JP5056099B2 - Curable resin composition, resin-impregnated base material, prepreg, substrate, metal foil with adhesive layer and printed wiring board - Google Patents

Description

  The present invention relates to a curable resin composition, a resin-impregnated base material, a prepreg, a substrate, a metal foil with an adhesive layer, and a printed wiring board.

  In recent years, the mounting density of electronic components has increased as electronic devices have been rapidly reduced in size and performance. For this reason, demands for multilayered printed wiring boards, reduced through-hole diameters, and reduced hole spacing are increasing, and printed wiring boards are strictly required to have electrical insulation characteristics. As the electrically insulating resin, thermosetting resins such as phenol resin, epoxy resin, polyimide resin, polyamideimide resin (see Patent Document 1), bismaleimide-triazine resin, etc. are widely used. Fluorine resin, polyphenylene ether resin A thermoplastic resin such as the above may be used.

  On the other hand, with the progress of miniaturization and high density of printed wiring boards, the mounting form is changed from a pin insertion type to a surface mounting type, and further an area array represented by BGA (ball grid array) using a plastic substrate. Progressing to mold. In a substrate on which a bare chip such as a BGA is directly mounted, the connection between the substrate and the chip is generally performed by wire bonding by thermosonic bonding. For this reason, the substrate on which the bare chip is mounted is exposed to a high temperature of 150 ° C. or higher, and a certain degree of high heat resistance is required for the electrically insulating resin in the substrate. In addition, it may be required that a so-called repair is possible, in which a chip once mounted is removed from the substrate. In repair, when the mounted chip is removed and the chip is mounted again, the same amount of heat is applied to the substrate as in the first chip mounting. Therefore, a substrate that requires repairability is required to have a high thermal shock resistance that can withstand a heat history that is cyclically applied. Generally, an electrically insulating resin is a fiber base material due to the lack of thermal shock resistance. In some cases, such as peeling between the resin and the resin. Also in this respect, high heat resistance is required for the electrically insulating resin in the substrate.

In addition, lead-free solder is being promoted from the viewpoint of environmental problems. However, since the melting temperature of the solder is increased accordingly, the substrate is required to have higher solder heat resistance. From the viewpoint of environmental problems, the requirement for halogen-free substrates is also increasing, and the use of brominated flame retardants has become difficult.
JP 2005-325162 A

  However, it has been difficult for conventional resin compositions to achieve a sufficiently satisfactory level in all of the halogen-free flame retardancy, heat resistance, flexibility and adhesiveness.

  Accordingly, an object of the present invention is to provide a curable resin composition that has sufficient flame retardancy while being halogen-free, and can have excellent flexibility, heat resistance, and adhesiveness. . Moreover, an object of this invention is to provide the prepreg obtained using this curable resin composition, the resin impregnation base material, a board | substrate, metal foil with an adhesive layer, and a printed wiring board.

  The curable resin composition of the present invention contains an acrylic rubber, a thermosetting resin, a phosphorus compound, and urea and / or a urea derivative.

  The curable resin composition of the present invention can be used in combination with the above components, and has sufficient flame retardancy and excellent flexibility, heat resistance and adhesiveness while being halogen-free. . Moreover, the printed wiring board obtained using the curable resin composition of this invention can prevent the insulation defect, conduction | electrical_connection breakdown, etc. by metal migration more favorably.

  The curable resin composition preferably contains urea silane as a urea derivative. Thereby, the adhesiveness between the metal and the resin can be further improved.

  The acrylic rubber has a glycidyl group, and the epoxy value of the acrylic rubber is preferably 2-18. By including such an acrylic rubber, the effect of improving the flexibility as well as being excellent in heat resistance and insulation properties becomes more remarkable.

  The weight average molecular weight of the acrylic rubber is preferably 10,000 to 2,000,000. By adjusting the weight average molecular weight within such a range, the flexibility of the curable resin composition can be further improved.

  The blending amount of the acrylic rubber is preferably 10 to 70% by mass with respect to the total amount of the curable resin composition.

