JP2014185228A - Curable epoxy composition, film, laminate film, prepreg, laminate, hardened material and composite body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable epoxy composition which can form an electric insulation layer excellent in desmear properties, electric characteristics, heat resistance and adhesiveness to a conductor layer.SOLUTION: A curable epoxy composition comprises (A-1) an epoxy compound having a specified structure, (B) an active ester compound and (C) a hardening accelerator.

Description

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

  With the pursuit of downsizing, multi-functionalization, high-speed communication, etc. of electronic devices, there is a need for higher density circuit boards used in electronic devices. To meet such demands for higher density, Circuit boards are being made multilayered. In such a multilayer circuit board, for example, an electrical insulation layer is laminated on an inner layer substrate composed of an electrical insulation layer and a conductor layer formed on the surface thereof, and a conductor layer is formed on the electrical insulation layer. Further, it is formed by repeatedly stacking these electrical insulating layers and forming the conductor layer.

  As a material for constituting such an electrical insulating layer of the multilayer circuit board, a ceramic or a thermosetting resin is generally used. Among these, epoxy resins as thermosetting resins are widely used because they are excellent in terms of balance between economy and performance.

  By the way, the conductor layer formed on the surface of the electrical insulating layer made of a cured product of such a thermosetting resin is made of metal wiring such as copper, for example, but in recent years, further miniaturization of wiring has progressed. Yes. That is, L / S indicating the dimension (L) in the width direction of the wiring and the dimension (S) in the width direction of the portion where the wiring is not formed has been further reduced. For this reason, it has been studied to further reduce the coefficient of linear expansion of the cured product of the thermosetting resin. In general, many fillers such as silica are blended in the thermosetting resin. However, when a large amount of filler is blended, it tends to agglomerate. As a result, for example, when a roughening treatment is performed prior to forming a conductor layer on the surface of the cured product, the agglomerated filler is separated and the cured product is removed. There was a problem that the surface roughness of the surface was increased.

  On the other hand, for example, in Patent Document 1, the dispersibility of the silica component is excellent, and the surface roughness of the cured product obtained by roughening the surface of the cured product can be reduced. When a metal layer is formed on the surface of the cured body, an epoxy resin, a curing agent, and silica particles are silane as an epoxy resin composition that can increase the adhesive strength between the cured body and the metal layer. A silica component surface-treated with a coupling agent, and the silica component is contained in a range of 25 to 400 parts by weight with respect to a total of 100 parts by weight of the epoxy resin and the curing agent, The average particle diameter of the silica particles is 1 μm or less, and the silane coupling agent is a silane compound having an amino group, a silane compound having a mercapto group, a silane compound having an isocyanate group, Is at least one selected from the group consisting of a silane compound having a silane compound and isocyanuric acid with an anhydride group, an epoxy-based resin composition is disclosed.

  In the multilayer circuit board, the conductor layers are generally connected to each other through via holes provided in the electrical insulating layer. In the formation of the via hole, a metal plating process is performed after providing a hole for the via hole in the electrical insulating layer by laser irradiation, but before that, the resin remaining on the lower conductor layer or in the electrical insulating layer generated by the laser irradiation. A desmear process for removing a residue (smear) is performed. The desmear treatment is performed, for example, by immersing the multilayer substrate in which the via hole is formed in a solution of a chemical oxidizing agent such as potassium permanganate or potassium dichromate and dissolving and removing the smear in the via hole. . If the desmear treatment is insufficient and the desmear property is not sufficiently secured, even if the metal plating treatment is performed on the via hole, the conductivity between the upper conductor layer and the lower conductor layer may not be sufficiently secured due to the smear. There is.

JP 2010-53334 A

  Then, when the present inventors examined, when the electrical insulation layer of a multilayer printed wiring board was formed using the epoxy-type resin composition of the patent document 1 mentioned above, heat resistance, an electrical property, etc. are inadequate. In addition, it became clear that it was inferior in desmear property.

  An object of the present invention is to provide a curable epoxy composition capable of forming an electrical insulating layer having excellent desmear properties, electrical properties, and heat resistance, and also having excellent adhesion to a conductor layer, and obtained using the same. It is providing the film, laminated | multilayer film, prepreg, laminated body, hardened | cured material, and composite which are manufactured.

  As a result of intensive studies to achieve the above object, the present inventors have found that the curable epoxy composition containing an epoxy compound represented by the following general formula (I), an active ester compound and a curing accelerator, The inventors have found that an electrical insulating layer having desired characteristics can be obtained, and have completed the present invention.

（式中、Ｒはｍ価の基を、ｍは１〜１０の整数を、ｎは１〜３０の整数を、それぞれ表す。）
で表されるエポキシ化合物（Ａ−１）と、活性エステル化合物（Ｂ）と、硬化促進剤（Ｃ）と、を含む硬化性エポキシ組成物、
〔２〕縮合多環構造及び／又はビフェニル構造を有する多価エポキシ化合物（Ａ−２）をさらに含む、前記〔１〕記載の硬化性エポキシ組成物、
〔３〕前記〔１〕又は〔２〕に記載の硬化性エポキシ組成物からなるフィルム、
〔４〕前記〔１〕又は〔２〕に記載の硬化性エポキシ組成物からなる接着層と、被めっき層用樹脂組成物からなる被めっき層と、を有する積層フィルム、
〔５〕被めっき層が、脂環式オレフィン重合体を５０重量％以上含むものである前記〔４〕記載の積層フィルム、
〔６〕前記〔３〕に記載のフィルム又は前記〔４〕若しくは〔５〕に記載の積層フィルムと、繊維基材と、からなるプリプレグ、
〔７〕前記〔３〕に記載のフィルム、前記〔４〕若しくは〔５〕に記載の積層フィルム又は前記〔６〕に記載のプリプレグを、基材に積層してなる積層体、
〔８〕前記〔１〕若しくは〔２〕に記載の硬化性エポキシ組成物、前記〔３〕に記載のフィルム、前記〔４〕若しくは〔５〕に記載の積層フィルム、前記〔６〕に記載のプリプレグ、又は前記〔７〕に記載の積層体を硬化してなる硬化物、
〔９〕前記〔８〕に記載の硬化物の表面に導体層を形成してなる複合体、並びに
〔１０〕前記〔８〕に記載の硬化物又は前記〔９〕に記載の複合体を構成材料として含む電子材料用基板、
が提供される。 That is, according to the present invention,
[1] The following general formula (I):

(In the formula, R represents an m-valent group, m represents an integer of 1 to 10, and n represents an integer of 1 to 30, respectively.)
A curable epoxy composition comprising an epoxy compound (A-1) represented by the formula (1), an active ester compound (B), and a curing accelerator (C),
[2] The curable epoxy composition according to [1], further including a polyvalent epoxy compound (A-2) having a condensed polycyclic structure and / or a biphenyl structure,
[3] A film comprising the curable epoxy composition according to [1] or [2],
[4] A laminated film having an adhesive layer made of the curable epoxy composition according to [1] or [2], and a plated layer made of a resin composition for a plated layer,
[5] The laminated film according to [4], wherein the layer to be plated contains 50% by weight or more of the alicyclic olefin polymer,
[6] A prepreg comprising the film according to [3] or the laminated film according to [4] or [5], and a fiber base material,
[7] A laminate obtained by laminating the film according to [3], the laminated film according to [4] or [5], or the prepreg according to [6] above,
[8] The curable epoxy composition according to [1] or [2], the film according to [3], the laminated film according to [4] or [5], and the film according to [6] A prepreg or a cured product obtained by curing the laminate according to [7],
[9] Consists of a composite formed by forming a conductor layer on the surface of the cured product according to [8], and [10] the cured product according to [8] or the composite according to [9]. A substrate for electronic materials, including as a material,
Is provided.

  According to the present invention, a curable epoxy composition capable of forming an electrical insulating layer having excellent desmear properties, electrical characteristics, and heat resistance, and also excellent adhesion to a conductor layer, and obtained using the same. Film, laminated film, prepreg, laminate, cured product, and composite are provided.

  The curable epoxy composition of the present invention may be abbreviated as an epoxy compound (A-1) represented by the general formula (I) [hereinafter referred to as an epoxy compound (A-1). ], An active ester compound (B), and a hardening accelerator (C), and is characterized by using the epoxy compound (A-1) as a thermosetting resin. The electrical insulating layer obtained by the present invention comprises a cured resin obtained by curing the epoxy compound (A-1) in the presence of an active ester compound (B) acting as a curing agent and a curing accelerator (C). However, such an electrical insulating layer can exhibit the desired characteristics. Hereinafter, the present invention will be described in detail.

[Epoxy compound (A-1)]
The epoxy compound (A-1) used in the present invention is a compound represented by the general formula (I). In the general formula (I), R represents an m-valent group. m shows the integer of 1-10, Preferably it is 1-8. n shows the integer of 1-30, Preferably it is 3-27. When m is 2 or more, the numbers of n in the groups in m parentheses may be the same or different.

As an epoxy compound (A-1), since favorable hardening reactivity is obtained, the epoxy equivalent is 100-1000 equivalent normally, Preferably the thing of 125-500 equivalent is suitable.
In the present specification, the “epoxy equivalent” is the number of grams (g / eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236.

  The epoxy compound (A-1) is, for example, a polyether resin obtained by polymerizing 4-vinylcyclohexene-1-oxide using an m-valent alcohol as an initiator, that is, a polycyclohexene having a vinyl group side chain. It can be produced by epoxidizing the vinyl group side chain of an oxide polymer with an oxidizing agent such as peracid (such as peracetic acid) (see Japanese Patent Publication No. 4-10471). In the epoxy compound (A-1) thus obtained, R in the general formula (I) corresponds to a residue other than the hydroxyl group involved in bonding of the m-valent alcohol.

  Examples of the m-valent alcohol include monovalent alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, and allyl alcohol; ethylene glycol, 1 , 2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol , Tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, etc. ; Glycerin, diglycerin, polyglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and a trihydric or higher alcohols such as sorbitol. The m-valent alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like. The m-valent alcohol is preferably an aliphatic alcohol having 1 to 10 carbon atoms, and more preferably an aliphatic polyhydric alcohol having 2 to 10 carbon atoms such as trimethylolpropane.

