WO2004086833A1

WO2004086833A1 - Printed wiring board, its manufacturing method, and curing resin molded article with support

Info

Publication number: WO2004086833A1
Application number: PCT/JP2004/004298
Authority: WO
Inventors: Yasuhiro Wakisaka; Kazuyuki Onishi
Original assignee: Zeon Corporation
Priority date: 2003-03-27
Filing date: 2004-03-26
Publication date: 2004-10-07
Also published as: JPWO2004086833A1

Abstract

A printed wiring board in which at least a first conductive layer (2), an electrical insulating layer (3), and a second conductive layer (4) are laminated in order of mention on an inner layer sheet (1), and the electrical insulating layer satisfies the conditions (1) to (3) below. (1) The surface roughness Ra of the surface in contact with the second conductive layer is 300 nm or less. (2) The electrical insulating layer contains a filler. (3) Letting the thickness of the electrical insulating layer in the cross section drawn when the printed wiring board is cut vertically be h1, the distance between the conductive layers in the cross section be h2, the region from the surface of the inner layer sheet to 80% of h1 toward the second conductive layer be region A, the region from the surface of electrical insulating layer in contact with the second conductive layer to 5% of h2 toward the inner layer sheet be region B, and the region between region A and region B be region C, a≥c>b and 0.1>(b/a)≥0 where a, b, and c are the specific surfaces of the filler having diameters of 50 nm or more contained per unit area in regions A, B, C, repetitively. According to the invention, a printed wiring board having a high adhesion between an electrical insulating layer and a conductive layer is provided.

Description

Description Printed wiring board, method for manufacturing the same, and curable resin molded body with support

The present invention relates to a printed wiring board, a method for manufacturing the same, and a curable resin molded article with a support that can be used for the printed wiring board. Background technology

Current multilayer printed wiring boards have been densified by a so-called build-up method in which a conductor layer having a conductor pattern and an electric insulating layer made of an organic material such as an electric insulating polymer are alternately stacked.

Such printed wiring boards are required to have various improvements in characteristics such as low thermal expansion and halogen-free flame retardancy due to thinning and miniaturization of semiconductor devices, and high dielectric strength for having a capacitor function. For the purpose of improving these properties, (a) reducing the thermal expansion by adding an electrically insulating inorganic filler to the electric insulating layer (Japanese Patent Laid-Open No. 11-46067), (b) Incorporating a filler having a flame retarding function to exhibit flame retardancy (Japanese Patent Application Laid-Open No. 2002-2012), and (c) an electric insulating layer containing a high dielectric filler. (Japanese Patent Application Laid-Open No. 11-163819) has been proposed.

However, in the above (a) to (c), when a printed wiring board is manufactured using a copper foil having a resin layer containing a filler formed on the surface, plating is applied to a conductor gap or the like when a conductor pattern is formed by a plating method. In some cases, abnormal deposition occurred, which was a problem. In order to solve this problem, Japanese Patent Application Laid-Open Publication No. 2001-119150 discloses that a resin layer not containing an electrically insulating whisker, which is a kind of filler, is provided on a rough surface of a metal foil. Forming a resin layer containing an electrically insulating whisker, laminating a metal foil having the two resin layers on an inner layer substrate, and then removing the metal foil by etching to form an electric insulating layer; A technique for forming a conductive layer is disclosed. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic view of a printed wiring board according to the present invention. In the figure, 1 is the inner layer board, the 2 first conductor layer, 3 is an electrical insulating layer, the second conductive layer 4, 1 ^ the smallest electrically insulating layer up to the height, h ₂ is electrically insulating layer Height, A is the region from the inner substrate surface to the second conductor layer side up to 80% of hi (region A), B is the inner layer from the surface of the electrically insulating layer Region of up to 5% of h ₂ toward the substrate side (area B), C represents respectively region (region C) between the regions A and B. Disclosure of the invention

Under the conventional technology, the present inventors actually produced the metal foil described in the embodiment of Japanese Patent Application Laid-Open No. 2001-119501 and manufactured a printed wiring board. However, although abnormal deposition of adhesion did not occur, the adhesion between the electrical insulating layer and the second conductor layer formed thereon was partially insufficient, and the patterning of the fine pattern was also performed. It turned out to be inferior. Partial decrease in adhesion is a serious problem in high-density wiring boards that require formation of fine conductor patterns.

The present inventors scrutinized the obtained printed wiring board. As a result, it was found that the filler-free layer of the electrical insulating layer was partly extremely thin. It was presumed that one of the causes was to use a roughened metal foil, and another was to roughen an electrical insulating layer to form a conductive layer. That is, when producing a metal foil having two resin layers, the roughened metal foil surface convex portions enter the resin layer surface not including the filler, and the resin layer of the electrical insulating layer containing no filler. In addition to the fact that the layer is partially thinned and that when the electrical insulating layer is roughened, the resin-containing layer without filler is roughened to the thinned portion, so that the layer without filler is partially removed. It becomes extremely thin.

The present invention has been made based on these findings, and is applicable to a printed wiring board having high adhesion between an electric insulating layer and a conductive layer, a method for manufacturing the same, and the printed wiring board. Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have formed an electric insulating layer having a smooth surface, and have provided an electric insulating layer. By controlling the amount of filler near the surface to a certain level or less, high adhesion between the electrical insulating layer and the conductor layer is ensured, and the printed wiring board that can easily form fine patterns with low force The inventors have found that the present invention can be obtained, and have completed the present invention.

According to a first aspect of the present invention, there is provided a printed wiring board in which a first conductor layer, an electric insulation layer and a second conductor layer are laminated on the surface of an inner substrate around the first time, A printed wiring board is provided, wherein the electrical insulating layer satisfies the following requirements (1) to (3).

(1) The surface roughness Ra of the surface in contact with the second conductor layer is 300 nm or less.

(2) Contains a filler. (3) of the section cut the printed wiring board in a vertical, electrically insulating layer thickness of 1 ^, when the conductor interlayer distance was h _2, 8 of hi from the inner layer substrate surface toward the second conductor layer side 0 region an area a of up to%, the second area an area B from the surface in contact with the conductive layer up to 5% of h ₂ toward the inner layer base plate side of the electrically insulating layer surface, between及Pi region a and B The area is expressed as area C, and the area ratio of a boiler with a diameter of 50 nm or more contained in each unit area of areas A, B, and C is expressed as a, b, and c. c> b, and 0.1> (bZa) ≥0.

