JP2008130592A - Manufacturing method of printed wiring board, and manufacturing method of multilayer printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a printed wiring board and a manufacturing method of a multilayer printed wiring board which are advantageous in the formation of fine wiring, the electrical characteristics and manufacturing cost, have high reliability and proper high-frequency characteristics. <P>SOLUTION: The manufacturing method of a printed wiring board has a step of coating/drying a thermosetting resin composition (A) on one surface of a mold release film; a step of pasting the mold-releasing film on both sides of an insulating base material so that the layer coated with the thermosetting resin composition can become the inside; a step of forming a through hole on a desired position of the insulating base material, having the mold release film pasted thereon; a step of filling the through hole with a conductive resin paste; a step of peeling only the mold-releasing films of both the surfaces, while leaving the thermosetting resin composition on the surface of the insulating base material; a step of heating and bonding a copper foil, on the surface of the insulating film with the thermosetting resin composition subjected to peeling of the mold-releasing film; and a step of patterning the copper foil on the surface of the insulating film. In the manufacturing method, the irregularities Rz of ten point heights of the copper foil is 2 μm or smaller. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a printed wiring board and a method for manufacturing a multilayer printed wiring board.

  As electronic devices have become smaller and higher in density in recent years, the adoption of double-sided and multi-layer boards for circuit-forming boards on which electronic components are mounted has increased from the conventional single-sided board, and more circuits can be integrated on the board. A density circuit forming substrate is being developed. For high-density circuit-formed substrates, the use of laser processing methods that enable finer processing at higher speeds instead of drilling holes that have been widely used in the past (through-hole) processing is being considered ( For example, Y. Yamanaka et al., ExcimerLaser Processing In The Microelectronics Fields, etc.). There has also been proposed a circuit-formed substrate that performs interlayer connection using fine hole processing by laser and connection means such as conductive paste (Japanese Patent Laid-Open No. Hei 6-268345).

  In the technique of forming fine holes and connecting the layers using a conductive paste, the base material and the copper foil are bonded simultaneously with the connection of the copper foil and the paste. For this reason, due to the problem of adhesion between the base material and the copper foil, it is common to use a copper foil having a surface ten-point average roughness exceeding Rz = 2.0 μm. However, in this case, since the roughness of the copper foil is large in the subtractive method, it is difficult to form fine wiring due to problems of side etching and copper residue.

JP-A-6-268345

  The present invention eliminates the disadvantages of known methods, is advantageous in terms of fine wiring formation, electrical characteristics, and manufacturing costs, and has high reliability and good high-frequency characteristics, and a printed wiring board manufacturing method and multilayer printing A method for manufacturing a wiring board is provided.

