TW201213112A - Metal-clad-laminated board and method for producing the same - Google Patents

Abstract

The present invention relates to a metal-clad-laminated board, comprising a prepreg 11 formed by impregnating at least one layer or more of a resin composition (I) comprising a thermal curing component and an inorganic filler as the essential components into a fiber base material 14; a metal foil 13 laminated on one side of the prepreg 11; and a primer resin layer 12 having a film thickness thinner than that of the prepreg 11, intervening between the prepreg 11 and the metal foil 13, by which the prepreg 11 adhered to the metal foil 13.

Description

201213112 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a metal clad laminate and a method of manufacturing the same. [Prior Art] In recent years, a copper-clad laminate having a prepreg containing a cyanate resin has been known. Patent Document 1 discloses that a novolak-type cyanate resin or a bisphenol A-type cyanate resin is contained in an amount of 20 to 40% by weight, and cerium oxide is 40 to 70% by weight based on the entire resin composition. A prepreg for a copper-clad laminate obtained by impregnating a resin composition with a resin composition of 2 to 40% by weight of a phenyl dimethylene type epoxy resin. In Patent Document i, the expansion ratio (αΐ) of the cured product obtained by curing the copper-clad laminate with a prepreg in the thickness direction is 12 ppm/° C. or more and 24 ppm/° C. or less. Copper-clad laminate with excellent heat resistance, connection reliability and flame retardancy. Further, since the inorganic filler is set to a specific content, it is particularly possible to reduce the water absorption. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-268136 (Draft of the Invention) (Problems to be Solved by the Invention) However, in the technique of Patent Document 1, the adhesive portion of the copper foil and the prepreg is still There is room for further improvement. Further, as a method of forming a fine wiring circuit, there is particularly a problem in terms of copper plating adhesion in a semi-additive process. Therefore, low thermal expansion, low anti-warping, and a copper-clad laminate which can form a fine 100129155 4 201213112 wiring circuit and have excellent reliability are required. The present invention has been made in view of the above circumstances, and its object is to provide one. A metal clad laminate which is improved in the purity of the prepreg, the body, and the metal layer of the (IV) and Lai materials. (Means for Solving the Problem) According to the present invention, the present invention provides a metal clad sheet which has a resin composition (1) containing a thermosetting component and an inorganic filler as essential components on the substrate at least - a prepreg formed of a layer or more; a metal crucible laminated on both sides or a single surface of the prepreg; and a film thickness thinner than a thickness of the prepreg, and a spacer existing in the prepreg and the Between the metals fl, a base resin layer in which the prepreg is adhered to the metal crucible. According to the present invention, a printed wiring board can be provided, which is processed by the above-mentioned metal clad laminate. The material supply device is mounted on the I7 brush wiring board. According to the present invention, the invention provides a metal clad laminate which is made of a metal layer which is impregnated with a substrate containing a thermosetting component and a tree (4) without (a) a step of two or a single surface of the prepreg formed of at least one layer or more, and a base resin layer having a thin film thickness of the above-mentioned pre-preg, and having a thickness of 100129155 201213112 in the prepreg and the metal The prepreg is adhered to the metal crucible via the base resin layer. According to the present invention, the prepreg is adhered to the metal foil by allowing the thin base resin layer to be interposed between the prepreg containing the thermosetting component and the inorganic filler as essential components and the metal foil. Therefore, in the process of manufacturing a semiconductor device such as etching a metal foil or performing a metal plating treatment on a prepreg, the problem of lowering the adhesion of the metal on the surface of the prepreg disappears. It is possible to strongly bond the prepreg with the metal layer. (Effect of the Invention) According to the present invention, it is possible to provide a metal clad laminate in which the adhesion between the prepreg containing the thermosetting component and the inorganic filler as an essential component and the metal bond is improved. [Embodiment] Hereinafter, embodiments of the present invention will be described using a drawing. In the drawings, the same component elements are denoted by the same reference numerals, and the description is omitted as appropriate. (First Embodiment) Fig. 1 is a cross-sectional view schematically showing a metal clad laminate 1 of the present embodiment (a symbol of a prepreg with a metal foil before heat curing is indicated by la). The metal clad laminate 1 of the present embodiment has a prepreg η obtained by impregnating the fiber base material 14 with at least one layer of the resin composition (I) containing the thermosetting component and the inorganic filler as essential components. a metal case 13 laminated on both sides of the prepreg 100129155 6 201213112 11; and a film thickness thinner than the prepreg 11 is present between the prepreg u and the metal case 13 so that Prepreg: 11 A base resin layer 12 which is adhered to the metal foil 13. , . Further, it is preferable that the elastic modulus of the base resin layer 12 measured at 3 ° C and 1 Hz is 1 gPa or more and 5 GPa or less. In addition, in the present specification, the term "modulus of elasticity" means using a DMA device (Dynamic: mechanical analyzer, τα ι she coffee company, product name: Q800), and at a temperature of 3 〇χ: The storage elastic modulus measured at a frequency of 1 Hz. Further, in the present embodiment, the thickness of the prepreg u after curing can be set to 20/xm or more and ΐ5〇μΐη or less. Hereinafter, each configuration will be described. <Metal foil 2 with a base resin layer> The base resin layer 12 can be formed of a resin composition (11) containing at least an aromatic polyamide resin and a thermosetting resin and filler particles. At this time, it is preferred that the base resin layer 12' is a compound containing no compound having a primary amino group and a compound having a secondary amino group. • i First 'Description of aromatic polyamide resin. The "aromatic polyamide resin" (Aromatic Polyamide) is obtained by reacting an aromatic polyamine resin with a rubber component, and specifically, it can be represented by the following formula (1). [Chemical 1] 100129155 7 201213112

οII

Art ΗΝ Η _ΑΓ2 Ν Ν S--χ· m (1) In the general formula (1), m represents the number of repeated units and is an integer of 50 to 5,000.

The Ar! and An lines represent divalent aromatic groups, which may be the same or different. The X system represents a group having a segment of a rubber component. The rubber component which reacts with the aromatic polyamide resin may be either natural rubber or synthetic rubber, and may be a modified rubber or an unmodified rubber. The synthetic rubber 'is not particularly limited, and examples thereof include acrylonitrile-butadiene rubber (NBR), acrylic rubber, polypyrene (p〇iybutadiene), and isoprene. Isoprene, NBR modified by addition of carboxylic acid, hydrogenated polybutadiene, p〇iybutadiene by epoxidation, and the like. Further, in order to improve compatibility with polyamidoximine, it is possible to use a modified or epoxy-modified one, or a hydrogen-converted synthetic rubber to prevent thermal deterioration, but it is more preferable to use NBR and polydiene. Further, an aromatic polyamine resin having a phenolic hydroxyl group is further improved. Thereby, in addition to the softness, the compatibility with the thermosetting resin is also excellent. For example, it is represented by the following formula (2). Order, [Chemical 2] 100129155 201213112

