JP2008254352A - Resin composite copper foil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composite copper foil which is excellent in adhesive force with a resin composition of a copper-clad laminated sheet, to which a copper foil with a copper foil matting face with an extremely small unevenness can be applied, and which is suitable for mass production, and to provide the copper clad-laminated sheet and a printed wiring board using this resin composite copper foil and having good heat resistance and good moisture absorbing heat resistance. <P>SOLUTION: The resin composite copper foil formed with a resin layer comprising a block copolymer polyimide resin (a) and 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane (b) on one face of the copper foil, the copper-clad laminated sheet in which the resin composite copper foil and a B-stage resin composition layer are laminated and molded, and the printed wiring board using this, are provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composite copper foil used for manufacturing a printed wiring board, a copper-clad laminate using the resin composite copper foil, and a printed wiring board using the copper-clad laminate. More specifically, since the adhesive layer component does not vary substantially even after continuous production and maintains performance such as heat resistance and excellent adhesion to copper foil, the unevenness of the copper foil (mat) surface The present invention relates to a resin copper foil to which an extremely small copper foil can be applied, a copper clad laminate using the resin composite copper foil, and a high-density printed wiring board suitable for forming a fine circuit using the copper clad laminate.

In recent years, printed wiring boards for mounting electronic components such as semiconductor components used in electronic devices have been required to be further thinned in circuit conductor width and inter-circuit insulating space, coupled with the ultra-high density of semiconductor circuits. ing. Conventionally, as a copper foil of a copper clad laminate used for a printed wiring board, an electrolytic copper foil having a good copper foil adhesive force and a large unevenness on a copper foil mat surface has been used. These electrolytic copper foils have good adhesive strength, but when forming a fine circuit by etching, due to the influence of the unevenness of the copper foil mat surface, some of the unevenness of the copper foil is on the insulating resin surface. It is easy to remain. In order to remove this completely, if the etching time is extended, the circuit is over-etched, and there is a problem that the positional accuracy of the circuit and the adhesive force are lowered. As these improvement means, what is called a low profile copper foil which suppressed the unevenness | corrugation of the copper foil surface is put into practical use.

  However, if this copper foil is used as a copper-clad laminate that is laminated with a heat-resistant thermosetting resin that has a low adhesive strength, it will cause a problem of insufficient adhesive strength in a fine circuit, which is a major obstacle to ultra-thin wires. It has become. Also, since long ago, in order to improve the adhesion between the copper foil and the insulating resin, a method of forming an insulating adhesive layer on the copper foil has been put into practical use. For example, in the case of paper phenolic resin copper-clad laminates, a phenol-butyral resin adhesive layer is formed on the copper foil, and in the case of glass epoxy resin copper-clad laminates, epoxy resin adhesive is formed on the copper foil. Things to do are known. As specific examples of these copper foils with adhesive, copper-clad laminates using a copper-clad laminate using a copper foil with a thin adhesive layer (for example, see Patent Document 1) and copper-clad using a semi-cured resin film are used. A laminated plate (see, for example, Patent Document 2) has also been proposed.

  However, the copper-clad laminate with the semi-cured resin film attached has problems in terms of heat resistance, adhesiveness, and moisture absorption heat resistance, and further improvement is necessary. In order to solve these problems, a polyimide adhesive composition (see, for example, Patent Document 3) has been proposed. However, since the original characteristics cannot be obtained if the diluted solvent remains, a drying treatment at a temperature higher than the boiling point of the diluted solvent is required. However, when the high-temperature heat drying treatment is continuously performed, the component maleimide compound [for example, (bis (4-maleimidophenyl) methane) is scattered, as a result, the characteristics are deteriorated, and there is a problem in mass productivity. There was a need to improve.

