JP3398226B2 - Metal film adherend - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for hardening an adhesive on a substrate.
The adhesive layer is formed by the chemical treatment, and is formed on the adhesive layer.
Metal film on the roughened surface
In particular, it provides an adhesive and an adhesive layer having excellent toughness without deteriorating heat resistance, electrical insulation, and chemical stability, and various metal film adherends having excellent adhesion to a coated metal. We propose the technology to provide it stably.

[0002]

2. Description of the Related Art In recent years, printed circuit boards and wiring boards on which LSIs are mounted have been required to have high densities and high reliability by fine patterns corresponding to the miniaturization or high speed of electronic equipment with the progress of the electronics industry. ing.

[0003] For this reason, recently, as a method of forming a conductor on a wiring board, an adhesive is applied to a substrate surface to form an adhesive layer, and the surface of the adhesive layer is roughened. The additive method of forming a conductor by applying a method has attracted attention. According to this method, a conductor is formed by performing electroless plating after forming a resist, so that wiring with high density and high pattern accuracy can be manufactured at a lower cost than an etched foil method (subtractive method) in which pattern formation is performed by etching. There is a feature that can be manufactured with.

In such an additive method, as a means for improving the adhesion between the conductor and the adhesive layer (hereinafter, referred to as "peel strength"), a method for improving the adhesion between the conductor and the adhesive layer is described below. A method of providing fine unevenness by chemical etching is known.

However, in recent additive type printed wiring boards requiring higher density wiring with high pattern accuracy, in order to form a fine resist pattern with high precision, it is formed by roughening the surface of an adhesive layer. It is necessary to make the anchor even smaller. for that reason,
As the anchor becomes smaller, the fracture area becomes smaller,
There was a problem that the peel strength was significantly reduced.

On the other hand, in the field of automobiles and transportation equipment,
In the fields of electronic components, machinery, household goods, civil engineering and construction, and medical care, metal parts have been replaced with resin parts in recent years due to improvements in engineering plastics. For example, a camera housing and a fixing ring made of polycarbonate, or a bearing made of polyacetal may be used. Furthermore, gears made of ultra-high molecular weight polyethylene have also been developed.

However, these resin parts sometimes need to be coated with a metal film on the surface of the parts in terms of design, corrosion resistance, wear resistance and the like. In such a case, as a means for coating the metal surface on the resin surface,
Conventionally, there has been proposed a method in which an adhesive layer is provided on the surface of a resin substrate, and the surface of the adhesive layer is roughened, and then a metal film is coated. For example, Japanese Patent Publication No. 58-44709 discloses an electroless plating adhesive composed of acrylonitrile butadiene rubber and an epoxy resin applied to the surface of an insulating substrate, and then dissolving and removing the epoxy resin portion on the surface of the adhesive layer. A method of obtaining a metal film coating by performing electroless plating after surface roughening is disclosed. In addition, JP-A-61-276875 discloses that an adhesive for electroless plating is prepared by dispersing a heat-resistant resin fine powder in a heat-resistant resin matrix on a substrate.
Next, a method is disclosed in which a heat-resistant resin fine powder is treated with an oxidizing agent to roughen the surface, and then electrolessly plated.

However, an engineering plastic (base resin) coated with a metal film via an adhesive layer
During the heat cycle, cracks occur due to the difference in thermal expansion coefficient between the base resin and the adhesive layer,
There has been a problem that cracks occur in the adhesive layer itself.

In order to solve such various problems, there is a method of increasing the strength of a coated metal or a heat-resistant resin matrix constituting an adhesive. However, according to experiments conducted by the inventors, copper is used as a coating metal, and a thermosetting resin or a photosensitive resin is used as a heat-resistant resin matrix constituting an adhesive. It was found that the peeling of the film was caused by the destruction of the heat resistant resin matrix. That is, they have found that the cause of the decrease in the adhesion strength is insufficient strength of the heat-resistant resin matrix constituting the adhesive. Furthermore, it was found that the cause of cracks generated during the heat cycle and cracks generated during the stress generation was also due to insufficient strength on the heat-resistant resin matrix side.

[0010]

SUMMARY OF THE INVENTION Therefore, in order to solve the above-mentioned various problems in the prior art, the main object of the present invention is to reduce heat resistance, electrical insulation and chemical stability without reducing the stability. Toughened heat-resistant resin matrix
Develop an adhesive with a coating and cure such an adhesive
Improve the adhesion between the treated adhesive layer and the metal film
To provide a metal film adherend . Still another object of the present invention is to establish a technology capable of stably providing various metal film adherends for printed wiring boards and other industrial parts having excellent peel strength even in high-density wiring with high pattern accuracy. It is in.

[0011]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies on the improvement of the strength of the heat resistant resin matrix constituting the adhesive, and as a result, the heat resistant resin matrix constituting the adhesive has been obtained. As an uncured thermosetting resin containing a resin in which a part of the functional group is substituted by a photosensitive group, and / or a mixed resin of an uncured photosensitive resin and a thermoplastic resin, and further subjected to a curing treatment. By using the resin composite formed as the adhesive layer, even if the anchor depth formed by the roughening treatment is small, it is possible to provide a metal film adherend such as a printed wiring board having excellent adhesive strength with a conductor metal even when the anchor depth is small. And found the present invention.

That is, (1) The composition of the adhesive used in the present invention is as follows: an uncured heat-resistant resin matrix contains a decomposable particulate substance, or an inorganic, metal, elastomer, or alkali-soluble material. In the adhesive obtained by dispersing at least one kind of dissolvable and removable particulate material selected from resin particles and resin particles soluble in a solvent, the heat-resistant resin matrix has a part of functional groups substituted by photosensitive groups. Thermosetting resin containing a cured resin (hereinafter simply referred to as “uncured thermosetting resin”) and / or a resin mixture of an uncured photosensitive resin and a thermoplastic resin. Has a compatibility that forms a resin composite having one of a quasi-homogeneous compatible structure, a bicontinuous structure and a spherical domain structure by a curing treatment. Characterized by comprising the integer. The resin mixture is preferably dissolved in a solvent to be in a compatible state or an incompatible state. When the resin mixture is in a compatible state, when curing it, by adjusting the phase separation rate and the curing rate, it is possible to obtain a pseudo-homogeneous compatible structure, a bicontinuous structure, and a spherical domain structure described below. it can. On the other hand, when the resin mixture is in an incompatible state, it can be cured as it is to obtain a spherical domain structure. Here, as the particulate substance that can be decomposed and removed, it is desirable to use an amino resin having a low degree of cross-linking, which has been subjected to suspension polymerization. Note that, in the present invention, "decomposition removal" is to cause decomposition of the particulate matter by adjusting the atmosphere without using a roughening liquid such as heating, pressurization, and humidity adjustment,
The term "dissolve and remove" means that a particulate substance is dissolved and decomposed by a chemical action using a roughening liquid such as an acid, an alkali, an oxidizing agent, water, and an organic solvent. Also,
In the present invention, the term “resin mixture of a thermosetting resin and / or a photosensitive resin and a thermoplastic resin” refers to. A resin mixture of a curable resin and a thermoplastic resin,. A resin mixture of a photosensitive resin and a thermoplastic resin, or. It means a resin mixture of a thermosetting resin, a photosensitive resin and a thermoplastic resin.

(2) Another constitution of the adhesive used in the present invention is that a resin which is not compatible with the matrix before curing and which can be dissolved and removed after curing in an uncured heat-resistant resin matrix In an adhesive obtained by dispersing a liquid, the heat-resistant resin matrix may be formed of a resin mixture in which the compatibility between an uncured thermosetting resin and / or an uncured photosensitive resin and a thermoplastic resin is adjusted. Features. (3) Still another configuration of the adhesive used in the present invention is that an uncured heat-resistant resin matrix is compatible with the matrix before curing, and can be separated and dissolved and removed after curing after curing. In the adhesive obtained by mixing the resin liquids, the heat-resistant resin matrix is made of a resin mixture in which the compatibility between the uncured thermosetting resin and / or the uncured photosensitive resin and the thermoplastic resin is adjusted. It is characterized by the following. When such a resin mixture is in a compatible state, when curing it, by adjusting the phase separation speed and the curing speed, a pseudo-homogeneous compatible structure, a bicontinuous structure, and a spherical domain structure, which will be described later, are obtained. be able to. On the other hand, when such a resin mixture is in an incompatible state, it can be cured as it is to obtain a spherical domain structure.

(4) The configuration of the adhesive layer used in the present invention is an adhesive layer having a roughened surface formed on a base, and this layer is described in (1) to (3) above. Characterized in that the adhesive is formed by curing the adhesive. That is, at least one selected from a particulate substance that can be decomposed and removed, or at least one selected from inorganic particles, metal particles, elastomer particles, alkali-soluble resin particles, and solvent-soluble resin particles.
Kinds of particles that can be dissolved and removed are formed into a pseudo-homogeneous compatible structure, a co-continuous structure or a spherical domain structure formed by curing a thermosetting resin and / or a resin mixture of a photosensitive resin and a thermoplastic resin. It is dispersed in a heat-resistant resin matrix composed of a resin composite having any of the resin structures.

(5) Another configuration of the adhesive layer used in the present invention is an adhesive layer having a roughened surface formed on a substrate, and this layer is made of a resin that can be dissolved and removed by heat. A cured, heat-resistant resin matrix comprising a resin composite of a curable resin and / or a photosensitive resin and a thermoplastic resin is dispersed in the form of islands in the sea to form a sea-island structure. It is preferable that the resin composite forms a pseudo-homogeneous compatible structure, a bicontinuous structure, or a spherical domain structure. Here, as the resin that can be dissolved and removed, the resin is not compatible with the uncured heat-resistant resin matrix before curing, and forms an “sea-island structure” in an uneven state with the resin matrix after curing. The resin to be cured is compatible with the uncured heat-resistant resin matrix before curing, and is phase-separated from the resin matrix in the course of curing, and after curing, is in a non-uniform state with the resin matrix “sea-island structure” It is desirable to use a resin that forms Phase separation in the process of curing means. Those which cause phase separation by curing of the matrix resin,. A phase separation is caused by curing of both the matrix and the resin to be dissolved and removed,. There is a type in which a phase is separated by heat (temperature) applied at the time of curing and a phase is fixed by curing. In the present invention, the “sea-island structure” refers to a sea having a heat-resistant resin matrix in which a portion having a high concentration of a resin that can be dissolved and removed is present in an island shape. It means a uniform state and the boundary between the sea and the island is unclear. This island may be independent in the sea, or the islands may be continuous.