OH (2) In the general formula (2), m and n represent the number of repeating units, and are 50 to 5, an integer of 〇〇〇. Aq and Ar2 represent a divalent aromatic group, and may be the same or different. X represents a group having a segment of a rubber component. The aromatic polyamine resin and the rubber component are preferably 30% by weight or more and 85% by weight or less based on the so-called aromatic polyamide resin, and the remainder is preferably a rubber component. When the resin composition (II) is used in an amount of 1 part by weight, the aromatic polyamine resin is preferably used in a mixing ratio of 5 parts by weight or more and 75 parts by weight or less, more preferably 20 parts by weight or more. 50 parts by weight or less. Examples of the thermosetting resin include epoxy resin (ep0Xyresins), cyanate resins, unsaturated polyester resins, and benzoCyCi〇butene resins. Resins) and bis-bis-bisphosphonimide triazine resins). It is more preferable to use an epoxy resin or a cyanate resin, and it is more preferable to use a combination of an epoxy resin and a cyanate resin. When the resin composition (11) is 1 part by weight, the thermosetting resin may be used in a mixing ratio of 5 parts by weight or more and 75 parts by weight or less. The blending ratio of the epoxy resin to the vinegar resin is preferably 5 parts by weight or more and 75 parts by weight or less. As the epoxy resin, a biphenyl type epoxy resin 100129155 9 201213112 (biphenyl type epoxy resin), a bisphenol type epoxy resin, or a stilbene type epoxy resin can be used. , phenol novolac type epoxy resin, cres 〇 novolac type epoxy resin, triphenolmethane type epoxy resin, alkane Aikyl-modified triphenolmethane type epoxy resin, epoxy resin containing a triazine uncleus, dicyclopentadiene type epoxy Resin), phenolaralkyl type epoxy resin, phenolbiphenylaralkyl type epoxy resin, naphthalene modified phenolic varnish type epoxy resin (naphthalene) "modified phenolic novolac type epoxy resin), etc. "These epoxy resins may be used alone or in combination of two or more. Among these, bisphenol type epoxy resin, dicyclopentadiene type epoxy resin, phenol aralkyl type epoxy resin, in particular, from the viewpoints of low water absorption, high adhesion of plating, and heat resistance, A phenol biphenyl aralkyl type epoxy resin or a naphthalene modified phenol novolac type epoxy resin is preferred. The cyanate resin is preferably an aromatic cyanate resin, and specific examples thereof include a phenol novolac type or a phenol phenol varnish type (cresol n〇v〇iac type). a varnish-type cyanate resin; a phenylaralkyl type cyanate resin; a biphenylaralkyl type cyanate resin; a naphthyl aralkyl type cyanide Acid 100129155 10 201213112 ester resin (naphthalenear alkyl type cyanate resin); bisphenol A type, bisphenol E type, tetramethyl bisphenol F type An acid ester resin or the like. Among these, a novolac type cyanate resin is preferred. Examples of the curing agent include benzyldimethylamine (BDMA) and 2,4,6-tris(dimethylaminomethyl)phenol. DMP-30) and other tertiary amine compounds; 2-methylimidazole, 2-ethyl-4-methylimidazole (EMI24), 2-phenyl 4-methyl-2-phenylimidazole (2P4MZ), 2-phenylimidazole (2PZ), 2-phenyl-4-mercapto-5-hydrogen A catalyzed hardening agent such as a Lewis acid such as a phenylidene triazole complex or a boron trifluoride complex. Further, for example, an aliphatic polyamine such as diethylenetriamine (DETA), triethylenetetramine (TETA), or m-xylylenediamine (MXDA); Except for aromatic polyamines such as 4,4'-diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diaminodiphenylsulfone (DDS) It is also possible to use a polyamine compound containing dicyandiamide (DICY), organic acid dihydrazide or the like; hexahydrophthalic acid needle 100129155 11 201213112 (hexzhydrophthalic anhydride, ΗΗΡΑ), 曱Alicyclic anhydrides such as methyltetrahydrophthalic anhydride (MTHPA), trimellitic anhydride (、), pyromellitic dianhydride (PMDA), diphenyl ketone Acid (benzophenone-3, 3', 4, 4'-tetracarboxylic acid, BTDA) and the like containing an aromatic acid anhydride or the like; phenol varnish type phenolic resin (novolac type phenolic resin), phenolic po Lymer) and other compounds; polysulfide (polysulphide), thioester (thioester), thioether (thioether) and other polythiol compounds; isocyanate prepolymer (isocyanate prepolymer), isocyanate A compound called isocyanate, such as blocked isocyanate, or a polyaddition hardening agent such as an organic acid such as a polyester resin having a carboxylic acid. Further, for example, a resin-based hardener such as a novolac type phenolic resin or a res phenol type phenolic resin may be used; and a thiol-containing urea resin may be used ( Urea resin has a condensed hardener such as a melamine resin such as a melamine resin having a methyrol group. The phenol resin-based curing agent refers to a monomer, an oligomer, and a polymer having two or more phenolic hydroxyl groups in one molecule, and the molecular weight and molecular structure thereof are not particularly limited, and examples thereof include a phenolic phenol varnish resin (phenolic). Novolac resin), cresol novolac resin, naphthol novolac resin, etc. 100129155 12 201213112 lacquer resin, triphenol methane phenolic resin Functionalized resin; modified terpene phenolic resin, dicyclopentadiene-modified phenolic resin, etc.; modified phenyl skeleton and/or extension a phenolic aralkyl resin of a phenyl skeleton, an aralkyl type resin such as a naphthol arylalkyl resin having a pendant phenyl group and/or a phenyl group extending; a bisphenol compound such as bisphenol A or bisphenol F, etc. The system may be used alone or in combination of two or more. Among these, 'the basis weight is 90 g/eq or more and 250 g/eq or less from the viewpoint of hardenability. As the packed particles 'crushed-silica, melted silica, crystaiiine silica, siuca nanoparticle, alumina can be used. (alumina), aluminium hydroxide, calcium carbonate, barium sulfonate, mica, taic, or a mixture of two or more. When the resin composition (II) is 100 parts by weight, the filler particles are preferably contained in an amount of from 5 parts by weight to 70 parts by weight, preferably from 1 part by weight to 60 parts by weight. Thereby, the effect of low thermal expansion and low water absorption can be obtained. Further, the volume of the volume-accumulated particle diameter 〇5 所得 obtained by the laser diffraction pacticle size analysis is preferably i 〇 nm or more and ι ηηη or less. More preferably, it is 1 〇 nm or more and 7 〇 nm or less. The dispersibility can be improved by setting the value of the volume cumulative particle diameter D5 of the filler particles to 100,129,155 13 201213112 to 10 nm or more. Further, by setting the value of the volume cumulative particle diameter Dm of the filler particles to ι〇〇ηιη or less, the drug resistance can be improved. In the resin composition (II), a decane type coupling agent is preferred. Examples of the decane type coupling agent include ep〇xy_functi〇nal silane coupling agents, amin〇_functi〇nal silane coupling agents, and ethylene base kiln coupling agents. (vinyi_functi〇nai silane coupling agents). Further, by using an epoxy decane type coupling agent, chemical bonding can be formed without curing the cyanate resin. Therefore, the interface between the prepreg 11 and the base resin layer 12 can be strongly bonded, and it is possible to surely bond the prepreg j j and the metal foil 13. The content of the decane type coupling agent is preferably 5% by weight or more and 5% by weight or less based on the filler particles. The aromatic polyamide resin, the thermosetting resin, the filler particles, the curing agent, and the decane coupling agent can be dissolved in an organic solvent to form a resin varnish (II). In the resin varnish (II), a hardening accelerator which is generally used may be contained. Further, as the curing accelerator, the same curing accelerator as used in the prepreg i j described later can be used. Further, in the resin composition, additives other than the above components may be added to the range of the densely prepreg 11 and the metal case 3 as needed. Further, the resin composition (H) is in the range of the densely prepreg 11 and the metal foil 13, and can be obtained by appropriately adjusting the raw material or the amount thereof. As the organic solvent, dimethylf〇rmaide, 100129155 14 201213112 dimethylacetamide, N-methyl, N-methylpyrrolidone or the like can be used as a solvent. The resin varnish (II) obtained in the above operation was applied onto the metal foil j 3 to be in a semi-hardened state, thereby obtaining a metal foil 2 to which a base resin layer was attached. The metal foil 13 is preferably made of copper or aluminum. The coating method at this time is not limited, and for example, there is a method of coating by each coater or a method of attaching by a blow, and it is preferable to use a gravure coater (7) (4) called maChine. . Further, the ratio of the resin varnish (8) is preferably greater than or equal to the ratio of the viscosity at a rotation number of 5 rpm to the viscosity at the number of rotations in the E-type viscmeter (E_type viscmeter). 〇The following. When it is set to G.7 or more, it can be a uniform thickness, and by setting it to 1,5 or less, it can prevent a bubble from being wounded. Further, the drying after the surface of the base resin layer 12 13 can be heated in accordance with the nature of the resin varnish (9), and the elastic modulus of the base resin layer 12 can be set. It is better to use the '_ strong receiving prepreg. The thickness of the metal box 13 is preferably 15 qing, which is more than 1,5 _? _ The following is better, more coarse (four) (10) shouted;; Y down. _ 13 Fine surface is preferred. And 3, the following electrolytic steel box or rolled copper 浸 immersion _ good, ~ two =: = 100129155 15 201213112 疋 2μιη and above and 1 or less. The layer thickness of the base resin layer I) is preferably at least the above lower limit in terms of improving the insulation reliability. Therefore, in the manufacture of the printed wiring board, the unevenness of the inner layer circuit can be filled and formed, and the thickness of the appropriate insulating resin layer can be ensured. <Prepreg 11> In the present embodiment, the prepreg 11 is such that at least the insulating resin layer 15 composed of the resin composition (1) containing the thermosetting component and the inorganic filler as an essential component is on the fibrous substrate 14. Impregnated with more than one layer. As the thermosetting component, preferred are a group of cyanate resins, epoxy resins, maleimide (m), and phenolic resins. The cyanate resin may be used, for example, by reacting a ii cyanide compound with a phenol, and prepolymerizing it by heating or the like as needed. Specifically, a novolac may be mentioned. 〇c〇lac type cyanate resin; aryl aralkyl type cyanate resin; a bisphenol A type cyanate resin Cyanate resin), bisphenol type cyanate resin such as biSphenol E type cyanate resin, tetramethyl bisphenol F type cyanate resin; An alkylene type cyanate resin, etc. Among them, a novolak type cyanate resin or an aryl alkyl group cyanate resin is preferred. 100129155 16 201213112 Cyanate vinegar Resin weight 1 level The weight-average molecular weight is not particularly limited, and is preferably 5.〇χ1〇2~4.5xl03, more preferably 6.0x1 〇2~3.OxlO3. When it is less than this value, there will be a prepreg. The adhesiveness is generated when the prepreg is in contact with each other, or the resin is transferred. Further, when it is larger than this value, the reaction becomes too fast, and there is a poor formation or interlayer. The content of the cyanate resin is not particularly limited, and is preferably 5% by weight or more and 60% by weight or less, and more preferably 1% by weight or more and 50% by weight or less based on the entire resin composition (1). By setting the content of the cyanate resin or the like to the lower limit, the heat resistance can be prevented from being lowered, and the thermal expansion can be reduced. Further, by the above upper limit, the moisture resistance can be prevented from being lowered. Examples of the phenol resin include, for example, n〇v〇lac type phenolic resins, cres〇i type phenoiic resins, and auyi aikylene type phen resins. 〇lic resins) and so on. Among other 'are aryl alkylene type phenol resin is preferred. Accordingly, the absorbent may be further improved solder heat resistance. The phenol resin is used in combination with a cyanate resin to increase the reactivity of the cyanate resin, whereby the formability of the laminate is improved. Examples of the aryl-based base type phenolic resin include a xylylene type phenolic resin and a biphenyl dimethyl phenolic resin. In particular, by combining the acid varnish type cyanate S resin with the aryl stretching base type alkali tree 100129155 17 201213112, the crosslinking density can be controlled, and the adhesion to the base resin layer η can be improved. The stem of the phenol tree sap is not particularly limited, and is preferably 1% by weight or more and 55% by weight or less, more preferably 5% by weight or more and 40% by weight or less or more preferably 8 parts by weight based on the entire resin composition (1). % or more and 2G% by weight or less. By setting the resin to the above lower limit value, the heat can be surely extracted, and if the upper limit is set, the water absorption can be low. The weight-average molecular weight of the phenol resin is not particularly limited. The average molecular weight is preferably 4 x 1 〇 2 to 1 · 8 χ 103, more preferably Hong (7) 2 χΐ〇 5 χΐ〇 3. When the weight I average molecular weight is set to the above lower limit value, the prepreg becomes less likely to cause problems such as tackiness, and when the above upper limit is used, the prepreg can be improved in the production of the prepreg. The impregnation of the substrate results in a more uniform article. The epoxy resin is not particularly limited, and examples thereof include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol e type epoxy resin. Resin (biSphen〇lEtypeepoxyresin), double-type S-type epoxy resin (10) i S type epoxy resin), bisphenol z-type epoxy resin, bisphenol P-type epoxy resin (biSphen〇1 p Type ep〇xy resin), double-aged epoxy resin (bisph(10) 1 M type ep0Xy resin); phen〇l novolac type epoxy resin, tannic acid A phenolic varnish-type epoxy resin such as a varnish-type epoxy resin (Laiwu 1 n〇v〇lac 100129155 18 201213112 type epoxy resin); a biphenyl type epoxy resin, a benzoic acid type Xylylene type epoxy resin, phenolaralkyl type epoxy resin, biphenylaralkyl type epoxy resin, biphenyl dialkyl fluorene type Epoxy resin (biphenyldimethylene type epoxy res In), trisphenolmethane novolac type epoxy resin, 1,1,2,2-(tetraphenyl)acetamidine (gycidyl ether of l, l, 2 , 2-(tetraphenol)ethane, trifunctional or tetrafunctional glycidylamine, aryl-alkyl-type epoxy resin such as tetramethylbiphenyl type epoxy resin (auyi aikylene type) Epoxy resin); naphthalene modified cresol novolac type epoxy resin, methoxynaphthalene modified cresol novolac type epoxy Resin-based epoxy resin (naphthalene type), methoxynaphthalene dimethylene type epoxy resin, naphthol alkylene type epoxy resin Epoxy resins); anthracene type epoxy resins; phen〇xy type epoxy resins; dicyclopentadiene type epoxy resins Tadiene type epoxy resins); rice-diluted epoxy tree 匕100129155 19 201213112 (norbornene type epoxy resins), adamantane type epoxy resins, type epoxy resin (fiu〇rme café view) Ns), flame-retardant epoxy resins in which the above epoxy resin is hs. Among these, one type or two or more types having different weight average molecular weights may be used in combination, and one type or two or more types may be used in combination with the above-mentioned prepolymers. These epoxy-based t, touch-free free silk-type epoxy resin, stretch naphthalene-based bone secrets _ county fine and ^ secret varnish-type materials, stretch-type epoxy (four) in the group At least one. In this way, in addition to improving operability, it is also readable and flame retardant. t as a thermosetting component, preferably comprising at least a combination of cyanide and epoxy or epoxy and _lipid, more preferably a group of human nitrogen containing cyanide and oxyphenol resin Acid _ fat and _ fat and biphenyl ^ is the dimensional stability of the W (four) surface of the combination of the secret varnish type ± ~ yttrium type epoxy resin. The content of the epoxy resin is not particularly high on the i weight (10) and is 55 44 q/k, preferably the resin composition (1) and 40% by weight or less. By more preferably 2% by weight or more, the content of the anti-gas content of the cyanide-resin can be prevented from being lowered as the moisture resistance of the product having the lower limit. Further, it is lowered to prevent a decrease in heat resistance of 16 obtained. The ring gas; is the above-mentioned upper limit value, and the weight average molecular weight of the T & 100129155 201213112 (weight-average molecular weight) is not particularly limited, and the weight average molecular weight is preferably 5x10 or more and 2χ103 or less, more preferably 8xl〇2 or more and 1.5xl〇3 or less. When the weight average molecular weight is set to the above lower limit value, the prepreg becomes less likely to cause adhesiveness, and when it is set to the above upper limit, it is possible to prevent impregnation with the substrate when the prepreg is produced. The reduction in the advantages of obtaining a more uniform product. One of the above-mentioned cyanate resin, epoxy resin and phenol resin in the resin composition (I) may be vinyl ester resins, melamine resins, and maleic acid. Other thermosetting resins such as maleimide resins, phenoxyxysins, polyimide resins, polyamideimide resins, polyphenylene ether resins ( Polyphenylene 〇xide resins), thermoplastic resins such as polyethersulfone resins. Examples of the inorganic filler □ include talc, alumina, glass, bismuth dioxide, mica, and the like. Among these, cerium oxide is preferred, and molten melting silica is preferred because of its low expansion property. The shape is a crushed shape or a spherical shape, and it can be used for the purpose of ensuring the impregnation property of the glass substrate and reducing the melt viscosity of the resin composition by using SpheriCal-shaped silica. Instructions. The average particle size of the inorganic filler is not particularly limited, and is preferably Ο.ΟΙμη or more and 5 μηι or less, more preferably 〇 2 μm or more and 100129155 21 201213112 and 2/πη or less. By setting the above lower limit value, the recording of the prepreg can be improved. Further, by using (4) as the cut-off value, precipitation of the inorganic filler in the varnish can be prevented. Further, (4) is a spherical molten gasified cerium having an average particle diameter of 5 / mi or less, and more preferably a spherical molten sulphur dioxide having an average particle diameter of 0·0_ or more and 2 Mm or less. Thereby, the filling property of the inorganic filler can be improved. The average particle size can be measured, for example, by a laser diffracti〇n partide size analyzer. The content of the inorganic filler is preferably from 80% by weight or more to 80% by weight of the total weight of the resin composition (1), more preferably from 4% by weight to 75% by weight. When the content of the inorganic filler is within the above range, it may be low in thermal expansion and low in water absorption. The resin composition (I) is not particularly limited, and it is preferred to further use a coupling agent. By blending the coupling agent, the wettability of the interface between the resin and the inorganic filler material is improved. 'The resin and the filler material can be uniformly fixed and adhered to the fiber base material 14' and the heat resistance, especially the moisture resistance after soldering, can be improved. Sex. The coupling agent can be used as a general user, and preferably an epoxy-functional silane coupling agent, a titan coupling agent, or an amine. One or more coupling agents are selected from the group consisting of an amino-functional silane coupling agent and a silicone oil type coupling agent. These coupling agents have higher wettability at the interface with the inorganic filler, and can further improve heat resistance by 100129155 22 201213112. The blending amount of the coupling agent is preferably 0.05% by weight or more and 3% by weight or less based on the inorganic filler. By setting the above-mentioned upper limit value, the filler can be sufficiently covered to obtain sufficient heat resistance, and by setting it as the lower limit value, the influence on the reaction can be ignored, and the bending strength and the like can be prevented from being lowered. . For the resin composition (I), a hardening accelerator may be used as necessary. As the hardening accelerator, a known substance can be used. For example, zinc zirconate, zallium naphthenate, tin octylate, cobalt octylate, zinc octylate, and diacetyl can be cited. Pyruvic acid g (II) (cobalt (II) bis (acetylacetonate), volume (co) (co) (co) (cobalt (III) tris (acetylacetonate)), etc.: metal salts, Tertiary amines such as triethylamine, tributhylamine, diazabicyclo[2,2,2] octane; dicyandiamide An aromatic diamine compound; 2-phenyl-4-phenylimidazole, 2-ethyl-4-methylimidazole, 2- Phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4,5-dihydroxyimidazole Imidazoles; phenol, bisphenol A, nonylphenol, etc.; acetic acid, benzoic acid, sailiCyiic acid, confrontation Organic such as p-toluene sulfonic acid And the like, or mixtures thereof. 100129155 23 201213112 Other specific examples of the hardening accelerator include an organic phosphine, a tetrasubstituted scale compound, a phosphoric acid beet test compound, an adduct of a phosphine compound and a ruthenium compound, an adduct of a symbiotic compound and a ruthenium compound, and the like. a compound that breaks atoms; 丨, 8_ dibicyclobicyclo(5,4,0)undecene-7 (1,8-diazabicyclo[5,4,0]undec-7-ene), benzyl-mercaptoamine ( A compound containing a nitrogen atom such as benzyldimethylamine or 2-methylimidazole. Among these, 'from the viewpoint of hardenability, a compound containing a phosphorus atom is preferred, and from the viewpoint of fluidity and hardenability, a tetrasubstituted scale compound, a phosphobetaine compound, a phosphine compound are used. It is preferred to have a latent catalyst such as an adduct of an anthracene compound, an adduct of a scale compound and a decane compound. When considering the fluidity point of view, it is particularly preferable to be a tetra-substituted squama compound. Further, in terms of solder resistance, it is particularly preferable to be a phosphoric acid betaine compound, an addition product of a phosphine compound and a ruthenium compound, and, in addition, to take into account the latent The sclerosing point of view is particularly preferred as an adduct of a scaly compound and a decane compound. Further, it is preferred to use a tetra-substituted scale compound from the viewpoint of formability. Examples of the organic phosphine include, for example, a primary phosphine such as ethylphosphine or phenylphosphine; a secondary phosphine such as dimethylphosphine or diphenylphosphine; and trimethylphosphine ( Trimethylphosphine), triethylphosphine, tributylphosphine, triphenylphosphine, and the like. The compound represented by the following general formula (3), 100129155 24 (3) (3) 201213112, and the like are exemplified as the tetra-substituted fluorene compound. [Chemical 3] R17 1 — - R18-P-R20 A AH 1 y