JP-A-8-216340 Japanese Patent Laid-Open No. 9-011397 Japanese Patent Laid-Open No. 9-011397

  The present invention is a copper foil (mat) by using a resin that does not scatter components even when continuously heated and dried, and as a result, maintains excellent performance such as adhesive strength, heat resistance, moisture absorption heat resistance, etc. Providing mass-productive resin composite copper foil using copper foil with extremely small surface irregularities, and forming copper-clad laminates and fine circuits with good heat resistance and moisture absorption heat resistance by using this resin composite copper foil It aims at providing the printed wiring board suitable for.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that a block copolymerized polyimide resin (a) and 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (b) are formed on one surface of a copper foil. The present inventors have found that a copper clad laminate suitable for mass production and excellent in adhesive strength and heat resistance can be obtained by using a resin composite copper foil having a resin layer formed of That is, the present invention provides a resin composite copper in which a resin layer comprising a block copolymerized polyimide resin (a) and 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (b) is formed on one surface of a copper foil. A resin composite copper foil in which the block copolymerized polyimide resin (a) is a block copolymerized polyimide resin having structural units represented by the general formulas (1) and (2). A copper-clad laminate obtained by laminating the resin composite copper foil and the B-stage resin composition layer, and a printed wiring board using the same.

... (1)

... (2)
(M and n in the formula are m: n = 1: 9 to 3: 1)

  The resin composite copper foil obtained in the present invention is excellent in productivity, and even when continuously produced, there is substantially no variation in the components of the resin layer of the resin composite copper foil, resulting in adhesive strength, heat resistance, moisture absorption. By maintaining excellent performance such as heat resistance, it is possible to apply copper foil with extremely small unevenness on the copper foil (mat) surface, and by using this resin composite copper foil, economic efficiency, heat resistance And a copper clad laminate having good moisture absorption and heat resistance. Since the mat surface unevenness of the copper foil can be made extremely small, this copper-clad laminate can be suitably used as a high-density printed wiring board having a fine circuit, so the industrial utility of the resin composite copper foil of the present invention is extremely high.

The block copolymerized polyimide resin (a) used in the resin composite copper foil of the present invention has a structure in which an imide oligomer composed of the second structural unit is bonded to the terminal of the imide oligomer composed of the first structural unit. If it is the copolymerization polyimide resin which has, it will not specifically limit. These block copolymerized polyimide resins are prepared by reacting a tetracarboxylic dianhydride and a diamine in a polar solvent to form an imide oligomer, and then further using a tetracarboxylic dianhydride and another diamine or another tetracarboxylic acid dianhydride. It is synthesized by a sequential polymerization reaction in which an anhydride and a diamine are added and imidized.

  Examples of the polar solvent to be used include polar solvents that dissolve polyimide, such as N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide, sulfolane, and tetramethylurea. It is also possible to use a mixture of a ketone or ether solvent. Examples of the ketone solvent include methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, and methyl-n-hexyl. Ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetylacetone, diacetone alcohol, cyclohexene-n-one are ether solvents such as dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, Tetrahydropyran, ethyl isoamyl alcohol, ethyl t-butyl ether, ethyl benzyl ether, diethylene glycol dimethyl ether, quedyl methyl Ether, anisole and phenetole can be used. Moreover, in order to remove the water produced | generated at the time of imidation reaction, the solvent azeotropically distilled with water, such as toluene and xylene, is added. In order to accelerate the reaction, an amine catalyst such as pyridine or a two-component catalyst of a base and a cyclic ester such as pyridine and γ-valerolactone is preferably used. The reaction temperature is 120-200 ° C. Solvents that azeotrope with water such as toluene and xylene, and catalysts such as pyridine are finally distilled out of the system, so that the polar solvent solution contains only block copolymerized polyimide resin. It is possible to obtain

  As the block copolymerized polyimide resin (a) used in the present invention, block copolymerized polyimide resins having structural units represented by the general formulas (1) and (2) are suitable. The tetracarboxylic dianhydride used in this block copolymerized polyimide resin is 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, and the diamine is 1,3-bis (3-aminophenoxy) Benzene and 2,2-bis {4- (4-aminophenoxy) phenyl} propane. Also, in order to control the molecular weight, the molar ratio of tetracarboxylic dianhydride and diamine is shifted from equimolar during the first stage reaction, and the terminal is acid anhydride or amine. A block copolymerized polyimide having a sufficient molecular weight can be obtained, for example, by reversing the molar ratio of anhydride to diamine to that of the first step.

