JP2001291961A - Multilayered printed wiring board and producing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multilayered printed wiring board, which has an opening in a desired form, improved in flame resistance, improved in reliability in connection by hardly peeling off between a conductor circuit and a resin insulating layer or hardly cracking the resin-insulating layer, and improved in opening property, when forming an opening for via hole at the time of producing the multilayered printed wiring board. SOLUTION: In the multilayered printed wiring board with which conductor circuits and resin insulating layers are successively formed on a substrate, and these conductor circuits are connected via the via hole, each of the resin insulating layers contains phosphorus and/or phosphide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer printed wiring board having excellent flame retardancy and the like and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, build-up multilayer printed wiring boards have been manufactured by a method disclosed in, for example, Japanese Patent Application Laid-Open No. 4-55555. That is, first, a through hole is formed in the copper-clad laminate to which the copper foil is attached, and then a through hole is formed by performing an electroless copper plating process. Subsequently, the surface of the substrate is etched into a conductor pattern to form a conductor circuit, and a roughened surface is formed on the surface of the conductor circuit. Then, after forming a layer made of a mixture of an epoxy resin and an acrylic resin on the conductor circuit having the roughened surface, an opening for a via hole is formed.
An interlayer resin insulation layer is formed through UV curing and main curing.

Further, after performing a roughening treatment on the interlayer resin insulating layer, a thin film conductor layer is formed, a plating resist is formed on the thin film conductor layer, and a thickening is performed by electroplating. The thin film conductor layer existing under the plating resist is removed by an etchant to form an independent conductor circuit. After repeating this process, the conductor circuit and the interlayer resin insulating layer are sequentially laminated, and then a solder resist composition is applied to form a solder resist layer for protecting the conductor circuit on the outermost layer, and the IC chip and the like are formed. An opening is formed for the connection, the exposed conductor circuit is plated, and a solder paste is printed to form a solder bump, thereby completing the manufacture of the build-up multilayer printed wiring board.

[0004]

Such multilayer printed wiring boards are used by mounting electronic components such as IC chips. Therefore, when an IC chip or the like is ignited for various reasons, it is desired to be able to withstand it. Specifically, those that pass the UL94 criterion in the UL test standard are desired, and in particular, those that pass the combustion time criterion of 94V-0 are desired.

[0005] Further, it is desired that the multilayer printed wiring board satisfies the above-described flammability criterion and is excellent in the opening property (shape retention at the time of opening) when forming an opening for a via hole or the like. It is rare. However, the conventional multilayer printed wiring board does not satisfy the flame retardancy and the opening property, and in particular, does not satisfy both at the same time.

Further, in the multilayer printed wiring board, in order to ensure the connection reliability, no peeling occurs between the conductor circuit and the resin insulating layer, and no crack occurs in the resin insulating layer. Things are desired. One cause of such peeling or cracking is considered to be a large difference in the coefficient of thermal expansion between the substrate or the solder resist layer and the interlayer resin insulating layer. Therefore, there is a demand for a multilayer printed wiring board in which the coefficient of thermal expansion of the substrate or the solder resist layer and the coefficient of thermal expansion of the interlayer resin insulating layer do not greatly differ.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide excellent flame retardancy, peeling between a conductor circuit and a resin insulating layer, and a resin insulating layer. Another object of the present invention is to provide a multilayer printed wiring board which is excellent in connection reliability because cracks are not easily generated and which is excellent in opening property when forming a via hole opening or the like in manufacturing a multilayer printed wiring board.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, a multilayer printed wiring board having a resin insulating layer containing phosphorus and / or a phosphorus compound formed thereon has a flame retardant property. It is a multilayer printed wiring board that is excellent in shape, and has excellent shape retention of openings when forming openings for via holes and the like.Moreover, in the multilayer printed wiring board, a resin insulating layer and a substrate or a solder resist layer Since there is no large difference in the coefficient of thermal expansion, it is found that cracks are not generated in the resin insulating layer and peeling between the resin insulating layer and the conductor circuit is hard to occur, and the contents described below are summarized as Reached the invention.

That is, the multilayer printed wiring board of the present invention is a multilayer printed wiring board in which a conductive circuit and a resin insulating layer are sequentially formed on a substrate, and the conductive circuits are connected via via holes. The resin insulating layer contains phosphorus and / or a phosphorus compound.

In the multilayer printed wiring board, the phosphorus is preferably red phosphorus. The phosphorus and the phosphorus compound preferably have a particle size of 0.1 to 15 μm. It is preferable that the phosphorus and / or the phosphorus compound be present in the resin insulating layer in an amount of 0.5 to 10% by weight.

[0011] The resin insulating layer may include a silicon compound,
It is desirable to include at least one selected from the group consisting of aluminum compounds and magnesium compounds.

Further, the resin insulating layer is made of epoxy resin,
Phenol resin, polyolefin resin, polyphenylene ether (PPE), polyphenylene oxide (P
PO), a fluororesin and a polyimide resin.

The resin insulating layer desirably includes a resin composite made of a thermosetting resin and a thermoplastic resin.

A first method of manufacturing a multilayer printed wiring board according to the present invention is a method of manufacturing a multilayer printed wiring board according to the present invention, and includes at least the following steps (1) and (2). Features. (1) a step of preparing an uncured resin composition containing phosphorus and / or a phosphorus compound; and (2) a step of forming the uncured resin composition on a substrate on which a conductor circuit is formed or a resin insulating layer on which a conductor circuit is formed. A step of forming a layer of the resin composition by applying the resin composition;

A second method of manufacturing a multilayer printed wiring board according to the present invention is a method of manufacturing a multilayer printed wiring board according to the present invention, which includes at least the following steps (1) and (2). Features. (1) a step of preparing a resin film containing phosphorus and / or a phosphorus compound; and (2) crimping the resin film on a substrate on which a conductor circuit is formed or a resin insulating layer on which a conductor circuit is formed. A step of forming a resin film layer;

According to a third method of manufacturing a multilayer printed wiring board of the present invention, the multilayer printed wiring board of the present invention is manufactured, wherein the resin insulating layer includes a resin composite comprising a thermosetting resin and a thermoplastic resin. A method comprising at least the following (1) to
It is characterized by including the step (5). (1) a step of preparing a resin composition A containing phosphorus and / or a phosphorus compound and a thermosetting resin; and (2) a step of preparing a resin composition B containing a thermoplastic resin.
(3) a step of preparing a curing agent component C containing a curing agent;
(4) a step of kneading the resin composition A, the resin composition B, and the curing agent component C to prepare a mixed composition D, and then preparing a resin film E including the mixed composition D; 5) a step of forming a layer of the resin film E by pressing the resin film E on a substrate on which the conductor circuit is formed or on a resin insulating layer on which the conductor circuit is formed.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The multilayer printed wiring board of the present invention
A multilayer printed wiring board in which a conductive circuit and a resin insulating layer are sequentially formed on a substrate, and these conductive circuits are connected via via holes, wherein the resin insulating layer includes phosphorus and / or
Alternatively, a phosphorus compound is included.

According to the multilayer printed wiring board of the present invention, since the resin insulating layer contains phosphorus and / or a phosphorus compound, it has excellent flame retardancy due to its presence. Also,
Since the resin insulating layer formed on the multilayer printed wiring board of the present invention contains phosphorus or a phosphorus compound, the opening property when forming an opening for a via hole or the like, particularly, the opening by irradiating a laser beam is reduced. It is excellent in opening property at the time of formation and has an opening of a desired shape.

Normally, when an opening is formed by laser irradiation, the resin around the laser irradiation site is burned by the heat of the laser irradiation, so that the inner wall of the opening does not have a smooth shape and unevenness is formed. It becomes what has.
However, the resin insulating layer of the multilayer printed wiring board of the present invention has flame retardancy due to the inclusion of phosphorus or a phosphorus compound, so that the resin around the laser irradiation site does not burn due to laser irradiation heat. The shape of the inner wall of the formed opening is smooth, and the desired shape is obtained.

Since the resin around the laser irradiation site is not burned by laser irradiation heat during laser irradiation, an opening having a desired shape can be formed even when high-energy laser light is irradiated. it can. Therefore, by irradiating high-energy laser light, an opening can be formed in a short time. In particular, when a pulsed laser is used, an opening can be formed in a single shot. Thus, since the multilayer printed wiring board of the present invention has a resin insulating layer in which an opening of a desired shape is formed and there is no resin residue or the like in the opening, the via hole formed in the opening is formed. It has excellent connection reliability between the upper and lower conductor circuits. Further, the multilayer printed wiring board has openings formed in a short time, and is excellent in productivity.

Further, the multilayer printed wiring board of the present invention has a thermal expansion coefficient of the substrate or the solder resist layer and a thermal expansion coefficient of the resin insulation layer which are adjusted by adjusting the amount of phosphorus or the phosphorus compound contained in the resin insulation layer. Can be easily adjusted to almost the same level.In this way, in a multilayer printed wiring board in which the coefficient of thermal expansion is adjusted, peeling occurs between the conductor circuit and the resin insulating layer, or the resin insulating layer Cracks are less likely to occur.

In the multilayer printed wiring board of the present invention, the resin insulating layer contains phosphorus and / or a phosphorus compound. The phosphorus is not particularly limited, and examples thereof include red phosphorus, yellow phosphorus, purple phosphorus, and red phosphorus. Among them, red phosphorus is desirable because it can impart sufficient flame retardancy to the multilayer printed wiring board with a small amount of compounding, and has high stability and excellent safety during work.

The phosphorus compound is not particularly limited.
Examples include phosphorus oxides such as diphosphorus trioxide and diphosphorus pentoxide, and metal phosphides such as iron phosphide, copper phosphide, titanium phosphide, nickel phosphide, and manganese phosphide. These phosphorus and phosphorus compounds may be used alone or in combination of two or more. Further, these phosphorus or phosphorus compounds may be coated with a resin such as a phenol resin or an inorganic compound such as aluminum hydroxide in order to enhance stability.

Commercial products of such phosphorus and phosphorus compounds include, for example, Nova Excel F manufactured by Rin Kagaku Kogyo KK
5. Hishigard CP and Hishigard T manufactured by Nippon Chemical Industry Co., Ltd.
P, Hishigarto EP-15, Hishigard master and the like.

The above phosphorus and the phosphorus compound preferably have a particle size of 0.1 to 15 μm. Phosphorus compounds having a particle size of less than 0.1 μm are not practical because they are difficult to form. On the other hand, if the particle size is greater than 15 μm, the opening property when forming openings for via holes and the like, In some cases, and it is difficult to uniformly disperse the resin in the resin insulating layer. More preferably, it is 1 to 3 μm.

The shape of the phosphorus and the phosphorus compound is not particularly limited, and examples thereof include a spherical shape, an elliptical spherical shape, a crushed shape, and a polyhedral shape. However, in the case of a pointed tip, a crack is easily generated in the resin insulating layer, and among these, a spherical shape is desirable.

The content of phosphorus and the phosphorus compound in the resin insulating layer is desirably 0.5 to 10% by weight. When the content is less than 0.5% by weight, the effect of improving the flame retardancy of the multilayer printed wiring board is poor, and when the content exceeds 10% by weight,
This may have an adverse effect on the opening properties and curability when forming openings for via holes and the like. More preferably, it is 1 to 5% by weight.