The epoxy compound (A) is available as a commercial product. As this commercial item, a brand name "EHPE3150" (made by Daicel Chemical Industries Ltd.) etc. are mentioned, for example.
The above epoxy compounds (A-1) can be used alone or in admixture of two or more.

[Polyvalent epoxy compound having condensed polycyclic structure and / or biphenyl structure (A-2)]
In the present invention, from the viewpoint of improving the electrical characteristics of the obtained electrical insulating layer, together with the epoxy compound (A-1), a polyvalent epoxy compound (A-2) having a condensed polycyclic structure and / or a biphenyl structure [below] , May be abbreviated as epoxy compound (A-2). ] Is preferably used in combination.

  The epoxy compound (A-2) used in the present invention is a compound having at least two epoxy groups (oxirane rings) in one molecule and at least one of a condensed polycyclic structure and a biphenyl structure.

The condensed polycyclic structure refers to a structure in which two or more monocycles are condensed (condensed). The ring constituting the condensed polycyclic structure may be an alicyclic ring or an aromatic ring, and may contain a hetero atom. The number of condensed rings is not particularly limited, but from the viewpoint of increasing the heat resistance and mechanical strength of the resulting cured resin, it is preferably 2 or more rings, and practically, the upper limit is about 10 rings. . Examples of such a condensed polycyclic structure include a dicyclopentadiene structure, a naphthalene structure, a fluorene structure, an anthracene structure, a phenanthrene structure, a triphenylene structure, a pyrene structure, and an ovalen structure. In the resulting cured resin, the condensed polycyclic structure usually constitutes the main chain of the resin, but may be present in the side chain.
The biphenyl structure refers to a structure in which two benzene rings are connected by a single bond. The biphenyl structure usually constitutes the main chain of the resin in the resulting cured resin, similarly to the condensed polycyclic structure, but may exist in the side chain.

The epoxy compound (A-2) used in the present invention has a condensed polycyclic structure, a biphenyl structure, or a condensed polycyclic structure and a biphenyl structure. From the viewpoint of increasing the heat resistance and mechanical strength of the resulting cured resin, As the epoxy compound (A-2), those having a condensed polycyclic structure are preferred, and those having a dicyclopentadiene structure are more preferred.
In the case where the epoxy compound (A-2) is used in combination with one having a condensed polycyclic structure (including those having both a condensed polycyclic structure and a biphenyl structure) and one having a biphenyl structure, an electrical insulating layer From the viewpoint of improving the heat resistance and electrical characteristics of the resin, the blending ratio is a weight ratio (a polyvalent epoxy compound having a condensed polycyclic structure / a polyvalent epoxy compound having a biphenyl structure), and usually 3/7 to 7 / 3 is preferred.

  As an epoxy compound (A-2), since favorable hardening reactivity is obtained, the epoxy equivalent is 100-1500 equivalent normally, Preferably the thing of 150-1000 equivalent is suitable.

Although the epoxy compound (A-2) used for this invention can be suitably manufactured in accordance with a well-known method, it can also be obtained as a commercial item.
Examples of commercially available epoxy compounds (A-2) having a condensed polycyclic structure are epoxy compounds having a dicyclopentadiene structure. For example, trade names “Epicron HP7200L, Epicron HP7200, Epicron HP7200H, Epicron HP7200HH, Epicron “HP7200HHH” (manufactured by DIC, “Epiclon” is a registered trademark), trade name “Tactix 558” (manufactured by Huntsman Advanced Materials, “Tactix” is a registered trademark), trade names “XD-1000-1L, XD- "1000-2L" (manufactured by Nippon Kayaku Co., Ltd.); and epoxy compounds having a fluorene structure, for example, trade names "ONCOAT EX-1010, ONCOAT EX-1011, ONCOAT EX-1012, ONCOAT EX -1020, on EX-1030, ONCOAT EX-1040, ONCOAT EX-1050, ONCOAT EX-1051 "(Nagase Sangyo Co., Ltd.," ONCOAT "is a registered trademark), trade names" Ogsol PG-100, Ogsol EG-200, Ogsol EG-250) "(Osaka Gas Chemical Co., Ltd.," Ogsol "is a registered trademark); In addition, for example, a trade name “1032H60, XY-4000” (manufactured by Mitsubishi Chemical Corporation), which is an epoxy compound having a polyphenol structure, can also be used as the epoxy compound (A-2).
Examples of commercially available products of the epoxy compound (A-2) having a biphenyl structure are epoxy compounds having a biphenyl aralkyl structure, for example, trade names “NC3000-FH, NC3000-H, NC3000, NC3000-L, NC3100”. (Nippon Kayaku Co., Ltd.).
The above epoxy compounds (A-2) can be used alone or in admixture of two or more.

(Other epoxy compounds)
In addition to the epoxy compound (A-1) and the epoxy compound (A-2), the curable epoxy composition of the present invention may appropriately contain other epoxy compounds other than those epoxy compounds as desired. . Examples of such other epoxy compounds include alicyclic epoxy compounds, cresol novolac type epoxy compounds, phenol novolac type epoxy compounds, bisphenol A novolac type epoxy compounds, trisphenol type epoxy compounds, and tetrakis (hydroxyphenyl) ethane type epoxy compounds. And aliphatic chain epoxy compounds. They are available as commercial products as appropriate.

  The content of the epoxy compound (A-1) in the total 100% by weight of the epoxy compound used in the curable epoxy composition of the present invention is preferably from the viewpoint of improving heat resistance in the obtained electrical insulating layer. It is 3% by weight or more, more preferably 5% by weight or more, and further preferably 10% by weight or more. On the other hand, from the viewpoint of satisfactorily exhibiting electrical characteristics, the upper limit is usually 100% by weight, preferably 80% by weight. The content ratio of the epoxy compound (A-2) is preferably 0 to 97% by weight, and more preferably 20 to 95% by weight, particularly from the viewpoint of improving electrical characteristics in the obtained electrical insulating layer. The content of the other epoxy compound is not particularly limited as long as it does not inhibit the expression of the desired effect of the present invention, but it is usually preferably 40% by weight or less.

[Active ester compound (B)]
The active ester compound (B) used in the present invention may be any compound having an active ester group, but in the present invention, a compound having at least two active ester groups in the molecule is preferable. The active ester compound (B) acts as a curing agent for the epoxy compound used in the present invention.

  The active ester compound (B) is obtained from a product obtained by reacting a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound from the viewpoint of enhancing the heat resistance of the obtained electrical insulating layer. Active ester compounds are preferable, and active ester compounds obtained by reacting a carboxylic acid compound with one or more selected from the group consisting of a phenol compound, a naphthol compound and a thiol compound are more preferable. An aromatic compound obtained from a reaction of an 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 (B) may be linear or multi-branched. For example, the active ester compound (B) is derived from a compound having at least two carboxylic acids in the molecule. When the compound having at least two carboxylic acids in the molecule contains an aliphatic chain, the compatibility with the epoxy compound can be increased, and when it has an aromatic ring, the heat resistance is improved. Can be high.

  Specific examples of the carboxylic acid compound for forming the active ester compound (B) include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. . Of these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, and phthalic acid, isophthalic acid, and terephthalic acid are more preferable, and isophthalic acid is more preferable from the viewpoint of increasing the heat resistance of the resulting cured resin. More preferred are acids and terephthalic acid.

  Specific examples of the thiocarboxylic acid compound for forming the active ester compound (B) include thioacetic acid and thiobenzoic acid.

  Specific examples of the hydroxy compound for forming the active ester compound (B) include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, and methylated bisphenol S. , Phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, tri Examples thereof include hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolac. Among them, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, from the viewpoint of improving the solubility of the active ester compound (B) and increasing the heat resistance of the obtained electrical insulating layer, Dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac are preferable, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolak are more preferable, More preferred are cyclopentadienyl diphenol and phenol novolac.

  Specific examples of the thiol compound for forming the active ester compound (B) include benzenedithiol and triazinedithiol.

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

  In the present invention, as the active ester compound (B), for example, an aromatic compound having an active ester group disclosed in JP-A-2002-12650 and a polyfunctional compound disclosed in JP-A-2004-277460 are disclosed. Polyester or commercially available products can be used. Examples of commercially available products include trade names “EXB9451, EXB9460, EXB9460S, Epicron HPC-8000-65T” (manufactured by DIC, “Epicron” is a registered trademark), and trade name “DC808” (manufactured by Japan Epoxy Resin). And trade name “YLH1026” (manufactured by Japan Epoxy Resin Co., Ltd.).

  The compounding amount of the active ester compound (B) in the curable epoxy composition of the present invention is preferably 20 to 140 parts by weight, more preferably 40 to 125 parts by weight with respect to 100 parts by weight of the total epoxy compound used. More preferably, it is in the range of 60 to 110 parts by weight. Further, the equivalent ratio of the epoxy compound to be used and the active ester compound (B) in the curable epoxy composition [the total number of epoxy groups in the epoxy compound to be used with respect to the total number of active ester groups in the active ester compound (B) The ratio (epoxy group amount / active ester group amount)] is preferably in the range of 0.5 to 1.25, more preferably 0.7 to 1.1, and still more preferably 0.8 to 1.05. By making the compounding quantity of an active ester compound (B) into the said range, the electrical property and heat resistance of the electrical insulation layer which are obtained can be improved, and a thermal expansion coefficient can be restrained small.

[Curing accelerator (C)]
The curing accelerator (C) used in the present invention is not particularly limited as long as it is a compound that can increase the curing rate of the active ester compound (B), which is a curing agent, and can rapidly accelerate the curing reaction of the epoxy compound. Such curing accelerators (C) are known, for example, aliphatic polyamines, aromatic polyamines, secondary amines, tertiary amines, acid anhydrides, imidazole derivatives, organic acid hydrazides, dicyandiamide and derivatives thereof, and urea derivatives. Etc. As a hardening accelerator (C), an imidazole derivative is preferable from a viewpoint of improving the storage stability of a varnish.