In the printed wiring board of the present invention, it is preferable that the electric insulating layer is composed of a filler and a component having a weight average molecular weight of 10,000 to 1,000,000.

In the printed wiring board according to the present invention, it is preferable that the electric insulating layer comprises an insulating resin layer (1) containing a filler and an insulating resin layer (2) not containing a filler.

According to the second aspect of the present invention, after forming the first conductor layer on the inner layer substrate, a filler-free curable resin layer (2) is formed on a support having a surface roughness Ra of 300 nm or less. A curable resin molded body with a support, in which a curable resin layer (1) containing a filler is laminated in this order, is laminated such that the curable resin layer (1) is in contact with the first conductor layer. After that, the support is removed, and then the curable resin layer (1) and the curable resin layer (2) are heated to form an electric insulating layer, and then a second conductor layer is formed. A method for manufacturing a printed wiring board according to the present invention is provided.

In the method for manufacturing a printed wiring board of the present invention, after forming a first conductive layer on an inner layer substrate, a curable resin layer (1) containing a filler is laminated, and then a curable resin layer containing no filler is formed. After laminating the resin layer (2), it is preferable to heat the curable resin layer (1) and the curable resin layer (2) to form an electric insulating layer, and then to form a second conductor layer.

According to the third aspect of the present invention, on a support having a surface roughness Ra of 300 nm or less, a curable resin layer containing no boiler (1) and a curable luster layer containing a boiler (2). ) And a curable resin molded article with a support in which are laminated in this order.

In the curable resin molded article with a support of the present invention, the curable resin layer (2) is preferably composed of a filler and a component having a weight average molecular weight of 10,000 to 1,000,000.

In the curable resin molded article with a support of the present invention, the same electrically insulating polymer may be contained as a component constituting the curable resin layer (1) and the curable resin layer (2). preferable. In the curable resin molded article with a support of the present invention, the support is preferably a resin film. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the printed wiring board of the present invention, a method for producing the same, and a curable resin molded article with a support that can be used for the printed wiring board will be described in detail.

The printed wiring board of the present invention is a printed wiring board in which a first conductor layer, an electric insulation layer, and a second conductor layer are laminated in this order on a surface of an inner layer substrate, wherein the electric insulation layer Satisfies the requirements (1) to (3). The inner layer substrate used in the present invention is made of an electric insulator, and may have one or more conductor layers therein. Further, the single-layer substrate may contain glass fiber, resin fiber, or the like for improving strength. Specific examples of such an inner layer substrate include a printed wiring board and an insulating substrate.

Examples of the electric insulator constituting the inner layer substrate include inorganic compounds such as acid hydride and alumina; alicyclic olefin polymer, epoxy resin, maleimide resin, (meth) acrylyl resin, and diaryl phthalate resin. Organic compounds such as triazine resin, aromatic polyether polymer, cyanate ester polymer, and insulating polymer such as polyimide.

The thickness of the inner layer substrate is usually 50 μm to 2 mm, preferably 60 μm to 1.6 mm, and more preferably 100 μm to 1 mm.

The first conductor layer (hereinafter referred to as “conductor layer 1”) is formed by laminating a conductor such as a conductive metal such as copper nickel on the inner layer substrate in a pattern. The method for forming the conductor layer 1 is not particularly limited, and a known method such as an electroless plating method, an electrolytic plating method, a sputtering method, or a vacuum deposition method can be employed. Also, the conductor layer 1 may be formed by combining two or more of these methods. For example, a metal thin film is formed on an inner substrate or an electrical insulating layer by electroless plating, a resist pattern for plating is formed on the metal thin film, and a conductive pattern is formed by electroplating using the metal thin film. After growing the resist, the resist is removed, and then the metal thin film is removed by etching the metal, whereby the conductor layer 1 can be formed. When the electric insulating layer is formed, the surface of the conductive layer 1 and, if necessary, the surface of the inner substrate are pre-treated so that the electric insulating layer and the conductive layer 1 formed on the inner substrate are formed. And the adhesiveness with the adhesive can be improved.

The method of pretreatment is not particularly limited, and may be performed by a conventional method. For example, if the conductor layer 1 is made of copper, a strong alkali salt of peracid such as sodium persulfate An aqueous solution of copper oxide on the surface of the inner layer substrate to form a tufted copper oxide layer on the surface of the conductor layer 1 and roughen it. Reduction method with sodium borohydride, formalin, etc .; method of depositing and roughening the conductive layer 1; and method of contacting with an organic acid to elute the copper grain boundaries of the conductive layer 1 and roughen it. And a method of forming a primer layer using a thiol compound / a silane compound or the like. Among these, from the viewpoint of easily obtaining a fine and good wiring pattern, a method of contacting with an organic acid to elute and roughen the copper grain boundaries of the conductor layer 1; a method of forming the primer layer with a thiol compound or a silane compound; The forming method is preferred.

The electrically insulating layer has a function of supporting the second conductor layer (hereinafter, referred to as “conductor layer 2”) and insulating between the conductor layers 1 and 2.

The electric insulating layer is composed of an insulating polymer and a filler.

As the insulating polymer, an insulating polymer generally used for forming an electric insulating layer of a printed wiring board can be used. For example, epoxy resin, maleimide resin, (meth) acrylic resin, diaryl phthalate resin, triazine resin, alicyclic olefin polymer, aromatic polyether polymer, benzocyclobutene polymer, cyanate ester polymer Coalescence, liquid crystal polymer, polyimide and the like. Among these, an alicyclic olefin polymer, an aromatic polyether polymer, a benzocyclobutene polymer, a cyanate ester polymer or a polyimide is preferable, and an alicyclic olefin polymer or an aromatic polyether polymer is more preferable. Preferred are alicyclic olefin polymers.

The alicyclic Orefuin polymer, 8 E Chiru tetracyclo [4. 4. 0. 1 2 '5. I 7' 1 0] Dodeka 3 E norbornene monomer ring-opening polymer of such emissions And hydrogenated products thereof, addition polymers of norbornene-based monomers, addition polymers of norbornene-based monomers and Bürich compounds, monocyclic cycloalkene polymers, alicyclic conjugated diene polymers, and bur-based fats Examples include cyclic hydrocarbon polymers and hydrogenated products thereof, aromatic hydrogenated aromatic aromatic polymers, and adducts thereof.

