TW201202334A - Resin composition - Google Patents

Abstract

Disclosed is a resin composition with superior flexibility having superior laminating properties when used in the form of an adhesive film, and the coefficient of linear thermal expansion of an insulating layer obtained by curing this resin composition is low. Specifically disclosed is a resin composition containing two functional phenol resins that contain imide skeletons.

Description

201202334 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a resin composition containing a specific phenol resin. Further, it relates to a film, a prepreg, and a circuit board which are formed using the resin composition. Further, a method of forming a fine wiring groove containing a specific inorganic cerium material in a resin composition. Further, it relates to a method of manufacturing a circuit board using the same. [Prior Art] In recent years, the miniaturization and high performance of electronic devices have been progressing. In order to increase the mounting density of electronic components, the thickness of the conductor wiring has continued to progress. In this regard, various measures have been taken. Patent Document 1 discloses a resin composition containing a solvent-soluble polyimine, and describes an insulating layer formed by the composition, thereby achieving surface roughness, peel strength, elastic modulus, breaking strength, and Breaking the balance and other resin properties. However, its performance is not satisfactory, and there is no record on the MIT folding endurance. Patent Document 2 describes the MIT folding resistance using a polyimide film, but it does not describe any low-line thermal expansion rate. In Patent Document 3, a resin composition using a quinone imine skeleton resin is described, but there is no description on the MIT folding resistance. [Prior Art Document] [Patent Document] -5-201202334 [Patent Document 1] [Patent Document 2] JP-A-2009-298065 [Patent Document 3] Japanese Laid-Open Patent Publication No. Hei. The object of the present invention is to provide a resin composition which is excellent in the lamination property when the film is used, and which has a low thermal expansion coefficient of the insulating layer which is obtained by curing the resin composition, and which is excellent in tortuosity. In order to solve the above problems, the present inventors have deliberately reviewed the results, and found that the present invention can be completed by a resin composition containing a specific phenol resin. That is, the present invention includes the following contents. [1] A resin composition comprising (A) a bifunctional phenol resin containing a quinone imine skeleton. [2] The resin composition according to the above [1], wherein the content of the (A) quinone imine skeleton-containing bifunctional phenol resin is 0.1% by mass based on 100% by mass of the nonvolatile component in the resin composition. (3) The resin composition according to the above [1] or [2], further comprising (B) an inorganic cerium filler. [4] The resin composition according to any one of the above [1] to [3] further comprising (C) an epoxy resin. [0012] The resin composition according to any one of the above [1] to [4], which is used for the resin composition of the insulating layer, and has a folding resistance of 50 or more. [6] The resin composition according to any one of the above [1] to [5], which is used for a resin composition of an insulating layer, and has a linear thermal expansion ratio of 4 to 40 ppm. [7] The resin composition described in any one of the above [1] to [6] is formed on the support film. [8] A prepreg characterized in that the resin composition according to any one of the above [1] to [6] is impregnated into a sheet-like fibrous base material formed of fibers [9] The circuit board is characterized in that an insulating layer is formed by the cured product of the resin composition according to any one of the above [1] to [6]. [1] A method for forming a fine wiring groove of an insulating layer, characterized in that the resin composition contains an inorganic ruthenium filler having an average particle diameter of 0.02 to 5/zm [11] as described in the above [1〇] A method of forming a fine wiring trench of a layer by laser irradiation from an upper portion of the insulating layer. [12] The method for forming a fine wiring groove of an insulating layer according to any one of [10] to [11], wherein a metal film layer is formed on the insulating layer. [1] The method of forming a fine wiring groove of an insulating layer according to the above [1 2], wherein the thickness of the metal film layer is 50 to 500 nm. [14] The method of forming a fine wiring groove of an insulating layer according to any one of [12] to [13] wherein the metal film layer is copper. [15] A method of manufacturing a groove type circuit board, comprising the method of forming a fine wiring groove of the insulating layer according to any one of the above-mentioned items 201202334 to [14], [16] as described above [15] The method for producing a groove type circuit substrate described above further comprises a desmear step. [17] The method for producing a trench-type circuit substrate according to any one of [15] to [16], further comprising a plating step. [18] The method for producing a groove type circuit board according to any one of the above [15] to [17], further comprising the step of removing the copper layer. [Effect of the Invention] The resin composition containing the resin having a bifunctional phenol resin containing a quinone imine skeleton of the present invention can provide an excellent performance in laminating properties when the film is used, and harden the resin composition. The obtained insulating layer has a low linear thermal expansion ratio and a resin composition excellent in tortuosity. [Embodiment] The present invention is a resin composition characterized by containing (A) a bifunctional phenol resin containing a quinone imine skeleton. [(A) Bifunctional phenol resin containing a quinone imine skeleton] The (A) quinone imine skeleton-containing bifunctional phenol resin used in the present invention is not particularly limited, but has two phenolic hydroxyl groups in one molecule. It is better with the quinone imine skeleton. Since only one of the phenolic hydroxyl groups is present in one molecule, the insulating layer of the resin composition after hardening has a moderate crosslink density, and the folding resistance and the lamination performance can be simultaneously exerted. For example, the following general formula (j) and the following general formula (4) are preferred, and the following general formula (2) and the following general formula (5) are more preferable, and the following general formula (3) and the following general formula are used. (6) It is even better, and the following general formula (7) is even better. [Chemical 1]

(1) (wherein R3 is a hydrogen atom, a hydrocarbon group having a carbon number of 1 to 10 or a halogen, and the plural r3 may be the same or different from each other. Further, two R3 bonded to a carbon atom adjacent to the benzene ring may be Bonding to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms. R4, R5 and R6 are each independently a hydrogen atom, a phenyl group or a hydrocarbon group having a carbon number of 1 to 10") [Chemical 2]

(wherein, 117 is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen, and a plurality of R7 groups may be the same or different from each other. Further, 2 R7 bonded to a carbon atom adjacent to the benzene ring may be bonded to each other. And a cyclic group containing an aromatic ring-9-201202334 having a carbon number of 4 to 20 is formed.) [Chemical 3]

(4) (wherein R3 is a hydrogen atom, a hydrocarbon group having a carbon number of 1 to 10 or a halogen, and the plural r3 may be the same or different from each other. Further, two R3 bonded to a carbon atom adjacent to the benzene ring may be bonded to each other. A cyclic group containing an aromatic ring having 4 to 20 carbon atoms is formed, and each of R4, Rs and R6 is independently a hydrogen atom, a phenyl group or a hydrocarbon group having 1 to 10 carbon atoms. Two R4, R5 and R6 may each be used. Further, R5 and R6 bonded to a carbon atom adjacent to the benzene ring may be bonded to each other to form a cyclic group having an aromatic ring having 4 to 20 carbon atoms. Y is a single bond, - A group selected from a divalent hydrocarbon group of S〇2-, -Ο-, -CO-, -C(CF3)2-, -S·, or a carbon number of 1 to 2〇.) -10- 201202334 [Chemical 5]

Wherein R7 is a hydrogen atom, a hydrocarbon group having a carbon number of 1 to fluorene, or a halogen, and the plurality of R7 may be the same or different from each other. Further, two R7 bonded to a carbon atom adjacent to the benzene ring may be bonded to each other. Forming a cyclic group containing an aromatic ring having 4 to 20 carbon atoms. Y is a single bond, _s〇2·, _〇·, _c〇, _c(CF3)2_, -S- or carbon number 〜2 A base selected from a divalent hydrocarbon group of hydrazine.) [Chem. 6]

(6) wherein Y is selected from a single bond, -S〇2-, -0-, -CO-, -C(CF3)2-, -S- or a divalent hydrocarbon group having 1 to 20 carbon atoms. Base.) [Chem. 7]

