TW201723039A - Method for manufacturing hardened resin film which can be produced at high efficiency and effectively inhibit the generation of defects such as wrinkles - Google Patents

Abstract

The object of the present invention is to provide a method for manufacturing a hardened resin film at high efficiency, which can effectively inhibit the generation of defects such as wrinkles. The solution of this invention is to provide a method for producing a hardened resin film comprising the following steps of: step 1, forming a prior-to-being-dried resin film, which is composed of a curable resin composition containing a curable resin and solvent, on a support; step 2, in a state where the aforementioned prior-to-being-dried resin film is formed on the support, drying the prior-to-being-dried resin film by moving it in a floating manner in a drying device to form into a curable resin film with a thermal weight loss of 0.5~7 wt%; step 3, thermally hardening the aforementioned curable resin film to form a hardened resin film; step 4, peeling off the aforementioned hardened resin film from the support.

Description

Method for producing cured resin film

The present invention relates to a method of producing a cured resin film.

In order to reduce the size, the versatility of the electronic device, and the high-speed communication, the circuit board used in the electronic device is required to be further increased in density, and in order to meet the demand for such high density, the circuit board is multilayered. . Such a multilayer circuit substrate is formed by, for example, laminating an electrically insulating layer on an inner layer substrate composed of an electrically insulating layer and a conductor layer formed on a surface thereof, and forming a conductor layer on the electrically insulating layer, and The lamination of the electrically insulating layers and the formation of the conductor layer are repeated.

As a thermosetting resin composition for forming an electrically insulating layer for forming such a multilayer circuit substrate, for example, Patent Document 1 discloses a ring having a specific skeleton containing a polyamide resin. A technique of a thermosetting resin composition of an oxygen resin and an epoxy resin hardener. Patent Document 1 describes a solution in which a thermosetting resin composition using dimethylformamide as a solvent is obtained, and the thickness is 25 μm after drying using a doctor blade applicator. The thermosetting resin composition layer was formed by coating on a release PET film and drying it in a floating drying oven set at 130 ° C for 15 minutes.

Prior technical literature Patent literature

[Patent Document 1] Japanese International Publication No. 2009/028170

In the case of the present invention, the inventors of the present invention have studied the technique described in Patent Document 1, and the technique of Patent Document 1 discloses that the layer of the thermosetting resin composition after drying is mechanically brittle and is attached to the mold. When the PET film is cured in a state of being cured, the shrinkage at the time of curing becomes large and defects such as wrinkles occur. Therefore, the obtained electrically insulating layer has a problem that reliability is not always sufficient.

An object of the present invention is to provide a method for producing a cured resin film which can effectively prevent defects such as wrinkles and foaming from being produced with high productivity.

In order to achieve the above object, the inventors of the present invention have found that in order to produce a cured resin film which is effective in preventing defects such as wrinkles and foaming from being produced with high productivity, it is preferred to form a curable resin and a solvent on the support. And a pre-drying resin film composed of a thermosetting resin composition, and a drying method by a floating method is used when drying the film, and when drying is performed by a floating method, it is important to set a specific range of heating loss. The present invention has been completed.

That is, provided in accordance with the present invention

[1] A method for producing a cured resin film, comprising the steps of: forming a pre-drying resin film comprising a thermosetting resin composition containing a curable resin and a solvent on a support; The second step, which will be described above The pre-drying resin film formed on the support is transported by floating in a drying device while being formed on the support, and is dried to obtain a curable resin film having a heating loss of 0.5 to 7% by weight. In the third step, the curable resin film is thermally cured to form a cured resin film, and the fourth step is to peel the support from the cured resin film.

[2] The method for producing a cured resin film according to the above [1], wherein, in the second step, the resin film before drying is formed on the support, and is set to 30~ a heating zone of 60 ° C, a drying device set to a drying zone having a higher temperature than the heating zone, is carried by floating means for drying, and the drying time of the resin film before drying is 30 to 300 seconds, when dry The dry air volume is 0.5~7m ³ /hour.

[3] The method for producing a cured resin film according to the above [2], wherein the heating zone and the drying zone are each divided into a plurality of regions, and the temperature of each region is set to be in accordance with the progress of the pre-drying resin film. A temperature that becomes higher in stages.

[4] The method for producing a cured resin film according to any one of the above [1], wherein, as the support, a film having a release layer on a surface thereof is used.

[5] The method for producing a cured resin film according to any one of the above [1], wherein the solvent content of the thermosetting resin composition is 5 to 40% by weight.

The method for producing a cured resin film according to any one of the above aspects, wherein the thermosetting resin composition further contains an inorganic filler in the thermosetting resin composition. The content ratio of the inorganic filler is 60% by weight or more in terms of solid content.

[7] The method for producing a cured resin film according to any one of the above [1] to [6], further comprising a step of forming another curable resin film, which is in the first step Before, a curable resin film containing another curable resin different from the curable resin is formed on the support; and in the first step, the other curable resin film formed on the support is formed as described above The resin film before drying.

[8] The method for producing a cured resin film according to the above [7], wherein the other curable resin film forming step includes the step of forming the other curable resin and the solvent on the support. a step of drying the other resin film before the drying of the other thermosetting resin composition; and the other resin film before drying which is formed on the support, in a state of being formed on the support, by The drying device is transported by means of a floating method to dry, and the heating is reduced by 0.5 to 7% by weight of the other curable resin film.

[9] A laminate obtained by laminating a cured resin film obtained by the production method according to any one of the above [1] to [8], and a substrate.

According to the production method of the present invention, it is possible to produce a cured resin film capable of effectively preventing defects such as wrinkles from being produced with high productivity.

10‧‧‧Pre-drying resin film with support

10a‧‧‧hardened resin film with support

20‧‧‧1st roller

30‧‧‧2nd roller

40‧‧‧ Coating device

50‧‧‧Drying device

60‧‧‧hot air blowout

Fig. 1 is a view showing an example of a manufacturing apparatus used in the present invention.

Form for implementing the invention

(Method for producing cured resin film)

First, the manufacturing method of the present invention will be described.

The manufacturing method of the present invention has the following steps: In the first step, a pre-drying resin film composed of a thermosetting resin composition containing a curable resin and a solvent is formed on the support, and a second step is performed by forming the support on the support. The pre-drying resin film is conveyed by floating in a drying device while being formed on the support, and is dried to obtain a curable resin film having a heating loss of 0.5 to 7% by weight; and a third step, This is a cured resin film by thermally curing the curable resin film, and a fourth step of peeling the support from the cured resin film.

(Step 1)

The first step of the production method of the present invention is a step of forming a pre-drying resin film composed of a thermosetting resin composition containing a curable resin and a solvent on a support.

The support used in the first step of the production method of the present invention is not particularly limited, and examples thereof include a film shape and a plate shape, 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, plate. A film-like glass substrate or the like. In order to facilitate the separation from the cured resin layer in the fourth step to be described later, it is preferable to have a release layer having a release treatment on the surface as a support, particularly in a state in which a support is provided. When the via hole and the via hole are formed by irradiating the laser from the support side, it is preferable to have a polymer film from the viewpoint of being able to form the via hole and the via hole well, and to have a mold release A layer of poly(ethylene terephthalate) film is preferred.

The thickness of the support used in the first step 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 resin film before drying formed on the support can be improved.

In addition, the thermosetting resin composition used in the present invention contains a curable resin and a solvent, and usually contains a curing agent in addition to these. The curable resin is not particularly limited as long as it exhibits thermosetting properties in combination with a curing agent and has electrical insulating properties, and examples thereof include an epoxy resin, a maleimide resin, and a (meth)acrylic acid. Resin, diallyl phthalate 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 a curable resin will be described.

The epoxy resin is not particularly limited, and for example, a 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, abbreviated as a case of the elemental epoxy compound (A)] having at least 2 epoxy groups in one molecule (ring) An oxyethylene ring) and a compound having at least one of a biphenyl structure and a condensed polycyclic structure.

The above-mentioned biphenyl structure refers to a structure in which a benzene ring is connected by two single bonds. In the obtained cured resin, a biphenyl structure usually constitutes a main chain of the resin, but a side chain may also be present.

Further, the above-mentioned condensed polycyclic structure means two or more single ring condensations. The structure of the ring). 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 such a condensed polycyclic structure include a dicyclopentadiene structure, a naphthalene structure, a fluorene structure, a fluorene structure, a phenanthrene structure, a tri-ortylene benzene structure, a fluorene structure, and an ovale structure. In the same manner as the above-described biphenyl structure, the obtained condensed polycyclic structure usually constitutes a main chain of a resin contained in the cured resin layer, but a side chain may be present.

The polyvalent epoxy compound (A) used in the present invention has a biphenyl structure, a condensed polycyclic structure, or a biphenyl structure and a condensed polycyclic structure, and the heat resistance of the obtained cured resin layer is improved. From the viewpoint of mechanical strength, as the polyvalent epoxy compound (A), those having a biphenyl structure are preferred, and those having a biphenyl aralkyl structure are preferred.