In order to solve the above problems, the present invention is characterized by the following.
1. A step of applying and drying the thermosetting resin composition (A) on one side of the release film, and a step of attaching the release film to both sides of the insulating base so that the thermosetting resin composition coating layer is on the inside. , A step of forming a through-hole at a desired position of the insulating base material bonded with the release film, a step of filling the through-hole with a conductive resin paste, and leaving the thermosetting resin composition on the surface of the insulating base material It has a step of peeling only the release film, a step of heat-bonding the copper foil to the surface of the insulating substrate with the thermosetting resin composition already peeled off, and a step of patterning the copper foil on the surface of the insulating substrate. It is a manufacturing method of a printed wiring board, Comprising: Ten-point average roughness of the surface of the said copper foil is Rz = 2micrometer or less.
2. The thermosetting resin composition (A) applied to the release film has a thickness of 0.1 to 10 μm, (a) a polyfunctional epoxy resin, (b) a polymer component capable of chemical roughening, (c The manufacturing method of the printed wiring board of claim | item 1 characterized by including polyfunctional phenol.
3. (A) The method for producing a printed wiring board according to Item 2, wherein the polyfunctional epoxy resin has a biphenyl structure.
4). (B) The method for producing a printed wiring board according to Item 2 or 3, wherein the polymer component capable of chemical roughening is crosslinked rubber particles.
5. (B) The chemically roughening polymer component is composed of at least one selected from acrylonitrile butadiene rubber, carboxylic acid-modified acrylonitrile butadiene rubber, carboxylic acid-modified acrylonitrile butadiene rubber particles, and core-shell particles of butadiene rubber-acrylic resin. Item 4. The method for producing a printed wiring board according to Item 2 or 3,
6). (B) The method for producing a printed wiring board according to Item 2 or 3, wherein the chemically roughening polymer component is a polyvinyl acetal resin or a carboxylic acid-modified polyvinyl acetal resin.
7). Item 7. The printed wiring board according to any one of Items 2 to 6, wherein (b) 0.5 to 25 parts by weight of a polymer component capable of chemical roughening is blended with 100 parts by weight of a polyfunctional epoxy resin. Production method.
8). (C) The method for producing a printed wiring board according to any one of Items 2 to 7, wherein the polyfunctional phenol is a triazine ring-containing novolac type phenol resin.
9. Item 9. The method for manufacturing a printed wiring board according to any one of Items 1 to 8, wherein the surface of the copper foil is not subjected to a roughening treatment for the purpose of promoting adhesion.
10. Item 10. The printed wiring board according to any one of Items 1 to 9, wherein the copper foil is a copper foil that has been rust-proofed by at least one selected from zinc, chromium, nickel, and oxides thereof. Manufacturing method.
11. Item 11. The method for producing a printed wiring board according to any one of Items 1 to 10, wherein the copper foil is a copper foil that has been surface-treated with a silane coupling agent.
12 Item 12. The method for producing a printed wiring board according to any one of Items 1 to 11, wherein the insulating base material is a prepreg obtained by impregnating a glass woven fabric or a nonwoven fabric with a thermosetting resin to form a B stage.
13. The base material which has a non-hardened resin layer is arranged on both surfaces of the printed wiring board produced from the manufacturing method of the printed wiring board in any one of claim | item 1 -12, Furthermore, copper foil (B) is arranged on the surface. Multilayer wiring by performing at least one or more steps of laminating and curing the printed wiring board and a base material having an uncured resin layer by heating and pressing and forming a circuit on the surface copper foil (B) by patterning. A method for producing a multilayer printed wiring board, wherein the ten-point average roughness of the surface of the copper foil (B) is Rz = 2 μm or less.

  According to the present invention, there are provided a method for manufacturing a printed wiring board and a method for manufacturing a multilayer printed wiring board, which are advantageous in terms of formation of fine wiring, electrical characteristics, and manufacturing cost, are highly reliable, and have high frequency characteristics. It becomes possible.

  As for the thickness of the said thermosetting resin composition (A) apply | coated to a release film, 0.1-10 micrometers is preferable. If it is less than 0.1 μm, the adhesiveness between the copper foil and the substrate is lowered, and if it exceeds 10 μm, the original properties of the substrate after pressing are lowered.

  The component (a) is preferably a novolac type epoxy resin having a biphenyl structure. The novolak-type epoxy resin having a biphenyl structure refers to a novolak-type epoxy resin containing an aromatic ring of a biphenyl derivative in the molecule, for example, the formula (1):

（式中、ｐは、１〜５を示す）で示されるエポキシ樹脂が挙げられる。これらは単独でも、２種以上を組み合せて用いてもよい。

(Wherein, p represents 1 to 5). These may be used alone or in combination of two or more.

  As a commercial item, NC-3000S (p is an epoxy resin of formula (1) with an average of 1.7) and NC-3000S-H (p is an average of formula 2.8 with an average of 2.8) manufactured by Nippon Kayaku Co., Ltd. Epoxy resin).

  The component (b) is preferably a crosslinked rubber particle, and specifically comprises 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. It is preferable.

  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 cited. An example is AC-3832 from Kogyo Corporation. The component (b) is preferably at least one selected from polyvinyl acetal resins and carboxylic acid-modified polyvinyl acetal resins.

  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 peel strength of the metal foil and the peel strength of the electroless plating after chemical roughening are further improved.

  The component (b) is preferably 0.5 to 25 parts by weight with respect to 100 parts by weight of the component (a). When the component (b) is less than 0.5 parts by weight, the peel strength and the peel strength of electroless plating after chemical roughening tend to be low. Moreover, when it exceeds 25 weight part, there exists a tendency for solder heat resistance etc. and insulation reliability to fall. In particular, when the amount of the crosslinked rubber particles and the polyvinyl acetal resin is 1 part by weight or more, the peel strength of the metal foil is improved, which is more preferable.

  The component (c) is preferably a triazine ring-containing novolac type phenol resin because the peel strength of the metal foil is improved.

