JP5272509B2 - Prepreg, metal foil-clad laminate and printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a prepreg exhibiting excellent folding resistance when formed into a printed wiring board, and to provide a metal foil-clad laminate and the printed wiring board obtained by using the prepreg. <P>SOLUTION: The prepreg comprises a fiber base material 10, a first resin layer 11 obtained by impregnating the fiber base material with a first thermosetting resin composition, and one or more resin layers formed on the first resin layer 11 out of a thermosetting resin composition. The first thermosetting resin composition and the second thermosetting resin composition for forming the outmost resin layer 12 of the prepreg in one or more resin layers formed out of the thermosetting resin compositions satisfy the following expression (1): Y [GPa]&lt;X [GPa]&le;3 [GPa] (1) (wherein, X is a modulus of a resin film formed out of the first thermosetting resin composition; and Y is a modulus of a resin film formed out of the second thermosetting resin composition). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a prepreg, a metal foil-clad laminate and a printed wiring board using the prepreg.

  With the rapid spread of information terminal electronic devices, electronic devices are becoming smaller and thinner, and the demand for higher density and thinner printed wiring boards is increasing. Furthermore, with the enhancement of functionality of electronic devices such as mobile phones, it has become necessary to connect various high-performance modules such as cameras and high-density printed wiring boards.

  On the other hand, the number of electronic component mounting points has also increased rapidly, and in order to mount a large number of electronic components in a limited space on a printed wiring board, not only the conventional rigid printed wiring board but also a soft board that can be bent freely Has become necessary. As a bendable printed wiring board, a laminate of a thermoplastic resin film and metal foil mainly using polyimide is mainly used. However, the thermoplastic resin film has a higher water absorption rate than conventional metal foil-clad laminates including glass cloth and glass nonwoven fabric, and has a problem of low dimensional stability when the metal foil is etched or after circuit processing. Yes.

  As a method of improving the dimensional stability of the thermoplastic resin film, a method of blending short glass fibers with a thermoplastic resin (see Patent Document 1 or the like) or a method of forming a plurality of polyimide resin layers having different thermal expansion coefficients ( A method of forming a resin layer having a low coefficient of thermal expansion on the metal foil side (see Patent Documents 2 and 3, etc.) is known.

  However, the method of blending short glass fibers described in Patent Document 1 and the like has higher dimensional stability than the case where a thermoplastic resin is used alone, but is still dimensionally stable for processing and connecting fine wiring. Sex is not enough. Further, even in a method of forming a plurality of polyimide resin layers having different thermal expansion coefficients described in Patent Documents 2 and 3, etc., and a method of forming a resin layer having a low thermal expansion coefficient on the metal foil side described in Patent Document 4, etc., There is a limit to the reduction of hygroscopicity and the improvement of dimensional stability, and there is a concern that the connection reliability of printed wiring boards that will become increasingly dense in the future will decrease.

On the other hand, as a method of reducing hygroscopicity and increasing dimensional stability, a prepreg in which a fiber base material is impregnated with a thermosetting resin can be used and a laminate of this prepreg and metal foil can be bent. There is a method of using as a printed wiring board (see, for example, Patent Document 5).
JP 49-25499 A JP-A-1-245586 JP-A-8-250860 JP-A-5-347461 International Publication No. 2006/001305 Pamphlet

  However, the conventional prepreg described in Patent Document 5 and the like has room for improvement in preventing the disconnection of the wiring when the printed wiring board is bent when the printed wiring board is formed using the prepreg. .

  Therefore, an object of the present invention is to provide a prepreg that exhibits excellent folding resistance when a printed wiring board is molded, and a metal foil-clad laminate and a printed wiring board using the prepreg. In this specification, “expressing excellent folding resistance” means that when a printed wiring board is formed using a prepreg, the wiring is sufficiently prevented from being broken when the printed wiring board is bent. Indicates that

The present invention provides a fiber base material, a first resin layer obtained by impregnating the fiber base material with the first thermosetting resin composition, and the thermosetting resin composition provided on the first resin layer. A prepreg comprising one or more resin layers formed from the outermost surface of the prepreg of the first thermosetting resin composition and the one or more resin layers formed from the thermosetting resin composition The 2nd thermosetting resin composition which forms this resin layer provides the prepreg which satisfy | fills following formula (1).
Y [GPa] <X [GPa] ≦ 3 [GPa] (1)
[In formula, X shows the elasticity modulus of the resin film formed from a 1st thermosetting resin composition, Y shows the elasticity modulus of the resin film formed from a 2nd thermosetting resin composition. ]

  According to the prepreg of the present invention, excellent folding resistance is exhibited when a printed wiring board is formed. The reason why the effect of exhibiting excellent folding resistance is obtained by the prepreg of the present invention is that a resin layer formed from a thermosetting resin composition having a high elastic modulus is arranged at the center of the prepreg, and the prepreg By arranging a resin layer formed from a thermosetting resin composition having a low elastic modulus on the outermost surface layer, the fiber base material is protected, and crack resistance is improved.

  The first thermosetting resin composition and the second thermosetting resin composition satisfy the above formula (1), even if they are the same kind of thermosetting resin composition, A thermosetting resin composition may be used.

  It is preferable that the first thermosetting resin composition and the second thermosetting resin composition include a resin having a glycidyl group. Thereby, the heat resistance of the prepreg becomes better.

  The first thermosetting resin composition and the second thermosetting resin composition preferably include an acrylic resin. Thereby, the folding resistance of a prepreg improves more.

  It is also preferable that the first thermosetting resin composition and the second thermosetting resin composition include a resin having an amide group instead of the acrylic resin. The resin having an amide group preferably includes a polyamideimide resin, and the polyamideimide resin preferably has a siloxane bond. Thereby, the heat resistance of the prepreg is further improved.