Further, when the polyphenylene compound (A) has a biphenyl structure (including both a biphenyl structure and a condensed polycyclic structure) and a condensed polycyclic structure, the heat resistance of the cured resin layer is obtained. From the viewpoint of improvement in electrical characteristics, the ratio of the blending ratio is a weight ratio (multi-epoxy compound having a biphenyl structure/polyvalent epoxy compound having a condensed polycyclic structure), usually 3/7 to 7 /3 is better.

The polyvalent epoxy compound (A) used in the present invention is a compound having at least two epoxy groups in one molecule and having a biphenyl structure and/or a condensed polycyclic structure, the structure of which is not limited, and the hardening resin is used. From the viewpoint of excellent heat resistance and mechanical strength of the layer, it has a biphenyl structure and/or a condensed polycyclic structure. A novolac type epoxy compound is preferred. Examples of the novolac type epoxy compound include a phenol novolak type epoxy compound and a cresol novolac type epoxy compound.

The epoxy equivalent of the polyvalent epoxy compound (A) is usually from 100 to 1,500 equivalents, preferably from 150 to 500 equivalents, since a good hardening reactivity can be obtained. 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) used in the present invention can be suitably produced according to a conventional method, and can also be obtained as a commercially available product.

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

Further, as an example of a commercially available product of the polyvalent epoxy compound (A) having a condensed polycyclic structure, a novolac type epoxy compound having a dicyclopentadiene structure is exemplified by the trade name "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 Materials, "Tactix" is a registered trademark), The product name is "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. And use.

Further, in the present invention, when a polyvalent epoxy compound (A) having a biphenyl structure and/or a condensed polycyclic structure is used, a ternary or higher polyepoxy propylene having a ternary or higher phenol other than the phenol novolak type epoxy compound may be used in combination. Further, by using such a trivalent or higher polyepoxypropyl group-containing epoxy compound (B), the heat resistance and electrical properties of the obtained cured resin layer can be further improved.

The ternary or higher epoxy group-containing epoxy compound (B) other than the phenol novolak type epoxy compound is an epoxy equivalent from the viewpoint of heat resistance and electrical properties of the obtained cured resin layer. A compound of 250 or less is preferred, and a compound of 220 or less is preferred.

Specifically, a polyhydric phenol type epoxy compound having a structure in which a hydroxy group of a trihydric or higher polyhydric phenol is epoxidized; and an amine ring of a compound containing a polyvalent amine phenyl group or more An oxypropylated epoxy epoxide compound; a polyepoxypropyl group obtained by epoxy-propylating a compound having a ternary or higher phenolic structure and an amine phenyl structure in the same molecule; Contains compounds and the like.

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

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

For example, as an example of a commercially available product of a hydroxyphenylmethane-based epoxy compound, the product names "EPPN-503, EPPN-502H, EPPN-501H" (above, manufactured by Nippon Kayaku Co., Ltd.), and the trade name " TACTIX-742 (above, manufactured by Dow Chemical Co., Ltd.), "jER 1032H60" (above, manufactured by Mitsubishi Chemical Corporation), and the like. In addition, as an example of the commercial item of the hydroxy phenyl ethane type epoxy compound, the brand name "jER 1031S" (above, Mitsubishi Chemical Corporation) etc. are mentioned. As the epoxy propylamine type epoxy compound, the quaternary epoxy propylamine type epoxy compound is exemplified by the trade name "YH-434, YH-434L" (above, Nippon Steel & Sumitomo Chemical Co., Ltd.) (product), the product name "jER604" (above, manufactured by Mitsubishi Chemical Corporation). a polyepoxypropyl group-containing compound obtained by epoxy-propylating a compound having a phenol structure and an amine phenyl structure in the same molecule, in the case of a ternary epoxypropylamine type epoxy compound For example, the product name "jER630" (above, manufactured by Mitsubishi Chemical Corporation) may be mentioned.

When a trivalent or higher epoxy group-containing epoxy compound (B) is used in combination, the content ratio of the trivalent or higher polyepoxypropyl group-containing epoxy compound (B) is not particularly limited, and an epoxy compound is used. The total amount of 100% by weight is preferably 0.1 to 4.0% by weight, more preferably 1 to 30% by weight, particularly preferably 3 to 25% by weight. In the thermosetting resin composition, the relationship between the content of the trivalent or higher polyepoxypropyl group-containing epoxy compound (B) and the above polyvalent epoxy compound (A) is in the above range. The heat resistance, electrical properties, and adhesion to the conductor layer of the obtained cured resin layer are further improved.

Further, the thermosetting resin composition used in the present invention can be used in addition to the above-mentioned polyvalent epoxy compound (A) and a trivalent or higher polyepoxypropyl group-containing epoxy compound (B). And make it properly contain the Other epoxy compounds other than epoxy compounds. As such another epoxy compound, a phosphorus-containing epoxy compound can be mentioned, for example. As the phosphorus-containing epoxy compound, an epoxy compound having a phosphaphenanthrene structure can be suitably used, and by further using an epoxy compound having such a phosphaphenanthrene structure, the heat resistance of the cured resin layer can be further improved. Electrical properties and adhesion to the conductor layer.

Further, as the other epoxy compound, in addition to or in addition to the epoxy compound having a phosphaphenanthrene structure, an alicyclic epoxy compound, a cresol novolak type epoxy compound, or a phenol novolac type epoxy resin may be used. a compound, a bisphenol A novolak type epoxy compound, a phenol type epoxy compound, a guanidine (hydroxyphenyl) ethane type epoxy compound, an aliphatic chain epoxy compound, etc., which can be suitably marketed. The way of the product is obtained.

Further, the thermosetting resin composition used in the present invention may contain a phenol resin (C) having a triazine structure. The benzene resin (C) having 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 is typically 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, each of R ¹ and R ² may be the same or different from each other, and when p is 2 or more, plural R ^{2 's} may be the same or different from each other. Further, in the formula (1), the hydrogen atom contained in the amine group may be substituted with another group (for example, an alkyl group or the like) for at least one of the amine groups.

The triazine-containing phenol resin (C) is a hardening resin obtained by the presence of a phenolic active hydroxyl group as a hardening agent for an epoxy compound, particularly a phenol resin (C) containing a triazine structure. The layer system shows excellent adhesion to the substrate.

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

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

The amount of the triazine-containing phenol resin (C) to be used in the thermosetting resin composition used in the present invention is from 1 to 60 parts by weight based on 100 parts by weight of the total of the epoxy compound to be used. Preferably, it is preferably 2 to 50 parts by weight, more preferably 3 to 40 parts by weight, particularly preferably 4 to 20 parts by weight.

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

Further, the thermosetting resin composition used in the present invention preferably contains the active ester compound (D) in addition to the above components. The active ester compound (D) may be an active ester group, and in the present invention, a compound having at least two active ester groups in one molecule is preferred. The active ester compound (D) is obtained by reacting an ester moiety with an epoxy group by heating, and is used as an epoxy compound hardener used in the present invention, similarly to the above-described triazine-structure-containing phenol resin (C). effect.

The active ester compound (D) is reacted from a carboxylic acid compound and/or a sulfuric 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. The active ester compound obtained by the above is preferably obtained by reacting a carboxylic acid compound with one or more selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound. The active ester compound is preferred, and an aromatic compound obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group and having at least two active ester groups in the molecule is particularly preferred. The active ester compound (D) may be linear or multi-branched, and it is exemplified that when the active ester compound (D) is derived from a compound having at least two carboxylic acids in the molecule, this has at least 2 in the molecule. When the carboxylic acid compound contains an aliphatic chain, it can improve compatibility with an epoxy compound, and when it has an aromatic ring, heat resistance can be improved.

Specific examples of the carboxylic acid compound for forming the active ester compound (D) include benzoic acid, acetic acid, succinic acid, maleic acid, and itaconic acid. Tannic acid, isophthalic acid, p-citric acid, pyrophoric acid, and the like. Among these, from the viewpoint of improving the heat resistance of the obtained cured resin layer, it is preferably succinic acid, maleic acid, itaconic acid, citric acid, isophthalic acid or citric acid. Preferably, citric acid, isophthalic acid, and citric acid are preferred, isophthalic acid, and citric acid are preferred.

Specific examples of the sulfur carboxylic acid compound for forming the active ester compound (D) include sulfuric acid, thiobenzoic acid, and the like.

Specific examples of the hydroxy compound for forming the active ester compound (D) include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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-di Hydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, cadaveric triol, benzenetriol, two Cyclopentadienyl diphenol, phenol novolak, and the like. In particular, from the viewpoint of improving the solubility of the obtained cured resin layer and improving the heat resistance of the obtained cured resin layer, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 , 6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, bicyclocyclopentadienyl diphenol, phenol novolac, preferably dihydroxydiphenyl Ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, bicyclocyclopentadienyl diphenol, phenol novolak is preferred, preferably dicyclocyclopentadienyl diphenol, phenol novolak .

Specific examples of the thiol compound for forming the active ester compound (D) include benzenedithiol 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, by the aforementioned carboxylic acid compound and / Or a condensation reaction of a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound.

As 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, and the like can be used. Sale. For example, the product name "EXB9451, EXB9460, EXB9460S, Epiclon HPC-8000-65T" (above, DIC company, "Epiclon" registered trademark), and product name "DC808" (JAPAN EPOXY RESINS) Company name), trade name "YLH1026" (manufactured by JAPAN EPOXY RESINS).