Among them, ring-opened polymers of norbornene-based monomers and hydrogenated products thereof, addition polymers of nonoleponolene-based monomers, addition polymers of norbornene-based monomers and bur compounds, and aromatic olefin polymers An aromatic ring hydrogenated product is preferred, and a hydrogenated product of a ring-opened polymer of a norportene-based monomer is particularly preferred.

The filler included in the electrical insulation layer must be unevenly distributed in the electrical insulation layer. Specifically, it is necessary that the number of the fillers is small near the conductor layer 2 and many around the conductor layer 1. If a large amount of filler is present near the conductor layer 2, the surface of the electrical insulation layer becomes rough, making it difficult to form a fine conductor pattern and causing electrical noise. And the adhesiveness between the conductor layer 2 and the electrical insulating layer is undesirably reduced. By unevenly distributing the filler, the surface roughness of the electric insulating layer can be reduced.

From these viewpoints, in the present invention, the degree of uneven distribution of the filler in the electric insulating layer is defined as follows.

The section cut the printed wiring board in the vertical, when h have the conductor layer distance electrically insulating layer thickness was h _2, region a region up to 80% of the 1 ^ towards the inner surface of the substrate on the conductor layer 2 side a, represents an electrically insulating layer surface region an area B up to 5% of h ₂ towards the inner substrate side, and the area between the regions a and B and region C, the region a, B,及Pi C Noso When the area ratio of a boiler with a diameter of 5 Onm or more included in each unit area is represented by a, b, and c, a≥c> b, and 0.1> (b / a) ≥0 (see Fig. 1). The preferred range of (b / a) is 0.01> (b / a) ≥0.

The filler is not particularly limited as long as it can be mixed with the insulating polymer and is a solid substance in the varnish (described later).

The fillers used are tanolek, calcined talc, clay, kaolin, titanium oxide, silica, silica balloon, calcium carbonate, bentonite, myriki, alumina, aluminum borate, magnesium borate, wollastonite, potassium titanate. Aluminum, basic magnesium sulfate, silicon nitride, α-alumina, aluminum hydroxide, magnesium hydroxide, zinc molybdate, calcium molybdate, calcium zinc molybdate, zinc titanate, calcium titanate, antimony pentoxide, trioxide Antimony, Zinc stannate, Zinc borate, Red phosphorus, Titanium dioxide-based ceramic, Strontium titanate-based ceramic, Calcium titanate-based ceramic, Μη-Ζη-type ferrite, Ni-Ζη-type ferrite, Ni-Cu- Ζ η blowjob Inorganic fillers such as it, iron, Fe—Ni alloy, Fe—Si alloy, etc .; ammonium polyphosphate, melamine polyphosphate, which is a (double) salt of a basic nitrogen compound and phosphoric acid; Organic fillers such as melem polyphosphate, melam polyphosphate, melam melamine polyphosphate double salt, and melam melam polyphosphate double salt; and the like.

Inorganic boilers usually have an electrical insulating layer on a printed wiring board with the purpose of lowering the linear expansion coefficient of the resin in order to prevent breakage of fine wiring due to thermal stress and damage to embedded passive components and thin semiconductors. It is added for the purpose of adding the function of a capacitor inductor to an electric insulation layer. Organic boilers are usually added as flame retardants to improve flame retardancy.

The particle size of the boiler used is usually 5 Onm or more, preferably 50 nm or more: L 0 μιη And more preferably 50 nm to l. Here, the particle diameter of the filler is the maximum length of each particle observed by an electric field emission scanning electron microscope.

The content of the boiler may be arbitrarily set according to the purpose of the filler. For example, when the filler is added as a flame retardant, the content of the filler is usually 0.1 to 100 parts by weight of the insulating polymer. 660 parts by weight, preferably 1 to 40 parts by weight.

In the present invention, the electric insulating layer can be formed by applying the following method while considering the concentration of the filler.

In general, as a method for forming an electric insulating layer on a printed wiring board, a curable resin molded body such as a dry film made of an insulating polymer is laminated on an inner substrate on which the conductor layer 1 is laminated, A method of curing as required (dry film lamination method) or a varnish in which an insulating polymer is dissolved in an arbitrary solvent is applied and dried on the inner layer substrate on which the conductor layer 1 is laminated, and if necessary, Curing method (varnish coating method) and the like.

Examples of the method for forming the electrical insulating layer using the dry film laminating method include the following methods (i) and (ii).

(i) Under the curable resin layer 1 having a filler and an insulating polymer as a curable resin molded body, a resin layer having a smaller amount of filler and an insulating polymer than the curable resin layer 1 However, a multi-layered curable resin molded article having at least one layer formed so that the filler content is sequentially reduced is laminated such that the curable resin layer 1 is in contact with the inner layer substrate on which the conductor layer 1 is laminated. Method of forming curable resin layer at one time (batch lamination method) (ii) Curable resin molded body 1 having a filler and an insulating polymer as curable resin molded body, and conductor layer 1 laminated After forming the curable resin layer 1 by laminating on the inner substrate, the curable resin molded body having a smaller amount of the filler and the insulating polymer than the curable resin molded body 1 is filled with the filler. Laminate one or more layers so that the curable resin layer decreases in order. How to formed (sequential lamination method)

As a method of forming the electrical insulating layer by applying the varnish coating method, for example, as a varnish, two or more kinds of base materials having different filler concentrations are prepared, and the varnish is applied in order from the one with the highest filler concentration, dried, and cured. A method of forming a conductive resin layer. Further, in the present invention, as a method of forming an electric insulating layer, a curable resin molded article including a filler is laminated on an inner layer substrate by a dry film laminating method, and then the content of the boiler is reduced by a varnish coating method (or (Not included) A method of forming a curable resin layer can also be employed.

Among these, the dry film laminating method is used because it is easy to control the uneven distribution of the filler in the electric insulating layer and to reduce the surface roughness of the electric insulating layer easily. The method of application is preferable, and from the viewpoint of excellent productivity, the batch lamination method (i) is particularly preferable.

In the case of employing a method applying the dry film laminating method, it is necessary to manufacture a curable resin molded body. The curable resin molded body is formed on the support by, for example, applying a varnish containing the above-described insulating polymer, the solvent, and, if necessary, the above-described filler to the support and drying the varnish. Can be.

The curable resin molded body used in the batch lamination method has two or more curable resin layers. For example, in order to obtain a curable resin molded body having two resin layers, a varnish (r 2) having a low filler content is applied to a support, dried if necessary, and then a resin having a low filler content is obtained. After forming the layer 2 and curing as required, a varnish (rl) having a filler content larger than that of the varnish (r 2) is applied on the resin layer 2 and dried to form a curable resin layer 1 You can.