  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 novolak 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 become too large, and when the thermosetting resin composition is used as a varnish, the solubility in the solvent is appropriate, and the residual amount of undissolved material Is 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. The amount of component (c) is preferably 5 to 19% by weight, more preferably 6 to 11% by weight, based on the total weight of components (a) to (c).

In addition to the components (a), (b) and (c), any reaction accelerator may be used, but various imidazoles and BF ₃ amine complexes which are latent thermosetting agents are used. It is preferable to mix. 2-Phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazolium from the viewpoints of storage stability of thermosetting resin composition, handleability at B-stage and solder heat resistance Trimellitate is preferred. The blending amount of the reaction accelerator is preferably in the range of 0.1 to 5 parts by weight, more preferably in the range of 0.3 to 1 part by weight with respect to 100 parts by weight of the (a) polyfunctional epoxy resin. Within these ranges, sufficient solder heat resistance, good storage stability of the thermosetting resin composition, and good handleability when the B stage is obtained can be obtained.

  Moreover, in order to improve a flame retardance, you may make the resin composition of this invention contain a phenolic hydroxyl group containing phosphorus compound. The phenolic hydroxyl group-containing phosphorus compound has the formula (2):

（式中、ｎが１の場合、Ｒ₄は、水素原子、直鎖状若しくは分枝状のアルキル基、シクロアルキル基、アリール基又はアラルキル基であり、ｎが２の場合、それぞれのＲ₄は独立して、水素原子、直鎖状若しくは分枝状のアルキル基、シクロアルキル基、アリール基又はアラルキル基であるか、２つのＲ₄は、それぞれが結合している炭素原子と一緒になって、非置換又はアルキル基若しくはシクロアルキル基で置換されているベンゼン環を形成し、ｘは、２以上の自然数である）で示されるような、フェノール性水酸基を含有するリン化合物が挙げられる。これらは、単独でも、２種以上を組み合せて用いてもよい。

(Wherein, 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, when n is 2, each R ₄ Is independently a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, or two R _{4 s} together with the carbon atom to which each is bonded. And a phosphorus compound containing a phenolic hydroxyl group as shown by the following formula: benzene ring which is unsubstituted or substituted with an alkyl group or a cycloalkyl group is formed, and x is a natural number of 2 or more. These may be used alone or in combination of two or more.

In the formula (2), when R ₄ is a linear or branched alkyl group, a C ₁ -C ₆ alkyl group is preferable, and when it is a cycloalkyl group, a C ₆ -C ₈ cycloalkyl group is preferable. In the case of an aryl group, a phenyl group is preferable, and in the case of an aralkyl, a C _{7 to} C ₁₀ 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. turned, to form a benzene ring which is unsubstituted or substituted alkyl or cycloalkyl group is unsubstituted or substituted by C ₁ -C ₄ alkyl or C ₆ -C ₈ cycloalkyl group A benzene ring is preferred.

  Specifically, formula (3) or formula (4):

（式中、Ｒ₅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）で示されるリン化合物が挙げられる。

(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.

  When imparting flame retardancy, the compounding amount of the phenolic hydroxyl group-containing phosphorus compound in the thermosetting resin composition of the present invention is preferably in terms of phosphorus atoms in the total weight of the components (a) to (c). Is in the range of 1.5 to 3.5% by weight, more preferably in the range of 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.

  The thermosetting resin composition in the present invention may contain (F) an inorganic filler in order to improve reliability. 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 amount of the inorganic filler as component (F) is preferably in the range of 5 to 35% by volume, more preferably 10 to 30 in the total volume of the components of the thermosetting resin composition (A). % By volume. 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 addition, in order to disperse | distribute an inorganic filler to the thermosetting resin composition (A) of this invention, known kneading | mixing methods, such as a kneader, a ball mill, bead mill, 3 rolls, can be used, for example.

  You may mix | blend additives, such as a pigment, a leveling agent, an antifoamer, and an ion trap agent, with the thermosetting resin composition (A) of this invention as needed.

  The thermosetting resin composition (A) produced as described above is, for example, diluted in a solvent to form a varnish and applied to a release film such as a PET film. 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 a thermosetting resin composition is not specifically limited, It can be set as the quantity conventionally used.

  In the process of applying and drying the thermosetting resin composition on one side of the release film, a comma coater or gravure coater is used, and the solvent is used so that the total solid content of the thermosetting resin composition is 10 to 30% by weight. It is preferable to adjust the amount used, but the amount can also be adjusted according to the equipment for film formation. This release film coated with a thermosetting resin composition on one side is semi-cured by treating for 3 to 30 minutes at a temperature of 80 to 180 ° C. to complete a release film with a thermosetting resin composition. To do.