R19 ′ X In the general formula (3), P represents a phosphorus atom, R17, R18, R19 and R20 each independently represent an aromatic group or an alkyl group, and A represents at least one selected from a hydroxyl group on the aromatic ring. An anion of an aromatic organic acid having any one of a carboxyl group and a hydrogenthio group; and AH is an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group or a thiol group on the aromatic ring, X and y is an integer from 1 to 3, z is an integer from 0 to 3, and x = y. The compound represented by the general formula (3) can be obtained, for example, by the following, but is not limited thereto. First, a tetrasubstituted town compound and an aromatic organic acid and a base are uniformly mixed in an organic solvent to produce an aromatic organic acid anion in the solution system. Next, by adding water, the compound represented by the general formula (3) can be precipitated. In view of the fact that the compound represented by the general formula (3) is excellent in the balance between the yield at the time of synthesis and the hardening promoting effect, it is preferred that R17, R18, R19 and R20 bonded to the phosphorus atom are benzene. And AH is a compound having a hydroxyl group on the aromatic ring, that is, a phenol compound, and A is an anion of the phenol compound. The phosphoric acid betaine compound may, for example, be a compound represented by the following general formula (4). 100129155 25 201213112[化4]

(4) In the general formula (4), XI represents an alkyl group having 1 to 3 carbon atoms, Y1 represents a trans group, f represents an integer of 0 to 5, and g is an integer of 0 to 4. The compound represented by the general formula (4) can be obtained, for example, as follows. First, a triaromatic substituted phosphine belonging to the tertiary phosphine is contacted with a diazonium salt and is obtained by a substitution step of a diazo substituted phosphine and a diazonium having a diazonium salt. However, it is not limited to this. The compound represented by the following general formula (5), and the like, may be mentioned as an adduct of the phosphine compound and the ruthenium compound. [Chemical 5]

In the general formula (5), P represents a phosphorus atom, and R21, R22 and R23 independently of each other represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R24, R25 and R26 are independent of each other. The ground represents hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, and R24 and R25 may be bonded to each other to form a ring. The phosphine compound used in the adduct of the phosphine compound and the hydrazine compound may, for example, be a preferred triphenylphosphine or a roll 100129155 26

S 201213112 (triphenyl) phosphine, tris (alkoxy phenyl) phosphine, trinaphthyl phosphine, benzyl (benzyl) phosphine (tris(benzyl) phosphine) or the like which is not substituted on the aromatic ring or has a substituent such as an alkyl group or an alkoxy group, and examples of the substituent such as an alkyl group or an alkoxy group include a carbon number of 1 to 6 By. From the viewpoint of easiness of availability, triphenyl phenyl is preferred. Further, 'g-quinone compound used as an adduct of a phosphine compound and a ruthenium compound' may be exemplified by ο-benzoquinone, p-benzoquinone, or anthraquinone. Among them, in terms of preservation stability, it is preferred to use benzopyrene. As a method for producing an adduct of a phosphine compound and a hydrazine compound, an adduct can be obtained by contact and mixing in a solvent in which both an organic tertiary phosphine and a benzopyrene can be dissolved. As the solvent, a ketone such as acetone or methyl ethyl ketone is preferred as a solvent having a low solubility in an adduct. However, it is not limited to this. The compound represented by the general formula (5) is a compound in which R21, R22 and R23 which are bonded to a phosphorus atom are a phenyl group, and R24, R25 and R26 are a hydrogen atom, that is, the semiconductor can be encapsulated and sealed. In terms of lowering the heating elastic modulus of the cured product of the resin composition, a compound obtained by adding 1,4-benzofluorene to triphenylphosphine is preferred. The compound represented by the following general formula (6), etc., may be mentioned as an adduct of the squamous compound and the stalk compound. [6] 100129155 27 201213112 R28

I

R27 — P — R29

I R30 In the general formula (6), P represents a phosphorus atom, and Si represents a ruthenium atom. R27, R28, R29 and R30 each independently represent an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring, and X2 represents an organic group to which the group Y2 and Y3 are bonded. X3 represents an organic group to which the group Y4 and Y5 are bonded. Y2 and Y3 are groups in which a proton-donating group releases a proton, and a group Y2 and Y3 in the same molecule are bonded to a ruthenium atom to form a chelate structure. Y4 and Y5 are groups in which a proton-donating group releases a proton, and a group Y4 and Y5 in the same molecule are bonded to a ruthenium atom to form a chelate structure. X2 and X3 can be the same or different, and Y2, Y3, Y4 and Y5 can be identical to each other or different. Z1 is an organic or aliphatic group having an aromatic ring or a heterocyclic ring. In the general formula (6), examples of R27, R28, R29 and R30 include a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydrogenphenyl group, a naphthyl group, a hydronaphthyl group, a benzyl group and a hydrazine group. a base, an ethyl group, an n-butyl group, an n-octyl group, a cyclohexyl group, etc., among which a aryl group, a nonylphenyl group, a decyloxyphenyl group, a hydrogen phenyl group, a hydronaphthyl group or the like has a substituent A group-based or unsubstituted aromatic group is preferred. Further, in the general formula (6), X2 is an organic group to which Y2 and Y3 are bonded. Similarly, the X3 group is an organic group to which Y4 and Y5 are bonded. Y2 and Y3 are groups in which a proton-donating group releases a proton, and a group Y2 and Y3 in the same molecule are bonded to a ruthenium atom to form a chelate structure. Similarly, Y4 and Y5 100129155 28 201213112 are groups in which a proton-donating group releases a proton, and a group Y4 and Y5 in the same molecule are bonded to a ruthenium atom to form a chelate structure. The bases X2 and X3 may be identical to each other or different from each other, and the bases Y2, Y3, Y4 and Y5 may be identical to each other or may be different. In the general formula (6), the base proton donor represented by -Y2-X2-Y3- and -Y4-X3-Y5- is composed of two protons, and is used as a proton donor. For example, catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2'- Biphenyl (2,2,-biphenol), U,-bi-2-naphthol (l,l,-bi-2-naphthol, BIN0L), salicylic acid, 1-hydro-2-naphthalene 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic add, 2-hydrogen Alkyl alcohol (2-hydroxybenzyl al C0h0l), n-cyclohexanediol (1,2-CyCl〇hexanedi〇l), 1,2-propanediol (1,2_pr〇panedi〇1), glycerine, and the like. Among these, catechol, quinone dihydronaphthalene, and 2,3_ two tables are preferred from the viewpoint of the balance between the ease of obtaining raw materials and the hardening promoting effect. Further, the Z1 system in the general formula (6) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring, and specific examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Alkyl groups such as hexyl and octyl groups, or aromatic groups such as phenyl, benzyl, zeoliyl and biphenyl, condensed ethoxypropyl propyl sulphate, and fluorene-substituted sulphate Material stability 100129155 29 201213112 In terms of aspect, a methyl group, an ethyl group, a phenyl group, a naphthyl group and a biphenyl group are preferred. As a method for producing an adduct of a scalar compound and a decane compound, a decane compound such as phenyltrimethoxysilane or 2,3-dihydroxynaphthalene or the like is added to a flask in which methanol is placed. The proton donor was dissolved and then a sodium methoxide-methanol solution (sodium meth〇xide) was added dropwise with stirring at room temperature. Further, a solution obtained by dissolving a tetra-substituted squamous halide in methanol, such as a tetraphenylphosphonium bromide prepared in advance, is added dropwise under stirring at room temperature to precipitate crystals. The precipitated crystals are filtered, washed with water, and dried in a vacuum to obtain an adduct of a scaly compound and a decane compound. However, it is not limited to this. In the resin composition (I), additives other than the above components may be added in accordance with the necessity without impairing the properties. Further, the resin composition (1) can be obtained by appropriately adjusting the raw material or the blending amount thereof within a range not impairing the properties. The solvent used in the resin varnish (I) preferably exhibits good solubility with respect to the resin composition (1), and a poor solvent can be used insofar as it does not adversely affect the range. Examples of the solvent which exhibits good solubility include mercaptoethyl ketone and cyclohexanone. The solid content of the resin varnish (I) is not particularly limited, and the solid content of the resin composition (I) is preferably 5 parts by weight or more and 9 parts by weight or less, more preferably 60 parts by weight or more and 80 parts by weight or less. Thereby, the impregnation property of the resin varnish (1) with respect to the fiber base material 14 can be further improved. The prepreg 11 can be obtained by impregnating the fiber base material 14 with the resin varnish (1) and drying it at a predetermined temperature, for example, δ 〇ΐ 100129155 30 201213112 or more and 200 C or less. The glass transition temperature of the cured product is not particularly limited, and is preferably 21 Å. More than C, more preferably 230 C or more. Further, the reduction in the modulus of elasticity is also suppressed by the adhesion of the gold wire and the bump connection property of the semiconductor wafer. The glass transition temperature can be measured, for example, by using a thermomechanical analysis apparatus (TMA), a dynamic mechanical analyzer (DMA), or a differential thermal analysis (DSC). Further, the condition for curing the prepreg is, for example, a case where the prepreg 11 is heated at 19 ° C or higher and 250 ° C or lower for 30 minutes or longer and 120 minutes or shorter. Examples of the fiber base material 14' include a glass fiber base material such as a woven glass cross or a non-woven glass cross, or an inorganic fiber base such as a woven fabric or a non-woven fabric containing an inorganic compound other than glass. Material, aromatic polyamide imide resin, polyamide resin, aromatic polyester resin, polyester resin, polyfluorene An organic fiber base material composed of an organic fiber such as a polyimide resin or a fluorocarbon polymer. Among these substrates, in terms of strength and water absorption, when a glass fiber substrate represented by a glass woven fabric is used, the mechanical strength and heat resistance of the printed wiring board can be improved. A method of impregnating the resin substrate (I) with the fiber base material 14 is exemplified by a method of impregnating the fiber base material 14 with the resin varnish (I) by a coating machine, for example, 100129155 31 201213112. The method, the method of blowing by a sprayer, and the like. Further, before the resin composition (I) is impregnated into the fibrous base material 14, the resin composition (I) may be applied to the metal foil 2 with the base resin layer, and the fibrous base material 14 may be impregnated with the resin. In the composition (1). Among these, a method of impregnating the fibrous base material 14 with the resin varnish (I) is preferred. Thereby, the impregnation property of the resin composition with respect to the fibrous base material 14 can be improved. Further, in the case where the fibrous base material 14 is impregnated into the resin varnish (1), a usual impregnation coating device can be used. For example, as shown in Fig. 2, while the roll-shaped fibrous base material ι 1 is taken up, it is impregnated into the resin varnish (1) 103 of the impregnation tank 102. The impregnation tank 1〇2 is provided with a dipping drum 1〇4 (three in FIG. 2), and the fiber substrate 101 is continuously passed through the resin varnish (1) 103 by the impregnation drum 1〇4, and the resin varnish 103 is impregnated into the fiber. The substrate was 1〇1. Next, the fiber substrate 101 which has been impregnated with the resin varnish (1) 1 〇 3 is pulled up to the vertical direction, and arranged in the horizontal direction so that the resin varnish is adjusted between the pair of face-to-face pressing rolls 105. (1) The impregnation amount of 103 on the fibrous substrate 1〇1. Alternatively, a point roller can be used instead of the squeeze roller. Thereafter, the fiber base material 101 impregnated with the resin varnish (1) 1〇3 is heated by the dryer 106 at a predetermined temperature, and the resin varnish (1) 103 is allowed to be volatilized while volatilizing the solvent in the applied varnish. Semi-hardened to produce a prepreg 11a. In addition, the upper drum 1〇8 in Fig. 2 is for moving the prepreg 11a in the traveling direction, and in the prepreg 100129155