Also, a varnish ( _r2 ) is applied on the support, and the varnish (r2) is dried if necessary. Then, a varnish (r1) is applied thereon, and the varnish is dried to form a resin layer. 1 may be formed. When the varnish (r1) is applied before the varnish (r2) is completely dried, the varnish (r2) may be dried at the same time as the varnish (r1) is dried. The method of simultaneously drying the varnishes (rl) and (r 2) is preferable because of excellent productivity.

In order to easily control the uneven distribution of the filler as defined above, the amount of the filler contained in the varnish (r 2) is usually 10% by weight or less based on the amount of the varnish (r 1) filler. Preferably, it is at most 5% by weight, more preferably at most 3% by weight, and particularly preferably, it is substantially free of filler (0% by weight). In the present invention, it is of course possible to further form a resin layer between the resin layer 1 and the resin layer 2 and obtain a curable resin molded body from three or more resin layers. From the viewpoint, it is preferable that the curable resin molded product has two to three resin layers. Further, it is preferable that the insulating polymers constituting the respective resin layers are the same polymer, because it is easy to secure good adhesion.

The curable resin molded body used in the sequential laminating method may have at least one curable resin layer, but like the varnish used for producing the curable resin molded body having a multilayer structure, the same as the varnish is used. It is better to use one manufactured using a varnish whose amount has been adjusted. It is preferable to use a curable resin molded article containing the same insulating polymer from the viewpoint of adhesion.

The thickness of the curable resin molded body may be arbitrarily designed according to the required electric insulating layer and the method of laminating the curable resin molded body, and is usually from 0.05 to 300 μπι, preferably from 0. 1 to 200 μπι, more preferably 1.0 to: 100 μπχ. Further, the thickness of the multilayered curable resin molded body used in the above-described bulk laminating method is usually 0.1 to 200.ηι, preferably :! ~ 150111, more preferably 10 ~: I0μπι. A solvent is used for the varnish used for forming the curable resin layer. Examples of the solvent used include aromatic hydrocarbon-based organic solvents such as toluene, xylene, ethylbenzene, and trimethylbenzene; aliphatic hydrocarbon-based organic solvents such as η-pentane, η-hexane, and η-heptane; cyclopentane Alicyclic hydrocarbon-based organic solvents such as cyclohexane and cyclohexane; halogenated hydrocarbon-based organic solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene; methylethylketone, methylisobutylketone, cyclopentanone, cyclohexane And ketone-based organic solvents such as hexanone. These organic solvents can be used alone or in combination of two or more.

A curing agent can be added to the varnish. As the curing agent, a general one such as an ionic curing agent, a radical curing agent, or a curing agent having both ionizing and radical properties can be used. Of these, polyhydric epoxy compounds such as glycidinoleatene epoxy compounds such as bisphenol-bis (propylene glycol glycidyl ether) ether, alicyclic epoxy compounds, and glycidyl ester type epoxy compounds are preferred.

For example, when a polyvalent epoxy compound is used as a curing agent, a curing accelerator or a curing aid such as a tertiary amine compound or a boron trifluoride complex compound is used in combination to accelerate the curing reaction. be able to.

The varnish may further contain a soft polymer, a heat stabilizer, a weather stabilizer, an anti-aging agent, a leveling agent, an antistatic agent, a slip agent, an anti-fogging agent, a lubricant, a dye, a pigment, a natural oil, if desired. Other components that dissolve in the varnish, such as synthetic oils, waxes, emulsions, and ultraviolet absorbers, can be added.

Among the components constituting the electrical insulating layer, the content of the component having a weight average molecular weight of 100,000 to 1,000,000 is 30% by weight to 1% of the total amount of the components excluding the filler. It is preferably from 0.0 to 100% by weight, more preferably from 45 to 100% by weight, more preferably from 45 to 100% by weight. When the content of the component having a weight-average molecular weight of 100,000 to 1,000,000 is within this range, excellent operability and anti-roughening property of the surface of the electrical insulating layer are obtained. Also, no migration occurs between wires even under high temperature and high humidity! /, A stable printed circuit board can be easily provided.

The varnish is agitated using a stirrer and a magnetic stirrer, a high-speed homogenizer, a displacer, a planetary stirrer, a twin-screw stirrer, a ball mill, three rolls, etc. The components can be prepared by mixing and stirring.

The solid content of the varnish can be arbitrarily designed according to the method of coating on the support and the required thickness of the curable resin layer, but the weight-average molecular weight is from 10,000 to 1,000,000. In order to obtain an electrical insulating layer having the above-mentioned ratio of the components, the solid content of the varnish should be in the range of 5% by weight to 50% by weight. It is preferable from the viewpoint of.

支持 Supports on which S is coated include metal foil ゃ resin films (carrier films).

Examples of the metal foil used include a copper foil and an aluminum foil.

As the resin film, a thermoplastic resin film is generally used, and specifically, polyethylene terephthalate phenol, polypropylene phenol, polyethylene phenol, polypropylene phenol, polyethylene naphthalate phenol, polyethylene phthalate, nylon Films and the like. Among these, resin films such as polyethylene terephthalate film and polyethylene naphthalate film are preferred from the viewpoints of heat resistance, chemical resistance, and peelability after lamination. The thickness of the support is not particularly limited, but is usually 1 μιη to 150 μm, preferably 2 μπ! ~ 100 μm, more preferably 3 μη! ~ 50 m.

The surface roughness Ra of the support is usually at most 300 nm, preferably at most 150 nm, more preferably at most 100 nm. If the surface roughness Ra of the support is too large, the surface roughness Ra of the electrical insulating layer becomes large, making it difficult to form a fine conductor pattern, and it is difficult to control uneven distribution of the filler in the electrical insulating layer. Could be. The method for applying the varnish to the support or one or more curable resin layers formed on the support is not particularly limited, and may be a dip coating method, a roll coating method, a curtain coating method, a die coating method, a slip coating method, or the like. Top coat method, gravure coat method, spin coat method

A known coating method such as a spray coating method can be employed.

The conditions for removing and drying the organic solvent are appropriately selected depending on the type of the organic solvent, and the drying temperature is usually 20 to 300 ° C, preferably 30 to 200 ° C. The drying time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.

Using the above-described curable resin molded body with a support, an electrical insulating layer is formed on the inner substrate having the conductor layer 1.

