JP5370794B2 - Copper foil with adhesive aid, laminated board using the same, printed wiring board, and method for manufacturing printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesion assisting agent fitted metal foil allowing electroless plating, a printed wiring board advantageous in the formation of fine wiring, electric properties and production costs, high in reliability and excellent in moisture absorbing and heat resisting property, and a process for producing the same. <P>SOLUTION: The adhesion assisting agent fitted metal foil has an adhesion assisting agent layer having a thickness of 0.1-10 &mu;m on metal whose surface has a ten-point average roughness Rz=2.0 &mu;m or less and allows electroless plating by chemically roughening an adhesion assisting agent surface with the metal chemically removed. The metal foil is a copper foil subjected to rustproofing by at least one kind selected from nickel, tin, zinc, chromium, molybdenum, cobalt and oxides thereof. The adhesion assisting agent contains (A) an epoxy resin, (B) a polymer component which is able to be chemically roughed, (C) an epoxy resin curing agent, and (D) a curing accelerator. Furtheremore, 10-80 wt.% of (A) the epoxy resin is a rubber-modified epoxy resin. The component (B) is at least one kind selected from acrylonitrile butadiene rubber, carboxylic acid modified acrylonitrile butadiene rubber, carboxylic acid modified acrylonitrile butadiene rubber particles, core-shell particles of butadiene rubber-acrylic resin, polyvinyl acetal resin and carboxylic acid modified polyvinyl acetal resin. Furthermore, the printed wiring board produced by a usual method using the foil and the process for producing the same are provided. <P>COPYRIGHT: (C)2013,JPO&amp;INPIT

Description

The present invention relates to a copper foil with an adhesion assistant, a laminated board using the copper foil , a printed wiring board, and a method for manufacturing the printed wiring board .

  In recent years, there has been an increasing demand for smaller, lighter, and faster electronic devices, and the density of printed wiring boards has been increasing. In recent years, a method for manufacturing printed wiring boards using a semi-additive method using electroplating has attracted attention. ing. In this semi-additive method, for example, as described in Patent Document 1, after forming a hole to be IVH with a laser or the like on the surface of a resin on which a circuit is to be formed, unevenness of several μm is formed on the resin by chemical roughening or plasma treatment. Forming, applying a Pd catalyst, performing electroless plating of about 1 μm, forming a pattern electroplating resist, forming a circuit by pattern electroplating, and then removing the power supply layer existing in portions other than the resist and the circuit This is a technique that enables finer wiring formation than a subtractive method with large side etching. Further, there is a method of forming a circuit on a metal foil with resin by a semi-additive method. In recent years, in order to reduce the thickness of the metal foil, for example, a peelable type metal foil in which a metal foil having a thickness of 5 μm or less is formed on a supporting metal foil as described in Patent Document 2 is used. In this method, it is not necessary to perform electroless plating on the surface of the insulating resin layer, and a printed wiring board with higher reliability can be manufactured. In addition, as disclosed in Patent Document 3, there is a method in which a copper layer of about 1 μm is formed on one side of a polyimide film using an electron beam vapor deposition apparatus, and is laminated on an inner layer circuit via an adhesive or a prepreg to form a power feeding layer. .

Japanese Patent Laid-Open No. 10-4254 JP 2003-158364 A JP-A-7-212444

  Among the above-mentioned known methods, the method of forming unevenness of several μm on a resin and the method of forming a circuit on a resin-coated metal foil by a semi-additive method not only hinders the formation of fine wiring, but also the roughened shape. In addition, the roughened shape causes a problem that the electrical characteristics are degraded. In addition, the method of forming a copper layer of about 1 μm on one side of the polyimide film using an electron beam vapor deposition apparatus and laminating it on the inner layer circuit via an adhesive or prepreg does not form a roughened shape, Although it is advantageous in terms of formation of fine wiring and electrical characteristics, the substrate itself becomes expensive, and versatility is poor.