(7) In the resin composition of the present invention, the content of the component (A) in the resin composition is not particularly limited, but the upper limit of the content of the component (A) in the resin composition is -11 to 201202334, if the film is laminated From the viewpoint of the improvement of the non-volatile content in the resin composition, it is preferably 30% by mass or less, more preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 1 〇 by mass. % is better and below. The lower limit of the content of the component (A) in the resin composition is 100% by mass based on the non-volatile content in the resin composition, from the viewpoint of lowering the linear thermal expansion ratio of the insulating layer obtained from the resin composition. In particular, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, more preferably 1.5% by mass or more, still more preferably 3% by mass or more, still more preferably 5% by mass or more. In the resin composition of the present invention, the weight average molecular weight of the component (A) is not particularly limited, but the upper limit of the weight average molecular weight of the component (A) is improved from the viewpoint of improving the buildup property of the film. It is preferably 1 500 or less, more preferably 1 000 or less, and even more preferably 750 or less. On the other hand, the lower limit 重量 of the weight average molecular weight of the component (A) is preferably 200% or more, more preferably 300 or more, and 400 or more, from the viewpoint of preventing crystallization in the resin composition varnish. good. The weight average molecular weight in the present invention is determined by a colloidal permeation chromatography (GPC) method (converted by polystyrene). Specifically, the weight average molecular weight of the GPC method is LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and the pipe column is Shodex K-800P/K-804L manufactured by Showa Denko Co., Ltd. K-804L was measured by using chloroform or the like as a mobile phase at a column temperature of 40 ° C and using a calibration curve of standard polystyrene. The number of times of folding of the cured product of the resin composition containing the component (A) of the present invention is grasped by the measurement method of -12-201202334 described in the measurement & evaluation of &lt;MIT folding resistance, which will be described later. The upper limit of the number of folding resistance of the cured product of the resin composition of the present invention is preferably 250 times, more preferably 300 times, more preferably 350 times, more preferably 400 times, more preferably 500 times, and even more preferably 800. It was especially good, 1 time was excellent, and 1 000 times was even better. The lower limit of the number of folding resistance of the cured product of the resin composition of the present invention is preferably 50 times, more preferably 100 times, more preferably 150 times, more preferably 170 times, more preferably 190 times, and even more preferably 210 times. Especially good. In the present invention, the linear thermal expansion ratio of the cured product of the resin composition containing the component (A) can be determined by the following: <Measurement and evaluation of glass transition temperature (Tg) and linear thermal expansion rate> Come to master. The cured product of the resin composition of the present invention has an upper limit of the linear thermal expansion ratio of 40 ppm, more preferably 39 ppm, and still more preferably 38 ppm. The lower limit of the linear thermal expansion rate of the cured product of the resin composition of the present invention is preferably 36 ppm, more preferably 35 ppm, more preferably 34 ppm, more preferably 33 ppm, still more preferably 30 ppm, and even more preferably 15 ppm. good. [(B) Inorganic enamel filler] The resin composition of the present invention may contain an inorganic ruthenium material in order to further reduce the thermal expansion ratio of the insulating layer from the resin composition. The inorganic cerium filling material is not particularly limited, but examples thereof include cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and nitrogen. Boron, aluminum borate, barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium titanate, calcium chromate, etc., of which more preferably cerium oxide. Among these, it is preferable to form cerium oxide, cerium dioxide, crystalline cerium oxide, synthetic cerium oxide, cerium cerium dioxide, hollow cerium oxide, and spherical cerium oxide. It is more preferable to melt cerium oxide and spherical cerium oxide. The average particle diameter of the inorganic ruthenium material may be one or a combination of two or more types, but the average particle diameter of the inorganic ruthenium material is not particularly limited, but from the viewpoint of increasing the tortuosity of the insulating layer from the resin composition. The fine wiring is formed on the insulating layer, and it is preferably 5 μm or less, more preferably 2.5 // m or less, more preferably 1 /zm or less, or less than 77#m from the viewpoint of improving the laser workability. It is even better, and it is more preferably 0_5//m or less and more preferably 0.45 ym or less. In addition, when the average particle diameter of the inorganic cerium material is too small, when the resin composition is used as a resin varnish, the average is improved from the viewpoint of avoiding an increase in the operability of the resin varnish and an increase in the dispersibility. The particle size is preferably 〇.〇2 // m or more, 0.05 private m or more is better, Ο. ίμιη is better, and 0.2//ra or more is even better. The average particle size of the inorganic ruthenium can be determined by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic cerium material can be produced on a volume basis by a laser diffraction type particle size distribution measuring apparatus, and the median diameter can be measured as an average particle diameter. It is preferable to use a sample in which the inorganic cerium is dispersed in water by ultrasonic waves. For the laser diffraction type particle size distribution measuring apparatus, it is possible to use LA-5 00 manufactured by the company. The upper limit of the amount of the inorganic cerium filling material is 100, in order to prevent the hardened material from becoming brittle, and the non-volatile content in the resin composition is 100% by mass, from the viewpoint of avoiding a decrease in the adhesion strength of the resin composition. It is preferably 70 mass-14 to 201202334% or less, more preferably 65 mass% or less, more preferably 60 mass% or less, more preferably 55 mass% or less, still more preferably 50 mass% or less. On the other hand, the lower limit of the amount of the inorganic cerium filling material is 5% by mass or more when the non-volatile content in the resin composition is 100% by mass, from the viewpoint that the thermal expansion ratio of the insulating layer is low. Preferably, it is more preferably 1% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more. The inorganic cerium filling material is a decane-based coupling agent, an acrylate-based decane coupling agent, a sulfide-based decane coupling agent, a vinyl decane coupling agent, a mercapto decane coupling agent, a styryl decane coupling agent, and an isocyanate system. A surface treatment agent such as a decane coupling agent, an organic argon nitrogen compound, an epoxy decane coupling agent, an amino decane coupling agent, a urea-based decane coupling agent, or a titanate coupling agent is surface-treated to have moisture resistance, It is better to increase the dispersion. These may be used alone or in combination of two or more. Examples of the surface treatment agent include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropyldiethoxymethyldecane, and N-phenyl- 3-aminopropyltrimethoxydecane, N-methylaminopropyltrimethoxydecane, N-2 (-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2 -Amino decane-based coupling agent such as -aminoethyl)-3-aminopropyldimethoxymethyl decane; urea-based decane coupling agent such as 3-ureidopropyltriethoxydecane: 3 - glycidoxypropyltrimethoxydecane, 3-epoxypropyloxypropyltriethoxydecane, 3-epoxypropyloxypropylmethyldiethoxydecane, 3- Epoxypropyloxypropyl (dimethoxy)methyl decane, propylene propyl trimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy fluorene-15 - 201202334 Epoxy decane coupling agent such as alkane; 3-mercaptopropyltrimethoxy sand, 3-mercaptopropyltriethoxydecane, 3-mercaptopropylmethyldimethoxyindole a decyl decane coupling agent such as 11-mercaptopurine-based trimethoxy decane; methyl trimethyl Pyridin, octadecyltrimethoxydecane, phenyltrimethoxy sand, methyl propyl decyloxypropyl trimethoxy sand, milazonese, triazine decane, t-butyltrimethoxy a decane-based coupling agent such as a decane or the like; a vinyl decane coupling agent such as vinyltrimethoxydecane, vinyltriethoxydecane or vinylmethyldiethoxydecane; P-styryltrimethoxy Styryl decane coupling agent such as decane, 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyl Acrylic decyl olefin coupling agent such as methoxy decane, 3-methacryloxypropyl triethoxy decane, 3-methyl propylene oxypropyl diethoxy decane; 3-isocyanate propyl group An isomeric acid ester decane coupling agent such as trimethoxy decane; a sulfide decane such as bis(triethoxymethyl propyl) disulfide or bis(triethoxymethyl propyl) tetrasulfide; Coupling agent: hexamethyldiazepine nitrogen, 1,3-divinyl-1,1,3,3-tetramethyldiazoxide, hexaphenyldifluorene, Niobium nitrogen, cyclotriazole nitrogen, 2,2,4,4,6,6·hexamethylcyclotriazide nitrogen, octamethylcyclotetrazolium nitrogen, hexabutyldiazoxide, hexaoctyldiazoxide, 1,3-Diethyltetramethyldiazide nitrogen, 1,3-di-η-octyltetramethyldiazide nitrogen, 1,3-diphenyltetramethyldiamine nitrogen, 1,3_two Methyl tetraphenyl diazide nitrogen, 1,3-diethyltetramethyl diazide nitrogen, hydrazine, 1,3,3·tetraphenyl-1,3-dimethyl diazide nitrogen, 1,3- Organic germanium nitrogen compound such as dipropyltetramethyldiazide nitrogen, hexamethylcyclotriazide nitrogen, dimethylaminotrimethylsulfonium nitrogen, tetramethyldiazoxide or the like; tetra-n-butyltitanate Ester Dimer, Titanium Small Propoxyoctyl Glycolate-16- 201202334 Ethyl Titanium, Titanate Tribasin] C } Acid Diammonium Phosphate Catalyzed C-propyl {Isobi-bis-diyl C , hydroxy double salt II, acid, vinegar, titanium acid dilute diethyl ether &gt; hydroxy acid diphosphate 'pyro titanium base · octyl-T acid one-n-amine C tetraol bis, ethyl ethoxyacetate Titanate, titanium tris-butoxybutyric monostearate, tetra-n-butyl titanate, tetrakis(2-ethylhexyl) titanate, tetraisopropylbis(dioctylphosphite) ester Titanate, tetraoctyldi(ditridecylphosphite) titanate, tetrakis(2,2-diallyloxymethyl-1-butyl)di(bistridecyl) Phosphate titanate, isopropyl trioctyl decyl titanate, isopropyl triisopropyl phenyl titanate, isopropyl triisostearate titanate, isopropyl isostearyl sulfonate Dipropylene sulphate, isopropyl dimethyl propylene isostearyl phthalate, isopropyl tris(dioctylphosphonate) titanate, isopropyl succinyl sulfonate A titanate coupling agent such as a titanate, an isopropyl hydrazide (dioctylpyrophosphate) titanate or an isopropyl tris(fluorene-nonylaminoethylaminoethyl titanate). [(C) Epoxy Resin] In the resin composition of the present invention, in order to improve the heat resistance of the insulating layer of the resin composition, the toughness of the insulating property, and the adhesion of the metal film, It contains an epoxy resin. There is no particular limitation on the epoxy resin, but bisphenolphthalein type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin are mentioned. , phosphorus-containing epoxy resin, bisphenol S-type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A Novolak type epoxy resin, -17- 201202334 Epoxy resin with butadiene structure, cyclohexane dimethanol type epoxy resin, epoxy propyl amine type epoxy resin, bisphenol diglycidyl ether a diepoxypropyl etherate of naphthalenediol, a epoxidized propyl ether of a phenol, a diepoxypropyl etherate of an alcohol, and an alkyl substituent or halide of the epoxy resin. And hydrides and the like. These may be used alone or in combination of two or more. In terms of epoxy resin, bisphenol A type epoxy resin and naphthol type epoxy resin are used in view of heat resistance, insulation reliability, tortuosity, and adhesion to a metal film. A naphthalene type epoxy resin, a biphenyl type epoxy resin, or an epoxy resin having a butadiene structure is preferred. Specifically, a liquid bisphenol A type epoxy resin ("Epicoat 828EL" manufactured by Nippon Epoxy Co., Ltd.) or a naphthalene type bifunctional epoxy resin (manufactured by Otsuka Ink Chemical Industry Co., Ltd.) "HP4032", "HP4032D]), naphthalene type 4-functional epoxy resin ("Higatsu Chemical Co., Ltd." "HP4700"), and naphthol type epoxy resin (Edo-Chemical Co., Ltd. "ESN-47 5V" ), epoxy resin having a butadiene structure ("PB-3600" manufactured by DAICEL Chemical Industry Co., Ltd.), epoxy resin having a biphenyl structure ("NC3000H" and "NC3000L" manufactured by Nippon Kayaku Co., Ltd. , Japan's epoxy resin (shares) "yx4000"). In the resin composition of the present invention, the content of the component (C) in the resin composition is not particularly limited, but the upper limit 含量 of the content of the component (C) in the resin composition is from the viewpoint of preventing film flexibility from being reduced. It is preferable that 60% by mass of the nonvolatile matter in the resin composition is 60% by mass, more preferably 50% by mass, and still more preferably 40% by mass. On the other hand, the lower limit ( of the content of the component (C) in the resin group -18-201202334 is from the viewpoint of increasing the glass transition temperature of the insulating layer and lowering the thermal expansion rate of the wire. The nonvolatile content in the product is preferably 5% by mass, more preferably 10% by mass, even more preferably 15% by mass. [(D) Hardener (excluding component (A))] The resin composition of the present invention is such that the heat resistance of the insulating layer from the resin composition is increased upward, the insulation reliability is improved, and the dissipation factor is lowered. Etc., it can be made to contain the component (D). In the case of the component (D), the function of the epoxy resin is not particularly limited, and specific examples thereof include a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a benzoxazine. A curing agent, a cyanate-based curing agent, and the like. These may be used alone or in combination of two or more. In the resin composition of the present invention, the content of the component (D) in the resin composition is not particularly limited, but the upper limit 含量 of the content of the component (D) in the resin composition is from the viewpoint of preventing film flexibility from being reduced. It is preferable that the non-volatile content of the resin composition is 50% by mass, more preferably 45% by mass, and even more preferably 40% by mass. On the other hand, the lower limit 含量 of the content of the component (D) in the resin composition is 5 in terms of 100% by mass of the nonvolatile component in the resin composition from the viewpoint of increasing the glass transition temperature of the insulating layer upward. The mass % is better, 1 〇 mass% is better, and 15 mass% is better. The ratio of the number of epoxy groups of the epoxy resin (C) to the total number of active hydrogen groups of the component (A) and the component (D) in the resin composition of the present invention is (1 -19 - 201202334 : 0.2) to (1: 2) It is better, (1: 0.3) ~ (1: 1_5) is better, (1: 0.4) ~ (1: 1) is better. If the equivalent ratio is outside the above range, the mechanical strength or water resistance of the cured product tends to decrease. The resin composition of the present invention can improve the heat resistance and the insulation reliability by including a phenol-based curing agent 'naphthol-based curing agent. In the case of the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferred from the viewpoint of heat resistance and water resistance. For the commercial products, MEH-7700, MEH-78 1 Ο, MEH-785 1 (made by Minghe Chemical Co., Ltd.) 'NHN ' CBN, GPH (Nippon Chemical Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Tohto Kasei Co., Ltd.), LA7052, LA7054 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.). The resin composition of the present invention can reduce the dissipation factor by containing an active ester-based curing agent. The active ester-based curing agent used in the present invention refers to an ester group having a high reactivity such as a phenol ester compound, a thiophenolate compound, an N-hydroxyamine ester compound, or an esterified compound of a heterocyclic hydroxy compound, and has a ring. The hardening effect of oxygen resin. The active ester-based curing agent is not particularly limited, but a compound having two or more active ester groups in one molecule is preferable, and one molecule obtained from a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group is preferable. An aromatic compound having two or more active ester groups, more preferably an aromatic compound obtained from a compound having at least two or more carboxylic acids in one molecule and an aromatic compound having a phenolic hydroxyl group, and in the aromatic compound The aromatic-20-201202334 family of compounds having more than two active ester groups in the molecule is more preferred. Further, it may be linear or multi-branched. In addition, when a compound having at least two or more carboxylic acids in one molecule is a compound containing an aliphatic chain, compatibility with an epoxy resin can be increased, and if a compound having an aromatic ring is used, heat resistance can be obtained. Becomes high. Particularly, from the viewpoint of heat resistance and the like, an active ester-based curing agent obtained from a carboxylic acid compound and a phenol naphthol compound is preferred. Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, horse, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and stearic acid. Among them, from the viewpoint of heat resistance, succinic acid, acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, isophthalic acid, and terephthalic acid are more preferable. Specific examples of the phenol compound or naphthol can be hydroquinone, resorcin, bis, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, and methylphenol F. , methylated bisphenol S, phenol, hydrazine-cresol, m-cresol, p-catechol, naphthol, anthracene naphthol, 1,5-dihydroxynaphthalene, 1,6-binaphthalene, 2,6-Dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyltetrahydroxydiphenyl ketone, gambogic acid, benzenetriol, dicyclopentadienyl di, phenol novolac, and the like. Among them, from the viewpoints of heat resistance and solubility, bisphenol hydrazine, bisphenol F, bisphenol S, methylated bisphenol quinone, methyl bisphenol F, methylated bisphenol S, catechol, 1, 5-dihydroxynaphthalene' 1,6-ylnaphthalene, 2,6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl, tetrahydroxydiphenyl ketone, gambogic acid, benzenetriol, bicyclo Pentadienyl phenol, phenol novolak is preferred, with catechol, 1,5-dihydroxynaphthalene, dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxy as aliphatic For the purpose of the acid or the coke, the honey is the bisphenol, hydroxy ketone, phenol, hydroxyphenol, phenol, phenol, dihydroxy ketone, 1,6-diphenyl Hydroxydiphenyl ketone, gambogic acid, benzenetriol, dicyclopentadienyl diphenol, phenol novolac, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6 - Dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, dicyclopentadienyl diphenol, phenol novolac, and more preferably, dihydroxydiphenyl ketone, three Hydroxydiphenyl ketone , tetrahydroxydiphenyl ketone, dicyclopentadienyl diphenol, phenol novolak is even better, and dicyclopentadienyl diphenol, phenol novolac lacquer is further better, dicyclopentadienyl Phenol is particularly preferable, and these may be used alone or in combination of two or more. The method for producing the active ester-based curing agent is not particularly limited, and it can be produced by a known method, but specifically, it can be obtained by a condensation reaction of a carboxylic acid compound and a hydroxy compound. As the active ester-based curing agent, an active ester-based curing agent described in JP-A-2004-277460 can be used, and a commercially available product can also be used. The commercially available active ester-based curing agent is preferably a structure containing a dicyclopentadienyl diphenol structure, an acetal of a phenol novolak, a benzamidine phenol phenol varnish, or the like, and a bicyclic ring thereof. The pentadienyl diphenol constructor is preferred. Specifically, EXB9460S-65T (made by DIC (product), active base equivalent: about 223), DC8 08 (made by Japanese epoxy resin (share), active basis equivalent of about 149), YLH 1 026 (Japanese ring) Oxygen resin (stock), active base equivalent of about 200), YLH 1 03 0 (made by Japan Epoxy Resin Co., Ltd., active base equivalent of about 201), YLH 1048 (Japanese epoxy resin (stock) system, active base equivalent About M5), etc., among which EXB9460S is preferable from the viewpoint of the preservation stability of the varnish and the thermal expansion rate of the cured product. -22-201202334 The resin composition of the present invention contains a benzoxazine-based curing agent to increase the glass transition temperature of the insulating layer. The benzoxazine-based curing agent is not particularly limited, and specific examples thereof include HFB2006M (Showa Polymer Co., Ltd.), Pd, Fa (manufactured by Shikoku Chemical Industries Co., Ltd.), and the like. The resin composition is reduced in the dissipation factor by containing a cyanate-based curing agent. The cyanate-based curing agent is not particularly limited, and examples thereof include a novolac type (phenol novolak type, an alkylphenol novolak type, etc.) cyanate resin, a dicyclopentadiene type cyanate resin, and a double Phenolic type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate resin and some of these prepolymers which are formed by three exposures can be used alone or The weight average molecular weight of the cyanate-based curing agent used in combination of two or more kinds is not particularly limited, but is preferably 500 to 4,500, more preferably 600 to 3,000. Specific examples of the cyanate-based curing agent include, for example, Bisphenol A dicyanate, polyphenol cyanate (oligo(3-methyl-1,5-phenylene), 4,4'-methyl(2,6-di) Methylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate) phenylpropane 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl) -1-(methylethylidene))benzene, bis(4-cyanate phenyl) sulfide, double (4- a bifunctional cyanate resin such as a cyanate phenyl) ether; a polyfunctional cyanate resin derived from a phenol novolak, a cresol novolak, a phenol resin containing a dicyclopentadiene structure, or the like; One part of the acid ester resin -23- 201202334 A prepolymer obtained by triazineization, etc. These may be used in one type or more. Commercially available cyanate resins include the following formula ( 8) Triphenylation of a part or all of the phenol novolac type polyfunctional cyanate resin (Lonza Japan (, PT30, cyanate equivalent 124), and the double solid cyanate represented by the following formula (9) Prepolymerized by a terpolymer, manufactured by Lonza Japan Co., Ltd., ΒΑ230, cyanate equivalent 23 2 ) (c) is a cyanate resin containing a dicyclopentadiene structure (Japan), DT- 4000, DT-7000) and so on. 2 苯 } } } } Α 、 、 、 、 、 、 、 、 、 、 、

[In the formula (8), η represents an arbitrary number of average enthalpies (preferably 〇 〜 20 ) [Chemical 9]

• 24- 201202334 [Chem. 10]