  The thermosetting resin is preferably an epoxy resin or a phenol resin, and the phenol resin preferably contains two or more phenolic hydroxyl groups. Thereby, the heat resistance and adhesiveness of the curable resin composition are further improved.

  Part of the phosphorus compound is preferably contained as a filler.

  The resin-impregnated base material of the present invention has a fiber base material and the curable resin composition impregnated therein. At that time, the thickness of the fiber base material is preferably 100 μm or less. The resin-impregnated base material may be a prepreg. Here, in the present specification, the curable resin composition that is A-stage, B-stage or C-stage is referred to as a “resin-impregnated substrate”, and among the resin-impregnated substrates, the curable resin composition. What is B-stage is called "prepreg".

  The substrate is obtained by heating and pressing a resin-impregnated base material.

  The metal foil with an adhesive layer includes a metal foil and an adhesive layer made of a curable resin composition provided on the metal foil.

  The substrate and the metal foil with an adhesive layer are formed using the curable resin composition of the present invention, so that the flexibility, heat resistance, and dimensional stability are excellent, and the adhesive layer and the fiber base material or the metal foil Excellent adhesion.

  The printed wiring board includes a substrate and a wiring pattern made of metal provided on at least one surface of the substrate. By forming the printed wiring board using the curable resin composition of the present invention, the printed wiring board can be bent, and a high-density circuit can be accommodated in the casing of the electronic device.

  ADVANTAGE OF THE INVENTION According to this invention, while being halogen-free, while having sufficient flame retardance, the curable resin composition which can have the outstanding flexibility, heat resistance, and adhesiveness is provided. Moreover, according to this invention, the prepreg obtained using this curable resin composition, the resin impregnation base material, a board | substrate, metal foil with an adhesive layer, and a printed wiring board are provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. Further, “(meth) acrylate” in the present specification means “acrylate” and “methacrylate” corresponding thereto.

  FIG. 1 is a partial perspective view showing an embodiment of a prepreg according to the present invention. A prepreg 100 shown in FIG. 1 is a sheet-like material composed of a fiber base material and a curable resin composition impregnated therein. Hereinafter, it demonstrates in order of the formation method of curable resin composition, a fiber base material, and a prepreg.

  The curable resin composition in the prepreg 100 contains acrylic rubber, a thermosetting resin, a phosphorus compound, and urea and / or a urea derivative. The curable resin composition in the prepreg 100 is in the B-stage state.

  Acrylic rubber is a rubber mainly composed of a copolymer containing (meth) acrylic acid alkyl ester as a monomer. The copolymer is generally produced by copolymerizing a (meth) acrylic acid alkyl ester and a compound having a double bond. In the (meth) acrylic acid alkyl ester, the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent. Examples of the substituent of the alkyl group include an alicyclic group, a glycidyl group, a C1-C6 alkyl group having a hydroxyl group, and a nitrogen-containing cyclic group. The compound having a double bond is not particularly limited as long as it is a compound that can be copolymerized with a (meth) acrylic acid alkyl ester.

  Specific examples of the (meth) acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, ethylene glycol methyl ether acrylate, Cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, acrylate amide, isodecyl acrylate, octadecyl acrylate, lauryl acrylate, allyl acrylate, N-vinylpyrrolidone acrylate, methacryl Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, isobutyl methacrylate, methacrylate Lenglycol methyl ether, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isobornyl methacrylate, methacrylic acid amide, isodecyl methacrylate, octadecyl methacrylate, lauryl methacrylate, allyl methacrylate, N methacrylate -Vinylpyrrolidone and dimethylaminoethyl methacrylate are mentioned.

  The acrylic rubber preferably has a glycidyl group, and glycidyl (meth) acrylate is preferably used as the (meth) acrylic ester. The epoxy value of the acrylic rubber can be adjusted by appropriately adjusting the copolymerization ratio when copolymerizing glycidyl (meth) acrylate and another monomer copolymerizable therewith.