The resin insulating layer desirably contains a silicon compound, an aluminum compound, a magnesium compound and the like. These compounds may be contained alone or in combination of two or more.

The silicon compound is not particularly restricted but includes, for example, silica and zeolite. The aluminum compound is not particularly limited, for example,
Alumina, aluminum hydroxide and the like can be mentioned.

The magnesium compound is not particularly restricted but includes, for example, magnesia, dolomite, basic magnesium carbonate and the like. When these compounds are contained in the resin insulating layer, the stress generated in the resin insulating layer is easily relieved, and as a result, cracks occur in the resin insulating layer and peeling occurs with the conductor circuit. Is less likely to occur. Further, the resin insulating layer may contain a phenol resin, dicyanamide, aluminum hydroxide, or the like. This is because the flame retardancy may be improved due to a synergistic effect.

The resin used as the material of the resin insulating layer is preferably a resin containing epoxy resin, phenol resin, polyolefin resin, PPO, PPE, fluororesin, polyimide resin and the like. These may be used alone or in combination of two or more.

Examples of the epoxy resin include cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, alkylphenol novolak type epoxy resin, biphenol F type epoxy resin, and naphthalene type epoxy resin. Resin, dicyclopentadiene type epoxy resin, epoxidized product of condensate of phenols and aromatic aldehyde having phenolic hydroxyl group,
Triglycidyl isocyanurate, alicyclic epoxy resin and the like. These may be used alone or in combination of two or more. Thereby, it becomes excellent in heat resistance and the like.

Examples of the polyolefin resin include polyethylene, polypropylene, polyisobutylene, polybutadiene, polyisoprene, cycloolefin resin, and copolymers of these resins. Among them, the dielectric constant and the dielectric loss tangent are low, and GHz
Even when a high frequency signal in a band is used, a cycloolefin-based resin is preferable because signal delay and signal error hardly occur, and further, mechanical properties such as rigidity are excellent.

As the above cycloolefin resin, 2
Homopolymers or copolymers of monomers comprising -norbornene, 5-ethylidene-2-norbornene or derivatives thereof are desirable. As the above derivative, the above 2-
Examples thereof include those in which an amino group for forming a crosslink, a maleic anhydride residue, or a maleic acid-modified one is bonded to a cycloolefin such as norbornene. Examples of monomers for synthesizing the copolymer include ethylene and propylene.

The cycloolefin resin may be a mixture of two or more of the above resins, or may contain a resin other than the cycloolefin resin. When the cycloolefin resin is a copolymer, it may be a block copolymer or a random copolymer.

The cycloolefin resin is preferably a thermosetting cycloolefin resin.
This is because by performing the heating to form the crosslinks, the rigidity is further increased and the mechanical properties are improved. The glass transition temperature (Tg) of the cycloolefin resin is 13
Desirably, the temperature is 0 to 200 ° C.

As the above cycloolefin-based resin, those already formed as a resin sheet (film) may be used, and a monomer or a low-molecular-weight polymer having a constant molecular weight may be used as a solvent such as xylene or cyclohexane. It may be in the state of an uncured solution dispersed in. In the case of a resin sheet, a so-called RCC (RESIN COATE
D COPER: resin-coated copper foil).

The cycloolefin resin may not contain a filler or the like, or may contain a flame retardant such as aluminum hydroxide, magnesium hydroxide, or a phosphate.

Examples of the fluororesin include ethyl / tetrafluoroethylene copolymer resin (ETFE) and polychlorotrifluoroethylene (PCTFE).

As the resin used as the material of the resin insulating layer, a resin composite composed of a thermosetting resin and a thermoplastic resin is also preferable. These resins may be photosensitive resins. Examples of the thermosetting resin include an epoxy resin, a phenol resin, and a polyimide resin. Examples of the photosensitive resin include those obtained by subjecting methacrylic acid, acrylic acid, or the like to an acrylate reaction with a thermosetting group. In particular, an acrylated epoxy resin is desirable. Among these, an epoxy resin having two or more epoxy groups in one molecule is more desirable.

Examples of the epoxy resin include a cresol novolak epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a phenol novolak epoxy resin, an alkylphenol novolak epoxy resin, a biphenol F epoxy resin, and a naphthalene epoxy resin. Resin, dicyclopentadiene type epoxy resin, epoxidized product of condensate of phenols and aromatic aldehyde having phenolic hydroxyl group,
Triglycidyl isocyanurate, alicyclic epoxy resin and the like. These may be used alone or in combination of two or more. Thereby, it becomes excellent in heat resistance and the like.

Examples of the thermoplastic resin include polyether sulfone (PES) and polysulfone (PS).
F), polyphenylene sulfone (PPS), polyphenylene sulfide (PPES), polyphenylene ether (PPE), polyetherimide (PI), phenoxy resin, fluororesin and the like.

The mixing ratio of the thermosetting resin and the thermoplastic resin in the resin composite is desirably thermosetting resin / thermoplastic resin = 95/5 to 50/50. This is because a high toughness value can be secured without impairing the heat resistance.

As a material of the resin insulating layer containing the above resin composite, for example, particles soluble in an acid or an oxidizing agent (hereinafter referred to as “soluble particles”) are resins that are hardly soluble in an acid or an oxidizing agent (hereinafter referred to as a hardly soluble resin). ) And a resin composition for forming a roughened surface dispersed therein. Note that the terms "sparingly soluble" and "soluble" are referred to as "soluble" for convenience when a substance having a relatively high dissolution rate is immersed in the same roughening solution for the same time, and the relative dissolution rate is relatively low. The slower one is called "poorly soluble" for convenience.

Examples of the soluble particles include resin particles soluble in an acid or an oxidizing agent (hereinafter referred to as “soluble resin particles”), inorganic particles soluble in an acid or an oxidizing agent (hereinafter referred to as “soluble inorganic particles”), and an acid or an oxidizing agent. Soluble metal particles (hereinafter referred to as “soluble metal particles”) and the like. These soluble particles may be used alone or in combination of two or more.

The shape (particle size, etc.) of the soluble particles is not particularly limited, but (a) soluble particles having an average particle size of 10 μm or less, and (b) aggregation of soluble particles having an average particle size of 2 μm or less. Particles, (c) average particle size is 2 to 10 μm
(D) either a heat-resistant resin powder or an inorganic powder having an average particle size of 2 μm or less on the surface of the soluble particles having an average particle size of 2 to 10 μm; (E) a mixture of soluble particles having an average particle size of 0.1 to 0.8 μm and soluble particles having an average particle size of more than 0.8 μm and less than 2 μm, ) Average particle size is 0.1 to 1.0 μm
It is desirable to use soluble particles of This is because these can form a more complicated anchor.

Examples of the soluble resin particles include those made of a thermosetting resin, a thermoplastic resin, and the like. When immersed in a solution containing an acid or an oxidizing agent, the soluble resin particles have a higher dissolution rate than the hardly soluble resin. If it is, there is no particular limitation. Specific examples of the soluble resin particles include, for example, those made of epoxy resin, phenol resin, polyimide resin, polyphenylene resin, polyolefin resin, fluororesin, amino resin (melamine resin, urea resin, guanamine resin), and the like. These resins may be composed of one kind or a mixture of two or more kinds of resins.

As the soluble resin particles, resin particles made of rubber can be used. Examples of the rubber include polybutadiene rubber, various modified polybutadiene rubbers such as epoxy-modified, urethane-modified, (meth) acrylonitrile-modified, and (meth) acrylonitrile-butadiene rubber containing a carboxyl group. By using these rubbers, the soluble resin particles are easily dissolved in an acid or an oxidizing agent. In other words, when dissolving the soluble resin particles using an acid, an acid other than a strong acid can be dissolved, and when dissolving the soluble resin particles using an oxidizing agent, permanganese having a relatively weak oxidizing power is used. It can also dissolve in acids. Even when chromic acid is used, it can be dissolved at a low concentration. for that reason,
Acid or oxidizing agent does not remain on the resin surface, and as described later, when a catalyst such as palladium chloride is applied after forming a roughened surface, the catalyst is not applied or the catalyst is oxidized. There is no.

Examples of the soluble inorganic particles include particles made of at least one selected from the group consisting of aluminum compounds, calcium compounds, potassium compounds, magnesium compounds and silicon compounds.

The aluminum compound includes, for example, alumina and aluminum hydroxide. The calcium compound includes, for example, calcium carbonate,
Calcium hydroxide and the like, as the potassium compound, for example, potassium carbonate and the like, as the magnesium compound, for example, magnesia, dolomite, basic magnesium carbonate and the like, as the silicon compound, For example, silica, zeolite and the like can be mentioned. These may be used alone or in combination of two or more.

The soluble metal particles include, for example,
Copper, nickel, iron, zinc, lead, gold, silver, aluminum,
Examples include particles made of at least one selected from the group consisting of magnesium, calcium, and silicon. These soluble metal particles may have a surface layer coated with a resin or the like in order to ensure insulation.

When two or more of the above-mentioned soluble particles are used in combination, the combination of the two types of soluble particles to be mixed is preferably a combination of resin particles and inorganic particles. Since both have low conductivity, insulation between the upper and lower conductor circuits can be ensured, and thermal expansion can be easily adjusted with the hardly-soluble resin. This is because peeling does not occur between the resin insulating layer and the conductor circuit.

The hardly soluble resin may be any resin that can maintain the shape of the roughened surface when the roughened surface is formed by using an acid or an oxidizing agent in the interlayer resin insulating layer. Can be used. In addition, as the hardly soluble resin, a resin composition for forming a roughened surface using only the thermosetting resin or the thermoplastic resin can also be used as a material of the resin insulating layer.

The mixing weight ratio of the soluble particles is desirably 5 to 50% by weight based on the solid content of the hardly soluble resin.
40% by weight is more desirable. If the mixing weight ratio of the soluble particles is less than 5% by weight, it may not be possible to form a roughened surface with sufficient roughness, and if it exceeds 50% by weight, the upper and lower conductor circuits between the upper and lower conductor circuits via the resin insulating layer may be formed. Insulation cannot be ensured, which may cause a short circuit.

The resin insulating layer having such a structure is excellent in flame retardancy because it contains the above-mentioned phosphorus or the phosphorus compound, and the multilayer printed wiring board on which the resin insulating layer is formed is UL94 (UL) (UL test standard). It satisfies the criterion of “flame retardancy test of polymer materials”.
This is to clear the criterion of V-0.

Since the content of phosphorus or a phosphorus compound contained in the resin insulating layer can be arbitrarily adjusted, the coefficient of thermal expansion of the resin insulating layer is determined by adjusting the coefficient of thermal expansion of the substrate or the solder resist layer. By adjusting the coefficient to the same extent, peeling between the conductor circuit and the resin insulation layer may occur,
Since a crack is not easily generated in the resin insulating layer, a multilayer printed wiring board having excellent connection reliability can be obtained.

The multilayer printed wiring board of the present invention is, for example,
It can be manufactured by the below-described first to third methods of manufacturing a multilayer printed wiring board of the present invention.