First, a curable resin molded body with a support is laminated on an inner substrate so that the molded body comes into contact with the conductor layer 1. There is no particular limitation on the method of laminating, and examples include pressurization and / or heating. The method of pressurization and / or heating is thermocompression bonding (lamination) Is common.

Heating and pressurizing are preferably performed in a reduced pressure environment, for example, when obtaining a multilayer printed wiring board, from the viewpoint of improving the wiring embedding property and suppressing the generation of bubbles and the like. Examples of the apparatus used for heating and pressurizing include pressurizing machines such as a pressurizing laminator, a vacuum laminator, a vacuum press, and a roll laminator. The press is usually provided with a press plate such as a heat-resistant rubber press plate or a metal press plate, and heats and presses the substrate and the molded product via the press plate. Depending on the properties of the compact, either a heat-resistant rubber press plate or a metal press plate may be used, or both may be used in combination.

The temperature of the press plate during heating and pressurization is usually 30 to 250 ° C, preferably 70 to 200. C, The crimping force is usually 10 kPa to 2 OMPa, preferably 10 kPa to 10 MPa, and the crimping time is usually 30 seconds to 5 hours, preferably 1 minute to 3 hours. When heating and pressurizing are performed in a reduced pressure environment, the pressure of the atmosphere is usually reduced to 100 kPa to 1 Pa, preferably 40 kPa to 10 Pa. '

The support may be peeled off from the curable resin molded body before or after the heating and pressurizing. However, from the viewpoint of easily obtaining a smooth electric insulating layer, the support is peeled off after the heating and pressurizing. Is good. When the support is peeled off before heating and pressing, it is preferable to use a heating plate or a pressing plate having a roughness Ra of 300 nm or less.

The electric insulating layer can be formed by laminating the curable resin molded bodies in this way, performing pretreatment as needed, and then curing.

The method of curing may be arbitrarily selected according to the curing agent, insulating polymer, and the like constituting the curable resin molded body, and includes, for example, heating and light irradiation. There is no particular limitation on the method of curing the curable resin molded article by heating, and it is sufficient to use, for example, an open method. The heating conditions can be arbitrarily set according to the heating method, but are usually 30 to 400 ° C, preferably 70 to 300 ° C, more preferably 100 to 200 ° C, and the curing time is usually 0.1 to 5 hours, preferably 0.5 to 3 hours.

The surface roughness Ra of the electric insulating layer formed as described above is 30 Onm or less, preferably 20 Onm or less, and more preferably 15 Onm or less. If the surface roughness Ra is too large, it is difficult to form a fine conductor pattern, and it tends to be susceptible to electric noise, which is not preferable.

In the present invention, for the purpose of ensuring the adhesion between the electric insulating layer and the conductor layer 2 described below, the surface of the electric insulating layer is subjected to a roughening treatment such as a sand mat treatment, a plasma treatment, and a primer layer. Pretreatments such as a formation treatment and an oxidation-reduction treatment can be performed. Above all, in order to maintain the range of the surface roughness Ra of the electrical insulating layer within the above range, The curable resin molded body before curing has metal coordination ability on the surface of the molded body, such as an imidazole compound such as 11- (2-aminoethyl) -12-methylimidazole, a pyrazole compound, and a triazonole compound. A method of forming a conductor layer 2 after curing after contacting the compound and then performing an oxidation treatment or a plasma treatment (Japanese Patent Application No. 2000-284 847) Wet the conductor layer 2 It is particularly suitable when formed by the attaching method.

The conductor layer 2 is formed by similarly laminating conductors in a pattern on an electric insulating layer laminated so as to cover the conductor layer 1. There is no particular limitation on the method of forming the conductor layer 2, and the conductor layer 2 can be formed by the same method as that of the conductor layer 1.

The printed wiring board of the present invention obtained as described above can be used as a printed wiring board for mounting semiconductor elements such as CPUs and memories, and other mounted components in electronic devices such as computers and mobile phones. In particular, those having fine wiring are suitable as high-density printed wiring boards, and as wiring boards for high-speed computers and mobile terminals used in high-frequency regions.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the examples, “parts” are based on mass unless otherwise specified.

The evaluation method performed in this example is as follows.

(1) Molecular weight

Unless otherwise specified, the measurement was made as a polystyrene equivalent value by gel permeation chromatography (GPC) using toluene as a solvent.

(2) Hydrogenation rate and maleic acid group content

Ratio of hydrogenation rate (hydrogenation rate) to mole number of unsaturated bond in polymer before hydrogenation and ratio of mole number of (anhydride) maleic acid residue to total number of monomer units in polymer (carboxyl group Content) was determined by —NMR spectrum.

(3) Glass transition temperature (T g)

It was measured by the differential scanning calorimetry (DSC method).

(4) Filler content of electrical insulation layer

The filler content of the electrical insulating layer was determined by cutting the printed wiring board to be evaluated vertically, observing the cross section of the electrical insulating layer with a field emission scanning electron microscope, and finding that the diameter of the evaluation area in each region was 50%. The area occupied by the particulate cross section of nm or more was measured, and the area ratio occupied by the filler was determined by the following equation.

Ratio of area occupied by boiler (%) = (Total area of cross-section of boiler with diameter of 50 nm or more / area of evaluation range) X 100 (5) Filler content of curable resin molding

The filler content of the curable resin molded product was determined by cutting the dry film to be evaluated vertically, observing the cross section of the electrical insulation layer with a field emission scanning electron microscope, and finding that the diameter was 50 nm or more. The area occupied by the particulate cross section was measured, and the area ratio occupied by the filler was determined by the following equation.

Filler area ratio (%) = (Area of evaluation area of total cross-sectional area of filler with diameter of 50 nm or more) 100

(6) Surface roughness of electrical insulation layer

The surface of the electrical insulating layer of the printed wiring board manufactured in the following Examples and Comparative Examples was analyzed using an atomic force microscope (manufactured by Digital Instrument, Na noscope 3a) with a Si single crystal strip cantilever (spring). Using the constant = 2 ON / m and a length of 125 μπι), it is the surface average roughness Ra measured in the atmospheric tapping mode.

However, in Comparative Example 2, the surface roughness was severe, and the surface roughness Ra could not be measured by the above method. For this reason, a non-contact optical surface shape measuring device (Keyence Corporation, color laser microscope VK-8500) was used to measure 5 points in a rectangular area of 20 im X 20 μπι, and the calculated average The value was defined as the surface roughness of the electrical insulation layer.

