TWI650371B - Curable epoxy composition, film, laminated film, prepreg, laminate, cured product and composite - Google Patents

Abstract

Provided are a curable epoxy composition, a film obtained by using the same, a laminated film, a prepreg, a laminate, a cured product, and a composite, wherein the curable epoxy composition comprises the following: a multi-ring An oxygen compound (A) having a biphenyl structure and/or a condensed polycyclic structure; a phosphorus-containing epoxy compound (B) having a structure represented by the following formula (1) or (2); and a triazine-containing structure Phenolic resin (C).

(In the formula (1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and a plurality of R ¹ and R ² groups may be the same or different, and m and n are each independently and represent 0 to 0. An integer of 4, in the formula (2), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and a plurality of R ¹ and R ² groups may be the same or different, and m and n are each independently and Indicates an integer from 0 to 5.)

Description

Curable epoxy composition, film, laminated film, prepreg, laminate, cured product and composite

The present invention relates to a curable epoxy composition, a film, a laminated film, a prepreg, a laminate, a cured product, and a composite.

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. In order to meet the demand for such high density, it is necessary to obtain a multilayer of the circuit board. Chemical. Such a multilayer circuit substrate is formed, for example, on an inner layer substrate composed of an electrically insulating layer and a conductor layer formed on a surface thereof, and an electrically insulating layer is laminated and a conductor layer is formed on the electrically insulating layer, and This is formed by repeating the lamination of these electrically insulating layers and the formation of a conductor layer.

As a material for constituting the electrically insulating layer of such a multilayer circuit substrate, ceramics, thermosetting resins, and the like are usually used. In particular, an epoxy resin which is a thermosetting resin is widely used because it is excellent in balance between economy and performance.

As an epoxy resin material for constituting such an electrically insulating layer, for example, Patent Document 1 discloses an cresol novolak containing (A) an epoxy resin, (B) an active ester compound, and (C) a triazine-containing cresol. Resin epoxy resin composition. Patent Document 1 describes that when such an epoxy resin composition is used, it is possible to form one The tube has a small thickness, but shows a high density on the plated conductor and a low linear expansion rate. Low dielectric loss tangent insulation layer.

Here, in the multilayer circuit board described above, each of the conductor layers formed on the multilayer circuit board has a structure in which the layers are connected to each other through a via hole provided in the electrically insulating layer. Further, when a via hole to be used in such interlayer connection is formed, a hole for a via hole is formed by irradiating a laser to the electrically insulating layer, and then a metal plating process is performed, in order to be irradiated by the laser before. The resulting resin residue (smear) remaining on the lower conductor layer and the electrically insulating layer is subjected to residue removal treatment. The residue removal treatment is performed, for example, by immersing a multilayer substrate having pores for via holes in a solution of a chemical oxidizing agent of potassium permanganate and potassium dichromate to dissolve and remove the residue in the pores. When the residue removal treatment is insufficient and the residue resistance cannot be sufficiently ensured, even if the via hole is subjected to metal plating treatment, the conductivity of the upper conductor layer and the lower conductor layer may not be sufficiently ensured due to the residue. Sex.

Further, in the multilayer circuit board, the conductor layer must be adhered to the electrically insulating layer, and when the adhesion is weak, peeling occurs in the manufacturing process of the multilayer circuit substrate and in the package, and in the use as the substrate for the electronic material. Reliability has the potential to be insufficiently ensured.

Prior technical literature Patent literature

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2011-132507

In this practical situation, the inventors of the present invention, etc. When the electrical insulating layer of the multilayer printed wiring board is formed using the epoxy resin composition described in Patent Document 1, the heat resistance and electrical properties are substantially good, but the residue is poor and the adhesion to the conductor layer is poor. Still not enough.

An object of the present invention is to provide a curable epoxy composition, and a film, a laminate film, a prepreg, a laminate, a cured product, and a composite obtained by using the same, wherein the curable epoxy composition can be formed An electrically insulating layer which is excellent in heat resistance, electrical properties, and degreasability, has a good balance, and is excellent in adhesion to a conductor layer.

In order to achieve the above object, the inventors of the present invention have found that a polyvalent epoxy compound having a biphenyl structure and/or a condensed polycyclic structure, a specific phosphorus-containing epoxy compound, and a phenol resin having a triazine structure are used. When the curable epoxy composition is formed, an electrically insulating layer having desired characteristics can be obtained, and the present invention has been completed.

That is, in accordance with the present invention, the following are provided:

[1] A curable epoxy composition comprising the following: a polyvalent epoxy compound (A) having a biphenyl structure and/or a condensed polycyclic structure; and a phosphorus-containing epoxy compound (B). a structure represented by the following formula (1) or (2); and a phenol resin (C) having a triazine structure,

(In the formula (1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and a plurality of R ¹ and R ² groups may be the same or different, and m and n are each independently and represent 0 to 0. An integer of 4, in the formula (2), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and a plurality of R ¹ and R ² groups may be the same or different, and m and n are each independently and Indicates an integer from 0 to 5.)

[2] The curable epoxy composition according to [1], wherein the phosphorus-containing epoxy compound (B) has an epoxy compound of a phosphaphenanthrene structure represented by the following formula (3),

[3] The curable epoxy composition according to [1] or [2], wherein the ratio of the polyvalent epoxy compound (A) to the phosphorus-containing epoxy compound (B) is "multiple epoxy" The weight ratio of the compound (A): phosphorus-containing epoxy compound (B)" is from 20:80 to 95:5.

[4] The curable epoxy composition according to any one of [1] to [3] wherein the content of the triazine-containing phenol resin (C) is relative to the curable epoxy The total amount of the epoxy compound contained in the composition is from 1 to 60 parts by weight based on 100 parts by weight.

[5] The curable epoxy composition according to any one of [1] to [4], further comprising an active ester compound (D).

[6] A film comprising the curable epoxy composition according to any one of the above [1] to [5].

[7] A laminate film comprising the adhesive layer comprising the curable epoxy composition according to any one of the above [1] to [5]; and a resin composition for a layer to be plated Form a layer to be plated.

[8] A prepreg comprising the film according to the above [6], or the laminated film according to the above [7], and a fibrous substrate.

[9] A laminated body obtained by laminating a film according to the above [6], a laminated film according to the above [7], or a prepreg as described in the above [8]. .

[10] A hardened epoxy composition according to the above [1], [2], [3], [4] or [5], the film according to the above [6], The laminated film according to the above [7], the prepreg according to the above [8], or the laminate according to the above [1] is cured.

[11] A composite obtained by forming a conductor layer on the surface of the cured product according to the above [10].

[12] A substrate for an electronic material, comprising the cured product according to the above [10] or the composite according to the above [11] as a constituent material.

According to the present invention, it is possible to provide a curable epoxy composition, a film obtained by using the same, a laminate film, a prepreg, a laminate, a cured product, and a composite, wherein the curable epoxy composition is capable of forming heat resistance An electrically insulating layer which is excellent in properties, electrical properties, and degreasability, has a good balance, and is excellent in adhesion to a conductor layer.

Form for implementing the invention

The curable epoxy composition of the present invention contains the following composition: a polyvalent epoxy compound (A) having a biphenyl structure and/or a condensed polycyclic structure; a phosphorus-containing epoxy compound (B); A phenolic resin (C) of a triazine structure.

[Multi-element epoxy compound (A) having a biphenyl structure and/or a condensed polycyclic structure]

The polyvalent epoxy compound (A) having a biphenyl structure and/or a condensed polycyclic structure used in the present invention [hereinafter, abbreviated as a polyvalent epoxy compound (A)] has at least 2 in one molecule. The epoxy group (oxirane ring) has at least one of a biphenyl structure and a condensed polycyclic structure, and does not have a compound having a structure represented by the formula (1) or (2) described later.

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

Moreover, the above-mentioned condensed polycyclic structure means a structure in which two or more single-ring condensations (condensed rings) are formed. The ring system 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 electrically insulating layer, it is preferably two 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-p-phenylene structure, a fluorene structure, and an ovalene structure. The condensed polycyclic structure is obtained in the same manner as the biphenyl structure described above. The hardened resin usually constitutes the main chain of the resin, but may also be present in the side chain.

The polyvalent epoxy compound (A) used in the present invention has both a biphenyl structure, a condensed polycyclic structure, or a biphenyl structure and a condensed polycyclic structure, and improves the heat resistance and mechanical properties of the obtained electrically insulating layer. From the viewpoint of strength, the polyvalent epoxy compound (A) is preferably a biphenyl structure, and a biphenyl aralkyl structure is preferred.

Further, the polyvalent epoxy compound (A) is a heat-resistant insulating layer when a biphenyl structure (including both a biphenyl structure and a condensed polycyclic structure) and a condensed polycyclic structure are used in combination. From the viewpoint of improvement in properties and electrical characteristics, the ratio of these ratios is based on the weight ratio (multicomponent epoxy compound having a biphenyl structure/polyvalent epoxy compound having a condensed polycyclic structure), usually 3/7~ 7/3 is better.

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

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

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

An example of a commercially available product of a 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, a 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, for example, the trade name "Epiclon HP7200L, Epiclon HP7200, Epiclon" HP7200H, Epiclon HP7200HH, Epiclon HP7200HHH" (above, DIC company, "Epiclon" registered trademark), trade name "Tactix556, Tactix756" (above, "Tactix" registered trademark of Huntsman Advanced Materials Co., Ltd.), product name" XD-1000-1L, XD-1000-2L" (manufactured by Nippon Kayaku Co., Ltd.); an epoxy compound having a ruthenium structure, for example, "ONCOAT EX-1010, ONCOAT EX-1011, ONCOAT EX-1012, ONCOAT" EX-1020, ONCOAT EX-1030, ONCOAT EX-1040, ONCOAT EX-1050, ONCOAT EX-1051" (above, "ONCOAT" registered trademark), trade name "OGSOL PG-100, OGSOL EG" -200, OGSOL EG-250)" (above, Osaka Gas Chemicals Co., Ltd., "OGSOL" is a registered trademark).

The above polyvalent epoxy compound (A) can be used singly or in combination of two or more kinds.

(phosphorus containing epoxy compound (B))

The phosphorus-containing epoxy compound (B) used in the present invention may be a phosphorus-containing epoxy compound having a structure represented by the following formula (1) or (2), and is not particularly limited.