  The weight average molecular weight (Mw) of the block copolymerized polyimide resin (a) used in the present invention is preferably 50,000 to 300,000. More preferably, it is 80,000-200,000. If the Mw is less than the lower limit of the above range, the polyimide resin layer tends to be brittle. On the other hand, if the Mw is higher than the upper limit, the solution viscosity becomes too high and coating becomes difficult. Moreover, in order to control the final molecular weight, it is also possible to synthesize by shifting the molar ratio of the tetracarboxylic dianhydride to be used and the diamine. The molar ratio of each unit polycondensate of general formula (1) and general formula (2) is general formula (1): general formula (2) = 1: 9-3: 1. More preferably, general formula (1): general formula (2) = 1: 3 to 3: 1. When the ratio of the structure of the general formula (1) is less than 10 mol%, a decrease in adhesive strength becomes a problem. When the ratio of the structure of the general formula (2) is less than 25 mol%, a decrease in solder heat resistance becomes a problem. 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (b) used in the present invention is represented by the formula (3).

・・・（３）

本発明の樹脂複合銅箔の樹脂層に使用するブロック共重合ポリイミド樹脂（ａ）と2,2-ビス〔4-(4-マレイミドフェノキシ)フェニル〕プロパン（ｂ）の重量配合比率は好ましくは90：10 〜 10：90であり、より好ましくは60：40 〜 40：60である。

... (3)

The weight blending ratio of the block copolymerized polyimide resin (a) and 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (b) used in the resin layer of the resin composite copper foil of the present invention is preferably 90. : 10 to 10:90, more preferably 60:40 to 40:60.

  The copper foil used for the resin composite copper foil of the present invention is not particularly limited as long as it is a known copper foil used for a printed wiring board, but is preferably an electrolytic copper foil, a rolled copper foil, and a copper alloy thereof. Is used. These copper foils that have been subjected to a known surface treatment such as nickel or cobalt treatment can also be used. The thickness of the copper foil is not particularly limited, but is preferably 35 μm or less. The surface roughness (Rz) of the copper foil surface forming the resin layer is preferably 4 μm or less, and more preferably 2 μm or less (Rz is the ten-point average roughness defined by JIS B0601. ).

  The thickness of the resin layer of the resin composite copper foil of the present invention can be adjusted according to the surface roughness level of the copper foil. Since drying tends to be insufficient and the heat resistance of the copper clad laminate used may be reduced, 1 μm to 10 μm is preferable, and 2 to 7 μm is more preferable.

  The resin composite copper foil of the present invention comprises 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (b) in a polar solvent solution of the block copolymerized polyimide resin (a) obtained by the synthesis method described above. ), And a solution obtained by stirring and dissolving at room temperature or while heating is directly applied to one side of the copper foil and dried. As a coating method, various methods such as a reverse roll, a rod (bar), a blade, a knife, a die, a gravure, and a rotary screen are possible. The drying is not particularly limited as long as it is a device capable of applying a temperature sufficient to remove the solvent used, such as a hot air dryer or an infrared dryer. In addition, in order to prevent oxidation of the copper foil, it is possible to dry at a temperature of 200 ° C. or lower for a long time, or to dry at a higher temperature in a vacuum or an inert atmosphere such as nitrogen.

  The resin composition used for the B-stage resin composition layer laminated with the resin composite copper foil of the present invention is not particularly limited as long as it is a known thermosetting resin composition used for printed wiring boards. Examples of these resins include epoxy resins, polyimide resins, cyanate ester resins, maleimide resins, double bond-added polyphenylene ether resins, and resin compositions such as bromine and phosphorus-containing compounds of these resins. Species or two or more are used in combination. From the viewpoint of reliability such as migration resistance and heat resistance, it is preferable to use a resin composition containing a cyanate ester resin as an essential component, for example, an epoxy resin. For these thermosetting resins, known catalysts, curing agents, and curing accelerators can be used as necessary.

  The cyanate ester resin suitably used for the resin composition used for the B-stage resin composition layer is a compound having two or more cyanato groups in the molecule. Specific examples include 1,3- or 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1,8-, 2 , 6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4-dicyanatobiphenyl, bis (4-dicyanatophenyl) methane, 2,2-bis (4-cyanato Phenyl) propane, 2,2-bis (3,5-dibromo-4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) ) Sulfone, tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, and cyanates obtained by the reaction of novolac and cyanogen halide.