  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, bis-2-ethyl-4-methylimidazole, 1- Alkyl-substituted imidazole compounds such as methyl-2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2 Aryl groups and aralkyl groups such as -methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2'-cyanoethyl) imidazole, etc. of Such as imidazole compounds substituted with a hydrocarbon group containing a structure. These can be used individually by 1 type or in combination of 2 or more types.

  As a compounding quantity of the hardening accelerator (C) in the curable epoxy composition of this invention, it is 0.1-10 weight part normally with respect to a total of 100 weight part of the epoxy compound to be used, Preferably 0.5- 8 parts by weight.

(Other ingredients)
In the curable epoxy composition of the present invention, the epoxy compound (A-1), the epoxy compound (A-2), the active ester compound (B) and the curing acceleration are appropriately selected within a range not inhibiting the expression of the effect of the present invention. Other components other than the agent (C) as described below may be further contained.

By mix | blending a filler with the curable epoxy composition of this invention, the electrically insulating layer obtained can be made into a low linear expansion thing. As the filler, any of known inorganic fillers and organic fillers can be used, but inorganic fillers are preferred. Specific examples of inorganic fillers include calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, hydrated alumina, magnesium hydroxide, aluminum hydroxide , Barium sulfate, silica, talc, clay and the like. In addition, the filler to be used may have been surface-treated with a silane coupling agent or the like in advance.
Although it does not specifically limit as content of the filler in the curable epoxy composition of this invention, It is 30 to 90 weight% normally in conversion of solid content.

  Further, by blending the curable epoxy composition of the present invention with an alicyclic olefin polymer containing an aromatic ring and / or a heteroatom and having no reactivity with an epoxy group, Without lowering the storage stability, it is possible to improve the flexibility of the below-described film and laminated film obtained using the composition, and to improve the handleability thereof. Such an alicyclic olefin polymer does not have reactivity with an epoxy group, but therefore does not substantially contain a functional group having reactivity with an epoxy group. Here, “substantially does not contain a functional group having reactivity with an epoxy group” means that an alicyclic olefin polymer inhibits a functional group having reactivity with an epoxy group, and the expression of the effect of the present invention is inhibited. It means that it does not contain to the extent to be done. Examples of the functional group having reactivity with an epoxy group include groups having a structure capable of reacting with an epoxy group to form a covalent bond, such as a primary amino group, a secondary amino group, a mercapto group, a carboxyl group, Examples include heteroatom-containing functional groups that react with epoxy groups to form covalent bonds, such as carboxylic anhydride groups, hydroxy groups, and epoxy groups.

  The alicyclic olefin polymer includes, for example, an alicyclic olefin monomer (a) containing no hetero atom and containing an aromatic ring, and an alicyclic olefin monomer containing no hetero ring and containing a hetero atom. Body (b), an alicyclic olefin monomer (c) containing both an aromatic ring and a heteroatom, and the alicyclic olefin monomer (a) not containing both an aromatic ring and a heteroatom It can be easily obtained by appropriately combining monomers (d) copolymerizable with (c) and polymerizing according to a known method. The resulting polymer may be further hydrogenated.

Specific examples of the alicyclic olefin monomer (a) include 5-phenyl-bicyclo [2.2.1] hept-2-ene, 1,4-methano-1,4,4a, 5,10. , 10a-hexahydroanthracene, tetracyclo [6.5.0.12,5.08,13] trideca-3,8,10,12-tetraene ("1,4-methano-1,4,4a, 9a- Hereinafter referred to as “MTF”, also referred to as “tetrahydrofluorene”), tetracyclo [6.6.0.12, 5.18,13] tetradeca-3,8,10,12-tetraene (“1,4-methano” -1,4,4a, 5,10,10a-hexahydroanthracene ”), 8-phenyl-tetracyclo [4.4.0.12,5.17,10] dodec-3-ene and the like. .
Specific examples of the alicyclic olefin monomer (b) include 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.12,5.17,10] dodec-3-ene, 5- Methoxy-carbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyano-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2 .1] Hept-2-ene; 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5 -Methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-5 -Enyl-2-methyl Propionate, bicyclo [2.2.1] hept-5-enyl-2-methyloctanoate; 5-cyanobicyclo [2.2.1] hept-2-ene, N-methylbicyclo [2.2.1] Hept-2-ene-5,6-dicarboxylic imide, N- (2-ethylhexyl) bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic imide (hereinafter abbreviated as “NEHI”) 8-methoxycarbonyltetracyclo [4.4.12, 5.17, 10.0] -dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.12,5. .17,10.0] -dodec-3-ene, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride (hereinafter abbreviated as “NDCA”) and the like. It is done.
Specific examples of the alicyclic olefin monomer (c) include N- (4-phenyl)-(5-norbornene-2,3-dicarboximide) (hereinafter abbreviated as “NBPI”), N- (4-methylphenyl)-(5-norbornene-2,3-dicarboximide), 2- (4-methoxyphenyl) -5-norbornene, 2-benzyloxycarbonyl-5-norbornene and the like can be mentioned.
Specific examples of the alicyclic olefin monomer (d) include bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethylidene-bicyclo [2.2.1] hept. Norbornenes such as 2-ene (hereinafter abbreviated as “EdNB”); dicyclo [4.3.0.12,5] deca-3,7-diene (common name: dicyclopentadiene) Cyclopentadienes; tetracyclododecenes such as tetracyclo [4.4.0.12, 5.17,10] dodec-3-ene (common name: tetracyclododecene, hereinafter abbreviated as “TCD”) An α-olefin having 2 to 20 carbon atoms such as ethylene and propylene; and a non-conjugated diene such as 1,4-hexadiene.

  In the curable epoxy composition of the present invention, the amount of the alicyclic olefin polymer containing an aromatic ring and / or a hetero atom and not having reactivity with the epoxy group is not particularly limited. Although there is not, it is 1-50 weight part normally with respect to a total of 100 weight part of the epoxy compound to be used, Preferably it is 2-35 weight part.

  Furthermore, the curable epoxy composition of the present invention is used for forming a general electrical insulating film such as a halogen-based flame retardant or a phosphate ester-based flame retardant for the purpose of improving the flame retardancy of the obtained electrical insulating layer. You may mix | blend suitably the flame retardant mix | blended with this resin composition.

  In addition, the curable epoxy composition of the present invention may further include a flame retardant aid, a heat resistance stabilizer, a weather resistance stabilizer, an anti-aging agent, an ultraviolet absorber (laser processability improver), a leveling agent, an antistatic agent, if desired. Known components such as an agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a natural oil, a synthetic oil, a wax, an emulsion, a magnetic substance, a dielectric property adjusting agent, and a toughening agent may be appropriately blended.

  The method for producing the curable epoxy composition of the present invention is not particularly limited, and the above components may be mixed as they are, or may be mixed in a state dissolved or dispersed in an organic solvent. Then, a composition in which a part of each of the above components is dissolved or dispersed in an organic solvent is prepared, and the remaining components may be mixed with the composition.

(the film)
The film of this invention is a molded object formed by shape | molding the curable epoxy composition of this invention mentioned above in a sheet form or a film form.

  When the curable epoxy composition of the present invention is molded into a sheet or film to obtain a molded product, the curable epoxy composition of the present invention is applied to a support with an organic solvent added as desired. It is preferably obtained by spraying or casting and then drying.

  Examples of the support used at that time include resin films and metal foils. Examples of the resin film include polyethylene terephthalate film, polypropylene film, polyethylene film, polycarbonate film, polyethylene naphthalate film, polyarylate film, and nylon film. Among these films, a polyethylene terephthalate film or a polyethylene naphthalate film is preferable 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-like molded body is not particularly limited, but is usually 1 to 150 μm, preferably 2 to 100 μm, more preferably 5 to 80 μm from the viewpoint of workability and the like.

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

  In the present invention, it is preferable that the curable epoxy composition of the present invention is in an uncured or semi-cured state as a sheet-shaped or film-shaped molded body. Here, uncured means a state in which substantially all of the epoxy compound is dissolved when the molded body is immersed in a solvent capable of dissolving the epoxy compound used in the preparation of the composition. Semi-cured is a state in which the epoxy compound is cured halfway to the extent that it can be cured by further heating. Preferably, a part of the epoxy compound is dissolved in a solvent capable of dissolving the epoxy compound used in the preparation of the composition. (Specifically, it is an amount of 7% by weight or more and an amount such that a part remains) or the volume after the molded body is immersed in a solvent for 24 hours is A state in which the volume before immersion is 200% or more (swelling rate).

  Moreover, after apply | coating the curable epoxy composition of this invention on a support body, you may dry if desired. The drying temperature is preferably a temperature at which the curable epoxy composition of the present invention is not cured, and is usually 20 to 300 ° C, preferably 30 to 200 ° C. If the drying temperature is too high, the curing reaction proceeds too much, and the resulting molded article may not be in an uncured or semi-cured state. The drying time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.

  And the film of this invention obtained in this way is used in the state made to adhere on a support body, or peeling from a support body.

(Laminated film)
The laminated film of the present invention has an adhesive layer composed of the curable epoxy composition described above and a layer to be plated composed of a resin composition for a layer to be plated.

  The plated layer is not particularly limited, but from the viewpoint of improving the electrical properties, water resistance and heat resistance of the laminated film, 50% by weight or more of the resin constituting the layer is made of the alicyclic olefin polymer. Is preferred. As a resin composition for a to-be-plated layer for forming such a to-be-plated layer, what contains the alicyclic olefin polymer which has a polar group, and a hardening | curing agent normally is preferable.

  The alicyclic olefin polymer having a polar group is not particularly limited, and examples of the alicyclic structure include those having a cycloalkane structure or a cycloalkene structure. From the viewpoint of mechanical strength, heat resistance, and the like. Those having a cycloalkane structure are preferred. The polar groups contained in the alicyclic olefin polymer include alcoholic hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, alkoxyl groups, epoxy groups, glycidyl groups, oxycarbonyl groups, carbonyl groups, amino groups, carboxylic acid anhydrides. Physical group, sulfonic acid group, phosphoric acid group and the like. Among these, a carboxyl group, a carboxylic acid anhydride group, and a phenolic hydroxyl group are preferable, and a carboxylic acid anhydride group is more preferable.