A first method for manufacturing a multilayer printed wiring board according to the present invention is a method for manufacturing a multilayer printed wiring board according to the present invention, and includes at least the following steps (1) and (2). I do. (1) a step of preparing an uncured resin composition containing phosphorus and / or a phosphorus compound; and (2) a step of forming the uncured resin composition on a substrate on which a conductor circuit is formed or a resin insulating layer on which a conductor circuit is formed. A step of forming a layer of the resin composition by applying the resin composition;

According to the first method for manufacturing a multilayer printed wiring board of the present invention, the multilayer printed wiring board of the present invention having excellent flame retardancy and connection reliability can be suitably manufactured. Further, in the manufacturing method according to the first aspect of the present invention, it is possible to form a via hole opening or the like having a desired shape in a short time. Here, the step of forming the resin insulating layer will be described first, and the overall method of manufacturing the multilayer printed wiring board will be described later in detail.

In the first production method of the present invention, when forming the resin insulating layer, first, an uncured resin composition containing phosphorus and / or a phosphorus compound is prepared. That is, the above-mentioned phosphorus and / or the phosphorus compound are added to one or two or more resin components as raw materials of the above-mentioned resin insulating layer and uniformly mixed, and then, the remaining constituent components are added and mixed. Thereby, the resin composition is adjusted. As the resin component to which phosphorus and / or the phosphorus compound are added first, a component containing a thermosetting resin is desirable. This will be described in detail when describing the third manufacturing method of the present invention.

The method for preparing the above resin composition is as follows.
The method is not limited to the above method, and any method may be used as long as phosphorus or a phosphorus compound can be dispersed almost uniformly in an uncured resin composition. May be mixed at the same time.

After preparing a dispersion in which the above-mentioned phosphorus or the phosphorus compound is dispersed in a solvent, adding the dispersion to make the resin composition contain the phosphorus or the phosphorus compound requires the addition of the phosphorus or the phosphorus compound. The state (structure, physical properties, etc.) may change, and it may be difficult to maintain safety during work, which is not preferable.

In the manufacturing method according to the first aspect of the present invention, after the above-mentioned steps, the uncured uncured material is placed on the substrate on which the conductor circuit is formed, that is, on the substrate on which the conductor circuit is formed directly. A layer of the resin composition was formed by applying the resin composition, or a resin insulating layer having a conductive circuit formed thereon, that is, one or more resin insulating layers and a conductive circuit were formed on a substrate. A layer of the resin composition is formed by applying the uncured resin composition on the conductor circuit of the substrate. Examples of a method for applying the uncured resin composition include a roll coater method. Specifically, after the uncured resin composition is adhered to the roll surface of the roll coater, the substrate on which the conductor circuit is formed in the outermost layer is vertically set, and is sandwiched between a pair of roll coaters. Is rotated to apply the resin composition to the substrate surface. By this step, a layer of the resin composition having a uniform thickness is formed on both surfaces of the substrate.

Next, the layer of the resin composition is dried, and an opening for a via hole and, if necessary, a through-hole are formed on the substrate on which the dried body of the resin composition is formed to form an interlayer resin insulating layer. . The via hole opening is preferably formed by using a laser process. In the case where a layer of a resin composition made of a photosensitive resin is formed, an opening for a via hole may be provided by performing exposure and development treatments. At this time, as a laser to be used, for example, carbon dioxide gas (C
O ₂ ) lasers, ultraviolet lasers, excimer lasers, etc., are preferred. Of these, excimer lasers and short-pulse carbon dioxide lasers are desirable.

As will be described later, the excimer laser can form a large number of via hole openings at once by using a mask or the like in which a through hole is formed in a portion where a via hole opening is formed. This is because the short-pulse carbon dioxide laser has a small amount of resin remaining in the opening, and damage to the resin around the laser irradiation site is particularly small.

Also, among the excimer lasers, it is desirable to use a hologram type excimer laser. The hologram method is a method of irradiating a target object with a laser beam through a hologram, a condensing lens, a laser mask, a transfer lens, and the like. Can be efficiently formed.

When a carbon dioxide laser is used, the pulse interval is desirably 10 ^-4 to 10 ^-8 seconds. The time for irradiating the laser for forming the opening is preferably 10 to 500 μsec. Further, the through-hole of the mask in which the through-hole is formed in the portion where the via-hole opening is formed needs to be a perfect circle in order to make the spot shape of the laser beam a perfect circle, and the diameter of the through-hole is ,
About 0.1 to 2 mm is desirable.

By irradiating a laser beam through an optical lens and a mask, a large number of via hole openings can be formed at once. This is because a plurality of portions can be simultaneously irradiated with laser light having the same intensity and the same irradiation intensity through the optical system lens and the mask.

When the opening is formed by a laser beam, particularly when a carbon dioxide gas laser is used, desmearing is preferably performed. The desmear treatment can be performed using an oxidizing agent composed of an aqueous solution such as chromic acid and permanganate. Alternatively, the treatment may be performed using oxygen plasma, a mixed plasma of CF ₄ and oxygen, corona discharge, or the like. The surface can also be modified by irradiating ultraviolet rays using a low-pressure mercury lamp. When a through-hole is formed in the substrate on which the layer of the resin composition is formed, the diameter is 50 to 300.
A through hole is formed using a μm drill, laser light, or the like.

Next, the entire method of manufacturing a multilayer printed wiring board according to the first embodiment of the present invention will be described in the order of steps. (1) In the first manufacturing method of the present invention, first, a substrate having a conductive circuit formed on a surface of an insulating substrate is prepared.

The insulating substrate is desirably a resin substrate. Specifically, for example, a glass epoxy substrate, a polyester substrate, a polyimide substrate, a bismaleimide-triazine resin substrate, a thermosetting polyphenylene ether substrate, a fluororesin substrate, Ceramic substrate, copper clad laminate, R
CC substrate and the like. At this time, a through hole may be provided in the insulating substrate. In this case, the through hole has a diameter of 10
It is desirable to form it using a 0 to 300 μm drill, laser light, or the like.

(2) Next, after performing electroless plating, a conductive circuit-shaped etching resist is formed on the substrate, and the conductive circuit is formed by performing etching. Copper plating is desirable as the electroless plating. In addition, when a through hole for a through hole is provided in an insulating substrate, a through hole is formed by simultaneously performing electroless plating on the wall surface of the through hole for the through hole, thereby forming a through hole between conductor circuits on both surfaces of the substrate. May be electrically connected.

After the electroless plating, the surface of the electroless plating layer and, if a through hole is formed, are usually subjected to a roughening treatment for the inner wall of the through hole. Examples of the roughening forming treatment method include blackening (oxidation) -reduction treatment, spray treatment with a mixed aqueous solution of an organic acid and a cupric complex, Cu treatment
-Ni-P needle-like alloy plating.

As a specific method of the above-mentioned blackening (oxidation) -reduction treatment, NaOH (10 g / l), NaClO ₂
(40 g / l), a blackening treatment using an aqueous solution containing Na ₃ PO ₄ (6 g / l) as a blackening bath (oxidizing bath), and NaO
A method of performing a reduction treatment using an aqueous solution containing H (10 g / l) and NaBH ₄ (6 g / l) as a reduction bath is exemplified.

In the mixed aqueous solution of an organic acid and a cupric complex used for the spray treatment, the organic acid includes, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, crotonic acid, and oxalic acid. Acid, malonic acid,
Examples include succinic acid, glutaric acid, maleic acid, benzoic acid, glycolic acid, lactic acid, malic acid, and sulfamic acid. These may be used alone or in combination of two or more. In the mixed solution, the content of the organic acid is desirably 0.1 to 30% by weight. This is because the solubility of the oxidized copper can be maintained and the stability of the catalyst can be ensured.

As the cupric complex, a cupric complex of an azole is desirable. This cupric complex of azoles is
It acts as an oxidizing agent that oxidizes metallic copper and the like. Examples of the azoles include diazole, triazole, tetrazole and the like. Among these, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-undecylimidazole are desirable. In the etching solution, the content of the cupric complex is desirably 1 to 15% by weight. This is because it is excellent in solubility and stability, and can also dissolve noble metals such as Pd constituting the catalyst core.

As a specific method of the plating process,
Copper sulfate (1-40 g / l), nickel sulfate (0.1-
6.0 g / l), citric acid (10-20 g / l), sodium hypophosphite (10-100 g / l), boric acid (1
0 to 40 g / l) and a surfactant (Surfynol 465, manufactured by Nissin Chemical Industry Co., Ltd.) (0.01 to 10 g / l)
And a method in which electroless plating is performed in an electroless plating bath having a pH of 9 and the like.

(3) Next, a layer of the resin composition is formed on the substrate on which the conductive circuit is formed by using the above-described method, and further, the above-described method is applied to the formed resin composition layer. Then, an opening for a via hole and a through hole are formed. That is, in this step, an interlayer resin insulating layer containing phosphorus and / or a phosphorus compound is formed.

(4) Next, if necessary, the surface of the resin insulating layer (interlayer resin insulating layer) including the inner wall of the via hole opening and the inner wall of the through hole when the through hole is formed in the above step. Then, a roughened surface is formed using an acid or an oxidizing agent. Examples of the acid include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and formic acid. Examples of the oxidizing agent include chromic acid, chromic sulfuric acid, and permanganates such as sodium permanganate.

Thereafter, when the roughened surface is formed by using an acid, an aqueous solution of an alkali or the like is used, and when the roughened surface is formed by using an oxidizing agent, a neutralizing solution is used. Neutralizes the inside of the through hole. By this operation, the acid and the oxidizing agent are removed so that the next step is not affected. The average roughness Rz of the roughened surface formed in this step is 0.1 to 5 μm.
m is desirable. The roughened surface may be formed by performing a plasma treatment or the like.

(5) Next, a catalyst is applied to the formed roughened surface, if necessary. Examples of the catalyst include palladium chloride. At this time, in order to reliably apply the catalyst, a dry treatment such as a plasma treatment with oxygen, nitrogen or the like or a corona treatment is performed to remove a residue of an acid or an oxidizing agent and modify the surface of the interlayer resin insulating layer. By doing so, the catalyst can be reliably applied, the metal can be deposited during electroless plating, and the adhesion of the electroless plating layer to the interlayer resin insulating layer can be improved. In particular, the bottom surface of the via hole opening can be improved. In the above, a great effect can be obtained.

(6) Next, a thin-film conductor layer made of tin, zinc, copper, nickel, cobalt, thallium, lead or the like is formed on the formed interlayer resin insulating layer by electroless plating, sputtering or the like, if necessary. . The above-mentioned thin film conductor layer may be a single layer, or may be composed of two or more layers. Among these, a thin film conductor layer made of copper, copper, and nickel is desirable in consideration of electrical characteristics, economy, and the like. When the through hole is formed in the step (3), a through-hole may be formed by forming a thin film conductor layer made of metal also on the inner wall surface of the through hole in this step.

When a through hole is formed in the step (6), it is desirable to perform the following processing steps. That is, the surface of the electroless plating layer and the inner wall of the through hole are subjected to blackening (oxidation) -reduction treatment, spray treatment with a mixed aqueous solution of an organic acid and a cupric complex, treatment with Cu-Ni-P needle-like alloy plating, and the like. To perform a roughening process. Thereafter, the inside of the through-hole is further filled with a resin filler or the like, and then the surface layer of the resin filler and the surface of the electroless plating layer are flattened by a polishing treatment method such as buffing. Further, by performing electroless plating and forming an electroless plating layer on the thin film conductor layer made of a metal already formed and the surface layer of the resin filler, a cover plating layer is formed on the through hole.