S 32 201213112 The direction of travel of the iia rotates in the same direction. Moreover, the conditions for drying the resin varnish (1) 103 are obtained by drying at a temperature of 9 〇 t: or more and 18 Å or less, for 1 minute or more and 1 G minutes or less, whereby a semi-cured pre-shallow body 11 a can be obtained. . • Also, the Zhao 11a system can be made by listening to the next step and manufacturing method. (a) The insulating resin layer 15 is superposed on one surface or both surfaces of the fibrous base material 14, and the bonding step (b) is bonded under reduced pressure to form a molten resin component 15 The step of preparing the prepreg n by heat treatment at a temperature higher than the temperature is first described with respect to the step (a). In the step of 〇), the insulating resin layer 15 and the fiber base material 14 are bonded under reduced pressure. By carrying out under reduced pressure, even if there is an unfilled portion inside the fibrous base material 14 or at the bonding portion of the insulating resin layer 15 and the fibrous base material 14, it can be regarded as a reduced pressure void or substantially Vacuum gap. The method of bonding the insulating resin layer 15 to the fiber base material 14 is not particularly limited. For example, a method of continuously supplying the fiber base material 14 and the insulating resin layer 15 and bonding them while being overlapped may be mentioned. In the step (a), when the insulating resin layer 15 is bonded to the fibrous base material 14, it is preferable to increase the temperature at which the fluidity of the resin component of the insulating resin layer 15 is increased. Thereby, the fibrous base material 14 and the insulating resin layer 15 can be easily bonded to 100129155 33 201213112. Further, at least a part of the insulating resin layer 15 is melted and impregnated into the inside of the fibrous base material 14, whereby the prepreg 11 having good impregnation properties can be easily obtained. The heating method is not particularly limited, and for example, a method of heating the resin to a predetermined temperature to a predetermined temperature may be employed. The heating temperature here varies depending on the type or blending of the resin forming the insulating resin layer, and can be performed at 6 (rc or more and 15 (r or less.) Next, the step (b) will be described. The step of bonding in the step (4) is followed by heat treatment at a temperature equal to or higher than the temperature of the insulating resin component constituting the insulating resin layer 15 to prepare the prepreg 11. This may cause the insulating resin layer 15 in the step (4). The reduced pressure void or the substantially vacuum void remaining when it is bonded to the fibrous base material 14 disappears, and the prepreg n having substantially no non-filled portions or substantially non-filled portions is produced. The lion's body can be implemented by, for example, a hot air drying device, an infrared heating device, a heating roller device, a flat hot plate pressing device, etc. Further, as the prepreg u of the present embodiment, Japanese Patent Laid-Open No. 2 can also be used. An example of the method of manufacturing the metal clad laminate 1 of the present embodiment will be described. 100129155 34 2012 13112 On the base resin layer 12 of the metal foil 2 with the base resin layer described above, after the resin varnish (I) is applied onto the base resin layer 12 using various coating devices, the material is dried. The resin varnish (1) is spray-coated on the base resin layer 12 by a spray coating, and the material is dried. The drying conditions at this time are such that the base resin layer 12 can be semi-hardened (become a b-plate state). For example, it is preferable to perform drying at 100 ° C or more and 180 ° C or less. Thereby, the insulating resin layer 15 can be formed on the base resin layer 12. The above coating device is not particularly limited, and for example, a roller can be used. A roll coater, a bar coater, a knife coater, a gravure coater, a die coater, a dot coater A comma coater, a curtain coater, etc. It is preferable to use a mold coater, a knife coater, and a spot coater. Effectively manufacturing without voids, having a uniform insulating resin layer 15 thickness In the insulating resin sheet 10 with a metal foil, the thickness of the insulating resin layer 15 is usually Ιμηη or more and 6〇μηι or less, preferably 5μηι or more and 50μηη or less. On the metal foil crucible 3, two metal foil-attached insulating resin sheets 10 which are sequentially laminated with the base resin layer 12 and the insulating resin layer 15 are prepared. Then, on both sides of the sheet-like fibrous base material 14, The insulating resin layer 15 of the insulating foil 10 having the metal foil is disposed face to face 100129155 35 201213112 (Fig. 3(a)) is heated in a vacuum (9). The conditions of c or more and Mot or less, and the pressure of O.IMPa or more and 5 MPa or less are laminated by both sides of the insulating tree m ο 附 with metal enamel'. The resin constituting the insulating resin layer 15 is contained in the fiber substrate. 14. At this time, the underlying resin layer 12 is still in a semi-hardened state. Thereby, a metal box-attached prepreg ia (Tuyer) before heat hardening can be obtained. Then, the metal clad laminate i is obtained by directly heating and press-molding the prepreg la provided with the metal crucible (Fig. 3 (10). The degree of heating/pressure forming and/or special limitation is more] It is preferable that (10). c or more and 25 generations are '^ particularly good 疋 150C or more and 23 〇〇 c or less. The heat and pressure forming i · force and / have a special limit ' to Q iMpa or more and $ a The following is preferable, and X 〇. 5 MPa or more and 3 MPa or less are particularly preferable. From these settings, the soil, the tree layer 12 and the insulating tree layer 15 can be hardened. In the present embodiment, since In the case of the substrate, the prepreg 1 is produced, so that the surface of the prepreg is high in smoothness, and it can be formed at a low pressure. Further, it can be used in a high temperature bath or the like in a high temperature tank or the like and 3 (9). The temperature is post-hardened. The laminate of the base metal is used as the core substrate, and the printed wiring board can be used. The printed wiring board can be used to manufacture a semiconductor device. Hereinafter, the printed wiring board and the semiconductor package are placed. The manufacturing method will be described. Fig. 4 is not a manufacturing method using the metal clad laminate 1 of the present embodiment. Fig. 4(a) shows an inner layer circuit board 218 in which a circuit pattern is formed by using a metal clad laminate 1 as a core to a substrate. First, a core substrate is bored using a drill to form a hole. Opening 100129155