  The epoxy value of the acrylic rubber is preferably 2 to 18 equivalent / kg, and more preferably 2 to 8 equivalent / kg. When the epoxy value is less than 2 equivalents / kg, the heat resistance of the substrate tends to decrease due to a decrease in the glass transition temperature of the cured product. When the epoxy value exceeds 18 equivalents / kg, the dimensional stability of the substrate increases due to an increase in storage elastic modulus. Tend to decrease. Usually, the acrylic rubber which has an epoxy value of 2-18 equivalent / kg is obtained by making the ratio of a monomer other than this into 5-15 weight part with respect to 100 weight part of glycidyl (meth) acrylates.

  As a commercially available product of acrylic rubber having an epoxy group, for example, “HTR860P3” (manufactured by Nagase ChemteX Corporation, trade name, epoxy value 3.05) is available.

  The weight average molecular weight of the acrylic rubber is preferably from 10,000 to 2,000,000, more preferably from 50,000 to 1,500,000 from the viewpoint of improving heat resistance, and from the viewpoint of reducing tackiness of the prepreg, from 300,000 to More preferably, it is 1.5 million. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) analysis and means a standard polystyrene equivalent value. GPC analysis can be performed using tetrahydrofuran (THF) as the eluent.

  The acrylic rubber is obtained, for example, by radical polymerization using a radical polymerization initiator that generates radicals. Radical polymerization initiators include persulfates such as azobisisobutyronitrile (AIBN), tert-butyl perbenzoate, benzoyl peroxide, lauroyl peroxide, potassium persulfate, cumene hydroperoxide, t-butyl hydroperoxide Dicumyl peroxide, di-t-butyl peroxide, 2,2′-azobis-2,4-dimethylvaleronitrile, t-butyl perisobutyrate, t-butyl perpivalate, hydrogen peroxide / ferrous salt, Examples thereof include persulfate / sodium acid sulfite, cumene hydroperoxide / ferrous salt, benzoyl peroxide / dimethylaniline, and the like. These may be used alone or in combination of two or more.

  In the curable resin composition, the blending amount of the acrylic rubber is preferably 10 to 70% by mass with respect to the total amount of the curable resin composition. When the blending amount of the acrylic rubber is less than 10% by mass, the glass transition temperature is drastically lowered and the heat resistance tends to be lowered, and when it exceeds 70% by mass, voids remain in the fiber base material such as glass cloth. It tends to be easier.

  As needed, acrylic rubber includes crosslinkers such as isocyanate and melamine, polymer compounds such as epoxy resins, flame retardants such as rubber elastomers and phosphorus compounds, inorganic fillers such as silica, conductive particles, cups You may mix | blend and use a ring agent, a pigment, a leveling agent, an antifoamer, an ion trap agent, etc.

  Examples of the thermosetting resin include an epoxy resin and a phenol resin.

  The epoxy resin is a polyepoxy compound having two or more epoxy groups as a crosslinkable functional group per molecule. The epoxy resin includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, naphthalene skeleton. -Containing epoxy resin, aralkylene skeleton-containing epoxy resin, phenol biphenyl aralkyl type epoxy resin, phenol salicylaldehyde novolak type epoxy resin, lower alkyl group-substituted phenol salicylaldehyde novolak type epoxy resin, dicyclopentadiene skeleton containing epoxy resin, polyfunctional glycidyl amine type An epoxy resin, a polyfunctional alicyclic epoxy resin, etc. are mentioned. These can be used alone or in combination of two or more.

  NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) as a biphenyl aralkyl type epoxy resin, ZX-1548 (trade name, manufactured by Toto Kasei Co., Ltd.) as a phosphorus-containing epoxy resin, EPICLON N-660 as a cresol novolac type epoxy resin (Trade name, manufactured by Dainippon Ink Co., Ltd.).

  The phenol resin is preferably a polyfunctional phenol resin having two or more phenolic hydroxyl groups per molecule as a crosslinkable functional group. Examples of the phenol resin include compounds containing a plurality of phenol rings or cresol rings in the molecule such as phenol resin and cresol resin. You may use these in combination of 2 or more type as needed. Examples of commercially available phenolic resins include aminotriazine-modified novolak resin Phenolite LA-1356 (manufactured by Dainippon Ink Co., Ltd., trade name), and biphenyl novolac MEH-7851 (manufactured by Meiwa Kasei Co., Ltd.). Product name).