  In addition to these, phenol novolac type cyanic acid described in JP-B-41-1928, 43-18468, 44-4791, 45-11712, 46-41112, 47-26853 and JP-A-51-63149, etc. Ester compounds and the like can also be used. Naphthalene-type cyanate ester compounds can also be used. Furthermore, a prepolymer having a molecular weight of 400 to 6,000 having a triazine ring formed by trimerization of cyanate groups of these cyanate ester compounds can be used. This prepolymer is obtained by polymerizing the above-mentioned cyanate ester monomers using, for example, acids such as mineral acids and Lewis acids; bases such as sodium alcoholates and tertiary amines; salts such as sodium carbonate and the like as catalysts. It is done. This resin also contains a partially unreacted monomer and is in the form of a mixture of a monomer and a prepolymer, and such a raw material is suitably used for the application of the present invention. Furthermore, cyanated polyphenylene ether resin can also be used. A monofunctional cyanate ester compound can also be added to these in an amount that does not significantly affect the properties. Preferably it is 1 to 10% by weight. These cyanate ester resins are not limited to those described above, and known ones can be used. These may be used alone or in combination of two or more.

  As an epoxy resin suitably used in combination with a cyanate ester resin, known resins can be used. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, resorcin type epoxy resin, Naphthalene type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, epoxidized polyphenylene ether resin; polyepoxy compounds with epoxidized double bonds such as butadiene, pentadiene, vinylcyclohexene, dicyclopentyl ether; polyol, hydroxyl group Examples thereof include polyglycidyl compounds obtained by the reaction of containing silicon resins with epichlorohydrin. Moreover, these well-known bromine addition resin, phosphorus containing epoxy resin, etc. are mentioned. These may be used alone or in combination of two or more.

  In the resin composition used for the B-stage resin composition layer, various additives can be blended as desired within a range that does not impair the original characteristics of the composition. These additives include unsaturated double bond-containing monomers such as unsaturated polyesters and prepolymers thereof; polybutadiene, maleated butadiene, butadiene-acrylonitrile copolymer, polychloroprene, butadiene-styrene copolymer, poly Low molecular weight liquid to high molecular weight elastic rubber such as isoprene, butyl rubber, fluoro rubber, natural rubber; polyethylene, polypropylene, polybutene, poly-4-methylpentene, polystyrene, AS resin, ABS resin, MBS resin, styrene-isoprene Rubber, acrylic rubber, these core-shell rubbers, polyethylene-propylene copolymers, 4-fluoroethylene-6-fluoroethylene copolymers; high molecular weight prepolymers such as polycarbonate, polyphenylene ether, polysulfone, polyester, polyphenylene sulfide Properly oligomer; are exemplified polyurethane, etc., it is suitably used.

  In addition, other known organic and inorganic fillers, dyes, pigments, thickeners, lubricants, antifoaming agents, dispersants, leveling agents, photosensitizers, flame retardants, brighteners, polymerization inhibitors, thixotropic properties Various additives such as an imparting agent are used in appropriate combination as desired. If necessary, the compound having a reactive group is appropriately mixed with a curing agent and a catalyst. In particular, when drilling with a carbon dioxide laser, an inorganic filler is suitably added to improve the hole shape. For example, generally known materials such as silica, spherical silica, alumina, talc, calcined talc, wollastonite, synthetic mica, titanium oxide, and aluminum hydroxide are used. Furthermore, those having a known shape such as these needle-like ones can also be used.

  The production method of the B-stage resin composition layer used in the present invention is not particularly limited. For example, the thermosetting resin composition is dissolved / dispersed in a solvent or a varnish without a solvent, and applied to one side of a release film, A method of drying to form a B-stage resin composition sheet, a method of applying to a base material, a method of drying to form a B-stage to form a prepreg, a B-stage resin composition by directly applying and drying on a substrate on which a conductor circuit is formed It is produced by a known method such as a method of forming a layer. The thickness of the B-stage resin composition layer is not particularly limited, but in the case of a sheet, it is preferably 4 to 150 μm, and the same applies when applied. In the case of a prepreg, the thickness is preferably 10 to 200 μm.

  In the B stage resin composition layer used in the present invention, it is preferable to use a base material from the characteristics of the obtained copper-clad laminate. As a base material to be used, if it is a well-known base material used for a printed wiring board, it will not specifically limit. Specific examples include generally known nonwoven fabrics and woven fabrics of glass fibers such as E, NE, D, S, and T glass. In order for these base materials to improve adhesiveness with a resin composition, it is preferable to perform well-known surface treatment to the base material.