The present invention solves the problems of the known methods, provides a copper foil with an adhesion assistant capable of electroless plating, and a wiring board that is advantageous in terms of formation of fine wiring, electrical characteristics, and manufacturing cost, In addition, the present invention provides a wiring board having high reliability and excellent moisture absorption heat resistance.

The present invention relates to the following inventions.
(1) ten-point average roughness of the thickness 0.1~10μm layer surface of the adhesive aid has on following copper Rz = 2.0 .mu.m, and was chemically removed copper foil adhesion auxiliary A metal foil with an adhesion aid that enables electroless plating by chemically roughening the surface of the agent, wherein the copper foil is selected from nickel, tin, zinc, chromium, molybdenum, cobalt, and oxides thereof A copper foil that has been rust-prevented by at least one of the above-mentioned adhesive adjuvants: (A) an epoxy resin, (B) a polymer component that can be chemically roughened, (C) an epoxy resin curing agent, and (D) 10% to 80% by weight of the (A) epoxy resin is a rubber-modified epoxy resin, and the component (B) is an acrylonitrile butadiene rubber, a carboxylic acid modified acrylonitrile butadiene rubber, a carboxylic acid modified acryloni. Lil butadiene rubber particles, butadiene rubber - core-shell particles of the acrylic resin, polyvinyl acetal resin, and is at least one selected from carboxylic acid-modified polyvinyl acetal resin, copper foil adhesion assistant.
(2) (A) relative to 100 parts by weight of component a copper foil adhesive auxiliary agent according to component (B) is 0.5 to 25 parts by weight (1).
(3) (C) Copper foil adhesive assistant having the constitution (1) or (2) the component is a novolac type phenol resin or a triazine ring-containing phenolic novolak resin.
(4) Copper foil adhesive auxiliary agent according to any one of the not roughened for the purpose of promoting adhesion to the copper foil surface, wherein the (1) to (3).
(5) A laminated plate obtained by laminating and integrating the copper foil with an adhesive auxiliary according to any one of (1) to (4) and a prepreg .
(6) A printed wiring board obtained by subjecting the laminated board according to (5) to circuit processing.
( 7 ) A printed wiring board having a step of obtaining a laminated board by laminating and integrating the copper foil with an adhesion auxiliary agent according to any one of (1) to (4) and a prepreg, and a step of processing the laminated board. Production method.

By using the copper foil with an adhesion aid of the present invention, it is possible to form fine wiring, but it can have a peeling strength almost equal to that in the case of using a normal copper foil, and has moisture absorption and heat resistance. A printed wiring board having excellent properties can be produced.

  The present invention relates to an adhesion aid having a layer of an adhesion aid having a thickness of 0.1 to 10 μm on a metal having a 10-point average roughness of the surface of Rz = 2.0 μm or less and chemically removing the metal. The present invention provides a metal foil with an adhesion aid that can be electrolessly plated by chemically roughening the surface. According to the present invention, it is advantageous in terms of fine wiring formation, electrical characteristics, and manufacturing costs. In addition, it is possible to provide a printed wiring board with high reliability, moisture absorption heat resistance, and high frequency characteristics.

As for the surface roughness of the metal foil used in the present invention, the 10-point average roughness (Rz) shown in JIS B0601 is preferably 2.0 μm or less on both sides in view of electrical characteristics. Although copper foil, nickel foil, aluminum foil, etc. can be used for metal foil, copper foil is usually used. In the case of a copper sulfate bath, the production conditions of the copper foil are sulfuric acid 50-100 g / L, copper 30-100 g / L, liquid temperature 20 ° C.-80 ° C., current density 0.5-100 A / dm ² , pyrophosphoric acid In the case of a copper bath, the conditions of potassium pyrophosphate 100-700 g / L, copper 10-50 g / L, liquid temperature 30 ° C.-60 ° C., pH 8-12, current density 1-10 A / dm ² are commonly used. In some cases, various additives may be added in consideration of the physical properties and smoothness of copper. The copper foil is usually subjected to a roughening process called a roughening process, but the present invention is characterized in that a substantial roughening process is not performed and the copper foil does not have a foot. “The copper foil does not have a foot” means that the copper foil has few irregularities. If the copper foil has few irregularities, the copper foil residue does not remain in the portion where there is no circuit on the resin during etching.
Further, if Rz = 2.0 μm or less, a glossy surface on which the copper foil is not roughened can be used.