  The phosphorus compound is contained in the curable resin composition as a flame retardant. Examples of phosphorus compounds include monomeric phosphate esters, condensed phosphate esters, red phosphorus, polyphosphoric acid, and phosphazene compounds. You may use these individually or in combination of 2 or more types. Part of the phosphorus compound is preferably present as a filler in the curable resin composition. In particular, it is preferable that a phosphorus compound is present as an insoluble filler after curing.

  Commercially available phosphorus compounds include, for example, “Reophos TPPP” (manufactured by Ajinomoto Fine Techno Co., Ltd.) which is a monomeric phosphate ester, “Leophos RDP” and “Leophos BAPP” which are condensed phosphate esters. (Ajinomoto Fine Techno Co., Ltd., trade name), red phosphorus “Nobaquel” (Rin Chemical Industry Co., Ltd., trade name), “Hishiguard” (Nippon Chemical Industry Co., Ltd., trade name) ), “PMP100” (trade name, manufactured by Nissan Chemical Co., Ltd.), “Exorit OP1311” (trade name, manufactured by Clariant Japan Ltd.), “SBP100” (Otsuka Chemical Co., Ltd.) ) And product name) are available. Moreover, as a filler containing a phosphorus compound, “OP930” (manufactured by Clariant Japan Co., Ltd., trade name) and “HCA-HQ” (manufactured by Sanko Co., Ltd., trade name) are commercially available.

  It is preferable that the compounding quantity of the phosphorus compound in curable resin composition is 0.1-10 mass%. If the content is less than 0.1% by mass, the flame retardancy tends to decrease, and if it exceeds 10% by mass, the flexibility tends to decrease.

  The average particle size of the filler is desirably 0.1 to 30 μm. If the average particle size exceeds 30 μm, the flexibility may be reduced. Moreover, there exists a possibility that a base material tack may increase that an average particle diameter is less than 0.1 micrometer. The average particle diameter can be measured by a dynamic light scattering method or a laser diffraction method.

Urea and urea derivatives are represented by the following general formula (1), for example.

R ¹ , R ² , R ³ and R ⁴ in the general formula (1) are each independently an organic group having a hydrogen atom, an alkyl group, an alkane group, an organic group having an alkene group, or an organic having an alkoxysilyl group. An organic group having an aromatic ring such as a group, a cyano group, a nitroso group, a nitro group, an acyl group or a phenyl group, or an organic group having a heterocyclic ring such as imidazole.

Examples of the urea derivative represented by the general formula (1) include N-monoalkyl urea, N, N-dialkyl urea, N, N′-dialkyl urea, N-allyl urea, and Np-ethoxyphenyl-N ′. -Chain and cyclic compounds such as biphenylurea, nitrosourea, biurea, biuret, guanylurea, hydantodyne, urea silane, ureido compound, isourea, isourea derivative, and semicarbazide compound. Of these, urea silane is preferred. Urea silane is a compound in which at least one of R ^{1 to} R ⁴ is an organic group having an alkoxysilyl group. Specific examples of urea silane include γ-carbamylalkyltrialkoxysilanes such as γ-carbamylpropyltriethoxysilane and γ-carbamyltriethoxysilane. Among these, γ-carbamylpropyltriethoxysilane is particularly preferable. These compounds are used alone or in combination of two or more.

  It is preferable that the compounding quantity of urea and / or a urea derivative is 0.1-10 mass parts with respect to 100 mass parts of epoxy resins. If it is less than 0.1 parts by mass, the adhesive strength with the metal foil tends to be reduced, and if it exceeds 10 parts by mass, the heat resistance tends to be reduced.

  In addition, amines and imidazoles can be used as thermosetting accelerators. Examples of amines include dicyandiamide, diaminodiphenylethane, and guanylurea. Imidazoles include 2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, etc. Imidazole compounds, benzimidazoles, and the like.

  When an epoxy resin is used as the thermosetting resin, the blending amount of the curing accelerator can be determined according to the total amount of epoxy groups in the curable resin composition, but generally the resin solids of the curable resin composition It is preferable to set it as 0.01-10 mass parts in 100 mass parts per minute.