(7) Next, a plating resist is formed on a part of the interlayer resin insulating layer using a dry film, and thereafter, electroplating is performed using the thin film conductor layer as a plating lead, and the plating resist is not formed. An electroplating layer thicker than the thickness of the plating resist is formed in the portion. It is desirable to use copper plating as the electroplating. At this time, the via hole opening may be filled with electroplating to form a field via structure, and after filling the via hole opening with a conductive paste or the like, a lid plating layer may be formed thereon to form a field via structure. Good. By forming a field via structure, a via hole can be provided immediately above the via hole.

(8) After forming the electroplating layer, the plating resist is peeled off, and the thin film conductor layer made of metal existing under the plating resist is removed by etching to form an independent conductor circuit. It is desirable to use copper plating as the electroplating. As an etchant, for example, a sulfuric acid-hydrogen peroxide aqueous solution, ammonium persulfate, sodium persulfate, a persulfate aqueous solution such as potassium persulfate,
An aqueous solution of ferric chloride, cupric chloride, or the like, hydrochloric acid, nitric acid, hot dilute sulfuric acid, or the like can be given. Further, a roughened surface may be formed at the same time as etching between conductor circuits using an etching solution containing the above-described cupric complex and an organic acid. Further, if necessary, the catalyst on the interlayer resin insulating layer may be removed using an acid or an oxidizing agent. By removing the catalyst, the metal such as palladium used for the catalyst disappears, so that a decrease in the electrical characteristics can be prevented.

(9) Thereafter, if necessary, the steps (3) to (8) are repeated. If it is necessary to form a roughened surface on the outermost conductor circuit, the above-described roughened surface is formed. A conductor circuit having a roughened surface is formed by using a forming method.

(10) Next, a solder resist layer is formed on the substrate surface including the outermost conductive circuit. Examples of the material of the solder resist layer include a solder resist composition comprising a polyphenylene ether resin, a polyolefin resin, a fluororesin, a thermoplastic elastomer, an epoxy resin, a polyimide resin, and the like. Specific examples of these resins include, for example, the same resins as those used for the resin insulating layer.

Examples of the solder resist composition other than those described above include, for example, a novolak-type epoxy resin (meth) acrylate, an imidazole curing agent, a bifunctional (meth) acrylate monomer, and a molecular weight of 500 to 50.
A paste-like fluid containing a polymer of about 00 (meth) acrylate, a thermosetting resin such as a bisphenol-type epoxy resin, a photosensitive monomer such as a polyvalent acrylic monomer, a glycol ether-based solvent, and the like. The viscosity is preferably adjusted to 1 to 10 Pa · s at 25 ° C. As a solder resist composition,
When such a photosensitive resin composition is used, a non-through hole can be formed by exposure and development.

(Meth) of the above novolak type epoxy resin
Examples of the acrylate include an epoxy resin obtained by reacting glycidyl ether of phenol novolak or cresol novolak with acrylic acid, methacrylic acid, or the like.

The bifunctional (meth) acrylic acid ester monomer is not particularly limited, and examples thereof include acrylic acid and methacrylic acid esters of various diols, and commercially available products of Nippon Kayaku Co., Ltd. R-604, PM
2, PM21 and the like.

The solder resist composition may contain an elastomer or an inorganic filler. By being blended with the elastomer, the formed solder resist layer can absorb or reduce the stress even when a stress acts on the solder resist layer due to the flexibility and rebound resilience of the elastomer. As a result, cracks and peeling can be suppressed from occurring in the manufacturing process of the multilayer printed wiring board and in the solder resist layer after mounting electronic components such as IC chips on the manufactured multilayer printed wiring board. Even when it occurs, the crack does not grow large.

It is desirable to use the above-mentioned solder resist composition containing phosphorus or a phosphorus compound as the above-mentioned solder resist composition. This is because the flame retardancy of the obtained multilayer printed wiring board is further improved by incorporating phosphorus or a phosphorus compound not only in the resin insulating layer but also in the solder resist layer.

The solder resist layer can be formed by applying the solder resist composition by a roll coater method or the like.
After the resin film of the solder resist composition is formed, the resin film is thermocompression-bonded, and then subjected to opening processing such as exposure, development processing, laser processing, and the like, and further subjected to curing processing and the like.

(11) Next, a corrosion-resistant metal layer made of Ni, Au, or the like is formed by plating, sputtering or vapor deposition at the opening of the solder resist layer, and then, a solder paste is printed on the IC chip connection surface. Thus, solder bumps are formed, and solder balls, pins, and the like are provided on the external substrate connection surface, thereby completing the manufacture of the printed wiring board. In addition, as a method of arranging the solder balls, pins, and the like, a conventionally known method can be used.

A plasma treatment with oxygen, carbon tetrachloride, or the like may be performed as needed for a character printing step for forming product recognition characters or the like or for modifying a solder resist layer. Although the above method is based on the semi-additive method, a full additive method may be employed.

A second method of manufacturing a multilayer printed wiring board according to the present invention is a method of manufacturing a multilayer printed wiring board according to the present invention, and includes at least the following steps (1) and (2). I do. (1) a step of preparing a resin film containing phosphorus and / or a phosphorus compound; and (2) crimping the resin film on a substrate on which a conductor circuit is formed or a resin insulating layer on which a conductor circuit is formed. A step of forming a resin film layer;

According to the second method for manufacturing a multilayer printed wiring board of the present invention, the multilayer printed wiring board of the present invention having excellent flame retardancy and connection reliability can be suitably manufactured. In the method for manufacturing a multilayer printed wiring board according to the second aspect of the present invention, a via hole opening or the like having a desired shape can be formed in a short time.

The method for manufacturing a multilayer printed wiring board according to the second aspect of the present invention is different from the method for manufacturing a multilayer printed wiring board according to the first aspect of the present invention in that a step of forming an interlayer resin insulating layer (the first step described in the order of steps). The method of the present invention differs only in the step (3)), and the other steps can be performed using the same method as the first manufacturing method of the present invention. Therefore, here, only the step of forming the resin insulating layer in the second manufacturing method of the present invention will be described.

In the second production method of the present invention, first, a resin film containing phosphorus and / or a phosphorus compound is prepared. That is, first, the phosphorus and / or the phosphorus compound are added to one or more resin components as raw materials of the resin film and uniformly mixed. By doing so, the composition for forming a resin film is adjusted. Next, the resin film forming composition is placed in a mold, dried and semi-cured to obtain a resin film. As the resin component to which phosphorus and / or the phosphorus compound are added first, a component containing a thermosetting resin is desirable. This will be described in detail when describing the third manufacturing method of the present invention.

The method for producing the above resin film is not limited to the above method.
A resin film-forming composition was prepared by simultaneously mixing other components as the raw material of the resin insulating layer, and then
A resin film may be obtained by placing the film in a molding die, drying and semi-curing as described above. Further, a metal layer such as a copper foil may be formed on one side of the molded resin film.

When a resin composition for forming a roughened surface is used as a material for forming a resin film, the soluble particles in the resin film to be formed are preferably dispersed almost uniformly in the poorly soluble resin. . It is possible to form a roughened surface having unevenness with a uniform roughness on the surface of the resin insulating layer, and even if a via hole or a through hole is formed in the resin insulating layer, the surface of the resin insulating layer can be formed with a metal layer of a conductive circuit formed thereon. This is because adhesion can be ensured.

Further, a resin film may be formed by adding soluble particles only to the surface layer forming the roughened surface.
In this case, since the portions other than the surface layer of the resin insulating layer are not exposed to the acid or the oxidizing agent, the insulation between the conductor circuits via the interlayer resin insulating layer is reliably maintained. The resin film containing the soluble particles only in the surface layer portion is, for example, a resin film composed of only the hardly soluble resin is formed by the method described above, and a resin film in which the soluble particles are substantially uniformly dispersed in the hardly soluble resin is formed thereon. It is formed by stacking.

In the above resin film, the amount of the soluble particles to be dispersed in the poorly soluble resin is preferably 3 to 40% by weight based on the resin film. If the amount of the soluble particles is less than 3% by weight, it may not be possible to form a roughened surface having desired irregularities. If the amount exceeds 40% by weight, the soluble particles may be dissolved using an acid or an oxidizing agent. In addition, the resin may be melted to a deep portion of the resin insulating layer, failing to maintain the insulating property between the conductor circuits via the interlayer resin insulating layer made of the resin film, which may cause a short circuit. The resin film may contain a curing agent, a solvent, other components, and the like, if necessary, in addition to the phosphorus and the phosphorus compound.

In the manufacturing method according to the second aspect of the present invention, after the above-described steps, the resin film is pressed on the substrate on which the conductor circuit is formed or on the resin insulating layer on which the conductor circuit is formed. To form As a method of pressure-bonding the resin film, for example, a method of pressure-bonding the resin film at a pressure of 2.0 to 10 kgf / cm ² under reduced pressure or vacuum using a vacuum laminator device or the like is preferable. When the pressure is less than 2.0 kgf / cm ² , the adhesion between the resin film and the conductor circuit may be insufficient. On the other hand, when the pressure is more than 10 kgf / cm ² , the phosphorus or the phosphorus compound may aggregate in the resin film. May occur. More preferable pressure is 3-7 kgf
/ Cm ² . When the resin film is pressure-bonded, first, the resin film may be temporarily pressure-bonded, and then, the resin film may be completely pressure-bonded under the above-described conditions.

The temperature at which the resin film is pressure-bonded is preferably 60 to 120 ° C. When the temperature is lower than 60 ° C., the effect of heating is hardly observed. When the temperature is higher than 120 ° C., when the resin film contains a curing agent or a solvent, the curing agent or the solvent volatilizes, and the curing is not performed. It may be sufficient or the curing may proceed too much.

The pressing time of the resin film is 1
0 to 120 seconds is preferred. If the crimping time is less than 10 seconds,
This is because the adhesiveness between the resin film and the conductor circuit may be insufficient, and even if it exceeds 120 seconds, the adhesiveness between the resin film and the conductor circuit hardly improves.

The degree of vacuum when the resin film is pressure-bonded is preferably 0.1 to 10 Torr. Making the degree of vacuum less than 0.1 Torr is not technically easy and takes time. On the other hand, when the degree of vacuum is 10 Torr
If it exceeds 300, the resin film may not be completely filled between the conductor circuits.

Thereafter, openings and through holes are formed in the resin film layer using the same method as the first manufacturing method of the present invention.

The third method of manufacturing a multilayer printed wiring board according to the present invention is to manufacture the multilayer printed wiring board according to the present invention, wherein the resin insulating layer includes a resin composite composed of a thermosetting resin and a thermoplastic resin. A method comprising at least the following (1)
And (5). (1) a step of preparing a resin composition A containing phosphorus and / or a phosphorus compound and a thermosetting resin; and (2) a step of preparing a resin composition B containing a thermoplastic resin.
(3) a step of preparing a curing agent component C containing a curing agent;
(4) a step of kneading the resin composition A, the resin composition B, and the curing agent component C to prepare a mixed composition D, and then preparing a resin film E including the mixed composition D; 5) a step of forming a layer of the resin film E by pressing the resin film E on a substrate on which the conductor circuit is formed or on a resin insulating layer on which the conductor circuit is formed.