  The thickness of the metal foil is not particularly limited. A metal foil having a thickness of 105 μm or less that is generally used for a printed wiring board may be used, but a metal foil having a surface roughness Rz of 2.0 μm or less on both sides may be used. In order to form finer wiring, it is preferable to use a metal foil that is a peelable type having a thickness of 5.0 μm or less and that has a surface roughness Rz of 2.0 μm or less on both sides. Instead of the peelable type, an etchable type copper foil having an aluminum carrier or a nickel carrier can also be used.

Rust prevention treatment performed on the resin adhesive surface of the metal foil can be performed using nickel, tin, zinc, chromium, molybdenum, cobalt and any of these oxides, or alloys thereof, but from zinc and chromium It is preferable to be performed by at least one selected. In these methods, a thin film is formed on a metal foil by sputtering, electroplating or electroless plating, but electroplating is preferable from the viewpoint of cost. Specifically, plating is performed using a plating layer containing one or more metal salts of nickel, tin, zinc, chromium, molybdenum, and cobalt. From the viewpoint of reliability and the like later, it is preferable to perform plating containing zinc. In order to facilitate the precipitation of metal ions, a complexing agent such as citrate, tartrate or sulfamic acid can be added in the required amount. The plating solution is usually used in an acidic region and is performed at a temperature of room temperature (25 ° C.) to 80 ° C. Plating is usually selected appropriately from the range of current density of 0.1 to 10 A / dm ² , energization time of 1 to 60 seconds, preferably 1 to 30 seconds. The amount of the rust-proofing metal varies depending on the type of metal, but is preferably 10 to 2000 μg / dm ^{2 in} total. If the rust preventive treatment is too thick, it may cause etching inhibition and deterioration of electrical characteristics, and if it is too thin, it may cause a reduction in peel strength with the resin.

Furthermore, if a chromate treatment layer is formed on the rust prevention treatment, it is useful because a reduction in peel strength with the resin can be suppressed. Specifically, it is performed using an aqueous solution containing hexavalent chromium ions. The chromate treatment can be performed by a simple immersion treatment, but is preferably performed by a cathode treatment. It is good to carry out on the conditions of sodium dichromate 0.1-50 g / L, pH 1-13, bath temperature 0-60 degreeC, current density 0.1-5 A / dm < ² >, and electrolysis time 0.1-100 second. It can also carry out using chromic acid or potassium dichromate instead of sodium dichromate.

In the present invention, it is preferable that a silane coupling agent is further adsorbed on the outermost layer of the metal foil. Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, epoxy-functional silanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and N-2. Amino-functional silanes such as-(aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, vinyltrimethoxysilane, vinylphenyltrimethoxysilane, vinyltris (2- Olefin functional silane such as methoxyethoxy) silane, acrylic functional silane such as 3-acryloxypropyltrimethoxysilane, methacryl functional silane such as 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Such as mercapto functional silane is used. Considering compatibility with an adhesion aid to be applied later, it is desirable to have an epoxy group or an amino group in the molecule. These can be used alone or in combination. These coupling agents are dissolved in a solvent such as water at a concentration of 0.1 to 15 g / L and applied to a metal foil at a temperature of room temperature (25 ° C.) to 50 ° C. or electrodeposited. Adsorb. These silane coupling agents form a film by condensation bonding with a hydroxyl group of a rust-preventing metal on the surface of the metal foil. After the silane coupling treatment, a stable bond is formed by heating, ultraviolet irradiation or the like. If heating, for example, it is dried at a temperature of 100 to 200 ° C. for 2 to 60 seconds. If it is ultraviolet irradiation, it will carry out in the range of 200-400 nm, 200-2500 mJ / cm < ² >, for example.