In such an adhesive layer, the roughened surface is
It is formed by decomposing or dissolving and removing the particulate material which can be decomposed and removed or which can be dissolved and removed, or the resin which has an island structure and which can be dissolved and removed, which is present on the surface of the adhesive layer. The substrate may be a substrate including a printed wiring board on which a conductor circuit is formed, or a substrate having various shapes that can be used industrially, such as a fiber, a bar, and a sphere.

The metal film-coated body according to the present invention has an adhesive layer having a roughened metal coating side on a substrate, and a metal film provided on the roughened surface of the adhesive layer. In this case, the adhesive layer is formed from the resin composite described in the above (4) . That is, the adhesive layer is capable of dissolving and removing at least one kind of particulate matter that can be decomposed and removed, or at least one selected from inorganic particles, metal particles, elastomer particles, resin particles soluble in alkali and resin particles soluble in a solvent. Quasi-homogeneous compatible structure formed by hardening a particulate mixture of a thermosetting resin and / or a resin mixture of a photosensitive resin and a thermoplastic resin,
It is dispersed in a heat-resistant resin matrix composed of a resin composite having either a bicontinuous structure or a spherical domain structure.

Another structure of the metal film-coated body according to the present invention comprises an adhesive layer having a roughened metal coating side on a base, and a metal film coated on the roughened surface of the adhesive layer. In what is provided, the adhesive layer is described in (5) above
It is characterized by being formed from such a resin composite.
That is, the adhesive layer is formed by curing a resin capable of being dissolved and removed in a sea of a heat-resistant resin matrix formed of a cured resin composition of a thermosetting resin and / or a photosensitive resin and a thermoplastic resin. It is characterized by being dispersed in an island shape to form a sea-island structure. The resin composite preferably forms a pseudo-homogeneous compatible structure, a co-continuous structure or a spherical domain structure. Here, as the resin that can be dissolved and removed, the resin is not compatible with the uncured heat-resistant resin matrix before curing, and forms an “sea-island structure” in an uneven state with the resin matrix after curing. The resin to be cured is compatible with the uncured heat-resistant resin matrix before curing, and is phase-separated from the resin matrix in the course of curing, and after curing, is in a non-uniform state with the resin matrix “sea-island structure” It is desirable to use a resin that forms The substrate may be a substrate including a printed wiring board on which a conductor circuit is formed, or a substrate having various shapes that can be used industrially, such as a fiber, a bar, and a sphere.

In the above-mentioned metal film-coated body according to the present invention, a substrate using a substrate as a substrate and etching the coated metal as necessary or coating the metal in a pattern shape becomes a printed wiring board. . Such a printed wiring board is provided with, for example, an adhesive layer formed by dispersing a particulate substance that can be dissolved and removed or decomposed and removed in a cured heat-resistant resin matrix on a substrate. A roughened surface is formed on the conductor forming surface of the adhesive layer, and a printed circuit board further provided with a conductor circuit on the roughened surface, wherein the heat-resistant resin matrix is formed by heat. It is composed of a resin composite of a curable resin and / or a photosensitive resin and a thermoplastic resin, and the resin composite has any one of a pseudo-homogeneous compatible structure, a bicontinuous structure, and a spherical domain structure. It is formed.
Another configuration of the printed wiring board is that a resin which can be dissolved and removed on a substrate is made of a thermosetting resin and / or a cured heat-resistant resin matrix composed of a resin composite of a photosensitive resin and a thermoplastic resin. An adhesive layer dispersed in the form of an island in the sea to form a sea-island structure is provided, and a conductor-formed surface of the adhesive layer is formed with a roughened surface. A conductor circuit is provided on the roughened surface,
The heat-resistant resin matrix comprises a thermosetting resin and / or
Alternatively, it is characterized by being composed of a resin composite of a photosensitive resin and a thermoplastic resin, and the resin composite has a resin structure of any of a pseudo-homogeneous compatible structure, a bicontinuous structure and a spherical domain structure. It is formed.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (1) The metal film adherend of the present invention
The feature is that the resin matrix of the adhesive forming the adhesive layer formed on the substrate is an uncured thermosetting resin and / or a resin mixture of an uncured photosensitive resin and a thermoplastic resin. The resin mixture has a quasi-homogeneous compatible structure by a curing treatment, its compatibility is adjusted so as to form a resin composite having a resin structure of either a bicontinuous structure or a spherical domain structure. In the uncured heat-resistant resin matrix, decomposable particulate matter, or at least one of inorganic particles, metal particles, elastomer particles, alkali-soluble resin particles and solvent-soluble resin particles is removed. The point is that a particulate material that can be dissolved or a resin that can be dissolved and removed is dispersed. In particular, in the adhesive used in the present invention , it is desirable that the resin mixture is homogeneously mixed in a compatible state. This allows
The resin matrix of the adhesive can be toughened without lowering heat resistance, electrical insulation and chemical stability.

The reason why the above-mentioned resin mixture in a compatible state is used as the heat-resistant resin matrix of the adhesive is that a thermosetting resin and / or a photosensitive resin obtained by curing and a thermoplastic resin are used. This is because the resin structure of the resulting resin composite can be easily controlled by the curing conditions.

As a method for uniformly mixing and dispersing an uncured thermosetting resin and / or an uncured photosensitive resin and a thermoplastic resin in a compatible state, a method in which the resin is dissolved in a solvent, There is a method of melting a thermoplastic resin by heating and then mixing a thermosetting resin or a photosensitive resin. Among them, a method in which a resin is dissolved in a solvent is suitably used. This is because the workability is good and the resin can be dissolved at a low temperature. Examples of the solvent include dimethylformamide (DMF), normal methylpyrrolidone (NMP), methylene chloride,
And diethylene glycol dimethyl ether (DMDG).

[0023] In the adhesive used in the present invention, the heat-resistant resin matrix, the compounding ratio of the photosensitive resin and the thermoplastic resin of the thermosetting resin and / or uncured uncured,
It is desirable that the content of the thermoplastic resin is 15 to 50% by weight. The reason is that if the content of the thermoplastic resin is less than 15 wt%, the toughness of the adhesive layer cannot be improved, while
If it exceeds 50% by weight, it is difficult to apply, and it is difficult to form a smooth and uniform adhesive layer.

The viscosity of the adhesive used in the present invention is desirably 0.5 to 10 Pa · s when measured at 25 ° C. The reason for this is that if it exceeds 10 Pa · s, the leveling property decreases and a smooth adhesive surface cannot be obtained. This is because a sufficient roughened surface cannot be obtained, and the adhesion to the coated metal decreases.

(2) The feature of the adhesive layer used in the present invention resides in that a resin composite formed by curing the adhesive described in (1) above under appropriate curing conditions is used. This makes it possible to stably provide an adhesive layer having excellent adhesion to the coated metal.

Here, the reason why a thermosetting resin and / or a resin composite of a photosensitive resin and a thermoplastic resin is used as the heat-resistant resin matrix of the adhesive layer is that when the resin composite is used, the thermosetting resin or the thermosetting resin is used. As a result of being able to express both the unique physical properties of the photosensitive resin and the toughness of the thermoplastic resin, the entire resin matrix can be produced without reducing heat resistance, elastic modulus, electrical insulation and chemical stability. It is because toughness can be improved.

Although the surface of the adhesive layer used in the present invention is roughened, the roughened surface is dispersed in the form of a particulate material that can be decomposed and removed, a particulate material that can be dissolved and removed, or an island shape. The resin which can be dissolved and removed is formed by a so-called octopus pot-shaped recess formed by decomposition or dissolution and removal. Therefore, in the recess, a metal film such as electroless plating is deposited to serve as an anchor, and the resin matrix constituting the recess has high toughness and does not easily break down the resin. The adhesion strength (peel strength) can be maintained high without peeling off from the roughened surface. Further, since the heat resistant resin matrix is excellent in toughness, it is hard to be broken even if the adhesive layer itself is deformed, and can be used even when the substrate is deformed or stressed.

The resin composite in the adhesive layer used in the present invention has a resin structure of any of a pseudo-homogeneous compatible structure, a co-continuous structure and a spherical domain structure. Here, (a). The pseudo-homogeneous compatible structure is a so-called LCST type (Low
Critical Solution Temperature) The resin composite of thermoplastic resin and thermosetting resin or photosensitive resin showing phase diagram has particle diameter of 0.1 μm or less as measured by transmission electron microscope observation. , Meaning that the resin has one glass transition temperature peak value by dynamic viscoelasticity measurement. This state is close to the ideal mixing state of the resin, and is a new concept originally conceived by the inventor. Here, the conditions of the dynamic viscoelasticity measurement in the present invention are as follows: vibration frequency 6.28 rad / sec, heating rate 5 ° C. /
Minutes. In other words, this pseudo-homogeneous compatible structure surpasses the physical properties of a thermoplastic resin such as polyethersulfone (PES) while maintaining the physical properties of a thermosetting resin such as an epoxy resin or a photosensitive resin such as an acrylic resin. It has a more homogenous structure showing the effect of introduction, and has a very strong interaction between the thermosetting resin or the photosensitive resin and the thermoplastic resin. The structure of such a resin composite can be seen from the fact that even if the fractured surface is etched using a solvent that dissolves the thermoplastic resin, the surface state is substantially unchanged from that before etching and is homogeneous. Resin composites that form such a pseudo-homogeneous compatible structure show higher values of fracture strength and tensile strength than those of the respective constituent resins alone.

The effect of the structure of the resin composite is as follows. The thermoplastic resin (for example, PE
This is particularly noticeable when the content of S) is 15 to 50 wt% in solid content. The reason is that the content of thermoplastic resin is 15wt%
If it is less, the effect of toughening is not sufficiently exhibited because the number of thermoplastic resin molecules entangled in the network of the resin component is small.
If the content of the thermoplastic resin exceeds 50 wt%, the interaction between the thermosetting resin or the photosensitive resin and the thermoplastic resin becomes small due to the decrease in the number of crosslinking points.

Such a pseudo-homogeneous compatible structure is obtained by dissolving an uncured thermosetting resin or an uncured photosensitive resin and a thermoplastic resin in a solvent as necessary and mixing them uniformly. It is formed by increasing the speed and / or reducing the phase separation speed so that the particle diameter of the constituent resin particles is 0.1 μm or less as measured by transmission electron microscopy.