(In the formula (1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and a plurality of R ¹ and R ² groups may be the same or different, and m and n are each independently and represent 0 to 0. An integer of 4.

In the formula (2), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and a plurality of R ¹ and R ² groups may be the same or different, and m and n are each independently and represent 0 to 5 Integer).

In the present invention, the above-mentioned polyvalent epoxy compound (A) having a biphenyl structure and/or a condensed polycyclic structure as an epoxy compound, and a structure having the structure of the above formula (1) or (2) When the phosphorus epoxy compound (B) is used in combination and the phenol resin (C) having a triazine structure is used as the curing agent, the obtained electrically insulating layer can be excellent in heat resistance, electrical properties, and residue resistance, and has a good balance. Moreover, the adhesion to the conductor layer (especially the adhesion to the conductor layer after the high-temperature and high-humidity test) is also excellent.

The phosphorus-containing epoxy compound (B) having the structure represented by the above formula (1) or (2) is particularly preferably an epoxy compound having a phosphaphenanthrene structure represented by the following formula (3).

The epoxy compound having a phosphaphenanthene structure is not particularly limited, and examples thereof include a biphenyl type epoxy compound having a phosphaphenanthene structure, a bisphenol type epoxy compound having a phosphaphenanthrene structure, and a phosphorus compound. A phenolic novolac type epoxy compound such as a phenanthrene structure.

The biphenyl type epoxy compound having a phosphaphenanthene structure can be exemplified by using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof. The method is to modify a biphenyl type epoxy resin, and various biphenyl type epoxy compounds having a phosphaphenanthrene structure can be obtained. The example of such a compound is not particularly limited, and an epoxy having a tetramethylbiphenyl structure can be used by using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. An epoxy compound obtained by modifying YX-4000 manufactured by Mitsubishi Chemical Corporation.

Further, examples of the bisphenol type epoxy compound having a phosphaphenanthrene structure can be exemplified by using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof. A bisphenol type epoxy compound having a phosphaphenanthrene structure obtained by modifying a bisphenol type epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin. The FX305EK70 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. is exemplified as an example of such a compound.

Further, as the phenolic novolac type epoxy compound having a phosphaphenanthrene structure, by using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof And a phenolic novolak type epoxy using a conventional method Various phenolic novolak type epoxy compounds having a phenanthroline structure obtained by resin modification. The example of such a compound is not particularly limited, and for example, FX289BEK75 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. is mentioned.

The phosphorus-containing epoxy compound (B) used in the present invention may have one or more epoxy groups in its molecule, but an electrically insulating layer obtained by increasing the crosslinking density. The mechanical strength, heat resistance, and linear expansion ratio are not easily lowered, and in terms of electrical characteristics, a polyvalent epoxy compound having at least two epoxy groups in the molecule is preferred.

The content of the phosphorus-containing epoxy compound (B) in the curable epoxy composition of the present invention is not particularly limited, but from the relationship with the above-mentioned polyvalent epoxy compound (A), "polyvalent epoxy compound" The weight ratio of (A): phosphorus-containing epoxy compound (B)" is preferably in the range of 20:80 to 95:5. By setting the content of the phosphorus-containing epoxy compound (B) in the curable epoxy composition of the present invention to the above range of the polyvalent epoxy compound (A), the obtained electricity can be obtained. The heat resistance, electrical properties, slag resistance, and adhesion to the conductor layer of the insulating layer are further improved. In addition, from the viewpoint of making the electrical characteristics of the obtained electrically insulating layer more excellent, the weight ratio of the "polyvalent epoxy compound (A): phosphorus-containing epoxy compound (B)" is used. The range of 60:40 to 95:5 is preferable, and the range of 60:40 to 80:20 is particularly preferable. Or from the viewpoint that the obtained electrically insulating layer can be more excellent in degreasability, it is preferably in the range of 20:80 to 55:45, and is preferably set to 25:75 to 55:45. The range is particularly good.

(other epoxy compounds)

Further, in the curable epoxy composition of the present invention, in addition to the above polycyclic ring In addition to the oxygen compound (A) and the phosphorus-containing epoxy compound (B), other epoxy compounds other than the epoxy compound may be appropriately contained as needed. As such another epoxy compound, for example, a trihydric or higher polyphenol type epoxy compound can be suitably used, and by using such a trihydric or higher polyphenol type epoxy compound, the obtained electrically insulating layer can be obtained. Heat resistance and electrical properties are further improved.

The trivalent or higher polyhydric phenol type epoxy compound may be an epoxy compound of a trihydric or higher polyhydric phenol, and is not particularly limited, and a trihydric or higher polyhydric hydroxyphenyl alkene 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 subjected to epoxidation.

Among such trivalent or higher polyhydroxyphenylene oxide type epoxy compounds, a three- to four-membered polyhydroxyphenylene type epoxy compound is preferred, especially a trishydroxyphenylmethane type epoxy compound, and four Hydroxyphenylethane type epoxy compounds are particularly suitable for use.

Specific examples of the trishydroxyphenylmethane-based epoxy compound are not particularly limited, and examples thereof include "EPPN-503, EPPN-502H, and EPPN-501H" (above, manufactured by Nippon Kayaku Co., Ltd.) and trade name " TACTIX-742 (above, manufactured by Dow Chemical Co., Ltd.), "jER 1032H60" (above, manufactured by Mitsubishi Chemical Corporation), and the like. In addition, the specific example of the tetrahydroxyphenylethane type epoxy compound is not particularly limited, and the product name "jER 1031S" (above, manufactured by Mitsubishi Chemical Corporation) and the like can be mentioned.

When the curable epoxy composition of the present invention contains a trihydric or higher polyphenol-type epoxy compound as the other epoxy compound, the content ratio of the trihydric or higher polyphenol-type epoxy compound is not inhibited by the effect of the present invention. Display The total amount of the epoxy compound contained in the curable epoxy composition of the present invention is preferably from 1 to 45% by weight, preferably from 3 to 40% by weight, based on 100% by weight of the total of the epoxy compound. In particular, when a trihydric or higher polyphenol type epoxy compound is used as the other epoxy compound and the content ratio thereof is in the above range, the heat resistance, electrical properties, and adhesion to the conductor layer of the obtained electrically insulating layer can be further improved. The effect of sexual improvement.

Further, as the other epoxy compound, in addition to the ternary or higher polyphenol type epoxy compound, an alicyclic epoxy compound, a cresol novolak type epoxy compound, a phenol novolak type epoxy compound, or an epoxide novolak type epoxy compound may be used. A bisphenol A novolak type epoxy compound, a phenol type epoxy compound, a fluorenyl (hydroxyphenyl) ethane type epoxy compound, an aliphatic chain epoxy compound, etc., which can be suitably marketed Acquired.

(phenolic resin containing triazine structure (C))

The phenol resin (C) having a triazine structure used in the present invention means an aromatic hydroxy compound such as phenol, cresol or naphthol, a compound having a triazine ring such as melamine or benzoguanamine, and formaldehyde. The condensation polymer. The phenol resin (C) having a triazine structure typically has a structure represented by the following formula (4).

(In the formula (4), R ³ and R ⁴ are a hydrogen atom or a methyl group, and p is an integer of 1 to 30. Further, each of R ³ and R ⁴ may be the same or different from each other, and when p is 2 or more Further, the plurality of R ⁴ groups may be the same or different from each other. Further, for the amine group of at least one of the formula (4), the hydrogen atom contained in the amine group may be other groups (for example, an alkyl group). Etc) replace)

The phenol resin (C) having a triazine structure functions as a hardener for the epoxy compound used in the present invention by the presence of a phenolic active hydroxyl group, particularly by containing a phenol resin having a triazine-containing structure. (C) The obtained electrically insulating layer exhibits excellent adhesion to the conductor layer laminated on the layer, particularly the conductor layer composed of copper.

The phenol resin (C) having a triazine structure can be produced by a conventional method, and can also be obtained as a commercially available product. As an example of such a commercial item, the brand name "LA7052, LA7054, LA3018, LA1356" (above, DIC company) etc. are mentioned. The phenol resin (C) having a triazine structure as described above can be used alone or in combination of two or more.

The compounding amount of the triazine-containing phenol resin (C) in the curable epoxy composition of the present invention is based on the total of the epoxy compounds used (that is, the polyvalent epoxy compound (A), 100 parts by weight of the phosphorus epoxy compound (B) and other epoxy compounds used as required, preferably 1 to 60 parts by weight, preferably 2 to 50 parts by weight, more preferably 3 to 40 parts by weight. The scope of the share.

Further, in the cured resin composition of the present invention, the equivalent ratio of the epoxy compound to the phenol resin (C) having a triazine structure [the total number of epoxy groups of the epoxy compound to be used is three The ratio of the total amount of active hydroxyl groups of the phenol resin (C) of the azine structure (the amount of active hydroxyl groups / the amount of epoxy groups) is preferably 0.01 to 1.1, preferably 0.05 to 0.6, more preferably 0.1 to 0.4. The scope. By setting the amount of the phenol resin (C) having a triazine structure to the above range, it is possible to further enhance Electrical properties and heat resistance of the obtained electrically insulating layer. Further, the equivalent ratio of the epoxy compound to be used to the phenol resin (C) having a 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 obtained.

[Active ester compound (D)]

Further, the curable epoxy composition of the present invention preferably contains the active ester compound (D) in addition to the above respective components. The active ester compound (D) may have an active ester group, and in the present invention, a compound having at least two active ester groups in the molecule is preferred.

The active ester compound (D) is reacted with an epoxy group by heating to have a hardener as an epoxy compound used in the present invention in the same manner as the above-described triazine-containing phenol resin (C). effect.

The active ester compound (D) is formed by reacting 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 electrically insulating layer. An active ester compound obtained by reacting one or more selected from the group consisting of a carboxylic acid compound, a phenol compound, a naphthol compound, and a thiol compound is preferred. Preferably, 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 the exemplified active ester compound (D) is derived from a compound having at least two carboxylic acids in the molecule, and this has at least 2 in the molecule. When the compound of a carboxylic acid contains an aliphatic chain, compatibility with an epoxy compound can be improved, 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, itaconic acid, citric acid, isodecanoic acid, and p-citric acid. Pyrophyllite and so on. Among these, from the viewpoint of improving the heat resistance of the obtained electrically insulating layer, succinic acid, maleic acid, itaconic acid, citric acid, isophthalic acid, and citric acid are preferred. Acid, isophthalic acid, and citric acid are preferred, and isophthalic acid and citric acid are more 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, cadaverin, benzenetriol, two Cyclopentadienyl diphenol, phenol novolak, and the like. In particular, from the viewpoint of improving the solubility of the active ester compound (D) while improving the heat resistance of the obtained electrically insulating layer, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6 - Dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, dicyclopentadienyl diphenol, phenol novolac, preferably dihydroxydiphenyl ketone, three Hydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, dicyclopentadienyl diphenol, and phenol novolak are preferred, and dicyclopentadienyl diphenol and phenol novolak are more preferred.