  For example, an adhesion aid containing an epoxy resin as a component is applied on a copper foil on a copper foil that has been treated with a silane coupling agent. The applied thickness is preferably 0.1 to 10 μm, and more preferably in the range of 0.1 to 5.0 μm.

  The adhesion aid of the present invention comprises (A) an epoxy resin, (B) a polymer component that can be chemically roughened, and (C) an epoxy resin curing agent, and 10 to 80% by weight of the component (A) is rubber. A modified epoxy resin is preferred.

  The component (A) preferably contains a novolac type epoxy resin or a novolac type epoxy resin. The novolac type epoxy resin in the present invention is preferably a novolac type epoxy resin having a biphenyl structure. The novolak-type epoxy resin having a biphenyl structure refers to a novolac-type epoxy resin containing an aromatic ring of a biphenyl derivative in the molecule, and examples thereof include an epoxy resin represented by the following formula (1).

（但し、式中、ｐは、１〜５を示す）

(In the formula, p represents 1 to 5)

  Commercially available products include Nippon Kayaku Co., Ltd. NC-3000S (epoxy resin of formula (1) where p is 1.7), NC-3000S-H (epoxy resin of formula (1) where p is 2.8) ).

  The rubber-modified epoxy resin contained in the component (A) can be used without particular limitation as long as it is a product marketed for adhesives or paints.

  Examples of commercially available products include EPICLON TSR-960 manufactured by Dainippon Ink & Chemicals, Inc., EPOTOHTO YR-102 manufactured by Tohto Kasei Co., Ltd., and Sumiepoxy ESC-500 manufactured by Sumitomo Chemical Co., Ltd.

  The content of the rubber-modified epoxy resin is preferably 10 to 80% by weight of the total epoxy resin. Addition of rubber-modified epoxy resin improves adhesion to the surface of metal foil that has not been roughened. However, if the amount is less than 10% by weight, the effect cannot be exhibited sufficiently, and if it exceeds 80% by weight, the heat resistance is poor. A range of 30 to 70% by weight is more preferable. Two or more rubber-modified epoxy resins may be used, but the total amount must be within the above-mentioned weight%.

The component (B) is preferably crosslinked rubber particles, and is preferably composed of at least one selected from acrylonitrile butadiene rubber particles, carboxylic acid-modified acrylonitrile butadiene rubber particles, and core-shell particles of butadiene rubber-acrylic resin.
The acrylonitrile butadiene rubber particles are those obtained by copolymerizing acrylonitrile and butadiene and partially cross-linking at the stage of copolymerization. It is also possible to obtain carboxylic acid-modified acrylonitrile butadiene rubber particles by copolymerizing together carboxylic acids such as acrylic acid and methacrylic acid. The core-shell particles of butadiene rubber-acrylic resin can be obtained by a two-stage polymerization method in which butadiene particles are polymerized by emulsion polymerization, followed by addition of monomers such as acrylic acid ester and acrylic acid. The size of the particles can be 50 nm to 1 μm as the primary average particle size. These may be used alone or in combination of two or more.

  For example, as a commercially available product of carboxylic acid-modified acrylonitrile butadiene rubber particles, XER-91 manufactured by Nippon Synthetic Rubber Co., Ltd. can be mentioned. An example is AC-3832 from Kogyo Corporation.

  It is also preferable that the component (B) is at least one selected from a polyvinyl acetal resin and a carboxylic acid-modified polyvinyl acetal resin.

  Although the kind of polyvinyl acetal resin, the amount of hydroxyl groups, and the amount of acetyl groups are not particularly limited, those having a polymerization degree of 1000 to 2500 are preferred. Within this range, solder heat resistance can be secured, and the viscosity and handling properties of the varnish are good. Here, the number average degree of polymerization of the polyvinyl acetal resin can be determined, for example, from the number average molecular weight of polyvinyl acetate as a raw material (measured using a standard polystyrene calibration curve by gel permeation chromatography). Moreover, a carboxylic acid modified product etc. can also be used.