  The curing agent contained in the resin composition for the layer to be plated is not particularly limited as long as it can form a crosslinked structure in the alicyclic olefin polymer having a polar group by heating, and is not particularly limited. The hardening | curing agent mix | blended with the resin composition for insulating film formation can be used. As the curing agent, it is preferable to use, as the curing agent, a compound having two or more functional groups capable of reacting with the polar group of the alicyclic olefin polymer having a polar group to be used to form a bond.

For example, as an alicyclic olefin polymer having a polar group, a curing agent suitably used when using an alicyclic olefin polymer having a carboxyl group, a carboxylic anhydride group, or a phenolic hydroxyl group includes a polyvalent epoxy. Examples thereof include compounds, polyvalent isocyanate compounds, polyvalent amine compounds, polyvalent hydrazide compounds, aziridine compounds, basic metal oxides, and organometallic halides. These may be used alone or in combination of two or more. Moreover, you may use as a hardening | curing agent by using together these compounds and a peroxide.
Among these, as the curing agent, the reactivity with the polar group of the alicyclic olefin polymer having a polar group is moderate, and the handling of the resin composition for the plated layer is facilitated. In particular, glycidyl ether type epoxy compounds and alicyclic polyvalent epoxy compounds are particularly preferably used.

  The blending amount of the curing agent in the resin composition for the plating layer is preferably 1 to 100 parts by weight, more preferably 5 to 80 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer having a polar group. Parts, more preferably in the range of 10 to 50 parts by weight. By making the compounding quantity of a hardening | curing agent into the said range, the mechanical strength and electrical property of the hardened | cured material obtained by hardening | curing the laminated | multilayer film of this invention can be made favorable.

  Moreover, the resin composition for to-be-plated layer used by this invention may contain the hindered phenol compound and the hindered amine compound other than the said component.

  The hindered phenol compound is a phenol compound having a hydroxyl group and having at least one hindered structure in the molecule that does not have a hydrogen atom at the β-position carbon atom of the hydroxyl group. Specific examples of the hindered phenol compound include 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis- (3-methyl-6- tert-butylphenol), 2,2-thiobis (4-methyl-6-tert-butylphenol), n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-tert-butylphenyl) propionate, And tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane.

  Although the compounding quantity of the hindered phenol compound in the resin composition for to-be-plated layers is not specifically limited, Preferably it is 0.04-10 weight part with respect to 100 weight part of alicyclic olefin polymers which have a polar group. More preferably, it is 0.3-5 weight part, More preferably, it is the range of 0.5-3 weight part. By making the compounding quantity of a hindered phenol compound into the said range, the mechanical strength of the hardened | cured material obtained by hardening | curing the laminated | multilayer film of this invention can be made favorable.

  The hindered amine compound is a compound having at least one 2,2,6,6-tetraalkylpiperidine group having a secondary amine or a tertiary amine at the 4-position in the molecule. As carbon number of alkyl, it is 1-50 normally. As the hindered amine compound, a compound having at least one 2,2,6,6-tetramethylpiperidyl group having a secondary amine or a tertiary amine at the 4-position in the molecule is preferable. In the present invention, it is preferable to use a hindered phenol compound and a hindered amine compound in combination, and by using these in combination, permanganate for a cured product obtained by curing the laminated film of the present invention. When the surface roughening treatment is performed using an aqueous solution of the above, the cured product after the surface roughening treatment can be kept at a low surface roughness even if the surface roughening treatment conditions change. .

  Specific examples of the hindered amine compound include bis (2,2,6,6, -tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1 [ 2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy } -2,2,6,6, -tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,2,3-triazaspiro [4,5] undecane-2, 4-dione etc. are mentioned.

  The blending amount of the hindered amine compound is not particularly limited, but is usually 0.02 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the alicyclic olefin polymer having a polar group. Preferably it is 0.25-3 weight part. By making the compounding quantity of a hindered amine compound into the said range, the mechanical strength of the hardened | cured material obtained by hardening | curing the laminated | multilayer film of this invention can be made favorable.

  Moreover, the resin composition for to-be-plated layer used by this invention may contain the hardening accelerator other than the said component. As the curing accelerator, a curing accelerator blended in a general resin composition for forming an electric insulation film may be used. For example, the same curing accelerator as that of the curable epoxy composition of the present invention described above is used. be able to. The blending amount of the curing accelerator in the resin composition for the layer to be plated may be appropriately selected according to the purpose of use, but is preferably 0 with respect to 100 parts by weight of the alicyclic olefin polymer having a polar group. 0.001 to 30 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.03 to 5 parts by weight.

  Furthermore, the resin composition for to-be-plated layer used by this invention may contain the filler other than the said component. As a filler, the thing similar to the filler used for the curable epoxy composition mentioned above can be used. The compounding 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, more preferably 3 to 35% by weight in terms of solid content. .

  Moreover, the resin composition for to-be-plated layer used by this invention is a hardening accelerator, a flame retardant, a flame retardant adjuvant, a heat-resistant stabilizer other than the said component similarly to the curable epoxy composition of this invention mentioned above, Weathering stabilizer, anti-aging agent, ultraviolet absorber (laser processability improver), leveling agent, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, natural oil, synthetic oil, wax, emulsion In addition, known components such as a magnetic material, a dielectric property adjusting agent, and a toughening agent may be appropriately blended. What is necessary is just to select suitably the mixture ratio of these arbitrary components in the range which does not impair the objective of this invention.

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

  And the laminated | multilayer film of this invention are manufactured using such a resin composition for to-be-plated layers, and the curable epoxy composition of this invention mentioned above. Specifically, the laminated film of the present invention has, for example, the following two methods: (1) The above-described resin composition for a layer to be plated is applied, spread or cast on a support, and is dried as desired. Next, a method of producing the above-described curable epoxy composition by further coating or casting thereon and drying as desired; (2) coating the above-described resin composition for a layer to be plated on a support; The molded body for a layer to be plated formed by spraying or casting and, if desired, dried to form a sheet or film, and the above-described curable epoxy composition applied, spread or cast on the support. Then, it can be produced by a method of producing a laminate by laminating and molding the adhesive layer molded body formed into a sheet or film after drying if desired. Among these production methods, the production method (1) is preferred because it is an easier process and is excellent in productivity.

  In the production method of (1) above, a curable epoxy is applied to the resin composition for a layer to be plated, which is applied, spread or cast on the support, and when the resin composition for the layer to be plated is applied, spread or cast. When the composition is applied, dispersed or cast, or in the production method of (2) above, the resin composition for the layer to be plated and the curable epoxy composition are formed into a sheet shape or a film shape for the layer to be plated. When forming the molded body and the molded body for the adhesive layer, the resin composition for the layer to be plated or the curable epoxy composition may be applied, spread or cast on the support by adding an organic solvent as desired. preferable.

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

  The thickness of the resin composition for the plating layer and the curable epoxy composition in the manufacturing method of (1) described above, or the thickness of the molded body for the plating layer and the molding of the adhesive layer in the manufacturing method of (2) described above. Although there is no particular limitation, the thickness of the layer to be plated when the laminated film is formed is preferably 1 to 10 μm, more preferably 1.5 to 8 μm, still more preferably 2 to 5 μm, and the thickness of the adhesive layer is The thickness is preferably 10 to 100 μm, more preferably 10 to 80 μm, and still more preferably 15 to 60 μm. If the thickness of the layer to be plated is too thin, the formability of the conductor layer may be reduced when the conductor layer is formed by electroless plating on the cured product obtained by curing the laminated film. If the thickness of the layer to be plated is too thick, the linear expansion of the cured product obtained by curing the laminated film may be increased. Moreover, when the thickness of an adhesive layer is too thin, there exists a possibility that the wiring embedding property of a laminated | multilayer film may fall.

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

  In addition, after the resin composition for a plating layer in the manufacturing method of (1) described above is applied, spread or cast on a support, or a curable epoxy composition is applied on the resin composition for a plating layer. After spraying or casting, or after applying the resin composition for a layer to be plated and the curable epoxy composition on the support in the production method of (2), drying may be performed as desired. . The drying temperature is preferably a temperature at which the resin composition for a layer to be plated and the curable epoxy composition are not cured, and is usually 20 to 300 ° C, preferably 30 to 200 ° C. The drying time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.

  In the laminated film of the present invention, it is preferable that the layer to be plated and the adhesive layer constituting the laminated film are in an uncured or semi-cured state. By making these into an uncured or semi-cured state, the laminated film of the present invention can be made highly adhesive.

(Prepreg)
The prepreg of the present invention comprises the above-described film of the present invention or the laminated film of the present invention and a fiber substrate.

  Examples of the fiber base material include organic fibers such as polyamide fiber, polyaramid fiber and polyester fiber, and inorganic fibers such as glass fiber and carbon fiber. Moreover, as a form of a fiber base material, the form of textiles, such as a plain weave or a twill, or the form of a nonwoven fabric, etc. are mentioned. The thickness of the fiber substrate is preferably 5 to 100 μm, and preferably in the range of 10 to 50 μm. If it is too thin, handling becomes difficult, and if it is too thick, the resin layer becomes relatively thin and the wiring embedding property may be insufficient.

  When the prepreg of the present invention is composed of the above-described film of the present invention and a fiber substrate, the prepreg of the present invention is obtained by impregnating the fiber substrate with the curable epoxy composition of the present invention. Can be manufactured. In this case, the method for impregnating the fiber base material with the curable epoxy composition of the present invention is not particularly limited, but an organic solvent is added to the curable epoxy composition of the present invention in order to adjust the viscosity and the like. And a method of immersing a fiber substrate in a curable epoxy composition to which an organic solvent has been added, a method of applying or spraying a curable epoxy composition to which an organic solvent has been added to the fiber substrate, and the like. In the method of coating or spraying, a curable epoxy composition to which an organic solvent is added can be applied or sprayed on a fiber substrate placed on a support. In the present invention, as the sheet-shaped or film-shaped composite molded body, the curable epoxy composition of the present invention is in an uncured or semi-cured state, similarly to the above-described sheet-shaped or film-shaped molded body. It is preferably contained.