  The manufacturing method of the copper clad laminated board in this invention arrange | positions the resin layer surface of the said resin composite copper foil facing the said B stage resin composition layer, and carries out lamination molding. Specifically, although the B stage resin composition layer is disposed or formed on both surfaces of the B stage resin composition layer or the laminated board on which the internal circuit is formed, the resin layer surface of the resin composite copper foil is opposed to at least one surface. And are laminated by heating and pressurizing, preferably under vacuum, to form a copper-clad laminate. In the case of producing a multilayer board, a B-stage resin composition layer is disposed or formed on both surfaces of the inner substrate on which the conductor circuit is formed, and the resin layer surface of the resin composite copper foil is disposed on the B-stage resin composition layer surface. It arrange | positions so that it may oppose, and it laminates and forms by heating, pressurization, preferably a vacuum, and it is set as a multilayer copper clad laminated board. A conductor circuit is formed on these copper-clad laminates and multilayer copper-clad laminates by a known method, followed by plating and the like to obtain the printed wiring board of the present invention.

  The kind of the laminated board formed with the inner layer circuit used for these is not particularly limited, and a known laminated board, a metal foil-clad board, preferably a copper-clad board for printed wiring board materials can be used. Specifically, inorganic fiber and / or organic fiber-based copper-clad laminates, heat-resistant film-based copper-clad plates using thermosetting resin compositions and / or thermoplastic resin compositions, and further these Known materials such as composite base material copper clad laminates combining these base materials, multilayer copper clad plates, multilayer copper clad plates prepared by the additive method, and the like can be used. The conductor thickness of the inner layer circuit board is not particularly limited, but is preferably 3 to 35 μm. On this conductor circuit, it is preferable to perform a known process for improving the adhesion of the B-stage resin composition layer to the resin, for example, a black copper oxide process, a chemical solution process (for example, CZ process of MEC).

  The lamination conditions of the present invention are not particularly limited. Preferably, the lamination is carried out at a temperature of 100 to 250 ° C., a pressure of 5 to 40 kgf / cm 2, and a degree of vacuum of 30 mmHg or less for 30 minutes to 5 hours. Lamination may be performed under these conditions from the beginning to the end, but it is also possible to laminate and form until the B-stage resin composition layer is gelled, and then take out and post-cure in a heating furnace.

Hereinafter, the present invention will be specifically described with reference to synthesis examples, comparative synthesis examples, examples, and comparative examples.

Synthesis Example A stainless steel vertical stirring bar, a trap with a nitrogen inlet tube and a stopcock, and a 20-liter three-necked flask equipped with a reflux condenser with a ball-mounted condenser tube were placed in 3, 4, 3 ', 4'-biphenyltetracarboxylic dianhydride 1765.32 g (6 mol), 1,3-bis (3-aminophenoxy) benzene 1315.49 g (4.5 mol), γ-valerolactone 60.07 g (0.6 mol), pyridine 71.19 g (0.9 mol), 4389 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 293 g of toluene, heated at 180 ° C. for 1 hour, cooled to near room temperature, then 3, 4, 3 ′, 4 ′ -Biphenyltetracarboxylic dianhydride 441.33 g (1.5 mol), 2,2-bis {4- (4-aminophenoxy) phenyl} propane 1231.53 g (3 mol), NMP 2926 g, toluene 585 g were added, and 1 hour at room temperature. After mixing, the mixture was heated at 180 ° C. for 4 hours to obtain a block copolymerized polyimide resin A component having a solid content of 38%. The block copolymerized polyimide resin had a general formula (1): general formula (2) = 3: 2, a number average molecular weight: 70000, and a weight average molecular weight: 150,000.

