; the curable resin composition layer with the support described above is formed on the surface side of the curable resin composition layer, and laminated on the substrate to obtain a substrate And a second step of the pre-hardening composite with the support comprising the curable resin composition layer with the support; the first heat of the composite is used to heat the curable resin composition layer a third step of curing the cured resin layer to obtain a cured composite having a support and a cured resin layer with a support; and the support from the hardened composite having the support described above a fourth step of forming a via hole in the hardened resin layer on the side; and peeling the support from the cured composite body with the support to obtain a hardened composite composed of a substrate and a cured resin layer a fifth step; a sixth step of performing the second heating on the hardened composite; a seventh step of removing the resin residue in the via hole of the hardened composite; and an inner wall surface of the via hole of the hardened composite; An eighth step of forming a conductor layer on the cured resin layer; and in the eighth step, forming the conductor layer of the via hole by electroless plating or a combination of electroless plating and electrolytic plating in the via hole [2] The method for producing a laminate according to the above [1], wherein the heating temperature of the second heating in the sixth step is higher than the heating in the third step [3] The method for producing a laminate according to [1] or [2], wherein the formation of the conductor layer on the hardened resin layer, electroless electroless plating, or a combination of electroless plating and electrolytic plating [4] A laminated body obtained by the method for producing a laminate according to any one of the above [1] to [3]; and [5] a multilayer circuit substrate comprising the above [4] The composition of the laminate described.

According to the production method of the present invention, it is possible to provide a laminate having excellent heat resistance (for example, solder heat resistance), a via hole having a small pore diameter, and a multilayer circuit board using the same.

The method for producing a laminate of the present invention is a method for producing a laminate having a conductor layer and a cured resin layer on a substrate, comprising: (1) forming a thermosetting resin composition on a support. (1) The first step of obtaining a curable resin composition layer with a support; (2) forming the curable resin composition layer with the support described above as a curable resin composition layer a second step of laminating the substrate to obtain a pre-cured composite having a support composed of a substrate and a curable resin composition layer with a support; (3) The cured resin composition layer is thermally cured to a cured resin layer by first heating the composite, thereby obtaining a hardened support with a support and a cured resin layer with a support. a third step of the composite; (4) a fourth step of forming a via hole in the cured resin layer by opening the support body side of the cured composite body with the support; (5) The fifth step of obtaining the hardened composite composed of the base material and the cured resin layer by peeling the support by the cured composite body with the support; (6) the sixth step of performing the second heating on the hardened composite; 7) a seventh step of removing the resin residue in the via hole of the hardened composite; and (8) an eighth step of forming a conductor layer on the inner wall surface of the via hole of the hardened composite and the cured resin layer.

Further, in the method for producing a laminate according to the present invention, in the eighth step, the formation of the conductor layer of the via hole is performed in the via hole by electroless plating or a combination of electroless plating and electrolytic plating. This is done by filling the conductor.

(Step 1)

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

The support to be 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-shaped member, and examples thereof include a polyethylene terephthalate film and a polypropylene film. , polyethylene film, polycarbonate film, polyethylene naphthalate film, polyarylate film, nylon film, polytetrafluoroethylene film and other polymer film, or plate. Film-like glass substrate Wait. The support can be more easily peeled off from the cured resin layer in the fifth step to be described later, and it is preferable to have a release layer for the release treatment on the surface, and to have a release layer having a release layer. An ethyl phthalate film is preferred.

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

Further, the thermosetting resin composition for forming the 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 curing agent and has electrical insulating properties, and examples thereof include an epoxy resin, a maleamide resin, a (meth)acrylic resin, and an orthobenzene. Diallyl dicarboxylate resin, triazine resin, alicyclic olefin polymer, aromatic polyether polymer, benzocyclobutene polymer, cyanate polymer, polyimine, and the like. These resins may be used alone or in combination of two or more.

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

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

The above-mentioned biphenyl structure means a structure in which two benzene rings are linked by a single bond. The biphenyl structure, in the obtained hardened resin, usually constitutes the main chain of the resin, but may be present in the side chain.

Further, the above-mentioned condensed polycyclic structure means a structure in which two or more single-ring condensations (condensed rings) are formed. The ring constituting the condensed polycyclic structure may be an alicyclic ring or an aromatic ring, or may be a hetero atom. The number of the condensed rings is not particularly limited, and from the viewpoint of improving the heat resistance and mechanical strength of the obtained cured resin layer, it is preferably 2 or more rings, and practically, the upper limit is about 10 rings. Examples of the condensed polycyclic structure include a dicyclopentadiene structure, a naphthalene structure, a fluorene structure, a fluorene structure, a phenanthrene structure, a triphenylene structure, a fluorene structure, and an egg benzene structure. The condensed polycyclic structure is the same as the above-described biphenyl structure, and the obtained cured resin layer usually constitutes a main chain of the resin contained in the cured resin layer, but may be present in the side chain.

The polyvalent 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 the heat resistance and mechanical strength of the hardened resin layer obtainable by the lift are obtained. From the viewpoint of the above, the polyvalent epoxy compound (A) is preferably one having a biphenyl structure and preferably having a biphenylalkyl structure.

Further, when the polyvalent epoxy 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 electric properties of the hardened resin layer are improved. From the viewpoint of the property characteristics, the ratio of the blending ratio is preferably 3/7 to 7/3 by weight (polyvalent epoxy compound having a biphenyl structure/polyvalent epoxy compound having a condensed polycyclic structure). .

The polyvalent epoxy compound (A) to be used in the present invention is not limited to a structure as long as it has at least two epoxy groups in one molecule and has 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. a phenolic epoxy compound, which may be exemplified by phenol A phenolic epoxy compound, a cresol novolac epoxy compound, or the like.

Since the polyvalent epoxy compound (A) can obtain good curing reactivity, the epoxy equivalent is usually from 100 to 1,500 equivalents, preferably from 150 to 500 equivalents. In the present specification, the term "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured in accordance with the method of JIS K 7236.

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

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

Further, as an example of a commercially available product of a polyvalent epoxy compound (A) having a condensed polycyclic structure, a phenolic epoxy compound having a dicyclopentadiene structure may be mentioned, for example, under the trade names "EPICLON HP7200L, EPICLON HP7200, EPICLON". HP7200H, EPICLON HP7200HH, EPICLON HP7200HHH" (above, DIC company, "EPICLON" is a registered trademark), trade name "Tactix556, Tactix756" (above, HUNTSMAN ADVANCED MATERIAL company, "Tactix" registered trademark), trade name [XD -1000-1L, XD-1000-2L" (above, manufactured by Nippon Kayaku Co., Ltd.).