  The present invention includes a substrate obtained by heating and pressing a laminate in which a predetermined number of the above prepregs are laminated, and a metal foil having a thickness of 0.01 to 30 μm provided on at least one surface of the substrate. Provided are a metal foil-clad laminate and a printed wiring board obtained by processing a circuit on the metal foil-clad laminate. Since the metal foil-clad laminate and the printed wiring board of the present invention use the prepreg of the present invention, they are excellent in folding resistance.

  According to the present invention, it is possible to provide a prepreg that exhibits excellent folding resistance and crack resistance when a printed wiring board is molded, and a metal foil-clad laminate and a printed wiring board using the prepreg. Furthermore, since the printed wiring board of the present invention is excellent in folding resistance, the printed wiring board of the present invention can be stored in a high density in a housing in which the printed wiring board is folded and mounted.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be, but the present invention is not limited to the following embodiments. 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.

  The prepreg of the present invention is provided on a fiber substrate, a first resin layer obtained by impregnating the fiber substrate with a first thermosetting resin composition, and a thermosetting resin. And one or more resin layers formed from the composition.

Furthermore, in the prepreg of the present invention, the first thermosetting resin composition and the second outermost resin layer of the prepreg among the one or more resin layers formed from the thermosetting resin composition are formed. The thermosetting resin composition satisfies the following formula (1).
Y [GPa] <X [GPa] ≦ 3 [GPa] (1)
[Wherein X represents the elastic modulus of the resin film formed from the first thermosetting resin composition, and Y represents the elastic modulus of the resin film formed from the second thermosetting resin composition. Show. ]

  In addition, as said resin film for measuring an elasticity modulus, what is produced by the following method can be used, for example. That is, on the copper foil having a thickness of 18 μm, the first or second thermosetting resin composition is applied so that the thickness of the resin after drying becomes 50 μm, and the residence time is 100 to 140 ° C. in a drying path. Heat-dry in 5 minutes to obtain a resin-coated copper foil. Thereafter, a roughened surface of a copper foil with a thickness of 18 μm is superimposed on the resin surface of the resin-coated copper foil, and a double-sided copper-clad laminate is produced under a press condition of 170 ° C., 90 minutes, 4.0 MPa, and then double-sided copper-clad laminate What carried out double-sided etching of the copper foil of the outer side of a board can be used as the said resin film.

  Moreover, the elasticity modulus of the said resin film can be measured with the following method, for example. That is, using an autograph (manufactured by Shimadzu Corporation, model number AG-100C), the elastic modulus can be measured for a test piece obtained by cutting the resin film into 80 mm × 10 mm. Measurement conditions can be a measurement length of 60 mm and a tensile speed of 5 mm / min.

  Here, X is preferably 2.5 GPa or less. This further improves the folding resistance of the prepreg. Y is preferably as low as possible, but is practically preferably 0.01 GPa or more.

  FIG. 1 is a schematic sectional view showing a preferred embodiment of a prepreg according to the present invention. The prepreg in FIG. 1 corresponds to the case where the number of resin layers formed from the thermosetting resin composition provided on the first resin layer is one, but the first resin layer Two or more resin layers formed from the thermosetting resin composition may be provided.

  A prepreg 100 shown in FIG. 1 is provided on a fiber substrate 10, a first resin layer 11 formed by impregnating the fiber substrate 10 with a first thermosetting resin composition, and the first resin layer 11. And the second resin layer 12 formed from the second thermosetting resin composition. In the prepreg 100, the entire surface of the first resin layer 11 is covered with the second resin layer 12, but the second resin layer 12 covers only a part of the first resin layer 11. May be.

  Although the fiber base material 10 will not be restrict | limited especially if it is used when manufacturing a metal foil tension laminated board and a multilayer printed wiring board, Usually, a woven fabric, a nonwoven fabric, etc. are used, It is preferable to use a woven fabric. Examples of the material of the fiber base material 10 include inorganic fibers such as glass, alumina, asbestos, boron, silica alumina glass, silica glass, tyrano, silicon carbide, silicon nitride, zirconia, aramid, polyether ether ketone, polyether imide, and the like. There are organic fibers such as polyethersulfone, carbon and cellulose, and mixed papers thereof, and glass fibers are particularly preferably used. Moreover, although the thickness of a base material is not specifically limited, Folding resistance further improves that it is 15-50 micrometers.

  Examples of the thermosetting resins contained in the first and second thermosetting resin compositions include epoxy resins, polyimide resins, triazine resins, phenol resins, melamine resins, polyester resins, cyanate ester resins, and modified products of these resins. And the like containing a thermosetting resin. As the thermosetting resin, a resin having a glycidyl group is preferable, and an epoxy resin is more preferable.

  Examples of the epoxy resin include polyglycidyl obtained by reacting polychlorophenol such as bisphenol A, novolak type phenol resin, orthocresol novolac type phenol resin or polyhydric alcohol such as 1,4-butanediol with epichlorohydrin. N-glycidyl derivatives of compounds having polyglycidyl esters, amines, amides or heterocyclic nitrogen bases obtained by reacting polybasic acids such as ether, phthalic acid and hexahydrophthalic acid with epichlorohydrin, alicyclic epoxy resins Etc. The above-mentioned thermosetting resins may be used alone or in combination of two or more.

  The first and second thermosetting resin compositions preferably further contain an acrylic resin or a resin having an amide group.

As the acrylic resin, it is possible to use a resin composed of an acrylic acid monomer, a methacrylic acid monomer, acrylonitrile, an acrylic monomer having a glycidyl group, or a copolymer obtained by copolymerizing a plurality of these. Although the molecular weight is not particularly defined, when three columns GMH _XL (manufactured by Tosoh Corporation) are directly connected and measured using THF as an eluent, the weight average molecular weight in terms of standard polystyrene is 30. 10,000 to 1,200,000, preferably 400,000 to 1,000,000 are used. An acrylic resin can be used individually by 1 type or in combination of 2 or more types.