C=N

(10) (In the formula (10), η represents a number of 0 to 5 of the average enthalpy [(Ε) hardening accelerator] In the resin composition of the present invention, from the viewpoint of hardening the resin ratio, The present invention is not particularly limited, and may be a chemical accelerator, an imidazole-based hardening accelerator, an amine-based hardening accelerator compound, an organic iron salt compound, etc. In terms of a metal-based hardening accelerator, Specific examples of the organometallic complex of a metal such as cobalt, copper, manganese or tin, or a metal complex of the metal complex, may be exemplified by an organic cobalt complex such as cobalt (III) ethylene-co-pyruvate (III). Organic copper complex of (II), etc. 'Organic nickel complex of zinc, such as zinc complex, iron (II) ethylene pyruvate, etc. In terms of β-organic metal salts such as organic ramicides, tin octylate, zinc naphthenate, cobalt naphthenate, and tin stearate. In terms of metal-based hardening accelerators, it is hardened and melted. 'It is a more effective hardening accelerator for the composition of cobalt (II) ethylene vinylacetonate and ethylene acetone. Agent, organic phosphine, ferrous, iron, nickel metal salts, organic iron complexes such as cobalt (II) organic acid (II), copper ethylene acetonate II), manganese acetylacetonate (II may be exemplified by zinc octoate, stearic acid) From the viewpoint of solubility of zinc, etc., cobalt (III), -25- 201202334, zinc (II) ethylene pyruvate, zinc naphthenate, iron (III) ethylene pyruvate, especially cobalt (II) ethylene pyruvate, Zinc naphthenate is preferred. These may be used alone or in combination of two or more. In order to harden the epoxy resin and the cyanate-based curing agent more efficiently, it is preferred to use a metal-based curing accelerator. When the amount of the metal-based hardening accelerator added is 1% by mass, the metal content of the metal-based hardening accelerator is preferably in the range of 25 to 500 ppm, and preferably in the range of 40 to 200 ppm. More preferably, when it is less than 25 ppm, it is difficult to form a conductor layer which is excellent in adhesion to the surface of the low-thickness insulating layer, and if it exceeds 500 ppm, the storage stability and insulation of the resin composition are lowered. The tendency to be an imidazole-based hardening accelerator 2-Methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole , 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole , 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyano Ethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole pyromellitate, 1-cyanoethyl-2-phenylimidazolium pyromellitate, 2, 4-Diamino-6-[2'-methylimidazolyl-(indenyl)]-ethyl-s-triazine, 2,4-diamino-6-[ 2'-undecyl imidazolyl- (1')]-Ethyl-3-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1,)]-ethyl-s- Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1,)]-ethyl-s-triazine isocylate cyanide, 2-phenylimidazole Cyanuric acid adduct, 2-phenyl-4,5-dihydroxymethyl-26- 201202334 imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro- 1H-pyrrole [l,2-a]benzene Imidazole compound of imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc. and adduct of imidazole compound and epoxy resin . Examples of the amine-based hardening accelerator include a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-gin ( An amine compound such as dimethylaminomethyl)phenol or 1,8-difluorenebicyclo(5,4,0)-undecene (hereinafter abbreviated as DBU). Examples of the organic phosphine compound and the organic squara salt compound include TPP, TPP-K, TPP-S, TPTP-S, TBP-DA, TPP-SCN, and TPTP-SCN (Beixing Chemical Industry Co., Ltd.). When the content of the hardening accelerator other than the metal-based hardening accelerator such as an imidazole-based hardening accelerator, an amine-based hardening accelerator, an organic phosphine compound, or an organic iron salt compound is 100% by mass in the resin composition, It is preferably in the range of 0.05 to 3% by mass, more preferably in the range of 0.07 to 2% by mass. When the amount is less than 0.05% by mass, the adhesion strength to the underlying conductor layer tends to decrease, and if it exceeds 3% by mass, the dissipation factor of the cured product tends to become large. When the combined metal-based hardening accelerator and other hardening accelerators (imidazole-based hardening accelerator, amine-based hardening accelerator, organic phosphine compound, organic scale salt compound, etc.) are used, the metal-based hardening accelerator and other hardening accelerators are used. The agent (imidazole-based hardening accelerator, amine-based hardening accelerator, organic phosphine compound, organic scale salt compound, etc.) is preferably within the above range. -27-201202334 [(F) Thermoplastic Resin] The resin composition of the present invention may contain an improvement in the film forming ability when the mechanical strength of the cured product or the film is used in the form of a film. (F) Thermoplastic resin. Examples of the (F) thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, a polyimine resin, a polyamidoximine resin, a polyether phthalimide resin, a poly maple resin, and a poly Ether-rolled resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, and the like. Among them, a polyvinyl acetal resin or a phenoxy resin is preferred. These may be used alone or in combination of two or more. (F) The thermoplastic resin is preferably a glass transition temperature of 8 (TC or more. The "glass transition temperature" is determined according to the method described in JIS K 7197. Further, the glass transition temperature is higher than the decomposition temperature. In fact, when the glass transition temperature cannot be observed, the visible decomposition temperature is the glass transition temperature in the present invention. Further, the decomposition temperature is defined as the mass reduction rate when measured in accordance with the method described in JIS K 7120. The temperature average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000, more preferably in the range of 10,000 to 150,000, more preferably in the range of 15,000 to 100,000, and in the range of 20,000 to 80,000. If it is smaller than this range, the film forming ability or the mechanical strength upward effect cannot be sufficiently exerted, and if it is larger than this range, the compatibility with the cyanate resin and the epoxy resin is lowered, and the insulating layer is lowered. The thickness of the surface after the roughening treatment is increased. Further, the weight average molecular weight in the present invention is measured by a colloidal permeation chromatography (GPC) method (in terms of polystyrene). PC method -28-201202334 The weight average molecular weight of the product is determined by using Shodex K-800P manufactured by Showa Denko Co., Ltd. for LC-9A/RID-6A manufactured by Shimadzu Corporation. /K-804L/K-804L, the mobile phase is chloroform, etc., and is measured at a column temperature of 4 (TC), and can be calculated using a standard polystyrene calibration line. For the phenoxy resin, From bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, anthracene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, One or more kinds of skeletons selected from the group consisting of an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The phenoxy resin may be used in combination of two or more kinds. The terminal of the phenoxy resin may be a phenolic hydroxyl group. In the case of a commercially available product, for example, 1256, 42 50 (phenoxy resin containing a bisphenol A skeleton) made of Japanese epoxy resin, and YX made of Japanese epoxy resin 8100 (phenoxy resin containing bisphenol S skeleton), YX69 made of bismuth epoxy resin 54 (phenoxy resin containing bisacetophenone ketone skeleton) or other FX2 8 0, FX293, Japanese epoxy resin (shares) YL7553, YL6954, YL6794, YL7213, YL7290, YL7482, etc. Specific examples of the polyvinyl acetal resin include the electric chemical industry (stock) system, Denka Butyral 4000-2, 5000-A, 6000-C, 6000-EP, and S-LEC manufactured by Sekisui Chemical Industry Co., Ltd. BH series, BX series, KS series, BL series, BM series, etc. Specific examples of the polyimide resin include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Chemical and Chemical Co., Ltd. Further, a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate -29 - 201202334 ester compound, and a tetrabasic acid anhydride (Japanese Patent Publication No. 2 006-3 708 3) A modified polyimine such as a polyfluorene-containing polyalkyleneimine (described in JP-A-2002- 12667, JP-A-2000-3149, etc.). Examples of the polyamidimide resin include a polyamidoquinone imine "VYLOMAX HR1 1NN" and "VYLOMAX HR1 6NN" manufactured by Toyobo Co., Ltd. Further, modified polyamidoquinone imines such as polyacrylamide skeletons "KS9100" and "KS9300", which are made of a polyoxyalkylene skeleton, manufactured by Hitachi Chemical Co., Ltd., may be mentioned. Specific examples of the polyether oxime resin include polyether maple "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like. The content of the (F) thermoplastic resin in the resin composition of the resin composition of SOLVAY Advanced Polymers Co., Ltd. is not particularly limited, and the content of the thermoplastic resin (P 1 700 j , Γ P3500, etc.) is not particularly limited. With respect to 100% by mass of the nonvolatile component in the resin composition, it is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass. (F) When the blending ratio of the thermoplastic resin is less than 0.5% by mass, since the viscosity of the resin composition is low, it is difficult to form a uniform resin composition layer, and when it exceeds 20% by mass, the viscosity of the resin composition is too high. It is difficult to embed the wiring pattern on the substrate. [(G) rubber particles] The resin composition of the present invention may contain (G) rubber particles from the viewpoint of improving the mechanical strength of the cured product and improving the stress relaxation effect. (G) When the rubber particles are insoluble in the preparation of the resin composition, there is a solvent of -30-201202334, and the composition of the resin composition such as an epoxy resin is not dispersed in the varnish of the resin composition. good. For example, rubber particles are generally prepared such that the molecular weight of the rubber component is so large that it is insoluble in a solvent or a resin, and is prepared in the form of particles. Examples of the rubber include core-shell type rubber particles, crosslinked acrylonitrile butadiene particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particle type particles are rubber having a core layer and a shell layer. The particles are, for example, a two-layer structure in which a shell layer of an outer layer is a glassy polymer, a core layer of an inner layer is a polymer, or a shell layer of an outer layer is a glassy compound, and an intermediate layer is a rubbery polymer or a core. The layer is a three-layer structure in which a glassy polymer is formed. The glassy polymer layer is composed of, for example, a polymer of methacrylic acid, and the rubbery polymer layer is made of, for example, an acrylic polymer (butyl rubber). Examples of the core-shell type rubber particles include STAPHYLOID AC3 832, AC3816N GANZ Chemical Co., Ltd., and METABLEN KW-4426 (RAYON). Specific examples of the acrylonitrile butadiene rubber (NBR) include XER-91C average particle diameters of 0.5 &quot;m, (manufactured by)). Examples of the styrene butadiene rubber (SBR) particles include XSK-500C average particle diameters of 0_5/zm, JSR (strand), and the like. Specific examples of the acrylic rubber particles include METABLEN W300A (average particle diameter of 0.1 m) and W450A (particle size of 0.5/zm) (manufactured by Mitsubishi Rayon Co., Ltd.). These may be used in combination of two or more kinds. The blended (G) rubber particles have an average particle diameter of 0.005 Å, such as organic rubber or the like. The rubbery poly(butyl ketone) system ' (Mitsubishi particles JSR system) can be used to obtain an average range of 1 1 β m -31 - 201202334, preferably 0.2~0.6/zm. The average particle diameter of the rubber particles in the present invention can be measured by a dynamic light scattering method. For example, the rubber particles can be uniformly dispersed by ultrasonic waves or the like in an appropriate organic solvent, and the particle size distribution of the rubber particles can be produced on a mass basis using FPRA-1000 (manufactured by Otsuka Electronics Co., Ltd.). The number diameter is measured as an average particle diameter. The content of the (G) rubber particles is preferably in the range of 1 to 1% by mass, and preferably in the range of 2 to 5% by mass, based on 1% by mass of the nonvolatile matter in the resin composition. good. [(Η) Flame Retardant] The resin composition of the present invention may further contain (Η) a flame retardant from the viewpoint of improving flame retardancy. (Η) The flame retardant may, for example, be an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polyoxygen-based flame retardant, or a metal hydroxide. In the case of the organophosphorus-based flame retardant, phenanthrene-type phosphorus compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., and phosphorus-containing benzenes such as HFB-2006M manufactured by Showa Polymer Co., Ltd. And the compound, Ajinomoto Fine_Techno (share) REOFOS 30, 50, 65, 90, 1 1 0, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, Beixing Chemical Industry PPQ of the (share) system, OP93 0 made by ciariant (share), phosphate ester compound of PX200 by Daeba Chemical Co., Ltd., and phosphorus-containing epoxy resin of FX289 and FX3 0 5 made by Toho Chemical Co., Ltd. , Phosphorus-containing epoxy resin such as ERF001 manufactured by Dongdu Chemical Co., Ltd., and phosphorus-containing epoxy resin such as YL7613 manufactured by Japan Epoxy Resin Co., Ltd. (32-201202334). In the case of the organic nitrogen-containing phosphorus compound, a phosphate phthalamide compound such as SP670 or SP703 manufactured by Shikoku Chemicals Co., Ltd., SPB100, SPE100, manufactured by Otsuka Chemical Co., Ltd., and Phosphorus-nitrogen compounds such as FP-series. Examples of the metal hydroxides include magnesium hydroxide such as UD65, UD650, and UD653 manufactured by Ube Materials Co., Ltd., and B-30, B-325, B-315, and B-308 manufactured by Batec Industries Co., Ltd. , B-303, UFH-20 and other aluminum hydroxide. These may be used alone or in combination of two or more. The resin composition of the present invention may be blended with a maleic imine compound, a bisallyl nadide-imide compound, a biphenyl base-based resin, or a range in which the effects of the present invention are exerted. A thermosetting resin other than an epoxy resin such as an ethylene benzyl ether resin. These may be used alone or in combination of two or more. Examples of the maleic imine resin include BMI1000 'BMI2000, BMI3000, BMI4000, BMI5100 (made by Daiwa Kasei Co., Ltd.), BMI, BMI-70, BMI-80 (made by KI Chemical Co., Ltd.), ANILIX- MI (MITSUI FINE CHEMICALS (manufactured by the company)), bisallyl naleximine compound, BANI-M, BANI-X (made by Jiushan Petrochemical Industry Co., Ltd.), vinyl benzyl resin For example, V5000 (made by Showa Polymer Co., Ltd.), and vinyl benzyl ether resin, V1000X and V1100X (made by Showa Polymer Co., Ltd.) are mentioned. The resin composition of the present invention may optionally contain various other resin additives other than the above in the range in which the effects of the present invention can be exhibited. Resin-33-201202334 Examples of the additives include organic hydrazines such as strontium powder, nylon powder, and fluororesin powder; tackifiers such as ALB EN and BENTON; and polyfluorene, fluorine, and polymer. Antifoaming agent or leveling agent, decane coupling agent, triazole compound, thiazole compound, triazine compound, porphyrin compound and the like adhesion promoter, anthraquinone blue, anthraquinone green, iodine green, A coloring agent such as disazo yellow or carbon black. The use of the resin composition of the present invention is not particularly limited, but it can be widely used for the adhesive film by using the resin composition of the present invention to achieve a laminate property, a tortuosity, and a low-line thermal expansion ratio. A sheet-like laminate material such as a prepreg, a circuit board, a solder resist, a bottom slab, a solid crystal material, a semiconductor sealing material, a boring resin, a part-embedded resin, and the like must be used for the resin composition. Among them, since the insulating layer is formed, it is suitable for the manufacture of a multilayer printed wiring board. The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer. However, in general, it is preferred to use a sheet-like laminated material such as a film or a prepreg. The softening point of the resin composition is preferably from 40 to 150 ° C from the viewpoint of the lamination property of the sheet-like laminate material. [Continuous film] The adhesive film of the present invention can be produced by a known method, for example, a resin varnish in which a resin composition is dissolved in an organic solvent, and the resin varnish is narrowed. A slit coating apparatus or the like is applied onto a support, and the organic solvent is dried by heating or hot air blowing to form a resin composition layer. -34- 201202334 The organic solvent may, for example, be a ketone such as acetone, methyl ethyl ketone or cyclohexanone; ethyl acetate, butyl acetate, celecoxicol acetate, propylene glycol monomethyl ether acetate, or card Acetate such as alcoholic acetate; carbitol of celecoxime, butyl carbitol, etc.; aromatic hydrocarbons such as toluene and xylene: dimethylformamide, dimethylacetamide And a guanamine-based solvent such as N-methylpyrrolidone. These may be used alone or in combination of two or more. The drying conditions are not particularly limited, and the organic solvent content ratio of the resin composition layer is preferably 10% by mass or less and more preferably 5% by mass or less. The drying conditions are set by appropriate experiments to set suitable drying conditions. Although the amount of the organic solvent in the varnish varies, the varnish containing 30 to 60% by mass of the organic solvent is dried at 50 to 150 ° C. 3 to 10 minutes or so is better. The thickness of the resin composition layer formed in the film is preferably 10 to 10 μm from the viewpoint of increasing the number of folding resistances when the MIT folding resistance test of the cured product of the resin composition is performed. 15~90/zm is better, 20~80/zm is better, 25~70; zm is better, 30~65 Mm and then better, 35~60; am especially good, 40~55#m Excellent. Examples of the support in the present invention include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter referred to as "PET"), and polyethylene naphthalate. Plastic films such as polyester, polycarbonate, and polyimide. In terms of plastic film, PET is especially preferred. A metal case such as a copper foil or an aluminum foil may be used as the support body, or as a film attached to the metal foil. Further, the support can be subjected to release treatment in addition to the application of rough surface treatment and corona treatment. Further, the release treatment may be carried out by using a release agent such as a polyoxyphthalocyanine-based release type -35 - 201202334 agent, an alkyd resin release agent, or a fluororesin release agent. The thickness of the support is not particularly limited, but is preferably 10 to 150 //m, more preferably 25 to 50//m. The support in the present invention may be peeled off after being laminated on an inner layer circuit board or the like, or after forming an insulating layer by heat curing. When the support is peeled off after the film is cured by heat curing, adhesion of dirt or the like during the hardening step can be prevented, and the surface smoothness of the insulating layer after hardening can be raised upward. When peeling after hardening, it is preferred to apply a release treatment to the support in advance. Further, the resin composition layer formed on the support is preferably formed so that the area of the layer is smaller than the area of the support. When the resin composition layer is not adhered to the surface of the support, a plastic film similar to the support can be further laminated as a protective film. The protective film may be subjected to a release treatment in addition to the matte treatment and the corona treatment. Further, the release treatment can be carried out by using a release agent such as a polyoxyxylene resin release agent, an alkyd resin release agent or a fluororesin release agent. The thickness of the protective film is not particularly limited, but is preferably 1 to 40 m. By laminating the protective film, adhesion or damage to the surface of the resin composition layer can be prevented. Then, the film can be stored in a roll and stored. [Multilayer Printed Wiring Board Using a Film Next] A multilayer printed wiring board can be manufactured using the adhesive film manufactured as described above. Next, an example of the method will be described. When the resin composition layer is protected by the protective film, after peeling off, the resin composition layer is directly connected to the inner layer circuit substrate and laminated on the single side or both sides of the inner layer circuit substrate. The present invention-36-201202334 Next, in the film, a method of laminating on the inner layer circuit substrate under reduced pressure by a vacuum lamination method is preferred. The method of lamination can be batch or continuous in a roller. Further, before the lamination, the film and the inner layer circuit substrate may be preheated (plate heating) as needed. The inner layer circuit board in the present invention mainly refers to a single side or both sides of a substrate such as an epoxy glass, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate. A pattern is formed to form a conductor layer. Further, in the case of manufacturing a multilayer printed wiring board in which a conductor layer and an insulating layer are formed alternately and a conductor layer formed by patterning on one side or both sides is formed, an intermediate layer of the insulating layer and the conductor layer should be formed. Also included in the inner layer circuit substrate in the present invention. In the inner layer circuit board, the surface of the conductor circuit layer is subjected to roughening treatment by blackening treatment or the like in advance, and it is preferable from the viewpoint of the insulating layer to the inner layer circuit board. The conditions for the lamination are such that the pressing temperature (lamination temperature) is preferably 70 to 140 ° C, the pressing pressure is preferably 1 to 11 kgf/cm 2 (9.8 M 04 to 107.9 x 10 4 N/m 2 ), and the air pressure is 20 mmHg. (26.7hPa) It is better to laminate the layers under the reduced pressure below. The vacuum lamination can be carried out using a commercially available vacuum laminator. For the vacuum laminating machine, for example, a VACUUM APPLICATOR manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Nihon Seiki Co., Ltd., a drum-type dry coating machine manufactured by Hitachi Industrials, and a Hitachi AIC. (Share) vacuum laminator, etc. Further, the step of laminating heating and pressurizing under reduced pressure may be carried out using a vacuum hot press such as -37 to 201202334. For example, a metal plate such as a heated SUS plate can be pressed by pressing from the side of the support layer. The pressing conditions are preferably such that the degree of pressure reduction is lxl 0_2 MPa or less, and more preferably lxltr3 MPa or less. Although the heating and the pressurization can be carried out in one step, it is preferably carried out in two or more stages from the viewpoint of controlling the bleeding of the resin. The pressure applied in the first stage is in the range of 70 to 150 ° C, the pressure is in the range of 1 to 15 kgf/cm 2 , and the pressure in the second stage is in the range of 150 to 200, and the pressure is in the range of 1 to 40 kgf/cm 2 . Implementation is better. The time of each stage is preferably 30 to 120 minutes. For the vacuum hot press, for example, MNPC-V-750-5-200 (manufactured by Nippon Seiki Co., Ltd.), VH 1 - 1 603 (made by Kitagawa Seiki Co., Ltd.), etc. After laminating the inner layer circuit board, peeling is performed when the support is peeled off, and an insulating layer can be formed on the inner layer circuit board by thermal hardening. The heat hardening condition may be selected from the range of 20 minutes to 180 minutes at 150 ° C to 220 ° C, more preferably 30 to 120 minutes at 160 ° C to 200 ° C. After the formation of the insulating layer, peeling is performed at this time when the support is not peeled off before the hardening. Next, the insulating layer formed on the inner layer circuit substrate is opened to form a through hole and a through hole. The opening is performed by a known method such as a drill, a laser, a plasma, or the like, and may be carried out by combining these methods as necessary. Among them, it is preferable to use a laser opening such as a carbon dioxide gas laser or a YAG laser. Next, the surface of the insulating layer is subjected to a roughening treatment. The roughening treatment in the present invention is preferably carried out by a wet roughening method using an oxidizing agent. The oxidant side -38-201202334 may, for example, be permanganate (potassium permanganate or sodium permanganate), dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid or the like. It is preferably an oxidizing agent which is widely used for the roughening of an insulating layer in the production of a multilayer printed wiring board formed by a stacking method, and is an oxidizing agent using an alkaline permanganic acid solution (potassium permanganate or sodium permanganate). It is preferred to carry out roughening in an aqueous sodium solution or the like. Next, on the surface of the resin composition layer on which the anchor anchors which are convex and concave due to the roughening treatment are formed, a conductor layer is formed by a combination of electroless plating and electrolytic plating. Further, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. Further, after the formation of the conductor layer, the annealing strength of the conductor layer is further improved by annealing at 150 to 200 ° C for 20 to 90 minutes, and the stability can be stabilized. Further, in the method of patterning the conductor layer and forming the circuit, for example, a subtractive color method, a semi-additive method, or the like which is well known to those skilled in the art can be used. [Prepreg] The prepreg of the present invention is produced by impregnating the resin composition of the present invention with a sheet-like fibrous base material by a heat fusion method or a solvent method, and semi-hardening by heating. That is, the resin composition of the present invention can be a prepreg impregnated with a sheet-like fibrous base material. In the case of the sheet-like fibrous base material, it is preferred to use a fiber made of a conventional fiber as a prepreg fiber such as a glass cloth or a amide fiber. The heating and melting method does not dissolve the resin in an organic solvent, but temporarily coats the resin on a coated paper having good peelability from the resin, and laminates it on the sheet-like fibrous substrate or by slit coating. The cloth device is directly coated, etc. -39-201202334 to manufacture a prepreg. Further, the solvent method is a method in which a substrate is impregnated with a resin varnish obtained by dissolving a resin in an organic solvent, and a resin varnish is impregnated into a sheet-like fibrous substrate to be dried. [Multilayer printed wiring board using prepreg] A multi-plate can be manufactured using the prepreg system manufactured as described above. An example of the method will be described later. In the inner layer circuit, one sheet of the prepreg of the present invention or a plurality of sheets are overlapped as needed, and sandwiched by a metal plate, and pressurized under heating and heating conditions, and heating conditions are preferably at a pressure of 5 to 40 kgf/ Cm2 3 92 xl04N/m2), 20° at a temperature of 120 to 200° C. Similarly to the subsequent film, the prepreg can be heat-hardened by vacuum-sampling the circuit board. Then, as described above, the surface of the cured prepreg is roughened, and then the multilayer printed wiring board is produced by the plating layer. [Semiconductor device] Further, the device is used by using the multilayer printed wiring board of the present invention. The semiconductor device is manufactured by the connection electrode conductor element on the multilayer printed wiring board. The semiconductor element is not particularly limited, and examples thereof include wire bonding mounting, flip chip orientation conductive film (ACF) mounting, and non-conductive NCF mounting. Similarly, in the flaky fiber, the layer is printed on the wiring substrate, and the release film is laminated by pressure. (49 X1〇4 ~ 100 minutes) The method of laminating the layer is also applied to form a semi-mounting method for forming a semiconductor portion to be bonded, and the film is mounted on a film (-40-201202334, on the other hand, by the resin composition) A specific wiring layer is formed in the insulating layer to form a fine wiring trench. The term "fine wiring trench" means a line (wiring) / space (interval) = 1 / 5 / m / 15 m or less, wherein 12/zm/12ym or less is more preferable, and 10/zm/10#m or less is better and lower is better. In the past, in the manufacturing technology of a multilayer printed wiring board, it is known to make an insulating layer on a core substrate. In the method of manufacturing a stacking method in which the conductor layers are alternately stacked, for example, a layer of a curable resin is laminated on the inner layer circuit board by a film, and the curable resin composition is cured to form an insulating layer. The through hole is formed by indirect continuation of the formation layer, and the oxidant such as an alkaline potassium permanganate solution is used to remove the slag from the bottom of the through hole and roughen the insulating layer, and the semi-additive method is used for the non-electrolysis on the rough surface thereof. Plating forms a plated seed layer, followed by Electrolytic plating forms a conductor layer. Then, an unnecessary plating seed layer is removed by etching to form a circuit. On the other hand, as in the patent document (Japanese Patent Laid-Open Publication No. 2010-21 301) or non-patent document (Advancing MICROELECTRONICS 1 1/ 12 2007 P22), a method of directly forming a trench which is a wiring for an insulating layer using a laser is expected to be applied to fine wiring. This method is similar to the manufacturing method by the above-described deposition method. An insulating layer is formed on the inner circuit board, and a trench and a via hole which are wirings are formed on the insulating layer by using a laser. However, the particle size of the cerium oxide is not described. Further, the potassium permanganate is used. An oxidizing agent such as a solution removes the slag from the bottom of the through hole and roughens the insulating layer, and performs electroless plating and electrical plating on the rough surface thereof, and finally removes the unnecessary copper layer of the surface layer to form an electric circuit. The slag may also be a dry method such as plasma-41 - 201202334. However, in the step of removing the slag, when the insulating layer is roughened, the resin at the corner portion of the groove formed may be removed, and the resin may not be maintained.The rectangular shape and the wiring formed thereafter cannot be a problem of the set fine wiring. Here, the film having the metal film layer formed on the support layer is formed with a metal film or formed on the support layer. a metal film layer on which a metal film of a curable resin composition layer is further formed, followed by a film, and after a metal film layer is provided on the insulating layer, a laser is used on the metal film layer to form an insulating layer. When the wiring groove is formed, the insulating layer can be maintained in a rectangular shape even after the desmear is removed, and a fine wiring groove shape can be obtained. Hereinafter, a film with a metal film and a film with a metal film attached will be described. &lt;Support body layer&gt; The support layer has a self-supporting film or a sheet, and a metal foil, a plastic film or the like can be used, and in particular, a plastic film is suitable for use. Examples of the metal foil include aluminum foil, copper foil, and the like. When a metal foil is used as the support layer, when the film with the metal film does not have a release layer, a metal foil made of a metal different from the formed metal film layer can be used. Examples of the plastic film include polyethylene terephthalate film, polyethylene naphthalate, polyimide, polyamidimide, polyamine, polytetrafluoroethylene, polycarbonate, etc. Among them, a polyethylene terephthalate film or a polyethylene naphthalate film is preferred, and a cheap polyethylene terephthalate is particularly preferred. Further, the surface of the body layer can be subjected to surface treatment such as corona treatment. On the surface of the support film layer on the side of the metal film layer or the release layer, -42-201202334 may also be subjected to surface treatment such as matte treatment or corona treatment. The surface of the support layer on the side where the release layer is formed is an arithmetic mean roughness (Ra 値) of 50 nm or less (0 or more and 50 nm or less) from the viewpoint of preventing cracks in the production of the film with the metal film. It is preferably 40 nm or less, and further 35 nm or less, or even 3 Onm or less. The arithmetic mean roughness of the surface of the support layer on the side where the release layer is not formed is also preferably in the same range as described above. The measurement of the arithmetic mean roughness (Ra 値) can be carried out by a known method, for example, using a device such as a non-contact surface roughness meter (for example, WYKO NT3 300 manufactured by Veeco Instruments Co., Ltd.). The support system can be used by a commercially available one, and for example, T60 (manufactured by TORAY Co., Ltd., polyethylene terephthalate film), A4100 (made by Toyobo Co., Ltd., polyethylene terephthalate film) , Q83 (Dynasty DUPON film (stock), polyethylene naphthalate film), LINTEC (stock), alkyd type release agent (AL-5) pay # polyethylene terephthalate film, Diafoil (registered trademark) B100 (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., polyethylene terephthalate film). The layer thickness of the support layer is preferably 10 to 7 〇 vm, more preferably 15 to 70 # m. If the layer thickness is too small, the handleability is poor, the peelability of the support layer is lowered, or the condition β which is uncomfortable to form a smooth metal film layer is generated. If the