The above polyvalent epoxy compound (A) may be used alone or in combination of two or more.

Further, in the present invention, the use of a biphenyl structure and/or condensation is used. In the case of the polyvalent epoxy compound (A) having a ring structure, an epoxy compound (B) containing a trivalent or higher polyvalent/polyvalent glycidyl group other than the above phenol novolac type epoxy compound may be used in combination, and this is further used. The epoxy compound (B) containing a trivalent or higher polyglycidyl 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 polyglycidyl group other than the phenol novolac type 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, the compound of 220 or less is more preferable.

Specifically, a polyhydric phenol type epoxy compound having a structure in which a hydroxy group of a trivalent or higher polyhydric phenol is glycidylated, and a glycidylation of an amine group containing a compound having a divalent or higher polyaminophenyl group can be exemplified. A glycerol amine type epoxy compound or a diglycidyl group-containing compound which glycidylates a trivalent or higher compound having the above phenol structure or aminophenyl structure in the same molecule.

The polyhydric phenol epoxy compound having a structure in which a hydroxy group of a trivalent or higher polyvalent phenol is glycidylated is not particularly limited, and a trivalent or higher polyhydroxyphenylene oxide epoxy compound is preferred. Here, the trivalent or higher polyhydroxyphenylene oxide type epoxy compound means a compound having a structure in which a hydroxyl group of an aliphatic hydrocarbon substituted with 3 or more hydroxyphenyl groups is glycidylated.

The epoxy compound (B) containing a trivalent or higher polyglycidyl group used in the present invention can be suitably produced according to a conventional method, but it can also be obtained from a commercially available product.

For example, examples of commercially available products of a trishydroxyphenylmethane type epoxy compound include, for example, trade names "EPPN-503, EPPN-502H, EPPN-501H" (above, day) The product name "TACTIX-742" (above, manufactured by Dow Chemical Co., Ltd.), "jER 1032H60" (above, manufactured by Mitsubishi Chemical Corporation). In addition, examples of the commercial product of the tetrahydroxyphenylethane type epoxy compound include, for example, the product name "jER 1031S" (above, manufactured by Mitsubishi Chemical Corporation). The glycidylamine type epoxy compound is, for example, a trade name "YH-434, YH-434L" (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) under the trade name "jER604", which is a tetravalent glycidylamine type epoxy compound. (above, manufactured by Mitsubishi Chemical Corporation). A polyglycidyl group-containing compound which is glycidylated with a trivalent or higher compound having a phenol structure or an aminophenyl structure in the same molecule, and a trivalent glycidylamine type epoxy compound may, for example, be a trade name. jER630" (above, manufactured by Mitsubishi Chemical Corporation).

When the epoxy compound (B) containing a trivalent or higher polyglycidyl group is used in combination, the content ratio of the epoxy compound (B) containing a trivalent or higher polyglycidyl group is not particularly limited, and is equivalent to the ring to be used. The total amount of the oxygen compound is preferably from 0.1 to 40% by weight, more preferably from 1 to 30% by weight, still more preferably from 3 to 25% by weight, based on 100% by weight of the total amount of the oxygen compound. In the thermosetting resin composition, the content of the epoxy compound (B) containing a trivalent or higher polyglycidyl group and the relationship of the above polyvalent epoxy compound (A) can further enhance the obtained cured resin in the above range. The heat resistance, electrical properties, and adhesion to the conductor layer of the layer.

In addition, the above-mentioned polyvalent epoxy compound (A) and the epoxy compound (B) containing a trivalent or higher polyglycidyl group are preferably used in the thermosetting resin composition of the present invention. An epoxy compound other than an epoxy compound. As such another epoxy compound, for example, an epoxy compound containing phosphorus can be mentioned. An epoxy compound containing phosphorus, which is excellent in an epoxy compound having a phosphaphenanthrene structure, by using such a phosphorus phenanthrene The epoxy compound of the structure further improves the heat resistance, electrical properties, and adhesion of the conductor layer of the obtained cured resin layer.

The epoxy compound having a phosphaphenanthene structure may have one or more epoxy groups in its molecule, but the bridge density is increased, whereby the mechanical strength and heat resistance of the obtained cured resin layer can be improved, and the line can be lowered. From the viewpoint of the expansion ratio and the improvement of the electrical properties, a polyvalent epoxy compound having at least two epoxy groups in the molecule is preferred.

When the thermosetting resin composition of 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, and the thermosetting resin is not particularly limited. The total amount of the epoxy compound contained in the composition is preferably from 20 to 90% by weight, more preferably from 30 to 70% by weight, based on 100% by weight of the total of the epoxy compound.

Further, as the other epoxy compound, in addition to other epoxy compounds having a phosphaphenanthrene structure, or an alicyclic epoxy compound, a cresol novolac type epoxy compound, or a phenol novolac type epoxy compound may be used. A bisphenol A novolac type epoxy compound, a trisphenol type epoxy compound, a tetrakis (hydroxyphenyl)ethane type epoxy compound, an aliphatic chain epoxy compound, etc., etc. are obtained from a suitable commercial item.

Further, the thermosetting resin composition used in the present invention may further 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 or naphthol, a compound having a triazine ring such as melamine or benzoguanamine, or a condensation polymer of formaldehyde. The phenol resin (C) having a triazine structure usually has a structure represented by the following formula (1).

(In the formula (1), R ¹ and R ² are a hydrogen atom or a methyl group, and p is an integer of 1 to 30. Further, R ¹ and R ² may be the same or different from each other, and further, p is 2 or more. The plural R ² may be the same or different from each other. Further, in the formula (1), at least one of the amine groups may be substituted with an amine group in another group (for example, an alkyl group or the like). Hydrogen atom.)

The phenol resin (C) having a triazine structure functions as a hardener for an epoxy compound by the presence of a phenolic active hydroxyl group, and particularly, a hardened resin obtained by a phenol resin (C) containing a triazine structure. The layer exhibits excellent adhesion to the substrate.

The phenol resin (C) containing a triazine structure can be produced by a conventional method, but it can also be obtained from a commercial item. As an example of such a commercial item, the brand name "LA7052, LA7054, LA3018, LA1356" (above, DIC company) is mentioned.