  The content of the acrylic resin in the first and second thermosetting resin compositions is preferably 15 to 70 parts by mass with respect to 100 parts by mass of the thermosetting resin, and 20 to 60 parts by mass. Is more preferable.

  As the resin having an amide group, a polyamideimide resin is preferable, and a siloxane-modified polyamideimide resin having a structure including a siloxane structure is more preferable. This siloxane-modified polyamideimide resin is obtained by reacting a mixture containing a diimide dicarboxylic acid obtained by reacting a mixture of a diamine having two or more aromatic rings and a siloxane diamine with trimellitic anhydride, and an aromatic diisocyanate. It is particularly preferable that it is obtained. The resin which has an amide group can be used individually by 1 type or in combination of 2 or more types.

  In the first and second thermosetting resin compositions, the content of the resin having an amide group is preferably 50 to 90 parts by mass, and 60 to 80 parts by mass with respect to 100 parts by mass of the thermosetting resin. It is more preferable that

  It is preferable that the first and second thermosetting resin compositions further contain a curing agent and / or a curing accelerator. In particular, when an epoxy resin is included as the thermosetting resin, polyfunctional phenols such as dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, phthalic anhydride, pyromellitic anhydride, phenol novolac and cresol novolac are used as curing agents. As the curing accelerator, an imidazole compound, an organic phosphorus compound, a tertiary amine, a quaternary ammonium salt, or the like can be suitably used. A hardening | curing agent and / or a hardening accelerator can be used individually by 1 type or in combination of 2 or more types.

  The content of the curing agent in the first and second thermosetting resin compositions is preferably 3 to 50 parts by mass with respect to 100 parts by mass of the thermosetting resin, and the content of the curing accelerator is the heat. It is preferable that it is 0.001-5 mass parts with respect to 100 mass parts of curable resin.

  The first and second thermosetting resin compositions may further contain a flame retardant, a flow regulator, a coupling agent, and the like.

  Examples of the flame retardant include aluminum hydroxide, phosphorus-containing filler, bromine-based compound, phosphorus-based compound, nitrogen-based compound, and hydrated metal compound.

  Examples of the flow regulator include silicon compounds and acrylic compounds.

  Examples of the coupling agent include a vinyl silane coupling agent, an epoxy silane coupling agent, an amino silane coupling agent, and a mercapto silane coupling agent.

  In addition, the 1st and 2nd thermosetting resin composition is good also as a solution of various solvents as needed. As the solvent, any alcohol-based, ether-based, ketone-based, amide-based, aromatic hydrocarbon-based, ester-based, nitrile-based, or the like may be used as long as the reactivity with the above-described components is sufficiently small. A mixed solvent can also be used.

  It is preferable that content of the solvent in the 1st and 2nd thermosetting resin composition shall be 30-80 mass% with respect to solid content in a thermosetting resin composition, and the total amount of a fiber base material.

  The first resin layer 11 is in a state where the first thermosetting resin composition is semi-cured (B-staged), and the second resin layer 12 is a second thermosetting resin composition. The product is in a semi-cured (B-stage) state.

  Although the thickness of the 1st resin layer 11 should just be the same thickness as the thickness of the fiber base material 10, or the thickness beyond it, it is preferable that it is thick about 0-10 micrometers from the thickness of the fiber base material 10. . If the difference between the thickness of the first resin layer 11 and the fiber base material 10 exceeds 10 μm, the folding resistance may be lowered.

  The thickness of the prepreg 100 is desirably 200 μm or less. If this thickness exceeds 200 μm, folding resistance may be reduced. Furthermore, the folding resistance of the fiber base material is improved when there is no difference in the thickness of the resin layers on both sides.

  In the prepreg according to the present invention, even when two or more resin layers formed from the thermosetting resin composition are formed on the first resin layer, the first resin layer and the prepreg The intermediate resin layer disposed between the outermost resin layer and the outermost resin layer is not particularly limited as long as the above formula (1) is satisfied. The intermediate resin layer can be formed from the same material as the first and second thermosetting resin compositions described above.

  The elastic modulus of the resin film formed from the thermosetting composition forming the intermediate resin layer is preferably equal to or smaller than the elastic modulus of the resin film formed from the first thermosetting resin composition. The elastic modulus of the resin film formed from the second thermosetting resin composition is preferably larger. When there are a plurality of intermediate resin layers, it is preferable that the elastic modulus of the resin film decreases stepwise from the first resin layer toward the outermost resin layer of the prepreg.

  The prepreg 100 can be manufactured as follows using the above-described first and second thermosetting resin compositions.

  First, the fiber substrate 10 is impregnated with the first thermosetting resin composition, and then the second thermosetting resin composition is formed from the first thermosetting resin composition. By applying on the layer and heating at 70 to 150 ° C. for 5 to 20 minutes, the second resin layer is formed and the prepreg 100 is obtained. Note that the first resin layer and the second resin layer are semi-cured by one of the two heating operations.

  Examples of the method of impregnating the fiber base material 10 with the first thermosetting resin composition include a method of applying with a coating machine.

  In the above production method, when a solvent is used, it is preferable that the solvent is dried at a temperature at which the solvent can be volatilized or more, and the used solvent is volatilized by 80% by mass or more.

  A prepreg having a plurality of intermediate resin layers disposed between the first resin layer and the outermost resin layer of the prepreg can be manufactured by repeating the above-described application and heating as appropriate.

  FIG. 2 is a partial cross-sectional view showing a preferred embodiment of a metal foil-clad laminate according to the present invention. The metal foil-clad laminate 200 includes a sheet-like substrate 30 obtained by heating and pressing a laminate in which a plurality of prepregs 100 are laminated, and two metal foils 20 provided in close contact with both surfaces of the substrate 30. It consists of.

  The substrate 30 is made of a laminate in which a plurality of fiber reinforced resin layers 3 derived from a plurality of prepregs 100 are laminated. In order to increase the flexibility of the metal foil-clad laminate and the printed wiring board, the thickness of the substrate 30 is preferably 10 to 200 μm.