(7) Evaluation of putter Jung property

When 100 wiring patterns are formed with a wiring width of 20 μm, a wiring distance of 20 μm, and a wiring length of 5 cm, and no deformation is observed at all, the shape is distorted to 1 or more. Was evaluated as △ when there was a defect but no defect was observed, and as X when one or more defects were observed.

(8) Evaluation of adhesion of metal wiring layer

On the outermost layer of the 150 mm square multilayer substrate for evaluation, four evaluation patterns of conductor peeling strength with a length of 80 mm defined in JIS C 501 28.1. A total of 12 patterns were formed.

After leaving this multilayer board in an atmosphere of a temperature of 25 ° C and a relative humidity of 65% for 24 hours, a conductor peeling strength test was performed over a length of 50 mm per piece according to JISC 50128.1, and a total of 12 The peel strength of the book was measured. The evaluation criteria are as follows.

〇: For all 12 rods, no area of less than 0.4 k NZm was generated for 4 mm or more, and the average peel strength exceeded 0.6 kN / m.

△: 1 or more out of 12 lines with an area of less than 0.4 kNZm occurred 4 mm or more 3 Less than one but with an average peel strength of more than 0.6 kNZin X: One or more of less than 3 and less than 0.4 kNZni with 4 mm or more With an average of more than 0.4 kN / m and less than 0.6 kNZm

Poor: 3 or more out of 12 lines with an area of less than 0.4 kN / m 4 mm or more, or those with an average peel strength of 0.4 kNZm or less

(9) Evaluation of flame retardancy

A portion of the printed wiring board without conductors, in which one layer of electrical insulation was laminated on both sides of the core material, was cut into a strip having a width of 13 mm and a length of 100 mm to prepare a test piece. Methane gas was burned in a Bunsempana with a tube diameter of 9.5 mm and a tube length of 100 mm to adjust the flame to a height of 19 mm, and the flame was ignited until the obtained test piece ignited. Immediately after ignition, the flame was removed and the time during which the test specimen was burning was measured. Immediately after the test piece extinguished, the flame was touched until the test piece ignited again. The flame was removed immediately after the second ignition and the time during which the specimen was burning was measured. The sum of the burning time of the first test piece and the burning time of the second test piece is 5 seconds or less, を more than 5 seconds and 10 seconds or less, and X is 10 seconds or more. evaluated.

(Production of insulating polymer)

According to a known method, 8-ethyl-tetracyclo [4.4.0. I ² ' ^5. I ⁷ ' ¹ °] dodeca-3-ene is subjected to ring-opening polymerization, followed by a hydrogenation reaction to obtain a number average molecular weight.

A hydrogenated polymer having (Mn) = 31,200, weight average molecular weight (Mw) = 55,800, and Tg = about 140 ° C. was obtained. The hydrogenation rate of the obtained polymer was 99% or more.

100 parts of the obtained polymer, 40 parts of maleic anhydride and 5 parts of dicumyl peroxide were dissolved in 250 parts of t-butylbenzene and reacted at 140 ° C. for 6 hours. The obtained reaction product solution was poured into 1000 parts of isopropyl alcohol, and the reaction product was solidified to obtain a maleic acid-modified hydrogenated polymer. This modified hydrogenated polymer was vacuum dried at 100 ° C. for 20 hours. The resulting modified hydrogenated polymer had Mn = 33,200, Mw = 68,300, and Tg = 170 ° C. The maleic acid group content was 25 monole%.

(Flame retardant slurry production)

300 parts of melammelamine polyphosphate having a volume average particle size of 2.2 μπι were stirred with a mixed solvent of 1020 parts of xylene and 680 parts of cyclopentanone in a separable flask with a 3-blade stirring blade. A slurry (flame retardant slurry) of 15 wt% melam melamine polyphosphate double salt was obtained. To 200 parts of the obtained slurry, 6 parts of bis (dioctylpyrophosphate) oxyacetate titanate was added and stirred, and 200 parts by volume of a slurry liquid prepared was mixed with 0.4 mm zirconia beads. Using a horizontal wet disperser filled with 500 parts by volume, pulverization treatment was carried out for 120 minutes while circulating for a residence time of 18 minutes to obtain micronized melammelamine double phosphate polysulfate slurry A.

(Preparation of varnish A without filler)

100 parts of the modified hydrogenated polymer obtained above, bisphenol A bis (propylene glycol glycidyl ether) ether 40 parts, 2_ [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) Phenyl) benzotriazole (5 parts) and 1-benzylidene 2-phenylimidazole (0.1 part) were dissolved in a mixed solvent consisting of xylene (215 parts) and cyclopentene pentanone (54 parts), and the mixture was stirred. The mixture was filtered using an m filter to obtain a varnish A of a curable resin composition.

(Production of curable resin molding A)

The varnish A obtained above was applied to a polyethylene naphthalene film (support) having a thickness of 400 mm square and a surface roughness of Ra 80 nm using a die coater. Then, it was dried at 80 ° C. for 10 minutes in an oven purged with nitrogen to obtain a curable resin molded product A having a resin thickness of 5 μπι on the support. When the area ratio of the filler was evaluated, it was 0.01% or less. Note that the particle-shaped cross section observed under a microscope is foreign matter mixed in at the time of forming the resin layer.

(Preparation of Varnish B with High Filament Content)

100 parts of the modified hydrogenated polymer obtained above, bisphenol A bis (propylene glycol glycidyl ether) ether 40 parts, 2- [2-hydroxy-3,5-bis (α, -dimethylbenzyl) phenyl] 5 parts of benzotriazole and 0.1 part of 1-benzyl-2-imidazole, 200 parts of the finely divided melammelamine double salt slurry of polyphosphoric acid obtained above were mixed with 40 parts of xylene and 25 parts of cyclopentanone. Was dissolved in a mixed solvent consisting of Next, this was dispersed and mixed in a planetary stirring mill using zirconia beads having a diameter of 0.3 mm, the beads were removed, and the mixture was further filtered using a 5 μηι filter to obtain a curable resin composition. Obtained varnish B.

(Production of curable resin molded product C1 with resin support)

A varnish B is applied using a die coater on the curable resin molded product 形成 formed on the support described above, and then dried at 80 ° C. for 10 minutes in an oven purged with nitrogen. Thus, a curable resin molded article C1 with a support having a resin thickness of 50 μπι was obtained. The content of the filler (I) occupying a range of 80% in thickness from the outside of the curable resin molded body C1 formed on the support and the content of filler (II) occupying a range of 5% in thickness from the carrier side ) Ratio (II) / (I) was about 0.0005.