The above phenol resin (C) containing a triazine structure may be used alone or in combination of two or more.

The phenol resin (C) having a triazine structure is preferably used in an amount of from 1 to 60 parts by weight based on 100 parts by weight of the total of the epoxy compound to be used, and the amount of the phenol resin (C) to be used in the thermosetting resin composition of the present invention is preferably from 2 to 60 parts by weight. More preferably, 50 parts by weight is further preferably 3 to 40 parts by weight, particularly preferably 4 to 20 parts by weight.

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

Further, the thermosetting resin composition used in the present invention preferably contains the active ester compound (D) in addition to the above respective components. The active ester compound (D) is not particularly limited as long as it has 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 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 above-described benzene resin (C) containing a 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 and the like. Preferably, the active ester compound is preferably one or more selected from the group consisting of a carboxylic acid compound, a phenol compound, a naphthol compound, and a thiol compound, and has a carboxylic acid compound and a phenolic property. An aromatic compound having a hydroxyl group is obtained by reacting an aromatic compound having at least two active ester groups in the molecule. The active ester compound (D) may be a linear or multi-chain chain, and the active ester compound (D) is exemplified by a case of a compound having at least two carboxylic acids in a molecule. When a compound having at least two carboxylic acids contains an aliphatic chain, compatibility with an epoxy compound can be improved, and when an aromatic ring is included, heat resistance can be improved.

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

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

Specific examples of the hydroxy compound used to form the active ester compound (D) include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, and methylated double. Phenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1 , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzene Trisphenol, 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, phenol novolac, preferably dihydroxybenzophenone, trihydroxy More preferably, benzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, or phenol novolac, and further preferably dicyclopentadienyl diphenol or phenol novolac.

Specific examples of the thiol compound used for the active ester compound (D) to be formed include phenyldithiol and triazinedithiol.

The method for producing the active ester compound (D) is not particularly limited, and it can be produced by a known method. For example, it can be obtained by a condensation reaction of the above carboxylic acid compound and/or thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound.

For the active ester compound (D), for example, an aromatic compound having an active ester group disclosed in JP-A-2002-12650, and a polyfunctional polyester disclosed in JP-A-2004-277460, or the like, may be used. Sale. For example, the product name "EXB9451, EXB9460, EXB9460S, EPICLON HPC-8000-65T" (above, DIC company, "EPICLON" registered trademark), trade name "DC808" (Japan epoxy resin company) (product), the trade name "YLH1026" (made by Nippon Epoxy Co., Ltd.).

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

Further, in the thermosetting resin composition of the present invention, the equivalent ratio of the epoxy compound to the active ester compound (D) used [the total number of reactive groups of the active ester compound (D) is relative to 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 from 0.5 to 1.2, more preferably from 0.6 to 0.9, further preferably from 0.65 to 0.85.

Further, in the thermosetting resin composition of the present invention, the equivalent ratio of the epoxy compound to the phenol resin (C) containing the triazine structure and the active ester compound (D) {the epoxy group of the epoxy compound to be used Total count pair contains three The ratio of the total number of active hydroxyl groups of the phenol resin (C) of the azine structure to the active ester group of the active ester compound (D) [the amount of epoxy groups / (amount of active hydroxyl groups + active ester groups)], usually less than 1.2 It is preferably 0.6~0.99, and the range of 0.65~0.95 is better. By setting the above equivalent ratio within the above range, it is possible to exhibit good electrical properties in the obtained cured resin layer. Further, the equivalent ratio of the epoxy compound to be used to the phenol resin (C) and the active ester compound (D) having a triazine structure can be determined from the total epoxy equivalent of the epoxy compound to be used, and the phenol resin having a triazine structure. The total active hydroxyl equivalent of (C) and the total active ester equivalent of the active ester compound (D) are determined.

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

By formulating a filler to the thermosetting resin composition, the obtained cured resin layer can be made into a low linear expansion property. As the filler, any of a conventional inorganic filler and an organic filler can be used, but an inorganic filler is preferred. Specific examples of the inorganic filler include calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium niobate, calcium niobate, zirconium silicate, water and alumina, magnesium hydroxide, and hydrogen. Alumina, barium sulfate, cerium oxide, talc, clay, and the like. Further, the filler to be used may be a surface treatment agent such as a silane coupling agent. The content of the filler to be used in the thermosetting resin composition of the present invention is not particularly limited, but is usually 30 to 90% by weight in terms of solid content.

Further, the thermosetting resin composition may be formulated with an alicyclic olefin polymer having a polar group. The polar group may, for example, be 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 with an epoxy group, and containing a hetero atom and a p-oxy group. A base that is not reactive is preferred. Such an alicyclic olefin polymer is not reactive toward epoxy groups Therefore, it is generally a functional group which does not contain an epoxy group. Here, the term "substantially free of a functional group reactive with an epoxy group" means an alicyclic olefin polymer, and does not inhibit the effect of the present invention, and does not contain reactivity with an epoxy group. The meaning of the functional group. The functional group reactive with an epoxy group may, for example, be a group having a structure capable of reacting with an epoxy group to form a covalent bond, and examples thereof include a primary amino group, a secondary amino group, a fluorenyl group, a fluorenyl group, and a carboxyl group. A functional group containing a hetero atom which forms a covalent bond with an epoxy group, such as a carboxylic anhydride group, a hydroxyl group, and an epoxy group.

The above alicyclic olefin polymer may, for example, be suitably combined: an alicyclic olefin monomer (a) containing no aromatic atom and containing an aromatic ring; and an alicyclic olefin monomer containing no aromatic ring and containing a hetero atom (b) An alicyclic olefin monomer (c) containing an aromatic ring and a hetero atom; and an aromatic ring and a hetero atom are not contained, and may be copolymerized with the above alicyclic olefin monomer (a) to (c) The body (d) can be easily obtained by polymerization in accordance with a conventional method. The obtained polymer can be further subjected to hydrogenation.

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

The thermosetting resin composition may further contain a hardening accelerator as needed. The hardening accelerator is not particularly limited, and examples thereof include an aliphatic polyamine, an aromatic polyamine, a secondary amine, a tertiary amine, an acid anhydride, an imidazole derivative, an organic acid hydrazine, a cyanic acid diamine, and a derivative thereof. Urea derivatives and the like. 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-methylimidine. Oxazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole, etc. Alkyl substituted imidazole compound; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl- a ring structure containing an aryl group or an aralkyl group, such as 2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1-(2'-cyanoethyl)imidazole, and substituted with a hydrocarbon group Imidazole compound. These may be used alone or in combination of two or more.