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, it can be obtained by a condensation reaction of the above carboxylic acid compound and/or a sulfuric acid compound with a hydroxy compound and/or a thiol compound.

In the present invention, as the active ester compound (D), for example, an aromatic compound having an active ester group disclosed in JP-A-2002-12650 and a polyfunctionality disclosed in JP-A-2004-277460 can be used. Polyester, commercial products, etc. As a commercial item, the brand name "EXB9451, EXB9460, EXB9460S, Epiclon HPC-8000-65T" (above, DIC company, "Epiclon" registered trademark), and product name "DC808" (JAPAN EPOXY RESINS company) )), the product name "YLH1026" (made by JAPAN EPOXY RESINS), etc.

The compounding amount of the active ester compound (D) in the curable epoxy composition of the present invention is based on the total of the epoxy compound used (that is, the polyvalent epoxy compound (A), and the phosphorus-containing epoxy compound. 100 parts by weight of the compound (B) and, if necessary, other epoxy compounds, preferably 10 to 150 parts by weight, preferably 15 to 130 parts by weight, more preferably 20 to 120 parts by weight. .

Further, in the cured resin composition of the present invention, the equivalent ratio of the epoxy compound to the active ester compound (D) is [the total number of epoxy groups relative to the epoxy compound used, and the active ester (D) The ratio of the total number of reactive groups (the amount of active ester groups / the amount of epoxy groups) 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 curable epoxy composition of the present invention, the epoxy compound to be used, the phenol resin (C) having a triazine structure, and the active ester compound (D) are used. The ratio of the ratio of {the active hydroxyl group of the phenol resin (C) containing the triazine structure and the active ester group of the active ester compound (D), the ratio of the total number of epoxy groups of the epoxy compound used [ring The amount of oxygen / (amount of active hydroxyl group + amount of active 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 and degreasability can be satisfactorily exhibited in the obtained electrically insulating layer. Further, the equivalent ratio of the epoxy compound to be used and the phenol resin (C) and the active ester compound (D) having a triazine structure can be derived from the total epoxy equivalent of the epoxy compound to be used and the 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) were determined.

(other ingredients)

The curable epoxy composition of the present invention may further contain other components as described below in addition to the above-described respective components, insofar as the effects of the present invention are not impaired.

By adding a filler to the curable epoxy composition of the present invention, the obtained electrically insulating layer can be made into a low linear expansion property. Any of the conventional inorganic fillers and organic fillers can be used as the filler, and an inorganic filler is preferred. Specific examples of the inorganic filler include calcium carbonate, magnesium carbonate, barium carbonate, and zinc oxide. Titanium oxide, magnesium oxide, magnesium niobate, calcium niobate, zirconium silicate, hydrated alumina, magnesium hydroxide, aluminum hydroxide, barium sulfate, cerium oxide, talc, clay, and the like. Further, the filler to be used may be a surface treated in advance using a decane coupling agent or the like. The content of the filler in the curable epoxy composition of the present invention is not particularly limited, but is usually 30 to 90% by weight in terms of solid content.

Further, the curable epoxy composition of the present invention can be added An alicyclic olefin polymer having a polar group. Examples of the polar group include a group having a structure capable of reacting with an epoxy group to form a covalent bond, and a group having a hetero atom and having no reactivity with an epoxy group, and containing a hetero atom and an epoxy group. It is preferred that the group has no reactivity. Since such an alicyclic olefin polymer is not reactive with an epoxy group, it does not substantially contain a functional group reactive with an epoxy group. Here, the term "substantially does not contain a functional group reactive with an epoxy group" means that the alicyclic olefin polymer does not contain an epoxy group which does not inhibit the effect of the present invention. Functionality of sex. The functional group reactive with an epoxy group is a group having a structure capable of reacting with an epoxy group to form a covalent bond, and examples thereof include a primary amine group, a secondary amine group, and a hydrogen sulfur. A hetero atom-containing functional group which forms a covalent bond by reacting with an epoxy group, such as a carboxyl group, a carboxyl group, a carboxylic anhydride group, a hydroxyl group, and an epoxy group.

The alicyclic olefin polymer is, for example, an alicyclic olefin monomer (a) which does not contain a hetero atom and contains an aromatic ring, and an alicyclic olefin monomer (b) which does not contain an aromatic ring and contains a hetero atom. An alicyclic olefin monomer (c) containing an aromatic ring and a hetero atom, and a monomer which can be copolymerized with the alicyclic olefin monomer (a) to (c) simultaneously without an aromatic ring and a hetero atom ( d) The polymerization is carried out in an appropriate manner and in accordance with a conventional method, and can be easily obtained. The obtained polymer can also be further hydrogenated.

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

The curable epoxy composition of the present invention may also be as needed Contains a hardening accelerator. 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-. An alkyl-substituted imidazole compound such as methylimidazole, 1-methyl-2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole or the like; 2-phenylimidazole , 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, benzimidazole, 2 An imidazole compound or the like which is substituted with a hydrocarbon group having a ring structure such as an aryl group or an aralkyl group, such as ethyl-4-methyl-1-(2'-cyanoethyl)imidazole. These can be used alone or in combination of two or more.

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

Further, in order to enhance the flame retardancy of the obtained electrically insulating layer, a curable epoxy composition of the present invention, for example, a halogen-based flame retardant or a phosphate-based flame retardant may be added as appropriate. A flame retardant for a resin composition for forming an electrically insulating film.

Further, in the curable epoxy composition of the present invention, a flame retardant auxiliary, a heat stabilizer, a weathering stabilizer, an antioxidant, an ultraviolet absorber (laser processing enhancer), and the like may be further appropriately added as needed. Leveling agent, antistatic agent, slip agent, anti-adhesive agent, anti-fogging agent, slip agent, dye, natural oil, synthesis A conventional component such as an oil, a wax, an emulsion, a magnetic material, a dielectric property modifier, and a toughening agent.

The method for producing the curable epoxy composition of the present invention is not particularly limited, and the above components may be directly mixed, or may be mixed in a state of being dissolved or dispersed in an organic solvent, or each of the above may be used. A part of the component is dissolved or dispersed in an organic solvent to prepare a composition, and the composition is mixed with the remaining component.

(film)

The film of the present invention is a molded article obtained by molding the above-described curable epoxy composition of the present invention into a sheet shape or a film form.

When the curable epoxy composition of the present invention is formed into a sheet form or a film form to form a molded body, the curable epoxy composition of the present invention is applied, sprayed or flowed by adding an organic solvent as needed. It is preferable to extend on the support and then dry it.

Examples of the support used in this case include a resin film, a metal foil, and the like. Examples of the resin film include a polyethylene terephthalate film, a polypropylene film, a polyethylene film, a polycarbonate film, a polyethylene naphthalate film, a polyarylate film, a nylon film, and the like. . Among these films, a polyethylene terephthalate film or a polyethylene naphthalate film is preferred because of excellent heat resistance, chemical resistance, and peelability. Examples of the metal foil include copper foil, aluminum foil, nickel foil, chrome foil, gold foil, and silver foil.

The thickness of the sheet-like or film-shaped molded body is not particularly limited, but is usually 1 to 150 μm , preferably 2 to 100 μm , and more preferably 5 to 80 μm from the viewpoint of workability and the like.

Examples of the method of applying the curable epoxy composition of the present invention include dip coating, roll coating, curtain coating, die coating, slit coating, gravure coating, and the like.

Further, in the present invention, it is preferable that the curable epoxy composition of the present invention is in a state of being unhardened or semi-cured as a sheet-like or film-like molded body. Here, the term "unhardened" refers to a state in which substantially all of the epoxy compound is dissolved when the molded article is immersed in a solvent capable of dissolving the epoxy compound used in preparing the composition. Further, the term "semi-hardening" refers to a state in which it is hardened to the extent that it can be cured at the time of further heating, and is preferably a solvent capable of dissolving an epoxy compound used for preparing the composition, and a part of the epoxy compound. (specifically, the amount is 7% by weight or more, and a part of the residual amount) is in a dissolved state, or the volume after the immersion of the molded body in the solvent for 24 hours is 200% or more of the volume before immersion (swelling) The state of the rate).

Further, after the curable epoxy composition of the present invention is applied onto a support, it may be dried as needed. The drying temperature is preferably a temperature at which the curable epoxy composition of the present invention does not harden, and is usually 20 to 300 ° C, preferably 30 to 200 ° C. When the drying temperature is too high, the hardening reaction proceeds excessively, so that the obtained molded body may not be in an unhardened or semi-hardened state. Further, the drying time is usually from 30 seconds to 1 hour, preferably from 1 minute to 30 minutes.

Then, the film of the present invention obtained in this manner is used in a state where it is adhered to the support or peeled off from the support.

(layered film)

The laminated film of the present invention has the above-mentioned curable epoxy composition An underlayer formed; and a plated layer composed of a resin composition for a layer to be plated.

The layer to be plated is not particularly limited, and from the viewpoint of improving the electrical properties and heat resistance of the laminated film, it is preferred that 50% by weight or more of the resin constituting the layer be composed of an alicyclic olefin polymer. The resin composition for a layer to be plated for forming such a layer to be plated is usually an alicyclic olefin polymer having a polar group and a curing agent.

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 because of its excellent mechanical strength, heat resistance and the like. Further, examples of the polar group contained in the alicyclic olefin polymer include a phenolic 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.

The curing agent contained in the resin composition for a layer to be plated may be a crosslinked structure in which an alicyclic olefin polymer having a polar group is formed by heating, and is not particularly limited, and may be added thereto. A hardener for a resin composition for forming a general electrical insulating film. As the curing agent, it is preferred to use a compound having two or more polar groups capable of reacting with a polar group-containing olefin polymer having a polar group to form a bond.