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, preferably 100 parts by weight based on 100 parts by weight of the total of the epoxy compound to be used. 15 to 130 parts by weight, more preferably 20 to 120 parts by weight.

Further, in the thermosetting resin composition used in the present invention, the equivalent ratio of the epoxy compound to the active ester compound (D) is [in comparison with the total number of epoxy groups of the epoxy compound to be used, activity The ratio of the total number of reactive groups of the ester (D) (the amount of the active ester group / the amount of the epoxy group) is preferably from 0.5 to 1.1, more preferably from 0.6 to 0.9, still more preferably from 0.65 to 0.85.

Further, in the thermosetting resin composition used in the present invention, the equivalent ratio of the epoxy compound to be used to the triazine-containing phenol resin (C) and the active ester compound (D) is relative to the triazine-containing compound. The total number of active hydroxyl groups of the phenol resin (C) and the active ester group of the active ester compound (D), and the ratio of the total number of epoxy groups of the epoxy compound used [the amount of epoxy groups / (the amount of active hydroxyl groups) +active The amount of the ester group)] is usually less than 1.1, preferably 0.6 to 0.99, more preferably 0.65 to 0.95. By setting the above equivalent ratio to the above range, electrical properties can be satisfactorily exhibited in the obtained cured resin layer. Further, the equivalent ratio of the epoxy compound to be used and the triazine-containing phenol resin (C) and the active ester compound (D) is a total epoxy equivalent of the epoxy compound to be used, and a triazine-containing structure. The total active hydroxyl equivalent of the phenol resin (C) and the total active ester equivalent of the active ester compound (D) are determined.

From the viewpoint of forming a pre-drying resin film composed of a thermosetting resin composition and then volatilizing and removing it by drying in the second step, it is preferred that the solvent has a boiling point of 30 to 250 ° C. 50 to 200 ° C is preferred. Specific examples of such a solvent include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, trimethylbenzene, and anisole; n-pentane, n-hexane, n-heptane, methyl ethyl ketone, and An aliphatic hydrocarbon such as isobutyl ketone; an alicyclic hydrocarbon such as cyclopentane, cyclohexane, cyclopentanone or cyclohexanone; a halogenated hydrocarbon such as chlorobenzene, dichlorobenzene or trichlorobenzene; . Among these, from the viewpoint of compatibility with each component constituting the thermosetting resin composition, toluene, anisole, cyclohexanone, cyclopentanone or the like can be suitably used.

The content of the solvent in the thermosetting resin composition is preferably from 5 to 40% by weight, preferably from 10 to 35% by weight, more preferably from 15 to 30% by weight. When the content of the solvent is too small, it may be difficult to form a resin film before drying. On the other hand, when the solvent content is too large, the formability of the resin film before drying is lowered, and it may become difficult to form a uniform film.

Moreover, it is preferable that the thermosetting resin composition used in the present invention contains an inorganic filler. By containing an inorganic filler, it is possible to obtain The cured resin film becomes a low linear expansion property. Specific examples of the inorganic filler include calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium citrate, calcium citrate, zirconium silicate, hydrated alumina, magnesium hydroxide, and hydrogen. Alumina, barium sulfate, barium oxide, talc, clay, etc. The filler to be used may be previously surface-treated with a decane coupling agent or the like. The content of the filler in the thermosetting resin composition used in the present invention is not particularly limited, and is preferably 60% by weight or more, and more preferably 62 to 90% by weight, more preferably in terms of solid content. It is 65~80% by weight. When the content of the inorganic filler is too small, the linear expansion ratio of the obtained cured resin film becomes high and the connection reliability may be deteriorated.

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

The thermosetting resin composition may contain a curing accelerator as needed. The curing accelerator is not particularly limited, and examples thereof include an aliphatic polyamine, an aromatic polyamine, a second amine, a third amine, an acid anhydride, an imidazole derivative, an organic acid hydrazine, and a dicyanodiamide. And its derivatives, urea derivatives and the like. In particular, 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, 2-ethyl-4-methylimidazole, and bis-2-ethyl-4-methyl. Alkyl substituted imidazole compounds such as imidazole, 1-methyl-2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole, etc.; 2-phenylimidazole, 2 -Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, benzimidazole, 2-B Base 4-methyl-1-(2'-cyanoethyl)imidazole and the like are taken from a hydrocarbon group having a ring structure such as an aryl group or an aralkyl group. Substituted imidazole compounds and the like. These can be used alone or in combination of two or more.

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

In addition, in order to obtain the purpose of improving the flame retardancy of the cured resin layer, the thermosetting resin composition may be appropriately formulated such that a halogen-based flame retardant or a phosphate-based flame retardant is usually formulated in an electrically insulating film. A flame retardant using a resin composition.

Further, in the thermosetting resin composition used in the present invention, a flame retardant auxiliary, a heat stabilizer, a weathering stabilizer, an antioxidant, and an ultraviolet absorber (laser processing enhancer) may be appropriately formulated as needed. ), leveling agent, antistatic agent, slip agent, anti-adhesive agent, anti-fogging agent, slip agent, dye, natural oil, synthetic oil, wax, emulsion, magnetic body, dielectric property modifier, toughener, etc. Know the ingredients.

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 mixed in a state in which an organic solvent is dissolved or dispersed to prepare a mixture. A composition in which a part of each of the above components is dissolved or dispersed in an organic solvent, and the remaining components are mixed in the composition.

In the first step of the production method of the present invention, the pre-drying resin film composed of the thermosetting resin composition is formed on the support by using the thermosetting resin composition described above, and the shape can be obtained. The resin film before drying on the support.

The method of forming the pre-drying resin film composed of the thermosetting resin composition on the support is not particularly limited, and the thermosetting resin composition is applied, sprayed, or cast on the support, and then carried out. The method of drying is preferred.

The thickness of the resin film before drying is not particularly limited, and is usually 10 to 100 μm, preferably 12 to 90 μm, and more preferably 15 to 80 μm from the viewpoint of workability and the like.

Examples of the method of applying the thermosetting resin composition include dip coating, roll coating, curtain coating, die coating, slit coating, gravure coating, and the like.

(Step 2)

In the second step of the production method of the present invention, the pre-drying resin film formed on the support is transported by floating in a drying device while being formed on the support, thereby becoming The composition of the curable resin film having a heating loss of 0.5 to 7% by weight.

In the production method of the present invention, the method of drying the resin film before drying which is formed on the support by floating in a drying apparatus is not particularly limited, and drying can be formed on the support. The front resin film is dried by being conveyed in a state in which it is supported by the hot air for drying (in a floating state) in the drying apparatus. For example, the manufacturing apparatus shown in Fig. 1 can be used. Here, Fig. 1 is a view showing an example of a manufacturing apparatus used in the manufacturing method of the present invention. Hereinafter, the second step of the manufacturing method of the present invention will be described by using the manufacturing apparatus shown in Fig. 1 .

The manufacturing apparatus shown in Fig. 1 is a device for performing the first step and the second step described above, and the manufacturing apparatus shown in Fig. 1 is taken from the winding apparatus. The first roller 20 having a long support is continuously wound up, and the thermosetting resin composition is applied onto the support by the coating device 40, whereby the support is continuously formed. The resin film 10 before drying. Then, the pre-drying resin film 10 with the support is continuously conveyed in the drying device 50, dried by the drying device 50, and the solvent is removed, and becomes the cured resin film 10a with the support, and is continuously The ground is taken up to the second roller 30. At this time, when the pre-drying resin film 10 with the support is continuously conveyed in the drying device 50, it is conveyed in a state of being supported by the hot air for drying (a state in which it is in a floating state), wherein the hot air system for drying is used. The plurality of hot air blowing ports 60 provided in the drying device 50 are blown out.

Moreover, in this case, in the present invention, the heating loss of the curable resin film obtained by drying is controlled in the range of 0.5 to 7% by weight.

Further, according to the present invention, the film pressure of the pre-drying resin film 10 with the support can be kept uniform in the drying device 50 by the floating method, whereby the curable resin film 10a with the support after drying can be obtained. In addition, the film thickness of the cured resin film obtained by the hardening is uniform, and the heat loss of the curable resin film can be reduced by 0.5 to 7% by weight, thereby suppressing heat shrinkage during curing. The high productivity provides a cured resin film which can effectively prevent defects such as wrinkles, foaming, and the like.

In the present invention, when the heating loss of the curable resin film obtained by drying is in the range of 0.5 to 7% by weight, when the heat loss is too small, when the curable resin film is laminated on the substrate having the wiring pattern, A void or the like is generated in the wiring closet, and the embedding property is poor (a phenomenon in which the wiring is completely buried and the entrapped air is not obtained) cannot be obtained. On the other hand, when the heating is reduced too much, When it is cured in a state in which the release-coated PET film is attached, it is affected by the residual solvent to cause foaming failure of the cured resin film. In the present invention, the heat-reducing resin film obtained by drying has a heating loss of 0.5 to 7% by weight, preferably 1 to 6% by weight, more preferably 1.3 to 5% by weight, still more preferably 1.5. ~4% by weight range. In addition, the heating loss of the curable resin film can be caused by heating by heating the curable resin film at 170 ° C for 15 minutes in a nitrogen atmosphere, for example, by using a differential thermogravimetric simultaneous measuring device (TG-DTA). The amount of weight reduction is sought.