In the thermosetting resin composition of the present invention, the amount of the curing accelerator is usually 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, per 100 parts by weight of the total of the epoxy compound to be used.

Further, the thermosetting resin composition may be suitably formulated for the purpose of improving the flame retardancy of the obtained cured resin layer, and a general blending such as a halogen-based flame retardant or a phosphate-based flame retardant may be formed in the electrical insulating film. A flame retardant for the resin composition used.

Further, the thermosetting resin composition used in the present invention may further suitably be formulated with a flame retardant auxiliary, a heat resistant stabilizer, a weathering stabilizer, an antiaging agent, an ultraviolet absorber (laser processing enhancer), Leveling agent, antistatic agent, slip agent, antiblocking agent, antifogging agent, slip agent, dye, natural oil, synthetic oil, wax, emulsion, magnetic material, dielectric property A conventional component such as a regulator or a toughener.

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

In the first step of the production method of the present invention, the curable resin composition layer composed of the thermosetting resin composition is formed on the support by using the thermosetting resin composition described above, and the curability with the support can be obtained. A layer of the resin composition.

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

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

Examples of the method of 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.

Further, 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, when the curable resin composition layer is immersed in a solvent which can dissolve a curable resin (for example, an epoxy resin) used to prepare a thermosetting resin composition, substantially the curable resin is completely dissolved. status. In addition, the semi-hardening is a state in which it is hardened by further heating, and is hardened to the middle, and a part of the curable resin (specifically, an amount of 7 wt% or more and a part remaining) is dissolved and dissolved. The state of the solvent of the curable resin of the thermosetting resin composition or the volume of the molded body after immersing in the solvent for 24 hours becomes a state of 200% or more (expansion ratio) of the volume before the immersion.

Further, after the thermosetting resin composition is applied onto the support, it may be dried as desired. The drying temperature is preferably such a temperature that the curable resin composition does not harden, and may be set according to the type of the curable resin to be used, and is usually 20 to 300 ° C, preferably 30 to 200 ° C. When the drying temperature is too high, the hardening reaction proceeds excessively, and the obtained curable resin composition layer may not be in an unhardened or semi-hardened state. Further, the drying time is usually from 30 seconds to 1 hour, preferably from 1 minute to 30 minutes.

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

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

Alicyclic olefin polymer having a polar group, there is no special limit The alicyclic structure may, for example, have a naphthene structure or a cycloolefin structure. Since it is excellent in mechanical strength, heat resistance, etc., it is preferable to have a naphthene structure. Further, examples of the polar group contained in the alicyclic olefin polymer include an alcoholic hydroxyl group, a phenolic hydroxyl group, a carboxyl group, an alkoxy group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amine group, and a carboxylic acid anhydride group. , sulfonic acid groups, phosphoric acid groups, and the like. Among them, a carboxyl group, a carboxylic anhydride group, and a phenolic hydroxyl group are preferred, and a carboxylic anhydride group is more preferred.

In addition, the curing agent to be contained in the second thermosetting resin composition is not particularly limited as long as it can form a bridging structure by heating the alicyclic olefin polymer having a polar group, and can be used in general 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 form a bonded functional group with a polar group of an alicyclic olefin polymer having a polar group to be used.

For example, when an alicyclic olefin polymer having a carboxyl group and a carboxylic acid anhydride group or a phenolic hydroxyl group is used as the alicyclic olefin polymer having a polar group, a hardener which can be suitably used may, for example, be a polyvalent epoxy compound or a polyvalent compound. An isocyanate compound, a polyamine compound, a polyvalent ruthenium compound, an aziridine compound, a basic metal oxide, an organometallic halide, or the like. These may be used alone or in combination of two or more. Further, it is also possible to use a peroxide as a curing agent by using these compounds in combination.

Among them, as the curing agent, since the reactivity with the polar group possessed by the alicyclic olefin polymer having a polar group is moderated, and the operation of the second thermosetting resin composition becomes easy, it is preferable to use a polyvalent epoxy compound. It is particularly preferable to use a glycidyl ether type epoxy compound or an alicyclic type polyvalent epoxy compound.

In the second thermosetting resin composition, the amount of the curing agent is adjusted, The amount is preferably from 1 to 100 parts by weight, more preferably from 5 to 80 parts by weight, even more preferably from 10 to 50 parts by weight, per 100 parts by weight of the alicyclic olefin polymer having a polar group. By setting the amount of the curing agent in the above range, the mechanical strength and electrical properties of the cured resin layer can be improved.

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

The amount of the hindered phenol compound to be added in the second thermosetting resin composition is not particularly limited, and is preferably 0.04 to 10 parts by weight, and preferably 0.3 to 5 parts by weight based on 100 parts by weight of the alicyclic olefin polymer having a polar group. The weight part is more preferably further in the range of 0.5 to 3 parts by weight. By setting the amount of the hindered phenol compound in the above range, the mechanical strength of the cured resin layer can be improved.

Further, 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 at the 4th position in the molecule. The alkyl group usually has a carbon number of 1 to 50. The hindered amine compound preferably has a compound having at least one 2,2,6,6-tetraalkylpyridyl group having a secondary amine or a tertiary amine at the 4th position in the molecule. Furthermore, in the present invention, it is preferable to use a hindered phenol compound in combination with a hindered amine compound, and when the surface is roughened by using an aqueous solution of permanganate or the like on the cured resin layer, even if the surface is roughened. When the treatment conditions are changed, the cured product after the surface roughening treatment can also keep the surface roughness low.

The amount of the hindered amine compound to be added is not particularly limited, and is usually 0.02 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.25 to 3 parts by weight based on 100 parts by weight of the polar group-containing alicyclic olefin polymer. The parts by weight are preferred. By setting the amount of the hindered amine compound in the above range, the mechanical strength of the cured resin layer can be improved.

Further, the second thermosetting resin composition may contain a curing accelerator in addition to the above components. The curing accelerator may be a curing accelerator which is usually blended in the resin composition for forming an electrical insulating film. For example, the same curing accelerator as the first thermosetting resin composition can be used. In the second thermosetting resin composition, the amount of the curing accelerator may be appropriately selected according to the purpose of use, and it is preferably 0.001 to 30 parts by weight based on 100 parts by weight of the alicyclic olefin polymer having a polar group. It is preferably 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight.