  The fiber substrate in the prepreg 100 is not particularly limited as long as it is used when producing a metal foil-clad laminate or a multilayer printed wiring board, and a fiber substrate such as a woven fabric or a nonwoven fabric is usually used.

  Examples of the fiber base material include glass, alumina, asbestos, boron, silica alumina glass, silica glass, tyrano, silicon carbide, silicon nitride, zirconia, and other inorganic fibers, aramid, polyether ether ketone, polyether imide, poly Organic fibers such as ether sulfone, carbon and cellulose, or mixed papers thereof are preferred, and glass cloths of 100 μm or less are particularly preferred. In addition, by using a glass cloth with a thickness of 50 μm or less, it becomes easier to manufacture a printed wiring board that can be bent arbitrarily, and to reduce dimensional changes due to temperature, humidity, etc. in the manufacturing process. Is possible.

  The prepreg 100 can be manufactured by impregnating a curable resin composition into a fiber base material and removing the solvent from the varnish by heating at 80 to 180 ° C. In the prepreg 100, the solvent used in the varnish may remain, but 80% by mass or more of the solvent contained in the varnish is preferably removed. In the above-described drying, the drying time is not particularly limited.

  The impregnation amount of the curable resin composition is preferably 30 to 90% by mass with respect to 100% by mass of the total amount of the curable resin composition and the fiber base material.

  FIG. 2 is a partial cross-sectional view showing an embodiment of a metal foil with an adhesive layer according to the present invention. The metal foil 200 with an adhesive layer shown in FIG. 2 includes a metal foil 10 and an adhesive layer 20 formed on the metal foil 10. The adhesive layer 20 is made of the curable resin composition. The metal foil with adhesive layer 200 can be manufactured by applying a curable resin composition on the metal foil 10. Application | coating can be implemented by a well-known method. Specific examples include a method using a comma coater, a dip coater, a kiss coater, and natural casting.

  As the metal foil 10, a copper foil or an aluminum foil is generally used. The thickness of the metal foil usually used for the laminate is 1 to 200 μm. Alternatively, as the metal foil 10, nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy or the like is used as an intermediate layer, and a copper layer of 0.5 to 15 μm and 10 to 300 μm on both sides. A three-layer composite foil provided with a copper layer or a two-layer composite foil in which aluminum and copper foil are combined can be used.

  FIG. 3 is a partial cross-sectional view showing an embodiment of a metal foil-clad laminate according to the present invention. A metal foil-clad laminate 300 shown in FIG. 3 includes a substrate 30 obtained by heating and pressing one prepreg 100 and two metal foils 10 provided in close contact with both surfaces of the substrate 30. The The substrate 30 may be formed from one prepreg 100 or may be formed by overlapping a plurality of substrates. Further, the metal foil 10 may be provided on both sides of the substrate 30 or may be provided on one side.

  The metal foil-clad laminate 300 is obtained, for example, by stacking the metal foil 10 on both sides of the prepreg 100 and heating and pressing it to cure the curable resin composition in the prepreg 100. The heating temperature at this time is preferably 130 to 250 ° C, and more preferably 150 to 210 ° C. Further, the pressure is preferably 0.5 to 20 MPa, more preferably 1 to 8 MPa.

  The metal foil 10 is the same as the metal foil 10 of the metal foil 200 with an adhesive layer described above.

  FIG. 4 is a partial cross-sectional view showing an embodiment of a printed wiring board according to the present invention. A printed wiring board 400 shown in FIG. 4 is mainly composed of the substrate 30 and the metal pattern 11 formed of patterned metal foil provided on both surfaces of the substrate 30. A plurality of through holes 70 are formed through the substrate 30 in a direction substantially perpendicular to the main surface, and a metal plating layer 60 having a predetermined thickness is formed on the hole wall of the through hole 70. . The printed wiring board 300 is obtained by forming a wiring pattern on the metal foil-clad laminate 200 described above. The wiring pattern can be formed by a conventionally known method such as a subtractive method. The printed wiring board 300 is particularly preferably used as a so-called flexible printed wiring board.