In addition, the method of setting the amount of heat loss of the curable resin film to the above-mentioned specific range is not particularly limited, and examples thereof include, for example, the type of curable resin and solvent to be used, the amount of solvent to be formulated, and the thickness of the resin film before drying. The drying temperature at the time of drying in the drying device 50, the distribution of the drying temperature in the drying device 50 (temperature gradient, etc.), the drying time (the residence time in the drying device 50), and the dry air volume at the time of drying are appropriately controlled ( The method of the amount of the hot air for drying which is blown from the hot air blowing port 60). Further, in the production method of the present invention, it is possible to set the specific range for each of the specific conditions and to reduce the amount of heating of the curable resin film to the above-described specific range, thereby making it possible to obtain a higher range. A cured resin film which can effectively prevent defects such as wrinkles and foaming is obtained in productivity.

In the production method of the present invention, the conditions for setting the heating loss of the curable resin film to the above-described specific range, for example, the following conditions can be exemplified, and it is preferable that the curable resin, the type of the solvent, the amount of the solvent, and the drying can be used. These conditions are appropriately controlled by the thickness of the front resin film or the like.

That is, in the manufacturing method of the present invention, the inside of the drying device 50 is set to have two zones of a warming zone and a drying zone, so that the temperature ranges become The range below is better. In this case, the temperature in the heating zone is preferably 30 to 60 ° C, preferably 40 to 60 ° C, and more preferably 45 to 55 ° C. When the temperature in the heating zone is too high, there is a possibility that bubbles are generated in the resin film before drying and the flatness is lowered. On the other hand, when the temperature in the heating zone is too low, the time required for drying is changed. The possibility of long and low production efficiency, or poor drying becomes insufficient.

Further, the temperature in the drying zone is preferably a temperature higher than the temperature in the heating zone, and is preferably 60 to 100 ° C, more preferably 60 to 95 ° C, and is set to 60. ~90 ° C is especially good. When the temperature in the drying zone is too high, bubbles are generated in the resin film before drying, and flatness is poor, and drying is excessive, and the curable resin film obtained by drying becomes brittle or hardens and reacts. The defect of the wiring embedding is poor. On the other hand, when the temperature of the drying zone is too low, there is a possibility that the time required for drying becomes long, the production efficiency is low, or the drying becomes insufficient.

Moreover, in the present invention, the temperature of the warming zone may be set to a uniform temperature throughout the warming zone, and it is preferable to further divide the warming zone into a plurality of zones, which are in accordance with the pre-drying resin film 10 with the support. The progress is made to gradually increase the temperature gradually. Similarly, the temperature of the drying zone may be set to a uniform temperature throughout the drying zone, and it is preferred to further divide the drying zone into a plurality of zones which are set to a temperature in accordance with the progress of the pre-drying resin film 10 of the support. In a phased manner, it gradually rises. In this case, the maximum temperature of the heating zone and the drying zone may be set to the above-described temperature range. For example, the temperature may be substantially the same in the boundary between the heating zone and the drying zone.

Further, the drying time of the resin film before drying in the present invention (drying The residence time in the apparatus 50 is preferably 30 to 300 seconds, preferably 60 to 180 seconds, more preferably 90 to 150 seconds. When the drying time is too long, the amount of heat applied to the support is increased. As a result, the heat shrinkage when the curable resin film 10a with the support after drying is cured is increased, and as a result, defects such as wrinkles are likely to occur. On the other hand, when the drying time is too short, there is a possibility that the drying is insufficient.

(Air volume air outlet 60 from the hot blown dry with hot air of) and in the wind when dry and dried before the resin film is dried to the present invention, based to 0.5 ~ 7m ^{3 /} hr preferably, preferably 1 ~ 6m ^{3 /} The hour is more preferably 2.5 to 4.5 m ^{3 /} hour. When the amount of dry air is too large, the resin film 10 before drying with the support causes turbulence during drying, or a phenomenon in which the width direction is shifted during transportation, or the film thickness uniformity of the resin film 10 before drying with the support is low. Moreover, the reliability of the obtained hardened resin film deteriorates. On the other hand, when the amount of dry air is too small, the support of the pre-drying resin film 10 with the support by the hot air for drying becomes insufficient, and the resin film 10 is deflected before drying with the support and the support is dried. The handling of the front resin film 10 becomes difficult.

The thickness of the curable resin film is not particularly limited, but is usually 1 to 100 μm, preferably 5 to 80 μm, and more preferably 10 to 60 μm from the viewpoint of workability and the like.

Further, in the present invention, the curable resin film is preferably in an unhardened or semi-cured state. Here, the term "unhardened" refers to a curable resin film, and is immersed in a solvent capable of dissolving a curable resin (for example, an epoxy resin) used in preparing a thermosetting resin composition, and the curable resin is substantially The state of all dissolution. Further, the term "semi-hardening" refers to a state in which it is hardened to the extent that it can be hardened when further heated, and it is preferable to be able to modulate heat hardening. A solvent in which the curable resin used in the composition of the resin is dissolved, and a part of the curable resin (specifically, an amount of 7 wt% or more and a part remaining) is in a dissolved state; or a molded body The volume after immersion in the solvent for 24 hours is in a state of 200% or more (swelling ratio) of the volume before the immersion.

In the second step of the production method of the present invention, the pre-drying resin film formed on the support as described above is dried to obtain a curable resin formed on the support and having a heating loss of 0.5 to 7% by weight. Film (curable resin film 10a with a support). In addition, when the manufacturing apparatus shown in FIG. 1 is used, the curable resin film formed on the support and having a heating loss of 0.5 to 7% by weight can be obtained by being wound up in the second roll 30.

(Other hardening resin film forming step)

Further, in the production method of the present invention, it is possible to provide a structure in which another curable resin film is formed in advance on the support before the first step, and the other curable resin contains the curable property described above. The other curable resin having a different resin is subjected to the first step and the second step, and the curable resin film described above is formed on the other curable resin film. In other words, a multilayer curable resin film having a curable resin film and a curable resin film formed by the first step and the second step may be provided on the support in the following order.

Further, in this case, for example, another curable resin film can be used as a plated layer for forming a conductor layer by electroless plating or the like, and the first step and the second step can be formed. The curable resin film is used as an adhesive layer for adhering to the substrate.

Further, in the following, the other curable resin film is set as the "second hardening" In the resin film, the other curable resin constituting the other curable resin film is used as the "second curable resin", and the thermosetting resin composition forming the other curable resin is used as the "second thermosetting resin composition". The other resin film before drying which is composed of another thermosetting resin composition is referred to as "the second pre-drying resin film". In the same manner, each of the first step and the second step of the curable resin film is used as the "first curable resin film", the "first curable resin", and the "first thermosetting resin composition". "The first resin film before drying".

Hereinafter, a method of forming the second curable resin film in the other curable resin film forming step will be described. In addition to the second thermosetting resin composition containing a second curable resin and a solvent different from the first curable resin, the second curable resin film is used instead of the first thermosetting resin containing the first curable resin and the solvent. Other than the resin composition, it can be formed in the same manner as the above-described first curable resin film.

In other steps, in the other curable resin film forming step, the second pre-drying resin film composed of the second thermosetting resin composition containing the second curable resin and the solvent is formed on the support, and secondly, The second pre-drying resin film formed on the support is conveyed and dried in a drying apparatus in a state of being formed on the support, thereby obtaining a second curable resin film. In this case, the total amount of heat loss of the first curable resin film and the second curable resin film is preferably 0.5 to 7% by weight, preferably 1 to 6% by weight, more preferably It is in the range of 1.3 to 5% by weight.

The second thermosetting resin composition contains a second curable resin and a solvent, and usually contains a curing agent in addition to these. The second curable resin is not particularly limited, and the electrical properties of the obtained cured resin film are not particularly limited. As for the improvement of heat resistance, it is preferred to contain an alicyclic olefin polymer having a polar group.

The alicyclic olefin polymer having a polar group is not particularly limited, and examples of the alicyclic structure include a naphthene structure and a cycloolefin structure. It is preferred to have a naphthene structure from the viewpoint of having excellent mechanical strength, heat resistance and the like. Moreover, 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, a hydroxycarbonyl group, a carbonyl group, and an amine group. A carboxylic anhydride group, a sulfonic acid group, a phosphoric acid group or the like. In particular, a carboxyl group, a carboxylic anhydride group, and a phenolic hydroxyl group are preferred, and a carboxylic anhydride group is preferred.

In addition, the curing agent contained in the second thermosetting resin composition can be formed into a crosslinked structure by forming an alicyclic olefin polymer having a polar group by heating, and is not particularly limited, and can be used in ordinary electricity. A curing agent formulated by a resin composition for forming an insulating film. As the curing agent, a compound having two or more functional groups capable of reacting with a polar group-containing olefin polymer having a polar group to form a bond is preferably used.