  The metal foil-clad laminate 200 is formed by stacking metal foil on both surfaces of a laminate in which a predetermined number (preferably 6 or less, more preferably 2 or less, particularly preferably 1) of prepregs 100 are laminated, It is obtained by pressurization. At this time, the heating temperature and pressure are not particularly limited, but the heating temperature is usually 80 to 250 ° C. (preferably 130 to 230 ° C.), and the pressure is usually 0.5 to 8.0 MPa (preferably 1.5 to 5.0 MPa). A vacuum press is suitably used for heating and pressurization.

  Examples of the metal foil 20 include a gold foil, a copper foil, and an aluminum foil, and a copper foil is preferable. As the metal foil 20, in order to improve the folding resistance of the metal foil-clad laminate and the printed wiring board, it is preferable to use the one having a thickness of 0.01 to 30 μm, and the one having a thickness of 5 to 20 μm is used. More preferably.

  The embodiment of the metal foil-clad laminate is not limited to the above aspect. For example, using one prepreg 100, the substrate may be composed of one fiber reinforced resin layer, or a metal foil may be provided on only one side of the substrate. Moreover, the printed wiring board which concerns on this invention can also be obtained by patterning the metal foil of a metal foil tension laminated board by photolithography, an etching, etc., and processing a circuit.

  FIG. 3 is a schematic cross-sectional view showing a preferred embodiment of a printed wiring board according to the present invention. A printed wiring board 300 shown in FIG. 3 is a multilayer printed wiring board, and includes an inner layer circuit board 315 formed by arranging inner layer circuits 313a and 313b on both sides of an insulating substrate 310 in which a through hole 311 is filled with a conductor 312. Insulating substrates 320a, b provided on both sides of the inner circuit board 315, with through holes 321a, b filled with conductors 322a, b, respectively, and circuits 323a formed outside the insulating substrates 320a, 320b , B.

  The printed wiring board 300 is formed as follows, for example. First, the prepreg 100 according to the present invention is laminated on both sides of the inner circuit board 315 and cured by heating and pressing to form insulating substrates 320a and 320b. Next, through holes 321a and b are provided in the insulating substrates 320a and 320b, and conductors 322a and b are filled therein. Then, patterned circuits 323a and 323b are formed outside the insulating substrates 320a and 320b, thereby completing the printed wiring board 300.

  Alternatively, the prepreg 100 according to the present invention is laminated on both sides of the inner layer circuit board 315, through holes 321a and b are provided, and conductors 322a and b are filled therein. Furthermore, after laminating a metal foil on the outside of the prepreg 100 and applying heat and pressure, the metal foil is patterned by etching or the like to form circuits 323a and b, thereby completing the printed wiring board 300.

  Since the metal foil-clad laminate 200 and the printed wiring board 300 use the prepreg of the present invention, they have excellent folding resistance.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

(Synthesis of siloxane-modified polyamideimide resin A)
Into a 5 liter separable flask equipped with a faucet with a cock connected to a reflux condenser, a thermometer and a stirrer, BAPP (2,2-bis [4- (4′-amino) as an aromatic diamine was added. Phenoxy) phenyl] propane) (produced by Wakayama Seika Co., Ltd.) 197.0 g (0.24 mol) and DDS (diaminodiphenylsulfone) (produced by Wakayama Seika Co., Ltd.) 119.2 g (0.24 mol), reacted as siloxane diamine Silicone oil KF8010 (manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 430) 26.4 g (0.12 mol), TMA (trimellitic anhydride) (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 484.1 g (1.26 mol), Charge 3190 g of NMP (N-methylpyrrolidone) as an aprotic polar solvent and stir at 80 ° C. for 30 minutes did.
Thereafter, 500 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 2 hours. While confirming that about 21.6 ml or more of water has accumulated in the moisture determination receiver and that water is no longer being distilled, while removing the distillate that has accumulated in the moisture determination receiver, about 190 The temperature was raised to 0 ° C. to remove toluene. Thereafter, the solution was returned to room temperature, and 360.4 g (0.72 mol) of MDI (4,4′-diphenylmethane diisocyanate) (manufactured by Nippon Polyurethane Co., Ltd.) was added as an aromatic diisocyanate and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of siloxane-modified polyamideimide resin A (resin solid content 31.2%) was obtained.

[Formulation Example 1]
The resin composition shown below was dissolved in methyl isobutyl ketone and adjusted so that the resin solid content was 30 wt% to obtain a varnish (thermosetting resin composition) of Formulation Example 1.
Biphenyl novolac epoxy resin (Nippon Kayaku Co., Ltd., trade name NC-3000H): 44 parts by mass Aminotriazine novolac epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name LA-3018): 11 parts by mass 2- Phenylimidazole (manufactured by JSR Corporation, trade name G-8809L): 0.2 parts by mass Acrylic resin (manufactured by Nagase ChemteX Corporation): 30 parts by mass

[Formulation Example 2]
The resin composition shown below was dissolved in methyl isobutyl ketone and adjusted so that the resin solid content was 30 wt%, whereby a varnish of Formulation Example 2 was obtained.
Biphenyl novolac epoxy resin (Nippon Kayaku Co., Ltd., trade name NC-3000H): 37 parts by mass Aminotriazine novolac epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name LA-3018): 9 parts by mass 2- Phenylimidazole (manufactured by JSR Corporation, trade name G-8809L): 0.2 parts by mass Acrylic resin (manufactured by Nagase ChemteX Corporation): 40 parts by mass

[Composition Example 3]
The resin composition shown below was dissolved in methyl isobutyl ketone and adjusted so that the resin solid content was 30 wt%, whereby a varnish of Formulation Example 3 was obtained.
Biphenyl novolac epoxy resin (Nippon Kayaku Co., Ltd., trade name NC-3000H): 33 parts by mass Aminotriazine novolac epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name LA-3018): 8 parts by mass 2- Phenylimidazole (manufactured by JSR Corporation, trade name G-8809L): 0.2 parts by mass Acrylic resin (manufactured by Nagase ChemteX Corporation): 45 parts by mass