Further, the second thermosetting resin composition may contain a filler in addition to the above components. As the filler, the same filler as that used for the first thermosetting resin composition can be used. In the second thermosetting resin composition, the amount of the filler to be added is usually from 1 to 50% by weight, preferably from 2 to 45% by weight, more preferably from 3 to 35% by weight, based on the solid content.

In addition, the second thermosetting resin composition may be formulated with a curing accelerator, a flame retardant, a flame retardant, a heat-resistant stabilizer, a weathering stabilizer, and an anti-aging agent, in addition to the above-described components, as in the case of the first thermosetting resin composition. Agent, UV absorber (laser processing enhancer), leveling agent, antistatic agent, slip agent, anti-adhesive agent, anti-fogging agent, slip agent, dye, natural oil, synthetic oil, wax, emulsion, magnetic A conventional component such as a material, a dielectric property modifier, or a toughener.

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

In the first step of the manufacturing method of the present invention, the first resin layer is used When the curable resin composition layer is formed in two layers of the second resin layer, for example, the following two methods may be used. In other words, (1) the second thermosetting resin composition is applied, sprayed or cast on a support, and dried to form a second resin layer as desired, and then the first thermosetting resin is further combined thereon. a method of coating or casting, drying to form a first resin layer as desired; and (2) applying, spraying or casting a second thermosetting resin composition on the support, according to The second resin layer with the support obtained by drying it, and the first thermosetting resin composition coated, sprayed or cast on another support are dried to have a support as desired. A method of laminating the first resin layer, integrating the molded bodies, and peeling off the support on the first resin layer side. Among these manufacturing methods, since it is excellent in productivity for an easy process, the manufacturing method of the above (1) is preferable.

In the production method of the above (1), when the second thermosetting resin composition is applied, sprayed or cast on the support, and applied to the second resin layer formed using the second thermosetting resin composition, the spray is sprayed or sprayed on the second resin layer formed using the second thermosetting resin composition. When the first curable resin composition is sprinkled or cast, or the second thermosetting resin composition and the first thermosetting resin composition are used in the production method of the above (2), the second resin layer with the support and the attached are obtained. When the first resin layer having a support is provided, it is preferable to apply an organic solvent to the second thermosetting resin composition or the first thermosetting resin composition, and to apply, spray or cast the support.

In the production methods of the above (1) and (2), the thickness of the second resin layer and the first resin layer is not particularly limited, and the thickness of the second resin layer is preferably 1 to 10 μm, and 1.5 to 8 μm. Preferably, the thickness is further preferably 2 to 5 μm, and the thickness of the first resin layer is preferably 4 to 45 μm, more preferably 7 to 40 μm, and further It is preferable to have a thickness of 9 to 29 μm. When the thickness of the second resin layer is too small, the second resin layer is used as the layer to be plated, and when the conductor layer is formed by electroless plating, the formability of the conductor layer is lowered. On the other hand, when the thickness of the second resin layer is too thick, the linear expansion of the cured resin layer becomes large. Further, when the thickness of the first resin layer is too small, the embedding property of the wiring may be lowered.

The method of applying the second thermosetting resin composition and the first thermosetting resin composition may, for example, be a dipping method, a roll coating method, a curtain coating method, a die coating method, a slit coating method, or a gravure coating method. Law and so on.

Further, the drying temperature is preferably such a temperature that the second thermosetting resin composition and the first thermosetting resin composition are not cured, and is usually 20 to 300 ° C and preferably 30 to 200 ° C. Further, the drying time is usually from 30 seconds to 1 hour, preferably from 1 minute to 30 minutes.

(Step 2)

In the second step of the production method of the present invention, the curable resin composition layer with the support obtained in the first step is laminated on the substrate side of the curable resin composition layer. A step of a pre-hardening composite having a support composed of a substrate and a layer of a curable resin composition with a support attached thereto.

The substrate is not particularly limited, and examples thereof include a substrate having a conductor layer on its surface. The substrate having the conductor layer on the surface has a conductor layer on the surface of the electrically insulating substrate, and the electrically insulating substrate may, for example, contain a conventional electrically insulating material (for example, an alicyclic olefin polymer or an epoxy). A resin composition of a compound, a maleinamide resin, a (meth)acrylic resin, a diallyl phthalate resin, a triazine resin, a polyphenylene ether, a glass, or the like is hardened and formed. Further, the conductor layer is not particularly limited, and usually includes a conductor such as a conductive metal. The layer of wiring formed may further contain various circuits. The configuration and thickness of the wiring and the circuit are not particularly limited. Specific examples of the substrate having a conductor layer on its surface include a printed circuit board, a tantalum wafer substrate, and the like. The thickness of the substrate having the conductor 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. Further, the height (thickness) of the wiring of the substrate having the conductor layer on the surface is usually 3 to 35 μm. In addition, when the cured resin layer is formed, the difference between the thickness of the curable resin composition and the height (thickness) of the wiring of the substrate having the conductor layer on the surface is hardened from the viewpoint of improving the wiring embedding property and the insulation reliability. The thickness of the resin composition - the height (thickness) of the wiring" is preferably 35 μm or less, more preferably 3 to 30 μm.

Further, in the substrate having the conductor layer on the surface of the present invention, in order to improve the adhesion to the curable resin composition layer, it is preferable to apply it to the surface of the conductor layer. The method of pretreatment is not particularly limited, and a conventional technique can be used. For example, when the conductor layer is composed of copper, the surface of the conductor layer is brought into contact with the strongly alkaline oxidizing solution, and a layer of copper oxide is formed on the surface of the conductor to be roughened by oxidation; after the surface of the conductor layer is oxidized by the aforementioned method, a method of reducing by sodium borohydride or formalin; a method of roughening plating by plating on a conductor layer; and a method of causing a conductor layer to contact with an organic acid to dissolve a grain boundary of copper to coarsen it; The conductor layer is a method of forming a primer layer by a thiol compound, a decane compound or the like. Among these, a method of making the conductor layer and the organic acid contact the grain boundary of the eluted copper to be roughened by the ease of maintaining the shape of the fine wiring pattern, and a thiol compound or a decane compound to the conductor layer. It is preferred to form a primer layer.