Examples 1-4
The block copolymerized polyimide resin solution obtained in the synthesis example was further diluted with NMP to obtain a block copolymerized polyimide resin solution having a solid content of 10%, and 2,2-bis [4- (4-maleimidophenoxy) phenyl] was added thereto. Propane B component (BMI-80, Kei Ii Kasei) was melt-mixed at a solid weight ratio shown in Table 1 at 60 ° C. for 20 minutes to obtain a resin solution. The obtained resin solution was applied to a mat surface of 12 μm thick electrolytic copper foil (F0-WS foil Rz = 1.5 μm, manufactured by Furukawa Circuit Foil) at 120 ° C. for 3 minutes at 160 ° C. using a reverse roll coating machine. After the continuous drying of 3000m under the dry condition for 3 minutes (primary drying process), the secondary drying process is performed at 300 ° C for 3 minutes in a nitrogen atmosphere using a continuous drying furnace. Then, a continuous heat treatment of 3000 m was performed to prepare a resin composite copper foil. On the other hand, 400 g of 2,2-bis (4-cyanatophenyl) propane was melted at 150 ° C., reacted for 4 hours with stirring, dissolved in methyl ethyl ketone, and further brominated bisphenol A type epoxy resin (Epicron 1123P, Dainippon Ink) (600 g) and zinc octylate (0.1 part) were added to make a varnish. This varnish is impregnated into a glass woven fabric substrate with a thickness of 100 μm, dried at 150 ° C. for 6 minutes, a B-stage resin composition layer having a resin amount of 45%, a thickness of 105 μm, and a gelation time (at 170 ° C.) of 120 seconds. A (prepreg) was prepared. The resin layer surface of the above resin composite copper foil is placed facing the top and bottom surfaces of the four prepregs that are stacked, and laminated and molded for 1 hour at a temperature of 220 ° C, a pressure of 40 kgf / cm2, and a vacuum of 30 mmHg or less. A 0.4 mm thick copper clad laminate was produced. The evaluation results are shown in Table 1.

Comparative Example 1
In the examples, bis (4-maleimidophenyl) methane C component (BMI-H, Kay Kasei) is used in place of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane. In the same manner as in the example, a copper clad laminate having a thickness of 0.4 mm was produced. The evaluation results are shown in Table 2.

Measurement method 1) Amount of volatile components during secondary drying (g)
An exhaust fan (air flow 13m3 / L) is installed in the continuous drying furnace, and a pipe with a pipe diameter of 200mm is covered with a metal mesh (200 mesh), and after processing a predetermined quantity under a drying condition of 300 ° C for 3 minutes, the mesh Collect the solidified component and measure its weight.
2) Overall thickness:
Average value of thickness measured at 5 points with a micrometer according to JIS C6481.
3) Copper foil adhesive strength:
Average value measured three times according to JIS C6481.
4) Heat resistance in air:
According to JIS C6481, the presence or absence of abnormal appearance change after 30 minutes of heat treatment was visually observed in a hot air dryer at 240 ° C. and 280 ° C. (○: No abnormality, ×: Swelling and peeling occurred)
5) Hygroscopic heat resistance:
All copper foil other than half of one side of a 50mm x 50mm square sample was removed by etching, treated at 121 ° C and 2 atm for a specified time with a pressurer cooker tester (Hirayama Seisakusho PC-3 type), then 260 ° C The solder bath was floated for 60 seconds, and the presence or absence of abnormal appearance change was visually observed. (○: No abnormality, ×: Swelling and peeling occurred)
6) Molecular weight measurement The number average molecular weight and the weight average molecular weight are measured in terms of polystyrene using gel permeation chromatography (TOSOH HLC-8220 type apparatus).

Claims (7)

A resin composite copper foil in which a resin layer comprising a block copolymerized polyimide resin (a) and 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (b) is formed on one surface of a copper foil. The resin composite copper foil according to claim 1, wherein the block copolymerized polyimide (a) has a structural unit represented by the general formula (1) and the general formula (2).

... (1)

... (2)
(M and n in the formula are m: n = 1: 9 to 3: 1) The ratio of the block copolymerized polyimide resin (a) forming the resin layer to 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (b) is from 10:90 to 90:10 by weight. The resin composite copper foil according to claim 1 or 2. The resin composite copper foil according to claim 1, wherein the resin layer has a thickness of 0.1 μm to 10 μm. 5. The resin composite copper foil according to claim 1, wherein the surface roughness (Rz) of the copper foil surface on the side on which the resin layer is formed is 4 μm or less. The copper clad laminated board which laminated-molded the resin composite copper foil in any one of Claims 1-5, and a B stage resin composition layer. A printed wiring board using the copper clad laminate according to claim 6.