36 S 201213112 221. The oxidizing agent such as the resin residue salt after the opening can be removed, and the material is: = 2 lignin is a clad laminate 1 as the core substrate: only the form of gold can be used, and the slag can be transferred to the county (four) (four) After - /, the name of the contact point of the 13th. Then, by the electroless female, the opening 22ng is subjected to the conduction treatment on both sides of the inner layer circuit board 218, and the metal is etched by the metal, and the inner layer circuit 217 is formed by etching the metal of the core substrate. In addition, the inner circuit board 218 can be used to capture the sound. Ai, P卩Γ7 plus " circuit points for blackening treatment special roughing. Further, the opening π portion 221 is suitable for proper filling of the slurry. The water or resin paste inner layer circuit 217 is made of a material which can be removed by U or by a peeling method when the inner layer circuit is formed. (4) It is called 对 用 用 ( 用 用 ( ( 隹 隹 隹 隹 隹 隹 隹 隹 隹 隹 隹In order to form such a circuit 2, the material of the gold member 13 can be selected, for example, as (4), a copper plate, a copper plate, an alloy, and a nickel. In particular, the copper plate and the copper alloy plate are not only: the choice of the electric anesthetic or the rolled product, but also the inner layer circuit 217 is preferably used because of various thicknesses (10) and (4). • Next, a base resin layer 12 and an insulating resin sheet with a metal case attached to the insulating resin layer 15 are laminated on the metal crucible U in order! The insulating resin layer 15 of G is set to the side of the inner layer circuit substrate 218, and is laminated by covering the inner layer circuit 217 (Fig. 4(b)). The method of laminating (lamination) of the laminated material for printed wiring boards is preferably carried out by vacuum pressing, atmospheric lamination, and heating under vacuum 100129155 37 201213112. The method of laminating H is preferable, and (4) A method of laminating a laminate which is heated and pressurized under vacuum. The temperature at which the insulating resin layer 15 is formed by heating to harden is not particularly limited, but is preferably in the range of 100 〇 c or more and 250 ° C or less. It is especially good for 15〇°c and 23〇. 〇The following. In addition, for the subsequent laser irradiation and easy removal of the resin residue, it is also possible to set the semi-hardened sorrow in advance. Further, the insulating resin layer 15 of the first layer is heated at a temperature lower than the usual heating temperature, whereby local hardening (semi-hardening) is performed, and further, one or a plurality of layers of the base resin layer 12 are further formed on the base resin layer 12. The upper portion is reheat-hardened to the extent that there is no problem in the practical semi-hardened insulating resin layer 15, whereby the adhesion between the insulating resin layers 15 and the insulating resin layer 15 and the circuit can be improved. The semi-hardening temperature at this time is preferably 8 Torr or more and 200 C or less. It is more preferably 100 C or more and 180 ° C or less. Then, the metal foil 13 is etched by a predetermined etching method to form an opening portion 222a (Fig. 4(c)). Then, the insulating resin layer 15 exposed at the bottom of the opening 222a is subjected to laser irradiation to form a hole opening portion 222 (Fig. 4 (d)). As the above-mentioned laser system, an excimer laser, a UV laser, a carb〇I1 dioxide laser, or the like can be used. The hole opening portion 222 formed by the above-described laser is formed so that the material of the insulating resin layer 15 is not related to the photosensitivity/non-photosensitivity, and the fine hole opening portion 222 can be easily formed. Therefore, it is particularly preferable to form a fine opening portion on the insulating resin layer 丨5. 100129155 38 201213112 In addition, a resin residue or the like after laser irradiation can be subjected to a desmear treatment by removing an oxidizing agent such as permanganate or dichromate. By the slag removal treatment, the surface of the smooth insulating resin layer 15 can be roughened at the same time, and the adhesion of the conductive wiring formed by the subsequent metal ore can be improved. According to the insulating resin sheet 10 to which the metal case is attached according to the embodiment, the adhesion between the base resin layer 12 and the outer layer circuit 220 can be maintained after the dross removal treatment. On the surface of the base resin layer 12, since the fine uneven shape is uniformly applied in the slag removal treatment, the adhesion to the outer layer circuit 220 can be improved. Further, since the surface of the insulating resin layer has high smoothness, the fine wiring circuit can be formed with high precision. Then, the outer layer circuit 220 is formed by etching by metal plating to achieve connection between the insulating resin layers (Fig. 4(e)). The method of forming the outer layer circuit 220 can be formed, for example, by a semi-additive method or the like according to a known method, but the present invention is not limited thereto. Next, a conductor stub (p〇st) 223 is formed (Fig. 5(a)). The method of forming the conductor stub 223 can be formed by electrolytic plating or the like according to a known method. For example, when the outer layer circuit 220 is used as a lead for electrolytic plating and copper electrolytic plating is performed, a copper stub can be formed in the hole opening portion 222 filled with copper. Further, by repeating the steps shown in Figs. 4(b) to (e) and Fig. 5(a), a plurality of layers can be formed. Further, in the case where the insulating resin layer 15 is made into a semi-hardened state as described above, there is also a case where post-hardening (p〇stcUre) is performed. Next, a solder resistance 224 is formed (Fig. 5(b)). Further, in Fig. 5(b), 100129155 39 201213112 can be formed into a multilayer structure having two layers of the insulating resin layer 15 by repeating the steps shown in Figs. 4(b) to 4(e) and 5(4). The method of forming the solder resist 224 is not particularly limited. For example, a method of laminating a solder resist material by a dry type of a film can be formed by exposure and development, or a method can be used to borrow (4) light money (10) Formed by the method of formation. In addition, the connection (4) is suitable for metal materials such as gold plating, lining and solder plating. A printed wiring board can be manufactured by the method. In addition, 'when the insulating resin sheet H with a thick metal enamel attached to the metal box is used, 'because it is difficult to optimize the tape in its subsequent circuit pattern, it will be used more than _ above and 5_ A thin copper box or a case where 12 (four) or more and 18 or less copper (10) are thinned to _ or more and one or less (half (four)). In addition, there are cases where (4) and the insulating layer are opened. At this time, the steel (9) is a thinner, half-cooked or extremely thin copper V white 0. Next, a cross-sectional view of a wiring device is performed on a semiconductor device in which a material is corrected. Children. Fig. 6 is a view showing the obtained semiconductor. As shown in Fig. 6, a plurality of electric pick-up electrodes are provided on one surface of the printed wiring board 226. This printed wiring board has an electrode corresponding to the connection. The semiconductor element of the solder bump 汹 is also connected to the printed wiring board π6 via the solder bump 329. 100129155 201213112 Then, the semiconductor element is sealed with the semiconductor element 3 in the printed wiring board. The semiconductor device 32 卩:= (4) The inner layer circuit board 218 is provided with an inner layer circuit 2: a layer 15, a base resin layer 12, and an outer layer circuit 220. The inner layer circuit 2] and the outer layer circuit _ are connected via the conductor stub 223 = The resin layer 15 is covered with a solder resist 224. The edge block is preferably made of an alloy containing tin (Sn), erbium (10), silver ((10), bismuth, bismuth). In the connection method, a flip chip bonding machine or the like is used, and after the electrode portion for connection of the electrode is aligned with the semiconductor element, the solder bump 329 is heated to a melting point or higher by a heat sink or another heating device. And connecting by connecting the printed wiring board 226 on the substrate and the solder bumps 329. In addition, in order to improve the connection reliability, it is also possible to form a metal layer having a relatively low melting point such as tin paste on the printed wiring board. 226 2 = electricity In the above, before the bonding step, the connection can be improved by solder bumps and/or the connection (4) of the soldering/wiring on the printed wiring board. The coating layer is next to the effect of the embodiment. According to the figure (4), according to the fourth embodiment, the thin hard resin layer _, the inorganic filler is an essential component, and the hard base 11 and the metal (four) are interposed with a thin base resin layer 12' to allow prepreg. The body u and the metal 13 wire. Therefore, the prepreg surface can be used in the manufacturing process of the conductor device in which the metal is blanked and the wire is processed or the gold is applied to the prepreg 100129155 2〇1213112. In the case where the adhesion of the metal is reduced, the prepreg u and the metal layer are strongly bonded. In particular, the metal clad laminate 1 of the present embodiment is excellent in hygroscopicity and heat resistance. The peel strength (N,) after treatment at 12 TC and 100% humidity for 72 hours was 0.7 kN/m or more and ISKN/m or less. Further, the peel strength (N) before moisture absorption and high heat treatment and moisture absorption and high heat absorption The difference (ΔΝ) of the peel strength (ΚΓ) after the treatment may be In the present embodiment, the case where the cyanate resin is contained in the thermosetting component of the prepreg 11 is not contained in the underlying resin layer 12, and is not included in the present embodiment. The compound of the primary amino group and the compound having a secondary amine group are preferred. When a compound having a -amino group-based compound and a highly reactive amine group having a secondary amine group is used, there is a base resin layer 12 The amine group promotes the curing of the cyanate resin only. Here, for example, a decane coupling agent is preferably an epoxy decane coupling agent as compared with the amino decane coupling agent, whereby the epoxy decane and the cyanic acid are used. The ester resin is appropriately kneaded and, because there is no hardening promoting action, a chemical bond is formed between the base resin layer 12 and the prepreg. Therefore, the adhesion at the interface between the prepreg 11 and the base resin layer 12 can be enhanced. Further, in the present embodiment, it is preferred that the nano-sized dioxide particles are contained in the base resin layer 12. Thereby, the effect of low thermal expansion and low water absorption can be obtained. Further, in the present embodiment, by controlling the combination of the money coupling agent and the nano smectite particles, the aggregation of the nano dioxin particles can be performed as 42 100129155.

S 201213112 is a metal clad laminate uniformly dispersed in the base resin layer 12]. (Second Embodiment) Fig. 7 is a schematic cross-sectional view showing a metal clad laminate 3 of the present embodiment (or a prepreg 3a with a metal case before heat hardening). As shown in Fig. 7, the metal clad laminate 3 of the present embodiment is formed by sequentially laminating a base resin layer 12 and an insulating resin layer 15 constituting an insulating layer of a printed wiring board on a metal foil. Further, since the base resin layer 12, the metal foil 13, and the insulating resin layer 15 can be used in the same manner as in the first embodiment, the description thereof will be omitted below. Hereinafter, a method of manufacturing the metal clad laminate according to the present embodiment will be described with reference to Fig. 8 . First, the resin compositions (I) and (11) used for the base resin layer 12 and the insulating resin layer 15 are prepared. In the resin composition (II) for the base resin layer 12, each component contained in the base resin layer 12 described in the first embodiment is acetone (acetatene) or methylethyl ketone. Methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexanone, tetrahydroanthracene Tetrahydrofurane), dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, Cellosolve, card In organic solvents such as carbitol and anisole, various mixed grease varnishes such as supersonic dispersion method, high-pressure conflict dispersion method, high-speed 100129155 43 201213112, high-speed twist dispersion method, and bead mill dispersion method are used ( I). The method, the high-speed cutting and dispersing method, and the spinning and revolving machine are dissolved, mixed, and stirred to obtain a tree. (10) The tree-like product (1) of the milk layer 15 is also an insulating resin layer as described in the first embodiment. The resin varnish (I) can be obtained by subjecting each of the above components contained in 15 to the same treatment. Next, the resin varnish (II) is applied to the release sheet by using various coatings I. After the application, the varnish (11) is applied to _16, and then it is applied. Thereby, the base resin layer 12 can be formed on the release sheet 100. Next, ft 曰 π lacquer (1) was applied onto the base resin I 12 by various coating means, and then dried. Alternatively, the resin varnish is applied to the base resin layer 12 by a spray device, and then dried. Thereby, the insulating resin layer 15 can be formed on the base resin layer 12. The insulating resin sheet 31 with the first film attached to the base resin layer 12 and the insulating resin layer 15 is sequentially laminated on the release sheet 16 in this manner. Further, the insulating resin sheet 32 having the second film of the insulating resin layer 15 laminated on the release sheet 16 is prepared. Examples of the release sheet 16 include polyester resins such as polyethylene terephthalate and polybutylylene terephthalate, and fluorocarbon resins. Polymeric thermoplastic resin film having heat resistance such as polyimine resin (polyimide 100129155 44 s 201213112 re_). From the viewpoint of the balance between the adhesion and the releasability of the film-based bottom layer 12 of the film, σ X is preferably a film composed of polyester. The thickness of the peeling slab 16 is not particularly limited, and is usually not more than 1 Mm, preferably 2 Å/mi or more. When the thickness of the peeling sheet 16 is easy to operate at the above-described range, the insulating resin layer 15 is excellent in flatness. Then, the insulating resin sheet 3 with the film is placed on both surfaces of the sheet-like fibrous base material 14 so that the insulating resin layer 15 faces the surface (Fig. 8(a)). The release sheet 16 is formed by laminating the insulating resin layer 15 with the base resin layer 12 interposed therebetween. Therefore, it is preferable to select an operation at the time of lamination. In addition, the second insulating film 3 2 with a film is used for laminating in a state in which the insulating resin layer 15 side is brought into contact with the inner layer circuit 217 in the case of the manufacturing process for the printed wiring board. It is preferable to remove the release sheet 16 so that it can be easily peeled off after lamination. Further, the first insulating film 31 with a film attached thereto may be a carrier with a release sheet 16 on which a resin composition (I) constituting the insulating resin layer 15 is impregnated on the fiber substrate 14 Obtained from the prepreg. In the present embodiment, the "prepreg having the carrier with the release sheet bundle 6" and the "prepreg obtained by impregnating the resin substrate (1) with the fiber substrate 14' and drying it" It can be simply referred to as a "prepreg". As the material of the fiber base 14, the one described in the first embodiment can be used. 100129155 45 201213112 As a method for producing a prepreg with a carrier, for example, a method of preparing a resin varnish (1) constituting the insulating resin layer 15 in advance to impregnate the fiber base material 14 with a solvent by heating and drying is prepared. The volatilized prepreg π is applied, followed by coating a resin varnish constituting the base resin layer 12 on the prepreg 11, followed by 'drying by heat drying to volatilize the solvent, and then attaching the release sheet 16 to the base resin layer 12 A method of forming a prepreg with a carrier; after impregnating the resin varnish (I) constituting the insulating resin layer 15 with the fibrous base material 14, the resin varnish (1) constituting the base resin layer 12 is applied immediately, and thereafter, The method of heating and drying to volatilize the solvent 'then' to attach the release sheet 16 to the base resin layer 12 to form a prepreg with a carrier. As a method of impregnating the resin varnish (I) with the fibrous base material 14, the method described in the first embodiment can be employed. Next, 'insulating the insulating resin layer from both sides of the insulating resin sheet with a film by heating in a vacuum of 6 〇 1 or more and l 3 〇 ° c or less, and pressing O.IMPa or more and 5 MPa or less. The resin composition (I) of 15 is impregnated into the fibrous base material 14. Thereby, the prepreg 42 with the carrier can be obtained (Fig. 8(b)). Next, the release sheet π of the prepreg 42 with the carrier is peeled off to obtain a prepreg 11 (Fig. 8(c)). Then, the insulating resin layers 15 of the two prepregs 11 are disposed to face each other, and the base resin layer 12 and the metal foil 13 are disposed face to face (Fig. 8(d)). Then, the metal clad laminate 3 is obtained by heat and pressure forming from both sides (Fig. 8(e)). Further, the metal foil 13 is as described in the first embodiment, 100129155 46

S 201213112 is preferably made of copper or aluminum. The temperature at the time of heat press molding is not particularly limited, but is preferably 120 ° C or more and 250 ° C or less, and particularly preferably 150 ° C or more and 230 ° C or less. The pressure at the time of heat press molding is not particularly limited, but is preferably from 0.1 MMPa to 5 MPa, particularly preferably from 0.5 MPa to 3 MPa. In the present embodiment, since the prepreg is formed by attaching the substrate, the surface of the prepreg has high surface smoothness and can be formed at a low pressure. Further, it may be post-hardened at a temperature of 150 ° C or more and 300 ° C or less in a high temperature bath or the like as necessary. Further, in the present embodiment, a metal foil-attached resin sheet 31 in which the first release film 16 of the insulating resin sheet with a film is replaced with the metal foil 13 is used, and two metal foils are attached on one side. In the dip, the release sheet 16 is peeled off, and then the metal clad laminate can be produced by bonding the insulating resin layers 15 to each other. Further, by using a plurality of prepregs 11 of Fig. 8(c), it is also possible to manufacture a metal clad laminate in which three or more layers of the prepreg 11 are laminated. In the present embodiment, the insulating resin layers 15 of the two first film-attached insulating resin sheets 31 are directly joined to each other without using the fibrous base material 14, and after the peeling sheets 16 are peeled off, the metal is removed. When the foil 13 is bonded to the exposed base resin layer 12, a metal clad laminate can also be produced. When the metal clad laminate 3 is used as a core substrate, a printed wiring board of 100129155 47 201213112 can be obtained. Fig. 9 illustrates a method of manufacturing a printed wiring board using the first insulating resin sheet 31 with a film-supplied film. In FIG. 9 (the inner layer circuit substrate 218 in which the metal clad laminate 3 is formed as a core substrate), the core board is formed by a circuit pattern. For example, the core board can be FR- A metal foil such as a steel foil is formed on both sides of the (Flame Retardant Type). First, as described in the first embodiment, the core substrate is bored by a drill and an etched wood to form an opening 221 Then, the electroless plating is performed by electroless plating, and the opening portion 221 is subjected to (four) processing to achieve conduction between both surfaces of the inner layer circuit substrate 218. Then, the copper material of the core substrate is called to form the circuit 217 (Fig. 9). (a)) Next, 'the insulating resin sheet 31 with a film is used to cover the inner acoustic circuit 2', and the insulating (four) layer 15 is laminated as the inner layer circuit board side (Fig. 9(b)). The method of insulating and insulating the insulating resin sheet η of the film does not have a method of layering a layer which is preferably a vacuum press, an atmospheric pressure laminator, and a laminate which is heated and pressurized under vacuum. More preferably, it is a method of using a laminate which is heated and pressurized under vacuum. Then, as described in the first embodiment, the insulating resin layer 15 is heated to be cured, and then the base resin layer 12 and the insulating resin layer 15 are irradiated with a laser to form a hole opening portion 222. (Fig. 9(4)). Then, the outer layer circuit 22 is formed (Fig. 9(d)). Thereafter, the same processing as in the first embodiment (Fig. 9(e), (〇)) is performed, and a printed wiring board can be obtained. Further, another method of manufacturing the inner layer circuit board 218 is shown below.