  Moreover, after impregnating the fiber base material with the curable epoxy composition of this invention, you may dry as desired. The drying temperature is preferably a temperature at which the curable epoxy composition of the present invention is not cured, and is usually 20 to 300 ° C, preferably 30 to 200 ° C. If the drying temperature is too high, the curing reaction proceeds too much, and the resulting composite molded article may not be in an uncured or semi-cured state. The drying time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.

  Alternatively, when the prepreg of the present invention is composed of the above-described laminated film and fiber substrate of the present invention, the prepreg of the present invention has an adhesive layer on one side and a layer to be plated on the other side. It is preferable to have a fiber substrate inside, and the production method thereof is not limited. For example, the following methods: (1) Curable epoxy composition film with support and resin for to-be-plated layer with support A method of manufacturing a composition film by laminating the resin layer side of each film so that the fiber base material is sandwiched between them, and laminating under conditions such as pressure, vacuum, and heating as required; (2) curing A prepreg is prepared by impregnating a fiber base material with either the curable epoxy composition or the resin composition for the layer to be plated and, if desired, drying, and the other resin composition is applied to the prepreg. Prolong Or the other method of producing a laminate by laminating a resin composition film with a support; (3) applying, dispersing or coating either a curable epoxy composition or a resin composition for a layer to be plated on a support; It is possible to manufacture by laminating by casting or the like, superimposing a fiber base material thereon, further laminating by applying, spreading or casting the other resin composition from above, and drying as desired. . In any method, an organic solvent is added to the composition as desired, and the viscosity of the composition is adjusted to improve the workability in impregnation into the fiber base material, application to the support, spraying or casting. It is preferable to control.

  In addition, as a support used in this case, a polyethylene terephthalate film, a polypropylene film, a polyethylene film, a polycarbonate film, a polyethylene naphthalate film, a polyarylate film, a nylon film, a copper film, an aluminum foil, a nickel foil, Metal foils, such as chrome foil, gold foil, and silver foil, are mentioned, and these may be attached not only to one side of the prepreg but also to both sides.

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

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

  Moreover, in the prepreg of this invention, it is preferable that the resin composition which comprises a prepreg is a non-hardened or semi-hardened state similarly to the film and laminated | multilayer film of this invention mentioned above.

  And the prepreg of this invention obtained in this way can be made into hardened | cured material by heating this and making it harden | cure.

  The curing temperature is usually 30 to 400 ° C, preferably 70 to 300 ° C, more preferably 100 to 200 ° C. The curing time is 0.1 to 5 hours, preferably 0.5 to 3 hours. The heating method is not particularly limited, and may be performed using, for example, an electric oven.

(Laminate)
The laminate of the present invention is obtained by laminating the above-described film, laminated film or prepreg of the present invention on a substrate. As the laminate of the present invention, at least the film of the present invention, the laminated film or the prepreg described above may be laminated, but the substrate having the conductor layer on the surface, the film of the present invention described above, and the laminate What laminates | stacks the electrical insulation layer which consists of a film or a prepreg is preferable.

  A substrate having a conductor layer on the surface has a conductor layer on the surface of the electrically insulating substrate. The electrically insulating substrate is a resin containing a known electrically insulating material (for example, alicyclic olefin polymer, epoxy compound, maleimide resin, (meth) acrylic resin, diallyl phthalate resin, triazine resin, polyphenylene ether, glass, etc.) It is formed by curing the composition. Although a conductor layer is not specifically limited, Usually, it is a layer containing the wiring formed with conductors, such as an electroconductive metal, Comprising: Various circuits may be included further. The configuration and thickness of the wiring and circuit are not particularly limited. Specific examples of the substrate having a conductor layer on the surface include a printed wiring board and a silicon wafer substrate. The thickness of the substrate having a conductor layer on the surface is usually 10 μm to 10 mm, preferably 20 μm to 5 mm, more preferably 30 μm to 2 mm.

  The substrate having a conductor layer on the surface used in the present invention is preferably pretreated on the surface of the conductor layer in order to improve adhesion to the electrical insulating layer. As a pretreatment method, a known technique can be used without any particular limitation. For example, if the conductor layer is made of copper, 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 copper oxide layer on the conductor surface and roughened, After oxidation with this method, reduce with sodium borohydride, formalin, etc., deposit and roughen the plating on the conductor layer, contact the organic acid with the conductor layer to elute the copper grain boundaries and roughen And a method of forming a primer layer with a thiol compound or a silane compound on the conductor layer. Among these, from the viewpoint of easy maintenance of the shape of a fine wiring pattern, a method in which an organic acid is brought into contact with a conductor layer to elute and roughen a copper grain boundary, and a primer using a thiol compound or a silane compound A method of forming a layer is preferred.

  The laminate of the present invention is usually a molded product obtained by molding the above-described film of the present invention (that is, the curable epoxy composition of the present invention into a sheet or film) on a substrate having a conductor layer on the surface. ), Laminated film (that is, a sheet-like or film-like molded article comprising an adhesive layer comprising the curable epoxy composition of the present invention and a layer to be plated), or a prepreg (from the film of the present invention and the fiber substrate). It can manufacture by heat-pressing the composite molded body which becomes or the composite molded body which consists of the laminated | multilayer film of this invention, and a fiber base material.

  As a method of thermocompression bonding, a molded body with a support or a composite molded body is superposed so as to be in contact with the conductor layer of the substrate described above, and a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like The method of carrying out thermocompression bonding (lamination) using is mentioned. By heating and pressurizing, bonding can be performed so that there is substantially no void at the interface between the conductor layer on the substrate surface and the molded body or composite molded body.

  The temperature of the thermocompression bonding operation is usually 30 to 250 ° C., preferably 70 to 200 ° C., the pressure applied is usually 10 kPa to 20 MPa, preferably 100 kPa to 10 MPa, and the time is usually 30 seconds to 5 seconds. Time, preferably 1 minute to 3 hours. The thermocompression bonding is preferably performed under reduced pressure in order to improve the embedding property of the wiring pattern and suppress the generation of bubbles. The pressure under reduced pressure at which thermocompression bonding is performed is usually 100 kPa to 1 Pa, preferably 40 kPa to 10 Pa.

(Cured product)
The cured product of the present invention is formed by curing the curable epoxy composition of the present invention, and is formed by curing the film, laminated film, prepreg, and laminate of the present invention that are composed of the composition. Any are included. Curing can be performed by appropriately heating the curable epoxy composition or film of the present invention under the curing conditions described below.

  For example, about the laminated body of this invention, it can be set as hardened | cured material by performing the process which hardens the film, laminated | multilayer film, or prepreg of this invention which comprises it. Curing is usually performed by heating the entire substrate on which the film, laminated film or prepreg of the present invention is formed on the conductor layer. Curing can be performed simultaneously with the above-described thermocompression bonding operation. Alternatively, the thermocompression may be performed after the thermocompression operation is performed under conditions that do not cause curing, that is, at a relatively low temperature and in a short time.

  In addition, for the purpose of improving the flatness of the electrical insulation layer and the purpose of increasing the thickness of the electrical insulation layer, two or more films, laminated films or prepregs of the present invention are bonded and laminated on the conductor layer of the substrate. Also good.

  The curing temperature is usually 30 to 400 ° C, preferably 70 to 300 ° C, more preferably 100 to 200 ° C. The curing time is 0.1 to 5 hours, preferably 0.5 to 3 hours. The heating method is not particularly limited, and may be performed using, for example, an electric oven.

(Complex)
The composite of the present invention is formed by forming a conductor layer on the surface of the cured product of the present invention described above.

  For example, when the laminate of the present invention forms a multilayer substrate, the composite of the present invention is obtained by forming another conductor layer on the electrical insulating layer of the laminate. As the conductor layer, metal plating or metal foil can be used. Examples of the metal plating material include gold, silver, copper, rhodium, palladium, nickel, and tin, and examples of the metal foil include those used as a support for the above-described film, laminated film, or prepreg. In the present invention, the method using metal plating as the conductor layer is preferred from the viewpoint that fine wiring is possible. Hereinafter, the manufacturing method of 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 or a through hole that penetrates the electrical insulating layer is formed in the laminate. The via hole is formed to connect the respective conductor layers constituting the multilayer circuit board when the multilayer circuit board is used. The via hole or the through hole can be formed by chemical processing such as photolithography or physical processing such as drilling, laser, or plasma etching. Among these methods, a laser method (carbon dioxide laser, excimer laser, UV-YAG laser, or the like) is preferable because a finer via hole can be formed without degrading the characteristics of the electrical insulating layer.

Next, the surface roughening process which roughens the surface of the electric insulation layer (namely, cured | curing material of this invention) of a laminated body is performed. The surface roughening treatment is performed in order to improve the adhesion with the conductor layer formed on the electrical insulating layer.
The surface average roughness Ra of the electrical insulating layer is preferably 0.05 μm or more and less than 0.5 μm, more preferably 0.06 μm or more and 0.3 μm or less, and the surface 10-point average roughness Rzjis is preferably 0.00. They are 3 micrometers or more and less than 5 micrometers, More preferably, they are 0.5 micrometers or more and 3 micrometers or less. In this specification, Ra is the arithmetic average roughness shown in JIS B0601-2001, and the surface ten-point average roughness Rzjis is the ten-point average roughness shown in JIS B0601-2001 appendix 1.

  Although it does not specifically limit as a surface roughening processing method, The method etc. which make an electrical insulating layer surface and an oxidizing compound contact are mentioned. Examples of the oxidizing compound include known compounds having oxidizing ability, such as inorganic oxidizing compounds and organic oxidizing compounds. In view of easy control of the surface average roughness of the electrical insulating layer, it is particularly preferable to use an inorganic oxidizing compound or an organic oxidizing compound. Examples of inorganic oxidizing compounds include permanganate, chromic anhydride, dichromate, chromate, persulfate, activated manganese dioxide, osmium tetroxide, hydrogen peroxide, periodate, and the like. . Examples of the organic oxidizing compound include dicumyl peroxide, octanoyl peroxide, m-chloroperbenzoic acid, peracetic acid, and ozone.