According to the third method of manufacturing a multilayer printed wiring board of the present invention, a resin composite having excellent flame retardancy and connection reliability, wherein the resin insulating layer comprises a thermosetting resin and a thermoplastic resin. A multilayer printed wiring board including a body can be suitably manufactured. Further, in the method for manufacturing a multilayer printed wiring board according to the third aspect of the present invention, a via hole opening or the like having a desired shape can be formed in a short time.

That is, the method of manufacturing a multilayer printed wiring board according to the third aspect of the present invention is different from the method of manufacturing a multilayer printed wiring board according to the first aspect of the present invention in that steps of forming an interlayer resin insulating layer (described in the order of steps). Only the process (3) of the production method of the first present invention is different, and the other steps can be performed using the same method as the production method of the first invention. Therefore,
Here, only the step of forming the interlayer resin insulating layer in the third manufacturing method of the present invention will be described.

In the third production method of the present invention, first, a resin composition A containing phosphorus and / or a phosphorus compound and a thermosetting resin, and a resin composition B containing a thermoplastic resin
And a curing agent component C containing a curing agent are separately prepared. The preparation of the resin composition A, the resin composition B, and the curing agent component C may be performed in parallel or in any order.

In preparing the resin composition A, the phosphorus or the phosphorus compound is mixed in advance with one or more thermosetting resins as raw materials of the resin composition A, and It is performed by mixing with other components. Thus, mixing phosphorus or a phosphorus compound into a thermosetting resin first is easy to uniformly mix the phosphorus or the phosphorus compound,
Further, during mixing, there is no possibility that the state of phosphorus or the phosphorus compound is changed, so that the operation is excellent in safety. In particular, when forming a resin insulating layer containing a resin composite composed of a thermosetting resin and a thermoplastic resin, phosphorus or a phosphorus compound is first mixed into the thermosetting resin. In addition, if the components which are the raw materials of the resin composition A, such as phosphorus, a phosphorus compound, and a thermosetting resin, can be uniformly mixed, all the raw materials are mixed at once and the resin composition A is mixed. May be prepared.

As the thermosetting resin contained in the resin composition A, the same thermosetting resin as the raw material of the resin insulating layer of the multilayer printed wiring board of the present invention can be used.

The preparation of the resin composition B is carried out by adding additives and solvents to the thermoplastic resin, if necessary, and then mixing them. As the thermoplastic resin contained in the resin composition B, the same thermoplastic resin as the raw material of the resin insulating layer of the multilayer printed wiring board of the present invention can be used. In this specification, the resin composition B
Include those made of a thermoplastic resin alone.

The curing agent component C is prepared by adding an additive or a solvent to the curing agent, if necessary, and then mixing. Examples of the curing agent contained in the curing agent component C include an imidazole-based curing agent and an amine-based curing agent. The imidazole-based curing agent is not particularly limited, but is preferably an imidazole-based curing agent that is liquid at 25 ° C. It is difficult to knead uniformly with powder,
This is because the liquid can be kneaded more uniformly.

Specific examples of such a liquid imidazole-based curing agent include, for example, 1-benzyl-2-methylimidazole (1B2MZ, manufactured by Shikoku Chemicals), 1-cyanoethyl-2-ethyl-4-methylimidazole ( Shikoku Chemicals Corporation 2E4MZ-CN), 4-methyl-2-ethylimidazole (Shikoku Chemicals Corporation 2E4MZ) and the like. In the present specification, the curing agent component C includes a curing agent alone.

Next, the above-mentioned resin composition A, the above-mentioned resin composition B and the above-mentioned curing agent component C are kneaded to prepare a mixed composition D, and thereafter, a resin film E made of the above-mentioned mixed composition D is produced. . In the preparation of the mixed composition D, first, the resin composition A and the resin composition B are mixed. At this time, a solvent, an additive, and the like may be added as necessary.
Thereafter, a mixed composition D is prepared by adding and mixing the curing agent component C. When mixing the curing agent component C, a necessary solvent, additive, and the like may be added.

It is to be noted that any method other than the method described above can be used as long as the method can uniformly knead the resin composition A, the resin composition B, and the curing agent component C. A, resin composition B, and curing agent component C
May be kneaded simultaneously, or after kneading two components of the resin composition A, the resin composition B and the curing agent component C,
The remaining components may be added and kneaded. Also in these cases, a solvent, an additive, and the like are added as necessary.

After preparing the mixed composition D, a resin film E made of the mixed composition D is prepared. in this case,
The same method as the method for producing the resin film of the second production method of the present invention can be used.

Next, the resin film E is formed on the substrate on which the conductor circuit is formed or on the resin insulating layer on which the conductor circuit is formed, by pressure bonding to form a layer of the resin film E. As a method for pressure-bonding the resin film E, the second method
The method similar to the method of pressing a resin film in the production method of the present invention can be used.

Thereafter, openings and through holes are formed in the layer of the resin film E by using the same method as the first manufacturing method of the present invention.

In the first to third production methods of the present invention, a resin insulating layer provided with flame retardancy by containing phosphorus or a phosphorus compound is formed. Therefore, when forming a via hole opening or the like using laser light, the resin around the laser irradiation site does not burn due to the heat of laser irradiation, and the shape of the inner wall of the formed opening is smooth and the shape of the opening is smooth. Is also desired.

Normally, when an opening is formed by laser irradiation, the resin around the laser irradiation part is burned by the heat of the laser irradiation, so that the inner wall of the opening does not have a smooth shape and unevenness is formed. It becomes what has. However, in the method for manufacturing a multilayer printed wiring board according to the present invention, since a layer forming an opening for a via hole or the like has flame retardancy, the resin around the laser irradiation site does not burn due to the laser irradiation heat, The shape of the inner wall of the formed opening is smooth, and the desired shape is obtained.

Further, since the resin around the laser irradiation site is not burned by laser irradiation heat during laser irradiation, an opening having a desired shape can be formed even when high energy laser light is irradiated. it can. Therefore, by irradiating high-energy laser light, an opening can be formed in a short time. In particular, when a pulsed laser is used, an opening can be formed in a single shot.

Therefore, by using the method for manufacturing a multilayer printed wiring board of the present invention, an opening having a desired shape can be obtained.
A multilayer printed wiring board having no resin residue or the like in the opening and having excellent connection reliability between the upper and lower conductor circuits via the via hole formed in the opening can be manufactured with high productivity.

[0127]

The present invention will be described in more detail below. Example 1 A. Preparation of resin composition for forming roughened surface of upper layer (1) First, a red phosphorus-based flame retardant (trade name, Nova Excel
F5) A resin solution 10 in which 5.5 parts by weight of a 25% acrylate of a cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., molecular weight: 2500) is dissolved in diethylene glycol dimethyl ether (DMDG) at a concentration of 80% by weight.
The mixture was mixed with 0 parts by weight to prepare a cresol novolak type epoxy resin solution containing phosphorus. Next, 400 parts by weight of the phosphorus-containing cresol novolak type epoxy resin solution, photosensitive monomer (Aronix M325, manufactured by Toagosei Co., Ltd.) 6
0 parts by weight, 5 parts by weight of an antifoaming agent (S-65 manufactured by San Nopco) and 35 parts by weight of N-methylpyrrolidone (NMP) were placed in a container, and mixed by stirring to prepare a mixed composition.

(2) Polyether sulfone (PES) 8
0 parts by weight, 72 parts by weight of an epoxy resin particle (manufactured by Sanyo Chemical Industries, polymer pole) having an average particle size of 1.0 μm and 31 parts by weight of an epoxy resin particle having an average particle size of 0.5 μm were placed in another container and mixed with stirring. And 257 parts by weight of NMP were further added and stirred and mixed by a bead mill to prepare another mixed composition.

(3) Imidazole curing agent (manufactured by Shikoku Chemicals, Inc.)
2E4MZ-CN), 20 parts by weight of a photopolymerization initiator (benzophenone), 4 parts by weight of a photosensitizer (EAB, manufactured by Ciba Specialty Chemicals) and NMP1
6 parts by weight were placed in another container and mixed by stirring to prepare a mixed composition. And (1), (2) and
The resin composition for forming a roughened surface was obtained by mixing the mixed composition prepared in (3). In addition, the phosphorus content of the obtained resin composition for forming a roughened surface after drying is 3% by weight.

B. Preparation of Resin Composition for Forming Rough Surface of Lower Layer (1) First, a red phosphorus-based flame retardant (trade name, Nova Excel)
F5) A resin solution 10 in which 5.8 parts by weight of a cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., molecular weight: 2500) is dissolved at a concentration of 80% by weight in diethylene glycol dimethyl ether (DMDG) at a concentration of 80% by weight.
The mixture was mixed with 0 parts by weight to prepare a cresol novolak type epoxy resin solution containing phosphorus. Next, 400 parts by weight of the phosphorus-containing cresol novolak type epoxy resin solution, photosensitive monomer (Aronix M325, manufactured by Toagosei Co., Ltd.) 6
0 parts by weight, 5 parts by weight of an antifoaming agent (S-65 manufactured by San Nopco) and 35 parts by weight of N-methylpyrrolidone (NMP) were placed in a container, and mixed by stirring to prepare a mixed composition.

(2) Polyether sulfone (PES) 8
0 parts by weight and 145 parts by weight of an epoxy resin particle (manufactured by Sanyo Kasei Co., Ltd., polymer pole) having an average particle size of 0.5 μm are placed in another container, mixed with stirring, and further mixed with NMP2.
85 parts by weight were added and mixed by stirring with a bead mill to prepare another mixed composition.

(3) Imidazole curing agent (manufactured by Shikoku Chemicals, Inc.)
2E4MZ-CN), 20 parts by weight of a photopolymerization initiator (benzophenone), 4 parts by weight of a photosensitizer (EAB, manufactured by Ciba Specialty Chemicals) and NMP1
6 parts by weight were placed in another container and mixed by stirring to prepare a mixed composition. And (1), (2) and
The resin composition for forming a roughened surface was obtained by mixing the mixed composition prepared in (3). In addition, the phosphorus content of the obtained resin composition for forming a roughened surface after drying is 3% by weight.

C. Preparation of resin filler (1) 100 parts by weight of bisphenol F type epoxy monomer (manufactured by Yuka Shell Co., molecular weight: 310, YL983U),
SiO ₂ spherical particles having an average particle diameter of 1.6 μm and a maximum particle diameter of 15 μm or less (CRS 1101 manufactured by Adtec Co., Ltd.) having a surface coated with a silane coupling agent.
-CE) 170 parts by weight and 1.5 parts by weight of a leveling agent (Perenol S4 manufactured by San Nopco) are placed in a container, and the mixture is stirred and mixed to have a viscosity of 23 to 1 ° C. and 45 to 45 ° C.
A resin filler of 49 Pa · s was prepared. As a curing agent, an imidazole curing agent (2E4MZ manufactured by Shikoku Chemicals Co., Ltd.)
-CN) 6.5 parts by weight.