[Formulation Example 4]
Polyamideimide resin (manufactured by Hitachi Chemical Coated Sand Co., Ltd., trade name CSD40) 24.87 kg (resin solid content 28.1% by mass), salicylaldehyde-novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name EPPN502H) ) 2.0 kg (methyl ethyl ketone solution with a resin solid content of 50% by mass), bifunctional naphthalene epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name HP4032D) 3.0 kg, biphenyl aralkyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) Product name NC3000) 1.0 kg (methyl ethyl ketone solution having a resin solid content of 50% by mass) and 8.0 g of 1-cyanoethyl-2-ethyl-1-methylimidazole were added, and further a phosphorus-containing filler (trade name, manufactured by Clariant) OP930) 1.0 kg, and aluminum hydroxide (Showa) Manufactured by Engineering Ltd., trade name HP360) was added to 1.5kg was stirred for about 3 hours until the resin became uniform. Then, it left still at room temperature for 24 hours for defoaming, and the varnish of the mixing example 4 was obtained.

[Formulation Example 5]
Polyamideimide resin (manufactured by Hitachi Chemical Co., Ltd., trade name KS7003) 23.18 kg (resin solid content 30.2 mass%), salicylaldehyde-novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name EPPN502H) 2 0.0 kg (methyl ethyl ketone solution having a resin solid content of 50% by mass), bifunctional naphthalenic epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name HP4032D) 3.0 kg, biphenyl aralkyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name) NC3000) 1.0 kg (methyl ethyl ketone solution having a resin solid content of 50% by mass) and 8.0 g of 1-cyanoethyl-2-ethyl-1-methylimidazole were added, and a phosphorus-containing filler (trade name OP930, manufactured by Clariant) 1.0kg and aluminum hydroxide (Showa Denko Co., Ltd. Ltd., trade name HP360) was added to 1.5kg was stirred for about 3 hours until the resin became uniform. Then, it left still at room temperature for 24 hours for defoaming, and the varnish of the compounding example 5 was obtained.

[Composition Example 6]
Polyamideimide resin (manufactured by Hitachi Chemical Co., Ltd., trade name: KS9900B) 22.44 kg (resin solid content: 31.2% by mass), salicylaldehyde-novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: EPPN502H) 2 0.0 kg (methyl ethyl ketone solution having a resin solid content of 50% by mass), bifunctional naphthalenic epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name HP4032D) 3.0 kg, biphenyl aralkyl epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name) NC3000) 1.0 kg (methyl ethyl ketone solution having a resin solid content of 50% by mass) and 8.0 g of 1-cyanoethyl-2-ethyl-1-methylimidazole were added, and a phosphorus-containing filler (trade name OP930, manufactured by Clariant) 1.0kg, aluminum hydroxide (Showa Denko KK , Trade name HP360) was added to 1.5kg was stirred for about 3 hours until the resin became uniform. Then, it left still at room temperature for 24 hours for defoaming, and the varnish of the mixing example 6 was obtained.

[Formulation Example 7]
The resin composition shown below was dissolved in propylene glycol monomethyl ether and adjusted so that the resin solid content was 70 wt% to obtain a varnish of Formulation Example 7.
Brominated bisphenol A type epoxy resin (epoxy equivalent: 530): 100 parts by mass Dicyandiamide: 4 parts by mass Imidazole (manufactured by Shikoku Kasei Co., Ltd., trade name 2E4MZ): 0.5 parts by mass

[Formulation Example 8]
2564 g of NMP solution of the above siloxane-modified polyimideimide resin A (solid content: 800 g), 400 g of EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin, 400 g (solid content: 200 g), 2-ethyl-4- After blending 40 g of methylimidazole 5% MEK solution (solid content 2 g) and stirring for about 1 hour until the resin became uniform, the mixture was allowed to stand for 24 hours at room temperature to obtain a varnish of Formulation Example 8.

(Preparation of copper foil with resin)
[Production Example 1]
On a copper foil having a thickness of 18 μm (trade name HLA18, manufactured by Nippon Electrolytic Co., Ltd.), the varnish of Formulation Example 1 was applied with a horizontal coating machine so that the thickness of the resin after drying was 50 μm. This was heat-dried at a residence time of 5 minutes in a drying furnace at 100 to 140 ° C. to produce a resin-coated copper foil of Production Example 1.

[Production Examples 2 to 7]
Resin-coated copper foils of Preparation Examples 2 to 7 were prepared in the same manner as Preparation Example 1 except that the varnishes of Formulation Examples 2 to 7 were used instead of the varnish of Formulation Example 1.

(Preparation of prepreg)
[Example 1]
A glass cloth WEX-1027 (manufactured by Asahi Schavel Co., Ltd., thickness 19 μm) was coated with a vertical coating machine so that the thickness of the first resin layer after drying of the formulation example 1 was 20 μm, and 70 ° C. Heated in a drying oven at ˜150 ° C. with a residence time of 1-5 minutes. Thereafter, the varnish of Formulation Example 2 was applied to both sides so that the thickness of the prepreg after drying was 50 μm, and was heat-dried at 120 to 150 ° C. for 10 minutes to obtain a prepreg.
A copper foil having a thickness of 18 μm (trade name: HLA18, manufactured by Nippon Electrolytic Co., Ltd.) was stacked on both sides of the prepreg, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. A conductive pattern circuit having a line width of 75 μm and a space between lines of 75 μm was produced on one surface of the double-sided copper foil-clad laminate, and the entire surface was etched on the opposite surface. Thereafter, the both sides of the laminate were laminated together with the resin-side surfaces of the resin-coated copper foil of Production Example 2, and a double-sided copper-clad laminate was produced at 170 ° C. for 90 minutes at 4.0 MPa. Then, what etched copper foil was made into the evaluation board | substrate.