  Polyvinyl acetal resin is, for example, a trade name, SLECK BX-1, BX-2, BX-5, BX-55, BX-7, BH-3, BH-S, KS-3Z, manufactured by Sekisui Chemical Co., Ltd. KS-5, KS-5Z, KS-8, KS-23Z, trade names manufactured by Denki Kagaku Kogyo Co., Ltd., and electrified butyral 4000-2, 5000A, 6000C, 6000EP, and the like can be used. These resins can be used alone or in admixture of two or more.

  When the crosslinked rubber particles and the polyvinyl acetal resin are used in combination as the component (B), the peeling strength of the metal foil and the peeling strength of the electroless plating after chemical roughening are further improved.

  (A) It is preferable that (B) component is 0.5-25 weight part with respect to 100 weight part of (A) component. If the component (B) is less than 0.5 parts by weight, the peel strength and peel strength of the electroless plating after chemical roughening are low, and if it exceeds 25 parts by weight, the solder heat resistance and the insulation reliability are reduced. Absent. In particular, when the amount of each of the crosslinked rubber particles and the polyvinyl acetal resin is 1 part by weight or more, the peel strength of the metal foil and the peel strength of the electroless plating after chemical roughening are further improved.

  The component (C) is preferably a novolak type phenol resin, and if it is a triazine ring-containing novolak type phenol resin, the peel strength of the metal foil and the peel strength of the electroless plating after chemical roughening are improved. preferable.

  The triazine ring-containing novolak type phenol resin in the present invention refers to a novolak type phenol resin containing a triazine ring in the main chain of the novolak type phenol resin, and may be a cresol novolac type phenol resin containing a triazine ring. The nitrogen content is preferably 10 to 25% by weight, more preferably 12 to 19% by weight in the triazine ring-containing novolac type phenol resin. When the nitrogen content in the molecule is within this range, the dielectric loss does not increase too much, and when the adhesion aid is used as a varnish, the solubility in the solvent is appropriate, and the remaining amount of undissolved substances can be suppressed. . As the triazine ring-containing novolac type phenol resin, one having a number average molecular weight of 500 to 600 can be used. These may be used alone or in combination of two or more.

  The triazine ring-containing novolak type phenol resin can be obtained by reacting phenol, aldehyde, and a triazine ring-containing compound under conditions of pH 5-9. When cresol is used instead of phenol, a triazine ring-containing cresol novolac type phenol resin is obtained. Any of o-, m-, and p-cresol can be used as the cresol, and melamine, guanamine and derivatives thereof, cyanuric acid and derivatives thereof can be used as the triazine ring-containing compound.

  As a commercially available product, Dainippon Ink & Chemicals, Inc., a triazine ring-containing cresol novolac type phenol resin phenolite EXB-9829 (nitrogen content 18% by weight) can be mentioned.

Any reaction accelerator may be used as the component (D) reaction accelerator, but it is preferable to blend various imidazoles and BF ₃ amine complexes which are latent thermosetting agents. 2-Phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate from the viewpoint of storage stability of adhesion aid, handling property at B stage and solder heat resistance Is preferred.

  The amount of component (D) is preferably in the range of 0.1 to 5 parts by weight and more preferably in the range of 0.3 to 1 part by weight with respect to 100 parts by weight of the epoxy resin (A) in the adhesion aid. . Within these ranges, sufficient solder heat resistance, good storage stability of the adhesion aid, and good handleability when using the B stage can be obtained.

  In order to improve flame retardancy, the adhesion aid of the present invention may contain (E) a phenolic hydroxyl group-containing phosphorus compound. (E) The phenolic hydroxyl group-containing phosphorus compound is a phosphorus compound containing a phenolic hydroxyl group, as represented by the following formula (2). These may be used alone or in combination of two or more.

In the formula (2), when n is 1, R ₄ is a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and when n is 2, R ₄ independently represents a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, or two R _{4 s} each represent a carbon atom to which each is bonded. Together, they form a benzene ring that is unsubstituted or substituted with an alkyl or cycloalkyl group, where x is a natural number of 2 or greater.