layer thickness is too large, it is not practical in terms of cost. &lt;release layer&gt; The film with a metal film and the film with a metal film in the present invention are used to support the metal layer to be efficiently transferred to the surface of the object to be attached, and to support the body layer and the metal of -43-201202334 It is preferred to have a release layer between the layers. The release layer may be formed of a fluororesin, an alkyd resin, a polyoxymethylene resin, a polyolefin resin, a polyvinyl alcohol resin, an acrylic resin, a polyester resin, a melamine resin, a cellulose resin or the like to form a release layer. . As the release layer, a metal film or a metal foil formed by a vapor deposition method, a sputtering method, an ion plating method, or the like can be used. In terms of metal, aluminum, zinc, lead, nickel, etc. may be mentioned, but aluminum is preferred. The release layer is obtained from the viewpoint of uniformly transferring the metal film layer and the cost of forming the release layer. It is preferred to form one or more kinds of water-soluble polymer release layers selected from water-soluble cellulose resins, water-soluble acrylic resins, and water-soluble polyester resins. These water-soluble polymer barrier layers are more advantageous on the cost side than the metal release layer because they are easy to form a release layer on the support layer. Further, after the hardenable resin composition of the adherend is cured, the support layer can be peeled off between the support layer and the release layer, the metal film layer is not easily damaged, and the release layer remaining on the metal film layer can be easily used as an aqueous solution. The metal film is uniformly formed on the adherend. Among these, a water-soluble cellulose resin and a water-soluble polyester tree P are more preferable, and a water-soluble cellulose resin is more preferable. These may be used alone or in combination of two or more. Further, the water-soluble polymer release layer may have a multilayer structure formed of one or two or more layers of different water-soluble polymers. Further, in the case of the release layer, when a water-soluble polymer release layer is used, between the water-soluble polymer release layer and the support layer, in order to enhance the peeling property between the layers, the polyoxin may exist. A release layer other than a resin, an alkyd resin, a fluororesin or the like. That is, when a water-soluble high score is applied to the release layer, the surface layer of at least the metal film may be formed by a water-soluble polymer release layer. The type layer is formed only by a water-soluble polymer release layer, or is formed by a water-soluble polymer release layer on the surface of the metal film, so that the water-soluble polymer release layer and other release layers are formed. The two-layer structure is formed. When the water-soluble polymer release layer is used at least in the surface of the metal film, the cured resin composition of the adherend is cured, and the support layer is peeled off between the support layer and the release layer, and thereafter, the residue remains. The release layer on the metal film layer can be easily removed by an aqueous solution, and a metal film excellent in uniformity can be formed on the adherend. Further, when the support layer between the support layer and the release layer is peeled off, if the release layer is formed only by the water-soluble polymer release layer, it can be applied to the interface between the support and the water-soluble polymer release layer. When the release layer is composed of a release layer other than an alkyd resin or the like, and two layers of the water-soluble polymer release layer, the release layer may be at the interface between the other release layer and the water-soluble polymer release layer. The thickness of the layer of the release layer is preferably 0.01/zm or more and 20/zm or less, more preferably 0.05/m or more and 10#m or less, more preferably 0.1#m or more and 5/zm or less, and more preferably 0.1/zm or more. 3ym or less is better, O.iym or more 2 is less than m, 〇·1 μm or more and 1 vm is particularly good, 〇. 2 仁m is more than 1 A m. Here, the "layer thickness" is the thickness when the release layer is a single layer, and when it is a plurality of layers, it means the total thickness of the plurality of layers. For example, when the release layer is composed of a water-soluble polymer release layer and a release layer other than a polyoxymethylene resin, an alkyd resin, a fluororesin or the like, the total layer of the release layer is as described above. Thickness is set in the above range. The layer thickness of the water-soluble polymer other than the -45-201202334 type layer is preferably in the range of 0.01 to 〇.2 #m. If the layer thickness of the release layer is too thick, when the curable resin composition layer is thermally cured, the thermal expansion rate of the metal film layer and the release layer is different, which may cause discomfort such as cracks or damage to the metal film layer. Further, if the layer thickness is too thin, the peeling property of the support layer may be lowered. (Water-soluble cellulose resin) The term "water-soluble cellulose resin" as used in the present invention means a cellulose derivative obtained by subjecting cellulose to a treatment for imparting water solubility, preferably a cellulose ether. , cellulose ether ester, and the like. A cellulose ether is an ether formed by converting one or more hydroxyl groups present in an anhydrous glucose repeating unit of one or more cellulose polymers by giving one or more ether linking groups to the cellulose polymer, and is an ether. The linking group may be an alkyl group substituted with one or more substituents selected from a hydroxyl group, a carboxyl group, an alkoxy group (having a carbon number of 1 to 4), and a hydroxyalkoxy group (having a carbon number of 1 to 4). Carbon number 1 to 4). Specific examples thereof include a hydroxyalkyl group such as 2-hydroxyethyl group, 2-hydroxypropyl group or 3-hydroxypropyl group (carbon number 1 to 4); 2-methoxyethyl group, 3-methoxy group Alkoxy group (carbon number 1 to 4) alkyl group (carbon number 1 to 4); 2-(2-hydroxyethoxy group) of propyl group, 2-methoxypropyl group, 2-ethoxyethyl group or the like a hydroxyalkoxy group (carbon number: 1 to 4) alkyl group (carbon number: 1 to 4) such as ethyl or 2-(2-hydroxypropoxy)propyl group: a carboxyalkyl group such as a carboxymethyl group (carbon number 1) The ether linkage group in the polymer molecule of ~4) et al. may be a single species or a plurality of species. That is, it may be a cellulose ether having a single ether linkage, or a cellulose ether having a plurality of ether linkages. -46- 201202334 Specific examples of the cellulose ether include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, and hydroxyethyl Cellulose, carboxymethylcellulose, and such water-soluble salts (e.g., alkali metal salts of sodium salts, etc.). Further, the average number of moles of the ether group substituted per unit of the glucose ring in the cellulose ether is not particularly limited, but is preferably 1 to 6. Further, the molecular weight of the cellulose ether is preferably about 20,000 to 60000 by weight average molecular weight, and the cellulose ether ester means a hydroxyl group having 1 or more and 1 or more suitable organic acids present in the cellulose or An intermediate formed between the reactive derivatives and thereby forming an ester linkage in the cellulose ether. Further, the term "cellulose ether" as used hereinabove means that the "organic acid" contains a fat. An aliphatic or aromatic carboxylic acid (carbon number 2 to 8), and the aliphatic carboxylic acid may be acyclic (minutes). Dendritic or non-branched) or cyclic, saturated or unsaturated. Specific examples of the aliphatic carboxylic acid include substituted or unsubstituted acyclic rings such as acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, fumaric acid, and maleic acid. An aliphatic dicarboxylic acid; a non-cyclic hydroxy-substituted carboxylic acid such as glycolic acid or lactic acid; a non-cyclic aliphatic hydroxy group such as malic acid, tartaric acid or citric acid, or a di- or tri-carboxylic acid. Further, the aromatic carboxylic acid is preferably an aryl carboxylic acid having 14 or less carbon atoms, and a phenyl group or a naphthyl group having 1 or more carboxyl groups (for example, a carboxyl group of 1, 2 or 3). The aryl carboxylic acid is particularly preferred. Further, the aryl group may be the same or different one or more (for example, 1, 2 or 3) selected from a hydroxyl group, an alkoxy group having a carbon number of 1 to 4 (for example, a methoxy group) and a sulfonyl group. Replaced by the base. Preferred examples of the aryl-47-201202334-based carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid or trimellitic acid (1,2,4-benzenetricarboxylic acid). When the organic acid has a carboxyl group of 1 or more, it is preferred to form an ester linkage to the cellulose ether by only the oxime carboxyl group in the acid. For example, in the case of hydroxypropylmethylcellulose succinate, the 1 carboxy group of each succinate group is ester-linked to cellulose, and the other carboxyl groups are present as free acids. The "ester linkage" is formed by reacting cellulose or a cellulose ether with a preferred organic acid or a reactive derivative thereof. The preferred reactive derivative may contain an acid anhydride such as anhydrous phthalic acid. The ester linking group in the polymer molecule may be a single species or a plurality of species. That is, it may be a cellulose ether ester having a single ester linking group, or a cellulose ether ester having a plurality of ester linking groups. For example, hydroxypropylmethylcellulose acetate succinate is a mixed ester of hydroxypropylmethylcellulose having both succinate groups and acetate groups. Preferred cellulose ether esters are esters of hydroxypropylmethylcellulose or hydroxypropylcellulose, and specific examples thereof include hydroxypropylmethylcellulose acetate and hydroxypropylmethylcellulose succinic acid. Ester, hydroxypropyl methylcellulose acetate succinate, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose trimellitate, hydroxypropyl methylcellulose acetate Phthalate, hydroxypropylmethylcellulose acetate trimellitate, hydroxypropylcellulose acetate phthalate, hydroxypropylcellulose butyrate phthalate, hydroxypropyl The cellulose acetate phthalate succinate and the hydroxypropyl cellulose acetate trimellitate succinate may be used alone or in combination of two or more. Among these, hydroxypropylmethylcellulose-48-201202334 phthalate, hydroxypropylmethylcellulose acetate succinate, hydroxypropylmethylcellulose acetate phthalate Esters are preferred. Further, the average number of moles of the ester group substituted per unit of the glucose ring in the cellulose ether ester is not particularly limited, but is preferably, for example, about 0.5% to 2%. Further, the molecular weight of the cellulose ether ester is preferably about 20,000 to 60000 by weight average molecular weight. The method for preparing cellulose ether and cellulose ether ester is known, and can be obtained by reacting an etherifying agent or an esterifying agent according to a fixing method, which can be obtained by using natural cellulose (pulp) as a raw material, and can also be used in the present invention. Product. For example, "HP-55" and "HP-50" (both hydroxypropylmethylcellulose phthalate) manufactured by Shin-Etsu Chemical Co., Ltd. can be cited. (Water-Soluble Polyester Resin) The "water-soluble polyester resin" in the present invention is generally used as a main raw material by using a polyvalent carboxylic acid or an ester-forming derivative thereof and a polyhydric alcohol or an ester-forming derivative thereof. In the same manner as the polycondensation reaction, a polyester resin composed of a linear polymer is used, and a hydrophilic group is introduced in a molecule or at a molecular end. Here, the hydrophilic group may, for example, be an organic acid group such as a sulfo group, a carboxyl group or a decanoic acid group or a salt thereof, and a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof is preferred. The water-soluble polyester resin is particularly preferably a sulfo group or a salt thereof and/or a carboxyl group or a salt thereof. Representative examples of the polyvalent carboxylic acid component of the polyester resin include terephthalic acid, isophthalic acid 'phthalic acid, anhydrous phthalic acid, 2,6-naphthalene dicarboxylic acid, and 1,4. - cyclohexanedicarboxylic acid 'adipic acid, etc., and these may be used alone or in combination of two or more. Further, together with the above various compounds, an unsaturated carboxylic acid such as a hydroxycarboxylic acid such as P-hydroxybenzoic acid, maleic acid, fumaric acid or itaconic acid may be used in a small amount. Representative examples of the polyol component of the polyester resin include ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, and 1,6-hexanediol. 1,4-cyclohexane methanol, xylylene glycol, dimethylolpropionic acid, glycerol, trimethylolpropane or poly(tetramethyloxy) diol, etc. Two or more types can also be used. The polyester resin may be subjected to a method of introducing a hydrophilic group into a molecule or a molecular terminal, but a method of copolymerizing an ester-forming compound (for example, an aromatic carboxylic acid compound, a hydroxy compound, or the like) containing a hydrophilic group. It is better. For example, when a sulfonate group is introduced, sodium 5-sulfonate isophthalic acid, ammonium sulfonate isophthalic acid, sodium 4-sulfonate isophthalic acid, ammonium 4-methylsulfonate 1 or 2 selected from the group consisting of isophthalic acid, sodium 2-sulfonate terephthalic acid, potassium 5-sulfonate isophthalic acid, potassium sulfonate isophthalic acid and potassium 2-sulfonate terephthalic acid. It is preferred that the above is copolymerized. Further, when a carboxylic acid group is introduced, for example, anhydrous trimellitic acid, trimellitic acid, anhydrous pyroghuric acid, pyrophoric acid, trimesic acid, cyclobutanetetracarboxylic acid, and dihydroxyl It is preferred that one or more selected from the group consisting of propionic acid and the like are copolymerized, and after the copolymerization, the carboxylate is obtained by neutralizing with an amine compound, ammonia or an alkali metal salt or the like. The base is introduced into the molecule. The molecular weight of the water-soluble polyester resin is not particularly limited, and the weight average molecular weight is preferably from 10,000 to 40,000. When the weight average molecular weight is less than -50 to 201202334 10000, the layer formability is lowered, and if it exceeds 40,000, the solubility is lowered. In the present invention, a commercially available product can be used as the water-soluble polyester resin, and for example, "PLASCOAT Z-561" (weight average molecular weight: about 27,000) and "PLASCOAT Z-565" manufactured by Mutual Chemical Industry Co., Ltd. Weight average molecular weight: about 25,000) and the like. (Water-soluble acrylic resin) The "water-soluble acrylic resin" in the present invention is an acrylic resin which is dispersed or even dissolved in water by containing a monomer having a carboxyl group as an essential component. The acrylic resin is more preferably a monomer having a carboxyl group. And (meth) acrylate is an essential monomer component, and an acrylic polymer which may contain other unsaturated monomers as a monomer component as needed. Among the above monomer components, examples of the carboxyl group-containing monomer include (meth)acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, pyroic acid, anhydrous maleic acid, and maleic acid. Methyl ester, tributyl maleate, monomethyl ortho-methicone, and tributyl orthoate, and one or more of these may be used. Among these, (meth)acrylic acid is preferred. Further, examples of the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and η-butyl (meth)acrylate. Base ester, isobutyl (meth)acrylate, η-pentyl (meth)acrylate, η-hexyl (meth)acrylate, η-heptyl (meth)acrylate, (meth)acrylic acid Η- -51 - 201202334 octyl ester, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, The alkyl methacrylate having an alkyl group having an alkyl group of octadecyl (meth) acrylate or the like is 1 to 18, and one or more of these may be used. Further, examples of the other unsaturated monomer include an aromatic alkenyl compound, a vinyl cyanide compound, a conjugated diene compound, a halogen-containing unsaturated compound, and a hydroxyl group-containing monomer. The aromatic alkenyl compound may, for example, be styrene 'α-methylstyrene, p-methylstyrene or p-methoxystyrene. Examples of the vinyl cyanide compound include a conjugated diene compound such as acrylonitrile or methacrylonitrile, and examples thereof include halogen-containing unsaturated compounds such as butadiene and isoprene. Such as vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, vinylidene fluoride and the like. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy butyl. A (meth) acrylate, a 4-hydroxybutyl acrylate, a 4-hydroxybutyl methacrylate, an α-hydroxy group, a methyl ethyl (meth) acrylate, or the like. These may be used in one type or two or more types. As described later, in the present invention, the release layer is preferably formed by a method in which a coating liquid containing water-soluble cellulose, a water-soluble polyester or a water-soluble acrylic resin is applied and dried on a support layer. When a water-soluble acrylic resin is used, the coating liquid can be used in the form of an emulsion or an aqueous solution. When a water-soluble acrylic resin is used in the form of an emulsion, a core-shell type milk-52-201202334 agent is preferred, and in a core-shell type emulsion, it is important that a carboxyl group is present in the shell of the core-shell particle, and therefore, the shell contains It is composed of a monomer of a carboxyl group and an acrylic resin of (meth)acrylate. A commercial product may be used as the dispersion (emulsion) of such core-shell particles, and may be, for example, JONCRYL 7600 (Tg: about 35 ° C), 7630 A (Tg: about 53 ° C), and 53 8 J (Tg: about 66 °). C), 3 52D (Tg: about 56 ° C) (both are made by BASF Japan Co., Ltd.). When a water-soluble acrylic resin is used in the form of an aqueous solution, the acrylic resin contains a carboxyl group-containing monomer and a (meth) acrylate acrylic resin, and it is important that it is a lower molecular weight. Therefore, the weight average molecular weight is preferably from 1,000 to 50,000, and if the weight average molecular weight is less than 1,000, the layer formability is lowered, and if the weight average molecular weight exceeds 50,000, the adhesion to the support layer becomes high and hardens. The peelability of the back support layer is reduced. A commercially available product can be used as the aqueous solution of the water-soluble acrylic resin. For example, JONCRYL 354J (manufactured by BASF Japan Co., Ltd.) or the like can be used. Further, the emulsion of the water-soluble acrylic resin and the aqueous solution are easily thinned due to the high molecular weight of the emulsion. Therefore, an emulsion of a water-soluble acrylic resin is preferred. &lt;Metal film layer&gt; Metals used in the metal film layer may be metal mono-53 such as gold, platinum, silver, copper, aluminum, cobalt, chromium, nickel, titanium, tungsten, iron, tin, indium or the like. - 201202334 The body or the use of two or more kinds of metals such as nickel and chromium alloys. However, from the viewpoints of versatility, cost, and etching of metal film formation, it is based on Ming, 錬, 钦, 錬· Alloy copper, nickel alloy, copper alloy, gold, silver and copper are preferred, nickel, chromium alloy, aluminum, zinc, gold, silver and copper are better. Further, the metal film layer may be a single layer or a composite layer formed of a different metal. The layer thickness of the metal film layer is not particularly limited, and is preferably 1 Onm-good, 20 nm to 2000 nm, 30 nm to 100 nm, and more preferably 500 nm, more preferably 50 nm to 400 nm, and further 300 nm. If the layer thickness is too small, the film with the metal film is prone to cracks in the metal film, and in the desmear step or the like, the surface of the insulating layer is roughened. On the other hand, if the layer thickness requires a long time for film formation, the cost is high, and the time is at the laser force. &lt;Curable Resin Composition Layer&gt; The adhesive film with a metal film according to the present invention further has a structure in which a curable layer is formed on the metal film layer of the above film. That is, the metal film in the present invention further has a hardened layer in addition to the support layer and the metal film layer. Further, similarly to the film with a metal film, it is preferred to have a release layer between the support layers. A hardenable resin composition used in a thin film-attached resin composition layer with a metal film (alloy. Removal difficulty: aluminum, bell, chromium, nickel, titanium, and copper layer 2 layers, 5 OOOnm is better, 50 nm is better, 50 nm~ After the manufacture, the metal film layer is too large, and the metal composition also requires a resin film with a metal film to form a film and a resin layer and a metal film. Hard, if it is hard-54- 201202334 compound has sufficient hardness and insulation, there is no particular limitation in use, including (a) epoxy resin, (b) thermoplastic resin and (c) hardening The agent is preferably used. Others, the rubber particles, flame retardant, various resin additives, maleimide compound, bisallyl nadeimide compound, vinylbenzyl resin, ethylene may be used as described above. The benzyl ether ether resin, the bismaleimide-triazine resin, the acrylic resin, etc. (a) The epoxy resin is not particularly limited, and examples thereof include a bisphenol A type epoxy resin and a biphenyl type ring. Oxygen resin, naphthol type epoxy resin, naphthalene ring Oxygen resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac epoxy resin, cresol Novolac type epoxy resin, bisphenol A novolac type epoxy resin, epoxy resin having butadiene structure, cyclohexane dimethanol type epoxy resin, epoxypropyl amine type epoxy resin, bisphenol Diepoxypropyl etherate, diepoxypropyl etherate of naphthalenediol, epoxy propyl etherate of phenol, and diepoxypropyl etherate of alcohol and alkylene of such epoxy resin (1) Epoxy resin, such as heat resistance, insulation reliability, tortuosity, and the like, may be used as the base, the halide, the hydride, and the like. From the viewpoint of the adhesion of the metal film, it is a bisphenol A type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and an epoxy having a butadiene structure. The resin is preferably a liquid bisphenol A type epoxy resin (Japanese Epoxy Resin Co., Ltd.) "picoat 828EL"), naphthalene type 2-functional epoxy resin ("HP4032", "HP4032D" manufactured by Dainippon Ink Chemical Industry Co., Ltd.), naphthalene type -55- 201202334 4-functional epoxy resin (Daily Ink Chemical Industry Co., Ltd. "HP4700"), naphthol type oxime resin ("Esnmhv" manufactured by Tohto Kasei Co., Ltd.), epoxy resin having a butadiene structure ("PB-36 00" manufactured by DAICEL Chemical Industry Co., Ltd.), Epoxy resin having a biphenyl structure ("NC300 0H", "NC3000L" manufactured by Nippon Kayaku Co., Ltd., "YX4000" manufactured by Nippon Epoxy Co., Ltd.), etc. Curability in the curable resin composition The content of the component (a) in the resin composition is not particularly limited, but the upper limit of the content of the component (a) in the curable resin composition is from the viewpoint of preventing the flexibility of the film from being reduced. The non-volatile content of the resin composition is preferably 60% by mass, more preferably 50% by mass, and even more preferably 40% by mass. On the other hand, in the curable resin composition (a) The lower limit of the content of the component, if the insulating layer is used From the viewpoint that the glass transition temperature is increased upward and the thermal expansion rate of the wire is lowered, the curability is preferably 5% by mass, more preferably 10% by mass, based on the non-volatile content of the resin composition. 15% by mass is better. (b) The thermoplastic resin is not particularly limited, and examples thereof include a phenoxy resin, a polyvinyl acetal resin, a polyimine resin, a polyamidimide resin, a polyether quinone resin, and a polyfluorene. Resin, polyether oxime resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, and the like. These may be used alone or in combination of two or more. Among these, a phenoxy resin or a polyvinyl acetal resin is preferred from the viewpoint of imparting moderate flexibility to the cured product. (b) The thermoplastic resin is preferably -56-201202334 in which the glass transition temperature is 80 °C or higher. Here, the "glass transition temperature" is determined according to the method described in JIS κ 7197. Further, the glass transition temperature is higher than the decomposition temperature, and when the glass transition temperature is not actually observed, the decomposition temperature can be regarded as the glass transition temperature in the present invention. In addition, the decomposition temperature is defined by the temperature at which the mass reduction rate is 5% as measured according to the method described in JIS Κ 7120. (b) The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000, more preferably in the range of 10,000 to 150,000, more preferably in the range of 15,000 to 100,000, and even better in the range of 20,000 to 80,000. . If it is smaller than this range, the film forming ability or the mechanical strength upward effect may not be sufficiently exhibited. If it is larger than this range, the compatibility with the cyanate resin and the epoxy resin may be lowered, and the surface of the insulating layer may be roughened. The thickness will increase. Further, the weight average molecular weight in the present invention is measured by a colloidal permeation chromatography (GPC) method (in terms of polystyrene). The weight average molecular weight measured by the GPC method is, in particular, LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-8 00P/K-804L manufactured by Showa Denko Co., Ltd. /K-804L is a column, and the mobile phase is measured using a chloroform or the like at a column temperature of 40 ° C, and is calculated using a standard polystyrene calibration line. Examples of the phenoxy resin include a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, an anthracene skeleton, and a dicyclopentadiene. Skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, trimethylcyclohexane skeleton -57-201202334 One or more kinds of skeletons selected. The phenoxy resin may be used in combination of two or more. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. For the commercially available product, for example, 1256, 4250 (phenoxy resin containing a bisphenol A skeleton) made of Japanese epoxy resin, and YX8100 (a phenoxy resin containing a bisphenol S skeleton) made of Japanese epoxy resin. , YX6954 made of Japanese epoxy resin (phenoxy resin containing bisphenol acetophenone skeleton) or other FX280, FX293, 曰 环氧树脂 环氧树脂 环氧树脂 YL YL75 53 ' YL6954, YL6794, YL7213 made by Dongdu Chemical Co., Ltd. , YL7290, YL7482, etc. Specific examples of the polyvinyl acetal resin include S-LEC BH manufactured by Denki Butyral 4000-2, 5000-A, 6000-C, 6000-EP, and Sekisui Chemical Industry Co., Ltd. Series, BX series, KS series, BL series, BM series, etc. Specific examples of the polyimide resin include RIKACOAT SN20 and RIKACOAT PN20 manufactured by Nippon Chemical and Chemical Co., Ltd. Further, a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (described in JP-A-2006-3 7083) and a polyoxyalkylene skeleton are mentioned. A modified polyimine such as a polyimine (described in JP-A-2002- 12667, JP-A-2000-3, 193, etc.). Examples of the polyamidimide resin include a polyamidoquinone imine "VYLOMAX HR1 1NN" and "VYLOMAX HR1 6NN" manufactured by Toyobo Co., Ltd. Further, modified polyamidoquinone imines such as polyacrylamide skeletons "KS9100" and "KS9300", which are made of a polyoxyalkylene skeleton, manufactured by Hitachi Chemical Co., Ltd., may be mentioned. -58- 201202334 Specific examples of the polyether maple resin include polyether maple "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of the poly-Maple resin include a polypethane "P1700" and a ΓP3500 manufactured by SOLVAY Advanced Polymers Co., Ltd. In the curable resin composition, the content of the (b) thermoplastic resin is not particularly limited, but the amount of the nonvolatile component in the curable resin composition is preferably from 0.5 to 20% by mass, more preferably Good for 1~1〇% by mass. (b) When the blending ratio of the thermoplastic resin is less than 0.5% by mass, the resin composition has a low viscosity, and it is difficult to form a uniform curable resin composition layer. When it exceeds 20% by mass, the viscosity of the resin composition changes. It is too high to be buried in the wiring pattern on the substrate. (c) The curing agent is not particularly limited, and examples thereof include an amine curing agent, an oxime curing agent, an imidazole curing agent, a benzene curing agent containing a triazine skeleton, a phenol curing agent, and a triazine skeleton. Naphthol-based curing agent, naphthol-based curing agent, acid anhydride-based curing agent, or such epoxy group addition or microencapsulation, cyanate-based curing agent, active ester-based curing agent, benzoxazine It is a hardener or the like. From the viewpoint of increasing the peeling strength of the plating, it is preferable that the hardener has a nitrogen atom in the molecular structure, and a bifunctional phenol containing a quinone imine skeleton or a phenol system containing a triazine skeleton. A hardener or a naphthol-based hardener containing a triazine skeleton is preferred, and a bisphenol having a quinone imine skeleton or a phenol novolak resin containing a triazine skeleton is preferred. These may be used alone or in combination of two or more. Specific examples of the phenolic curing agent, the phenolic curing agent containing a triazine skeleton, and the naphthol-based curing agent include, for example, MEH-7700, MEH-7810, -59-201202334 MEH-7851 (B-month and Huacheng) )), NHN, CBN, GPH (Nippon Chemical Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN3 75, SN395 (Dongdu Chemical Co., Ltd.), TD2090, LA7052, LA7054, LA3018, LA1356 (Daily Ink Chemical Industry Co., Ltd.), etc. The cyanate-based curing agent, the active ester-based curing agent, and the benzoxazine-based curing agent can be used as described above. (a) The ratio of the epoxy equivalent of the epoxy resin to the active hydrogen equivalent of the hardener is preferably (1:0.2) to (1:2), (1:0_3) to (1:1.5). Better, (1 : 0.4 ) ~ (1 : 1 ) is even better. When the equivalent ratio is outside the above range, the mechanical strength or water resistance of the cured product is lowered. The curable resin composition may contain the curable resin composition more efficiently from the viewpoint of more effectively curing the curable resin composition. (d) a hardening accelerator. (d) The curing accelerator is not particularly limited, and examples thereof include a metal-based hardening accelerator, an imidazole-based curing accelerator, an amine-based curing accelerator, an organic phosphine compound, and an organic squara salt compound. In a specific example, the above-mentioned recorder can be used. (d) The content of the hardening accelerator is preferably the content described above. In the curable resin composition, in order to further reduce the thermal expansion ratio of the insulating layer obtained from the curable resin composition, (e) an inorganic cerium filler may be contained. The inorganic cerium filling material is not particularly limited, but examples thereof include cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and nitrogen. Boron, aluminum borate, barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, oxidized -60-201202334 titanium, barium zirconate, calcium zirconate, etc., of which cerium oxide is preferred. Among these, amorphous cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, pulverized cerium oxide, hollow cerium oxide, spherical cerium oxide, and molten cerium oxide are preferred. Spherical cerium oxide is preferred. These may be used alone or in combination of two or more. (e) The average particle size of the inorganic ruthenium material is not particularly limited. From the viewpoint of forming a fine wiring groove toward the insulating layer and improving the workability by laser, it is 5/zm or less. Good, 2.5//m or less is better, lym is better and below, 〇.7&quot;m is better and below, 〇5//m is better and below, and 0.45/zm is especially good. In addition, when the average particle diameter of the inorganic cerium material is too small, when the curable resin composition is used as a resin varnish, the viscosity of the varnish increases, and the operability is lowered and the dispersibility is improved. The average particle diameter is preferably 0.02 am or more, more preferably 0.05/zm or more, more preferably 0.1/zm or more, and even more preferably 0.2/zm or more. (e) The average particle size of the inorganic cerium material is measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic cerium material was determined on a volume basis by a laser diffraction type particle size distribution measuring apparatus, and the median diameter was measured as an average particle diameter. It is preferable to use a sample in which the inorganic cerium is dispersed in water by ultrasonic waves. For the laser diffraction type particle size distribution measuring apparatus, a LA-500 manufactured by a market can be used. (e) The upper limit of the amount of the inorganic cerium filler added, from the viewpoint of preventing the cured product from becoming brittle and avoiding the decrease in the adhesion strength of the curable resin composition -61 - 201202334, when the curable resin composition is not When the volatile component is 100% by mass, it is preferably 70% by mass or less, more preferably 65% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, still more preferably 50% by mass or less. On the other hand, the lower limit of the amount of the inorganic cerium filler added is 5% by mass when the nonvolatile content in the curable resin composition is 100% by mass from the viewpoint of lowering the thermal expansion ratio of the insulating layer. Preferably, it is more preferably 10% by mass, more preferably 20% by mass, more preferably 30% by mass, still more preferably 40% by mass, and even more preferably 50% by mass. (e) the inorganic ruthenium is a decane-based coupling agent, an acrylate-based decane coupling agent, a sulfide-based decane coupling agent, a vinyl-based decane coupling agent, a mercapto decane-based coupling agent, a styryl-based decane coupling agent, A surface treatment agent such as an isocyanate-based decane coupling agent, an organic ruthenium-nitrogen compound, an epoxy decane