[Example 2]
A glass cloth WEX-1027 (manufactured by Asahi Schavel Co., Ltd., thickness 19 μm) was coated with a vertical coating machine so that the thickness of the first resin layer after drying of the formulation example 1 was 20 μm, and 70 ° C. Heated in a drying oven at ˜150 ° C. with a residence time of 1-5 minutes. Thereafter, the varnish of Formulation Example 3 was applied to both sides so that the thickness of the prepreg after drying was 50 μm, and was heat-dried at 120 to 150 ° C. for 10 minutes to obtain a prepreg.
A copper foil having a thickness of 18 μm (trade name: HLA18, manufactured by Nippon Electrolytic Co., Ltd.) was stacked on both sides of the prepreg, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. A conductive pattern circuit having a line width of 75 μm and a space between lines of 75 μm was produced on one surface of the double-sided copper foil-clad laminate, and the entire surface was etched on the opposite surface. Thereafter, the resin-side surfaces of the resin-coated copper foil of Production Example 3 were laminated on both sides of the laminate, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. Then, what etched copper foil was made into the evaluation board | substrate.

[Example 3]
A glass cloth WEX-1027 (manufactured by Asahi Schavel Co., Ltd., thickness 19 μm) was coated with a vertical coating machine so that the thickness of the first resin layer after drying of the formulation example 1 was 30 μm, and 70 ° C. Heated in a drying oven at ˜150 ° C. with a residence time of 1-5 minutes. Thereafter, the varnish of Formulation Example 3 was applied to both sides so that the thickness of the prepreg after drying was 50 μm, and was heat-dried at 120 to 150 ° C. for 10 minutes to obtain a prepreg.
A copper foil having a thickness of 18 μm (trade name: HLA18, manufactured by Nippon Electrolytic Co., Ltd.) was stacked on both sides of the prepreg, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. A conductive pattern circuit having a line width of 75 μm and a space between lines of 75 μm was produced on one surface of the double-sided copper foil-clad laminate, and the entire surface was etched on the opposite surface. Thereafter, the resin-side surfaces of the resin-coated copper foil of Production Example 3 were laminated on both sides of the laminate, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. Then, what etched copper foil was made into the evaluation board | substrate.

[Example 4]
A glass cloth WEX-1027 (manufactured by Asahi Schavel Co., Ltd., thickness 19 μm) was applied with a vertical coating machine so that the thickness of the first resin layer after drying of the formulation example 1 was 40 μm, and 70 ° C. Heated in a drying oven at ˜150 ° C. with a residence time of 1-5 minutes. Thereafter, the varnish of Formulation Example 3 was applied to both sides so that the thickness of the prepreg after drying was 50 μm, and was heat-dried at 120 to 150 ° C. for 10 minutes to obtain a prepreg.
A copper foil having a thickness of 18 μm (trade name: HLA18, manufactured by Nippon Electrolytic Co., Ltd.) was stacked on both sides of the prepreg, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. A conductive pattern circuit having a line width of 75 μm and a space between lines of 75 μm was produced on one surface of the double-sided copper foil-clad laminate, and the entire surface was etched on the opposite surface. Thereafter, the resin-side surfaces of the resin-coated copper foil of Production Example 3 were laminated on both sides of the laminate, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. Then, what etched copper foil was made into the evaluation board | substrate.

[Example 5]
A glass cloth WEX-1027 (manufactured by Asahi Schavel Co., Ltd., thickness 19 μm) was coated with a vertical coating machine so that the thickness of the first resin layer after drying of the varnish of Formulation Example 2 was 20 μm, and 70 ° C. Heated in a drying oven at ˜150 ° C. with a residence time of 1-5 minutes. Thereafter, the varnish of Formulation Example 3 was applied to both sides so that the thickness of the prepreg after drying was 50 μm, and was heat-dried at 120 to 150 ° C. for 10 minutes to obtain a prepreg.
A copper foil having a thickness of 18 μm (trade name: HLA18, manufactured by Nippon Electrolytic Co., Ltd.) was stacked on both sides of the prepreg, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. A conductive pattern circuit having a line width of 75 μm and a space between lines of 75 μm was produced on the double-sided copper foil-clad laminate, and the entire surface of the opposite surface was etched. Thereafter, the resin-side surfaces of the resin-coated copper foil of Production Example 3 were laminated on both sides of the laminate, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. Then, what etched copper foil was made into the evaluation board | substrate.

[Example 6]
A glass cloth WEX-1027 (manufactured by Asahi Schavel Co., Ltd., thickness 19 μm) is coated with a vertical coating machine so that the thickness of the first resin layer after drying of the formulation example 6 is 20 μm, and 70 ° C. Heated in a drying oven at ˜150 ° C. with a residence time of 1-5 minutes. Thereafter, the varnish of Formulation Example 3 was applied to both sides so that the thickness of the prepreg after drying was 50 μm, and was heat-dried at 120 to 150 ° C. for 10 minutes to obtain a prepreg.
A copper foil having a thickness of 18 μm (trade name: HLA18, manufactured by Nippon Electrolytic Co., Ltd.) was stacked on both sides of the prepreg, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. A conductive pattern circuit having a line width of 75 μm and a space between lines of 75 μm was produced on one surface of the double-sided copper foil-clad laminate, and the entire surface was etched on the opposite surface. Thereafter, the resin-side surfaces of the resin-coated copper foil of Production Example 3 were laminated on both sides of the laminate, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. Then, what etched copper foil was made into the evaluation board | substrate.