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

Since the reactivity with the polar group possessed by the alicyclic olefin polymer having a polar group is gentle, the operation of the resin composition for the plated layer becomes easy, and as the hardener, especially a polyvalent epoxy compound is preferable. It is particularly suitable to use a epoxidized propyl ether type epoxy compound and an alicyclic type polyvalent epoxy compound.

The amount of the curing agent in the resin composition for a layer to be plated is preferably from 1 to 100 parts by weight, preferably from 5 to 80 parts by weight based on 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 product obtained by curing the laminated film of the present invention can be improved.

Further, the resin composition for a layer to be plated used in the present invention may contain a hindered phenol compound and a hindered amine compound in addition to the above components.

The hindered phenol compound refers to a phenol compound having a hydroxyl group and having at least one hindered structure in the molecule in which the carbon atom at the β position of the hydroxyl group does not have a hydrogen atom. Specific examples of the hindered phenol compound include 1,1,3-gin-(2-methyl-4-hydroxy-5-tri-butylphenyl)butane and 4,4'-butylene double. -(3-methyl-6-tri-butylphenol), 2,2-thiobis(4-methyl-6-tert-butylphenol), propionate n-octadecyl-3-(4' -hydroxy-3',5'-di-tert-butyl-phenyl) ester, fluorene-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl) Propionate] methane and the like.

Adjustment of hindered phenol compounds in the resin composition for the plated layer The amount of the alicyclic olefin polymer having a polar group is preferably from 0.04 to 10 parts by weight, preferably from 0.3 to 5 parts by weight, more preferably from 0.5 to 3 parts by weight, per 100 parts by weight of the alicyclic olefin polymer having a polar group. The scope. By setting the amount of the hindered phenol compound to the above range, the mechanical strength of the cured product obtained by curing the laminated film of the present invention can be improved.

Further, the hindered amine compound means 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 the hindered amine compound, 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 preferred to use a hindered phenol compound and a hindered amine compound in combination, and a permanganic acid is used for the cured product obtained by curing the laminated film of the present invention by using a hindered phenol compound and a hindered amine compound in combination. When the surface roughening treatment of the salt aqueous solution or the like is performed, even if the surface roughening treatment conditions are changed, the cured product after the surface roughening treatment can be kept to have a low 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 amount of the hindered amine compound to be added is not particularly limited, and is usually 0.02 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.25 to 3 parts by weight per 100 parts by weight of the alicyclic olefin polymer having a polar group. Parts by weight. By When the amount of the hindered amine compound is in the above range, the mechanical strength of the cured product obtained by curing the laminated film of the present invention can be improved.

Further, the resin composition for a layer to be plated used in the present invention may contain a curing accelerator in addition to the above components. As the curing accelerator, a curing accelerator added to a general resin composition for forming an electric insulating film may be used. For example, a curing accelerator similar to the above-described curable epoxy composition of the present invention can be used. The amount of the curing accelerator in the resin composition for a layer to be plated may be appropriately selected according to the purpose of use, and may be 0.001 to 30 by weight based on 100 parts by weight of the alicyclic olefin polymer having a polar group. The portion is preferably from 0.01 to 10 parts by weight, more preferably from 0.03 to 5 parts by weight.

Further, the resin composition for a layer to be plated used in the present invention may contain a filler in addition to the above components. As the filler, the same as the filler used in the above-described curable epoxy composition can be used. The blending amount of the filler in the resin composition for a layer to be plated is usually 1 to 50% by weight, preferably 2 to 45% by weight, and preferably 3 to 35% by weight, in terms of solid content.

Further, in the resin composition for a plated layer to be used in the present invention, in addition to the above-mentioned components, a curing accelerator and a flame retardant may be appropriately added in the same manner as the above-described curable epoxy composition of the present invention. Agent, flame retardant auxiliary, heat stabilizer, weathering stabilizer, anti-aging agent, ultraviolet absorber (laser processing enhancer), leveling agent, antistatic agent, slip agent, anti-adhesive agent, anti-fogging agent Conventional ingredients such as slip agents, dyes, natural oils, synthetic oils, waxes, emulsions, magnetic materials, dielectric property modifiers, and tougheners. The blending ratio of these optional components may be appropriately selected within the range not impairing the object of the present invention.

The method for producing the resin composition for a plated layer to be used in the present invention is not particularly limited, and the above components may be directly mixed, or a part of each component may be dissolved or dispersed in an organic solvent. The composition is prepared and the remaining components are mixed in the composition.

The laminated film of the present invention can be produced by using the resin composition for a layer to be plated and the curable epoxy composition of the present invention. Specifically, the laminated film of the present invention can be produced, for example, by the following two methods: (1) applying, spraying, or casting the above-mentioned resin composition for a plated layer onto a support and a method of drying the above-mentioned hardened resin composition by applying or casting the above-mentioned hardened resin composition and drying it as needed, and (2) using the resin composition for the above-mentioned plated layer a molded article for a plated layer formed by coating, spraying, or casting on a support and drying it as needed to form a sheet or a film, and applying the above-mentioned curable epoxy composition. A method of laminating or casting the formed body into a laminate or a film formed by laminating or casting it into a sheet shape or a film shape, and integrating these molded bodies. Among these manufacturing methods, the production method of the above (1) is preferable because it is an easy process and has excellent productivity.

In the production method of the above (1), when the resin composition for a plating layer is applied, sprayed, or cast on a support, and the curable epoxy composition is applied, sprayed, or cast, In the case of the resin composition for a layer to be plated after being sprayed or cast, or in the production method of the above (2), the resin composition for a layer to be plated and the curable epoxy composition are formed into a sheet shape or When the film is formed into a molded article for a plated layer and a molded article for a backing layer, the resin composition for a plated layer or the curable epoxy composition is applied and sprayed by adding an organic solvent as needed. Or casting on the support is better.

Examples of the support used at this time include a resin film, a metal foil, and the like. Examples of the resin film include a polyethylene terephthalate film, a polypropylene film, a polyethylene film, a polycarbonate film, a polyethylene naphthalate film, a polyarylate film, and a nylon film. Among these films, a polyethylene terephthalate film or a polyethylene naphthalate film is preferred from the viewpoints of heat resistance, chemical resistance, and peelability. Examples of the metal foil include copper foil, aluminum foil, nickel foil, chrome foil, gold foil, and silver foil. Further, the surface average roughness Ra of the support is usually 300 nm or less, preferably 150 nm or less, preferably 100 nm or less.

The thickness of the resin composition for a plated layer and the curable epoxy composition in the production method of the above (1), or the molded article for the plated layer and the adhesive layer for the production method of the above (2). The thickness of the body is not particularly limited, and the thickness of the plated layer when the film is laminated is preferably 1 to 10 μm , preferably 1.5 to 8 μm , more preferably 2 to 5 μm . Further, the thickness of the subsequent layer is preferably 10 to 100 μm , more preferably 10 to 80 μm , and even more preferably 15 to 60 μm . When the thickness of the layer to be plated is too thin, when the conductor layer is formed by electroless plating on the cured product obtained by curing the laminated film, the formation of the conductor layer may be lowered; on the other hand, When the thickness of the plating layer is too thick, the cured product obtained by hardening the laminated film may have a large linear expansion. Further, when the thickness of the subsequent layer is too thin, the wiring embedding property of the laminated film may be lowered.

Examples of the method of applying the resin composition for a layer to be plated and the curable epoxy composition include dip coating, roll coating, curtain coating, die coating, slit coating, gravure coating, and the like.

Further, in the production method of the above (1), after the resin composition for a plating layer is applied, sprayed or cast on the support, the curable epoxy composition is coated, sprayed or cast. After the resin composition for the plating layer is applied, or the resin composition for the plating layer and the curable epoxy composition are applied onto the support, the method of the above (2) may be carried out as needed. dry. The drying temperature is preferably a temperature at which the resin composition for the plating layer and the curable epoxy composition are not cured, and is usually 20 to 300 ° C, preferably 30 to 200 ° C. Further, the drying time is usually from 30 seconds to 1 hour, preferably from 1 minute to 30 minutes.

In the laminated film of the present invention, the plated layer and the subsequent layer constituting the laminated film are preferably in an unhardened or semi-hardened state. By laminating these layers in an uncured or semi-hardened state, the laminated film of the present invention can be made to have high adhesion. Further, the laminated film of the present invention can impart a more excellent peel strength of the plating layer to the layer to be plated.

(prepreg)

The prepreg according to the present invention is one in which the film of the present invention or the laminated film of the present invention contains a fiber base material.

Examples of the fiber base material include organic fibers such as polyamide fibers, polyarylene fibers, and polyester fibers, and inorganic fibers such as glass fibers and carbon fibers. In addition, examples of the form of the fiber base material include a form of a woven fabric such as a plain weave or a twill weave, and a form of a non-woven fabric. The thickness of the fibrous substrate is preferably from 5 to 100 μm, preferably from 10 to 50 μm . When it is too thin, the operation becomes difficult, and when it is too thick, the resin layer is relatively thin, and the wiring embedding property is insufficient.

In the prepreg of the present invention, when the film of the present invention contains a fibrous base material, the prepreg of the present invention can be produced by impregnating the fibrous base material with the curable epoxy composition of the present invention. In this case, the method of impregnating the fiber substrate with the curable epoxy composition of the present invention is not particularly limited, and an organic solvent is added to the curable epoxy composition of the present invention to adjust the viscosity and the like. A method of impregnating a fibrous base material with a curable epoxy composition obtained by adding an organic solvent; and a method of applying or spraying a curable epoxy composition obtained by adding an organic solvent to a fibrous base material. In the method of coating or spraying, a fibrous substrate can be placed on a support, and a curable epoxy composition obtained by adding an organic solvent is coated or sprayed on the fibrous substrate. Further, in the present invention, the sheet-like or film-like composite molded article contains the curable epoxy composition of the present invention in an unhardened or semi-cured state in the same manner as the above-mentioned sheet-like or film-form molded article. It is better.

Further, after the fibrous base material is impregnated with the curable epoxy composition of the present invention, it may be dried as needed. The drying temperature is preferably a temperature at which the curable epoxy composition of the present invention does not harden, and is usually 20 to 300 ° C, preferably 30 to 200 ° C. The drying temperature is too high, the hardening reaction proceeds excessively, and the resulting composite molding system has a possibility that it is not in an unhardened or semi-hardened state. Further, the drying time is usually from 30 seconds to 1 hour, preferably from 1 minute to 30 minutes.