  The present invention has been described in detail based on the embodiments. However, the present invention is not limited to the above embodiment. The present invention can be variously modified without departing from the gist thereof.

  Examples of the present invention will be specifically described below, but the present invention is not limited thereto.

Example 1
HTR860-P3 (trade name, manufactured by Nagase Chemtex Co., Ltd.) as an acrylic rubber, 10 g (weight of solid content, the same applies hereinafter), EPICLON N-660 (trade name, manufactured by Dainippon Ink Co., Ltd.) as an epoxy resin 40 g, MEH-7851 (product name) manufactured by Meiwa Kasei Co., Ltd. as a phenol resin, 10 g, 0.2 g 2-phenylimidazole as a curing accelerator, 12 g PMP100 (product name) manufactured by Nissan Chemical Co., Ltd. 2 g of γ-carbamyltriethoxysilane was mixed and stirred as urea silane. Methyl ethyl ketone was added thereto, and the viscosity at 25 ° C. was adjusted to 700 cP to prepare a varnish for the curable resin composition.

(Example 2)
A curable resin composition varnish was produced in the same manner as in Example 1 except that the blending amount of the acrylic rubber was changed to 120 g.

(Example 3)
HTR860-P3 (trade name, manufactured by Nagase Chemtex Co., Ltd.) 30 g as acrylic rubber, Epicoat 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) 40 g as epoxy resin, LA-1356 (Dainippon, Japan) as phenol resin 50 g of Ink Co., Ltd., trade name), 0.2 g of 2-ethyl-4-methylimidazole as a curing accelerator, 12 g of PMP100 (trade name, manufactured by Nissan Chemical Co., Ltd.), and γ as urea silane -2 g of carbamyltriethoxysilane was mixed and stirred. Methyl ethyl ketone was added thereto, and the viscosity at 25 ° C. was adjusted to 700 cP to prepare a varnish for the curable resin composition.

Example 4
A curable resin composition varnish was produced in the same manner as in Example 1 except that the blending amount of the acrylic rubber was changed to 200 g.

(Example 5)
A curable resin composition varnish was prepared in the same manner as in Example 2 except that 2 g of urea was mixed instead of γ-carbamyltriethoxysilane.

(Example 6)
A curable resin composition varnish was prepared in the same manner as in Example 2 except that 1 g of γ-carbamyltriethoxysilane and 1 g of urea were blended in place of 2 g of γ-carbamyltriethoxysilane.

(Comparative Example 1)
A curable resin composition varnish was produced in the same manner as in Example 1 except that the acrylic rubber and the urea derivative were not blended.

(Comparative Example 2)
A curable resin composition varnish was produced in the same manner as in Example 1 except that no acrylic rubber was blended.

(Comparative Example 3)
A curable resin composition varnish was produced in the same manner as in Example 1 except that the urea derivative of Example 1 was not blended.

(Preparation of prepreg and copper-clad laminate)
After impregnating the varnishes produced in Examples 1 to 6 and Comparative Examples 1 to 3 with a glass cloth 1037 having a thickness of 0.028 mm (trade name, manufactured by Asahi Schavel Co., Ltd.), the varnish was heated and dried at 120 ° C. for 20 minutes. To obtain a prepreg. 8 sheets of this prepreg are stacked, and 18 μm thick electrolytic copper foil F2-WS-18 (product name, manufactured by Furukawa Circuit Foil Co., Ltd.) is stacked on both sides of the prepreg so that the adhesive surface is combined with the prepreg to obtain a laminate. It was. And it heated and pressurized on 200 degreeC from the both surfaces of the laminated body for 30 minutes on the vacuum press conditions of a pressure of 4 Mpa, and produced the double-sided copper clad laminated board for an evaluation test of a flexibility, heat resistance, and copper foil adhesiveness.