In the second step of the manufacturing method of the present invention, a support is attached The curable resin composition layer is formed on the surface side of the curable resin composition layer, and is laminated on the substrate. For example, a thermosetting resin composition layer with a support is provided, and a curable resin composition layer is used. A method of forming a surface side by thermocompression bonding to a substrate or the like.

The method of thermocompression bonding is to laminate a molded body or a composite molded body with a support, in such a manner as to contact the conductor layer of the above substrate, using pressure lamination, pressing, vacuum lamination, vacuum pressing, roll lamination A method of thermocompression bonding (lamination) by a press machine of the like. By heating and pressurizing, the interface between the conductor layer on the surface of the substrate and the molded body or the composite molded body can be bonded without substantially having a void. The molded body or the composite molded body is usually laminated on the conductor layer of the substrate in an unhardened or semi-hardened state.

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

(Step 3)

The third step of the production method of the present invention is carried out by using the base material and the pre-hardening composite with a support comprising a curable resin composition layer with a support obtained in the second step. The first heating is performed by thermally curing the curable resin composition layer to form a cured resin layer.

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

Step 4)

In the fourth step of the production method of the present invention, the support-attached hardened composite obtained in the third step is subjected to a step of forming a via hole in the cured resin layer by opening the support side.

In the fourth step, the method of forming the via holes is not particularly limited, and may be formed by performing physical processing such as a drill, a laser, or a plasma etching method on the side of the support. Among these methods, a method of laser (carbon dioxide laser, excimer laser, UV-YAG laser, etc.), that is, a method of forming a via hole by irradiating a laser from a support side, It is preferable that a finer via hole can be formed without lowering the characteristics of the hardened resin layer. In the manufacturing method of the present invention, by forming a via hole from the side of the support and forming a via hole in the cured resin layer, a via hole having a small aperture (for example, a top diameter (diameter) can be formed at a high aperture ratio (bottom diameter / top diameter). ), preferably 15 to 65 μm, more preferably 15 to 55 μm).

(Step 5)

The fifth step of the production method of the present invention is a step of obtaining a hardened composite composed of a substrate and a cured resin layer by peeling the support from the cured composite body with the support. The method of peeling off a support is not specifically limited.

(Step 6)

The sixth step of the manufacturing method of the present invention is the hardening after peeling off the support The step of performing the second heating on the composite.

In the production method of the present invention, the curable resin composition layer is thermally cured in a state in which the support is attached, and after the cured resin layer is formed, a via hole is formed in the cured resin layer, and then peeled off from the cured resin layer. After the support, the second heating is further performed, and in addition to curing the cured resin layer sufficiently, the volatile component contained in the cured resin layer (for example, used in preparing the first thermosetting resin composition or the second thermosetting resin combination) The organic solvent or the like of the substance is appropriately removed, whereby the heat resistance (for example, solder heat resistance) of the cured resin layer can be improved. In particular, when the support is not peeled off and the heat is cured in a state in which the support is held, the volatile component or the like cannot be appropriately removed due to the influence of the support (in particular, it is impossible to remove the vicinity of the support). In the case of a volatile component or the like in the region, the obtained cured resin layer may have insufficient heat resistance due to the influence of such a volatile component or the like. On the other hand, in the production method of the present invention, the heat is hardened (first heating) in a state in which the support is attached without peeling off the support, and the second heating is performed after peeling off the support. The volatile component or the like which cannot be removed by the influence of the support at the time of the first heating is removed, whereby the heat resistance (for example, solder heat resistance) can be sufficiently improved.

In the sixth step, the heating temperature of the second heating is not particularly limited, and the cured resin layer after heating has good adhesion to the conductor layer formed on the cured resin layer. The temperature at which the heating temperature of the first heating in the third step is low is preferably a temperature lower than the heating temperature of the first heating by 10 ° C or higher, and more preferably 30 ° C or higher lower than the heating temperature of the first heating. Further, the heating temperature of the second heating can be in a boiling state with an organic solvent for preparing the first thermosetting resin composition or the second thermosetting resin composition. The relationship of the dots is preferably set to be higher than the boiling point of the organic solvent to be used by 5 ° C or more, and more preferably 10 ° C or more higher than the boiling point of the organic solvent to be used. Specifically, the heating temperature of the second heating is preferably in the range of 130 to 170 ° C, and more preferably in the range of 140 to 160 ° C. When the heating temperature of the second heating is in the above range, the heat resistance of the cured resin layer can be improved, and the resin residue in the via hole can be more appropriately removed in the seventh step described later, whereby the via hole can be removed. The conduction reliability is better.

Further, the heating time of the second heating in the sixth step is usually 0.1 to 3 hours, preferably 0.25 to 1.5 hours. The method of heating is not particularly limited, and for example, it may be carried out using an electric furnace or the like. Further, the heat hardening is preferably carried out under air from the viewpoint of productivity.

(Step 7)

The seventh step of the production method of the present invention is a step of removing the resin residue in the via hole by 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 performing desmear treatment on the cured composite body after peeling off the support. The method of the slag removal treatment is not particularly limited, and for example, a method of contacting a solution (de-slag liquid) of an oxidizing compound such as permanganate. Specifically, the laminate in which the via holes are formed can be immersed for 1 to 50 minutes in an aqueous solution of 60 to 80 ° C in which the concentration of sodium permanganate is adjusted to 60 g/liter and the sodium hydroxide concentration is adjusted to 28 g/liter. , to the slag treatment.

Further, in the production method of the present invention, the surface roughening treatment for roughening the surface of the cured resin layer may be performed before or after the slag removal 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 of 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. The oxidizing compound may, for example, be 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 surface average 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, activated manganese dioxide, osmium tetroxide, hydrogen peroxide, and periodate. Examples of the organic oxidizing compound include dicumyl peroxide, octanoyl peroxide, m-chloroperoxybenzoic acid, peracetic acid, and peracetic acid. Ozone, etc.

Further, in the production method of the present invention, the surface roughening treatment of the cured resin layer may be performed while removing the resin residue in the via hole.

(Step 8)

The eighth step of the production 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 body after removing the resin residue in the via hole in the eighth step, and on the cured resin layer.

In the eighth step of the manufacturing method of the present invention, the conductor is filled in the via hole by electroless plating or in combination of electroless plating and electrolytic plating, and at least a conductor layer is formed on the inner wall surface of the via hole. A conductor layer excellent in adhesion can be formed in the via hole with high productivity.