Alternatively, in the prepreg of the present invention, when the laminated film of the present invention contains a fibrous base material, the prepreg of the present invention has an adhesive layer on one surface and a coated layer on the other surface. A fiber substrate is preferred, and a method for producing the film is not limited. For example, the following method can be used. (1) A film of a resin composition having a support and a film of a resin composition for a layer to be coated with a support, and a resin of each film so as to sandwich the fiber substrate therebetween a method in which the layers are joined together and laminated as required under conditions of pressurization, vacuum, heating, etc.; (2) by impregnating the fibrous substrate with a hardenable epoxy composition or a coated layer Any one of the resin compositions, and dried as needed to produce a prepreg, and the prepreg is coated or cast on the other resin composition, or is laminated by the other side. a method of producing a resin composition film of a support; (3) laminating a curable epoxy composition or a resin composition for a layer to be plated by applying a spray or a casting onto the support. The fiber base material is superposed thereon, and the other resin composition is applied, sprayed, or cast thereon, laminated, and dried as necessary to produce. Further, in any of the methods, it is preferable to adjust the viscosity of the composition by adding an organic solvent to the composition as needed, thereby controlling the workability of impregnation on the fibrous substrate and coating, spraying or casting on the support.

Further, examples of the support used in this case include a polyethylene terephthalate film, a polypropylene film, a polyethylene film, a polycarbonate film, a polyethylene naphthalate film, and a polyarylate film. A resin film such as a nylon film; a metal foil such as a copper foil, an aluminum foil, a nickel foil, a chrome foil, a gold foil, or a silver foil; these are not only one side of the prepreg, but may be attached to both sides.

The thickness of the prepreg of the present invention is not particularly limited, and the thickness of the plated layer is preferably 1 to 10 μm , preferably 1.5 to 8 μm , more preferably 2 to 5 μm , and The thickness of the layer is preferably 10 to 100 μm , preferably 10 to 80 μm , more preferably 15 to 60 μm .

When manufacturing the prepreg of the present invention, it is used as a coating layer for coating Examples of the resin composition and the curable epoxy composition include dip coating, roll coating, curtain coating, die coating, slit coating, gravure coating, and the like.

Further, in the prepreg of the present invention, similarly to the film and the laminated film of the present invention, the resin composition constituting the prepreg is preferably in an unhardened or semi-cured state.

Further, the prepreg of the present invention obtained in this manner can be cured by heating and hardening it.

The curing temperature is usually 30 to 400 ° C, preferably 70 to 300 ° C, preferably 100 to 200 ° C. Further, the hardening time is 0.1 to 5 hours, preferably 0.5 to 3 hours. The heating method is not particularly limited, and it may be carried out, for example, using an electric oven or the like.

(layered body)

The laminate of the present invention is obtained by laminating the above-mentioned film, laminate film or prepreg of the present invention on a substrate. The laminated body of the present invention may be obtained by laminating at least the above-mentioned film, laminated film or prepreg of the present invention, a substrate having a conductor layer laminated on the surface thereof, and a film or laminated film of the present invention. Or an electrically insulating layer composed of a prepreg is preferred.

A substrate having a conductor layer on its surface is a conductor layer on the surface of the electrically insulating substrate. The electrically insulating substrate will contain a conventional electrically insulating material (for example, an alicyclic olefin polymer, an epoxy compound, a maleimide resin, a (meth)acrylic resin, a diallyl phthalate resin, A resin composition of a triazine resin, a polyphenylene ether, or a glass is hardened and formed. The conductor layer is not particularly limited, and is usually a layer containing 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, the circuit, and the like are not particularly limited. Specific examples of the substrate having the conductor layer on the surface include a printed circuit board, a germanium wafer substrate, and the like. The thickness of the substrate having the conductor layer on the surface is usually 10 μm to 10 mm, preferably 20 μm to 5 mm, preferably 30 μm to 2 mm.

The substrate having the conductor layer on the surface used in the present invention is preferably pretreated on the surface of the conductor layer in order to improve the adhesion to the electrically insulating layer. The method of the pretreatment is not particularly limited, and a conventional technique can be used. For example, when the conductor layer is made of copper, the following method may be used: an oxidation treatment method in which a strong alkali oxidizing solution is brought into contact with the surface of the conductor layer to form a layer of copper oxide on the surface of the conductor; Method for oxidizing the surface of the conductor layer, followed by reduction using sodium borohydride, formalin or the like; a method of roughening the plating layer on the conductor; and bringing the organic acid into contact with the conductor layer and dissolving the grain boundary of the copper And a method of forming a primer layer on a conductor layer using a thiol compound, a decane compound or the like. Among these methods, from the viewpoint of easiness in maintaining the shape of the fine wiring pattern, a method in which an organic acid is brought into contact with a conductor layer, a grain boundary of copper is dissolved and coarsened, and a thiol compound or a decane compound is used. Preferably, the conductor layer forms a primer layer.

In the laminate of the present invention, the film of the present invention (i.e., the curable epoxy composition of the present invention is formed into a sheet or a film) by a substrate having a conductor layer on its surface. a molded article), a laminated film (that is, a sheet-like or film-like formed body composed of an adhesive layer and a plated layer, wherein the adhesive layer is composed of the curable epoxy composition of the present invention), or a dip material (a composite molded body comprising a fibrous base material in the film of the present invention, or a composite molded body comprising a fibrous base material in the laminated film of the present invention) Heated and pressed to make.

The method of heating and pressure-bonding is a method in which a molded body or a composite molded body with a support is placed so as to be in contact with the conductor layer of the above-mentioned substrate, and a press bonding machine or a press (press) is used. A press machine such as a vacuum laminator, a vacuum press, or a roll laminator performs heating and pressure bonding (layering). By heating and pressurizing, the interface between the conductor layer on the surface of the substrate and the molded body or the composite molded body can be bonded without substantially voids. The molded body or the composite molded body is usually laminated on the conductor layer of the substrate in an unhardened or semi-hardened state.

The 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 the generation of bubbles, the heating and pressure bonding is preferably performed 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.

(hardened)

The cured product of the present invention is obtained by curing the curable epoxy composition of the present invention, and comprises curing the film, laminated film, prepreg, and laminate of the present invention comprising the composition. By. The curing can be carried out by appropriately heating the curable epoxy composition, film, or the like of the present invention by using the curing conditions described later.

For example, the laminate of the present invention can be cured by curing the film, laminate film or prepreg of the present invention. The hardening system usually consists of forming a thin film, a laminate of the present invention on a conductor layer. The entire substrate of the film or the prepreg is heated. The hardening can be performed simultaneously with the above-described heating and pressure bonding operation. Further, it is also possible to first perform hardening under the condition that no hardening occurs, that is, at a relatively low temperature and for a short time. Although the film of the present invention or the like is formed using the curable epoxy composition of the present invention, the ring is provided by a phenol resin (C) having a triazine structure and a living ester compound (D) having a function as a curing agent. When the oxygen compound is cured, since the melt viscosity at the time of heating is low and excellent resin fluidity can be exhibited, the electrical insulation system composed of the obtained cured resin exhibits good wiring embedding property.

Further, in order to improve the flatness of the electrically insulating layer and to increase the thickness of the electrically insulating layer, two or more films, laminated films or prepregs of the present invention may be contacted and bonded to the substrate. The conductor layers are stacked on top of each other.

The curing temperature is usually 30 to 400 ° C, preferably 70 to 300 ° C, preferably 100 to 200 ° C. Further, the hardening time is usually 0.1 to 5 hours, preferably 0.5 to 3 hours. The heating method is not particularly limited, and it may be carried out, for example, using an electric oven or the like.

(Complex)

The composite of the present invention is obtained by forming a conductor layer on the surface of the cured product of the present invention described above.

For example, when the laminated system of the present invention forms a multilayer substrate, the composite system of the present invention is formed by further forming another conductor layer on the electrically insulating layer of the laminated body. As such a conductor layer, metal plating or a metal foil can be used. Examples of the metal plating material include gold, silver, copper, rhodium, palladium, nickel, and tin. Examples of the metal foil include the above-mentioned film, laminated film, or used as a prepreg. The support of the material. Further, in the present invention, as the conductor layer, a method of using metal plating is preferable for the fine wiring. Hereinafter, a method of manufacturing the composite of the present invention will be described by exemplifying a multilayer circuit board using metal plating as a conductor layer as an example of the composite of the present invention.

First, a via hole and a through hole penetrating the electrically insulating layer are formed in the laminated body. In the case of a multilayer circuit substrate, the via holes are formed to connect the respective conductor layers constituting the multilayer circuit substrate. The via hole and the via hole can be formed by chemical treatment such as lithography, or physical treatment such as drilling, laser, plasma etching, or the like. Among these methods, it is possible to form a fine via hole without degrading the characteristics of the electrical insulating layer, and it is preferable to use a laser method (carbon dioxide gas laser, excimer laser, UV-YAG laser, etc.). .

Next, the surface roughening treatment of the surface of the electrically insulating layer (that is, the cured product of the present invention) of the roughened laminate is performed. The surface roughening treatment is performed in order to improve the adhesion to the conductor layer formed on the electrically insulating layer.

The surface roughness Ra of the electrically insulating layer is preferably 0.05 μm or more and less than 0.5 μm , preferably 0.06 μm or more and 0.3 μm or less, and the surface ten-point average roughness Rzjis is 0.3 μm. The above is preferably less than 5 μm , preferably 0.5 μm or more and 3 μm or less. Further, in the present specification, Ra is an arithmetic mean roughness disclosed in JIS B0601-2001, and a surface ten-point average roughness Rzjis is a ten-point average roughness disclosed in JIS B0601-2001 Annex 1.