For example, as the alicyclic olefin polymer having a polar group, a hardener which can be suitably used when an alicyclic olefin polymer having a carboxyl group, a carboxylic anhydride group or a phenolic hydroxyl group is used is a polyvalent epoxy compound. A polyisocyanate compound, a polyamine compound, a polyvalent ruthenium compound, an anthracene cyclopropane compound, a basic metal oxide, an organometallic halide, or the like. These may be used alone or in combination of two or more. Further, these compounds may be used in combination with a peroxide as a curing agent.

In particular, as a hardener, the reactivity with a polar group possessed by an alicyclic olefin polymer having a polar group is slow, so that the second thermosetting resin is composed. The handling of the material becomes easy, and a polyvalent epoxy compound is preferred, and a epoxy propyl ether type epoxy compound and an alicyclic type polyvalent epoxy compound are particularly suitable for use.

The amount of the curing agent in the second thermosetting resin composition is preferably from 1 to 100 parts by weight, preferably from 5 to 80 parts by weight, per 100 parts by weight of the alicyclic olefin polymer having a polar group. More preferably, it is in the range of 10 to 50 parts by weight. By setting the amount of the curing agent to 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 hindered phenol compound is a phenol compound having at least one carbon atom having a hydroxyl group at the β position of the hydroxyl group and having a hindered structure having no hydrogen atom. Specific examples of the hindered phenol compound include 1,1,3-gin-(2-methyl-4-hydroxy-5-t-butylphenyl)butane and 4,4,-butylene bis- (3-methyl-6-tert-butylphenol), 2,2-thiobis(4-methyl-6-tert-butylphenol), n-octadecyl-3-(4'-hydroxy-3) ',5'-di-t-butyl.phenyl)propionate, hydrazine-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propane Acid ester] methane, etc.

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

Further, the hindered amine compound is a compound having at least one 2,2,6,6-tetraalkylpiperidinyl group having a secondary amine or a tertiary amine at the fourth position in the molecule. The carbon number of the alkyl group is usually from 1 to 50. As a hindered amine compound, Preferably, a compound having at least one 2,2,6,6-tetramethylpiperidinyl group having a secondary amine or a tertiary amine at the fourth position in the molecule is preferred. Further, in the present invention, it is preferable to use a hindered phenol compound and a hindered amine compound in combination, and when the surface is roughened by using an aqueous solution of permanganate or the like for the cured resin film, the surface roughening treatment is performed. The condition is changed, and the cured product after the surface roughening treatment can be maintained to have a lower surface roughness.

Specific examples of the hindered amine compound include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and bismuth azelaic acid (1, 2, 2, 6, 6). -pentamethyl-4-piperidinyl), 1[2-{3-(3,5-di-t-butyl-4-hydroxyphenyl)propenyloxy}ethyl]-4-{ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoxy}-2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9 , 9-tetramethyl-3-octyl-1,2,3-triazaspiro[4,5]undecane-2,4-dione, and the like.

The compounding amount of the hindered amine compound 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 alicyclic olefin polymer having a polar group. Share. When the amount of the hindered amine compound is in the above range, the mechanical strength of the cured resin film can be improved.

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

Further, the second thermosetting resin composition may contain an inorganic filler in addition to the above components. As the inorganic filler, the same as the filler used in the first thermosetting resin composition can be used. The amount of the inorganic filler to be added to the second thermosetting resin composition is preferably 10% by weight or more, preferably 15 to 60% by weight, and more preferably 20 to 40% by weight in terms of solid content.

In addition to the above-mentioned components, the second thermosetting resin composition may be appropriately blended with a curing accelerator, a flame retardant, a flame retardant, a heat stabilizer, and the like, in the same manner as the first thermosetting resin composition. Weathering stabilizer, anti-aging agent, ultraviolet absorber (laser processing enhancer), leveling agent, antistatic agent, slip agent, anti-adhesive agent, anti-fogging agent, slip agent, dye, natural oil, synthetic oil, A conventional component such as a wax, an emulsion, a magnetic material, a dielectric property modifier, and a toughening agent.

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

The other curable resin film forming step is carried out in the same manner as in the first step and the second step, and the second support can be formed on the support by using the same support, for example, by using the manufacturing apparatus shown in Fig. 1 . The front resin film is dried by a floating method to obtain a second curable resin film having a support formed by forming a second curable resin film on the support. Then, using the second curable resin film with the support obtained as described above, In the first step and the second step, the multilayer curable resin film in which the first curable resin film and the second curable resin film are formed on the support can be obtained.

Moreover, the drying conditions (that is, the temperature conditions of the heating zone and the drying zone, the drying time, and the dry air volume) when the resin film before the second drying is floated can be the same as the second step described above.

In addition, the thickness of the resin film before the second drying is not particularly limited, but is usually 5.0 to 40 μm, preferably 8.0 to 30 μm, more preferably 12 to 25 μm, and the thickness of the second curable resin film after drying is usually 1.0 to 6.0 μm, preferably 1.5 to 5.5 μm, more preferably 2.5 to 4.5 μm.

Further, in the present invention, the second curable resin film is preferably in an unhardened or semi-cured state as in the case of the first curable resin film. Here, the term "unhardened" means that the second curable resin film is immersed in a solvent capable of dissolving a second curable resin (for example, an epoxy resin) used in preparing the second thermosetting resin composition. The second curable resin is in a state of being substantially completely dissolved. In addition, the term "semi-hardening" refers to a state in which the hardening is hardened to the extent of further curing, and it is preferable that the second curable resin used in preparing the second thermosetting resin composition is dissolved. The solvent, a part of the second curable resin (specifically, an amount of 7 wt% or more, and a part remaining) is in a dissolved state; or a volume system in which the molded body is immersed in a solvent for 24 hours becomes impregnated The state of the front volume of 200% or more (swelling rate).

Moreover, in the manufacturing method of the present invention, in order to make the second curable resin film uncured or semi-hardened, it is preferred to form the first pre-drying resin film on the second curable resin film and dry it. The drying conditions are set as the conditions after considering the second curable resin constituting the second curable resin film, that is, It is preferable to set the condition that the second curable resin does not undergo a hardening reaction.

(Step 3)

The third step of the production method of the present invention is a step of forming a cured resin film by thermally curing a curable resin film or a multilayer curable resin film formed on a support.

The heating temperature in the third step can be appropriately set in accordance with the curing temperature of the curable resin film, preferably 100 to 250 ° C, preferably 120 to 220 ° C, and more preferably 150 to 210 ° C. Further, the heating time in the third step is usually 0.1 to 3 hours, preferably 0.25 to 1.5 hours. The heating method is not particularly limited and can be carried out, for example, using an electric oven or the like. Also, from the viewpoint of productivity, heat hardening is preferably performed under the atmosphere.

Further, in the third step of the production method of the present invention, before the curable resin film is thermally cured, the curable resin film formed on the support is preferably formed into a surface of the curable resin film (designed as When the multilayer curable resin film composed of the first curable resin film and the second curable resin film is laminated on the substrate, the first curable resin film forming surface is laminated on the support. A composite of a curable resin film and a substrate is formed in this order, and the laminate is thermally cured in a state of such a laminate to form a curable resin film and a base on the support in the following order. A hardened composite made of wood. In this case, the laminate of the cured resin film of the present invention and the substrate can be obtained by peeling the support from the cured composite in the fourth step to be described later.

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

Further, in the substrate having the conductor layer on the surface used in the present invention, in order to improve the adhesion to the curable resin composition layer, it is preferred to perform pretreatment on the surface of the conductor layer. As a method of pretreatment, a conventional technique can be used without particular limitation. For example, as long as it is composed of copper of a conductor layer, the following method may be mentioned: an oxidation treatment method in which a strong alkali oxidizing solution is brought into contact with a surface of a conductor layer, and a copper oxide layer is formed on the surface of the conductor and roughened; Method: After the surface of the conductor layer is oxidized, the method is carried out by using sodium borohydride or fumarin; the conductor is chromatographed and roughened; and the conductor layer is contacted with the organic acid to dissolve and coarsen the grain boundary of copper. And a method of forming a primer layer on a conductor layer using a thiol compound, a decane compound or the like. From the dimension From the viewpoint of easiness of the shape of the fine wiring pattern, a method in which the conductor layer is contacted with an organic acid to elute and coarsen the grain boundary of copper; and a method of forming a primer layer using a thiol compound or a decane compound It is better.

The method of laminating the curable resin film formed on the support on the substrate is, for example, a curable resin film formed on the support, and the surface of the curable resin film is heated and adhered to the substrate. The method above.

As a method of heating and pressure-bonding, the curable resin film formed on the support can be pressurized by a press bonding machine, a press machine, a vacuum laminator, a vacuum press machine, a roll laminator or the like. The method of laminating and heating and bonding (bonding) to the conductor layer of the above substrate. By heating and pressurizing, it is possible to bond the conductor layer on the surface of the substrate and the molded body or the composite molded body without substantially forming a void. The above-mentioned molded body or composite molding system is usually laminated on the substrate conductor layer in an unhardened or semi-hardened state.

The temperature of the heat-pressing operation 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. Preferably, it is from 1 minute to 3 hours. Further, in order to improve the embedding property of the wiring pattern and suppress generation of bubbles, it is preferred to heat the pressure-bonding system under reduced pressure. The pressure under reduced pressure for heating and pressure bonding is usually 100 kPa to 1 Pa, preferably 40 kPa to 10 Pa.