Specifically, as a first method, when a thermosetting resin is used, one selected from the curing temperature of the thermosetting resin, the type of curing agent, and the presence or absence of photosensitivity.
At a curing rate exceeding the quasi-homogeneous phase formation point determined by the species or two or more factors, on the other hand, when a photosensitive resin is used, the photocuring factors of the photosensitive resin, such as an initiator, a sensitizer, There is a method of curing at a curing speed exceeding a quasi-homogeneous phase formation point determined by monomers, exposure conditions, and the like. Here, the quasi-homogeneous phase formation point means that the particle size of the resin particles constituting the composite is 0.1 μm as measured by TEM observation.
It means the lower limit of the curing rate at which the following pseudo-homogeneous compatible structure can be obtained.

As a second method, the formation of a quasi-homogeneous phase determined by at least one of the number of functional groups or the molecular weight in one molecule of an uncured thermosetting resin or an uncured photosensitive resin. There is a method of curing at a phase separation rate not exceeding the point. The quasi-homogeneous phase formation point is defined as the upper limit of the phase separation speed at which a quasi-homogeneous compatible structure in which the particle size of the resin particles constituting the composite is 0.1 μm or less as measured by TEM observation can be obtained. Means

Further, as a third method, there is a method of curing at a curing speed exceeding the above-mentioned pseudo-homogeneous phase formation point and at a phase separation rate not exceeding the above-mentioned pseudo-homogeneous phase formation point. This means a method in which the factors determining the curing rate and the phase separation rate interact.

Next, the interrelation of the above-mentioned various factors which determine the curing rate or the phase separation rate will be described. First, as for the factors that determine the curing speed, assuming that other factor conditions are constant, the higher the curing temperature of the thermosetting resin, the faster the curing speed. Therefore, when the thermosetting resin is cured beyond the lower limit of the curing temperature required to obtain a curing speed exceeding the quasi-homogeneous phase formation point, the structure of the obtained resin composite becomes a quasi-homogeneous compatible structure. The shorter the gelling time, the faster the curing speed. Therefore, when the thermosetting resin is cured using a curing agent that does not exceed the upper limit of the gelation time necessary to obtain a curing rate exceeding the quasi-homogeneous phase formation point, the structure of the obtained resin composite becomes pseudo- A homogeneous compatible structure results. The curing speed increases as the photosensitivity increases. Therefore, in a combination in which another factor condition forms a pseudo-homogeneous compatible structure, by imparting photosensitivity to the resin, the obtained resin composite has a more homogeneous pseudo-homogeneous compatible structure. The method of imparting photosensitivity includes a method of introducing a photosensitive group into a thermosetting resin or a thermoplastic resin, and a method of blending a photosensitive monomer. If necessary, a photoinitiator and a photosensitizer may be used. May be blended. Further, a photosensitive resin such as an acrylic resin can be used instead of the thermosetting resin. In this case, it is necessary to cure the photosensitive resin at a curing rate exceeding a pseudo-homogeneous phase formation point determined by a photocuring factor such as an initiator, a sensitizer, a photosensitive monomer, and exposure conditions. However, when photosensitivity is given to the thermosetting resin or when a photosensitive monomer is added to improve the resolution of development, the uncured thermosetting resin and / or the uncured photosensitive resin may be used. And the thermoplastic resin have reduced compatibility and cause phase separation even at relatively low temperatures (see FIGS. 10 to 12). Therefore, when imparting photosensitivity to a thermosetting resin or when imparting a photosensitive monomer, the adhesive is dried at a low temperature (30 to 60 ° C.) and vacuum-dried as necessary, and then exposed and cured once. Then, by performing heat curing (80 to 200 ° C.), a pseudo-homogeneous compatible structure can be obtained.

In view of the above facts, when one kind of the above-mentioned variable factor is involved in the compounding of the thermosetting resin or the photosensitive resin and the thermoplastic resin, the value of the factor corresponding to the quasi-homogeneous phase formation point is One point is decided. Therefore, when there are two or more of the above-mentioned variables, various combinations of the values of the factors corresponding to the pseudo-homogeneous phase formation point can be considered. That is, the particle size of the constituent resin particles is a value measured by TEM observation.
A combination exhibiting a curing speed of 0.1 μm or less can be selected.

Next, regarding the factors that determine the phase separation rate, assuming that other factors are constant, the larger the number of functional groups in one molecule of the uncured thermosetting resin or the uncured photosensitive resin, the more the phase separation becomes. Less likely to occur (phase separation speed is slower).
Accordingly, an uncured thermosetting resin or an uncured photosensitive resin having a number of functional groups in one molecule exceeding the lower limit of the number of functional groups in one molecule necessary to obtain a phase separation rate not exceeding the quasi-homogeneous phase formation point When the resin composite is cured using, the structure of the obtained resin composite becomes a pseudo-homogeneous compatible structure. As the molecular weight of the uncured thermosetting resin or uncured photosensitive resin increases, phase separation is less likely to occur (the phase separation speed decreases). Therefore, when cured using an uncured thermosetting resin or uncured photosensitive resin having a molecular weight exceeding the lower limit of the molecular weight required to obtain a phase separation rate not exceeding the pseudo-homogeneous phase formation point, the resulting resin composite The body structure is a quasi-homogeneous compatible structure.

In consideration of such a fact, when one kind of the above-mentioned variable factor is used in the compounding of the thermosetting resin or the photosensitive resin and the thermoplastic resin, the value of the factor corresponding to the quasi-homogeneous phase formation point is reduced. One point is decided. Therefore, when the above-mentioned variable factors are two kinds, various combinations of the values of the factors corresponding to the quasi-homogeneous phase formation point can be considered. That is, the particle size of the constituent resin particles is a value measured by TEM observation.
A combination that exhibits a phase separation speed of 0.1 μm or less can be selected.

In such a quasi-homogeneous compatible structure of the resin composite, an epoxy resin can be used as the thermosetting resin.
It is desirable to use about 1000. The reason is that it is difficult to produce an epoxy resin having an epoxy equivalent of less than 100, while if it exceeds 1,000, it is difficult to mix it with a thermoplastic resin such as PES, and the Tg point is lowered, so that it is harder to cure. This is because phase separation easily occurs during heating, and it is difficult to obtain a pseudo-homogeneous compatible structure. The molecular weight of the epoxy resin is preferably from 200 to 10,000.
The reason is that if the molecular weight of the epoxy resin is less than 200, a sufficient reaction rate cannot be obtained, and even if the epoxy resin is cured, the cured product is too hard and brittle. This is because the compatibility is reduced. PES can be used as the thermoplastic resin, and the molecular weight of PES is desirably 3000 to 100,000. The reason for this is that if the molecular weight of PES is less than 3000, the effect of improving toughness due to the pseudo-homogeneous compatible structure cannot be obtained, while if it exceeds 100000, a compatible state with the thermosetting resin or the photosensitive resin cannot be formed. Because.

As described above, a resin composite exhibiting a quasi-homogeneous compatible structure has specific properties exhibited by a thermosetting resin such as an epoxy resin or specific properties exhibited by a photosensitive resin such as an acrylic resin. At the same time, a physical property value higher than the original physical property of a thermoplastic resin such as PES can be exhibited. That is, the PES-modified epoxy resin or the PES-modified acrylic resin according to the present invention has a higher strength than the resin strength of PES alone, and has an unprecedented toughening effect of the epoxy resin or acrylic resin.

(B) The bicontinuous structure means a composite structure in which interconnected spherical particles rich in a thermosetting resin such as an epoxy resin exist in a matrix rich in a thermoplastic resin such as PES. (Takashi Inoue, POLYMER, 30, p662
(1989)). In the structure of such a resin composite, when the fracture surface thereof is etched using a solvent that dissolves the thermoplastic resin, the matrix portion rich in the thermoplastic resin is melted, and only spherical particles such as connected epoxy resin are observed. It is understood from that. The resin composite forming such a co-continuous structure is a tougher resin than a single thermosetting resin such as an epoxy resin because a thermoplastic resin having excellent toughness exists as a continuous phase.

(C). The spherical domain structure mainly refers to a structure in which spherical domains made of a thermosetting resin or a photosensitive resin are independently and uniformly dispersed in a resin matrix of a thermoplastic resin. Point. The structure of such a resin composite is such that when a fracture surface thereof is etched using a solvent that dissolves a thermoplastic resin, a thermoplastic resin-rich matrix portion is melted and independently and uniformly dispersed in a thermosetting resin. It can be seen from the observation that only spherical particles are observed.
A resin complex forming such a spherical domain structure is:
Since the thermosetting resin spherical particles are dispersed in the “sea” of the thermoplastic resin, the resin becomes tougher than the thermosetting resin alone.

The effect of the bicontinuous structure and the spherical domain structure of the resin composite is that the content of the thermoplastic resin (eg, PES) in the composite is 15 to 50 wt.
% Is particularly noticeable. The reason is that if the content of the thermoplastic resin is less than 15 wt%, the effect of toughening is not sufficiently exhibited because the number of thermoplastic resin molecules entangled in the network of the resin component is small, while the content of the thermoplastic resin is 50 wt%. %, The interaction between the thermosetting resin or the photosensitive resin and the thermoplastic resin decreases due to the decrease in the number of crosslinking points.

In such a resin composite, the average particle diameter of the spherical particles constituting the bicontinuous structure or the spherical domain structure is preferably more than 0.1 μm and 5 μm or less. The reason for this is that the average particle size of the spherical particles is
If it is less than 0.1 μm, it is difficult to form a bicontinuous structure or a spherical domain structure, while if it exceeds 5 μm,
This is because the toughness cannot be improved, and the photosensitive characteristics and heat resistance also decrease.

The above-mentioned co-continuous structure or spherical domain structure controls the substitution ratio of a functional group involved in thermosetting of a thermosetting resin with a photosensitive group, or adjusts the type and molecular weight of the photosensitive resin. Or mixing the uncured thermosetting resin and / or the uncured photosensitive resin with the thermoplastic resin in a compatible state or incompatible state, and then adjusting the drying conditions and the curing conditions. Thus, the particles are formed by setting the average particle diameter of the spherical particles to be more than 0.1 μm and 5 μm or less. In addition, a thermosetting resin and / or a photosensitive resin may be used as the resin matrix, and a thermoplastic resin may be used as a resin that forms mutually connected or independent spherical domains.

As described above, the adhesive layer used in the present invention is formed of a resin composite having a resin structure of any of a pseudo-homogeneous compatible structure, a bicontinuous structure and a spherical domain structure. However, it is preferable to form a quasi-homogeneous compatible structure because a resin formed from a quasi-homogeneous compatible structure can obtain higher resin strength than a bicontinuous structure or a spherical domain structure. Is more preferable as the resin matrix of the adhesive layer.