The surface roughening treatment method is not particularly limited, and examples thereof include a method of bringing the surface of the electrically insulating layer into contact with an oxidizing compound. The oxidizing compound may, for example, be a conventional compound having an oxidizing ability such as an inorganic oxidizing compound or an organic oxidizing compound. According to the surface roughness of the control electrical insulation layer The degree of ease is particularly preferably an inorganic oxidizing compound, an organic oxidizing compound or the like. 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 electrically insulating layer using an inorganic oxidizing compound, an organic oxidizing compound or the like is not particularly limited. For example, a method of bringing an oxidizing compound solution into contact with the surface of an electrically insulating layer prepared by dissolving the oxidizing compound in a solvent capable of dissolving is mentioned. The method of bringing the oxidizing compound solution into contact with the surface of the electrically insulating layer is not particularly limited, and may be, for example, any of the following methods: impregnation of the electrically insulating layer in an oxidizing compound solution; use of an oxidizing compound solution a liquid holding method in which an oxidizing compound solution is placed on an electrically insulating layer; and a spray method in which an oxidizing compound solution is sprayed on an electrically insulating layer. By performing the surface roughening treatment, the adhesion between the electrically insulating layer and other layers such as the conductor layer can be improved.

The temperature, time, and the like of contacting the oxidizing compound solution with the surface of the electrically insulating layer may 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 100 ° C, preferably 20 ~90 ° C, the time 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 electrically insulating layer after the surface roughening treatment is washed with water. Further, when a substance which cannot be washed by water is adhered, the washing liquid which can dissolve the substance is further washed or brought into contact with other compounds. After the method becomes a water-soluble substance, it is washed with water. 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 an electrically insulating layer, a mixture of hydroxylamine sulfate and sulfuric acid may be used for the purpose of removing the manganese dioxide film produced. After the neutral aqueous solution is subjected to neutralization and reduction treatment, it is washed with water.

Next, after the surface roughening treatment is performed on the electrically insulating layer of the laminated body, a conductor layer is formed on the surface of the electrically insulating layer and the inner wall surface of the via hole and the through hole.

The method of forming the conductor layer is preferably carried out by using an electroless plating method from the viewpoint of being able to form a conductor layer having excellent adhesion.

For example, when a conductor layer is formed by electroless plating, first, a catalyst core such as silver, palladium, zinc, or cobalt is usually adhered to the electrically insulating layer before the metal thin film is formed on the surface of the electrically insulating layer. The method of attaching the catalyst core to the electrically insulating layer is not particularly limited, and examples thereof include metal compounds such as silver, palladium, zinc, and cobalt, salts of these metals, and complex compounds, which are 0.001. A method in which a concentration of 10% by weight is dissolved in an organic solvent such as water or an alcohol or chloroform (including an acid, a base, a complexing agent, a reducing agent, etc. as needed), and then the metal is reduced.

As the electroless plating solution used in the electroless plating method, a conventional self-catalytic type electroless plating solution may be used, and the type of metal contained in the plating solution, the type of reducing agent, and the binder may be used. The type, the hydrogen ion concentration, the dissolved oxygen concentration, and the like are not particularly limited. For example, the following electroless plating solution can be used: an electroless copper plating solution using ammonium hypophosphite, hypophosphorous acid, ammonium borohydride, hydrazine, and fumarine as a reducing agent; and electroless nickel using sodium hypophosphite as a reducing agent. - Phosphorus plating Electrolyte; 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 nickel-cobalt-phosphorus plating solution using sodium hypophosphite 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 an rustproof treatment. Further, after the metal thin film is formed, the metal thin film can also be heated to improve adhesion and the like. The heating temperature is usually 50 to 350 ° C, preferably 80 to 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 machine or a pressurizing heat roll machine can be mentioned. The applied pressure is usually 0.1 to 20 MPa, preferably 0.5 to 10 MPa. If it is this range, the high adhesion of a metal thin film and an electrically insulating layer can be ensured.

A resist pattern for plating is formed on the metal thin film formed in this manner, and further, the plating layer is grown (thickened and plated) by wet plating such as electrolytic plating, and then the photoresist is removed and The etching etches the metal thin film into a pattern 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.

When a metal foil is used instead of metal plating as a conductor layer which comprises a multilayer circuit board, it can manufacture by the following method.

In other words, first, in the same manner as described above, a laminated body composed of an electrically insulating layer made of a film or a prepreg and a conductor layer made of a metal foil is prepared. As such a laminate, it is preferable to form the curable epoxy composition to have a curing degree capable of maintaining each desired characteristic, and to carry out subsequent formation. In the case of processing, it is preferable that the multilayer circuit board is not problematic, and it is particularly preferable to form it by laminating under vacuum. Further, the laminated body composed of the electrically insulating layer composed of the film or the prepreg and the conductor layer composed of the metal foil can be used, for example, by a conventional subtractive process. In the printed wiring board.

Then, the prepared laminated body is formed in the same manner as described above to form a via hole and a through hole penetrating through the electrically insulating layer, and secondly, in order to remove the resin residue formed in the via hole, the laminated body in which the through hole is formed is removed. Residue treatment. The method of the residue treatment is not particularly limited, and examples thereof include a method of contacting a solution (de-slag liquid) of an oxidizing compound such as permanganate. Specifically, it can be immersed in an aqueous solution adjusted to a sodium permanganate concentration of 70 g/liter and a sodium hydroxide concentration of 40 g/liter at 60 to 90 ° C for 1 to 50 minutes by forming a laminate having via holes. , to carry out the residue treatment.

Next, after the residue is subjected to the residue treatment, a conductor layer is formed on the inner wall surface of the via hole. The method for forming the conductor layer is not particularly limited, and any of the electroless plating method and the electrolytic plating method can be used, and from the viewpoint of being able to form a conductor layer having excellent adhesion, metal plating is formed. Similarly to the above-described method of the conductor layer, it can be carried out by an electroless plating method.

Next, after forming a conductor layer on the inner wall surface of the via hole, a resist pattern for plating is formed on the metal foil, and the plating layer is further grown (thickened and plated) by wet plating such as electrolytic plating, and secondly, The photoresist is removed, and the metal foil 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 foil and a plating formed thereon.

The multilayer circuit board obtained as described above is used as a substrate for manufacturing the above-described laminate, and is heat-pressed and cured with the above-mentioned molded body or composite molded body to form an electrically insulating layer, and further thereon. By forming the conductor layer by the above method and repeating these steps, it is possible to further increase the number of layers, thereby making it possible to form a multilayer circuit board.

The composite of the present invention (and the multilayer circuit substrate as an example of the composite of the present invention) obtained in this manner has an electrically insulating layer composed of the curable epoxy composition of the present invention (cured product of the present invention) Because the electrical insulation layer has excellent heat resistance, electrical properties and residue resistance and has a good balance, and adhesion to the conductor layer (especially after the high temperature and high humidity test with the conductor layer) The adhesive body of the present invention (and the multilayer circuit board which is an example of the composite of the present invention) can be suitably used for various purposes. In particular, since the electrically insulating layer composed of the curable epoxy composition of the present invention has good degreasability, when a conductor layer is formed on the inner wall surface of the via hole, conduction failure due to the residue can be effectively prevented. According to the present invention, it is possible to provide a multilayer circuit board having high reliability with excellent electrical conductivity between the respective conductive layers.

(substrate for electronic materials)

The substrate for an electronic material of the present invention is composed of the above-described cured product or composite of the present invention. The electronic material substrate of the present invention comprising the cured product or the composite of the present invention can be suitably used in a mobile phone, a PHS, a notebook personal computer, a personal digital assistant (PDA: Personal Digital Assistant), and a portable device. Videophone, personal computer, supercomputer, server, router, LCD projector, engineering workstation (EWS), pager (pager), word processor, TV, View Finder or video tape recorder, terminal device, electronic organizer, electronic desktop computer, car navigation device, POS terminal Equipment, various electronic devices equipped with devices such as touch panels.

Example

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 weight basis unless they are specifically notified in advance. Various physical properties were evaluated in accordance with the following methods.

(1) Number average molecular weight (Mn), weight average molecular weight (Mw) of an alicyclic olefin polymer

Tetrahydrofuran was used as a developing solvent and measured by gel permeation chromatography (GPC) and determined in terms of polystyrene.

(2) Hydrogenation rate of alicyclic olefin polymer

The molar number of the hydrogenated unsaturated bond was determined by ¹ H-NMR spectroscopy at 400 MHz, and the ratio of the molar number of the unsaturated bond in the polymer before hydrogenation was set as the hydrogenation rate. .

(3) Glass transition temperature (heat resistance)

From the film-like cured product, a small piece having a width of 6 mm, a length of 15.4 mm, and a thickness of 40 μm was cut out, and a thermomechanical analysis device (TMA/SDTA840: manufactured by METTLER-TOLEDO Co., Ltd.) had a distance between the fulcrums of 10 mm and a temperature increase rate of 10 ° C/ The stress-temperature curve was obtained under the conditions of a minute, and the tangential line was drawn at the inflection point of the stress-temperature curve, and the glass transition temperature (Tg) of the film-like cured product was obtained from the intersection of the tangent, and evaluated according to the following Benchmarks were used to evaluate heat resistance. The higher the glass transition temperature, the more excellent the heat resistance.

(evaluation benchmark)

A: Glass transition temperature is above 150 °C

B: glass transition temperature is 145 ° C or more and less than 150 ° C

C: glass transition temperature is less than 145 ° C

(4) Dielectric loss tangent (electricity)

A small piece having a width of 2.0 mm, a length of 80 mm, and a thickness of 40 μm was cut out from the film-like cured product, and a dielectric loss tangent at 10 GHz was measured using a resonant cavity perturbation method dielectric constant measuring device. The electrical characteristics were evaluated in accordance with the following evaluation criteria.