(Step 4)

The fourth step of the production method of the present invention is a step of separating the support from the cured resin film.

Further, in the manufacturing method of the present invention, when the hardened resin film and the hardened laminate of the substrate are formed in this order on the support, the support may be peeled off. After the front or after peeling, a via hole and a through hole penetrating through the cured resin film are formed. When a laminate comprising a cured resin film and a substrate obtained by the production method of the present invention (hereinafter, simply referred to as "layered body") is used for a multilayer circuit board, the via hole and the via hole are used to Each of the conductor layers constituting the multilayer circuit substrate is connected and formed. The via hole and the via hole can be formed using physical processing such as drilling, laser, plasma etching, or the like. Among these methods, a fine via hole and a via hole can be formed without lowering the characteristics of the cured resin layer, and a laser method (carbon dioxide gas laser, excimer laser, UV-YAG laser, etc.) can be used. It is better. Further, when the via hole and the via hole are formed by using a laser in a state where the resin film is cured before the support is peeled off, it is preferable to form the via hole and the via hole by irradiating the laser from the support side. Thereby, a finer via hole and a via hole can be formed with a higher aperture ratio (bottom diameter / top diameter).

Further, in the production method of the present invention, after the support is peeled off, the surface of the cured resin film may be roughened by roughening the aqueous solution of permanganate. When the laminate obtained by the production method of the present invention is used in a multilayer circuit substrate, the surface roughening treatment is performed in order to improve the adhesion to the conductive layer formed on the cured resin film.

The surface roughness Ra of the cured resin film is preferably 0.05 μm or more and less than 0.3 μm, more preferably 0.06 μm or more and 0.2 μm or less, and the surface ten-point average roughness Rzjis is preferably 0.3 μm or more and less than 4 μm. It is preferably 0.5 μm or more and 2 μm or less. Further, in the present specification, the Ra center is the center line average roughness expressed in JIS B0601-2001, and the surface ten-point average roughness Rzjis is the ten-point average roughness expressed in Annex 1 of JIS B0601-2001.

The method for treating the surface roughness is not particularly limited, and examples thereof include A method of bringing the surface of the cured resin film 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. From the viewpoint of easiness of controlling the average roughness of the surface of the cured resin film, it is particularly preferable to use an inorganic oxidizing compound and an organic oxidizing compound. Examples of the inorganic oxidizing compound include permanganate, chromic anhydride, dichromate, chromate, persulfate, activated manganese dioxide, osmium tetroxide, hydrogen peroxide, and periodate. Examples of the organic oxidizing compound include dicumyl peroxide, octyl peroxide, m-chloroperbenzoic acid, peracetic acid, ozone, and the like.

The method of roughening the surface of the cured resin film using an inorganic oxidizing compound and an organic oxidizing compound is not particularly limited. For example, a method in which the oxidizing compound is dissolved in a solvent capable of being dissolved to prepare an oxidizing compound solution to be in contact with the surface of the cured resin film is mentioned. The method of bringing the oxidizing compound solution into contact with the surface of the cured resin film is not particularly limited. For example, any of the following methods may be employed: impregnation of the cured resin film in an oxidizing compound solution; and surface tension of the oxidizing compound solution. The liquid accommodating method in which the oxidizing compound solution is placed on the cured resin film, the spray method in which the oxidizing compound solution is sprayed on the cured resin film, or the like. By performing the surface roughening treatment, the adhesion between the cured resin film and other layers such as the conductor layer can be improved.

The temperature and time at which the oxidizing compound solution is brought into contact with the surface of the cured resin film can be arbitrarily set in consideration of the concentration, type, contact method, and the like of the oxidizing compound, and the temperature is usually 10 to 250 ° C, preferably 20 to 180 ° C. The time system is usually 0.5 to 60 minutes, preferably 1 to 40 minutes.

Further, after the surface roughening treatment, in order to remove the oxidizing compound, The surface of the cured resin film after the surface treatment was washed with water. Further, when a substance which cannot be washed by using water is adhered, it is further washed with a washing liquid capable of dissolving the substance, or is made into a water-soluble substance by contacting it with another compound, and then water is used. Wash. For example, when an alkaline aqueous solution such as a potassium permanganate aqueous solution or a sodium permanganate aqueous solution is brought into contact with a cured resin film, a mixed liquid of hydroxylamine sulfate and sulfuric acid can be used for the purpose of removing the manganese dioxide film to be produced. After the acidic aqueous solution is subjected to neutralization and reduction treatment, it is washed with water.

When the production method according to the present invention is carried out in this manner, a laminate in which a cured resin film is formed on a substrate can be obtained, and the laminate obtained in this manner is obtained by using the above-described production method of the present invention. A cured resin film which can effectively prevent defects such as wrinkles and foaming, and a laminate including the cured resin film can be obtained with high productivity.

(multilayer circuit board)

The multilayer circuit board of the present invention is formed by further forming another conductor layer on the cured resin film of the laminate obtained by the above-described production method of the present invention. Hereinafter, a method of manufacturing the multilayer circuit substrate of the present invention will be described.

First, the laminate obtained by the production method of the present invention is subjected to a treatment for forming a via hole and a via hole in the cured resin film according to the above method, and secondly, a surface roughening treatment of the cured resin film is performed.

Next, after the surface of the cured resin film of the laminate is roughened, a conductor layer is formed on the surface of the cured resin film and the inner wall surface of the via hole and the via hole.

The method of forming the conductor layer is not particularly limited, and has excellent adhesion from formation. From the viewpoint of the conductive layer, the plating method is preferred.

The method of forming the conductor layer by the plating method is not particularly limited. For example, a method of forming a metal thin film on the cured resin film by plating or the like, and then increasing the thickness of the metal layer by thick plating can be employed.

For example, when a metal thin film is formed by electroless plating, a catalyst core such as silver, palladium, zinc, or cobalt is usually adhered to the cured resin film before the metal thin film is formed on the surface of the cured resin film. The method of attaching the catalyst core to the cured resin film is not particularly limited, and for example, it is immersed in a metal compound such as silver, palladium, zinc or cobalt, and the salts and complexes are dissolved at a concentration of 0.001 to 10% by weight. A method in which a metal is formed in water, an organic solvent such as an alcohol or chloroform (including an acid, a base, a binder, a reducing agent, etc. as necessary), and then the metal is reduced.

As the electroless plating solution used in the electroless plating method, a conventional self-catalytic electroless plating solution can be used, and the type of metal contained in the plating solution, the type of reducing agent, the type of the wrong agent, and The hydrogen ion concentration, the dissolved oxygen concentration and the like are not particularly limited. For example, an electroless copper plating solution in which ammonium hypophosphite, hypophosphorous acid, ammonium borohydride, hydrazine, and fumarine are used as a reducing agent, and an electroless nickel-phosphorus plating solution in which sodium hypophosphite is used as a reducing agent can be used; Electroless nickel-boron plating solution using dimethylamine borane as reducing agent; electroless palladium plating solution; electroless palladium-phosphorus plating solution using sodium hypophosphite as reducing agent; electroless gold plating Liquid; electroless silver plating solution; electroless plating solution such as electroless nickel-cobalt-phosphorus plating solution in which sodium hypophosphite is used as a reducing agent.

After the metal thin film is formed, the surface of the substrate can be brought into contact with the rust preventive agent to perform rustproof treatment. Further, after the metal thin film is formed, the metal thin film can also be heated to improve the adhesion. The heating temperature is usually 50 to 350 ° C, preferably 80~250°C. Further, at this time, heating may be carried out under pressurized conditions. As the pressurization method at this time, for example, a method using a physical pressurizing means such as a hot press or a pressurized heat roll machine can be mentioned. The applied pressure is usually 0.1 to 20 MPa, preferably 0.5 to 10 MPa. In this range, high adhesion between the metal thin film and the cured resin film can be ensured.

The resist pattern for plating is formed on the metal thin film formed in this manner, and the plating is grown by thick plating such as electrolytic plating (thickening plating), and then the photoresist is removed and borrowed. The metal thin film is etched into a pattern by etching to form a conductor layer. Therefore, the conductor layer formed by this method is usually composed of a patterned metal thin film and a plating layer grown thereon.

In the above-described manufacturing method of the present invention, the multilayer circuit board obtained as described above is formed as a substrate for producing a laminate and laminated with a curable resin film having a support, and is cured to form a cured resin film ( In the third step), a laminate is obtained by peeling off the support (fourth step), and further, by forming the conductive layer thereon according to the above method, by repeating the above, it is possible to further multilayer Thereby, it can become a required multilayer circuit board.

The multilayer circuit board of the present invention obtained in this manner has a laminate obtained by the production method of the present invention because the laminate system is provided with a cured resin film which can effectively prevent defects such as wrinkles and foaming. Since the insulating layer), the multilayer circuit board of the present invention can be suitably used in various applications.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. In addition, the "parts" and "%" in each case are weights as long as they are not notified in advance. Benchmark. The measurement and evaluation were carried out in accordance with the following methods for various physical properties.