D. Manufacturing method of printed wiring board (1) Glass epoxy resin or BT with a thickness of 0.8 mm
The starting material was a copper-clad laminate in which 18 μm copper foils 8 were laminated on both sides of a substrate 1 made of (bismaleimide triazine) resin (see FIG. 1A). First, the copper-clad laminate was drilled, subjected to an electroless plating treatment, and etched in a pattern to form a lower conductor circuit 4 and a through hole 9 on both surfaces of the substrate 1.

(2) Through hole 9 and lower conductor circuit 4
After the substrate on which was formed was washed with water and dried, NaOH (1
0 g / l), NaClO ₂ (40 g / l), Na ₃ PO
₄ A blackening treatment using an aqueous solution containing (16 g / l) as a blackening bath (oxidizing bath), NaOH (19 g / l), NaB
A reduction treatment was performed using an aqueous solution containing H ₄ (5 g / l) as a reduction bath, and roughened surfaces 4 a and 9 a were formed on the entire surface of the lower conductor circuit 4 including the through holes 9 (see FIG. 1 (b)). ).

(3) After preparing the resin filler described in the above C, within 24 hours after the preparation by the following method, the conductive circuit non-formed portion and the conductive circuit in the through hole 9 and on one side of the substrate 1 A layer of the resin filler 10 was formed on the outer edge portion of No. 4. That is, first, the resin filler was pushed into the through holes using a squeegee, and then dried at 100 ° C. for 20 minutes. Next, a mask having an opening corresponding to the conductive circuit non-forming portion is placed on the substrate, and a layer of the resin filler 10 is formed in the conductive circuit non-forming portion having a concave portion using a squeegee. Drying was performed at 20 ° C. for 20 minutes (see FIG. 1C).

(4) One surface of the substrate after the treatment of the above (3) is subjected to belt sander polishing using # 600 belt abrasive paper (manufactured by Sankyo Rikagaku) to form the surface of the inner layer copper pattern 4 and the through holes 9. Polishing was performed so that the resin filler 10 did not remain on the land surface, and then buffing was performed to remove scratches caused by the belt sander polishing. Such a series of polishing was similarly performed on the other surface of the substrate. Then, at 100 ° C for 1 hour, at 120 ° C for 3 hours, at 150 ° C
For 1 hour and a heat treatment at 180 ° C. for 7 hours to cure the resin filler 10.

In this way, the surface portion of the resin filler 10 formed in the through-hole 9 and the portion where the conductor circuit is not formed and the surface of the lower conductor circuit 4 are flattened, and the resin filler 10 and the side surface of the lower conductor circuit 4 are flattened. 4a is firmly adhered through the roughened surface, and the inner wall surface 9a of the through hole 9 and the resin filler 10
Was obtained, thereby obtaining an insulating substrate firmly adhered through the roughened surface (see FIG. 1D). By this step, the resin filler 10
And the surface of the lower conductor circuit 4 are flush with each other.

(5) After the above substrate is washed with water and acid degreased, it is soft-etched, and then an etching solution is sprayed on both surfaces of the substrate by spraying, so that the surface of the lower conductive circuit 4 and the land surface of the through hole 9 and the inner wall are formed. Thus, roughened surfaces 4a and 9a were formed on the entire surface of lower conductor circuit 4 (see FIG. 2A). As an etching solution, an etching solution (Mec etch bond, manufactured by Mec Co.) consisting of 10 parts by weight of imidazole copper (II) complex, 7 parts by weight of glycolic acid, and 5 parts by weight of potassium chloride was used.

(6) The resin composition for forming a roughened surface of the above B (viscosity: 1.5 Pa · s) was applied to both surfaces of a substrate by a roll coater, and allowed to stand in a horizontal state for 20 minutes. 3
Drying was performed for 0 minutes to form a roughened surface forming resin layer 2a. Further, the roughened surface forming resin composition (viscosity: 7 Pa · s) is applied on the roughened surface forming resin layer 2 a using a roll coater, and left in a horizontal state for 20 minutes. Drying was performed at 60 ° C. for 30 minutes to form a roughened surface forming resin layer 2b, and a 35 μm thick roughened surface forming resin layer was formed (see FIG. 2B).

(7) A photomask film on which a black circle having a diameter of 85 μm is printed is brought into close contact with both surfaces of the substrate 1 on which the resin layer for forming a roughened surface has been formed in the above (6), and is 500 mJ / cm by an ultra-high pressure mercury lamp. After exposure at ^two intensities, it was spray-developed with a DMDG solution. Thereafter, the substrate was further exposed to 3000 mJ / cm ² intensity using an ultrahigh pressure mercury lamp,
Heat treatment at 0 ° C. for 1 hour, 120 ° C. for 1 hour, and 150 ° C. for 3 hours, and a 35 μm thick interlayer resin having a via hole opening 6 of 85 μm in diameter and excellent in dimensional accuracy equivalent to a photomask film. An insulating layer 2 was formed (FIG. 2
(C)).

(8) The substrate in which the via hole opening 6 was formed was placed in a 70 ° C. solution containing 800 g / l chromic acid for 19 hours.
For 2 minutes, the surface of the interlayer resin insulation layer 2 was roughened (3 μm depth) by dissolving and removing the epoxy resin particles present on the surface of the interlayer resin insulation layer 2 (see FIG. 2D).

(9) Next, the substrate after the above treatment was immersed in a neutralizing solution (manufactured by Shipley) and washed with water. Further, by applying a palladium catalyst (manufactured by Atotech) to the surface of the substrate subjected to the surface roughening treatment, catalyst nuclei were attached to the surface of the interlayer resin insulating layer 2 and the inner wall surface of the via hole opening 6.

(10) Next, the substrate was immersed in an aqueous electroless copper plating solution having the following composition to form an electroless copper plating layer 12 having a thickness of 0.8 μm on the entire rough surface (FIG. 3 (a)). )reference). [Electroless plating aqueous solution] NiSO ₄ 0.003 mol / l tartaric acid 0.200 mol / l copper sulfate 0.030 mol / l HCHO 0.050 mol / l NaOH 0.100 mol / l α, α'-bipyridyl 40 mg / l Polyethylene glycol (PEG) 0.10 g / l [Electroless plating conditions] 40 minutes at a liquid temperature of 35 ° C

(11) Next, a commercially available photosensitive dry film is attached to the electroless copper plating layer 12, and a mask is placed thereon.
Exposure was performed at 100 mJ / cm ² , and development treatment was performed with a 0.8% aqueous sodium carbonate solution to provide a plating resist 3 having a thickness of 25 μm (see FIG. 3B).

(12) Then, the substrate was washed with water at 50 ° C., degreased, washed with water at 25 ° C., further washed with sulfuric acid, and then subjected to electrolytic copper plating under the following conditions. The layer 13 was formed (see FIG. 4C). [Aqueous electrolytic plating solution] Sulfuric acid 2.24 mol / l Copper sulfate 0.26 mol / l Additive 19.5 ml / l (Acapec Japan, Capparaside GL) [Electroplating conditions] Current density 1 A / dm ² hours 65 minutes temperature 22 ± 2 degrees

(13) Further, the plating resist 3 is coated with 5% KO
After stripping and removing with H, the electroless plating layer 12 under the plating resist 3 was dissolved and removed by etching with a mixed solution of sulfuric acid and hydrogen peroxide to form an independent conductor circuit 5 (including the via hole 7). (See FIG. 3D).

(14) The same treatment as in the above (5) was performed, and a roughened surface was formed with an etching solution containing a cupric complex and an organic acid (see FIG. 4A). (15) By repeating the above steps (6) to (14), a conductor circuit of a further upper layer was formed, and a multilayer wiring board was obtained (FIG. 4).
(B) to FIG. 5 (b)).

(16) Next, a solder resist composition was prepared by the following method. Next, diethylene glycol dimethyl ether (DMD
G), a cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.), which is dissolved to a concentration of 60% by weight, and a sensitized oligomer (molecular weight: 4000) having 50% of epoxy groups acrylated. 80 parts by weight of bisphenol A type epoxy resin dissolved in methyl ethyl ketone (manufactured by Yuka Shell Co., Epicoat 100
1) 6.67 parts by weight, 1.6 parts by weight of imidazole curing agent (2E4MZ-CN, manufactured by Shikoku Chemicals), 4.5 parts by weight of bifunctional acrylic monomer, and similarly polyvalent acrylic monomer (DPE6A, manufactured by Kyoei Chemical Co., Ltd.) 1.5 parts by weight, 0.36 parts by weight of a leveling agent (Polyflow No. 75, manufactured by Kyoei Chemical Co., Ltd.) made of an acrylic acid ester polymer is placed in a container, stirred and mixed to prepare a mixed composition. By adding 2.0 parts by weight of benzophenone (manufactured by Kanto Kagaku) as a photopolymerization initiator, 0.2 parts by weight of Michler's ketone (manufactured by Kanto Kagaku) and 0.6 parts by weight of DMDG to the product, Viscosity 1.4 ± 0.3P at 25 ° C
A solder resist composition adjusted to a · s was prepared.
The viscosity was measured using a B-type viscometer (DVL, manufactured by Tokyo Keiki Co., Ltd.).
-B type) and at 60 rpm, the rotor No. 4, 6r
pm, the rotor No. According to 3.

(17) Next, the above-mentioned solder resist composition was applied to both sides of the multilayer wiring board in a thickness of 20 μm,
After drying at 20 ° C. for 20 minutes and at 70 ° C. for 20 minutes, a 5 mm-thick photomask on which a pattern of the opening of the solder resist is drawn is brought into close contact with the solder resist layer, and an ultraviolet ray of 900 mJ / cm ² is applied. And developed with pure water to form an opening having a diameter of 125 μm. And
In addition, UV cure under the condition of 3000 mJ / cm ² ,
The solder resist layer is cured by performing a heat treatment at 80 ° C. for 1 hour, 100 ° C. for 1 hour, 120 ° C. for 1 hour, and 150 ° C. for 3 hours, and has an opening having a thickness of 25 μm. A solder resist layer 14 was formed.

(18) Next, the substrate on which the solder resist layer 14 was formed was replaced with nickel chloride (30 g / l), sodium hypophosphite (10 g / l), and sodium citrate (10 g / l).
g / l) in the electroless nickel plating solution with pH = 5.
This was immersed for 0 minutes to form a nickel plating layer 15 having a thickness of 5 μm in the opening. Further, the substrate was subjected to potassium gold cyanide (2 g / l), ammonium chloride (75 g / l),
It was immersed in an electroless plating solution containing sodium citrate (50 g / l) and sodium hypophosphite (10 g / l) at a temperature of 93 ° C. for 23 seconds to form a 0.03 μm thick nickel plating layer 15 on the nickel plating layer 15. A gold plating layer 16 was formed.

(19) Thereafter, a solder paste is printed in the openings of the solder resist layer 14 and reflowed at 200 ° C. to form solder bumps (solder bodies) 17.
A multilayer wiring printed board having the solder bumps 17 was manufactured (see FIG. 5C).