(evaluation benchmark)

A: dielectric loss tangent is less than 0.0065

B: dielectric loss tangent is above 0.0065 and less than 0.070

C: dielectric loss tangent is 0.0070 or more

(5) Degreasability

A surface of a core material obtained by impregnating a glass fiber with a varnish containing a glass filler and a halogen-free epoxy compound, and a double-sided coating having a thickness of 0.8 mm and a length of 150 mm and a width of 150 mm is formed by coating a copper having a thickness of 18 μm . The copper surface of the copper substrate is etched by an etchant (trade name "CZ-8100", manufactured by MEC Corporation) to a thickness of about 0.5 μm, and then a film formed body having a support is laminated on both sides thereof, and only the support is peeled off. Further, the film formed body was cured by heating at 180 ° C for 30 minutes in an air atmosphere to form a resin layer composed of a film-like cured product. In the obtained laminate cured product, a CO ₂ laser device (LC-2G212/2C, manufactured by Hitachi, Ltd.) was used, and the output was 0.65 W, the number of shots was 3, and the processing diameter (top surface) was 55 μm . In the following, under the condition of 50 μm , a substrate for the evaluation of the residue of the via hole for forming the via hole penetrating the copper surface was formed. The substrate was immersed in an aqueous solution of 60 ° C prepared by swelling ("Swelling Dip Securiganth P", Atotech Co., Ltd., "SECURIGANTH") 500 mL/L, and sodium hydroxide 3 g/L for 15 minutes. Washed with water. Then, the aqueous solution of 80 ° C prepared by immersing in an aqueous solution of permanganate ("Concentrate Compact CP", Atotech Co., Ltd.) of 640 mL / L and sodium hydroxide concentration of 40 g / L was shaken for 5 minutes, and then washed with water. Then, the laminate cured product was immersed in an aqueous solution of 40 ° C prepared by using a hydroxylamine sulfate aqueous solution ("REDUCTION SECURIGANTH P 500", Atotech Co., Ltd., "SECURIGANTH" registered trademark) 100 mL/L, and sulfuric acid 35 mL/L for 5 minutes. After the neutralization reduction treatment, water washing was performed. The lower surface and the cross section of the hole portion for the via hole of the substrate thus obtained were observed by an electron microscope (magnification: 5000 times), and the residue was evaluated according to the following evaluation criteria.

(evaluation benchmark)

A: There is no resin residue in either the bottom of the passage or the passage.

B: There is no resin residue at the bottom of the passage and there are some resin residues around the passage.

C: Resin residue in either the bottom of the path or around the path

(6) Initial adhesion

The surface of the electrolytic copper foil having a thickness of 35 μm was etched by about 0.5 μm using an etchant (trade name "CZ-8100", manufactured by MEC Corporation). The etched surface of the obtained electrolytic copper foil is laminated so that the surface of the film formed body is in contact with the surface of the resin layer, and the degree of vacuum is 1 kPa or less, 90 ° C, 30 seconds, and pressure by a vacuum laminator. Heating and pressing under conditions of 0.7 MPa. Next, the support is peeled off from the surface of the film formed body opposite to the resin layer, and the glass epoxy copper-clad laminate (FR-4) obtained by etching the etching agent by about 2 μm is etched. The surface was superposed on the surface of the developed resin layer, and heat-pressed under the same conditions as described above using a vacuum laminator. The composite molded body obtained in this manner was heated at 180 ° C for 90 minutes in an oven to obtain a laminate cured product. The strength of the copper foil peeled from the obtained laminate cured product was measured in accordance with JIS C6481 and evaluated in accordance with the following evaluation criteria.

(evaluation benchmark)

A: Peel strength is 0.55kN/m or more

B: Peel strength is 0.50 kN/m or more and less than 0.55 kN/m

C: Peel strength is less than 0.50kN/m

(7) Adhesion after high temperature and high humidity test

The copper foil on the surface of the cured product of the laminate obtained in the same manner as in the above (6) was subjected to a sample having a width of 10 mm and the other portion of the copper foil was peeled off, and the sample was subjected to a constant temperature bath at a temperature of 130 ° C and a humidity of 98% RH. After allowing to stand for 100 hours, the strength of the copper foil peeled from the obtained laminate cured product was measured in accordance with JIS C6481 and evaluated according to the following evaluation criteria.

(evaluation benchmark)

A: Peel strength is 0.30 kN/m or more

B: Peel strength is 0.25 kN/m or more and less than 0.30 kN/m

C: Peel strength is less than 0.25kN/m

Example 1

(Modulation of hardenable epoxy composition)

A biphenyl dimethylene skeleton novolac type epoxy resin (trade name "NC-3000L", a chemical compound of Japan, which is a polyvalent epoxy compound (A) having a biphenyl structure. A phenolic novolak type epoxy compound having a phosphaphenanthrene structure (product name "FX-289BEK75", Nippon Steel & Sumitomo Chemical Co., Ltd.) a methyl ethyl ketone solution having a solid content of 75%, a phosphorus content of 2%, an epoxy equivalent of 305), 93.2 parts (70 parts in terms of an epoxy compound), and a phenol resin (C) having a triazine structure. The triazine structure contains cresol novolak resin (trade name "PHENOLITE LA-3018-50P", non-volatile 50% propylene glycol monomethyl ether solution, DIC company, active hydroxyl equivalent 154) 30 parts (with triazine) In the conversion of cresol novolak resin, 15 parts), as an active ester compound of active ester compound (D) (trade name "Epiclon HPC-8000-65T", 65% non-volatile toluene solution, DIC company, Active ester group equivalent: 223) 89.2 parts (58 parts in terms of active ester compound), 320 parts of cerium oxide (trade name "SC2500-SXJ", manufactured by ADMATECHS Co., Ltd.) as a filler, and a hindered phenol system as an anti-aging agent Antioxidant (product name "IRGANOX (registered trademark) 3114", made by BASF) 1 part, and anisole 1 Ten parts were mixed and stirred using a planetary mixer for 3 minutes. Further, here, 8.3 parts of a solution obtained by dissolving 1-benzyl-2-phenylimidazole 30% in anisole as a hardening accelerator (V is 2.5 in terms of 1-benzyl-2-phenylimidazole) The mixture was mixed and stirred using a planetary mixer for 5 minutes to obtain a varnish of a curable epoxy composition. Further, in the varnish, the content of the filler was 64% in terms of solid content.

(Manufacture of film molded body)

Next, the varnish of the curable epoxy composition obtained above was applied to a polyethylene terephthalate having a size of 300 mm × 300 mm in width and a thickness of 38 μm and a surface average viscosity Ra of 0.08 μm using a die coater. The ester film (support: manufactured by Lumirror (registered trademark) T60 TORAY Co., Ltd.) was further dried at 80 ° C for 10 minutes in a nitrogen atmosphere to obtain a film molded body of a curable epoxy composition having a thickness of 43 μm on a support. Using the obtained film molded body, the residue resistance, the initial adhesion, and the adhesion after the high-temperature and high-humidity test were evaluated in accordance with the above method. The results are shown in Table 1.

(Manufacture of film-like cured product)

Next, in a copper foil having a thickness of 10 μm , a small piece obtained by cutting a film formed body of the obtained curable epoxy composition using a vacuum laminator having a heat-resistant rubber pressure plate on the upper and lower sides is used. The curable epoxy composition was placed inside while the support was attached, and the laminate was heated and pressure-bonded for 60 seconds under reduced pressure to 200 Pa at a temperature of 110 ° C and a pressure of 0.1 MPa, and then the support was peeled off and then Heat hardened in air at 180 ° C for 120 minutes. After the hardening, the copper foil-cured resin was cut out, and the copper foil was dissolved in a 1 mol/L ammonium persulfate aqueous solution to obtain a film-like cured product. Using the obtained film-like cured product, the glass transition temperature and the dielectric loss tangent were measured in accordance with the above method. The results are shown in Table 1.

Examples 2 to 4 and Comparative Examples 1 to 4

A varnish of a curable epoxy composition was obtained in the same manner as in Example 1 except that the composition of the curable epoxy composition of Examples 2 to 4 and Comparative Examples 1 to 4 of Table 1 was changed. The film molded body and the film-like cured product were measured and evaluated in the same manner. The results are shown in Table 1.

In addition, in Table 1, "anthracene hydroxyphenylethane type epoxy compound" is a tetrahydroxyphenylethane type epoxy compound (trade name "jER 1031S", manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 200, softening point, 90 ° C), "bisphenol A type epoxy compound" is a bisphenol A type epoxy compound (trade name "jER 828EL", manufactured by Mitsubishi Chemical Corporation, and Oxygen equivalent 186, liquid).

As shown in Table 1, when the curable epoxy composition of the present invention is used, a film-like cured product having excellent heat resistance, electrical properties, residue resistance, and adhesion after initial and high-temperature and high-humidity tests can be obtained. (Examples 1 to 4). Therefore, when the curable epoxy composition of the present invention is used, it is known that an electrically insulating layer having such excellent characteristics can be formed.

On the other hand, when the phosphorus-containing epoxy compound (B) is not contained, the obtained film-like cured product is inferior in heat resistance and residue resistance (Comparative Example 1), and does not contain a biphenyl structure and/or When the polyvalent epoxy compound (A) having a polycyclic structure was condensed, the obtained film-like cured product was a result of poor adhesion after the high-temperature and high-humidity test (Comparative Example 2).

Further, when the phenol resin (C) having a triazine-containing structure is not contained, the obtained film-like cured product is a result of poor adhesion after initial stage and high-temperature and high-humidity test (Comparative Example 3); use of bisphenol A type ring When the oxygen compound is used in place of the phosphorus-containing epoxy compound (B), the obtained film-like cured product is heat-resistant, degreased, and high in temperature. The result of poor adhesion after the wet test (Comparative Example 4).

Synthesis Example 1

As the first stage of polymerization, 5-ethylene-bicyclo[2.2.1]hept-2-ene 35 moles, 1-hexene 0.9 moles, and fennel were added to a nitrogen-substituted pressure-resistant glass reactor. Ether 340 mol parts and 0.005 mol parts of C1063 were subjected to polymerization at 80 ° C for 30 minutes while stirring to obtain a solution of a norbornene-based ring-opening polymer.

Next, as a second stage of polymerization, the polymerization system is added in the first stage tetracyclic resultant solution [6.5.0.1 ^2,5 .0 ^8,13] tridecyl -3,8,10,12- tetraene 45 Mo Ear, bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic anhydride 20 mol parts, anisole 250 mol parts and 4-ethyloxybenzylidene group as lanthanide polymerization catalyst (dichloro)(4,5-dibromo-1,3-methyl-4-imidazolin-2-ylidene) (tricyclohexylphosphine) oxime (C1063, manufactured by Wako Pure Chemical Industries, Ltd.) 0.01 mol, The polymerization reaction was carried out at 80 ° C for 1.5 hours with stirring to obtain a solution of a norbornene-based ring-opening polymer. When the gas chromatography was measured for this solution, it was confirmed that substantially no monomer remained and the polymerization conversion ratio was 99% or more.