48 S 201213112 Prepare two of the above-mentioned $日日三卜, and then attach it to the film of the edge of the resin sheet 31 (a) with the film-coated insulating resin sheet face-to-face. Both sides of the flaky fiber substrate Η (Fig., then, in the direct air w 0 1MP ^, heating more than 6 且 and 130. (:: below, pressurization «•IMPa or more and 5Μρ& knife edge & sheet 3 丨The condition, Wei has an insulating resin fiber substrate 14. Thus, the resin constituting the insulating resin layer 15 is impregnated into the prepreg 45 to which the HX member is attached (Fig. 100;); There is a film sheet; ^, the peeling sheet 16 of the pre-substrate 45 is peeled off to obtain the prepreg 11 (Fig. 1〇f into 1)). Then, the prepreg 11 is advanced by a drilling machine to form an opening portion 221 (Fig. 2). 12 ^ ...de-plating, a plating metal layer 13a is formed on the inner surface of the base resin layer exposed on both sides and the inner wall of the opening portion 1 (Fig. 10 (phantom). Further, the base layer is covered with a layer of ruthenium The plated metal layer 13a on the 12 is patterned, etched, and formed to form the inner layer circuit 217 (Fig. 10(f)). In the present red form, the use of the metallized layer 13a having a small layer thickness becomes A fine inner layer circuit or the like can be formed. Further, the obtained printed wiring board can be manufactured in accordance with the first embodiment, and the embodiment of the present invention will be described with reference to the drawings. However, these various configurations other than the above may be employed. (Examples) 100129155 49 201213112 (Example 1) A metal clad laminate shown in Fig. 1 was produced by the method shown in Fig. 3. 1) Preparation of Resin Varnish (II) 30.0 parts by weight of a decyloxynaphthalene type epoxy resin (EPICLON HP-5000, manufactured by DIC Corporation) as an epoxy resin, and a phenol varnish as a cyanate resin Type cyanate resin (Primaset PT-30, manufactured by LONZA) 20.0 parts by weight of a hydroxyl group-containing polyamine resin (KAYAFLEX® 155, manufactured by Nippon Kayaku Co., Ltd.), which is modified with a rubber of an aromatic polyamide resin, and a miscible catalyst (manufactured by Shikoku Chemicals Co., Ltd.) 0.3 parts by weight of a mixture of dimethyl hydrazine and methyl ethyl ketone was stirred for 30 minutes to dissolve. Then, an epoxy decane coupling agent as a coupling agent (manufactured by Unicar, Japan, Α187) was added. 0.2 parts by weight of cerium oxide nanoparticle as an inorganic filler (nano-cerium oxide, average particle diameter: 56 nm), 39.5 parts by weight, stirred by a high-speed stirring device for 1 minute, to obtain a resin varnish having a solid content of 30% (π). The combination of the resin varnish (II) is shown in Table! (2) The metal foil 2 with the base resin layer is formed by a dot coating device to dry (after semi-hardening) the base resin layer. 12 The resin varnish (II) obtained above was applied to a copper foil having a thickness of 3 μΐΏ ("MT18SD-H", thickness 3μηι (with 18 μιη carrier), manufactured by Mitsui Mining Co., Ltd.). On one side, the metal foil 2 with the base resin layer was produced by drying it with a drying device of 16 (TC) for 10 minutes. 100129155

S 50 201213112 (3) Production of resin varnish (I) The cooperation of "core 1" of Table 2 is made. Specifically, the cerium dioxide particles ("S〇25R, average particle size 〇5 division" manufactured by Admatech Co., Ltd.) S9 7 wt•%, epoxy resin (Nippon Chemical Co., Ltd., NC3000, biphenyl group) Acryl-based epoxy resin, weight average molecular weight: 1300, softening point: 57 〇 c, epoxy equivalent: 276 g/eq) 11.2% by weight, cyanate resin (manufactured by L〇NZA, Primaset Pt-30, phenol phenolic) Varnish type cyanate resin, weight average molecular weight: 380) 20.0% by weight, phenol resin (manufactured by Megumi Chemical Co., Ltd., MEH785i) 88% by weight, epoxy decane coupling agent (A187 manufactured by Uiiicar Co., Ltd.) 〇 3 weight % was dissolved/mixed in mercaptoethyl ketone, and stirred with a high-speed stirring device to obtain a resin varnish (I) having an epoxy resin composition of 7 Å by weight based on the solid content. (4) The insulating resin layer 15 is applied to the laminate of the metal foil 2 with the base layer by a dot coating apparatus and the resin varnish (1) is applied in the manner of the thickness of the insulating resin layer 15 as described above. On the base resin layer 12 of the metal foil 2 to which the base layer is attached, 16 turns are used. (: The drying device dries it for 10 minutes to prepare an insulating resin sheet with copper foil (semi-hardening). The insulating resin layer 15 is in contact with the fiber substrate μ, and the obtained copper foil is insulated. The resin sheet was placed on both sides of the fiber base material 14 (thickness 48/mi, E-glass woven fabric, WEA4280), and heated under vacuum at a pressure of 0.5 MPa and a temperature of 140 C for 1 minute. Pressurization, the insulating resin layer 15 is impregnated into the fibrous base material 14. At this time, the total thickness of the edge resin layer 15 and the fibrous base material 14 is 60 μm. Then, heating is performed at a pressure of 110 MPa and a temperature of 220 ° C. After press molding for 2 hours, a metal clad laminate 1 having a thickness of 112 μm and having a carrier-attached copper foil (metal foil 13) on both sides was produced. (5) Production of a printed wiring board is shown in Figs. The method is carried out. The carrier copper is peeled off, and the ultra-thin copper foil (metal foil 13) is further removed by etching. Next, a through hole is formed by a carbonic acid laser. Then, the inside of the hole and the surface of the base resin layer are immersed. /Bei 80 C swelling fluid It was immersed for 5 minutes in an aqueous solution of potassium permanganate (Concentrate Compact CP, manufactured by Admatechs Co., Ltd., manufactured by Admatechs Co., Ltd., manufactured by Admatech Co., Ltd.), neutralized and coarsened. After the step of degreasing, catalyst addition, and activation, a plating resistance of about 1 μm is formed on the electroless copper plating film, and an electroless copper plating film is used as an electric layer to form a pattern electroplated copper. The micro-circuit is processed by ι/ρυ/υμηι. Then, after annealing for 60 minutes in a hot air drying device, the electrode layer is removed by flash etching. Next, 'printing solder resist (solar ink manufacturing ( )R), psR_4〇〇〇AUS703) 'The semiconductor device is mounted with a spacer or the like, and exposed, developed, and cured with a predetermined mask to form a solder resist layer thickness of 12 μm on the circuit. The solder resist layer is exposed on the circuit layer and is formed to contain no 100129155

S 52 201213112 Electrolytic nickel plating layer 3μηι, and a plating layer of electroless gold plating layer 〇.1μηι thereon, to obtain a multilayer printed wiring board for a semiconductor device. (6) Production of semiconductor device A semiconductor device shown in Fig. 6 was produced. Specifically, in the semiconductor device, a semiconductor device having a solder bump (a TEG wafer size of 8 mm x 8 mm and a thickness of 0.1 mm) is mounted on the multilayer printed wiring board for the semiconductor device by press-bonding by a flip chip bonding machine. Then, the solder bumps were melt-bonded by an IR reflow furnace, and then filled with a liquid sealing resin (CRP-4152S, manufactured by Sumitomo Bakelite Co., Ltd.) and cured by curing the liquid sealing resin. In addition, the liquid sealing resin is cured at a temperature of 15 (rc, 12 minutes, and the like, and the welding of the above-mentioned semiconductor element is formed by a eutectic composition composed of Sn/Pb'). The router was cut into a size of 14 mm x 14 mm to obtain a semiconductor device (Example 2). Except that the resin varnish (II) was subjected to the cooperation of Table 1, the same procedure as in Example 1 was carried out. Specifically, in addition to changing the blending amount of the resin varnish („) to a phenol novolac type cyanate resin as a cyanate resin, “·· u reset ^ 4 points, as a fragrant polyamidamine tree The light base contains 300 parts of polyammonium wax, and the cerium oxide nanoparticle 24 5 . mn ^ , which is an inorganic filler, is treated in the same manner as in Example 1. 3) In the same example, except that the resin varnish (II) was blended according to Table 1, 100129155 53 201213112 specific μ, except that the amount of the resin varnish m) was changed to a methoxy naphthene type as an epoxy resin. The epoxy resin is in parts by weight, as the secret of the acid § resin, the lacquer type qi acid _lipid 2 Parts by weight, (iv) the aromatic polyamide resin as the resin containing polylactic times _ in parts by weight, as the addition of the inorganic filler-dioxo Qienai Mi particles 95 parts by weight, the process described in Example 1. (Example 4) Except that the resin varnish (1) was blended in accordance with "2" of Table 2, and treated with a glass woven fabric (thickness m, Nitto Kokubun, woven fabric, wm_ other than (4) Example 3) Specifically, in addition to the blending of the resin varnish (1), it is defined as 69.7 wt% of the silica dioxide particles, 84 wt% of the epoxy resin, 15.0 wt% of the cyanide resin, and 6.6% by weight of the epoxy resin. In the same manner as in Example 3, the above-mentioned glass woven fabric was treated with the above-mentioned glass woven fabric. (Example 5) Except that the resin varnish (1) was subjected to the "core 3" of Table 2, The treatment was carried out in the same manner as in Example 3. Specifically, in addition to the resin varnish (1), the cerium oxide particles were 69.7 wt%, and the epoxy resin (manufactured by DIC Corporation, EXA7320, methoxynaphthalene diterpene type epoxy tree) The softening point: π., epoxy equivalent: 255 g/eq) 14.9 wt%, hardening catalyst (manufactured by Sumitomo Bakelite Co., Ltd., C05-MB, phosphorus-based catalyst) 3.3% by weight, epoxy decane The mixture was treated with 〇.4% by weight and was not treated with phenol resin. The treatment was carried out in the same manner as in Example 3. 54 100129155