[Example 7]
A glass cloth WEX-1027 (manufactured by Asahi Schavel Co., Ltd., thickness 19 μm) was coated with a vertical coating machine so that the thickness of the first resin layer after drying of the formulation example 4 was 20 μm, and 70 ° C. Heated in a drying oven at ˜150 ° C. with a residence time of 1-5 minutes. Thereafter, the varnish of Formulation Example 5 was applied to both sides so that the thickness of the prepreg after drying was 50 μm, and was heat-dried at 120 to 150 ° C. for 10 minutes to obtain a prepreg.
A copper foil having a thickness of 18 μm (trade name: HLA18, manufactured by Nippon Electrolytic Co., Ltd.) was stacked on both sides of the prepreg, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. A conductive pattern circuit having a line width of 75 μm and a space between lines of 75 μm was produced on one surface of the double-sided copper foil-clad laminate, and the entire surface was etched on the opposite surface. Thereafter, the resin-side surfaces of the resin-coated copper foil of Preparation Example 5 were laminated together on both sides of the laminate, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. Then, what etched copper foil was made into the evaluation board | substrate.

[Example 8]
A glass cloth WEX-1027 (manufactured by Asahi Schavel Co., Ltd., thickness 19 μm) is coated with a vertical coating machine so that the thickness of the first resin layer after drying of the formulation example 6 is 20 μm, and 70 ° C. Heated in a drying oven at ˜150 ° C. with a residence time of 1-5 minutes. Thereafter, the varnish of Formulation Example 5 was applied to both sides so that the thickness of the prepreg after drying was 50 μm, and was heat-dried at 120 to 150 ° C. for 10 minutes to obtain a prepreg.
A copper foil having a thickness of 18 μm (trade name: HLA18, manufactured by Nippon Electrolytic Co., Ltd.) was stacked on both sides of the prepreg, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. A conductive pattern circuit having a line width of 75 μm and a space between lines of 75 μm was produced on the double-sided copper foil-clad laminate, and the entire surface of the opposite surface was etched. Thereafter, the resin-side surfaces of the resin-coated copper foil of Preparation Example 5 were laminated together on both sides of the laminate, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. Then, what etched copper foil was made into the evaluation board | substrate.

[Example 9]
A glass cloth WEX-1027 (manufactured by Asahi Schavel Co., Ltd., thickness 19 μm) was coated with a vertical coating machine so that the thickness of the first resin layer after drying of the formulation example 8 was 20 μm, and 70 ° C. Heated in a drying oven at ˜150 ° C. with a residence time of 1-5 minutes. Thereafter, the varnish of Formulation Example 3 was applied to both sides so that the thickness of the prepreg after drying was 50 μm, and was heat-dried at 120 to 150 ° C. for 10 minutes to obtain a prepreg.
A copper foil having a thickness of 18 μm (trade name: HLA18, manufactured by Nippon Electrolytic Co., Ltd.) was stacked on both sides of the prepreg, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. A conductive pattern circuit having a line width of 75 μm and a space between lines of 75 μm was produced on the double-sided copper foil-clad laminate, and the entire surface of the opposite surface was etched. Thereafter, the resin-side surfaces of the resin-coated copper foil of Production Example 3 were laminated on both sides of the laminate, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. Then, what etched copper foil was made into the evaluation board | substrate.

[Comparative Example 1]
A glass cloth WEX-1027 (manufactured by Asahi Schavel Co., Ltd., thickness 19 μm) is coated with a vertical coating machine so that the prepreg (first resin layer) after drying the varnish of Formulation Example 1 has a thickness of 50 μm. , 120 to 150 ° C., and dried by heating in 10 minutes to obtain a prepreg.
A copper foil having a thickness of 18 μm (trade name: HLA18, manufactured by Nippon Electrolytic Co., Ltd.) was stacked on both sides of the prepreg, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. A conductive pattern circuit having a line width of 75 μm and a space between lines of 75 μm was produced on one surface of the double-sided copper foil-clad laminate, and the entire surface was etched on the opposite surface. Thereafter, the resin-side surfaces of the resin-coated copper foil of Preparation Example 1 were laminated on both sides of the laminate and laminated, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. Then, what etched copper foil was made into the evaluation board | substrate.

[Comparative Example 2]
A glass cloth WEX-1027 (manufactured by Asahi Schavel Co., Ltd., thickness 19 μm) is coated with a vertical coater so that the prepreg (first resin layer) after drying the varnish of Formulation Example 7 has a thickness of 50 μm. , 120 to 150 ° C., and dried by heating in 10 minutes to obtain a prepreg.
A copper foil having a thickness of 18 μm (trade name: HLA18, manufactured by Nippon Electrolytic Co., Ltd.) was stacked on both sides of the prepreg, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. A conductive pattern circuit having a line width of 75 μm and a space between lines of 75 μm was produced on one surface of the double-sided copper foil-clad laminate, and the entire surface was etched on the opposite surface. Thereafter, the resin-side surfaces of the copper foil with resin of Preparation Example 7 were laminated on both sides of the laminate, and a double-sided copper-clad laminate was produced at 170 ° C. for 90 minutes at 4.0 MPa. Then, what etched copper foil was made into the evaluation board | substrate.

[Comparative Example 3]
A glass cloth WEX-1027 (manufactured by Asahi Schavel Co., Ltd., thickness 19 μm) is coated with a vertical coating machine so that the thickness of the first resin layer after drying of the varnish of Formulation Example 7 is 20 μm. Heated in a drying oven at ˜150 ° C. with a residence time of 1-5 minutes. Thereafter, the varnish of Formulation Example 3 was applied to both sides so that the thickness of the prepreg after drying was 50 μm, and was heat-dried at 120 to 150 ° C. for 10 minutes to obtain a prepreg.
A copper foil having a thickness of 18 μm (trade name: HLA18, manufactured by Nippon Electrolytic Co., Ltd.) was stacked on both sides of the prepreg, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. A conductive pattern circuit having a line width of 75 μm and a space between lines of 75 μm was produced on one surface of the double-sided copper foil-clad laminate, and the entire surface was etched on the opposite surface. Thereafter, the resin-side surfaces of the resin-coated copper foil of Production Example 3 were laminated on both sides of the laminate, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. Then, what etched copper foil was made into the evaluation board | substrate.