  There is no particular limitation on the method of roughening the surface of the electrical insulating layer using an inorganic oxidizing compound or an organic oxidizing compound. For example, there is a method in which an oxidizing compound solution prepared by dissolving the oxidizing compound in a soluble solvent is brought into contact with the surface of the electrical insulating layer. The method of bringing the oxidizing compound solution into contact with the surface of the electrical insulating layer is not particularly limited. For example, the dipping method in which the electrical insulating layer is immersed in the oxidizing compound solution, the surface tension of the oxidizing compound solution is used. Any method may be used, such as a liquid filling method in which the oxidizing compound solution is placed on the electric insulating layer, or a spray method in which the oxidizing compound solution is sprayed on the electric insulating layer. By performing the surface roughening treatment, it is possible to improve the adhesion between the electrical insulating layer and another layer such as a conductor layer.

  The temperature and time for bringing these oxidizing compound solutions into contact with the surface of the electrical insulating layer may be set arbitrarily in consideration of the concentration and type of the oxidizing compound, the contact method, etc. It is 100 degreeC, Preferably it is 20-90 degreeC, and time is 0.5 to 60 minutes normally, Preferably it is 1 to 40 minutes.

  Note that the surface of the electrical insulating layer after the surface roughening treatment is washed with water in order to remove the oxidizing compound after the surface roughening treatment. In addition, if a substance that cannot be washed with water is attached, the substance can be further washed with a dissolvable cleaning solution or brought into contact with other compounds to make it soluble in water. Wash with water. For example, when an alkaline aqueous solution such as an aqueous potassium permanganate solution or an aqueous sodium permanganate solution is brought into contact with the electrical insulating layer, a mixed solution of hydroxylamine sulfate and sulfuric acid is used to remove the generated manganese dioxide film. It can wash | clean with water, after neutralizing-reducing process with the acidic aqueous solution of this.

Next, after surface roughening treatment is performed on the electrical insulating layer of the laminate, a conductor layer is formed on the surface of the electrical insulating layer and the inner wall surfaces of the via holes and through holes.
The conductive layer is preferably formed by an electroless plating method from the viewpoint that a conductive layer having excellent adhesion can be formed.

  For example, when forming a conductor layer by an electroless plating method, first, before forming a metal thin film on the surface of the electrical insulation layer, catalyst nuclei such as silver, palladium, zinc, and cobalt are formed on the electrical insulation layer. It is common to attach. The method for attaching the catalyst nucleus to the electrical insulating layer is not particularly limited. For example, a metal compound such as silver, palladium, zinc, or cobalt, or a salt or complex thereof is added to water or an organic solvent such as alcohol or chloroform to 0.001. Examples include a method of reducing a metal after dipping in a solution dissolved at a concentration of 10 wt% to 10 wt% (which may optionally contain an acid, an alkali, a complexing agent, a reducing agent, etc.).

  As the electroless plating solution used in the electroless plating method, a known autocatalytic electroless plating solution may be used, and the metal species, reducing agent species, complexing agent species, hydrogen ion concentration, The dissolved oxygen concentration is not particularly limited. For example, electroless copper plating solution using ammonium hypophosphite, hypophosphorous acid, ammonium borohydride, hydrazine, formalin, etc. as a reducing agent; electroless nickel-phosphorous plating solution using sodium hypophosphite as a reducing agent Electroless nickel-boron plating solution using dimethylamine borane as a reducing agent; electroless palladium plating solution; electroless palladium-phosphorous plating solution using sodium hypophosphite as a reducing agent; electroless gold plating solution; electroless silver Plating solution: An electroless plating solution such as an electroless nickel-cobalt-phosphorous plating solution using sodium hypophosphite as a reducing agent can be used.

  After forming the metal thin film, the substrate surface can be brought into contact with a rust preventive agent to carry out a rust prevention treatment. Moreover, after forming a metal thin film, a metal thin film can also be heated in order to improve adhesiveness. The heating temperature is usually 50 to 350 ° C, preferably 80 to 250 ° C. In this case, heating may be performed under a pressurized condition. As a pressurizing method at this time, for example, a method using a physical pressurizing means such as a hot press machine or a pressurizing and heating roll machine can be cited. The applied pressure is usually 0.1 to 20 MPa, preferably 0.5 to 10 MPa. If it is this range, the high adhesiveness of a metal thin film and an electrically insulating layer is securable.

  A resist pattern for plating is formed on the metal thin film thus formed, and further, plating is grown thereon by wet plating such as electrolytic plating (thick plating), then the resist is removed, and further etched. The metal thin film is etched into a pattern to form a conductor layer. Therefore, the conductor layer formed by this method usually consists of a patterned metal thin film and plating grown thereon.

  Alternatively, when a metal foil is used instead of metal plating as the conductor layer constituting the multilayer circuit board, it can be manufactured by the following method.

  That is, first, in the same manner as described above, a laminate composed of an electrically insulating layer made of a film or prepreg and a conductor layer made of a metal foil is prepared. As such a laminated body, when it is laminated, the curable epoxy composition has a degree of curing that can maintain each required characteristic, and there is no problem when it is processed afterwards or when a multilayer circuit board is formed. In particular, it is desirable to form by laminating under vacuum. In addition, the laminated body comprised from the electrically insulating layer which consists of such a film or a prepreg, and the conductor layer which consists of metal foil can be used also for a printed wiring board by a well-known subtractive method, for example.

  Then, in the same manner as described above, via holes and through holes penetrating the electrical insulating layer are formed in the prepared laminated body, and then the laminated body in which through holes are formed in order to remove the resin residue in the formed via holes. About desmear processing. Although the method of a desmear process is not specifically limited, For example, the method of contacting the solution (desmear liquid) of oxidizing compounds, such as a permanganate, is mentioned. Specifically, the laminated body in which the via holes are formed is rock-immersed for 1 to 50 minutes in an aqueous solution at 60 to 90 ° C. adjusted to have a sodium permanganate concentration of 70 g / liter and a sodium hydroxide concentration of 40 g / liter. Thus, desmear processing can be performed.

  Subsequently, after performing a desmear process about a laminated body, a conductor layer is formed in a via hole inner wall surface. The method for forming the conductor layer is not particularly limited, and either an electroless plating method or an electrolytic plating method can be used. From the viewpoint that a conductor layer having excellent adhesion can be formed, metal plating is used as the above-described conductor layer. It can carry out by the electroless-plating method similarly to the method of forming.

  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 further, plating is grown on the metal foil by wet plating such as electrolytic plating (thick plating). Then, the metal foil is etched into a pattern by etching to form a conductor layer. Therefore, the conductor layer formed by this method usually consists of a patterned metal foil and plating grown thereon.

  The multilayer circuit board obtained as described above is used as a substrate for manufacturing the above-described laminate, and this is thermocompression-bonded with the above-described molded body or composite molded body and cured to form an electrical insulating layer. Further, by further forming a conductor layer according to the above-described method and repeating these, further multilayering can be performed, whereby a desired multilayer circuit board can be obtained.

  The composite of the present invention thus obtained (and the multilayer circuit board as an example of the composite of the present invention) has an electrical insulating layer (cured product of the present invention) comprising the curable epoxy composition of the present invention. Since the electrical insulating layer is excellent in electrical characteristics, heat resistance, wiring embedding flatness, and flexibility, the composite circuit of the present invention (and the multilayer circuit board as an example of the composite of the present invention) ) Can be suitably used for various applications.

(Electronic material substrate)
The board | substrate for electronic materials of this invention consists of the hardened | cured material or composite_body | complex of this invention mentioned above. The substrate for electronic material of the present invention comprising such a cured product or composite of the present invention is a mobile phone, PHS, notebook computer, PDA (personal digital assistant), mobile video phone, personal computer, supercomputer, server, Router, liquid crystal projector, engineering workstation (EWS), pager, word processor, TV, viewfinder type or monitor direct view type video tape recorder, electronic notebook, electronic desk calculator, car navigation device, POS terminal, device with touch panel It can use suitably for various electronic devices.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the examples, “parts” and “%” are based on weight unless otherwise specified. Various physical properties were evaluated according to the following methods.

(1) Number average molecular weight (Mn) and weight average molecular weight (Mw) of alicyclic olefin polymer
It was measured by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent, and was determined as a polystyrene equivalent value.

(2) Hydrogenation rate of alicyclic olefin polymer The ratio of the number of moles of unsaturated bonds hydrogenated to the number of moles of unsaturated bonds in the polymer before hydrogenation was determined by 1H-NMR spectrum measurement at 400 MHz. This was determined as the hydrogenation rate.

(3) Desmear property
The core material obtained by impregnating glass fiber with a varnish containing a glass filler and a halogen-free epoxy compound was coated with 18 μm thick copper, 0.8 mm thick, 150 mm long × 150 mm wide After laminating a film molded body with a support on both sides of the double-sided copper-clad substrate, only the support is peeled off, and the film molded body is cured by heating at 180 ° C. for 30 minutes in an air atmosphere to form a film. A resin layer made of a product was formed. Using the CO ₂ laser device (LC-2G212 / 2C, manufactured by Hitachi, Ltd.), the obtained laminate cured product is output 0.65 W, shot count 3, processed diameter (upper surface) 55 μm, processed diameter (lower surface) Under the condition of 50 μm, a desmear property evaluation substrate in which a via hole penetrating to the copper surface was formed in the resin layer was produced. This substrate was rock-immersed in an aqueous solution at 80 ° C. adjusted to have a permanganic acid concentration of 70 g / L and a sodium hydroxide concentration of 40 g / L for 20 minutes. Next, the substrate was immersed in a water tank for 1 minute and further immersed in another water tank for 1 minute for washing with water. Subsequently, the substrate was immersed in an aqueous solution at 40 ° C. adjusted to have a hydroxylamine sulfate concentration of 18 g / L and sulfuric acid 65 g / L for 5 minutes, neutralized and reduced, and then washed with water. The bottom surface and cross section of the hole portion for the via hole of the substrate thus obtained were observed with an electron microscope (magnification: 5000 times), and desmear property was evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: No resin residue B: Resin residue partially, but no problem in practical use C: Resin residue

(4) Dielectric loss tangent A small piece having a width of 2.6 mm, a length of 80 mm, and a thickness of 40 μm is cut out from the film-like cured product, and the dielectric loss tangent (tan δ) at 10 GHz is measured using a cavity resonator perturbation method dielectric constant measuring device. It was. If tan δ is 0.01 or less, it can be evaluated that the electrical characteristics are excellent.