coupling agent, an amino decane coupling agent, a urea-based decane coupling agent, or a titanate coupling agent is surface-treated to make it moisture-resistant Sexuality and dispersibility are better. These may be used alone or in combination of two or more. Examples of the surface treatment agent include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropyldiethoxymethyldecane, and N-phenyl- 3-aminopropyltrimethoxydecane, N-methylaminopropyltrimethoxydecane, N-2 (-aminoethyl)-3-aminopropyltrimethoxydecane, N-( 2 - an amine decane-based coupling agent such as -aminoethyl)-3-aminopropyldimethoxymethyl decane; a urea-based decane coupling agent such as 3-ureidopropyltriethoxy decane; - glycidoxypropyltrimethoxydecane, 3-epoxypropyloxypropyltriethoxydecane, 3-epoxypropyloxypropylmethyldiethoxydecane, 3- Epoxypropyloxypropyl (dimethoxy)methyl decane, epoxy propyl butyl-62- 201202334-trimethoxy decane '2-(3,4-epoxycyclohexyl)ethyl decane, etc. Epoxy decane-based coupling agent; 3-mercaptopropyltrimethyl, 3-mercaptopropyltriethoxydecane, 3-mercaptopropylmethyldialkyl, 11-decylundecyltrimethoxy a mercapto group such as decane: methyltrimethoxydecane, octadecyltrimethoxydecane, a decane-based alkenyl trimethoxy decane, vinyl triethoxy decane, ethylene such as decane, methacryloxypropyltrimethoxy decane, triazine decane, t-butyltrimethoxy decane or the like a vinyl decane coupling agent such as ethoxy decane; a styrene based decane coupling agent such as p-styryl decane; 3-propenyl methoxy methoxy decane, 3-methyl propylene methoxy propyl trimethyl Oxyalkyl propylene methoxy propyl dimethoxy decane, 3-methyl propylene hydride triethoxy decane, 3-methyl propylene methoxy propyl di ethoxy acrylate decane coupling agent: 3 - isocyanate propyl trimethoxy isocyanate decane coupling agent; sulfane coupling agent such as bis(triethoxymethyl propyl propionate, bis (triethoxy decyl propyl) tetrasulfide; hexamethyldiazine Nitrogen, 1,3-divinyl-1,1,3, diazoxide, hexaphenyldiazane nitrogen triterpenoid nitrogen, cyclotriazole nitrogen, 2, hexamethylcyclotriazide nitrogen, octamethyl ring Tetrazolium, hexabutyldiindenyl diazide, 1,3-diethyltetramethyldiazide, 1,3-di-n-diazonium, 1,3-diphenyltetra Base two nitrogen, 1 , 3-dimethyl diazide nitrogen, 1,3-diethyltetramethyl diazide nitrogen, 1,1,3,3-tetradimethyl diazide nitrogen, 1,3-dipropyltetramethyl a trimethoxyoxydecane methoxy oxime coupling agent phenyl trimethazine decane mixture such as argon nitrogen, hexamethyl nitrogen, dimethylaminotrimethyl hydrazine nitrogen, tetramethyl diazide nitrogen or the like; ethyl methyl two a base of a decane such as a trimethoxypropyltrioxane or a 3-methoxypropyl decane. The disulfide system is ruthenium, 3-tetramethyl 2,4,4,6,6-nitrogen, hexacytene. Tetramethyltetraphenylphenyl-1,3-ylcyclotriphenylorganoindole nitrogen-63- 201202334 compound; tetra-n-butyl titanate dimer, titanium-i-propoxyoctyl glycolate Salt, tetra-n-butyl titanate, titanium octate glycolate, titanium diisopropoxy bis(triethanolamine), titanium dihydroxydilactic acid, dihydroxybis(ammonium lactate) titanium, bis(dioctyl) Ethyl pyrophosphate) ethylene titanate, bis(dioctylpyrophosphate)oxyacetate titanate, tris-n-butoxystea monostearate, tetra-n-butyl titanate, tetra 2-ethylhexyl) titanate, tetraisopropylbis(dioctylphosphite) titanic acid Tetraoctyldi(ditridecylphosphite) titanate, tetrakis(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanic acid Ester, isopropyl trioctyl decyl titanate, isopropyl triisopropyl phenyl titanate, isopropyl triisostearate titanate, isopropyl isostearyl decyl propylene Acid ester, isopropyl dimethyl propylene isostearyl decyl titanate, isopropyl tris(dioctylphosphoric acid) titanate, isopropyl stilbene-dodecyl benzene sulfonate titanate, A methacrylate-based coupling agent such as isopropyl ginate (dioctylpyrophosphate) titanate or isopropyl tris(indole-nonylaminoethylaminoethyl titanate). The curable resin composition is not particularly limited, but preferably contains the component (a), preferably contains the component (a) and the component (b), and contains the component (a) and the component (b) and (c). The composition is better, and the components (a) and (b) and (c) and (d) are further preferably. The method of preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of mixing a compound, a solvent, and the like, and mixing using a rotary mixer or the like. Among them, from the viewpoint of effectively dispersing the inorganic cerium material, it is preferred to carry out the dispersion treatment by a high-pressure homogenizer. The resin composition can be dispersed by a high-pressure homogenizer, -64-201202334 From the viewpoint of shortening the treatment time, a part of the resin composition is prepared into a suspension, which is then subjected to dispersion treatment by a high-pressure homogenizer, and then the remaining resin composition is additionally mixed and stirred to prepare The resin composition varnish is preferred. Further, in the dispersion treatment by the high-pressure homogenizer, the temperature of the composition rises, and the residual resin composition is subjected to dispersion treatment by a high-pressure homogenizer, such as an epoxy hardener. Adding is better. In the present invention, when a suspension is prepared, a known stirring and heating dissolution apparatus can be used. However, in order to dissolve it uniformly, a stirring and heating dissolution apparatus equipped with a high-speed rotary wing such as a homogenizer or a dispersion wing can be used. It is better. Specific examples of the stirring and heating dissolving device include TKHOMOMIXER, TKHOMODISPER, TKCombi Mix, TKHIVIS DISPER MIX, (the above are PRIMIX (trade name), and CLEARMIX (M TECHNIQUE). Vacuum emulsification stirring device (product name of MIZUHO Industrial Co., Ltd.), vacuum mixing device "NERIMAZE DX" (MIZUHO Industrial Co., Ltd. - trade name), BDM2 axis MIXER, CDM core 2 axis MIXER, PD MIXER ( The above is the name of the product produced by Inoue Co., Ltd.). The stirring temperature varies depending on the solvent used, but it is preferable to apply it in the range of 30 °C to 80 °C. The viscosity of the suspension is preferably from 10 to 100 mP a.s, preferably from 100 to 500 mPa's. When the viscosity is high, the viscosity of the liquid suppresses the diffusion of particles in the conflicting portion, and the dispersion tends to be uneven as a whole. Further, the viscosity can be measured by a rotary viscometer such as an E-type viscometer. The content of the inorganic cerium filling material in the suspension is preferably the mass % of the suspension i 而 -65-201202334, preferably 30 to 60% by mass, more preferably 40 to 60% by mass. If it is less than 30% by mass, the chance of particles of the inorganic cerium filling material colliding with each other is reduced, and sufficient shearing force cannot be obtained, resulting in insufficient dispersion treatment by a high-pressure homogenizer. If it exceeds 60% by mass, the conflicting portion The amount of inorganic ruthenium filling in the unit area is increased, and the dispersion treatment by the high-pressure homogenizer is insufficient, and the wear of the conflicting parts of the high-pressure homogenizer becomes more intense. The suspension prepared as described above can be dispersed by a high pressure homogenizer. The high-pressure homogenizer is a device that pulverizes, disperses, and emulsifies by pressurizing the raw material to a high pressure and using a shear force when the slit (gap) is removed. In the case of the high-pressure homogenizer, it is preferable that the material of the inorganic ruthenium material which is in conflict with the high pressure is made of tungsten carbide or diamond, and it is preferable because the foreign matter due to collision wear can be prevented from entering. In addition, because the treatment of the high-pressure homogenizer is not carried out in a batch dispersion manner, but in a continuous dispersion manner, the productivity is improved upwards, the risk of organic solvent vapor emission can be reduced, and the cost side can be reduced. The burden of the environment. Specific examples of the high-pressure homogenizer include a high-pressure homogenizer made of engineering (unit), a high-pressure homogenizer made by IZUMI FOOD MACHINERY, and a high-pressure homogenizer made by Niro Soavi (Italy). The dispersion pressure of the high-pressure homogenizer is preferably 10 to 300 MPa, more preferably 15 to 100 MPa, more preferably 20 to 60 MPa, and if the dispersion pressure is too low, the dispersion treatment may be insufficient, but if it is too high, the suspension liquid is too high. The temperature will rise and the components in the suspension will react and the shape of the inorganic cerium will change. In order to suppress the reaction of the components in the suspension, it is preferred that the liquid temperature after the dispersion treatment is 60 ° C or lower. Further, after the dispersion treatment, it is preferable to rapidly lower the liquid temperature to 40 ° C or less by using a cooling device of -66 - 201202334. For the apparatus which mixes the suspension which disperse|distributed by the high-pressure homogenizer, and the components which are the temperature-affecting components, such as the epoxy hardening agent which is a residual resin composition, it is used, for example, the Known agitation mixing devices such as propeller blades and fixed anchor blades. Specific examples of the stirring and mixing device include PLANETARY MIXER, TRI-MIX, and BUTTERFLY MIXER (the above is a product name manufactured by Inoue Co., Ltd.), VMIX stirring tank, MAXBLEND, and SWIXE RMIXING SYSTEM (above: IZUMI FOOD) Product name: MACHINERY, Hi-FMIXER (commodity name of TECNIX), JET AJITER (product name of Shimazaki Manufacturing Co., Ltd.). Further, the stirring and heating dissolving device described above can be used, and it can be carried out in a general stirring operation. In order to remove foreign matter in the resin composition varnish and secondary agglomerates of the inorganic ceramium, it is preferred to subject the resin composition varnish to filtration treatment after being dispersed by a high-pressure homogenizer. A well-known method can be used for the filtration method. For example, the resin composition varnish is used to quantitatively pump the liquid, and it is filtered separately or continuously through a card filter, a capsule filter or the like. The filtration pressure (differential pressure) at this time is preferably 〇4 MPa or less in order to avoid opening the filter mesh. Further, a known pumping system can be used, but in order to maintain a constant filtration pressure, it is preferred that the pulsation is small. The mesh size of the furnace is preferably ~30/zm. Further, the curable resin composition layer may be a prepreg in which the above-mentioned curable resin composition is impregnated into the sheet-like fibrous base material. For the flaky fiber substrate, for example, glass cloth or amide fiber, which is commonly used as a fiber for prepreg, can be used. In the prepreg system, the curable resin composition is impregnated into the sheet-like fibrous base material by a heat fusion method or a solvent method, and is formed by semi-hardening by heating. Further, the heat-melting method does not dissolve the resin composition in the organic solvent, but temporarily applies the resin composition to the coated paper which is excellent in peelability from the resin composition, and laminates it on the sheet-like fibrous substrate. Or a method of manufacturing a prepreg by directly coating a slit coater or the like. Further, the solvent method is a method in which a flaky fiber substrate is impregnated with a varnish obtained by dissolving a resin composition in an organic solvent, and the varnish is impregnated into a sheet-like fibrous base material, followed by drying. In the adhesive film with a metal film used in the present invention, the thickness of the curable resin composition layer varies depending on the thickness of the inner layer circuit conductor layer, etc., but from the viewpoint of improving the insulation reliability between the layers, etc., It is preferably from 1 0 to 150 μm and more preferably from 15 to 80/im. &lt;Method for Producing Film with Metal Film and Film Attached to Metal Film&gt; The method for producing the film with a metal film and the film for attaching a metal film used in the present invention is not particularly limited, but the following method is good. A film with a metal film, for example, a metal film layer formed on the support layer. When the release layer is provided, the metal layers are formed first, and then the release layer is formed on the surface of the support layer, and a metal film layer is formed on the surface of the release layer. The method for forming the release layer is not particularly limited, and a known lamination method such as hot pressing, hot roll lamination, extrusion lamination, application/drying of a coating liquid, or the like can be employed, but it is simple and easy to form a property having high uniformity. From the point of view of the layer, etc. -68-201202334, it is preferred to apply a coating liquid containing a material used in the release layer and dry it. The formation of the metal film layer is preferably carried out by one or more methods selected by a vapor deposition method, a sputtering method, or an ion plating method, and is particularly formed by a vapor deposition method and/or a sputtering method. good. These methods can be used in combination, or any method can be used alone. A vapor deposition method (vacuum vapor deposition method) may be a known method. For example, the support may be placed in a vacuum vessel, and the metal may be heated and evaporated onto the support (when the release layer is provided, the release layer) Upper) The formation of a film. A known method can be used for the sputtering method. For example, the support can be placed in a vacuum vessel, an inert gas such as argon or the like can be introduced, and after the application of a direct current voltage, the ionized inert gas collides with the target metal by being knocked. The metal is formed on the support (on the release layer when the release layer is formed). The formation of the film can also be carried out by a known method. For example, the support can be placed in a vacuum container for glow. In a discharge atmosphere, the metal is heated and evaporated, and the film is formed on the support by the ionized evaporated metal (on the release layer when the release layer is provided). The adhesive film with a metal film can be produced by forming a curable resin composition on the surface of the metal film layer after the step of forming the metal film layer of the film with the metal film. The method of forming the curable resin composition layer can be carried out by a known method, for example, by dissolving a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish to a resin by a slit coater or the like. On the metal film layer of the film of the metal film, the organic solvent is dried by heating or hot air-69 - 201202334 to form a resin composition layer, and the organic solvent may, for example, be acetone or methyl ethyl. Ketones, ketones, etc.; acetates such as ethyl acetate, butyl acetate, ceramide acetate monomethyl ether acetate, carbitol acetate, etc. Alcohols; hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrole. The organic solvent may be used alone or in combination of two or more. The drying conditions are not particularly limited, but the content of the agent in the resin composition layer is preferably 10% by mass or less and preferably 5% by mass. The amount of the organic solvent in the varnish is preferably such that the varnish containing 30 to 60% by mass of the organic solvent is dried at 50 to 30 for 10 to 10 minutes due to the boiling point of the organic solvent to form a resin composition layer. Further, a film of a metal film is formed by disposing a film of a metal film on a support to form a layer of a curable resin composition, and then thinning the film of the metal film and the adhesive film to form a film of a metal film. The method in which the layer contact is applied under heating conditions. Further, when the curable resin composition layer is a prepreg, it may be laminated on the support layer by, for example, a vacuum lamination method. Then thin is manufactured by a known method. Next, the support layer and the resin composition layer of the film are the same as described above. The bonding is performed by hot pressing, hot rolling, or the like. Heating: preferably 60 to 140 ° C, more preferably 80 to 120 ° C. The pressure system 111{20.1112 (9.8\104~107.9 parent 1041^/1112) is better in the production of cyclohexanone ester, C: anthraquinone, etc., but the organic solvent is more different, but ^ 1 5 0 °C, the film, and the hardening method to prepare the prepreg film system can be used to adjust the temperature of the tree to 1~-70-, 2~201202334 7kgf/cm2 (19.06xl04~68.6xl04N/m2) The range is better. &lt;Manufacturing Method of Multilayer Printed Wiring Board Using Film Attached with Metal Film or Adhesive Film Attached to Metal Film&gt; Multilayer printing can be manufactured using a film of a metal film or a film attached with a metal film manufactured as described above Wiring board. An example of the method is described below. In addition, the "inner layer circuit board" has a single surface or both sides of a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The conductor layer of the type of processing, even if it is an intermediate product in which an insulating layer and a conductor layer are to be formed, and when a film with a metal film is used, the layer of the curable resin composition may be used as a bonding surface, and laminated on the inner layer. On the circuit board. On the other hand, when a film with a metal film is used, the metal film layer is laminated on the surface of the curable resin composition layer which is interposed between the film of the metal film and the inner layer circuit substrate. For the formation of the curable resin composition layer on the inner layer circuit board, a known method can be used, for example, a thin film formed of a layer of a curable resin composition layer on the support layer as described above is laminated on the inner layer circuit substrate. And, by removing the support layer, the curable resin composition layer can be formed on the inner layer circuit substrate. The layering conditions of the film are the same as those of the film of the metal film to be described later. When a prepreg is used as the curable resin composition layer, the multilayer prepreg layer formed by laminating a single prepreg or a plurality of prepregs is laminated on the substrate - 71 - 201202334 laminated body The prepreg of the single-sided or double-sided surface layer is laminated so that the metal film of the film with the metal film is laminated on the surface of the prepreg. The laminate of the film of the metal film and the film of the metal film is laminated on the surface of the object to be attached by a roll or a pressing force, in view of workability and ease of obtaining the same contact state. Among them, it is preferred to carry out lamination under reduced pressure by a vacuum lamination method. Further, the method of laminating can be carried out in batch or in a continuous manner by a roller. The heating temperature is preferably 60 to 140 ° C, more preferably 80 to 120 ° C. The pressing pressure is preferably in the range of 1 to 11 kgf/cm 2 (9·8 χ 104 to 107.9 x 10 4 N/m 2 ), and 2 to 718 Å. 1112 (19.6\104~68.6 The range of &lt;104&gt;^/1112) is particularly good. It is preferable to laminate the layer under a reduced pressure of 20 mmHg (26.7 hPa) or less under an air pressure. The vacuum lamination can be carried out using a commercially available vacuum laminator. For example, a vacuum laminating machine MVLP-500 manufactured by Nippon Seiki Co., Ltd., a VACUUM APPLICATOR manufactured by Nichigo-Morton Co., Ltd., and a drum type dry type manufactured by Indicas Industrial Co., Ltd. Coating machine, Hitachi AIC (stock) vacuum laminator, etc. Further, the step of laminating heating and pressurizing under reduced pressure can be carried out using a general vacuum hot press. For example, it can be carried out by pressing a metal plate such as a heated SUS plate from the side of the support layer. The pressure-receiving condition is preferably such that the degree of pressure reduction is lxl (T2 MPa or less is preferably 1 x 10 '3 MPa or less. Heating and pressurization are performed in one stage, but from the viewpoint of controlling resin bleeding, 2 It is better to enter the conditions above -72-201202334. For example, the pressure applied in the first stage is 70~150. (:, the pressure is in the range of 1~1 5kgf/cm2, and the second stage is applied. The pressure is preferably in the range of 150 to 200 ° C and a pressure of 1 to 40 kgf / cm 2 . The time in each stage is preferably 30 to 120 minutes. Commercially available vacuum hot presses can be exemplified. For example, MNP CV-7 5 0-5-200 (manufactured by Nihon Seiki Co., Ltd.), VH 1 - 1 603 (made by Kitagawa Seiki Co., Ltd.), etc. The film with the metal film attached to the film or the metal film is laminated. After the inner layer circuit board, the curable resin composition layer is cured to form an insulating layer. The curing conditions vary depending on the type of the curable resin, etc., but the curing temperature is 120 to 200 t and the curing time is 15 to 90 minutes. In addition, from the viewpoint of preventing wrinkles on the surface of the formed insulating layer, it is The hardening temperature is hardened stepwise to a high hardening temperature, or it is hardened by raising its temperature. The removal of the support layer can generally be carried out by mechanical peeling by a manual or automatic peeling device. When the foil is used for the support layer, the support layer can be removed by etching. The support layer is preferably removed after the hardening treatment of the curable resin composition layer to form the insulating layer. When the support layer is removed before the hardening treatment, The metal film layer is not sufficiently adhered, and even after the hardening resin composition layer is hardened, cracks may occur on the metal film layer. There is a release layer between the support layer and the metal film layer, and the release layer is removed after the support layer is removed. When the metal film layer remains on the metal film layer, the release layer is removed. The support layer and/or the release layer may be removed before or after the step of forming the wiring trench by laser, but the wiring may be formed in the laser. Step forward behavior of the groove -73- 201202334 Good. Removal of the release layer, if it is a metal release layer, it is preferably removed by dissolving the metal etching solution. The molecular release layer is preferably removed by aqueous solution. Further, in terms of the release layer, the water solubility of one or more selected from the group consisting of water-soluble cellulose resin, water-soluble acrylic resin, and water-soluble polyester resin is high. When the molecular resin is used as the release layer, the aqueous solution for dissolving and removing the release layer is preferably made of 0.5 to 10% by mass of sodium carbonate, sodium hydrogencarbonate, sodium hydroxide or potassium hydroxide. An alkaline aqueous solution or the like which is dissolved in water, and which contains an alcohol such as methanol, ethanol or isopropyl alcohol in an aqueous solution in a range where there is no problem in the production of a circuit board or the like. The method of dissolving and removing the substrate in the aqueous solution after the support layer is removed, and the method of dissolving and removing the substrate in a spray or mist-like aqueous solution, and the like are exemplified. The temperature of the aqueous solution is preferably from room temperature to 80 ° C, and when it is carried out by an aqueous solution such as water immersion or boiling, the treatment time is preferably from 10 seconds to 10 minutes. For the alkaline aqueous solution, an alkali type developing solution (for example, 0.5 to 2% by mass aqueous sodium carbonate solution, 25 ° C to 40 ° C) used in the production of a multilayer printed wiring board can be used, and a dry film peeling machine can be used. The peeling liquid (for example, 1 to 5 mass% of sodium hydroxide aqueous solution, 40 to 60 ° C), and the swelling liquid used in the desmear step (for example, an alkali aqueous solution containing sodium carbonate, sodium hydroxide or the like, 60~) 80t) and so on. A metal wiring layer is formed on the insulating layer, and laser irradiation is performed from the upper portion of the metal film layer to form a fine wiring trench. Also, a laser can be used to form a through hole. Further, by including an inorganic ruthenium filler having an average particle diameter of 0.02 to 5 -74 to 201202334 in the insulating layer, the fine wiring trench can be formed more easily. In the method of the present invention, when the support layer is a plastic film, a fine wiring trench may be formed on the insulating layer from the support layer before removing the support layer or after removing the support layer from the metal film layer. However, from the viewpoint of preventing the processing speed from being slow, it is preferable to use a laser from the metal film layer after removing the support layer to form a fine wiring groove on the insulating layer. Further, when the release layer remains after the support layer is removed, a fine wiring trench can be formed on the insulating layer by using a laser from the release layer. The release layer has a small effect on the processing speed due to its thin thickness. For laser processing machines, carbon dioxide gas lasers, UV-YAG lasers, and excimer lasers can be used. In order to improve the laser processability, it is possible to contain a laser absorbing component in the release layer to increase the processing speed. Examples of the laser absorbing component include metal compound powder, carbon powder, metal powder, and black dye. The blending amount of the laser-absorbing component is preferably from 0.05 to 40% by mass, more preferably from 0.1 to 20% by mass, still more preferably from 1 to 1% by mass, based on the total of the components constituting the release layer. For example, when the content of the water-soluble polymer resin and the entire content of the water-soluble polymer resin is 100% by mass in the release layer formed of the water-soluble polymer resin, it is preferred to blend the above content. . Examples of the carbon powder include powders of carbon black such as furnace black, grooved carbon black, acetylene black, thermally cracked carbon black, and black, graphite powder, or a mixture of such powders. Examples of the metal compound powder include titanium oxides such as titanium oxide, magnesium oxides such as magnesium oxide, iron oxides such as iron oxide, nickel oxides such as nickel oxide, zinc oxides such as manganese dioxide, and zinc oxide. a cobalt oxide such as a cerium oxide, a cerium oxide, an aluminum oxide, a rare earth oxide or a cobalt oxide, or a tin oxide such as a tin oxide, or a tungsten oxide such as a tungsten oxide, a tungsten carbide or the like, a tungsten carbide, or a tungsten nitride. Boron, nitriding sand, titanium nitride, aluminum nitride, barium sulfate, rare earth acid sulfide or a mixture of such a powder. Examples of the metal powder include silver, aluminum, lanthanum, lanthanum, copper, iron, magnesium, manganese, molybdenum, nickel, palladium, iridium, ruthenium, tin, titanium, sail, tungsten, zinc, or the like, or Powder of the mixture, etc. Examples of black dyes include azo (monoazo, disazo, etc.) dyes, azo primary methyl dyes, anthraquinone dyes, sormine dyes, ketimine dyes, fluorone dyes, nitro dyes. , dibenzopyran dye, ethane naphthalene dye, quinoline yellow dye, aminoketone dye, methine dye, anthraquinone dye, coumarin dye, purple ketone dye 'tripty base dye, triene Methane dyes, anthraquinone dyes, ink benzoic acid dyes, anthraquinone dyes or mixtures thereof. The phthalocyanine dye is preferably a solvent-soluble black dye in order to enhance the dispersibility in the water-soluble polymer resin. These laser energy absorbing components may be used singly or in combination of different types. The laser energy absorbing component is preferably carbon powder, particularly carbon black, from the viewpoint of conversion efficiency of laser energy to heat or its versatility. In the method of the present invention, the desmear step can be further carried out. After the wiring is formed using a laser, it is preferable to carry out the desmear step. The step of removing the slag can be carried out by a known method such as a dry method such as plasma or a wet method such as an oxidizing agent such as an alkaline permanganic acid solution. The desmear step mainly removes the resin residue generated by the formation of the blind vias or the formation of the wiring trenches, and the wall surface of the via holes or the wiring trenches can be roughened. In particular, the slag removal by the oxidant is because the smear of the through hole bottom or the wiring trench is removed, the wall surface of the through hole is roughened by the oxidant, and the plating adhesion strength can be made to -76-201202334. It is better to look at the point of improvement. The step of removing the slag by the oxidizing agent is preferably carried out by swelling the swelling liquid, roughening with an oxidizing agent, and neutralizing with a neutralizing liquid. The swelling solution may, for example, be an alkali solution or a surfactant solution, and is preferably an alkali solution. Examples of the alkali solution include a sodium hydroxide solution and a potassium hydroxide solution. As a commercially available swelling liquid, for example, Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, etc., manufactured by ATOTECH JAPAN Co., Ltd., may be mentioned. The oxidizing agent may, for example, be an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment by the oxidizing agent such as an alkaline permanganic acid solution is preferably carried out in an oxidizing agent solution heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. Further, the concentration of permanganate in the alkaline permanganic acid solution is usually about 5 to 10% by weight. The commercially available oxidizing agent may, for example, be an alkaline permanganic acid solution such as Concentrate Compact CP or Dosing solution Securighanth P manufactured by ATOTECH JAPAN Co., Ltd. In addition, as for the neutralization liquid, an acidic aqueous solution is preferred, and a commercially available product is a reduction solution Securighanth P (neutralization solution) manufactured by ATOTECH JAPAN Co., Ltd. In the method of the present invention, the electroless plating step can be further performed. It is preferred to carry out the electroless plating step after the desmear step. By the electroless plating step, an electroless plating layer can be formed on the surface of the insulating layer. The electroless plating step can be carried out by a known method. For example, the surface of the insulating layer can be treated by a surfactant or the like, and after being impregnated with an ore-plating catalyst such as palladium, it is impregnated into the electroless plating solution. To form an electroless plating layer. In the method of the present invention, the electrolytic plating step can be further performed. -77- 201202334 It is preferred to carry out the electrolytic plating step after the electroless plating step. The conductor layer can be formed by an electrolytic plating step. The electrolytic plating step can be carried out by a known method. For example, after forming an electroless plating layer (plating seed layer) on the insulating layer by 0.1 to 2/zm, a conductor layer is formed by electrolytic plating. The conductor layer is preferably copper, and the thickness thereof varies depending on the depth of the laser processing groove and the height of the wiring groove formed, but is preferably 3 to 35 / ί η, more preferably 5 to 25 / ^ m. In the method of the present invention, the step of removing the conductor layer can be further carried out. It is preferred to carry out the step of removing the conductor layer after the electrolytic plating step. Since the electroless plating step and the electrolytic plating step form a copper layer on the entire surface of the insulating layer, the step of removing the surface of the conductor layer by exposing the insulating layer to the surface can form a trench type wiring. A schematic diagram of the trench type circuit substrate is shown in FIG. The step of removing the conductor layer on the surface can be carried out by a known method, for example, by mechanical honing and/or by etching and removing a solution in which copper is dissolved. [Examples] Hereinafter, the present invention will be described in more detail by using the examples, but the invention is not limited thereto. In addition, in the following description, "part j means "parts by mass". &lt;Measurement method. Evaluation method&gt; First, various measurement methods and evaluation methods will be described. -78- 201202334 &lt;Measurement and evaluation of MIT folding resistance&gt; The adhesive film produced in the examples and the comparative examples was cured at 190 ° C for 90 minutes, and 5 pieces of 110 mm were formed using a cutter. &lt;15 mm sample for evaluation. The MIT Folding Fatigue Tester "ΜΙΤ-DA" manufactured by Toyo Seiki Co., Ltd., based on JIS C-5016, has a load of 2.5N, a meandering angle of 135 degrees, a meandering speed of 175 times per minute, and a radius of curvature of 0.38 mm. The MIT folding endurance test was carried out, and the number of folding resistances was measured. The average enthalpy of the number of folding resistances of the five evaluation samples was obtained. When the number of times of folding is less than 50, the evaluation is "X", 50 times or more, and when it is less than 100 times, it is evaluated as "△", and when it is 100 times or more and less than 200 times, it is evaluated as "〇". When it was evaluated as "◎" at 200 or more and less than 300 times, and when it was 300 or more times, it was evaluated as "◎〇j. &lt;Evaluation of the buildup&gt; The laminate film produced in the examples and the comparative examples was a batch type vacuum pressure laminator MVLP-5 00 (trade name, manufactured by a famous machine), and the conductor thickness was 3 5 . // m is layered on the conductor pattern of L (line: wiring width) / S (space: spacing width) = 160 #m/160/zm. The laminate was depressurized for 30 seconds to have a gas pressure of 13 hPa or less, and then pressed at 30 seconds, 100 ° C, and a pressure of 0.74 MPa. The appearance of the resin composition layer after lamination was examined. Further, the PET film was peeled off from the laminated adhesive film, and the resin composition was cured at 180 ° C for 30 minutes to form an insulating layer, and the unevenness on the insulating layer (Rt : maximum peak-to-valley) The non-contact surface roughness meter is used (Veeco -79- 201202334