The thickness of the adhesive layer used in the present invention is desirably 10 to 200 μm. The reason for this is that if the thickness of the adhesive layer is less than 10 μm, the adhesion strength (peel strength) decreases, while if it exceeds 200 μm, it is difficult to remove the solvent in the adhesive, and drying and curing occur. Is difficult.

(3) The feature of the metal film-coated body according to the present invention is that a substrate has a roughened adhesive layer on its surface, and a metal film is provided on the roughened surface of the adhesive layer. In the metal film adherend, the adhesive layer has a resin composite as described in the above (2), that is, any one of a resin structure of a pseudo-homogeneous compatible structure, a bicontinuous structure or a spherical domain structure. It is in the point formed.

The surface of the adhesive layer in the metal film-coated body of the present invention is roughened, but the roughened surface is formed of particulate matter, inorganic particles, metal particles, elastomer particles, which can be decomposed and removed. At least one kind of particulate matter selected from alkali-soluble resin particles and solvent-soluble resin particles, or an island-shaped dissolvable resin, which can be decomposed and removed or dissolved and removed, so-called octopus pot-shaped Are formed. Therefore, this recess is
Since the coating metal such as electroless plating is deposited and serves as an anchor, and the resin matrix that constitutes the concave portion has high toughness and the resin does not easily break down, the metal coating may peel off from the roughened surface of the adhesive layer. Therefore, the adhesion strength (peel strength) can be kept high.

In the metal film-coated body according to the present invention, a printed wiring board can be obtained by using a substrate as a substrate and etching or coating the coated metal in a pattern. Further, such a printed wiring board can be formed into a multilayer. In this case, it is preferable that the roughened surface has R _max = 1 to 20 μm. The reason for this is that if it is less than 1 μm, the adhesion strength between the coating metal and the adhesive layer decreases, and if it exceeds 20 μm, it becomes difficult to manufacture a fine-pattern printed wiring board with a pattern interval of 100 μm or less. .

According to such a printed wiring board, the heat-resistant resin matrix constituting the adhesive can be toughened without lowering the heat resistance, the elastic modulus, the chemical stability and the electric insulation. In addition, it is possible to stably provide a wiring board having excellent peel strength even in a wiring having a higher density and a higher pattern accuracy.

In the adhesive, adhesive layer and metal film adherend of the present invention as described above, the thermosetting resin used for the heat-resistant resin matrix may be a phenol resin, a melamine resin or an amino resin such as a urea resin. , An epoxy resin, an epoxy-modified polyimide resin, an unsaturated polyester resin, a polyimide resin, a urethane resin, a diallyl phthalate resin, and the like. The reason for this is that these resins have excellent thermal and electrical properties. As the thermosetting resin, a resin in which a part of a functional group that partially contributes to thermosetting is substituted with a photosensitive group can be used. For example, an acrylate of 5 to 70% of an epoxy resin is preferable.

The thermoplastic resin used for the heat-resistant resin matrix includes polyethersulfone (PES), polysulfone (PSF), phenoxy resin, polyetherimide (PEI), polystyrene, polyethylene, polyarylate, polyamideimide, polyphenylene sulfide, and the like. Polyether ether ketone, polyoxybenzoate, polyvinyl chloride, polyvinyl acetate, polyacetal, polycarbonate and the like can be used. The reason for this is
These thermoplastics have high heat resistance, are tough,
In addition, the use of a solvent makes it compatible with the thermosetting resin.

In particular, the above-mentioned thermosetting resin and thermoplastic resin are preferably epoxy resin and polyether sulfone (PES), respectively. The reason for this is that the epoxy resin, which is a component of the resin matrix, and PES are mixed and dispersed in a solvent such as methylene chloride or dimethylformamide to easily form a quasi-homogeneous compatible structure, a bicontinuous structure, and a spherical domain structure. is there. Moreover,
When a mixed system of an epoxy resin and PES is used, the matrix is toughened by forming a pseudo-homogeneous compatible structure of the PES-modified epoxy resin, and the tensile strength and the tensile elongation are both higher than those of the epoxy resin alone.
It was found that it improved 1.5 times or more. Furthermore, due to the toughness of this resin matrix, even when the anchor depth is the same, the peel strength of the electroless plating film in the printed wiring board using the adhesive or the adhesive layer of the present invention is such that only epoxy resin is used as the resin matrix. The inventors have confirmed that the value is higher than that in the case of using.

In the present invention, as the above-mentioned thermosetting resin and / or thermoplastic resin, a resin to which a photosensitive group is added, or a resin to which a photosensitive resin or a monomer is added can be used. The reason for this is that, in the case of a resin composite having a quasi-homogeneous compatible structure, by imparting a photosensitive group to a thermosetting resin or the like, the thermosetting resin is cured in a short time by exposure and phase separation does not proceed. This is because a composite can be formed and a pseudo-homogeneous compatible structure can be easily formed. On the other hand, in the case of a resin composite having a bicontinuous structure or a spherical domain structure, the shape (particle size, etc.) of the particles having a bicontinuous structure or a spherical domain structure
Is easy to control.

In the present invention, a photosensitive resin can be used instead of providing a photosensitive group to a thermosetting resin or the like. As such a photosensitive resin, an acryloyl group, a methacryloyl group, an allyl group, those having one to several unsaturated double bonds in the molecule such as a vinyl group can be used,
Epoxy acrylate, polyester acrylate, polyether acrylate, silcon acrylate, polybutadiene acrylate, polystyrene ethyl methacrylate, vinyl / acrylic oligomer (monomers with branched acids, acid anhydrides, hydroxy groups, glycidyl groups and vinyl or acrylic polymers Copolymerized and then reacted with an acrylic monomer), polyethylene / thiol (copolymer of olefin and mercaptan) and the like are preferably used.

Here, photoinitiators which are important as photocuring factors of the photosensitive resin include intramolecular molecules such as benzoisobutyl ether, benzyldimethyl ketal, diethoxyacetophenone, acyloxime ester, chlorinated acetophenone, and hydroxyacetophenone. Bond cleavage type,
Benzophenone, Michler's ketone, dibenzosuberone,
Any one or more of intramolecular hydrogen abstraction types such as 2-ethylanthraquinone and isobutylthioxanthone are preferably used.

Examples of the photoinitiating aid include triethanolamine, Michler's ketone, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid (n-butoxy). Any one or more of ethyl, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and polymerizable tertiary amine are used.

Suitable sensitizers include Michler's ketone, Irgacure 651, isopropylthioxanthone, and the like. Some of the above photoinitiators act as a sensitizer. The composition ratio of the photoinitiator to the sensitizer is, for example, benzophenone / Michler's ketone = 5 parts by weight / 0.5 parts by weight Irgacure 184 / Irgacure 651 = 5 parts by weight / 0.5 parts by weight with respect to 100 parts by weight of the photosensitive resin. Parts Irgacure 907 / isopropyl thioxanson = 5 parts by weight / 0.5 parts by weight is preferred.

As a photosensitive monomer or a photosensitive oligomer constituting the photosensitive resin, epoxy acrylate, epoxy methacrylate, urethane acrylate, polyester acrylate, polystyryl methacrylate and the like are preferably used.

When an epoxy resin is used as the thermosetting resin, an imidazole-based curing agent, diamine, polyamine, polyamide, organic acid anhydride, vinyl phenol, or the like can be used as the curing agent for the resin matrix of the present invention. On the other hand, when a thermosetting resin other than the epoxy resin is used, a known curing agent can be used.

Next, the dissolvable particulate material or the dissolvable particulate material used in the present invention and the dissolvable resin used in the form of islands dispersed in the sea of the heat-resistant resin matrix will be described. This will be described in detail.
. The particulate matter that can be dissolved and removed includes, as such a substance, “dissolved and removed at least one or more selected from inorganic particles, metal particles, elastomer particles, alkali-soluble resin particles, and solvent-soluble resin particles. "Possible particulate matter" can be used. (a). Examples of the inorganic particles include oxides such as silica, alumina, zirconia, zinc oxide, magnesia, cordierite, and titania; carbides such as silicon carbide and boron carbide; and nitrides such as aluminum nitride, boron nitride, and silicon nitride. And carbonates such as calcium carbonate and sodium carbonate, sulfates such as barium sulfate, and talc. The reason for using such inorganic particles is that there is an effect of reducing the coefficient of thermal expansion of the heat-resistant resin matrix (resin composite), and the heat cycle resistance can be improved. In particular, when inorganic particles having high thermal conductivity such as silicon carbide and aluminum nitride are used, the thermal conductivity of the adhesive layer can be improved. (b) As the metal particles, aluminum, nickel, magnesium, copper, zinc, iron and the like can be used. The reason why such metal particles are used is that electromagnetic characteristics can be imparted to the adhesive layer itself. (c). Examples of the elastomer particles include polybutadiene rubber, butadiene styrene rubber, butadiene acrylonitrile rubber, polychloroprene rubber, polyisoprene rubber, acrylic rubber, polysulfuric synthetic rubber, urethane rubber, fluorine rubber, silicone rubber and ABS resin. Rubber-based resin, polyester elastomer, polystyrene-polybutadiene-polystyrene (SBS) thermoplastic elastomer, polyolefin-based thermoplastic elastomer (TP
O) and thermoplastic elastomers such as polyvinyl chloride-based thermoplastic elastomers. The reason for using such elastomer particles is that they are non-heat-resistant particles, are relatively inexpensive, and are effective in reducing costs. (d). As the alkali-soluble resin particles, cellulose resins such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, cellulose propionate, and ethyl cellulose can be used. The reason for using such alkali-soluble resin particles is that there is no need for a neutralization treatment such as that found in an oxidizing agent, and that it is economical. This is because it is easy and safety is excellent. (e).
Thermoplastic resin powders such as styrene-based resins, vinyl chloride-based resins, and vinyl acetate-based resins can be used as the resin particles dissolved in the above-mentioned solvents (particularly, organic solvents). The reason for using resin particles that dissolve in such a solvent is that the surface of the adhesive layer can be roughened without using an oxidizing agent such as chromic acid, so that there is no need to neutralize the waste liquid, and the production is simplified. This is because the cost can be reduced. Since the inorganic particles and the metal particles are insoluble in a diluting solvent that dissolves a thermosetting resin, a photosensitive resin, and a thermoplastic resin, the inorganic particles are reduced by reducing the viscosity of the resin solution with the diluting solvent. And metal particles are uniformly dispersed in the resin solution. Further, when obtaining a resin composite having a quasi-homogeneous compatible structure, a solvent is used to mix a thermosetting resin or a photosensitive resin in a compatible state with a thermoplastic resin. The metal particles do not dissolve in the solvent and can form a distinct anchor

[0062] As the particulate substance that can be decomposed and removed, an amino resin (melamine resin, urea resin, guanamine resin) having a low degree of cross-linking and emulsion-polymerized can be used as such a substance. The reason for using such a particulate material that can be decomposed and removed is, for example, that the emulsion-polymerized low-crosslinking melamine resin particles have high humidity, high temperature,
Decomposes under high pressure to form formalin and melamine monomers. Therefore, for the roughening treatment of the adhesive layer surface,
This is because there is no need to specially immerse in the roughening liquid, and the production equipment is simplified, which is advantageous.