S 201213112 (Synthesis Example 1) Cyanate resin (naphthyl aralkyl type cyanate resin) Addition of naphthol aryl-based resin (manufactured by Nippon Steel Chemical Co., Ltd., SN485N, base equivalent: 215 g/eq) 101 g ( 0.47 mole of mercapto) and 400 g of decyl isobutyl ketone (hereinafter abbreviated as MIBK) were stirred and dissolved at room temperature. After dissolution, it was cooled to -1 o ° C. When cyanogen bromide (hereinafter referred to as BrCN) 110 g (purity: 95% '0.987 mol) was added at -1 ° C, when the internal temperature became, it took 1 hour to drip triethylamine (hereinafter abbreviated as TEA) 100 g (hereinafter referred to as TEA). Mixture of 0.99 moles with MIBK 600g. After the dropping, the aging was further carried out for 30 minutes, and the ripening was further carried out for about 2 hours to complete the reaction. To the obtained solution, 400 ml of pure water was added to carry out liquid separation, and then 1000 ml of a 5% hydrochloric acid aqueous solution (HC1) was added thereto to carry out liquid separation. Further, the mixture was washed twice with 500 g of 10% saline, and washed twice with 500 ml. After the organic layer was dehydrated with anhydrous sodium sulfate, the solvent was removed under reduced pressure to obtain a solid resin. After the obtained solid matter is washed with cyclohexane, the naphthyl aralkyl type cyanate resin can be obtained by drying under reduced pressure. The naphthyl aralkyl type cyanate resin obtained by the treatment was analyzed by infrared spectroscopy (IR prestige-21 manufactured by Shimadzu Corporation, KBr penetration method), and the absorption band of the phenolic hydroxy ίί was 3200 to 3600 cm _1 . When it disappeared, it was confirmed that the absorption band of the nitrile of the cyanate resin was around 2264 cm·1. (Example 6) The same procedure as in Example 3 was carried out except that the resin varnish (I) was carried out in accordance with the "core 4" of Table 2. 100129155 55 201213112 Specifically, in addition to the resin varnish (1), cerium oxide particles (S025R, manufactured by Admatech Co., Ltd., average particle size 〇5/m〇517% by weight, cerium oxide particles (manufactured by Shin-Etsu Chemical Co., Ltd., KMp6) were used. 〇〇, average particle size: 5/Xm) 9. 〇 weight ° / 〇, epoxy resin (Nippon Chemical Co., Ltd., NC3000, phenyl aryl alkyl type oxygen resin, weight average molecular weight: 13 〇 〇, softening point: 57C, epoxy equivalent: 276g/eq) 15.4% by weight, epoxy resin (made by DIC Corporation, HP4032D, naphthalene type epoxy resin (semi-solid at normal temperature), epoxy equivalent: 152g/eq) 1.9% by weight, cyanate ester (SN485 derivative) synthesized in Synthesis Example i, 12.7% by weight, maleic acid imide resin (manufactured by KI Chemical Co., Ltd., BMI70), 8.5% by weight, hardening catalyst (Osaki Industrial Co., Ltd., zinc octoate) 〇 4% by weight, 0.3% by weight of an epoxy resin coupling agent, and treated in the same manner as in Example 3 (Example 7) 5". Specifically, in addition to the resin varnish (I), the use of dioxide (manufactured by Admatech Co., Ltd., S025R, average particle diameter: 0. 5 μηι), 39.8 wt%, aluminum hydroxide (manufactured by Sakamoto Light Metal Co., Ltd., ΒΕ033, average particle diameter: 2/xm), 19.9% by weight, talc (manufactured by Fuji Talc Co., Ltd., LMS200 'Average particle diameter: 5/mi) 10.0% by weight, epoxy resin (manufactured by DIC Corporation, N665EXPS, cresol novolak type epoxy resin, softening point: 70 ° C, epoxy equivalent: 209 g / eq) 17.8 weight %, phenol resin (manufactured by Sumitomo Durez Co., Ltd., PR51470, novolac type phenol resin, OH equivalent: 105), 11.9% by weight, hardening catalyst (manufactured by Degussa, dicyandiamide) 〇3 100129155 56 201213112% by weight, ring The oxygen oxysulfide coupling agent was 0.4% by weight, and was treated in the same manner as in Example 3 except that the cyanic acid S resin was not added. (Example 8) Except that the resin varnish (II) was blended in accordance with Table 1, Example 1 The treatment was carried out, except that the blending of the resin varnish (II) was changed to 40.0 parts by weight of bisphenol A type epoxy resin (EPICODE 828EL, manufactured by Nippon Epoxy Co., Ltd.) as an epoxy resin, and it was used as cyanic acid. Ester resin phenol novolak type cyanate resin 2 0.0 parts by weight, the hydroxyl group of the aromatic polyamide resin contains 30.0 parts by weight of a polyamide resin, 0.1 parts by weight of an epoxy decane coupling agent as a coupling agent, and 9.6 parts by weight of cerium oxide nanoparticles as an inorganic filler. The treatment was carried out in the same manner as in Example 1. (Example 9) The same procedure as in Example 1 was carried out except that the resin varnish (II) was blended in accordance with Table 1. Specifically, the blending of the resin varnish (II) was changed to 40.0 parts by weight of a phenol aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000H) as an epoxy resin, and it was used as a cyanate resin. 20.0 parts by weight of the phenol novolac type cyanate resin, 30.0 parts by weight of the hydroxyl group of the aromatic polyamide resin, and 9.5 parts by weight of the cerium oxide nanoparticles as the inorganic filler. Example 1 was processed. (Example 10) The same procedure as in Example 1 was carried out except that the resin varnish (II) was blended in accordance with Table 1. Specifically, in addition to the resin varnish (II), 40.0 parts by weight of an epoxy resin (HP-7200, manufactured by DIC Corporation) having an epoxy resin and having a dicyclopentadiene skeleton as an epoxy resin was used as a cyanide. 20.0 parts by weight of the phenol novolac type cyanate resin of the acid ester resin, 30.0 parts by weight of the hydroxyl group of the aromatic polyamide resin, 0.1 part by weight of the epoxy decane coupling agent as a coupling agent, and inorganic filler The same procedure as in Example 1 was carried out except that 9.6 parts by weight of the cerium oxide nanoparticles were used. (Example 11) The same procedure as in Example 1 was carried out except that the thickness of the base resin layer 12 after drying (after semi-hardening) was 10/mi and the thickness of the copper-clad laminate was 122/xm. (Comparative Example 1) The treatment was carried out in the same manner as in Example 1 except that the base resin layer was removed. (Comparative Example 2) The same procedure as in Example 1 was carried out except that the resin varnish (II) was blended in accordance with Table 1. Specifically, the treatment was carried out in the same manner as in Example 1 except that the blending of the resin varnish (II) was changed to 39.5 parts by weight of the cerium dioxide particles (S025R, average particle diameter 0.5 μηι) manufactured by Admatech Co., Ltd. as an inorganic filler. . (Comparative Example 3) The same procedure as in Example 1 was carried out except that the resin varnish (II) was blended in accordance with Table 1. Specifically, the resin varnish (II) was changed to 39.5 parts by weight of a nonoxynaphthalene aralkyl type epoxy resin as an epoxy resin, and a phenol novolac type cyanate resin 30.0 as a cyanate resin.重量份为为100129155 58 201213112 , * The hydroxyl group of the fragrant surface polyamide resin contains 30.0 parts by weight of polyamidamide resin, 5 parts by weight of imidazole oxime which is a curing catalyst, and no coupling agent and kiln filler are used. n ^ . . Coherent Example 1 for processing. (Comparative Example 4) The same procedure as in Example 1 was carried out except that the varnish (H) was carried out in accordance with Table 1. θ _ , specifically, 'in addition to changing the resin varnish (π), 35.0 parts by weight of a methoxynaphthalene-based epoxy resin as a oxyn epoxide, and a phenol novolak-type cyanide as a cyanoester resin 25.0 parts by weight of an acid ester resin, an epoxy Wei coupling agent as a coupling agent. The treatment was carried out in the same manner as in Example 1 except that the weight fraction was 39.4 parts by weight of the cerium oxide nanoparticles as the inorganic filler, and the aromatic polyamine resin was not used. (Comparative Example 5) The thickness of the base resin layer after drying (after semi-hardening) was set to 3j [mi], and the thickness of the copper-clad laminate was set to 1 除了, except that the resin varnish (II) was blended according to Table i. Processing was carried out in the same manner as in Example 1 except for 8 μm. Specifically, in addition to changing the hydroxyl group of the aromatic polyamide resin, 60 parts by weight of the polyamide resin, 0.3 parts by weight of the epoxy decane coupling agent as a coupling agent, and the cerium oxide nanoparticle 39.7 as an inorganic filler. The same as in Example 1 except that the resin varnish (11) was prepared without using an epoxy resin, a cyanate resin, and a curing catalyst. The numerical unit of the resin material in Table 1 is "parts by weight". 100129155 59 2 1X 1X 3 1X2 1Xo2 [Id I-1 1 s Discussion*—< Invite 1 UJ 1 inch § Q m 3 3 1 You ω Q 1 8 1 Invite 1 ω Ring (7) 1 o _ ΓΠ 3 S ω honey - 牮% ω 1ST 1 o § SS ο «F 1 υα Ιο 苏— s 苕S ·—· 1 κη W Field ω 盏OS IS 1 1 1 3 s § w-> Tulu ω 念 00 IS 1 1 § § 3 S 1 ν-> Tj invites 1 to I- 1 1 1 S s Τ »Τ) ωω fvo 1 1 1 3 s 1 inch Chu I ω 1 S s 3 s 1 ^Τ) . «ff UQ Accumulated 1 1 Case 3 s 1 (N I3f Η Italian m Su 1 1 s S3 S s Discussion f ω I- Handle 1 1 1 S s ω 1 | _ 3 s _ f ω ♦ l 4〇 Bg § ei 翁 翁 1 i 蜃1 I ild I^I 酴 also S | l§ like 56] i I fi ? a)qi 1 f 1| ilnr SI! iim 珥 garlic! *=m CQ <1 M 4 li % 〇L 1 I 1 Fragrance II ϊν〇"<0 § Igp Ιϊδ i II® i)D 1)01 @11 4isS ilm !i I g 1 _ i -V i φ m mm tin 韬09 ¢-6-001 s 201213112 1:3⁄4. "%¥_", #和蚌mfw^tog r-&-(N^ Core 5 WEA1280 60μτη 17.8 11.9 39.8 19.9 10.0 ro 〇 Core 4 WEA1280 60jUin 15.4 Ο) 12.7 IT) OO 51.7 rn Core 3 WEA1280 60/ Rni 14.9 14.9 69.7 cn inch 〇 core 2 WTX1280 1 βΟμεη , 3 15.0 v〇Vd 69.7 inch · core 1 WEA1280 60/m 11.2 20.0 oo od 59.7 NC3000 HP4032D N665EXPS EXA7320 PT30 SN485 derivative MEH7851 1_ PR51470 BMI70 S025R KMP600 BE033 LMS200 BMT- 3L Phosphorus Catalyst Zinc Oxide Ί Ί 环氧 Epoxy > 5 夕 t t W9- Formulation Epoxy Cyanate Vinegar Resin Resin Butanimide Resin F Filler Inorganic Filler Hardening Catalyst Coupler 19- 163102 201213112 The measurement method is as follows. 1. The particle size of the cerium oxide nanoparticle is in the middle of the osmosis by using the ultrasonic wave to make the cerium cerium particle (the cerium dioxide particle). The 'LB-550' was measured on a volume basis to measure the particle size distribution of the rice dioxide particles (earth dioxide particles). Specifically, the average particle diameter 矽 of the inorganic filler such as oxygen brother particles and dioxo particles is defined by the volume cumulative particle diameter Dm. 2. Linear expansion ratio (the copper layer of the copper-clad laminate obtained in the respective examples and comparative examples is removed by silver engraving, and the base resin layer and core layer (prepreg) from which the copper foil has been removed are removed. A test piece of 4 mm x 2 mm was prepared with a core layer of a base resin layer, and a TMA (thermo-mechanical analysis) device (manufactured by TA Equipment Co., Ltd., q4 〇〇) was used, and the temperature was around 3 G to 3 GG ° C, 10 ° C. The linear expansion coefficient (CTE) in the plane direction (χγ direction) at 50 to 150 ° C in the second cycle was measured under a condition of a load of 5 g/min. The CTE of the base resin layer was set to the core layer. The CTE of the dip) was set to %, and the cTE of the core layer with the base resin layer was set to %. The results are shown in Table 3. 3. The modulus of elasticity (E) was obtained by etching in the examples and comparative examples. The copper foil of the copper-clad laminate was removed, and a test piece of 8 mm x 30 mm was prepared from the base resin layer, the core layer, and the core layer with the base resin layer, and DMA (dynamic viscoelasticity measurement 100129155 62) was used.