In the formula (2), when R ₄ is a linear or branched alkyl group, a C1-C6 alkyl group is preferable, and when it is a cycloalkyl group, a C6-C8 cycloalkyl group is preferable. In the case of an aryl group, a phenyl group is preferable, and in the case of an aralkyl, a C7 to C10 aralkyl group is preferable. x is preferably 2. Also, in formula (2), n is 2, and two R ₄ are together with the carbon atom to which each is bonded, and two R ₄ are together with the carbon atom to which each is bonded. When forming a benzene ring that is unsubstituted or substituted with an alkyl group or a cycloalkyl group, a benzene ring that is unsubstituted or substituted with a C1-C4 alkyl group or a C6-C8 cycloalkyl group is preferred. .

  Specifically, the phosphorus compound shown by following (3) or Formula (4) is mentioned.

（式中、Ｒ_５は、水素原子、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル基、シクロヘキシル基を表す）

(Wherein R ₅ represents a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl group, or cyclohexyl group)

  In particular, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof are preferred.

  As a commercial item, Sanko Co., Ltd. HCA-HQ is mentioned.

  In the case of imparting flame retardancy, the blending amount of the (E) phenolic hydroxyl group-containing phosphorus compound in the adhesion aid of the present invention is 1 in terms of phosphorus atoms in the total weight of the components (A) to (D). The range is preferably from 5 to 3.5% by weight, and more preferably from 1.8 to 2.5% by weight. When the blending amount is within this range, the flame retardancy is good, the insulation reliability is excellent, and the Tg of the cured coating film is not too low.

  In order to improve reliability, the adhesion aid in the present invention may contain (F) an inorganic filler.

  In the present invention, the (F) inorganic filler is not particularly limited, and examples thereof include silica, fused silica, talc, alumina, aluminum hydroxide, barium sulfate, calcium hydroxide, aerosil and calcium carbonate. Inorganic fillers include those treated with various coupling agents such as silane coupling agents for the purpose of enhancing dispersibility. These may be used alone or in combination of two or more. Silica is preferred from the viewpoint of dielectric properties and low thermal expansion.

  The blending amount of the inorganic filler as component (F) is preferably in the range of 5 to 35% by volume, more preferably 10 to 30% by volume, in the total volume of components (A) to (E). is there. When the blending amount is within this range, the thermal expansion coefficient and the dielectric loss are not increased, and a sufficient flow can be obtained for forming the insulating layer on the inner layer circuit. In order to disperse the inorganic filler in the adhesion aid of the present invention, a known kneading method such as a kneader, a ball mill, a bead mill, or a three roll can be used.

  You may mix | blend additives, such as a pigment, a leveling agent, an antifoamer, and an ion trap agent, with the adhesion adjuvant of this invention as needed.

  The adhesion aid produced as described above is, for example, diluted in a solvent to form a varnish, and is applied to a copper foil. Solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, aromatic hydrocarbons such as benzene, xylene, and toluene, alcohols such as ethylene glycol monoethyl ether, esters such as ethyl ethoxypropionate, N, N -Amides such as dimethylformamide and N, N-dimethylacetamide. These solvents may be used alone or in combination of two or more. The usage-amount of the solvent with respect to an adhesion adjuvant is not specifically limited, It can be set as the quantity currently used conventionally.

  The adhesion assistant of the present invention and the above varnish are applied to one side of a metal foil and semi-cured to complete a metal foil with an adhesion assistant.

  In the case of coating the metal foil with a comma coater or gravure coater using the adhesion assistant as a varnish, it is preferable to adjust the amount of the solvent used so that the total solid content of the adhesion assistant is 10 to 30% by weight. Also, the amount can be adjusted according to the equipment for film formation.

  In the method for producing a substrate using the metal foil with an adhesion auxiliary agent as described above, the metal foil with an adhesion auxiliary agent and the prepreg are laminated and integrated by a conventionally known method to obtain a laminate. Furthermore, the laminated board can be processed by a conventionally known method to obtain a printed wiring board.