Example 2 A. Preparation of Resin Film for Interlayer Resin Insulating Layer (1) Preparation of Resin Composition A First, a red phosphorus-based flame retardant (trade name, Hishigard CP) 1
8.9 parts by weight were mixed with 100 resins of a bisphenol A type epoxy resin (epoxy equivalent: 469, Epicoat 1001 manufactured by Yuka Shell Epoxy Co., Ltd.) to prepare a phosphorus-containing bisphenol A type epoxy resin. Next, 30 parts by weight of the phosphorus-containing bisphenol A type epoxy resin and 40 cresol novolak type epoxy resins (epoxy equivalent: 215, Epicron N-673 manufactured by Dainippon Ink and Chemicals, Inc.)
Parts by weight and a resin composition A.

(2) Preparation of Resin Composition B Triazine structure-containing phenol novolak resin (phenolic hydroxyl equivalent: 120, manufactured by Dainippon Ink and Chemicals, Inc.)
30 parts by weight of phenolite KA-7052) were used as resin composition B. (3) Preparation of Hardener Component C 1.5 parts by weight of a pulverized 2-phenyl-4,5-bis (hydroxymethyl) imidazole product was used as the hardener component C.

(4) Preparation of Mixed Composition D The above resin composition A and the above resin composition B were dissolved by heating in 20 parts by weight of ethylene glycol acetate and 20 parts by weight of solvent naphtha while stirring, and the above-mentioned curing was carried out. By adding and mixing the agent component C, 15 parts by weight of a terminal epoxidized polybutadiene rubber (Denalex R-45EPT manufactured by Nagase Kasei Kogyo Co., Ltd.), 2 parts by weight of finely divided silica, and 0.5 part by weight of a silicon-based antifoaming agent. A mixed composition D (epoxy resin composition) was prepared.

(5) Preparation of Resin Film for Interlayer Resin Insulating Layer The obtained mixed composition D was applied on a 38 μm-thick PET film using a roll coater so that the thickness after drying was 50 μm. At 80 to 120 ° C. for 10 minutes to produce a resin film for an interlayer resin insulating layer. The phosphorus content of the obtained resin film for an interlayer resin insulation layer after drying was 4% by weight.

B. Manufacturing method of printed wiring board (1) 1.0 mm thick glass epoxy resin or BT
A starting material was a copper-clad laminate in which 18 μm copper foils 8 were laminated on both sides of a substrate 1 made of (bismaleimide triazine) resin (see FIG. 6A). First, the copper-clad laminate was etched in a pattern to form a lower conductive circuit 4 on both surfaces of the substrate 1.

(2) The substrate was washed with water and acid degreased, and then soft-etched. Then, an etching solution was sprayed on both sides of the substrate by spraying, and the etching solution was conveyed to the substrate surface by conveyance rolls. Is etched to form a roughened surface 4a on the entire surface of the lower conductive circuit 4 (see FIG. 6B). As an etchant,
An etching solution (Mec etch bond, manufactured by Mec) comprising 10 parts by weight of imidazole copper (II) complex, 7 parts by weight of glycolic acid, and 5 parts by weight of potassium chloride was used.

(3) On both sides of the substrate, a resin film for an interlayer resin insulating layer slightly larger than the substrate prepared in A was placed on the substrate, and the pressure was 4 kgf / cm ² , the temperature was 80 ° C., and the compression time was 10 seconds. After temporary compression bonding and cutting, a layer of a resin film for an interlayer resin insulation layer was formed by bonding using a vacuum laminator under the following conditions (FIG. 6).
(C)). That is, a resin film for an interlayer resin insulation layer is placed on a substrate, and the degree of vacuum is 0.5 Torr and the pressure is 4 k.
The final press bonding was performed at gf / cm ² , at a temperature of 80 ° C. and a pressing time of 60 seconds, and thereafter, thermosetting was performed at 170 ° C. for 30 minutes.

(4) Next, a CO ₂ gas laser having a wavelength of 10.4 μm was applied through a mask having a through-hole having a thickness of 1.2 mm on a resin film for an interlayer resin insulating layer.
Under the conditions of a beam diameter of 4.0 mm, a top hat mode, a pulse width of 8.0 μsec, a diameter of a through hole of the mask of 1.0 mm, and one shot, an opening 6 for a via hole having a diameter of 80 μm is formed. And Further, the substrate on which the interlayer resin insulating layer 2 is formed is drilled to form a through hole 18.
Was formed (see FIG. 6D).

(5) The substrate in which the via hole opening 6 and the through hole 18 were formed was immersed in a solution containing 60 g / l of permanganic acid at 80 ° C. for 10 minutes to form the interlayer resin insulating layer 2.
The surface of the interlayer resin insulating layer 2 was roughened by dissolving and removing the epoxy resin particles present on the surface of FIG.
(A)). Furthermore, surface roughening treatment (roughening depth 6 μm)
Palladium catalyst (made by Atotech) on the surface of the substrate
The catalyst nuclei were attached to the surfaces of the interlayer resin insulating layer 2 and the through holes 18 and the inner wall surfaces 6 of the via hole openings.

(6) Next, the substrate is immersed in an electroless copper plating aqueous solution having the following composition, and has a thickness of 0.6 to 3.
A 0 μm electroless copper plating film 12a was formed (FIG. 7).
(B)). [Electroless plating aqueous solution] NiSO ₄ 0.003 mol / l tartaric acid 0.200 mol / l copper sulfate 0.030 mol / l HCHO 0.050 mol / l NaOH 0.100 mol / l α, α'-bipyridyl 40 mg / l Polyethylene glycol (PEG) 0.10 g / l [Electroless plating conditions] 40 minutes at a liquid temperature of 35 ° C

(7) The substrate on which the electroless plated film 12a was formed was washed with water and dried, and then NaOH (10 g / l), N
aClO ₂ (40 g / l), Na ₃ PO ₄ (6 g / l)
Blackening to blackening bath (oxidizing bath) an aqueous solution containing, and, NaOH (10g / l), NaBH 4 (6g / l)
A reduction treatment was performed using an aqueous solution containing Pb as a reduction bath to form a roughened surface on the entire surface of the electroless plating film 12a.

(8) After preparing the resin filler described in B above, the resin filler 10 was filled in the through hole 29 within 24 hours after the preparation by the following method. That is,
After the resin filler was pushed into the through hole 29 using a squeegee, it was dried at 100 ° C. for 20 minutes. After the drying, buffing was performed to flatten the surface of the electroless plating film 12a and the surface layer portion 10a of the resin filler. Next, at 100 ° C. for 1 hour, at 120 ° C. for 3 hours,
Heat treatment was performed at 150 ° C. for 1 hour and at 180 ° C. for 7 hours to cure the resin filler 10 (see FIG. 7C).

(9) Next, a palladium catalyst (manufactured by Atotech Co.) was applied to the surface layer 10a of the resin filler, whereby catalyst nuclei were attached to the surface layer 10a of the resin filler.
Further, electroless plating is performed under the same conditions as in (6) above,
On the electroless plating film 12a formed in the above (6) and the surface portion 10a of the resin filler, a thickness of 0.6 to 3.0 μm is further added.
m of the electroless plating film 12b was formed (see FIG. 7D). By this step, a cover plating layer could be formed on the through hole 29.

(10) A commercially available photosensitive dry film is adhered to the electroless copper plating film 12b, and a mask is placed thereon.
Exposure was performed at 0 mJ / cm ² , and development was performed with a 0.8% aqueous sodium carbonate solution to provide a plating resist 3 having a thickness of 30 μm (see FIG. 8A).

(11) Then, the substrate was washed with water at 50 ° C., degreased, washed with water at 25 ° C., further washed with sulfuric acid, and then subjected to electrolytic copper plating under the following conditions to give a thickness of 20 μm. Was formed (see FIG. 8B). [Electroplating aqueous solution] sulfuric acid 2.24 mol / l copper sulfate 0.26 mol / l additive 19.5 ml / l (manufactured by Atotech Japan, Capparaside HL) [electroplating conditions] current density 1 A / dm ² hours 65 minutes Temperature 22 ± 2 ℃

(12) After the plating resist 3 is peeled and removed with 5% NaOH, the electroless plating films 12a and 12b under the plating resist 3 are dissolved and removed by etching with a mixed solution of sulfuric acid and hydrogen peroxide. A conductor circuit (including the via hole 7) 5 having a thickness of 18 μm including the electroless copper plating film 12 and the electrolytic copper plating film 13 was formed (see FIG. 8C).

(13) The same treatment as in (5) was performed, and a roughened surface was formed with an etching solution containing a cupric complex and an organic acid (see FIG. 8D). (14) By repeating the above steps (6) to (13), a conductor circuit of an upper layer was further formed to obtain a multilayer wiring board (see FIGS. 9A to 10A).

(15) Next, a solder resist composition was prepared in the same manner as in Example 1. Thereafter, the solder resist composition was applied to both surfaces of the multilayer wiring board in a thickness of 20 μm, and then heated at 70 ° C. After performing a drying process for 20 minutes at 70 ° C. for 20 minutes, a 5 mm-thick photomask on which a pattern of a solder resist opening is drawn is brought into close contact with the solder resist layer and exposed to ultraviolet light of 900 mJ / cm ^2. Then, the resultant was subjected to pure water development to form an opening having a diameter of 125 μm. Then, under the condition of 3000 mJ / cm ² , U
V cure, 80 ° C for 1 hour, 100 ° C for 1 hour, 12
Heat treatment was performed at 0 ° C. for 1 hour and at 150 ° C. for 3 hours to cure the solder resist layer, thereby forming a solder resist pattern layer 14 having an opening and a thickness of 25 μm.

(16) Next, the substrate on which the solder resist layer 14 was formed was coated with nickel chloride (2.3 × 10 ^-1 mol / mol).
l), sodium hypophosphite (2.8 × 10 ⁻¹ mol /
l), sodium citrate (1.6 × 10 ⁻¹ mol /
2) in the electroless nickel plating solution having pH = 4.5 containing l)
This was immersed for 0 minutes to form a nickel plating layer 15 having a thickness of 5 μm in the opening. Furthermore, the substrate gold potassium cyanide ^{(7.6 × 10 -3 mol / l} ), ammonium chloride ^{(1.9 × 10 -1 mol / l} ), sodium citrate (1.2 × 10 ^-1 mol / l), immersed in an electroless gold plating solution containing sodium hypophosphite (1.7 × 10 ^-1 mol / l) for 7.5 minutes at 80 ° C. A gold plating layer 16 of 0.03 μm was formed.

(17) Thereafter, a solder paste containing tin-lead is printed on the opening of the solder resist layer 14 on the surface of the substrate on which the IC chip is to be mounted, and the opening of the solder resist layer 14 on the other surface is further printed. A solder paste containing tin-antimony is printed on the solder paste, the pins are placed on the solder paste, and then reflowed at 200 ° C. to form solder bumps (solder bodies) 17 on the surface on which the IC chip is placed. PGA was formed on the other surface, and a multilayer wiring printed board was manufactured (see FIG. 10B).

Example 3 In the steps A and B of Example 1, when the mixed compositions prepared in (1), (2) and (3) were mixed, 3 parts by weight of alumina having an average particle size of 0.05 μm was used. Parts were added and mixed to prepare the upper layer roughened surface forming resin composition containing the aluminum compound and the lower layer roughened surface forming resin composition, in the same manner as in Example 1, except that the resin composition was prepared. A wiring board was manufactured.