(Production of curable resin molded product C2 with resin support)

The varnish B was coated on a polyethylene naphthalate film (support) having a thickness of 30 Omm, a thickness of 40 μΐη, and a surface roughness Ra of 8 nm using a die coater, and then placed in a nitrogen-purged oven. It was dried at ° C for 10 minutes to obtain a curable resin molded product C2 with a support having a resin thickness of 50 µπι. The ratio of the filler content (I) occupying 80% of the thickness from the outside of the curable resin molded body C2 formed on the support to the filler content (II) occupying 5% of the thickness from the carrier side ( II) / (I) is about 1 and 7 pieces.

(Production of curable resin molded body C3 with copper foil support)

Curable resin molding with resin support, except that rough support copper foil GTS-1MP (Furukawa Circuit Oil Co., Ltd.) with a surface roughness Ra of 1.05μιη and a thickness of 18m was used as the support. A curable resin molded product C3 with a support made of copper foil was obtained in the same manner as in Product C1.

Example 1

A 0.8 mm thick inner layer substrate (glass filler and Haguchigen) with a conductor width of 50 μm, a conductor thickness of 18 μm, and a surface micro-etched with an organic acid on the surface. A core material obtained by impregnating a glass cloth with a varnish containing an epoxy resin containing no resin), the above-described curable resin molded product C1 with a support is placed on the surface of the first conductive material. It was superposed on both sides of the inner layer substrate so as to be in contact with the layer. This was pressure-compressed to 200 Pa using a vacuum laminating apparatus equipped with heat-resistant rubber press plates on the upper and lower sides as a primary press, and heated and pressed at a temperature of 120 ° C and a pressure of IMPa for 60 seconds. Then, using a vacuum laminator equipped with a heat-resistant rubber press plate covered with a metal press plate on the top and bottom, the pressure was reduced to 2 O OP a at a temperature of 140 ° C and a pressure of 1.0 MPa for 60 seconds. It was heated and pressed. Then, only the polyethylene naphthalate film was peeled off and left in a nitrogen oven at 170 ° C. for 120 minutes to form electric insulating layers on both surfaces of the inner substrate.

Via holes of 30 πι in diameter were formed in each of the obtained electric insulating layers using a UV-YAG laser. Next, on the surface of the substrate on which the via hole was formed, a plasma gas was used under a processing condition of a frequency of 13.56 MHz, an output of 100 W, and a gas pressure of 0.8 Pa using a mixed gas having a volume ratio of argon gas to nitrogen gas of 50:50. Processing was performed. The processing temperature was 25 ° C and the processing time was 5 minutes.

The plasma-treated electrical insulating layer was subjected to RF sputtering under a 13.56 MHz _N output, 400 W gas pressure, 0.8 Pa gas atmosphere in an argon atmosphere. As a result, a 30-nm-thick chromium film was formed at a rate of 0.46 nm / sec, and then a 300-nm-thick copper thin film was formed at a rate of 0.91 nm_sec.

A commercially available photosensitive dry film was bonded to the surface of the copper thin film by thermocompression bonding, and a mask having a predetermined pattern was brought into close contact with the dry film, exposed, and then developed to obtain a resist pattern. Next, electroless copper plating was applied to the non-resist-forming portions to form an electrolytic copper plating film having a thickness of 12 μππι. Next, the resist pattern was stripped and removed with a stripper, and the sputtered copper thin film hidden under the resist-formed portion was removed with a mixed solution of cupric chloride and hydrochloric acid to form a wiring pattern. Finally, annealing was performed at 170 for 30 minutes to obtain a printed wiring board.

The obtained printed wiring board was evaluated for the filler content, surface roughness, patterning property of the conductive pattern, adhesion of the metal wiring layer, and flame retardancy of the electrical insulating layer. Table 1 shows the evaluation results.

Example 2

In the formation of the electrical insulating layer, the curable resin molded body C2 with a resin support is laminated on the inner layer substrate, and after the support is peeled off, the curable resin molded body と共に is laminated with the support, and the support is formed. A printed wiring board was obtained in the same manner as in Example 1 except that the body was peeled off.

The obtained printed wiring board was evaluated for the filler content, surface roughness, patterning property of the conductor pattern, and adhesion and flame retardancy of the metal wiring layer of the electric insulating layer. Table 1 shows the evaluation results.

Example 3

In Example 1, the curable resin molded product C1 with a support was laminated and the support was peeled off. Then, the substrate was immersed in an aqueous solution adjusted so that 1- (2-aminoethyl) _2-methylimidazole was adjusted to 0.3% at 30 ° C. for 10 minutes. Then, after immersing in water at 25 ° C. for 1 minute, an excess solution was removed with an air knife, and then left in a nitrogen oven at 170 ° C. for 60 minutes.

Via holes of 30 m in diameter were formed in the insulating layer portion of the obtained laminate using the U-V-YAG laser third harmonic to obtain a multilayer substrate with via holes.

The above-described multilayer substrate with via holes was rock-immersed in an aqueous solution at 70 ° C. adjusted to a permanganic acid concentration of 60 g / liter and a sodium hydroxide concentration of 28 g / liter for 10 minutes. Next, the substrate was immersed in a water bath for 1 minute while rocking, and further immersed in another water bath for 1 minute to wash the substrate. Subsequently, the substrate was immersed in a 25 ° C aqueous solution adjusted to a hydroxylamine concentration of 170 g liter and sulfuric acid at 80 g / liter for 5 minutes to perform a neutralization reduction treatment. Rinse and spray with nitrogen Water was removed.

As a pre-plating treatment, activator MAT-11A (manufactured by Uemura Kogyo Co., Ltd.) has a multilayer substrate of 20 基板 πι 1 liter, and activator MAT-1B (manufactured by Uemura Egyo Co., Ltd.) has a capacity of 30 m 1. Immersion for 5 minutes in a plating solution containing Pd salt at 60 ° C adjusted to 1 g / liter sodium hydroxide. Then, after washing the substrate in the same manner as described above, reducer MRD-2-A (Uemura Kogyo Co., Ltd.) was 18 m 1 liter and reducer MR D-2-C (Uemura Kogyo Co., Ltd.). It was immersed in a solution adjusted to 6 Oml / liter at 35 ° C for 5 minutes to reduce the plating catalyst.