  By the method described above, a laminated board composed of two layers is completed. The core substrate manufactured as described above preferably has a conductor circuit surface roughness of Rz = 2.0 μm or less, and an insulating layer surface roughness of the core substrate of Rz = 2.0 μm or less in terms of electrical characteristics.

Example 1
The following resin composition A was produced.
(Preparation of resin composition A)
・ Novolak type epoxy resin having biphenyl structure, NC3000S-H (manufactured by Nippon Kayaku Co., Ltd.) 35 parts by weight Rubber-modified epoxy resin, EPICLON TSR-960 (manufactured by Dainippon Ink & Chemicals, Inc.) 30 parts by weight Carboxylic acid Modified acrylonitrile butadiene rubber particles, 5 parts by weight of XER-91SE-15 (manufactured by JSR Corporation), carboxylic acid-modified polyvinyl acetal resin, 10 parts by weight of KS-23Z (manufactured by Sekisui Chemical Co., Ltd.), cresol novolac type phenol containing triazine ring Resin, Phenolite LA-3018 (nitrogen content 18% by weight, hydroxyl group equivalent 151, manufactured by Dainippon Ink & Chemicals, Inc.) 20 parts by weight imidazole derivative compound, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2PZ- CNS (Shikoku Chemicals 0.3 parts by weight / solvent, methyl ethyl ketone

(Preparation of metal foil A)
The resin composition A was applied to a photoselective surface of an electrolytic copper foil having a width of 510 mm and a thickness of 12 μm (product name F0-WS12: manufactured by Furukawa Circuit Foil Co., Ltd. Rz = 1.2 μm) to prepare a metal foil A. After coating, drying was performed at 160 ° C. for about 10 minutes so that the residual solvent was 5% by weight or less. The thickness of the coated resin composition A was 3.0 μm.

  Glass foil base material high Tg epoxy resin prepreg GEA-679F (thickness 0.1 mm) manufactured by Hitachi Chemical Co., Ltd. and metal foil A so that the surface coated with resin composition A on the top and bottom thereof is in contact with the prepreg Laminated and press-molded under the conditions of 180 ° C. and 2.5 MPa for 1 hour to produce a copper-clad laminate. The copper foil was chemically removed, the surface of the resin composition A was chemically roughened, and further electroless (copper) plating was performed.

  Next, dry film photoresist RY-3325 (manufactured by Hitachi Chemical Co., Ltd., trade name) is laminated on the surface of the electroless (copper) plating layer, and a photomask that masks the place where electrolytic copper plating is performed is used. Then, ultraviolet rays were exposed and developed to form a plating resist.

  A circuit pattern was formed by electrolytic copper plating so that the minimum circuit conductor width / circuit conductor interval (L / S) = 20/20 μm.

  Next, the dry film was removed with HTO (trade name, manufactured by Nichigo Morton Co., Ltd.) which is a resist stripping solution. The surface roughness Rz of the insulating layer of the core substrate was 1.2 μm, and the surface roughness Rz of the conductor circuit was 1.1 μm. The surface roughness was measured based on JIS-B-0601.

(Example 2)
In Example 1, when producing the metal foil A, a substrate was produced in the same manner as in Example 1 except that the resin composition A was applied to a thickness of 8 μm.

(Example 3)
In Example 1, 50 parts by weight of the novolac type epoxy resin (NC3000S-H) having a biphenyl structure, 30 parts by weight of the rubber-modified epoxy resin (TSR-960), carboxylic acid-modified acrylonitrile butadiene rubber particles (XER-91SE-15) 2 parts by weight, carboxylic acid-modified polyvinyl acetal resin (KS-23Z) 5 parts by weight, triazine ring-containing cresol novolac type phenol resin (Phenolite LA-3018) The blending amount was 13 parts by weight. Others were performed in the same manner as in Example 1.

Example 4
In Example 1, instead of 5 parts by weight of carboxylic acid-modified acrylonitrile butadiene rubber particles, 5 parts by weight of core shell particles of butadiene rubber-acrylic resin, EXL-2655 (Kureha Chemical Industry Co., Ltd.) were used. Others were performed in the same manner as in Example 1.