As for the surface roughness of the metal foil used in the present invention, it is preferable in terms of electrical characteristics that the 10-point average roughness (Rz) shown in JIS-B-0601 is 2 μm or less on both sides. 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 treatment called a roughening treatment, but the present invention is characterized in that no substantial roughening treatment is performed and the copper foil has no legs. “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.

  The thickness of the metal foil is not particularly limited. Generally, a metal foil having a thickness of 105 μm or less used for a printed wiring board may be used, but a metal foil having a surface roughness Rz of 2 μm or less on both sides may be used.

In order to form fine wiring, it is preferable to use a metal foil of a peelable type having a thickness of 3 μm or less and a surface roughness Rz of 2 μm or less on both sides. Here, the peelable type metal foil is a metal foil having a carrier, which is a metal foil that can be peeled off by the carrier. For example, in the case of a peelable type ultra-thin copper foil, a metal oxide or organic layer to be a release layer is formed on a carrier foil having a thickness of 10 to 50 μm, and a sulfuric acid 50 to 100 g / h is used on the copper sulfate bath. L, copper 30-100 g / L, liquid temperature 20 ° C.-80 ° C., current density 0.5-100 A / dm ² condition, potassium pyrophosphate bath 100-700 g / L potassium pyrophosphate, copper 10-50 g / L, a liquid temperature of 30 ° C. to 60 ° C., a pH of 8 to 12, and a current density of 1 to 10 A / dm ² are produced by forming a metal foil having a thickness of 0.3 to 3 μm. When such a foil is used for the power feeding layer, the wiring formability is good as described later. Note that an etchable type copper foil having an aluminum carrier or a nickel carrier may be used instead of the peelable type.

The rust prevention treatment performed on the resin adhesive surface of the metal foil can be performed using nickel, tin, zinc, chromium, molybdenum, cobalt, or any of these oxides, or an alloy thereof. 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 necessary amount of a complexing agent such as citrate, tartrate or sulfamic acid can be added. The plating solution is usually used in an acidic region and is performed at a temperature of room temperature to 80 ° C. The 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 silane coupling agents 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, etc. And mercapto-functional silane is used. Considering compatibility with a thermosetting resin composition to be applied later, it is desirable to have an epoxy group or an amino group in the molecule.

These may 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 to 50 ° C. or electrodeposited to be adsorbed. 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 it is heating, it is dried at a temperature of 100 to 200 ° C. for 2 to 60 seconds. In the case of ultraviolet irradiation, it is performed in the range of 200 to 400 nm and 200 to 2500 mJ / cm ² .

  A thermosetting resin composition containing an epoxy resin as a component is applied on the copper foil on the copper foil subjected to the silane coupling agent treatment. The applied thickness is preferably 0.1 to 10 μm, and more preferably in the range of 0.1 to 5.0 μm. When the thickness is in the range of 0.1 to 5.0 μm, characteristics such as heat resistance and dielectric properties of the interlayer insulating material are hardly deteriorated.

  Hereinafter, examples of the present invention will be described. The present invention is not limited to these examples.

(Example 1)
A varnish having the following composition was prepared. This varnish was applied on a PET film of about 20 μm using a comma coater. This coated material was treated at a temperature of 160 ° C. for 10 minutes to obtain a release film with a thermosetting resin composition. The coating thickness of the thermosetting resin composition at this time was 2.0 μm.
・ Novolak type epoxy resin having biphenyl structure, NC3000S-H (manufactured by Nippon Kayaku Co., Ltd.) 65 parts by weight ・ Carboxylic acid modified acrylonitrile butadiene rubber particles, XER-91SE-15 (manufactured by JSR Corporation) 5 parts by weight carboxylic acid modified Polyvinyl acetal resin, KS-23Z (manufactured by Sekisui Chemical Co., Ltd.)
10 parts by weight-triazine ring-containing cresol novolac type phenol resin, phenolite EXB-9829 (nitrogen content 18%, hydroxyl group equivalent 151, manufactured by Dainippon Ink & Chemicals, Inc.)
20 parts by weight / imidazole derivative compound, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2PZ-CNS (manufactured by Shikoku Chemicals Co., Ltd.) 0.3 part by weight / solvent, methyl ethyl ketone