[Comparative Example 4]
A glass cloth WEX-1027 (manufactured by Asahi Schavel Co., Ltd., thickness 19 μm) is coated with a vertical coating machine so that the thickness of the first resin layer after drying of the formulation example 3 is 20 μm, and 70 ° C. Heated in a drying oven at ˜150 ° C. with a residence time of 1-5 minutes. Thereafter, the varnish of Formulation Example 1 was applied to both sides so that the thickness of the prepreg after drying was 50 μm, and was heat-dried at 120 to 150 ° C. for 10 minutes to obtain a prepreg.
A copper foil having a thickness of 18 μm (trade name: HLA18, manufactured by Nippon Electrolytic Co., Ltd.) was stacked on both sides of the prepreg, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. A conductive pattern circuit having a line width of 75 μm and a space between lines of 75 μm was produced on one surface of the double-sided copper foil-clad laminate, and the entire surface was etched on the opposite surface. Thereafter, the resin-side surfaces of the resin-coated copper foil of Preparation Example 1 were laminated on both sides of the laminate and laminated, and a double-sided copper-clad laminate was produced under 170 ° C., 90 minutes, 4.0 MPa pressing conditions. Then, what etched copper foil was made into the evaluation board | substrate.

(Preparation of sample for measuring elongation characteristics (elastic modulus))
On a copper foil having a thickness of 18 μm, the varnishes of Formulation Examples 1 to 7 were applied with a horizontal coating machine so that the resin thickness after drying was 50 μm, and the residence time was 5 minutes in a drying furnace at 100 to 140 ° C. And dried with heat to obtain a copper foil with resin. Thereafter, a roughened surface of a copper foil with a thickness of 18 μm (trade name HLA18, manufactured by Nippon Electrolytic Co., Ltd.) is superimposed on the resin surface of the resin-coated copper foil, and double-sided copper-clad lamination is performed at 170 ° C. for 90 minutes and 4.0 MPa pressing conditions. A plate was made. The copper foil outside the double-sided copper-clad laminate was etched on both sides.

(Measurement of elongation characteristics (elastic modulus))
The elastic modulus was measured using an autograph (manufactured by Shimadzu Corporation, model number AG-100C). A resin plate obtained by etching both sides of the copper foil of the double-sided copper-clad laminate was cut into 80 mm × 10 mm to obtain a test piece. The measurement conditions were a measurement length of 60 mm and a tensile speed of 5 mm / min at 25 ° C.

(Evaluation of bendability (fold resistance) (MIT test))
The bendability of the evaluation substrates of Examples 1 to 9 and Comparative Examples 1 to 4 was evaluated using an MIT testing machine (manufactured by Toyo Seiki Co., Ltd., model number 2101101-00). Under the conditions of a bending radius of 0.38 mm, a load of 500 g, a bending angle of 135 degrees, and a speed of 175 cpm (cycles per minute), the number of bending until disconnection was evaluated five times for each evaluation substrate. Table 1 shows the number of times of folding when the number of times of bending until the disconnection is observed is minimum, and the number of times of bending when it is maximum.

  The results of the above measurement and evaluation are shown in Table 1. From Table 1, it is clear that the prepregs of Examples 1 to 9 have a good folding resistance and the number of times of bending until the wire breaks in any case as compared with the prepregs of Comparative Examples 1 to 4. .

FIG. 1 is a schematic sectional view showing a preferred embodiment of a prepreg according to the present invention. FIG. 2 is a partial cross-sectional view showing a preferred embodiment of a metal foil-clad laminate according to the present invention. FIG. 3 is a schematic cross-sectional view showing a preferred embodiment of a printed wiring board according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 3 ... Fiber reinforced resin layer, 10 ... Fiber base material, 11 ... 1st resin layer, 12 ... 2nd resin layer, 20 ... Metal foil, 30 ... Board | substrate, 100 ... Pre-preg, 200 ... Metal foil tension laminated board, 300 ... printed circuit board, 313a, 313b, 323a, 323b ... circuit, 315 ... inner layer circuit board, 311, 321a, 321b ... through hole, 312, 322a, 322b ... conductor, 310, 320a, 320b ... insulating substrate.

Claims (8)

A fiber substrate;
A first resin layer formed by impregnating the fiber base material with a first thermosetting resin composition;
A prepreg comprising: one or more resin layers provided to cover the entire surface of the first resin layer and formed from a thermosetting resin composition,
The 2nd thermosetting resin composition which forms the resin layer of the outermost surface of the said prepreg among the 1st thermosetting resin composition and the 1 or more resin layer formed from the said thermosetting resin composition A prepreg that satisfies the following formula (1).
Y [GPa] <X [GPa] ≦ 3 [GPa] (1)
[Wherein X represents the elastic modulus of the resin film formed from the first thermosetting resin composition, and Y represents the elastic modulus of the resin film formed from the second thermosetting resin composition. Show. ]   The prepreg according to claim 1, wherein the first thermosetting resin composition and the second thermosetting resin composition include a resin having a glycidyl group.   The prepreg according to claim 1 or 2, wherein the first thermosetting resin composition and the second thermosetting resin composition include an acrylic resin.   The prepreg according to claim 1 or 2, wherein the first thermosetting resin composition and the second thermosetting resin composition include a resin having an amide group.   The prepreg according to claim 4, wherein the resin having an amide group includes a polyamideimide resin.   The prepreg according to claim 5, wherein the polyamideimide resin has a siloxane bond. A substrate obtained by heating and pressurizing a laminate obtained by laminating a predetermined number of the prepregs according to claim 1;
A metal foil-clad laminate comprising: a metal foil having a thickness of 0.01 to 30 μm provided on at least one surface of the substrate. A printed wiring board obtained by processing a circuit on the metal foil-clad laminate according to claim 7.

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