(1) Heating reduction of the second curable resin film and the first curable resin film

The obtained second curable resin film and the first curable resin film were peeled off from the polyethylene terephthalate film, and measured in a nitrogen atmosphere using a differential thermogravimetric simultaneous measurement device (TG-DTA) at 170. The total amount of heat loss of the second curable resin film and the first curable resin film at the time of heating at ° C for 15 minutes.

(2) Film handling properties during drying

The deviation in the width direction of the film conveyance in the drying apparatus 50 at the time of drying of the resin film before the second drying and the drying of the resin film before the first drying was measured, and the film conveyability was evaluated based on the following criteria.

(evaluation benchmark)

A: The deviation of the width direction of the film is less than ±1 mm.

B: The deviation of the width direction of the film is ±1 mm or more and less than ±2 mm.

C: The deviation in the width direction of the film is ±2 mm or more.

(3) Evaluation of embedding property of the second curable resin film and the first curable resin film

In the obtained laminated substrate, the number of voids was measured by observing the wiring between the wiring layers of the inner layer substrate, and the second curable resin film and the first curable resin film were buried based on the following criteria. Into sex.

(evaluation benchmark)

A: no gap

B: The gap is 1 or more and less than 10

C: 10 or more voids

(4) Foaming of hardened resin film

The cured resin film obtained was visually observed to confirm the presence or absence of foaming in the cured resin film, and was evaluated based on the following criteria.

(evaluation benchmark)

A: no foaming

B: Foaming is 1 or more and less than 10

C: Foaming is 10 or more

(5) Wrinkles of the cured resin film

The surface of the cured resin film of the obtained laminate was visually observed to confirm the presence or absence of wrinkles on the surface of the cured resin film, and was evaluated based on the following criteria.

(evaluation benchmark)

A: Wrinkles cannot be observed.

B: It was confirmed that wrinkles were in an area of less than 10%.

C: It is possible to confirm that the wrinkles are in an area of 10% or more.

Synthesis Example 1

For the first stage of the polymerization, a nitrogen-substituted pressure-resistant glass reactor was charged with 35 mol parts of 5-ethylene-bicyclo[2.2.1]hept-2-ene, 0.9 mol parts 1-hex. Alkene, 340 moles of anisole and 0.005 moles of 4-ethyloxybenzylidene (dichloro) (4,5-dibromo-1,3-di-2,4) as a ruthenium polymerization catalyst , 6-trimethylphenyl-4-imidazolin-2-ylidene) (tricyclohexylphosphine) ruthenium (C1063, manufactured by Wako Pure Chemical Industries, Ltd.), and polymerization was carried out at 80 ° C for 30 minutes with stirring to obtain decene. A solution of a ring opening polymer.

Next, in the second stage of the polymerization, 45 moles of tetracyclic rings [6.5.0.1 ^{2, 5} .0 8, ¹³ ] thirteen groups - 3, 8 are added to the solution obtained in the first stage of the polymerization. 10,12-tetraene, 20 moles of bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic anhydride, 250 moles of anisole and 0.01 moles of C1063 at 80 ° C with stirring The polymerization reaction was carried out for 1.5 hours to obtain a solution of a norbornene-based ring-opening polymer. When the gas chromatography method was measured for this solution, it was confirmed that substantially no monomer remained and the polymerization conversion ratio was 99% or more.

Next, the obtained ring-opening polymer solution was added to a autoclave equipped with a nitrogen-substituted mixer, and 0.03 mol of C1063 was added thereto, and the mixture was stirred at 150 ° C under a hydrogen pressure of 7 MPa for 5 hours to carry out hydrogenation reaction to obtain decene. A solution of a fused ring of an alicyclic olefin polymer (1) of a ring-opening polymer. The alicyclic olefin polymer (1) had a weight average molecular weight of 60,000, a number average molecular weight of 30,000, and a molecular weight distribution of 2. Further, the hydrogenation rate was 95%, and the content of the repeating unit having a carboxylic anhydride group was 20 mol%. The solid content concentration of the solution of the alicyclic olefin polymer (1) was 22%.

Example 1

(Preparation of the first thermosetting resin composition)

50 parts of a biphenyl dimethylene skeleton novolac type epoxy resin (trade name "NC-3000L", manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269) which is a polyvalent epoxy compound (A) having a biphenyl structure.肆 hydroxyphenylethane type epoxy compound (product name "jER 1031S", manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 200, softening point) as a trivalent or higher polyepoxypropyl group-containing epoxy compound (B) 50 parts of 90% C, a cresol novolak resin containing a triazine structure as a triazine structure-containing phenol resin (C) (trade name "PHENOLITE LA-3018-50P", non-volatile 50% C Glycol monomethyl ether solution, DIC company, active hydroxyl equivalent 154) 30 parts (15 parts of cresol novolak resin containing triazine structure), active ester compound (product name " as active ester compound (D) Epiclon HPC-8000-65T", 65% non-volatile toluene solution, DIC company, active ester group equivalent 223) 115.3 parts (75 parts by weight of active ester compound), cerium oxide as a filler (trade name "SC2500" 350 parts of -SXJ", manufactured by ADMATECHS Co., Ltd., a hindered phenolic antioxidant (trade name "IRGANOX (registered trademark) 3114", manufactured by BASF), and 110 parts of anisole as an antioxidant, and used in a planetary manner. Stir the mixer for 3 minutes. Further, here, 8.3 parts of a solution obtained by dissolving 30% of anisole as a hardening accelerator, 1-benzyl-2-phenylimidazole (2.5 parts by weight of 1-benzyl-2-phenylimidazole), and The varnish of the first thermosetting resin composition was obtained by stirring for 5 minutes using a planetary mixer. Further, the content of the filler in the varnish was 64% in terms of solid content.

(Preparation of the second thermosetting resin composition)

454 parts of a solution of the alicyclic olefin polymer (1) obtained in Synthesis Example 1 (in terms of 100 parts by weight of the alicyclic olefin polymer (1)), and a dimer having a dicyclopentadiene skeleton as a curing agent Epoxy compound (trade name "Epiclon HP7200L", DIC company, "Epiclon" is a registered trademark) 36 parts, cerium oxide as an inorganic filler (trade name "ADMERFINE SO-C1", ADMATECHS company, average particle size 0.25 Mm, "ADMERFINE" is a registered trademark) 24.5 parts, as an antioxidant (3,5-di-t-butyl-4-hydroxybenzyl)-isocyanate (trade name "IRGANOX (registered trademark) 3114", manufactured by BASF Corporation), 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole as a UV absorber And 0.5 part of 1-benzyl-2-phenylimidazole as a hardening accelerator, mixed The mixture was mixed with anisole and mixed so as to have a concentration of the compounding agent of 16% to obtain a second thermosetting resin composition.

(Formation of the second curable resin film)

The second thermosetting resin composition obtained above and the polyethylene terephthalate film (support, thickness: 50 μm) having a release layer on the surface thereof were used, and the manufacturing apparatus shown in Fig. 1 was used. A second curable resin film is formed on the polyethylene terephthalate film. Specifically, the polyethylene terephthalate film is continuously wound up from the first roll 20 in which a long strip of polyethylene terephthalate film is taken up, and the second thermosetting resin composition is used. The second pre-drying resin film having a thickness of 20 μm was formed on the polyethylene terephthalate film by continuous application using the coating device 40. Then, it is continuously conveyed in the drying device 50 by a floating method, and the anisole as a solvent is removed to form a second curable resin film, which is continuously wound up using the second roll 30, and is A second curable resin film having a thickness of 3.5 μm was formed on the long strip of polyethylene terephthalate film.

Further, the drying conditions at this time are as follows.

<warming area>

The heating was divided into four zones and the temperature was set to be gradually higher toward the progress direction of the polyethylene terephthalate film, and the lowest temperature was set to 30 ° C, and the highest temperature was set to 60 ° C.

<Drying zone> The drying is divided into four zones and the temperature is set to gradually increase toward the progress direction of the polyethylene terephthalate film, and the minimum temperature is set to 60 ° C, and the maximum temperature is set to 90 ° C.

<drying time (time passing through the drying device 50) > 60 seconds

<dry air volume> 3.5m ^{3 /} hour

Then, the first thermosetting resin composition obtained as described above was used on the polyethylene terephthalate film formed by forming the second curable resin film by using the production apparatus shown in Fig. 1 . A first curable resin film is formed on the second curable resin film forming surface. Specifically, the polyethylene terephthalate film formed by forming the long curable resin film is obtained by winding a polyethylene terephthalate film formed with a second curable resin film. The 1 roll cylinder 20 is continuously wound up, and the first thermosetting resin composition is continuously coated by the coating device 40, and the first pre-drying resin having a thickness of 50 μm is formed on the polyethylene terephthalate film. membrane. Then, it is continuously conveyed in the drying device 50 by a floating method, and the anisole as a solvent is removed to form a first curable resin film, and the second roll 30 is continuously wound up by using the second roll 30. A first curable resin film having a thickness of 37.5 μm was formed on the second curable resin film on the long strip of polyethylene terephthalate film. In addition, the drying conditions at this time are the same as those in the case of forming the second curable resin film. In the present embodiment, the film transportability in the drying apparatus 50 during the drying of the resin film before the second drying and the drying of the resin film before the first drying are evaluated in accordance with the above method. The results are shown in Table 1.