Further, there is no particular limitation on the method of forming the conductor layer on the hardened resin layer. In view of the fact that the conductor layer having excellent adhesion can be formed in the same manner, it is preferably carried out by electroless plating or a combination of electroless plating and electrolytic plating.

When the conductor layer is formed by electroless plating, first, before the metal film layer is formed on the inner wall surface of the via hole and the surface of the electrically insulating layer, a catalyst core such as silver, palladium, zinc or cobalt is generally adhered to the conduction. The inner wall surface of the hole and the electrically insulating layer. The method of attaching the catalyst core to the inner wall surface of the via hole and the electrically insulating layer is not particularly limited, and examples thereof include a metal compound impregnated with silver, palladium, zinc, cobalt, or the like, and the salt or the like. A method of reducing a metal after dissolving it in an organic solvent such as water, alcohol or chloroform at a concentration of 0.001 to 10% by weight (may also contain an acid, a base, a binder, a reducing agent, etc.) Wait.

The electroless plating solution used for the electroless plating method may be a conventional autocatalytic electroless plating solution, and the metal type, the type of the reducing agent, the type of the wrong agent, the hydrogen ion concentration, the dissolved oxygen concentration, and the like included in the plating solution. There is no special limit. For example, an electroless copper plating solution using ammonium hypophosphite, hypophosphorous acid, ammonium borohydride, hydrazine, formalin or the like as a reducing agent; an electroless nickel-phosphorus solution using sodium hypophosphite as a reducing agent; Electroless nickel-boron solution with methylamine borane as reducing agent; electroless palladium plating solution; electroless palladium-phosphorus solution with sodium hypophosphite as reducing agent; electroless gold plating liquid; electroless silver plating solution; An electroless plating solution for electroless nickel-cobalt-phosphorus solution such as sodium phosphate as a reducing agent.

After the metal thin film is formed, the surface of the substrate is brought into contact with the rust preventive agent to be subjected to a rustproof treatment. Further, after the metal thin film is formed, the metal thin film may be heated to improve adhesion or the like. The heating temperature is usually 50 to 350 ° C, preferably 80 to 250 ° C. Further, the heating at this time may be carried out under pressurized conditions. The pressurization method at this time may be, for example, a physics using a hot press or a pressurizing heating roll mill. The method of pressurization means. The applied pressure is usually 0.1 to 20 MPa, more preferably 0.5 to 10 MPa. Within this range, high adhesion between the metal thin film and the electrically insulating layer can be ensured.

Then, electrolytic plating is further performed on the metal thin film formed by the electroless plating method to increase the thickness of the plating film. Thereby, the conductor can be filled in the via hole by electroless plating and electrolytic plating, and the thick coating can be performed on the hardened resin layer. By electrolytic plating, it is carried out on the hardened resin layer, and 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 coating is grown, and then the resist is removed, and the metal film is further etched into a pattern by etching to form a conductor layer. Then, the conductor layer formed by this method is usually composed of a patterned metal thin film and a plating layer grown thereon.

Since the laminate obtained by the production method of the present invention is obtained through the above-described first to eighth steps, heat resistance (for example, solder heat resistance) is excellent, and a via hole having a small pore diameter can be formed, so that it can be utilized. Such characteristics are suitably used as a multilayer circuit substrate.

Further, the laminate obtained by the production method of the present invention is used in the substrate used as the second step of the above-described production method of the present invention, and the third to eighth steps are repeated, and the multilayering can be further multilayered. Thereby, the desired multilayer circuit substrate can be obtained.

[Examples]

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

(1) Small aperture via formation

After the via hole is formed, the slag removal treatment and the cured composite after the second heating are performed, and the via hole after the slag removal treatment is observed by an electron microscope (magnification: 1000 times), and the aperture diameter of the via hole is measured to perform a small aperture. The evaluation of the formation of the via holes was evaluated on the basis of the following criteria.

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) slag removal

After the formation of the via holes, the slag removal treatment and the cured composite after the second heating were performed, and the via holes after the slag treatment were observed by an electron microscope (magnification: 5000 times) to carry out resin residue in the via holes (smear) The observation of )) was evaluated on the basis of the following criteria.

A: In the via hole, the existing area of the slag is less than 3% of the measured area.

B: In the via hole, the existence area of the slag is more than 3% of the measured area, less than 10%

C: In the via hole, the existence region of the slag is 10% or more of the measurement area.

(3) Solder heat resistance

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

(evaluation benchmark)

A: No expansion is confirmed

C: One or more expansions were observed.

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 4-Ethyloxybenzylidene (dichloro) (4,5-dis-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.) was placed as a ruthenium catalyst in a nitrogen-substituted pressure-resistant glass reactor and polymerized at 80 ° C under stirring. The reaction was carried out for 30 minutes to obtain a solution of a norbornene-based ring-opening polymer.

Next, as the second-stage polymerization, a 45-mole tetracyclic ring [6.5.0.1 ^2, 5.08, ¹³ ] thirteen-carbon-3,8,10,12-tetraene was added to the solution obtained in the first-stage polymerization. 20 Mohr bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, 250 mol of anisole and 0.01 mol of C1063, polymerization was carried out at 80 ° C for 1.5 hours with stirring. A solution of norbornene-based open-loop polymer. Gas chromatography was measured for the solution, and as a result, it was confirmed that substantially no monomer remained, and the polymerization conversion ratio was 99% or more.

Next, the solution of the obtained ring-opening polymer was placed in an autoclave equipped with a nitrogen-substituted stirrer, and 0.03 mol of C1063 was added thereto, and hydrogenation reaction was carried out at 150 ° C under a hydrogen pressure of 7 MPa for 5 hours to obtain a hydrogenation reaction. A solution of a norbornene ring-opening polymer hydride alicyclic olefin polymer (1). 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. Further, the hydrogenation rate was 95%, and the content of the repeating unit having a carboxylic anhydride group was 20 mol%. The alicyclic olefin polymer (1) solution had a solid concentration of 22%.