The multi-layer substrate obtained in this way was prepared using Sulcup PRX-1-A (manufactured by Uemura Kogyo Co., Ltd.) at 15 Oml / liter and Sulcup PRX-11B (Kamineo Kogyo Co., Ltd.) at 10 Oml / liter. Sulcup PRX—I—C (manufactured by Uemura Kogyo Co., Ltd.) is immersed in an electroless plating solution at 25 ° C adjusted to 20 mlZ liter for 15 minutes while blowing air to perform electroless plating. went. The multilayer substrate on which the metal thin film layer was formed by the electroless plating treatment was further washed with water in the same manner as described above, dried, and subjected to a heat-proof treatment to obtain a multilayer substrate having an electroless plating film formed thereon.

A dry film of a commercially available photosensitive resist is bonded by thermocompression bonding to the surface of the multilayer substrate that has been subjected to the heat-proofing treatment, and a mask having a pattern corresponding to an adhesion evaluation pattern is adhered onto the dry film. After exposure, development was performed to obtain a resist pattern. Next, immersion in a solution of 100 g / liter of sulfuric acid at 25 ° C for 1 minute to remove the protective agent, electrolytic copper plating on the non-resist-forming part, forming an electrolytic copper plating film with a thickness of 18 μπι I let it. Next, the resist pattern was stripped and removed with a stripping solution, and an etching treatment was performed with a mixed solution of copper chloride and hydrochloric acid, thereby forming a conductor pattern composed of the metal thin film and the electrolytic copper plating film. A multilayer substrate was obtained. Finally, annealing treatment was performed at 170 ° C. for 30 minutes to obtain a printed wiring board. The obtained printed wiring board was evaluated for the filler content, the surface roughness, the patterning property of the conductor pattern, and the plating adhesion of the electric insulating layer. Table 1 shows the evaluation results.

Comparative Example 1

A printed wiring board was obtained in the same manner as in Example 1, except that the curable resin molded product C1 with a resin support was changed to the curable resin molded product C2 with a resin support.

The obtained printed wiring board was evaluated for the filler content, surface roughness, patterning property of the conductor pattern, and adhesion and flame retardancy of the metal wiring layer of the electric insulating layer. Table 1 shows the evaluation results. Comparative Example 2

The curable resin molded product with a support was changed to a curable resin molded product C3 with a resin support, and the method of peeling the support was changed to a sodium persulfate aqueous solution at 60 ° C (concentration: 1 mol Z liter). ) For 30 minutes, followed by washing with water, and do not contact the substrate surface after peeling the support with 1- (2-aminoethyl) 1-2-methylimidazole. Except for the above, a printed wiring board was obtained in the same manner as in Example 3. The printed wiring board obtained was evaluated for the content of the electrical insulation layer, the surface roughness, the patterning property of the conductor pattern, and the adhesion and flame retardancy of the metal wiring layer. Table 1 shows the evaluation results.

Table 1

From Table 1, it can be seen that when an electric insulating layer with a smooth surface is formed, the amount of filler near the surface of the electric insulating layer is controlled to a certain amount or less, and the surface roughness is reduced (Examples 1-3), It can be seen that a printed wiring board having excellent abrasion resistance and adhesion can be obtained. On the other hand, the ratio of the filler content (I) in the range of 80% in thickness from the outside to the filler content (II) in the range of 5% in thickness from the carrier side (II) and (I) is about 1. When the curable resin molded product C2 with a resin support was used (Comparative Example 1), the resulting printed wiring board was slightly inferior in pattern jungling property and poor in adhesion to the metal wiring layer. In addition, when the curable resin molded product C3 with a support made of copper foil having a surface roughness of 110 nm was used (Comparative Example 2), the obtained printed wiring board was inferior to Putterjung'I raw However, the adhesion of the metal wiring layer was slightly inferior.

Claims

The scope of the claims

1. A printed wiring board in which a first conductor layer, an electric insulation layer, and a second conductor layer are laminated in this order on the surface of an inner substrate, wherein the electric insulation layer has the following (1) ~

A printed wiring board which satisfies the requirement of (3).

(2) Contains a filler.

(3) of the section cut the printed wiring board in the vertical, when the h have conductor layer distance electrically insulating layer thickness was h _2, from the inner layer substrate surface toward the second conductor layer side 1 ^ 80% region an area a to an area of the region from the second surface in contact with the conductive layer of the electrically insulating layer surface up to 5% of h ₂ towards the inner substrate side B, and a region a region between the regions a and B C, and when the area ratio of the filler having a diameter of 50 nm or more included in each unit area of the regions A, B, and C is represented by a, b, and c, ac> b, and , 0.1> (bZa) ≥0.

2. The printed wiring board according to claim 1, wherein the electric insulating layer comprises a filler and a component having a weight average molecular weight of 10,000 to 1,000,000.

3. The printed wiring board according to claim 1, wherein the electric insulating layer comprises an insulating resin layer containing a filler and an insulating resin layer containing no filler.

4. After forming the first conductor layer on the inner substrate, on a support with a surface roughness Ra of 30 Onm or less, a curable resin layer without filler (2) and a hardener containing filler After a curable resin molded body with a support, in which the curable resin layer (1) and the curable resin layer (1) are laminated in this order, is laminated on the first conductor layer so that the curable resin layer (1) is in contact with the first conductive layer, Removing the body, and then heating the curable resin layer (1) and the curable resin layer (2) to form an electrical insulating layer, and then forming a second conductor layer. Item 1. The method for producing a printed wiring board according to Item 1.

5. After forming the first conductor layer on the inner substrate, laminating the curable resin layer (1) containing the filler, and then laminating the curable resin layer (2) containing no boiler, The printed wiring board according to claim 1, wherein the curable resin layer (1) and the curable resin layer (2) are heated to form an electrical insulating layer, and then a second conductor layer is formed. Manufacturing method.

6. On a support having a surface roughness Ra of 300 nm or less, a curable resin layer containing no filler (1) and a curable resin layer containing filler (2) are laminated in this order. Curable resin molded article with a support.

7. The curable resin molded article with a support according to claim 6, wherein the cured resin layer (2) comprises a filler and a component having a weight average molecular weight of 10,000 to 1,000,000.

S. Curing with a support according to claim 6, wherein the same electrically insulating polymer is contained as a component constituting the curable resin layer (1) and the curable resin layer (2). Resin moldings.

9. The curable resin molded article with a support according to claim 6 wherein the support is a resin film.