Next, a solution of the obtained ring-opening polymer was added to an autoclave with a stirrer substituted with nitrogen, 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 a hydrogenation reaction. A solution of a hydride-containing alicyclic olefin polymer (1) of a decene-based ring-opening polymer is obtained. The alicyclic olefin polymer (1) has a weight average molecular weight of 60,000, a number average molecular weight of 30,000, and a molecular weight distribution system of 2. Further, the hydrogenation ratio 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 5

(resin composition for plating layer)

454 parts of a solution of the alicyclic olefin polymer (1) obtained in Synthesis Example 1 (100 parts in terms of alicyclic olefin polymer (1)), and a dicyclopentane as a curing agent 36 parts of a olefinic polyene compound (trade name "Epiclon HP7200L", DIC company, "Epiclon" registered trademark), and cerium oxide as an inorganic filler (trade name "ADMERFINE SO-C1", ADMATECHS, 24.5 parts of an average particle diameter of 0.25 μm and "ADMERFINE" registered trademark, and ginseng (3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate as an anti-aging agent (trade name) "IRGANOX (registered trademark) 3114", manufactured by BASF Corporation), 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzene as a UV absorber 0.5 part of triazole and 0.5 part of 1-benzyl-2-phenylimidazole as a hardening accelerator, mixed with anisole and mixed at a concentration of 16% of the compounding agent to obtain a resin for plating layer Varnish of the object.

(Manufacturing of laminated film)

The varnish of the resin composition for a plated layer obtained above was applied onto a polyethylene terephthalate film (support) having a thickness of 38 μm using a wire bar, and secondly, at 80 ° C in a nitrogen atmosphere. This was dried for 10 minutes to obtain a support-attached film formed with a plated layer having a thickness of 3 μm composed of a resin composition for an unhardened layer to be plated.

Next, the varnish of the curable epoxy composition obtained in Example 1 was coated on a film with a support using a doctor blade (manufactured by TESTER Industries, Inc.) and an automatic film coater (manufactured by TESTER Industries, Inc.). The surface on which the plated layer formed of the resin composition for the plating layer was formed, and then dried at 80 ° C for 10 minutes in a nitrogen atmosphere to obtain a total thickness of 43 μm. A laminated film with a support attached to the cladding and the subsequent layer. The laminated film with a support is formed with a support, a plated layer composed of a resin composition for a plated layer, and an adhesive layer composed of a curable epoxy composition in the following order.

(Manufacture of laminate hardened material)

In addition, in addition to the above, the surface of the core material obtained by impregnating the glass fiber with a varnish containing a glass filler and a halogen-free epoxy compound is formed by coating a copper having a thickness of 18 μm and having a thickness of 0.8 mm and 150 mm square. The surface of the double-sided copper-clad substrate of 150 mm and 150 mm in width was brought into contact with an organic acid, and a conductor layer having a wiring width and a wiring distance of 50 μm and a thickness of 18 μm was formed by micro-etching treatment to obtain an inner layer substrate.

On both sides of the inner layer substrate, the laminated film with the support obtained as described above is cut into a 150 mm square, and the surface of the resin layer on the back layer is bonded to the inside. Pressurize once. The primary pressurization was carried out by using a vacuum laminator equipped with a heat-resistant rubber pressure plate on the upper and lower sides, and heat-pressed at a pressure of 110 ° C for 90 seconds under a reduced pressure of 200 Pa at a pressure of 0.1 MPa. Further, a hydraulic pressurizing device having a metal pressurization on the upper and lower sides was used, and heat-pressing was carried out for 90 seconds at a pressure-bonding temperature of 110 ° C and 1 MPa. Then, the support body is peeled off to obtain a laminate of a resin layer composed of a curable epoxy composition and a resin composition for a layer to be plated, and an inner layer substrate. Further, the laminate was allowed to stand in an air atmosphere at 180 ° C for 60 minutes to harden the resin layer, and an electrically insulating layer was formed on the inner substrate.

(swelling treatment step)

The obtained laminate cured product is immersed in a shake to become a swelling liquid ("Swelling Dip Securiganth P", Atotech Co., Ltd., "SECURIGANTH" registered trademark) 500 ° C aqueous solution prepared by dissolving 500 mL / L and sodium hydroxide 3 g / L for 15 minutes, and then washing with water.

(oxidation treatment step)

Then, the aqueous solution of 80 ° C prepared by immersing in an aqueous solution of permanganate ("Concentrate Compact CP", manufactured by Atotech Co., Ltd.) at 640 mL/L and a sodium hydroxide concentration of 40 g/L was shaken for 15 minutes. Washed.

(neutralization and reduction processing steps)

Then, the laminate cured product was immersed in a 40 ° C solution prepared by using a hydroxylamine sulfate aqueous solution ("REDUCTION SECURIGANTH P 500", Atotech Co., Ltd., "SECURIGANTH" registered trademark) 100 mL/L, and sulfuric acid 35 mL/L. After the aqueous solution was subjected to a neutralization reduction treatment for 5 minutes, it was washed with water.

(cleaning conditioner step)

Then, the laminate cured product was immersed in a 50 ° C adjusted to a concentration of 50 ml/L in an aqueous solution of a clean conditioner ("ALCUP MCC-6-A", manufactured by Uemura Industrial Co., Ltd., "ALCUP"). The aqueous solution was taken for 5 minutes for cleaning conditioner treatment. Next, the laminate hardened product was immersed in water washing water at 40 ° C for 1 minute, and then washed with water.

(soft etching process step)

Next, the layered body cured product was immersed in an aqueous solution prepared to have a sulfuric acid concentration of 100 g/L and sodium persulfate of 100 g/L for 2 minutes, and then subjected to a soft etching treatment, followed by washing with water.

(pickling treatment step)

Next, the layered body cured product was immersed in an aqueous solution prepared to have a sulfuric acid concentration of 100 g/L for 1 minute, and subjected to pickling treatment, followed by washing with water.

(catalyst giving step)

Next, the laminate cured product is immersed in the ALCUP Activator MAT-1-A (trade name, manufactured by Uemura Industrial Co., Ltd., "ALCUP" registered trademark) at 200 mL/L, ALCUP Activator MAT-1-B (trade name, The PLC salt-containing plating catalyst aqueous solution prepared by the method of the "ALCUP", which is manufactured by Uemura Industrial Co., Ltd., and the "ALCUP" registered trademark) was 30 mL/L and sodium hydroxide was 0.35 g/L, and was washed with water for 5 minutes.

(activation step)

Then, the laminate cured product was immersed at 35 ° C to obtain ALCUP Reducer MAB-4-A (trade name, manufactured by Uemura Industrial Co., Ltd., "ALCUP" registered trademark) of 20 mL / L, ALCUP Reducer MAB-4-B ( The product name, the "ALCUP" registered trademark of the company, and the "ALCUP" registered trademark) was adjusted to 200 mL/L for 3 minutes to reduce the plating catalyst, and then washed with water.

(Accelerator processing step)

Then, the laminate cured product was immersed in an aqueous solution prepared by using ALCUP Accelerator MEL-3-A (trade name, manufactured by Uemura Industrial Co., Ltd., "ALCUP" registered trademark) at 50 mL/L for 1 minute at 25 °C.

(electroless plating step)

In order to become Thru-Cup PEA-6-A (trade name, manufactured by Uemura Industrial Co., Ltd., "Thru-Cup" registered trademark) 100 mL/L, Thru-Cup PEA-6-B-2X (trade name, Uemura Industrial Co., Ltd.) 50 mL/L, Thru-Cup PEA-6-C (trade name, manufactured by Uemura Industrial Co., Ltd.) 14 mL/L, Thru-Cup PEA-6-D (trade name, Uemura) An electroless copper plating solution prepared by a method of 15 mL/L, Thru-Cup PEA-6-E (trade name, manufactured by Uemura Industrial Co., Ltd.), 50 mL/L, and 37% of a formalin aqueous solution of 5 mL/L. While the air is blown, the cured product obtained by the above-described process is immersed at a temperature of 36 ° C for 20 minutes to carry out electroless copper plating treatment, and is formed on the surface of the cured body of the laminate (from the resin composition for the layer to be plated) The surface of the layer to be plated forms an electroless plating film.

Next, a cured product of the laminate having an electroless plating film was formed, and annealed at 150 ° C for 30 minutes in an air atmosphere.

The annealed laminate hardened material was subjected to electrolytic copper plating to form an electrolytic copper plating film having a thickness of 30 μm . Then, the laminate cured product is heat-treated at 180 ° C for 60 minutes to obtain a double-sided layer of a conductor layer formed of the metal thin film layer and the electrolytic copper plating film formed on the cured product of the laminate. Multilayer printed wiring board.

Claims (11)

A laminated film having an adhesive layer; and a plated layer composed of a resin composition for a plated layer, wherein the adhesive layer is formed of a curable epoxy composition containing the following: a polyvalent epoxy compound ( A) having a biphenyl structure and/or a condensed polycyclic structure; a phosphorus-containing epoxy compound (B) having a structure represented by the following formula (1) or (2); and a phenol resin having a triazine structure (C), (In the formula (1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and a plurality of R ¹ and R ² groups may be the same or different, and m and n are each independently and represent 0 to 0. An integer of 4, in the formula (2), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and a plurality of R ¹ and R ² groups may be the same or different, and m and n are each independently and Indicates an integer from 0 to 5.) The laminated film according to the first aspect of the invention, wherein the phosphorus-containing epoxy compound (B) has an epoxy compound of a phosphaphenanthrene structure represented by the following formula (3), The laminated film according to claim 1, wherein the ratio of the polyvalent epoxy compound (A) to the phosphorus-containing epoxy compound (B) is "polyvalent epoxy compound (A): phosphorus-containing ring The weight ratio of the oxygen compound (B) is 20:80 to 95:5. The laminated film according to the first aspect of the invention, wherein the content of the benzene resin (C) containing the triazine structure is 100% by weight based on the total of the epoxy compound contained in the curable epoxy composition. It is 1 to 60 parts by weight. The laminated film according to claim 1, wherein the curable epoxy composition further contains an active ester compound (D). A prepreg comprising a laminate film as described in claim 1, 2, 3, 4 or 5, and a fibrous substrate. A laminated body obtained by laminating a substrate as described in the first, second, third, fourth or fifth aspect of the patent application. A hardened material, which is a laminated film as described in claim 1, 2, 3, 4 or 5, or a prepreg as described in claim 6 or as claimed in claim 7 The layered body is hardened. A composite body formed by forming a conductor layer on a surface of a cured product as described in claim 8 of the patent application. A substrate for an electronic material comprising the cured product according to item 8 of the patent application as a constituent material. A substrate for an electronic material comprising the composite according to claim 9 of the patent application as a constituent material.