WYKO NT 3 3 0 0 ) manufactured by Instruments, which is obtained by using V S I contact mode and 10 times lens to obtain a measurement range of 1.2 mm χ 0.9 1 mm. Thereafter, the determination is made as follows. 〇: The appearance of the laminate has no voids, and the difference in unevenness on the insulating layer is less than 5 μm. △: The appearance of the laminate has no voids, and the difference in unevenness on the insulating layer is 5 μm or more. x: voids after lamination And the difference in unevenness on the insulating layer could not be measured. <Measurement and evaluation of glass transition temperature (Tg) and linear thermal expansion rate> The film obtained in the examples and the comparative examples was thermally cured at 90 ° C for 90 ° C. It has a flaky hardened material. The cured product was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and subjected to thermomechanical analysis by a tensile weighting method using a thermal mechanical analysis device (Thermo Plus TMA83 1 0) manufactured by RIGAKU. After the test piece was placed in the above apparatus, the test piece was continuously measured twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5 t/min. The average linear thermal expansion rate from 25 ° C to 150 ° C in the second target measurement was calculated. When the enthalpy of the linear thermal expansion rate is 41 ppm or more, it is referred to as "χ", and when it is 3 ppm or less and less than 41 ppm, it is referred to as "△", and when it is less than 37 ppm, it is referred to as "〇". Further, the glass transition temperature (°C) was calculated from the point where the slope of the dimensional change signal in the second target measurement was changed. (Example 1) -80-201202334 14 parts of a liquid bisphenol A type epoxy resin (epoxy equivalent weight 180, "JER82 8EL" made from Nippon Epoxy Resin Co., Ltd.) and a biphenyl aralkyl type ring 14 parts of oxygen resin (epoxy equivalent 269, "N33000L" manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy resin (epoxy equivalent, "YX4000H" manufactured by Nippon Epoxy Co., Ltd.) 5 Part, phenoxy resin (weight average molecular weight 3 8000, "YL7553 BH30" manufactured by Nippon Epoxy Resin Co., Ltd., 1:1 solution of MEK and cyclohexanone in 30% by mass), bismuth imine 10 parts of a bifunctional phenol resin (phenolic hydroxyl equivalent 2 52, manufactured by Nippon Epoxy Resin Co., Ltd., and the above general formula (7)), and placed in DMAcl 5 parts of 'cyclohexanone 15 parts while stirring Allow to dissolve by heating. In the above, a mixed biphenyl aralkyl type phenol resin (phenolic hydroxyl equivalent 242, "MEH78 5 1 -4H" manufactured by Minghe Chemical Co., Ltd., and a 50% by mass solid cyclohexanone solution) 40 parts of dicyano 2 parts of diammonium ("DICY7" made by Nippon Epoxy Co., Ltd.), hardening catalyst (4E4MZ by Shikoku Chemicals Co., Ltd.), 0.1 parts, spherical cerium oxide (average particle size 〇·5μιη) 50 parts of the "amino decane treated product of "SΟC2" manufactured by ADMATECHS) was uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish. Next, on a polyethylene terephthalate (thickness 38/zm, hereinafter abbreviated as "PET"), the thickness of the resin after drying was 40 &quot;m, 80 by a slit coating apparatus. Dry at ~120 °C (average l〇〇t:) for 7 minutes (about 2% by mass of residual solvent). Next, a polypropylene film having a thickness of 15/zm was bonded to the surface of the resin composition and wound up in a roll shape. The roll-shaped adhesive film was cut into a width of 5 07 mm, and thereby a thin film of -507 - 201202334 of 507 x 3 3 6 mm was obtained. (Example 2) In addition, 50 parts of the spherical cerium oxide (average particle diameter 〇.5/zm, (A) of ADMATECHS "SOC2" oxime treated product) of Example 1 was changed to such spherical oxidization. The film was carried out in the same manner as in the first embodiment except that the ruthenium (average particle diameter: 0.25 Vm, (manufactured by ADMATECHS), "SOC1"). (Comparative Example 1) 10 parts of the bifunctional phenol resin containing the quinone imine skeleton of Example 1 (phenolic hydroxyl equivalent 25, manufactured by Nippon Epoxy Resin Co., Ltd., and the above general formula (7)) The same procedure as in Example 1 was carried out except that 60 parts of a polyfunctional phenol resin ("V-8003" manufactured by DIC Co., Ltd. and a DM Ac solution having a solid content of 16% by mass) containing quinone imine skeleton was changed. It is followed by a film. (Comparative Example 2) In addition to the quinone imine skeleton-containing bifunctional phenol resin of Example 1 (phenolic hydroxyl equivalent 252, manufactured by Nippon Epoxy Resin Co., Ltd., and described in the above general formula (7)) In the same manner as in Example 1, except that 10 parts of a bifunctional phenol resin ("bisphenol A" manufactured by Tokyo Chemical Industry Co., Ltd.) was changed, the film was obtained. -82-201202334 (Comparative Example 3) The bifunctional phenol resin containing the quinone imine skeleton of Example 1 (phenolic hydroxyl equivalent 252, Japanese epoxy resin), and the above general formula (7) are described. In the same manner as in Example 1, except that 10 parts of the bifunctional phenol resin ("bisphenol S" manufactured by Tokyo Chemical Industry Co., Ltd.) was changed to 10 parts, a film was obtained. The results are shown in Table 1. [Table 1] Component (non-volatile content for so (parts by mass) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) Component 2-functional phenol resin containing a quinone imine skeleton 10 10 ί 1 Polyfunctional phenolic resin of acid imine skeleton V-8 0 0 3 9.6 2-functional phenol bisphenol A 10 bisphenol S 10 epoxy resin NC3000L 14 14 14 14 14 YX4000H 5 5 5 5 5 jER828EL 14 14 14 14 14 Hardener DICY7 2 2 2 2 2 MEH7851-4H 20 20 20 20 20 Thermoplastic resin YL7553BH30 6 6 6 6 6 Inorganic strontium S0C2 50 50 50 50 S0C1 50 Hardening accelerator 2E4MZ 0. 1 0.1 0.1 0. 1 0.1 Solid component 121.1 121.1 120.7 121. 1 121.1 Content of inorganic cerium filling material (% by mass) 41.3 41.3 41.4 41.3 41.3 Content of (A) component (% by mass) 8.3 8.3 1.3 0.0 0.0 ΜΠ»Folding (times) ◎ (250) ◎〇 (320) 〇(180) X (45) X (32) 槙 layer 〇〇X 〇〇 line thermal expansion rate (ppm) 〇(36) 〇(37) 〇(33) X (56) X (41) Bokkan transfer temperature rc) 154 152 157 134 162 -83- 201202334 In Examples 1 and 2, it is understood that the invention of the present invention has been achieved. As is apparent from Comparative Example 1, even if the resin containing a quinone imine skeleton contains a polyfunctional phenolic hydroxyl group, the crosslinking density is increased and the buildup property is deteriorated. This can be a fatal disadvantage in the manufacture of printed wiring boards. Further, from Comparative Example 2'3, it is understood that when a bifunctional phenol resin having no quinone imine skeleton is used, the linear thermal expansion ratio is increased, and the number of times of folding resistance is low. (Example 3) &lt;Production of film with metal film&gt; Hydroxypropyl methylcellulose benzene was deposited on a polyethylene terephthalate (hereinafter referred to as "PET") film having a thickness of 38/zm. 10% by weight of methyl ethyl ketone (hereinafter referred to as "MEK") and N,N-dimethylformamide (hereinafter referred to as "HP-55" manufactured by Shin-Etsu Chemical Co., Ltd.) "DMF" 1:1 solution is applied by a slit coater, and the solvent is removed by heating at room temperature at a heating rate of 3 ° C / sec to 140 ° C using a hot air drying oven. A layer of hydroxypropylmethylcellulose phthalate of about 0.6 μm was formed thereon. Next, a copper film layer of about 200 nm was formed on the hydroxypropylmethylcellulose phthalate layer by a sputtering method to prepare a film with a metal film. &lt;Preparation of a film having a curable resin composition layer&gt; 28 parts of a liquid bisphenol F type epoxy resin (epoxy equivalent 170, "Epicoat 806H" manufactured by Nippon Epoxy Co., Ltd.), and Naphthalene type 4-functional epoxy resin (epoxy equivalent 163, Dainippon Ink Chemical Industry Co., Ltd. -84-201202334 "HP4700") 28 parts, phenoxy resin ("XX6954BH30" made by Japan Epoxy Resin Co., Ltd." 20 parts of a non-volatile component (30% by mass of a 1:1 solution of MEK and cyclohexanone) was dissolved in 15 parts of MEK and 15 parts of cyclohexanone while stirring. Among them, a mixture of a triazine-containing phenol novolak resin (hydroxyl equivalent of 125, DIC ("LA7054", and 60% by mass of a MEK solution) was used, and a naphthol-based hardener (hydroxyl equivalent 215, Dongdu) was mixed. 27 parts of MEK solution with a solid content of 50% by mass and 0.1 part of a hardening catalyst ("2E4MZ" manufactured by Shikoku Chemicals Co., Ltd.), spherical cerium oxide (average 70 parts of a solid content of 0.25/zm, (meth) oxime treated product of "SOC1" manufactured by ADMATECHS), and 15 parts of polyvinyl butyral resin ("KS-1" manufactured by Sekisui Chemical Co., Ltd.) A solution of 30% of a 1:1 solution of ethanol and toluene was uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish. The varnish was applied to a PET film (manufactured by LINTEC Co., Ltd.) having a thickness of 38/zm and an alkyd type release agent (AL-5), and the solvent was removed by a hot air drying oven. A film in which a thickness of the curable resin composition layer is 50/zm is formed. &lt;Production of a film with a metal film.&gt; A copper film layer of the film of the cured film and the film of the metal film. The contact was rolled up at 90 ° C to obtain a film with a metal film attached thereto. &lt;Lamination and Hardening of Adhesive Film Attached to Metal Film on Inner Circuit Board&gt; -85- 201202334 On a copper circuit in which a glass epoxy substrate of 18/zm thick copper circuit is formed on both sides, CZ81 00 (azole) The copper complex and the surface treatment agent (manufactured by MEC) containing an organic acid are treated to be roughened. Next, the PET film with the alkyd type release agent (AL-5) attached to the metal film attached to the film was peeled off, and the curable resin composition layer was brought into contact with the surface of the copper circuit, and the batch vacuum pressure laminator MVLP was used. -500 C (share) manufactured by Nihon Seiki Co., Ltd.), laminated on both sides of the substrate. The build-up was carried out under reduced pressure for 30 seconds to bring the gas pressure below 13 hPa. Thereafter, heat hardening was performed at 160 ° C for 30 minutes to form an insulating layer. &lt;Removal of support layer, laser processing, removal of release layer, and desmear treatment&gt;