[0063] The resin that can be dissolved and used in the form of islands dispersed in the sea of the heat-resistant resin matrix is not compatible with the uncured heat-resistant resin matrix before curing, and the resin matrix after curing. The resin that forms the "sea-island structure" in an inhomogeneous state is compatible with the uncured heat-resistant resin matrix before curing, but after curing, separates from the resin matrix and becomes inhomogeneous with the resin matrix And a resin that forms a “sea-island structure”. Examples of the former resin include an epoxy-terminated silicone resin. Examples of the latter resin include rubber resins such as the above-mentioned butadiene and ABS resin, and thermoplastic resins such as polyester elastomer. For example, the rubber-based resin is soluble in the compatibilizing solvent of the uncured heat-resistant resin matrix, but is not compatible with the uncured heat-resistant resin matrix itself, and the region (island) where the concentration of the rubber-based resin is high is uncured. It is formed in a heat-resistant resin matrix (sea) and exhibits a non-uniform concentration (sea-island structure). Such a resin liquid forming the “sea-island structure” is called “island”
It is difficult to control the size of the product, and it is difficult to control the quality. In this point, it is disadvantageous in mass production as compared with a resin that does not require a curing treatment such as a resin that has been cured in advance and inorganic or metal particles that can easily control the particle size by controlling the particle size by classification or the like. Furthermore, in order for the uncured heat-resistant resin matrix to have a pseudo-homogeneous compatible structure, curing conditions must be adjusted. Also in this respect, if the uncured resin liquid as described above is present, it is disadvantageous that the conditions for curing the resin liquid must be adjusted. However, the resin liquid that forms the “sea-island structure” does not include solid components such as pre-cured resin, inorganic particles, and metal particles, so that kneading time can be reduced and the adhesive solution can be used. It is excellent in that it can be easily prepared. Further, since the viscosity can be easily reduced, the coating film has excellent smoothness and leveling property. In addition, in place of the above-mentioned decomposable and removable particulate material, dissolvable and removable particulate material or dissolvable and removable resin, use of a cured heat-resistant resin powder soluble in an acid or an oxidizing agent. Can also. The heat-resistant resin powder becomes insoluble in a diluting solvent that dissolves a thermosetting resin, a photosensitive resin, and a thermoplastic resin by a curing process. This is because the used heat-resistant resin powder is uniformly dispersed in the resin solution. When a resin composite having a quasi-homogeneous compatible structure is obtained, a solvent is used to mix a thermosetting resin or a photosensitive resin in a compatible state with a thermoplastic resin. Since the above heat-resistant resin powder is not dissolved in the solvent, a clear anchor can be formed.
In addition, the reason that it is desirable to be soluble in an acid or an oxidizing agent is that the oxidizing agent has a strong decomposing ability, can form a clear anchor in a short time, is excellent in productivity, and is formed by this oxidizing agent. The adhesive layer with the anchors provided is
This is because there is almost no dissolution or deterioration under a normal use environment. On the other hand, acids are economical because they do not require a neutralization treatment as found in oxidizing agents, and are easier to dispose of waste liquid than oxidizing agents, etc. It is because it is also excellent in nature. As the heat-resistant resin powder, epoxy resin, amino resin (melamine resin, urea resin, guanamine resin), polyester resin, bismaleidotriazine resin, and the like can be used.

In the present invention, as the particulate matter, various shapes such as a spherical shape, a hollow shape, and a crushed piece shape can be used. In particular, (1) particles having an average particle size of 10 μm or less, (2) average particle size
Agglomerated particles having an average particle size of 2 to 10 μm by agglomerating powder of 2 μm or less; (3) a mixture of powder having an average particle size of 2 to 10 μm and a powder having an average particle size of 2 μm or less; 2-10
It is desirable to select from pseudo particles obtained by adhering at least one selected from powder having an average particle size of 2 μm or less or inorganic powder having an average particle size of 2 μm or less on the surface of the powder having a particle size of μm. The reason for this is that if the average particle size exceeds 10 μm, the anchor becomes deeper and a so-called fine pattern of 100 μm or less cannot be formed.On the other hand, the aggregated particles of the above (2), a mixture of (3) or (4) Pseudo-particles are desirable because they can form complex anchors and improve peel strength. It is desirable that the surface of the particulate matter is coated with silica sol or the like in order to prevent aggregation. The compounding amount of this particulate matter is 100% of the resin solid content of the heat resistant resin matrix.
Is preferably 5 to 100 by weight. The reason is that if the weight ratio is less than 5, an anchor cannot be formed, and if it exceeds 100, kneading becomes difficult, and the amount of the heat resistant resin matrix is relatively reduced, and the adhesive layer This is because the strength of the steel is reduced.

In the present invention, an epoxy resin is used as a thermosetting resin component constituting a heat-resistant resin matrix which is hardly soluble in a roughening liquid such as an acid or an oxidizing agent. Epoxy resin powder can also be used as the heat-resistant resin powder soluble in the roughening liquid. This point will be described below by taking solubility in an oxidizing agent as an example. Epoxy resins are controlled by controlling the type of prepolymer (a relatively low molecular weight polymer with a molecular weight of about 300 to 10,000), the type of curing agent, and the crosslinking density.
Their physical properties can differ greatly. This difference in physical properties is no exception to the solubility in the oxidizing agent, and the solubility can be adjusted to an arbitrary value by appropriately selecting the skeleton structure of the monomer, the curing agent, the crosslinked structure, and the crosslink density. , Becomes the main factor, and uses the secondary. Here, regarding the skeleton structure of the monomer, generally, the aliphatic epoxy has the highest solubility, and then the glycidylamine type and the glycidyl ether type have the lowest solubility. Regarding the crosslinked structure, for example, a hydroxyether structure obtained by a reaction of an epoxide and an amine has particularly high solubility, and an ether structure obtained by reacting an epoxide with imidazole as a curing catalyst has particularly low solubility. The crosslink density decreases as the epoxy equivalent increases, resulting in higher solubility. In addition, the decrease in solubility is achieved by polyfunctionalizing the epoxy monomer. In the phenol novolak type, the repeating unit n of the monomer is from 0 to 1, 2
, The solubility decreases. Therefore, based on the solubility difference with respect to the oxidizing agent, for example, as the “epoxy resin soluble in the oxidizing agent” constituting the heat-resistant resin powder, (A) “aliphatic epoxy is used as an epoxy prepolymer, and An epoxy resin which is gently crosslinked with an epoxy equivalent of about 265 using an aromatic amine curing agent "is used. On the other hand, as a thermosetting resin component of the heat-resistant resin matrix, "a hardly soluble (including insoluble) epoxy resin" in an oxidizing agent,
(B) "Bisphenol A as epoxy prepolymer
Epoxy resin with an epoxy equivalent of around 170 using an epoxy resin with an epoxy equivalent of about 170 using an aromatic diamine-based curing agent as a curing agent, and (C) a phenol novolac epoxy as an epoxy prepolymer. An epoxy resin having an epoxy equivalent of about 136 using a resin and an imidazole curing agent as a curing agent ”is used. In addition, the epoxy resin (B) can be used as an “epoxy resin soluble in an oxidizing agent”. In this case, the epoxy resin (C) is used as an “epoxy resin hardly soluble in an oxidizing agent”.

As can be understood from the above-described examples, whether soluble or hardly soluble (or insoluble) in a roughening solution such as an acid or an oxidizing agent depends on relative to the roughening solution such as an acid or an oxidizing agent. It means the difference in dissolution rate. That is, as a resin soluble in a roughening liquid such as an acid or an oxidizing agent, or an insoluble resin powder, those having a difference in solubility may be arbitrarily selected. The means for giving a difference in solubility to the resin is not limited to the adjustment of the type of prepolymer, the type of curing agent, and the crosslinking density, but may be other means. Table 1 lists the relative values of the prepolymer, curing agent, epoxy equivalent, and solubility for each of the above epoxy resins.

[0067]

[Table 1]

In the present invention, a roughening treatment with an oxidizing agent or the like is performed for a certain period of time by utilizing the difference in solubility between the epoxy resins as described above. By performing such a treatment, the soluble epoxy resin fine powder having the highest solubility in the oxidizing agent or the like is strongly dissolved, and a large concave portion is formed. At the same time, an epoxy resin matrix containing a thermoplastic resin that is hardly soluble in an oxidizing agent or the like remains, and FIG.
The roughened surface (anchor) shown in FIG.

In the present invention, a thermosetting resin such as an epoxy resin is used as a heat-resistant resin matrix.
A mixture of such thermoplastic resins is used, and by including such a thermoplastic resin, a tendency is observed that the solubility in acids, oxidizing agents, and the like is reduced. In particular,
When a resin composite having a quasi-homogeneous compatible structure was used as a heat-resistant resin matrix, the solubility was significantly reduced.

Next, a method for manufacturing the metal film-coated body of the present invention will be described. . First, the adhesive of the present invention, an adhesive mainly composed of a resin mixture of an uncured thermosetting resin and / or an uncured photosensitive resin and a thermoplastic resin, is applied onto a substrate, or An adhesive layer is provided by laminating a film obtained by semi-curing the adhesive itself, or by forming the substrate itself with the adhesive. Further, the adhesive layer is dried and hardened to form an adhesive layer in which the resin composite constituting the resin matrix has any one of a pseudo-homogeneous compatible structure, a co-continuous structure and a spherical domain structure.