Then, using the obtained film in which the second curable resin film and the first curable resin film are formed on the polyethylene terephthalate film, the second curable resin film and the first measurement are performed according to the above method. The total amount of heat loss of the curable resin film. The results are shown in Table 1.

(manufacturing of laminates)

Next, in addition to the above, the surface of the core material obtained by impregnating the varnish containing the glass filler and the halogen-free epoxy compound with a glass fiber having a thickness of 18 μm is formed into a thickness of 0.8 mm and 160 mm. 160mm, horizontal The surface of the double-sided copper-clad substrate of 160 mm) was microetched by contact with an organic acid on the surface to obtain an inner layer substrate on which a conductor layer having a wiring width, a wiring distance of 50 μm, and a wiring height (thickness) of 18 μm was formed.

The film obtained by forming the second curable resin film and the first curable resin film on the polyethylene terephthalate film obtained as described above is cut into a 150 mm square, and the polyethylene terephthalate is attached. In the state of the ester film, the surface of the first layer of the inner layer substrate is bonded to the inner surface of the inner layer substrate, and the vacuum bonding machine having the heat-resistant rubber pressure plate on the upper and lower sides is used. The laminate was heated and pressure bonded to 200 Pa at a temperature of 110 ° C and a pressure of 0.1 MPa for 60 seconds. Using the obtained laminated substrate, the embedding property evaluation was performed according to the above method. After allowing to stand at room temperature for 30 minutes, the second curable resin film and the first curable resin film are cured by heating at 180 ° C for 30 minutes to form a cured resin film (electrically insulating layer). . Using the obtained curable resin film, evaluation of foaming was performed according to the above method. Thereafter, the support is peeled off from the cured resin film to obtain a laminate comprising a cured resin film and an inner layer substrate. Using the obtained laminate, the wrinkles of the cured resin film were measured in accordance with the above method. The results are shown in Table 1.

Example 2

In addition to changing the maximum temperature of the heating zone during drying of the second pre-drying resin film and the first pre-drying resin film from 60 ° C to 40 ° C, the maximum temperature of the drying zone is changed from 90 ° C to 60 ° C, and The drying time (the time in the drying apparatus 50) was changed from 60 seconds to 180 seconds, and the second curable resin film and the first hardening were formed on the polyethylene terephthalate film in the same manner as in Example 1. A film made of a resin film and a laminate were evaluated in the same manner. The results are shown in Table 1.

Example 3

In addition to changing the maximum temperature of the heating zone during drying of the second pre-drying resin film and the first pre-drying resin film from 60 ° C to 35 ° C, the maximum temperature in the drying zone is changed from 90 ° C to 60 ° C, and The drying time (the time in the drying apparatus 50) was changed from 60 seconds to 280 seconds, and the second curable resin film and the first hardening were formed on the polyethylene terephthalate film in the same manner as in Example 1. A film made of a resin film and a laminate were evaluated in the same manner. The results are shown in Table 1.

Example 4

The maximum temperature in the drying zone when the second pre-drying resin film and the first pre-drying resin film are dried is changed from 90 ° C to 65 ° C and the drying time (time in the drying device 50) is changed from 60 seconds to 60 seconds. In the same manner as in the first embodiment, a film obtained by forming a second curable resin film and a first curable resin film on a polyethylene terephthalate film and a laminate were obtained in the same manner as in Example 1 and the same. Conduct an evaluation. The results are shown in Table 1.

Example 5

In addition to changing the maximum temperature of the heating zone during drying of the second pre-drying resin film and the first pre-drying resin film from 60 ° C to 50 ° C, the maximum temperature in the drying zone was changed from 90 ° C to 110 ° C, and dried. The time (the time passed in the drying apparatus 50) was changed from 60 seconds to 30 seconds, and the dry air volume was changed from 3.5 m ³ /hr to 8.0 m ³ /hr, and the same procedure as in Example 1 was carried out to obtain a polyparaic acid. A film obtained by forming a second curable resin film and a first curable resin film on the ethylene glycol film and a laminate were evaluated in the same manner. The results are shown in Table 1.

Comparative example 1

In addition, the drying method at the time of drying the second pre-drying resin film and the first pre-drying resin film is changed to a roll supporting method (the manufacturing device shown in Fig. 1 uses a film to convey a film by a roller) In the same manner as in the first embodiment, a film obtained by forming a second curable resin film and a first curable resin film on a polyethylene terephthalate film and a laminate were obtained in the same manner. Evaluation. The results are shown in Table 1.

Comparative example 2

In addition to changing the maximum temperature of the heating zone during drying of the second pre-drying resin film and the first pre-drying resin film from 60 ° C to 70 ° C, the maximum temperature in the drying zone was changed from 90 ° C to 110 ° C and dried. The time (the time passed through the drying apparatus 50) was changed from 60 seconds to 30 seconds, and the dry air volume was changed from 3.5 m ^{3 /} hour to 11.0 m ^{3 /} hour, and the same procedure as in Example 1 was carried out to obtain a poly-parameter. A film obtained by forming a second curable resin film and a first curable resin film on the ethylene glycol film and a laminate were evaluated in the same manner. The results are shown in Table 1.

Comparative example 3

In addition to changing the maximum temperature of the heating zone during drying of the second pre-drying resin film and the first pre-drying resin film from 60 ° C to 30 ° C, the maximum temperature in the drying zone was changed from 90 ° C to 50 ° C and dried. The second curable resin film and the first curable property were obtained on the polyethylene terephthalate film in the same manner as in Example 1 except that the time (the time in the drying device 50) was changed from 60 seconds to 360 seconds. A film made of a resin film and a laminate were evaluated 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, since the film transportability and the wiring embedding property are excellent at the time of drying, a cured resin film having high productivity and effectively preventing defects such as wrinkles and foaming and a resin are provided. A laminate of films (Examples 1 to 5).

On the other hand, when the resin film before drying was dried by the roll support method, wrinkles were formed in the obtained cured resin film, and the reliability as an electrical insulating layer was inferior (Comparative Example 1).

In addition, when the drying condition of the resin film before drying is set to be high, and the heating loss of the second curable resin film and the first curable resin film is less than 0.5% by weight, wrinkles are formed in the obtained cured resin film, and electricity is generated. The reliability of the insulating layer is poor, and the film transportability at the time of drying is also low, the productivity is poor, and the result of foaming of the cured resin film obtained in this case is obtained because of poor wiring embedding (Comparative Example 2) ).

Moreover, when the drying condition of the resin film before drying is set to be low, When the amount of heat loss of the curable resin film and the first curable resin film is more than 7% by weight, the obtained cured resin film is foamed by the influence of a residual solvent or the like, and the reliability as an electrically insulating layer is deteriorated. (Comparative Example 3)

Claims (9)

A method for producing a cured resin film, comprising the steps of: forming a pre-drying resin film comprising a thermosetting resin composition containing a curable resin and a solvent on a support; The pre-drying resin film formed on the support is transported by floating in a drying device while being formed on the support, and the heating loss is 0.5~. 7 wt% of a curable resin film; a third step of curing the curable resin film to form a cured resin film; and a fourth step of peeling the support from the cured resin film. The method for producing a cured resin film according to claim 1, wherein in the second step, the pre-drying resin film is set to 30 to 60 in a state of being formed on the support. The heating zone of °C and the drying zone of the drying zone set to a higher temperature than the heating zone are carried by floating, and the drying time of the resin film before drying is 30 to 300 seconds, and drying is performed during drying. The air volume is 0.5~7m ³ /hour. The method for producing a cured resin film according to claim 2, wherein the heating zone and the drying zone are each divided into a plurality of regions, and the temperature of each region is set to be in accordance with the progress of the resin film before drying. A temperature that becomes higher in stages. The method for producing a cured resin film according to any one of claims 1 to 3, wherein the support is used as a release mold on the surface Film of the layer. The method for producing a cured resin film according to any one of claims 1 to 4, wherein a solvent content of the thermosetting resin composition is 5 to 40% by weight. The method for producing a cured resin film according to any one of claims 1 to 5, wherein the thermosetting resin composition further contains an inorganic filler, and the inorganic filler is formed in the thermosetting resin composition. The content ratio of the agent is 60% by weight or more in terms of solid content. The method for producing a cured resin film according to any one of claims 1 to 6, further comprising a step of forming another curable resin film, which is formed on the support before the first step The other curable resin film of the other curable resin having different curable resins; and in the first step, the pre-drying resin film is formed on the other curable resin film formed on the support. The method for producing a cured resin film according to claim 7, wherein the other curable resin film forming step includes the step of forming the other curable resin and the solvent on the support. a step of forming another resin film before drying by the other thermosetting resin composition; and the other resin film before drying which is formed on the support, in a state of being formed on the support, by drying The inside of the apparatus is conveyed by a floating method to be dried, and the step of heating is to reduce the amount of the other curable resin film of 0.5 to 7% by weight. A laminate which is as claimed in any one of claims 1 to 8 The cured resin film obtained by the production method and the substrate are laminated.