  Next, the release film is heated on both surfaces of a prepreg GEA-679F (t0.06) (manufactured by Hitachi Chemical Co., Ltd.) which is a B-stage by impregnating a glass woven fabric with a thermosetting resin as an insulating substrate. The curable resin composition coating layer was placed on the inner side, and lamination was performed with a 140 ° C. heating roll. A through hole having a diameter of 200 μm was formed at a predetermined position using a laser. Thereafter, the conductive paste is filled into the through-holes by using means such as printing, the upper and lower PET films are peeled off, the copper foil A shown below is arranged up and down, and heated and pressed by a hot press, A substrate material in which the copper foils A were electrically connected was obtained. Next, the double-sided circuit formation board which has a circuit pattern was obtained by patterning copper foil A to a desired shape.

(Metal foil A)
A chromium plating layer (peeling layer) having a thickness of 1.0 mg / dm ² is formed by continuously performing chromium plating on the light selective surface of an electrolytic copper foil (carrier copper foil) having a width of 510 mm and a thickness of 12 μm under the following conditions. did. The surface roughness after the chromium plating was Rz = 0.5 μm. The surface roughness was measured based on JIS-B-0601.
Chromium plating condition liquid composition: chromium trioxide 250 g / L, sulfuric acid 2.5 g / L
Bath temperature: 25 ° C
Anode: Lead current density 20 A / dm ²

Next, electrolytic copper plating with a thickness of 2.0 μm was performed under the photoselective plating conditions shown below. The surface roughness of the metal foil after completion of the electrolytic copper plating was Rz = 0.6 μm.
Copper sulfate plating condition solution composition: copper sulfate pentahydrate 100 g / L, sulfuric acid 150 g / L, chloride ion 30 ppm
Bath temperature: 25 ° C
Anode: Lead current density: 10 A / dm ²
Next, as shown below, zinc rust prevention treatment was performed by electroplating.
Liquid composition: Zinc 20 g / L, sulfuric acid 70 g / L
Bath temperature: 40 ° C
Anode: Lead current density: 15 A / dm ²
Electrolysis time: 10 seconds Next, the following chromate treatment was performed.
Liquid composition: chromic acid 5.0 g / L
pH 11.5
Bath temperature: 55 ° C
Anode: Lead immersion time: 5 seconds Next, the following silane coupling treatment was performed.
Liquid composition: 3-aminopropyltrimethoxysilane 5.0 g / L
Liquid temperature 25 ° C
Immersion time 10 seconds After the silane coupling treatment, the metal foil was dried at 120 ° C. to adsorb the coupling agent on the surface of the metal foil. The metal foil surface roughness at that time was Rz = 0.6 μm.

(Example 2)
In Example 1, a substrate was prepared in the same manner as in Example 1 except that the coating thickness of the thermosetting resin composition was 2.0 μm.

(Example 3)
In Example 1, 80 parts by weight of the novolac type epoxy resin having a biphenyl structure (NC3000S-H) in the resin composition A and 2 parts of the carboxylic acid-modified acrylonitrile butadiene rubber particles (XER-91SE-15) 5 parts by weight, 5 parts by weight of the carboxylic acid-modified polyvinyl acetal resin (KS-23Z), and 13 parts by weight of the triazine ring-containing cresol novolac type phenol resin (Phenolite EXB-9829). The same operation as in Example 1 was performed.

Example 4
In Example 1, in place of 5 parts by weight of the carboxylic acid-modified acrylonitrile butadiene rubber particles in the resin composition A, 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 in the resin composition A, 15 parts by weight of phenol novolac resin, HP-850N (Hitachi Chemical Industry Co., Ltd.) was used. Others were performed in the same manner as in Example 1.

(Example 6)
In Example 1, 55 parts by weight of the novolac type epoxy resin (NC3000S-H) having a biphenyl structure in the resin composition A and the amount of the triazine ring-containing cresol novolac type phenol resin (Phenolite EXB-9829) 15 parts by weight, and further 15 parts by weight of a phenolic hydroxyl group-containing phosphorus compound, HCA-HQ (manufactured by Sanko Co., Ltd.). Others were performed in the same manner as in Example 1.

(Example 7)
In Example 6, 20 parts by weight of an inorganic filler, spherical silica, and Admafine SC-2050 (manufactured by Admatechs Co., Ltd.) were further blended in the resin composition A. Others were performed in the same manner as in Example 1.