(Example 5)
In Example 1, instead of 20 parts by weight of the triazine ring-containing cresol novolac type phenol resin, 15 parts by weight of phenol novolac resin, HP-850N (Hitachi Chemical Co., Ltd.) was used. Others were performed in the same manner as in Example 1.

(Comparative Example 1)
In Example 1, a substrate was prepared in the same manner as in Example 1 except that F0-WS12 foil was laminated instead of laminating metal foil A.

(Comparative Example 2)
A substrate was prepared in the same manner as in Example 1 except that EPICLON TSR-960 was not used and Resin composition A of Example 1 was changed to 65 parts by weight of NC-3000S-H.

(Measurement of conductor peeling strength)
The conductor peeling strength of the evaluation samples for Examples 1 to 5 and Comparative Examples 1 and 2 was measured. For peeling, the vertical peeling strength was measured. Measurements were always made at 20 ° C. The measuring method conformed to JIS-C-6482.

(Hygroscopic heat resistance test)
The moisture absorption heat test of Examples 1-5, the substrates for Comparative Examples 1-2, and the sample for evaluation was done. In the substrate test, each sample was treated for 2 hours under the conditions of 121 ° C, 100% humidity and 2 atmospheres, and then immersed in a solder bath at 260 ° C for 20 seconds to check whether the substrate was swollen. It was. A saturation type PCT apparatus PC-242 manufactured by Hirayama Seisakusho was used for the test.

(Test results)
The test results are shown in Table 1 below. The substrates and evaluation samples prepared in Examples 1 to 5 all had a high conductor peeling strength of 0.6 kN / m or higher. On the other hand, the substrates and evaluation samples obtained in Comparative Examples 1 and 2 had weak conductor peeling strength, and swelling occurred between the inner conductor and the insulating layer after the moisture absorption heat test. Also, good connection reliability was not obtained.

Claims (7)

Ten-point average roughness of the thickness 0.1~10μm layer surface of the adhesive aid has on following copper Rz = 2.0 .mu.m, and the adhesive auxiliaries surface chemically removing the copper foil A copper foil with an adhesion assistant that can be electrolessly plated by chemical roughening, wherein the copper foil is selected from nickel, tin, zinc, chromium, molybdenum, cobalt, and oxides thereof It is a copper foil that has been rust-proofed by one type, and the adhesion aid is (A) an epoxy resin, (B) a chemically roughening polymer component, (C) an epoxy resin curing agent, and (D) a curing accelerator. 10 to 80% by weight of the epoxy resin (A) is a rubber-modified epoxy resin, and the component (B) is acrylonitrile butadiene rubber, carboxylic acid modified acrylonitrile butadiene rubber, carboxylic acid modified acrylonitrile butane. Diene rubber particles, butadiene rubber - core-shell particles of the acrylic resin, polyvinyl acetal resin, and is at least one selected from carboxylic acid-modified polyvinyl acetal resin, copper foil adhesion assistant. (A) relative to 100 parts by weight of component, (B) a copper foil adhesive aid as claimed in claim 1, wherein component is 0.5 to 25 parts by weight. (C) Copper foil adhesive auxiliary agent according to claim 1 or 2 components, characterized in that a novolak type phenolic resin or a triazine ring-containing phenolic novolak resin. Copper foil adhesive auxiliary agent according to any one of claims 1 to 3, characterized in that the copper foil surface is not roughened for the purpose of promoting adhesion. The laminated board obtained by carrying out lamination | stacking integration of the copper foil with an adhesion adjuvant in any one of Claims 1-4, and a prepreg. A printed wiring board obtained by circuit-processing the laminated board according to claim 5. A method for producing a printed wiring board, comprising: a step of obtaining a laminated board by laminating and integrating the copper foil with an adhesion auxiliary agent according to claim 1 and a prepreg; and a step of performing circuit processing on the laminated board.