Example 1 (Preparation of the first thermosetting resin composition)

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

(Second thermosetting resin composition)

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

(Production of hardened composite)

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

Then, the varnish of the first thermosetting resin composition obtained above was coated with a doctor blade (manufactured by TESTER Industries, Inc.) and an automatic film applicator (manufactured by TESTER Industries, Inc.). The surface of the second resin layer composed of the second thermosetting resin composition of the film layer of the support is dried at 80 ° C for 5 minutes in a nitrogen atmosphere to obtain a second resin layer having a total thickness of 30 μm and A curable resin composition layer with a support attached to the first resin layer (adhesive layer). The curable resin composition layer with a support is a support, and the second thermosetting resin composition is the second. 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, a varnish containing a glass filler and a halogen-free epoxy compound is immersed on the surface of a core material obtained by immersing the glass fiber, and a copper having a thickness of 18 μm is adhered to a thickness of 0.8 mm. A 160 mm square (length 160 mm, width 160 mm) double-sided copper substrate surface was subjected to micro etching treatment to form a conductor layer having a wiring width and a wiring pitch of 50 μm and a thickness of 18 μm to obtain an inner layer. Substrate.

The layer of the curable resin composition with a support obtained as described above is cut into a 150 mm square, and the surface of the curable resin composition layer side is placed inside, and the both sides of the inner layer substrate are adhered to each other with the support attached thereto. Then, using a vacuum laminator having a heat-resistant rubber pressure plate on the upper and lower sides, the pressure was 200 Pa, and the laminate was heated and pressure-bonded for 60 seconds at a temperature of 110 ° C and a pressure of 0.1 MPa. After allowing to stand at room temperature for 30 minutes, the curable resin composition layer is cured by heating (first heating) at 180 ° C for 30 minutes to form a cured resin layer (electric insulating layer).

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

(second heating step)

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

(to the slag processing step)

Then, the cured composite after the second heating was prepared into an aqueous solution ("Swelling Dip Securiganth P", manufactured by Atotech Co., Ltd., "Securiganth" is a registered trademark), 500 mL/L, and a sodium hydroxide solution of 3 g/L. After shaking for 15 minutes, it was washed with water.

Subsequently, the mixture was immersed in an aqueous solution of permanganate ("Concentrate Compact CP", manufactured by Atotech Co., Ltd.) at 640 mL/L and an aqueous solution having a sodium hydroxide concentration of 40 g/L for 15 minutes, and then washed with water.

Next, the hardened composite was immersed in a 40 ° C aqueous solution prepared by dissolving a hydroxylamine sulfate aqueous solution ("Reduction Securiganth P500", Atotech Co., Ltd., "Securiganth" as a registered trademark), 100 mL/L, and sulfuric acid 35 mL/L for 5 minutes to neutralize. After the reduction treatment, it is washed with water. Then, the slag-removing treatment thus obtained and the hardened composite after the second heating were subjected to the evaluation of the small-diameter via-hole formation property and the slag-removing property in accordance with the above method. The results are shown in Table 1.

(clean.conditioner step)

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

(soft etching processing step)

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

(pickling treatment step)

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

(catalyst attached step)

Next, the hardened composite was prepared into an 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.) The "Alcup" is a registered trademark of 30 mL/L and sodium hydroxide 0.35 g/L of a 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.) The "Alcup" is a registered trademark) 200 mL/L aqueous solution was immersed at 35 ° C for 3 minutes, and the plating catalyst was reduced, followed by washing with water.

(accelerated processing steps)

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

(electroless plating step)

For the production of Thru-cup PEA-6-A (trade name, manufactured by Uemura Industrial Co., Ltd., "Thru-cup" is a registered trademark) 100 mL/L, Thru-cup PEA-6-B-2X (trade name, Uemura Industrial Co., Ltd.) 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 Kogyo Co., Ltd.) 50 mL/L, 37% of the aqueous solution of the Famaline aqueous solution 5 mL/L of the electroless copper plating solution, while blowing the air, the resulting hardened composite was immersed at 36 ^c C for 20 minutes. The electroless copper plating treatment 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).

Then, the hardened composite in which the metal thin film was formed was immersed in a rust preventive solution of 10 mL/L prepared by AT-21 (trade name, manufactured by Uemura Kogyo Co., Ltd.) for 1 minute at room temperature, and then washed with water. Further, by drying, a rust-preventing and hardening composite is produced. The hardened composite subjected to the rust-preventing treatment was subjected to an annealing treatment at 150 ° C for 30 minutes in an air atmosphere.

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

Example 2

The cured composite and the 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 the evaluation was performed in the same manner. The results are shown in Table 1.

Comparative example 1

The cured composite and the 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 the evaluation was performed in the same manner. The results are shown in Table 1.

Comparative example 2

After the curable resin composition layer with the support is adhered to both surfaces of the inner substrate, the support is peeled off, and the first heating and the formation of the via holes are performed while the support is peeled off, and the second heating is performed. In the procedure, the cured composite and the 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, and the evaluation was carried out in the same manner. The results are shown in Table 1.

As shown in Table 1, according to the production method of the present invention, it was found that a via hole having a small pore diameter can be formed, and a laminate having excellent heat resistance can be obtained (Examples 1 and 2).

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

Further, when the first heating and the formation of the via holes were performed in a state where the support was peeled off, a via hole having a small aperture was not formed (Comparative Example 2).

Claims (5)

A method for producing a laminate, comprising: forming a curable resin composition layer having a support by forming a curable resin composition layer composed of a thermosetting resin composition on a support; In the first step, the curable resin composition layer with the support is formed on the surface side of the curable resin composition layer, and the substrate is laminated on the substrate to obtain a curable resin composition with a support and a support. a second step of forming a pre-hardening composite having a support composed of a layer; and thermally curing the curable resin composition layer to a cured resin layer by first heating the composite to obtain a substrate, and The third step of the cured composite body with the support of the cured resin layer of the support; the opening of the support body side of the hardened composite body with the support; the formation of the conductive resin layer The fourth step of the hole; the fifth step of obtaining the hardened composite composed of the substrate and the cured resin layer by peeling the support from the cured composite having the support; and the hardened composite a sixth step of the second heating; a seventh step of removing the resin residue in the via hole of the hardened composite; and a conductor layer formed on the inner wall surface of the via hole of the hardened composite and the cured resin layer In the eighth step, the formation of the conductor layer of the via hole is performed by filling the conductor in the via hole by electroless plating or a combination of electroless plating and electrolytic plating. The method for producing a laminate according to the first aspect of the invention, 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 producing a laminate according to the first or second aspect of the invention, 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 laminate obtained by the method for producing a laminate according to any one of claims 1 to 3. A multilayer circuit substrate comprising the laminate described in the fourth application of the patent application.