(5) Glass transition temperature A small piece having a width of 6 mm, a length of 15.4 mm, and a thickness of 40 μm was cut out from the film-like cured product, and a thermomechanical analyzer (TMA) under the conditions of a distance between supporting points of 10 mm and a heating rate of 10 ° C./min. / SDTA840: manufactured by METTLER TOLEDO) The glass transition temperature (Tg) of the film-like cured product was drawn tangent to the curve before and after the glass transition temperature, and Tg was determined from the intersection of these tangents. If Tg is 145 degreeC or more, it can be evaluated that it is excellent in heat resistance.

(6) Heat resistance A substrate similar to the desmear evaluation substrate prepared in the evaluation of the “(3) desmear property” is manufactured, and the steps after (swelling treatment step) in Example 3 described later are performed. A conductor layer composed of an electroless plating film and an electrolytic plating film was formed on the substrate. Next, a small piece of 50 mm length x 50 mm width was cut out from the substrate (heat resistance evaluation substrate) to obtain a test piece. The test piece is floated in a solder bath at a soldering temperature of 260 ° C. for 10 seconds, left at room temperature for 30 seconds, and a test for confirming the presence or absence of blistering of the conductor layer is repeated until blistering is confirmed. The heat resistance of the film-like cured product against solder was evaluated. The greater the number of repetitions of the test, the better the solder heat resistance. Each evaluation was repeated five times using five similar test pieces.
(Evaluation criteria)
A: The number of test repetitions is 10 or more for all five test pieces B: The number of test repetitions is 10 or more for four of the five test pieces C: The number of test repetitions is Less than 10 times for all 5 specimens

(7) Peel strength Measured according to JIS C6481 when the conductor layer was peeled off from the substrate on which the conductor layer was formed, prepared in the evaluation of “(6) heat resistance”, and according to the following evaluation criteria: Peel strength was evaluated.
(Evaluation criteria)
A: More than 0.4 N / mm B: 0.4 N / mm or less

Synthesis example 1
MTF 80 mol part, NBPI 20 mol part, 1-hexene 1 mol part, anisole 590 mol part and 4-acetoxybenzylidene (dichloro) (4,5-dibromo-1,3-dimesityl-4-imidazoline) as ruthenium-based polymerization catalyst -2-ylidene) (tricyclohexylphosphine) ruthenium (C1063, manufactured by Wako Pure Chemical Industries, Ltd.) in an amount of 0.015 mol was charged into a pressure-resistant glass reactor substituted with nitrogen, and a polymerization reaction was carried out at 80 ° C. for 1 hour with stirring. Thus, a ring-opened polymer solution was obtained. When this solution was measured by gas chromatography, it was confirmed that substantially no monomer remained, and the polymerization conversion rate was 99% or more.
Next, the obtained ring-opened polymer solution was charged into an autoclave equipped with a stirrer purged with nitrogen, and a hydrogenation reaction was performed by stirring at 150 ° C. and a hydrogen pressure of 7 MPa for 5 hours. The obtained hydrogenation reaction solution was concentrated to obtain an alicyclic olefin polymer (1) solution (solid content concentration 55.5%). The obtained alicyclic olefin polymer (1) had a weight average molecular weight of 50,000, a number average molecular weight of 20,000, and a hydrogenation rate of 97%.

Example 1
(Preparation of curable epoxy composition)
100 parts of an alicyclic epoxy compound (trade name “EHPE3150”, manufactured by Daicel, epoxy equivalent 180) as the epoxy compound (A-1), an active ester compound (trade name “Epicron HPC-” as the active ester compound (B) 8000-65T ", 65% non-volatile toluene solution, DIC, active ester group equivalent 223) 189.5 parts (active ester compound 123.2 parts), alicyclic olefin polymer obtained in Synthesis Example 1 18.1 parts of solution (10 parts of alicyclic olefin polymer), silica as a filler (trade name “SC2500-SXJ”, average particle size 0.5 μm, surface treatment of aminosilane coupling agent, manufactured by Admatechs) 441 parts, hindered phenolic antioxidant (trade name “Irganox 3114”, BASF 1.5 parts) and 110 parts of anisole were mixed and stirred with a planetary stirrer for 3 minutes.
Furthermore, 10.4 parts (3 parts of curing accelerator) of 30% 1-benzyl-2-phenylimidazole dissolved in anisole as mixing accelerator (C) was mixed and stirred for 5 minutes with a planetary stirrer. Thus, a varnish of a curable epoxy composition was obtained.

(Production of film molding)
Subsequently, the varnish of the curable epoxy composition obtained above is a polyethylene terephthalate film having a size of length 300 mm × width 300 mm, thickness 38 μm, and surface average roughness Ra 0.08 μm using a die coater. [Support: Lumirror (registered trademark) T60 manufactured by Toray Industries, Inc.] and then dried in a nitrogen atmosphere at 80 ° C. for 10 minutes to form a 43 μm thick resin composition film molding on the support. Obtained. Using the obtained film molded body, a desmear property evaluation substrate and a heat resistance evaluation substrate were prepared according to the above-described methods, and desmear property and heat resistance were evaluated. In addition, peel strength was evaluated using a substrate for heat resistance evaluation. The results are shown in Table 1.

(Preparation of cured film)
Next, on a copper foil having a thickness of 10 μm, a small piece cut out from the film molding of the obtained curable resin resin composition, with the support attached, the curable epoxy composition is on the inside, Using a vacuum laminator equipped with heat-resistant rubber press plates at the top and bottom, the pressure was reduced to 200 Pa, heat-press lamination was performed at a temperature of 110 ° C. and a pressure of 0.1 MPa for 60 seconds, and then the support was peeled off for 120 minutes at 180 ° C. Heat cured in air. After curing, a copper foil of a cured resin with a 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 according to the above method. The results are shown in Table 1.

Example 2
50 parts of the compounding amount of the epoxy compound (A-1) and 50 parts of dicyclopentadiene type epoxy compound (trade name “Epiclon HP7200HH”, manufactured by DIC, epoxy equivalent 280) as the epoxy compound (A-2) Furthermore, the varnish of the curable epoxy composition, the film molded body, and the same as in Example 1 except that the amount of the active ester compound (B) was 155.4 parts (101 parts of the active ester compound). A film-like cured product was obtained, and similarly measured and evaluated. The results are shown in Table 1.

Comparative Example 1
100 parts of the dicyclopentadiene type epoxy compound as the epoxy compound (A-2) is blended without using the epoxy compound (A-1), and the compounding amount of the active ester compound (B) is 121.8 parts (active ester) Except that it was set as compound 79.2 parts), it carried out similarly to Example 1, and obtained the varnish of the curable epoxy composition, the film molding, and the film-like hardened | cured material, and measured and evaluated similarly. The results are shown in Table 1.

Comparative Example 2
Without using the epoxy compound (A-1), 50 parts of dicyclopentadiene type epoxy compound as the epoxy compound (A-2), and bisphenol A type epoxy compound as other epoxy compound (trade name “jER828EL”, Mitsubishi Chemical Corporation) Manufactured in the same manner as Example 1 except that 50 parts of epoxy equivalent 189) were blended, and the blending amount of the active ester compound (B) was 150.7 parts (98 parts of active ester compound 79.2 parts). Similarly, the varnish of the curable epoxy composition, the film molding, and the film-like cured product were obtained, and similarly measured and evaluated. The results are shown in Table 1.

  As shown in Table 1, according to the curable epoxy composition of the present invention, a film-like cured product having excellent desmear properties, electrical properties, and heat resistance and excellent adhesion to the conductor layer can be obtained. Therefore, according to this composition, it turns out that the electrical insulating layer which has such an outstanding characteristic can be formed.

Synthesis example 2
As the first stage of polymerization, 35 mol part of 5-ethylidene-bicyclo [2.2.1] hept-2-ene (hereinafter abbreviated as “EdNB”), 0.9 mol part of 1-hexene, 340 mol part of anisole and 4-acetoxybenzylidene (dichloro) (4,5-dibromo-1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium (C1063, manufactured by Wako Pure Chemical Industries) as a ruthenium-based polymerization catalyst 005 mol part was charged into a pressure-resistant glass reactor substituted with nitrogen, and a polymerization reaction was carried out at 80 ° C. for 30 minutes with stirring to obtain a solution of a norbornene-based ring-opening polymer.
Subsequently, tetracyclo [9.2.1.02,10.03,8] tetradeca-3,5,7,12-tetraene (methanotetrahydrofluorene) 45 was added to the solution obtained in the first stage of polymerization as the second stage of polymerization. Mol part, 20 mol part of bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, 250 mol part of anisole and 0.01 mol part of C1063 are added and stirred at 80 ° C. A norbornene-based ring-opening polymer solution was obtained by performing a polymerization reaction for 1.5 hours. When this solution was measured by gas chromatography, it was confirmed that substantially no monomer remained, and the polymerization conversion rate was 99% or more.
Next, the solution of the obtained ring-opening polymer was charged into an autoclave equipped with a stirrer substituted with nitrogen, 0.03 mol part of C1063 was added, and the mixture was stirred at 150 ° C. and a hydrogen pressure of 7 MPa for 5 hours to conduct a hydrogenation reaction. Thus, a solution of the alicyclic olefin polymer (2), which is a hydrogenated product of a norbornene-based ring-opening polymer, was obtained. The resulting alicyclic olefin polymer (2) had a weight average molecular weight of 60,000, a number average molecular weight of 30,000, and a molecular weight distribution of 2. The hydrogenation rate was 95%, and the content of repeating units having a carboxylic anhydride group was 20 mol%. The solid content concentration of the alicyclic olefin polymer (2) solution was 22%.