Here, examples of the base include the following bases made of metal, resin, and paper, and are formed into a predetermined shape. (Magnetic media) Polyethylene terephthalate film, hard magnetic disk (electromagnetic shield) Filter paper (automobile) Disk brake body, disk brake piston,
Clutch hubs, oil pump cams, transmission gear shafts (industrial machinery) Screws, bearings (electrical and electronic industries) Printed wiring boards, semiconductor mounting boards (building materials) Phenolic resin impregnated core paper

[0072] Next, dispersed on the surface of the adhesive layer, "decomposable and removable particulate material", "inorganic particles, metal particles, elastomer resin, selected from alkali-soluble resin particles and solvent-soluble resin particles. At least one type of particulate matter ", or at least a part of" island-like resin in a sea-island structure "is dissolved and removed using a roughening liquid such as an acid, an oxidizing agent, an alkali, water, an organic solvent, or Decompose and remove under high temperature, high humidity and high pressure conditions. As a method using the above-mentioned roughening solution, the substrate on which the adhesive layer is formed can be immersed in the roughening solution, or can be carried out by means such as spraying the roughening solution on the substrate.
As a result, the surface of the adhesive layer can be roughened. The oxidizing agent is preferably chromic acid, chromate, permanganate, ozone, or the like, and the acid is preferably hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, or an organic acid. As the alkali, sodium hydroxide, sodium carbonate, potassium hydroxide, ammonia and the like are preferable. Examples of the organic solvent include methyl ethyl ketone, benzene, toluene, dioxane,
Acetone, trichloroethylene, ethylene dichloride, carbon disulfide, ethyl acetate, butyl acetate, tetrahydrofuran, cyclohexanone, nitroethane, pyridine, chloroform, carbon tetrachloride and the like are preferred.

The particulate matter which can be dissolved and removed as described above or sea-
The relationship between the island-shaped resin in the island structure and the roughening solution for removing them will be described. Among the inorganic particles, silica,
Hydrofluoric acid is suitable for alumina, hydrochloric acid for carbonates such as calcium carbonate and sodium carbonate, and water for aluminum nitride and the like that decompose with water. Since aluminum nitride is decomposed by water and gradually oxidized by oxygen in the air, a metal film adherend using aluminum nitride needs to be sealed with nitrogen or argon before use. For metal particles, oxidizing agents such as chromate, chromate, permanganate, ozone,
Acids such as hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, and organic acids are preferred. In particular, since amino resin can use hydrochloric acid containing no heavy metal as a roughening liquid, waste liquid treatment is easy and practical. For an elastomer such as a rubber-based resin, chromic acid, a mixed solution of chromic acid and sulfuric acid, and an oxidizing agent such as chromate, permanganate, and ozone are preferable as the roughening liquid.
Particulate matter that can be dissolved and removed with an organic solvent (thermoplastic resin)
Among them, styrene resins include methyl ethyl ketone, benzene, toluene, dioxane, acetone, trichloroethylene, ethylene dichloride, carbon disulfide, ethyl acetate, and butyl acetate, and vinyl chloride resins include tetrahydrofuran, cyclohexanone, nitroethane, and pyridine. Organic solvents are suitable as roughening liquids.

[0074] Next, a metal film is coated on the surface-roughened adhesive layer on the substrate. As a method of coating the metal film, there are methods such as electroless plating, electrolytic plating, and sputtering. As the electroless plating, for example, electroless copper plating, electroless nickel plating, electroless tin plating,
Examples include electroless gold plating and electroless silver plating, and in particular, electroless copper plating, electroless nickel plating and electroless gold plating, electroless cobalt-nickel-phosphorus plating, and electroless copper-nickel-phosphorous plating. Preferably, at least one of them is used. It should be noted that, after the electroless plating is performed, a different type of electroless plating or electroplating may be performed, or solder may be coated. In the case of electroless plating, various patterns can be drawn by plating by forming a plating resist or the like. Alternatively, the entire surface may be subjected to electroless plating and then etched. Further, as a metal to be deposited by a method such as sputtering, Cu, Ni,
There are Cr, Ti, Mo, Au and alloys thereof.

In the automobile industry, the metal film adherend thus manufactured is applied to various parts such as a disc brake body, a clutch hub, a fuel injection nozzle, a fuel transport pipe, a gear, and the electric and electronic industries. In the field, lead frames, hermetic seals, ceramic packages, connectors, capacitors, resistors, solar electrodes,
Applications to hard disks and the like, and in the industrial machinery industry, applications to pumps, valves, heat exchangers, filters, screws, dies, bearings, etc. are possible.

Next, a method of manufacturing a printed wiring board as the metal film-coated body will be described. . First, a substrate is used as a substrate, and the substrate is mainly composed of an adhesive of the present invention, a so-called uncured thermosetting resin and / or a resin mixture of an uncured photosensitive resin and a thermoplastic resin. An adhesive layer is provided by applying an adhesive, laminating a film obtained by semi-curing the adhesive itself, or forming the substrate itself with the adhesive. Further, the adhesive layer is dried and cured to form an adhesive layer in which the resin composite constituting the resin matrix has a pseudo-homogeneous compatible structure, a co-continuous structure or a spherical domain structure.

[0077] Next, at least a part of the degradable and removable particulate material dispersed on the surface of the adhesive layer, the dissolvable and removable particulate material, or the island-shaped resin in the sea-island structure, an acid or an oxidizing agent, It is dissolved and removed using a roughening liquid such as an alkali, water and an organic solvent, or decomposed and removed under high temperature, high humidity and high pressure conditions. As a method using the above-mentioned roughening solution, using the same roughening solution as described above, the substrate on which the adhesive layer is formed is immersed in the solution, or the roughening solution is sprayed on the substrate. For example, the surface of the adhesive layer can be roughened.

[0078] Next, the surface roughened adhesive layer on the substrate is subjected to electroless plating. As this electroless plating,
Examples include electroless copper plating, electroless nickel plating, electroless tin plating, electroless gold plating, and electroless silver plating, and in particular, any one of electroless copper plating, electroless nickel plating, and Preferably, it is at least one. It should be noted that, after the electroless plating is performed, a different type of electroless plating or electroplating may be performed, or solder may be coated. Further, in providing the metal deposition layer, a method such as electrolytic plating or sputtering may be used instead of electroless plating. Cu, Ni, Cr, T
i, Mo, Au, and alloys thereof.

In the case of electroless plating, by forming a plating resist or the like, a wiring pattern can be drawn directly by plating. Alternatively, the entire surface can be electrolessly plated and then etched to draw a conductor circuit.

Examples of the printed wiring board obtained as described above include a single-sided printed wiring board formed by forming a plating resist and a conductive circuit on a substrate via the above-mentioned adhesive layer; Double-sided printed wiring board formed with a plating resist and a conductor circuit through a substrate, and interlayer insulation having via holes on a substrate (may have a through hole or may be a multilayer) on which a conductor layer is formed A build-up multilayer wiring board in which conductive circuits are formed in multiple layers via a layer (the adhesive layer) can be given.

[0081]

EXAMPLES (Example 1) (1) Cresol novolak type epoxy resin (manufactured by Nippon Kayaku, trade name; EOCN-104S, epoxy equivalent 220, molecular weight 50)
00) 65 parts by weight, polyether sulfone (PES) (IC
I, product name: Victrex, molecular weight 17000) 40 parts by weight, imidazole-based curing agent (Shikoku Chemicals, trade name: 2E4MZ-CN)
5 parts by weight and 20 parts by weight of a rubber-based resin fine powder (manufactured by Nippon Synthetic Rubber) having an average particle size of 5.5 μm, and an average particle size of 0.5 μm
After mixing 10 parts by weight of the above, the viscosity was adjusted to 120 CPS with a homodisper stirrer while adding NMP (normal methylpyrrolidone), followed by kneading with three rolls to obtain an adhesive solution. At this time, the viscosity at room temperature is 2 to 5 Pa
・ S. (2) Using a roller coater (manufactured by Thermotronics Trading), apply this adhesive solution onto a glass epoxy insulating board (manufactured by Toshiba Chemical) on which no copper foil is adhered, and then apply the adhesive at 80 ° C. for 2 hours. 5 hours at 120 ° C, 2 hours at 150 ° C,
After drying and curing, an adhesive layer having a thickness of 20 μm was formed. (3) The substrate on which the adhesive layer is formed is immersed in a chromic acid aqueous solution (CrO ₃ , 500 g / l) at 70 ° C. for 15 minutes to roughen the surface of the adhesive layer. ) And washed with water. Roughened surface is, R _max = 10 [mu] in JIS-B-0601
m. (4) A palladium catalyst (manufactured by Shipley) is applied to the substrate having the surface of the adhesive layer roughened to activate the surface of the adhesive layer. Then, a plating resist is provided according to a conventional method. For electroless plating solution for additive of composition
It was immersed for 11 hours, and subjected to electroless copper plating with a plating film thickness of 25 μm to produce a printed wiring board (see FIG. 1).

[0082]

[Table 2]

The cured product obtained by thermosetting only the resin corresponding to the resin matrix of the adhesive used in this example under the above conditions was observed by TEM. As a result, resin particles having an average particle size of 0.1 μm or less were found. Was done. A cured product obtained by curing a mixture of a resin composition not mixed with the rubber-based resin fine powder was subjected to a viscoelasticity measurement test under the conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min. However, there was one peak of the glass transition temperature Tg (see FIG. 2). Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure (see FIG. 3).

Example 2 (1) 70 parts by weight of cresol novolac type epoxy resin (manufactured by Nippon Kayaku, trade name: EOCN-103S), 30 parts by weight of polyether sulfone (PES) (manufactured by ICI, trade name: Victrex) Part, imidazole curing agent (Shikoku Chemicals, trade name: 2PHZ
-CN) 10 parts by weight and 20 parts by weight of silica spherical fine powder (manufactured by Nippon Shokubai Kogyo Co., Ltd.) having an average particle size of 5.5 μm, and an average particle size of 0.
After mixing 10 parts by weight of 5 μm, the viscosity was adjusted to 120 CPS with a homodisper stirrer while adding an NMP solvent, and then kneaded with three rolls to obtain an adhesive solution. (2) Using a roller coater (manufactured by Thermotronics Trading), apply this adhesive solution onto a glass epoxy insulating board (manufactured by Toshiba Chemical) on which no copper foil is adhered, and then at 80 ° C. for 3 hours. 3 hours at 120 ° C, 5 hours at 150 ° C,
After drying and curing, an adhesive layer having a thickness of 20 μm was formed. (3) The substrate on which the adhesive layer is formed is immersed in hydrofluoric acid at 70 ° C for 15 minutes.
The surface of the adhesive layer was roughened by immersion for a minute, and then immersed in a neutralizing solution (made by Shipley) and then washed with water. (4) A palladium catalyst (manufactured by Shipley) is applied to the substrate having the surface of the adhesive layer roughened to activate the surface of the adhesive layer. Then, a plating resist is provided according to a conventional method. For electroless plating solution for additive of composition
It was immersed for 11 hours, and subjected to electroless copper plating with a plating film thickness of 25 μm to produce a printed wiring board.