201213112 (available from ΤΑ Equipment Co., Ltd., q8〇〇), the tensile elastic bond was measured under the conditions of a temperature range of 3 〇 to 3 5 叱, 5 ^ / min, a frequency of 1 Hz, and washing. The number of elastic layers of the base resin layer was set to ErH (prepreg), and the modulus of elasticity of the core layer with the base resin layer was set to & and the results are shown in Table 3. 4. Peel strength (N) Copper was removed by etching from the copper-clad laminate obtained in the examples and the comparative examples, and immersed in a swelling liquid at 60 ° C (manufactured by Admatechs, swelling DIP Secudganth®) 10 The mixture was further neutralized and subjected to a roughening treatment after being immersed for 5 minutes in an aqueous solution of 8 〇 <t of potassium persulfate ("c〇ncentrate compact CP" manufactured by Admatech Co., Ltd.). After the steps of degreasing, catalyst application, and activation, an electroless copper plating film of about Ιμηι and electroplating copper 30 μm was formed in a hot air drying apparatus at 2 Torr. (: The annealing treatment was carried out for 4 minutes in the 4th step. A test piece of l〇〇mmx20nini was produced according to JIS-C-6481, and the peel strength at 23 ° C was measured. The results are shown in Table 3. 5. Moisture peeling (Ν' The test piece of l〇〇nim><20 mm obtained as described above was subjected to one-side etching, and was treated by a pressure cooker at 121 ° C and a humidity of 1% for 72 hours. The peel strength measurement was based on JIS- C-6481. The results are shown in Table 3. 6. Fine line processability evaluation The appearance inspection and conduction test of the thin line of the L/S=12/12 pattern obtained in the examples and the comparative examples by using a laser microscope The results are shown in Table 3. The results are shown in Table 3. The symbols are as follows: ◎: There is no problem in shape and conduction. No knowledge, no wiring, no problem. X: Short circuit, wiring cut Case 7. Insulation reliability evaluation replaces the solder resistance on the pattern of L / s = 丨 2 / 12 obtained in the examples and comparative examples. _ layer / hardened with 4 layers (Sumitomo Electric Wood, dedicated gs) , continuous evaluation under conditions of temperature not, humidity 85%, and application of μ 3 · 3 ν Insulation resistance. In addition, (4) Anti-value coffee is regarded as a failure. The results are shown in Table 3. The symbols are as follows: ◎: No problem for more than 300 hours 150: 150~ less than 300 hours X: less than 150 hours 8. Semiconductor device Warpage evaluation regarding the dimensions of the main conductor device obtained in the examples and comparative examples

MmmxHnnn reads music at room temperature and 26 (rc), and manufactures a temperature-variable laser three-dimensional measuring machine (manufactured by Hitachi Technology and Services Co., Ltd., form LS220-MT! 00MT5 0), and is based on the semiconductor component surface. Placed in the sample chamber of the above measuring machine, the height direction (displacement, the maximum value of the difference is regarded as the amount of warpage. The results are shown in Table 3. The % is the following. Normal temperature (23 ° C) ◎ : < 150μιη 100129155 64 201213112

〇: 150 〜 200 μιη X · > 200 μπι 260 〇 C ◎ : < ΙΟΟμπι 〇: 100 〜 150 / mi X : > 150 μηη 9. Thermal shock test The semiconductor device obtained in the examples and the comparative examples was used for fluorine. The treatment machine was set to one cycle at -55 ° C for 30 minutes and 125 ° C for 30 minutes, and was taken out every 100 cycles, and the presence or absence of abnormality was evaluated by a conduction detector. The results are shown in Table 3. The symbols are as follows. ◎ : No abnormality in 1000 cycles or more 500: 500 to less than 1000 cycles have an abnormality X: less than 500 cycles have an abnormality 10. The shaking ratio is obtained by using the resin varnish (II) obtained in the examples and the comparative examples in E The viscosity of the type a (manufactured by Toki Sangyo Co., Ltd. 'RE-550 type) was calculated by the rotation ratio of 5 rpm and 50 rpm (shake ratio = 5 rpm / 50 rpm). The measurement temperature is set at 25 °C. The results are shown in Table 3. 11. Uniformity of coated surface The copper foil with the base resin layer obtained in the examples and the comparative examples was visually observed to have a width of 250 mm and a length of 5 m. The results are shown in Table 3. Symbol 100129155 65 201213112 is as follows. ◎: No defects on the coated surface 〇: Defects substantially free of defects X: A large number of defects occurred 100129155 66 3 112 1X20 2 Meals a 〇5 ro 〇CN 00 ΓΟ o <N ◎ XX 〇X Comparative Example 4 I 〇1 -H rn 〇v〇ο inch〇o XXXXX 〇p X § TH CN 00 ο r〇dl〇CN ◎ XX 〇X <N £ ^ Ο rH i—HX s CO g § ggg § § § § £ ^ Ο 1-H 1 1 1 VO ο 寸 do 卜 CN XX 〇〇〇 ^ - Ο 1-H f—( ◎ s in cn ο r—4 ο o TH (N ◎ 〇〇〇 ◎ Read 2 Ο »-H tH ◎ O c4 ΙΓϊ Ό \ Ο g Ο or·^ <N ◎ ◎ 〇〇 ◎ Ο r—Η ( ◎ o ί—H o CS ^Τ) α\ ο 00 ο o T·^ (N ◎ ◎ 〇〇 ◎ 碧竺Ο y-4 ◎ o rH 0 01 00 ο !S Ο o (N 〇〇〇〇〇ο 1-Η iH ◎ oo CN ιη Ον Ο gdo 00 CN ◎ ◎ 〇〇〇 5 5 ο <N rH ◎ o »-H o CN 〇\ ο goo Art ◎ ◎ 〇〇〇00 rH ◎ oo (N 〇\ ο so 00 ON (N ◎ ◎ ◎ ◎ ◎ 雀 inch ^H ◎ o 〇CN νη Ον Ο so VO ◎ ◎ ◎ ◎ ◎ Series 2 and Army ο »-Η i H ◎ o rH 〇CN OS Ο § oo »—H <T) (N ◎ ◎ 〇〇〇母< 军ο τ-Η <N ◎ in 卜^Ti <N 00 ο soo (N ◎ ◎ 〇〇〇省二ο m 〇s ^T) JO ο cn O o CN 〇〇〇〇〇0斗S α Οη o 1 a Oh aa (3⁄4 O kN/m kN/msaa <n ϋ 1 1 Assessment content CTE(a2) Elastic modulus (e2) Shake ratio (5 rpm/50 rpm) Uniformity of coated surface i CTE (4) Elastic modulus 03⁄4) SAP peel strength (A)(N) ^ δ 娥5 4ttL »—' Double? 3 « [r CTE(c^) Elastic modulus (E3) Thin line workability (LS=12/12) Insulation reliability (LS=12/12, BHAST under 3V) New song (normal temperature) Warp 06〇 . 〇Λ ^ Is 41 3 9 Award 0 ^ 1^- Core material evaluation (including substrate) Substrate evaluation O i5 S' ^ ^ a, ^ s-6-02 201213112 [Simplified illustration] Figure 1 is a schematic representation A cross-sectional view of an example of a metal clad laminate according to the first embodiment. Fig. 2 is a view showing an example of a method of producing a metal clad laminate according to the first embodiment. Fig. 3 is a cross-sectional view schematically showing an example of a method of producing a metal clad laminate according to the first embodiment. Fig. 4 is a cross-sectional view schematically showing an example of a method of manufacturing a printed wiring board using the metal clad laminate according to the first embodiment. Fig. 5 is a cross-sectional view schematically showing an example of a method of manufacturing a printed wiring board using the metal clad laminate according to the first embodiment. Fig. 6 is a view schematically showing an example of a semiconductor device using the metal clad laminate according to the first embodiment. Fig. 7 is a cross-sectional view schematically showing a metal clad laminate according to a second embodiment. Fig. 8 is a view showing an example of a method of producing a metal clad laminate according to a second embodiment. Fig. 9 is a cross-sectional view schematically showing an example of a method of manufacturing a printed wiring board using the metal clad laminate according to the second embodiment. Fig. 10 is a cross-sectional view schematically showing an example of a method of manufacturing a printed wiring board using the metal clad laminate according to the second embodiment. [Description of main component symbols] 100129155 68 201213112 1 la 2 ψ ' 3 3a 10 11 11a 12 13 13a 14 15 16 31 # 32 42 45 101 Metal-clad-laminated board Pre-attached with metal foil Prepreg with metal foil Metal foil with primer resin layer Metal-clad-laminated board Metal foil prepreg (Prepreg with metal foil) Insulation resin sheet Prepreg Semi-cured prepreg Primer resin layer Metal foil Metal layer Fiber substrate (Fiber) Insulation resin sheet (Insulation resin sheet) First insulating film sheet with first film (Insulating resin sheet with second film) Prepreg with carrier Prepreg with carrier Fiber base material 100129155 6 9 201213112 102 103 104 105 106 108 217 218 220 221 222 222a 223 224 226 325 327 328 329 330 Impregnation tank Resin varnish Dip roll Squeeze roll Dryer (Dryer) Upper Roller Internal-layer circuit Internal-layer circuit board External-layer circuit Opening (Opening) Opening (Opening) Conductive post Solder resist Printed wiring device Semiconductor device Electrode part for connection Semiconductor chip Solder bump Liquid encapsulation resin 100129155 70

Claims (1)

201213112 VII. Patent application scope: 1. A metal clad laminate comprising: a prepreg comprising a resin composition containing a thermosetting component and an inorganic filler as essential components (1) impregnating at least one layer of the substrate. And a metal foil laminated on both sides or a single surface of the prepreg; and between the prepreg and the gold radiant to make the prepreg and the gold base resin layer The thickness is thinner than the film thickness of the above prepreg, and the partition is densely attached to the foil. The above-mentioned maleimide II. The metal-clad laminate thermosetting component of claim 31 of claim 31 is composed of cyanide, epoxy resin, cis resin and lysine. Select at least two or more of the constituent groups. 3. The metal clad laminate according to claim 1 or 2, wherein the base tree I layer is composed of a resin composition containing at least an aromatic polyamide resin and a thermosetting resin and a green filler. ) formed. 4. The metal clad laminate according to claim 3, wherein the aromatic polyamine resin is a compound represented by the following general formula (1), [Chemical Formula 1] An and Ah represent a divalent aromatic group, and may be the same or different; X series 100129155 71 201213112 represents a group having a rubber component. 5. The metal clad laminate according to claim 3, wherein the thermosetting resin comprises an epoxy resin and a vinegar resin. The metal-clad laminate-filled particles of the third aspect of the patent application include the cerium oxide nanoparticles. In the upper part of the patent range, the sixth item is exhausted _ layer board, in which the volume cumulative particle size of the upper # and the second (four) nano particles... two: pass below 100nm. Above and 8. If you apply for a patent Fan Park, the above base tree w layer can not pass! ^2 metal clad laminate, wherein the amine compound. (3) A compound having a -amino group and having a second order. The elastic modulus of the base resin layer of the above-mentioned base resin layer is a. 10. A printed wiring board is formed by processing a laminated laminate. The gold standard of the item is made by mounting the semiconductor component on the patent application model. 12. A method for producing a metal-clad niobium plate comprising a resin composition comprising a metal ferrocyanating component and (4) a colloidal ore containing a thermosetting filler as an essential component. (J) impregnating the substrate with at least one layer or more; 100129155 S 201213112 A base resin layer having a film thickness thinner than the thickness of the prepreg is interposed between the prepreg and the metal foil, via The base resin layer adheres the prepreg to the metal crucible. 4. The method for producing a metal clad laminate according to claim 12, wherein the thermosetting component is a cyanate resin, an epoxy resin, a butadiene diimide resin, and a resin. Select at least two or more of the constituent groups. The method for producing a metal clad laminate according to claim 12, wherein the base resin layer is a resin composition containing at least an aromatic polyamide resin and a thermosetting resin and filler particles. And (11) forming the base resin layer by semi-hardening the base resin layer in the prepreg and the metal crucible (4) to harden the base resin layer by heating and/or pressurizing The dip is densely bonded to the above metal foil. , ^, as in the application of the patent scope of the 12th or 13th metal clad laminate method, the method of "in the above-mentioned metal box in the above steps of the prepreg, so that at 3 (TC, 1Hz The base resin layer having a measured elastic modulus of iGpa or more and 5 GPa or less is interposed between the prepreg and the metal ion n to make the pre-adhesive and the gold I closely adhered. The method of forming the metal-clad laminate of the U-item, and the gold-plating of the towel, before the step of the prepreg, further comprises the step of forming the prepreg of the pre-baked layer of the surface resin layer. a step on the face of the shirt, and the above-mentioned base resin having a rocking ratio (a ratio of a viscosity at a rotation number of 5 rpm obtained by using ε' type adhesive 100129155 73 201213112 to a viscosity at 50 rpm) of 0.7 or more and 1.5 or less The method of manufacturing the metal-clad laminate according to the invention of claim 12, wherein the step of laminating the metal foil on the prepreg comprises: Base resin layer The insulating resin layer of the above resin composition (I) is formed on a metal foil, and two steps of providing an insulating resin layer with a metal foil; and insulating the above-mentioned substrate in the above two metal box-attached insulating materials The steps of forming the above prepreg between the resin layers under pressure reduction and heat treatment are performed. 100129155 74