Example 3
(Resin composition for plated layer)
454 parts of the alicyclic olefin polymer (2) solution obtained in Synthesis Example 2 (100 parts in terms of alicyclic olefin polymer (2)), polyvalent epoxy compound (A) having a condensed polycyclic structure 36 parts of an epoxy resin having a dicyclopentadiene skeleton ("Epiclon HP7200L", manufactured by Dainippon Ink & Chemicals, "Epicron" is a registered trademark), silica as an inorganic filler ("Admafine SO-C1", Made by Mattex, average particle size 0.25 μm, “Admafine” is a registered trademark 24.5 parts, tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate (anti-aging agent) "Irganox 3114", manufactured by Ciba Specialty Chemicals) 1 part, 2- [2-hydroxy-3,5-bis (α, α-) as a UV absorber Dimethylbenzyl) phenyl] -2H-benzotriazole 0.5 part and 0.5 part of 1-benzyl-2-phenylimidazole as a curing accelerator are mixed with anisole so that the concentration of the compounding agent is 16%. The varnish of the resin composition for to-be-plated layer was obtained by mixing.

(Production of laminated film)
The varnish of the resin composition for a layer to be plated obtained above was applied onto a polyethylene terephthalate film (support) having a thickness of 38 μm using a wire bar, and then dried at 80 ° C. for 10 minutes in a nitrogen atmosphere. Thus, a film with a support on which a layer to be plated having a thickness of 3 μm made of an uncured resin composition for a layer to be plated was formed was obtained.

  Next, the varnish of the curable epoxy composition obtained in Example 1 was applied to the surface of the layer to be plated formed of the resin composition for the layer to be plated of the film with support, with a doctor blade (manufactured by Tester Sangyo Co., Ltd.) Coating with an auto film applicator (manufactured by Tester Sangyo Co., Ltd.), followed by drying at 80 ° C. for 10 minutes in a nitrogen atmosphere to form a laminate with a support on which a layer to be plated and an adhesive layer having a total thickness of 43 μm are formed A film was obtained. The laminated film with a support was formed in the order of a support, a plated layer made of a resin composition for a plated layer, and an adhesive layer made of a curable epoxy composition.

(Preparation of cured laminate)
Next, separately from the above, the surface of the core material obtained by impregnating glass fiber with a varnish containing a glass filler and a halogen-free epoxy compound was bonded with copper having a thickness of 18 μm, a thickness of 0.8 mm, On a 150 mm square (150 mm long, 150 mm wide) double-sided copper-clad substrate surface, a conductor layer having a wiring width and distance between wirings of 50 μm, a thickness of 18 μm, and a microetched surface by contact with an organic acid is formed. An inner layer substrate was obtained.

  After the laminated film with the support obtained above was cut into 150 mm squares on both surfaces of the inner layer substrate, the surfaces were bonded so that the surface on the resin composition side for the adhesive layer would be inside, and then the primary press Went. The primary press is thermocompression bonding at a temperature of 110 ° C. and a pressure of 0.1 MPa for 90 seconds under a reduced pressure of 200 Pa using a vacuum laminator provided with heat-resistant rubber press plates at the top and bottom. Furthermore, using a hydraulic press device provided with metal press plates at the top and bottom, thermocompression bonding was performed at a pressure bonding temperature of 110 ° C. and 1 MPa for 90 seconds. Next, the support was peeled off to obtain a laminate of a resin layer and an inner layer substrate composed of a curable epoxy composition and a resin composition for a layer to be plated. Further, the laminate was allowed to stand at 180 ° C. for 30 minutes in an air atmosphere to cure the resin layer and form an electrical insulating layer on the inner layer substrate.

(Swelling process)
The obtained laminate cured product was prepared to have a swelling liquid (“Swelling Dip Securigant P”, manufactured by Atotech, “Securigant” is a registered trademark), 500 mL / L, and sodium hydroxide 3 g / L. After dipping in an aqueous solution at 15 ° C. for 15 minutes, it was washed with water.

(Oxidation process)
Next, after dipping in an aqueous solution at 70 ° C. for 15 minutes in an aqueous solution of permanganate (“Concentrate Compact CP”, manufactured by Atotech) at 640 mL / L and a sodium hydroxide concentration of 40 g / L. , Washed with water.

(Neutralization reduction process)
Subsequently, hydroxylamine sulfate aqueous solution (“Reduction Securigant P500”, manufactured by Atotech Co., Ltd., “Securigant” is a registered trademark) is 100 mL / L, and an aqueous solution at 40 ° C. prepared to be 35 mL / L sulfuric acid is added to the laminate. The cured product was immersed for 5 minutes, neutralized and reduced, and then washed with water.

(Cleaner / conditioner process)
Next, the laminate cured product was added to an aqueous solution at 50 ° C. adjusted to a concentration of 50 ml / L with an aqueous cleaner / conditioner aqueous solution (“Alcup MCC-6-A”, manufactured by Uemura Kogyo Co., Ltd., “Alcup” is a registered trademark) for 5 minutes. Immersion and treatment with cleaner and conditioner were performed. Next, the laminate cured product was immersed in 40 ° C. washing water for 1 minute, and then washed with water.

(Soft etching process)
Next, the laminate cured product was immersed for 2 minutes in an aqueous solution prepared to have a sulfuric acid concentration of 100 g / L and sodium persulfate of 100 g / L, and then washed with water.

(Pickling process)
Next, the laminate cured product was immersed in an aqueous solution prepared so as to have a sulfuric acid concentration of 100 g / L for 1 minute to perform pickling, and then washed with water.

(Catalyst application process)
Next, Alcup Activator MAT-1-A (trade name, manufactured by Uemura Kogyo Co., Ltd., “Alcup” is a registered trademark) is 200 mL / L, Alcup Activator MAT-1-B (upper product name, manufactured by Uemura Kogyo Co., Ltd., “Alcup”) Was immersed in a 60 ° C. Pd salt-containing plating catalyst aqueous solution prepared so that the registered trademark was 30 mL / L and sodium hydroxide was 0.35 g / L, and then washed with water.

(Activation process)
Subsequently, Alcup Redeusa MAB-4-A (trade name, manufactured by Uemura Kogyo Co., Ltd., “Alcup” is a registered trademark) is 20 mL / L, Alcup Redeusa MAB-4-B (trade name, manufactured by Uemura Kogyo Co., Ltd., “ “Alcup” was a laminate obtained by immersing the laminate cured product in an aqueous solution adjusted to 200 mL / L at 35 ° C. for 3 minutes to reduce the plating catalyst, and then washed with water.

(Accelerator processing process)
Next, the cured product of the laminate was immersed in an aqueous solution prepared so that Alcap Accelerator MEL-3-A (trade name, manufactured by Uemura Kogyo Co., Ltd., “Alcup” is a registered trademark) at 50 mL / L at 25 ° C. for 1 minute. did.

(Electroless plating process)
The laminate cured product thus obtained was obtained by using Sulcup PEA-6-A (trade name, manufactured by Uemura Kogyo Co., Ltd., “Sulcup” is a registered trademark), 100 mL / L, Sulcup PEA-6-B-2X (trade name). , Uemura Kogyo Co., Ltd.) 50 mL / L, Sulcup PEA-6-C (trade name, manufactured by Uemura Kogyo Co., Ltd.) 14 mL / L, Sulcup PEA-6-D (trade name, manufactured by Uemura Kogyo Co., Ltd.) 15 mL / L, Sulcup PEA -6-E (trade name, manufactured by Uemura Kogyo Co., Ltd.) 50 mL / L, 37% soaked in electroless copper plating solution prepared to be 5 mL / L formalin aqueous solution at a temperature of 36 ° C. for 20 minutes while blowing air. Then, an electroless plating process was performed to form an electroless plating film on the surface of the cured laminate (the surface of the layer to be plated made of the resin composition for the layer to be plated).

  Next, the laminate cured product on which the electroless plating film was formed was immersed in an anticorrosive solution prepared so that AT-21 (trade name, manufactured by Uemura Kogyo Co., Ltd.) was 10 mL / L at room temperature for 1 minute, and then washed with water. . Furthermore, the rust-proof laminated body hardened | cured material was produced by drying. The laminate cured product subjected to the rust prevention treatment was annealed at 150 ° C. for 30 minutes in an air atmosphere.

  An electrolytic copper plating film was applied to the cured laminate obtained by annealing to form an electrolytic copper plating film having a thickness of 18 μm. Subsequently, the multilayer cured product is heat-treated at 180 ° C. for 60 minutes to form a double-sided, two-layer multilayer printed wiring board in which a circuit is formed on the cured laminate by the conductor layer composed of the metal thin film layer and the electrolytic copper plating film. Got.

Claims (10)

The following general formula (I):

(In the formula, R represents an m-valent group, m represents an integer of 1 to 10, and n represents an integer of 1 to 30, respectively.)
The curable epoxy composition containing the epoxy compound (A-1) represented by these, an active ester compound (B), and a hardening accelerator (C).   The curable epoxy composition according to claim 1, further comprising a polyvalent epoxy compound (A-2) having a condensed polycyclic structure and / or a biphenyl structure.   A film comprising the curable epoxy composition according to claim 1.   A laminated film having an adhesive layer made of the curable epoxy composition according to claim 1 and a plated layer made of a resin composition for a plated layer.   The laminated film according to claim 4, wherein the layer to be plated contains 50% by weight or more of the alicyclic olefin polymer.   A prepreg comprising the film according to claim 3 or the laminated film according to claim 4 or 5 and a fiber substrate.   The laminated body formed by laminating | stacking the film of Claim 3, the laminated film of Claim 4 or 5, or the prepreg of Claim 6.   A curable epoxy composition according to claim 1 or 2, a film according to claim 3, a laminated film according to claim 4 or 5, a prepreg according to claim 6, or a laminate according to claim 7. Cured product obtained by curing.   The composite_body | complex formed by forming a conductor layer in the surface of the hardened | cured material of Claim 8.   An electronic material substrate comprising the cured product according to claim 8 or the composite according to claim 9 as a constituent material.