Example 4 In the step (4) of A in Example 2, 3 parts by weight of alumina having an average particle diameter of 0.05 μm was further added and mixed to obtain a mixed composition D containing an aluminum compound. Example 2 except for adjustment
A multilayer printed wiring board was manufactured in the same manner as described above.

Comparative Example 1 A multilayer printed wiring board was manufactured in the same manner as in Example 1 except that the red phosphorus-based flame retardant was not used in the steps A and B of Example 1.

Comparative Example 2 A multilayer printed wiring board was manufactured in the same manner as in Example 2 except that the red phosphorus-based flame retardant was not used in the step A of Example 2.

Comparative Example 3 In step (A) of Example 1, 35.0 parts by weight of a red phosphorus-based flame retardant was blended, and in step (1) B, a red phosphorus-based flame retardant was added. Example 1 except that 0 parts by weight were blended.
A multilayer printed wiring board was manufactured in the same manner as described above. Note that the phosphorus content of the formed interlayer resin insulating layer is 15% by weight.

Comparative Example 4 A multilayer printed wiring board was manufactured in the same manner as in Example 2 except that 147 parts by weight of a red phosphorus-based flame retardant was used in the step (1) of A of Example 2. Note that the phosphorus content of the formed interlayer resin insulating layer is 15% by weight.

Next, Examples 1 to 4 and Comparative Examples 1 to 4
For the multilayer printed wiring board manufactured in the above, by the following methods, the flame retardancy, the opening property, the shape of the inner wall surface of the opening, the occurrence of peeling between the interlayer resin insulating layer and the conductive circuit and the The presence or absence of cracks was evaluated. The results are shown in Table 1.

[0180]Evaluation method  (1) Evaluation of flame retardancy The multilayer printed wiring board is cut in accordance with UL94 standard.
And perform a flame retardancy test by the vertical method.
To evaluate. The dimensions of the test piece were 12.7 mm × 1
27 mm × specified thickness. Evaluation criteria ：: Passed the criteria of 94V-0. X: Failure of the criteria of 94V-0.

(2) Evaluation of Opening Properties In Examples 1 to 4 and Comparative Examples 1 to 4, openings for via holes were formed and cured, and the shape of the openings was changed before forming a plating layer in the openings. Observed under a microscope, and further, after the production of the multilayer printed wiring board is completed, the multilayer printed wiring board is cut at a portion where a via hole is formed, and the cut section is observed with a microscope to form an interlayer resin insulating layer. The cross-sectional shape of the opening thus formed is observed with a microscope and evaluated according to the following evaluation criteria.

Evaluation Criteria 開口: The shape of the opening in plan view is desired, and there is no resin residue on the conductor circuit surface exposed from the opening. ×: The shape of the opening is tapered, and there is a resin residue on the surface of the conductor circuit exposed from the opening, or the opening is unopened.

(3) Observation of the shape of the inner wall surface of the opening In each of Examples 1 to 4 and Comparative Examples 1 to 4, after forming the opening for the via hole, and before forming the roughened surface on the surface of the resin insulating layer. Then, the wiring board having the resin insulating layer is cut at the portion where the opening is formed, and the cut cross section is observed with a microscope to observe the shape of the inner wall surface of the opening, and evaluated according to the following evaluation criteria.

Evaluation criteria ：: The shape of the inner wall surface is smooth. X: The inner wall surface has unevenness.

(4) Observation of Presence or Absence of Peeling or Crack In the same manner as in (2) above, the multilayer printed wiring board after completion of the production was cut, and the cross section was observed with a microscope.
It is observed whether or not peeling has occurred between the interlayer resin insulating layer and the conductor circuit, and further, whether or not cracks have occurred in the interlayer resin insulating layer. In addition, the multilayer printed wiring board was subjected to a heat cycle test in which a cycle of maintaining at −65 ° C. for 3 minutes and then maintaining at 130 ° C. for 3 minutes was repeated 1,000 times, and then, in the same manner as above. Then, it is observed whether peeling has occurred between the interlayer resin insulating layer and the conductor circuit, and further, whether cracks have occurred in the interlayer resin insulating layer.

[0186]

[Table 1]

As shown in Table 1, the multilayer printed wiring boards manufactured in Examples 1 to 4 pass the 94V-0 criterion in the UL94 test standard. Also,
The multilayer printed wiring board is excellent in opening property when forming an opening for a via hole and the like, the shape of the inner wall surface of the opening is smooth, and cracks occur and peeling occurs with a conductor circuit. Nothing to do.

On the other hand, the multilayer printed wiring boards manufactured in Comparative Examples 1 and 2 had a long burning time, and thus had a 94V-0
Does not pass the judgment criteria, and is inferior in flame retardancy. Further, since the multilayer printed wiring board of Comparative Example 2 did not contain phosphorus or the like, when the opening was formed by laser irradiation, the shape of the inner wall surface had unevenness.

The multilayer printed wiring boards of Comparative Examples 3 and 4 passed the criterion of 94V-0 in the UL94 test standard, but had poor opening properties, and exhibited tapered shapes and unopened openings. This is considered to be due to the large amount of phosphorus. Furthermore, peeling and cracks occurred after the heat cycle test, which is considered to be caused by phosphorus movement during the heat cycle test.

[0190]

As described above, the multilayer printed wiring board of the present invention is excellent in flame retardancy, and causes peeling between the conductor circuit and the resin insulating layer and cracks in the resin insulating layer. Connection reliability is excellent. Further, the multilayer printed wiring board of the present invention is excellent in opening property when forming an opening for a via hole and the like and has an opening of a desired shape. Excellent connection reliability. Further, since the method for manufacturing a multilayer printed wiring board of the present invention has the above-described configuration, the multilayer printed wiring board of the present invention can be manufactured with high productivity.

[Brief description of the drawings]

FIGS. 1A to 1D are cross-sectional views showing a part of a manufacturing process of a multilayer printed wiring board according to the present invention.

FIGS. 2A to 2D are cross-sectional views showing a part of a manufacturing process of the multilayer printed wiring board of the present invention.

FIGS. 3A to 3D are cross-sectional views illustrating a part of the manufacturing process of the multilayer printed wiring board according to the present invention.

FIGS. 4A to 4C are cross-sectional views showing a part of the manufacturing process of the multilayer printed wiring board of the present invention.

FIGS. 5A to 5C are cross-sectional views showing a part of the manufacturing process of the multilayer printed wiring board of the present invention.

FIGS. 6A to 6D are cross-sectional views showing a part of the manufacturing process of the multilayer printed wiring board of the present invention.

FIGS. 7A to 7D are cross-sectional views showing a part of the manufacturing process of the multilayer printed wiring board of the present invention.

FIGS. 8A to 8D are cross-sectional views illustrating a part of the manufacturing process of the multilayer printed wiring board according to the present invention.

FIGS. 9A to 9C are cross-sectional views showing a part of the manufacturing process of the multilayer printed wiring board of the present invention.

FIGS. 10A and 10B are cross-sectional views showing a part of the manufacturing process of the multilayer printed wiring board of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Interlayer resin insulation layer (resin layer for forming a roughened surface) 3 Plating resist 4 Lower layer conductor circuit 4a Roughened surface 5 Conductor circuit 6 Opening for via hole 7 Via hole 8 Copper foil 9, 29 Through hole 9a Roughened surface DESCRIPTION OF SYMBOLS 10 Resin filler 12 Electroless copper plating layer 12a Ni metal layer 12b Cu metal layer 13 Electroplating layer 14 Solder resist layer 15 Nickel plating layer 16 Gold plating layer 17 Solder bump 19 Solder 20 pin

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/36 C08K 3/36 C08L 101/00 C08L 101/00 H01L 23/12 H05K 3/28 C H05K 3 / 28 3/38 A 3/38 H01L 23/12 N (72) Inventor: Yukihiko Toyoda 1-1, Ibikawa-cho, Ibi-gun, Gifu Prefecture Ibiden Co., Ltd. Ogaki Kita Plant F-term (reference) 4J002 BB001 BD121 CC031 CC101 CD001 CH071 CM041 DA056 DE077 DE147 DE217 DH006 DH016 DJ007 DJ017 FD017 FD136 GQ00 5E314 AA27 AA32. EE37 EE52 ER16 ER18 ER33 ER39 FF04 GG13 GG16 5E346 AA12 CC04 CC08 CC09 CC10 CC13 CC14 CC16 DD25 DD47 EE08 EE33 EE39 FF03 FF15 FF1 8 FF22 GG15 GG17 GG22 HH07 HH18

Claims (10)

[Claims] 1. A multilayer printed wiring board in which a conductive circuit and a resin insulating layer are sequentially formed on a substrate, and the conductive circuits are connected via via holes, wherein the resin insulating layer includes phosphorus and / or A multilayer printed wiring board comprising a phosphorus compound. 2. The multilayer printed wiring board according to claim 1, wherein said phosphorus is red phosphorus. 3. The multilayer printed wiring board according to claim 1, wherein the phosphorus and the phosphorus compound have a particle size of 0.1 to 15 μm. 4. The content of the phosphorus and the phosphorus compound is as follows:
The multilayer printed wiring board according to claim 1, wherein the content is 0.5 to 10% by weight. 5. The multilayer printed wiring board according to claim 1, wherein the resin insulating layer contains at least one selected from the group consisting of a silicon compound, an aluminum compound, and a magnesium compound. 6. The resin insulating layer is made of an epoxy resin, a phenol resin, a polyolefin resin, a polyphenylene ether (PPE), a polyphenylene oxide (PP).
The multilayer printed wiring board according to any one of claims 1 to 5, comprising at least one selected from the group consisting of O), a fluorine resin and a polyimide resin. 7. The multilayer printed wiring board according to claim 1, wherein the resin insulating layer includes a resin composite made of a thermosetting resin and a thermoplastic resin. 8. The method for manufacturing a multilayer printed wiring board according to claim 1, comprising at least the following steps (1) and (2): Manufacturing method. (1) a step of preparing an uncured resin composition containing phosphorus and / or a phosphorus compound; and (2) a step of forming the uncured resin composition on a substrate on which a conductor circuit is formed or a resin insulating layer on which a conductor circuit is formed. A step of forming a layer of the resin composition by applying the resin composition; 9. The method for manufacturing a multilayer printed wiring board according to claim 1, comprising at least the following steps (1) and (2): Manufacturing method. (1) a step of preparing a resin film containing phosphorus and / or a phosphorus compound; and (2) crimping the resin film on a substrate on which a conductor circuit is formed or a resin insulating layer on which a conductor circuit is formed. A step of forming a resin film layer; 10. The method for manufacturing a multilayer printed wiring board according to claim 7, comprising at least the following steps (1) to (5). (1) a step of preparing a resin composition A containing phosphorus and / or a phosphorus compound and a thermosetting resin; and (2) a step of preparing a resin composition B containing a thermoplastic resin.
(3) a step of preparing a curing agent component C containing a curing agent;
(4) a step of kneading the resin composition A, the resin composition B, and the curing agent component C to prepare a mixed composition D, and then preparing a resin film E made of the mixed composition D; 5) a step of forming a layer of the resin film E by press-bonding the resin film E on a substrate on which the conductor circuit is formed or on a resin insulating layer on which the conductor circuit is formed.