The cured product obtained by thermosetting only the resin corresponding to the resin matrix of the adhesive used in this example under the above conditions was observed with a TEM in the same manner as in Example 1, and the average particle size was 0.05 μm. The following resin particles were found. The cured product obtained by curing the mixture of the resin composition without mixing the silica fine powder was subjected to a viscoelasticity measurement test under the conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min. The glass transition temperature Tg had one peak. Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure.

Example 3 (1) A butadiene-acrylonitrile copolymer oligomer (CTBN) and a bisphenol A type epoxy resin were mixed, and the mixture was heated at 160 ° C. for 2 hours to obtain an epoxy-modified CTBN.
Got. (2) Bisphenol A type epoxy resin (made by Yuka Shell,
Product name: Epicoat 828, epoxy equivalent 190, molecular weight 380
) 70 parts by weight, polyether sulfone (PES) (IC
I, 30 parts by weight of Victrex), 10 parts by weight of an imidazole-based curing agent (trade name: 2E4MZ-CN, manufactured by Shikoku Chemicals) and 30 parts by weight of the above-mentioned epoxy-modified CTBN were mixed.
While adding the MP solvent, adjust the viscosity with a homodisper stirrer.
It was adjusted to 120 CPS and then kneaded with three rolls to obtain an adhesive solution. (3) This adhesive solution is applied on a glass epoxy insulating plate (manufactured by Toshiba Chemical) on which no copper foil is stuck, using a roller coater (manufactured by Thermotronics Trading), and then at 80 ° C. for 1 hour. 2 hours at 120 ° C, 4 hours at 150 ° C,
After drying and curing, an adhesive layer having a thickness of 20 μm was formed. (4) The substrate on which the adhesive layer is formed is immersed in a chromic acid aqueous solution (CrO ₃ , 500 g / l) at 70 ° C. for 15 minutes to roughen the surface of the adhesive layer. ) And washed with water. (5) A palladium catalyst (manufactured by Shipley) is applied to the substrate having the surface of the adhesive layer roughened to activate the surface of the adhesive layer. Then, a plating resist is provided according to a conventional method. For electroless plating solution for additive of composition
It was immersed for 11 hours, and subjected to electroless copper plating with a plating film thickness of 25 μm to produce a printed wiring board.

The cured product obtained by thermosetting only the resin corresponding to the resin matrix of the adhesive used in this example under the above conditions was observed with a TEM in the same manner as in Example 1, and the average particle size was 0.1 μm. The following resin particles were found. A cured product obtained by curing a mixture of a resin composition not mixed with the rubber-based resin was subjected to a viscoelasticity measurement test under the conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min. The glass transition temperature Tg had one peak. Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure. Further, when this resin matrix was observed by SEM, an “island structure” of a butadiene-acrylonitrile copolymer resin was observed in the sea of the cured resin matrix. That is, when the surface of the adhesive layer is treated with an oxidizing agent, the island structure is dissolved and removed, and the surface is roughened.

Example 4 Basically the same as Example 1 and the following was used as the adhesive solution. Bisphenol A type epoxy resin (manufactured by Yuka Shell, Epicoat 828) 65 parts by weight, polyether sulfone (PES) (manufactured by ICI, trade name: Victrex)
35 parts by weight, 5 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E4MZ-CN) and 20 parts by weight of a rubber-based resin fine powder (manufactured by Nippon Synthetic Rubber) having an average particle size of 5.5 μm,
After mixing 10 parts by weight of an average particle diameter of 0.5 μm, the mixture is mixed with a dimethylformamide / butyl cellosolve (1/1) mixed solvent with a homodisper stirrer to give a viscosity of 100 CPS.
And then kneading with three rolls to obtain an adhesive solution.

A cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Example 1 was etched in methylene chloride for dissolving PES, and then subjected to SEM. Observed, average particle size
A continuous structure (co-continuous structure) of spherical objects considered to be rich in epoxy resin of 0.2 to 2 μm was observed.

(Example 5) Basically, it is the same as Example 1, and the following was used as an adhesive solution. Bisphenol A type epoxy resin (manufactured by Yuka Shell, Epicoat 828) 50 parts by weight, polyether sulfone (PES) (manufactured by ICI, trade name: Victrex)
50 parts by weight, 5 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E4MZ-CN) and 20 parts by weight of a rubber-based resin fine powder (manufactured by Nippon Synthetic Rubber) having an average particle size of 5.5 μm,
After mixing 10 parts by weight of an average particle size of 0.5 μm, DM
An adhesive solution obtained by adjusting the viscosity to 100 CPS with a homodisper stirrer while adding F (dimethylformamide), and then kneading with three rolls.

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Example 1 was etched on its cross section with methylene chloride to dissolve PES, and then subjected to SEM. As a result of observation, a spherical product having an average particle size of about 2 to 5 μm, which is considered to be rich in epoxy resin, was observed. Moreover, the resin matrix had a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres floated on the PES-rich base (see FIG. 4).

Example 6 (1) A photosensitive dry film (manufactured by DuPont) was laminated on a glass epoxy copper-clad laminate (manufactured by Toshiba Chemical).
The image was printed by exposing to ultraviolet light through a mask film on which a desired conductive circuit pattern was drawn. Then, 1,1,
After developing with 1-trichloroethane and removing copper in the non-conductive portion using a cupric chloride etching solution, the dry film was peeled off with methylene chloride. As a result, a wiring board having a first-layer conductor circuit including a plurality of conductor patterns on the substrate was prepared. (2) 200 g of alumina particles (trade name: AX34, manufactured by Nippon Light Metal Co., Ltd., average particle size: 3.9 μm) were stirred into a suspension of alumina particles obtained by dispersing in 5 l of acetone in a Henschel mixer while stirring. Alumina powder (manufactured by Nippon Light Metal Co., Ltd .; trade name: AX3)
4. A suspension obtained by dispersing 300 g of an average particle diameter of 0.5 μm) was added dropwise to adhere the alumina powder to the surface of the alumina particles, the acetone was removed, and then heated to 150 ° C. Thus, alumina pseudo particles were prepared.
The pseudo particles had an average particle size of about 4.3 μm, and about 75% by weight was present in a range of ± 2 μm around the average particle size. (3) 70 parts by weight of a 50% acrylate of a cresol novolak type epoxy resin (manufactured by Yuka Shell, epoxy equivalent 210, molecular weight 2000), polyethersulfone (PES) 30 parts by weight, diallyl terephthalate 15 parts by weight, 2-methyl -1-
4 parts by weight of [4- (methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba-Geigy), 4 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name; 2E4MZ-CN), and After mixing 50 parts by weight of the alumina pseudo particles prepared in (2), while adding butyl cellosolve, the viscosity was adjusted to 250 cps with a homodisper stirrer, and then kneaded with three rolls to obtain a photosensitive adhesive solution. Prepared. (4) This photosensitive adhesive solution is applied to the wiring board prepared in the above (1) using a roll coater, and
After leaving it for 20 minutes, it was dried at 70 ° C. to form a photosensitive adhesive layer having a thickness of about 50 μm. (5) A photomask film on which a black circle of 100 μmφ was printed was brought into close contact with the wiring board subjected to the treatment of (4), and was exposed with an ultrahigh pressure mercury lamp of 500 mj / cm ² . This was subjected to ultrasonic development treatment with a DMDG (diethylene glycol dimethyl ether) solution to form an opening serving as a 100 μmφ via hole on the wiring board. Further, the wiring board was exposed to light at about 3000 mj / cm ² by an ultra-high pressure mercury lamp.
By performing a heat treatment at 150 ° C. for 5 hours for 5 hours, an adhesive layer having an opening with excellent dimensional accuracy corresponding to a photomask film was formed. (6) After the wiring board treated in the above (5) is treated with hydrofluoric acid, 70% potassium permanganate (KMnO ₄ , 500 g / l) is added.
C. for 15 minutes to roughen the surface of the adhesive layer,
After being immersed in a neutralization solution (manufactured by Shipley), it was washed with water. (7) A palladium catalyst (manufactured by Shipley) is applied to the substrate having the surface of the adhesive layer roughened to activate the surface of the adhesive layer. After immersion for an hour, electroless copper plating with a plating film thickness of 25 μm was performed. (8) After repeating the steps (4) to (7) twice,
Further, by performing the step (1), a build-up multilayer wiring board having four wiring layers was manufactured (see FIG. 5).

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example under the above conditions was etched by methylene chloride on the cross section, and the SE was removed.
Observation of M revealed that the continuous structure (co-continuous structure) of spherical objects considered to be rich in epoxy resin with an average particle size of 0.2 to 2 μm
(See FIG. 6). The cured product obtained by curing the mixture of the resin composition not mixed with the alumina pseudo particles was subjected to a viscoelasticity measurement test under the conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min. The glass transition temperature Tg had two peaks (see FIG. 7). Therefore, it is considered that the resin matrix of the adhesive used in this example has a bicontinuous structure.