(Comparative Example 1)
In Example 1, a substrate was produced in the same manner as in Example 1 except that the thermosetting resin composition was not applied to the release film.

  The double-sided circuit-formed substrates obtained in Examples 1 to 7 and Comparative Example 1 were evaluated for copper foil peel strength (normal state, 150 ° C.) and solder heat resistance. The results were as shown in Table 1.

The test method was as follows.
Copper foil peeling strength: Measured according to JIS C 6481.
Solder heat resistance: Cut into 50 mm × 50 mm, floated on 288 ° C. solder, and time was measured until blistering occurred.

  As shown in Table 1, it can be seen that Examples 1 to 7 have better copper foil peel strength (normal state, 150 ° C.) and solder heat resistance than Comparative Example 1.

Claims (13)

  A step of applying and drying the thermosetting resin composition (A) on one side of the release film, and a step of attaching the release film to both sides of the insulating base so that the thermosetting resin composition coating layer is on the inside. , A step of forming a through-hole at a desired position of the insulating base material bonded with the release film, a step of filling the through-hole with a conductive resin paste, and leaving the thermosetting resin composition on the surface of the insulating base material It has a step of peeling only the release film, a step of heat-bonding the copper foil to the surface of the insulating substrate with the thermosetting resin composition already peeled off, and a step of patterning the copper foil on the surface of the insulating substrate. It is a manufacturing method of a printed wiring board, Comprising: Ten-point average roughness of the surface of the said copper foil is Rz = 2micrometer or less.   The thermosetting resin composition (A) applied to the release film has a thickness of 0.1 to 10 μm, (a) a polyfunctional epoxy resin, (b) a polymer component capable of chemical roughening, (c 2. The method for producing a printed wiring board according to claim 1, comprising polyfunctional phenol.   (A) A polyfunctional epoxy resin has a biphenyl structure, The manufacturing method of the printed wiring board of Claim 2 characterized by the above-mentioned.   The method for producing a printed wiring board according to claim 2 or 3, wherein the polymer component capable of chemical roughening is crosslinked rubber particles.   (B) The chemically roughening polymer component is composed of at least one selected from acrylonitrile butadiene rubber, carboxylic acid-modified acrylonitrile butadiene rubber, carboxylic acid-modified acrylonitrile butadiene rubber particles, and core-shell particles of butadiene rubber-acrylic resin. The method for manufacturing a printed wiring board according to claim 2, wherein the printed wiring board is a manufacturing method.   (B) The method for producing a printed wiring board according to claim 2, wherein the polymer component capable of chemical roughening is a polyvinyl acetal resin or a carboxylic acid-modified polyvinyl acetal resin.   The printed wiring board according to any one of claims 2 to 6, wherein (b) 0.5 to 25 parts by weight of a polymer component capable of chemical roughening is blended with 100 parts by weight of a polyfunctional epoxy resin. Manufacturing method.   (C) Polyfunctional phenol is a triazine ring containing novolak-type phenol resin, The manufacturing method of the printed wiring board of any one of Claims 2-7 characterized by the above-mentioned.   The method for producing a printed wiring board according to claim 1, wherein the surface of the copper foil is not subjected to a roughening treatment for the purpose of promoting adhesive force.   The printed wiring according to any one of claims 1 to 9, wherein the copper foil is a copper foil that has been rust-proofed by at least one selected from zinc, chromium, nickel, and oxides thereof. A method for manufacturing a substrate.   The method for manufacturing a printed wiring board according to claim 1, wherein the copper foil is a copper foil that has been surface-treated with a silane coupling agent.   The method for producing a printed wiring board according to claim 1, wherein the insulating base material is a prepreg obtained by impregnating a glass woven fabric or a nonwoven fabric with a thermosetting resin to form a B stage.   A base material having an uncured resin layer is disposed on both sides of a printed wiring board produced by the method for producing a printed wiring board according to any one of claims 1 to 12, and a copper foil (B) is further disposed on the surface thereof. Multilayered by performing at least one or more times the step of laminating and curing the substrate having the printed wiring board and the uncured resin layer and the step of forming a circuit by patterning the copper foil (B) on the surface. A method for producing a multilayer printed wiring board, wherein wiring is performed, wherein the ten-point average roughness of the surface of the copper foil (B) is Rz = 2 μm or less.