After peeling off the PET film of the support layer, a UV-YAG laser is used to form a wiring trench (line (wiring)/space (interval) = 8/8 μm. Depth 12#m) and a top 70//m layer indirect continuation Through hole. Next, the hydroxypropylmethylcellulose phthalate layer was dissolved and removed in a 1% by weight aqueous sodium carbonate solution. Next, in terms of the desmear step, it was immersed in Swelling Dip Securiganth P as a swelling liquid in ATOTECH JAPAN at a temperature of 80 ° C for 10 minutes, and then immersed in a coarsening solution at 80 ° C for 20 minutes. ATOTECH JAPAN's Concentrate Compact P (KMn04: 60g/L, NaOH: 40g/L aqueous solution), and finally immersed in ATOTECH JAPAN as a neutralizing solution for 5 minutes at 40 °C. Reduction solution Securighanth P. Thereafter, it is washed with water and dried. -86- 201202334 &lt;Etching to remove the metal film layer and the surface of the underlying base metal layer by uranium&gt; The substrate was immersed in a copper dichloride aqueous solution at 25 ° C for 1 minute to form a copper film on the insulating layer. The layer was etched and removed, and the surface of the through-hole copper circuit was etched. Thereafter, the layer was washed with water, and "S-4800" manufactured by Hitachi High-Technologies Co., Ltd. was used, and the wiring trench was observed by SEM at a magnification of 2,000. The photo is shown in Figure 2. &lt;Conductor layer formation, wiring formation&gt; Electroless copper plating (using an electroless copper plating process using ATOTECH JAPAN pharmaceutical liquid) was performed on the insulating layer on which the copper film layer was etched. The film thickness of the electroless copper ruthenium coating is 0.8 # m. Thereafter, the electrolytic copper is plated with a thickness of about 25 μm, and the trench of the wiring is buried with copper. Thereafter, the copper (conductor layer) of the outermost surface is removed by mechanical honing until the insulating layer is applied to the surface. Circuit board. Observing the cross section of the wiring shape is a good substrate with a good line (wiring)/space (interval) = 8/8#m. (Comparative Example 4) After the support, the release layer and the copper film layer were removed, the same procedure as in Example 3 was carried out except that the laser treatment was applied, and SEM observation of the wiring trench was performed. The SEM photograph of the wiring trench is shown in Fig. 3. Further, in the same manner as in the third embodiment, the circuit board was obtained, and the cross section of the wiring shape was observed. The upper portion of the space (interval) was expanded to 12 // m or more, and the -87 - 201202334 was not formed. It is known from the third embodiment that a fine wiring groove is formed in the edge layer by using the method of the present invention. Further, the uppermost layer of the desmear step is protected by the copper layer and maintained in a good shape. [Industrial Applicability] The resin composition containing the resin having a bismuth imine skeleton-containing resin of the present invention can provide an excellent performance in the subsequent buildup property and harden the resin composition. The tree having a low linear thermal expansion rate and excellent in tortuosity can further provide a film, a prepreg, and a multi-plate using the same. It is even equipped with such computers, mobile phones, digital devices, etc., or carriers such as motorcycles, cars, and trams. Moreover, the present invention can provide a fine wiring trench, a circuit board including a fine wiring trench, and an electric product such as a brain, a mobile phone, a digital camera, a television, a motorcycle, a car, a ship, an aircraft, and the like. [Simplified description of the drawing] [Fig. 1] shows a schematic diagram of the groove type circuit substrate. Fig. 2 is a view showing the shape of a wiring of the third embodiment. FIG. 3 is a view showing a wiring shape of Comparative Example 4. FIG. In addition, the insulating layer of the phenolic tree film can be used as an insulating layer, printed wiring camera, television, ship, navigation method, or even electricity, or an automatic object. -88- 201202334 [Explanation of main component symbols] 1 : Copper wiring 2 : Insulation layer 3 : Inner layer circuit board 89 -