(Measuring method)
The flexibility was evaluated as follows. First, a test piece having a size of 10 mm in width and 100 mm in length was cut out from a prepreg and a laminate obtained by etching a copper foil-clad laminate. An aluminum plate having a thickness of 5 mm was placed on these test pieces so as to be orthogonal to the length direction of the test pieces. Then, when the end portion of the aluminum plate was used as a fulcrum and the test piece was bent upward at 90 degrees therefrom, the presence or absence of cracks was observed. As a result of observing the presence or absence of cracks, ◯ marks indicate no abnormality, Δ marks indicate whitening due to partial cracks, and X marks indicate whitening due to entire cracks. The results are shown in Table 1.

  The flame retardancy was evaluated based on the results of a thin material vertical combustion test based on the UL-94 standard. The results are shown in Table 1.

  The solder heat resistance was evaluated as follows. First, a double-sided copper-clad laminate was cut into a 50 mm square to obtain a test piece. The test piece was immersed in a solder bath at 288 ° C., and the time elapsed from that point until the point at which the swelling of the test piece was visually observed was measured. The results are shown in Table 1.

  Copper foil adhesiveness was evaluated as follows. First, the copper foil of the double-sided copper-clad laminate was partially etched to form a 1 mm wide copper foil line. Next, the double-sided copper foil laminate after forming the copper foil line was immersed (hydrochloric acid treatment) in an 18% by mass hydrochloric acid aqueous solution at 30 ° C. for 1 hour. And each copper foil line of the normal double-sided copper foil laminated board which is not immersed in hydrochloric acid aqueous solution, and the double-sided copper foil laminated board after being immersed in hydrochloric acid is 50 mm / min in a 90 degree direction with respect to an adhesive surface. It peeled off at speed. The load at that time was measured, and the maximum load was peeled off. The results are shown in Table 1.

It is a fragmentary perspective view which shows one Embodiment of the prepreg by this invention. It is a fragmentary sectional view showing one embodiment of metal foil with an adhesion layer by the present invention. It is a fragmentary sectional view showing one embodiment of a metal foil tension laminate sheet by the present invention. It is a fragmentary sectional view showing one embodiment of a printed wiring board by the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Metal foil, 11 ... Wiring pattern, 20 ... Adhesion layer, 30 ... Board | substrate, 60 ... Metal plating layer, 70 ... Through-hole, 100 ... Prepreg, 200 ... Metal foil with an adhesion layer, 300 ... Metal foil tension laminated board, 400: Printed wiring board.

Claims (12)

A resin-impregnated substrate having a fiber substrate and a curable resin composition impregnated therein,
The curable resin composition is
Acrylic rubber,
A thermosetting resin;
A phosphorus compound;
Urea and / or urea derivatives;
Contain,
A resin-impregnated base material, wherein the fiber base material has a thickness of 100 μm or less. The resin-impregnated base material according to claim 1, wherein the urea derivative is urea silane. The resin-impregnated substrate according to claim 1 or 2, wherein the acrylic rubber has a glycidyl group, and the epoxy value of the acrylic rubber is 2-18. The resin impregnated base material according to any one of claims 1 to 3, wherein the acrylic rubber has a weight average molecular weight of 10,000 to 2,000,000. The resin-impregnated base material according to any one of claims 1 to 4, wherein a blending amount of the acrylic rubber is 10 to 70 mass% with respect to a total amount of the curable resin composition. The resin-impregnated substrate according to any one of claims 1 to 5, wherein the thermosetting resin is an epoxy resin or a phenol resin. The resin-impregnated base material according to claim 6, wherein the phenol resin has two or more phenolic hydroxyl groups . The resin-impregnated base material according to claim 1, wherein a part of the phosphorus compound is contained as a filler. The resin-impregnated base material according to any one of claims 1 to 8 , which is a prepreg. Substrate obtained by applying heat and pressure to the resin-impregnated substrate according to any one of claims 1-9. A printed wiring board comprising: the substrate according to claim 10; and a wiring pattern made of a metal provided on at least one surface of the substrate. A metal foil, a metal foil with the adhesive layer comprising an adhesive layer, a made of hardening resin composition provided on the metal foil,
The curable resin composition is
Acrylic rubber,
A thermosetting resin;
A phosphorus compound;
Urea and / or urea derivatives;
Containing
Metal foil with adhesive layer.

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