Claims (1)

201202334 VII. Patent application: 1. A resin composition characterized in that it contains (A) a bifunctional phenol resin containing a quinone imine skeleton. 2. The resin composition of claim 1, wherein the content of the (A) quinone imine skeleton-containing bifunctional phenol resin is 〇" to 30% by mass based on 100% by mass of the nonvolatile component in the resin composition. 3. The resin composition of claim 1 or 2, wherein (A) the bifunctional phenol resin containing a quinone imine skeleton has a weight average molecular weight of 200 to 1 500. 4. The resin composition according to any one of claims 1 to 3, further comprising (B) an inorganic ruthenium material. 5. The resin composition of claim 4, wherein (B) the inorganic ruthenium filler material The average particle diameter is 0.02/zm to 5/zm. 6. The resin composition according to any one of claims 1 to 5, wherein the cured product of the resin composition has a folding resistance of 50 or more and 1,000,000 or less. 7. The resin composition according to any one of claims 1 to 6, wherein the cured product of the resin composition has a linear thermal expansion ratio of 4 to 40 ppm. 8. A film which is characterized in that a resin composition according to any one of claims 1 to 7 is layered on a support film. A prepreg characterized in that the resin composition according to any one of claims 1 to 7 is impregnated into a sheet-like fibrous base material made of fibers. 10. A circuit board which is characterized in that an insulating layer is formed by a cured product of the resin composition according to any one of claims 1 to 7. -90- 201202334 • A semiconductor device characterized by the use of a circuit board as claimed in claim 1 . A method of forming a fine wiring trench, characterized in that a metal film layer is formed on an insulating layer formed by curing a resin composition of claim 5, and laser irradiation is performed from an upper portion of the metal film layer. A method of manufacturing a groove type circuit board, comprising the method of forming a fine wiring groove according to claim 12. A method of forming a fine wiring trench, characterized in that a metal film layer is formed on an insulating layer and laser irradiation is performed from an upper portion of the metal film layer. 15. The method of forming a fine wiring trench according to claim 14, characterized in that the insulating layer contains an inorganic cerium filled with an average particle diameter of 〇2 to SAm. 16. The method of forming a fine wiring trench according to claim 14 or 15, wherein the thickness of the metal film layer is 50 to 500 nm. A method of manufacturing a trench type circuit substrate, comprising the method of forming a fine wiring trench according to any one of claims 14 to 16. 18. The method of manufacturing a trench type circuit substrate according to claim 17, wherein the step of removing the step comprises a desmear step. A method of manufacturing a trench type circuit substrate according to claim 17 or 18, further comprising a plating step. The method of manufacturing a trench type circuit substrate according to any one of claims 17 to 19, which further comprises the step of removing the conductor layer. -91 -