Example 7 (1) A photosensitive dry film (manufactured by DuPont) was laminated on a glass epoxy copper-clad laminate (manufactured by Toshiba Chemical).
The image was printed by exposing to ultraviolet light through a mask film on which a desired conductive circuit pattern was drawn. Then, 1,1,
After developing with 1-trichloroethane and removing copper in the non-conductive portion using a cupric chloride etching solution, the dry film was peeled off with methylene chloride. As a result, a wiring board having a first-layer conductor circuit including a plurality of conductor patterns on the substrate was prepared. (2) A cresol novolak type epoxy resin dissolved in DMDG (diethylene glycol dimethyl ether) 25% of the epoxy groups of the cresol novolak type epoxy resin is acrylated to impart photosensitivity (CNA25, molecular weight 4000), PES (molecular weight 17000), imidazole-based curing agent ( 2E4MZ-CN, manufactured by Shikoku Chemicals, acrylated isothiocyanate, a photosensitive monomer (trade name, manufactured by Toagosei, Aronix M)
215), photoinitiator (Ciba Geigy, trade name: I-907)
And an NMP solvent having the following composition, and further, 20 parts by weight of a rubber-based resin fine powder (manufactured by Nippon Synthetic Rubber Co., Ltd.) having an average particle size of 5.5 μm and an average particle size of 0.
After mixing 10 parts by weight of 5 μm, the viscosity was adjusted to 120 CPS with a homodisper stirrer, followed by kneading with three rolls to obtain a photosensitive adhesive solution. Resin composition: photosensitized epoxy / PES / M215 / I-907 / imidazole = 75/25/10/5/5/5/5 (3) Apply this photosensitive adhesive solution to the wiring board prepared in (1) above. And apply it using a roll coater.
After standing for 20 minutes, drying was performed at 60 ° C. (4) A photomask film having a black circle of 100 μmφ printed thereon was brought into close contact with the wiring board subjected to the treatment of (3), and was exposed with an ultrahigh pressure mercury lamp of 500 mj / cm ² . This is subjected to ultrasonic development processing with a DMDG solution, so that a 100 μm
An opening to be a via hole of φ was formed. Further, the wiring board is exposed at about 3000 mj / cm ² by an ultra-high pressure mercury lamp,
By performing a heat treatment at 100 ° C. for 1 hour and at 150 ° C. for 5 hours, a 50 μm-thick adhesive layer having openings having excellent dimensional accuracy corresponding to a photomask film was formed. (5) The wiring board subjected to the treatment of (4) is immersed in potassium permanganate (KMnO ₄ , 500 g / l) at 70 ° C. for 15 minutes to roughen the surface of the adhesive layer, and then neutralized. After being immersed in a solution (made by Shipley), it was washed with water. (6) A palladium catalyst (manufactured by Shipley) is applied to the substrate having the surface of the adhesive layer roughened to activate the surface of the adhesive layer. After immersion for an hour, electroless copper plating with a plating film thickness of 25 μm was performed. (7) After repeating the steps (3) to (6) twice,
Further, by performing the step (1), a build-up multilayer wiring board having four wiring layers was manufactured.

Only the resin corresponding to the resin matrix of the adhesive used in this example was dried, UV cured,
The cured product obtained by heat curing was subjected to TEM in the same manner as in Example 1.
Upon observation, resin particles having an average particle size of 0.1 μm or less were observed. Further, a cured product obtained by curing a mixture of a resin composition in which the rubber-based resin fine powder is not mixed has a vibration frequency
A viscoelasticity measurement test was conducted under the conditions of 6.28 rad / sec and a heating rate of 5 ° C./min.
Was one. Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure (see FIG. 3). 8 and 9 show SEM cross-sectional photographs of the adhesive layer before and after curing, respectively.

(Example 8) Basically, it is the same as Example 7, and the following was used as the adhesive solution. Epoxy oligomer with photosensitization (CNA25, molecular weight 4000), in which 25% of epoxy groups of cresol novolac type epoxy resin are acrylated, PES
(Molecular weight: 17000), imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E4MZ-CN), acrylated isothiocyanate as a photosensitive monomer (manufactured by Toagosei, trade name: ARONIX M215), photoinitiator (manufactured by Ciba Geigy, Product Name: I
-907), using NMP (dimethylformamide) with the following composition, and further adding 20 parts by weight of a rubber-based resin fine powder (manufactured by Nippon Synthetic Rubber) with an average particle size of 5.5 μm to the mixture. A photosensitive adhesive solution obtained by mixing 10 parts by weight of an average particle diameter of 0.5 μm, adjusting the viscosity to 120 CPS with a homodisper stirrer, and kneading with a three-roll mill. Resin composition: photosensitized epoxy / PES / M215 / I-907 / imidazole = 75/25/10/5/5 This adhesive is cured at 80 ° C, UV cured, and then heat cured. I went.

The cured product obtained by drying and curing only the resin corresponding to the resin matrix of the adhesive used in this example under the above conditions was etched with methylene chloride, and the cross section thereof was observed by SEM. A continuous structure (co-continuous structure) of spheres having a diameter of 0.2 to 2 μm and considered to be rich in epoxy resin was observed.

Example 9 Basically, it was the same as Example 7, and the following was used as the adhesive solution. Epoxy oligomer with photosensitization (CNA25, molecular weight 4000), in which 25% of epoxy groups of cresol novolac type epoxy resin are acrylated, PES
(Molecular weight: 17000), imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E4MZ-CN), acrylated isothiocyanate as a photosensitive monomer (manufactured by Toagosei, trade name: ARONIX M215), photoinitiator (manufactured by Ciba Geigy, Product name; I
-907) and NMP with the following composition, and further, fine rubber-based resin powder was added to this mixture with an average particle size of 5.
20 parts by weight for 5 μm, 10 for average particle size 0.5 μm
After mixing parts by weight, the viscosity is 120C with a homodisper stirrer.
A photosensitive adhesive solution obtained by adjusting to PS and then kneading with three rolls. Resin composition: photosensitized epoxy / PES / M215 / I-907 / imidazole = 75/25/10/5/5/5 This adhesive is cured at 100 ° C and dried by UV.
After curing, heat curing was performed.

The cured product obtained by drying and curing only the resin corresponding to the resin matrix of the adhesive used in the present example under the above conditions was etched with methylene chloride for dissolving PES and observed by SEM. However, the average particle size 2
Epoxy resin-rich spheres of about 5 μm were observed. Moreover, the resin matrix had a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres floated on the PSF-rich base.

As in Examples 7 to 9 described above, by changing the drying conditions, a cured product having a quasi-homogeneous phase dissolved structure, a bicontinuous structure, and a spherical domain structure can be obtained from an adhesive having the same composition. understood. The reason for this is that in the case of a photosensitive adhesive, if it has a uniform structure at the time of drying, it is quickly cured by light curing, and phase separation due to subsequent thermal curing is relatively unlikely to occur. The phase diagrams are shown in FIGS. 10 to 12 for reference. These phase diagrams are different from those in Examples 7 to 9 in that the conditions for forming the adhesive are different, and that the sensitized epoxy / PES /
TMPTA / I-907 / imidazole = 75/25/20/5/5.

(Example 10) Basically, it is the same as Example 7, and the following was used as the adhesive solution. 100% acrylated photosensitive epoxy oligomer of cresol novolak type epoxy resin (manufactured by Yuka Shell), PES, imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E4MZ-CN), photosensitive monomer acrylic NMP with the following composition, using fluorinated isothiocyanate (trade name, manufactured by Toagosei Co., Aronix M215) and photoinitiator (trade name, manufactured by Ciba Geigy; trade name: I-907)
, And then finely powder rubber-based resin (Nippon Synthetic Rubber) with an average particle size of 5.5 μm.
A photosensitive adhesive solution obtained by mixing 20 parts by weight and 10 parts by weight having an average particle size of 0.5 μm, adjusting the viscosity to 120 CPS with a homodisper stirrer, and then kneading with three rolls. Resin composition: Photosensitized epoxy / PES / M215 / I-907 / imidazole = 80/20/10/5/5

The resin obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Example 7 was observed with a TEM in the same manner as in Example 1.
Resin particles having an average particle size of 0.1 μm or less were found. A cured product obtained by curing a mixture of a resin composition not mixed with the rubber-based resin fine powder has a vibration frequency of 6.28 rad / sec,
When a viscoelasticity measurement test was conducted under the condition of a temperature rising rate of 5 ° C./min, one peak of the glass transition temperature Tg was found. Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure (see FIG. 3).

(Example 11) Basically the same as in Example 7, the following was used as the adhesive solution. It is a photosensitive epoxy oligomer, phenoxy resin, imidazole-based curing agent (trade name: 2E4MZ-CN), a cresol novolak type epoxy resin (manufactured by Yuka Shell), which is 100% acrylated. Using acrylated isothiocyanate (trade name; Aronix M215, manufactured by Toagosei Co., Ltd.) and photoinitiator (trade name: I-907, manufactured by Ciba Geigy), DMF was mixed with the following composition, and the mixture was further averaged. Agglomerated rubber-based resin fine powder having a particle size of 3.5 μm (JP-A-1-30
After mixing 30 parts by weight of the production method disclosed in Example 1 of Japanese Patent Publication No. 1775), the mixture was adjusted to a viscosity of 120 CPS with a homodisper stirrer while adding a DMF solvent. A photosensitive adhesive solution obtained by kneading with Resin composition: photosensitized epoxy / phenoxy / M215 / I-907
/ Imidazole = 79/30/10/5/5

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Example 7 has a cross section in which the phenoxy resin is dissolved.
-Etching with butanone and observation by SEM showed a continuous structure (co-continuous structure) of an epoxy resin-rich spherical material having an average particle size of 0.2 to 2 µm.

(Example 12) Basically, it is the same as Example 7, and the following was used as the adhesive solution. 100% acrylated photosensitive epoxy oligomer of cresol novolak type epoxy resin (manufactured by Yuka Shell), PSF, imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E4MZ-CN), photosensitive monomer acrylic Isothiocyanate (trade name, manufactured by Toagosei Co., Aronix M215), photoinitiator (trade name: I-907, manufactured by Ciba Geigy) and DMF having the following composition
And further mixed with the average particle size of 3.
5 μm agglomerated rubber-based resin fine powder (see the production method disclosed in Example 1 of JP-A-1-301775)
After mixing 30 parts by weight, the viscosity was adjusted to 120 CPS with a homodisper stirrer while adding a DMF solvent.
A photosensitive adhesive solution obtained by kneading with this roll. Resin composition: Photosensitized epoxy / PSF / M215 / I-907 / imidazole = 60/40/10/5/5

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Example 7 was etched on its cross section with methylene chloride to dissolve PSF and then subjected to SEM. As a result of observation, spheres thought to be rich in epoxy resin having an average particle size of about 2 to 5 μm were found. Moreover, this resin matrix had a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres floated on the PSF-rich base.

(Example 13) Basically, it is the same as Example 5, except that zirconia (trade name: NS-OY-S, manufactured by Nippon Shokubai Chemical Industry Co., Ltd.) was used.
), And the roughened liquid was hydrofluoric acid. The resin structure of the resin matrix of the adhesive used in this example was a spherical domain structure. (Example 14) It is basically the same as Example 8, except that the rubber-based resin fine powder is magnesia (trade name: MTK-30, manufactured by Iwatani Chemical Industry Co., Ltd.)
The crude solution was 6N hydrochloric acid. The resin structure of the resin matrix of the adhesive used in this example was a co-continuous structure. (Example 15) Basically, it is the same as Example 9, except that the rubber-based resin fine powder was converted to aluminum hydroxide (trade name; manufactured by Nippon Light Industries Co., Ltd .;
T), and the roughening solution was an aqueous ammonia solution. The resin structure of the resin matrix of the adhesive used in this example was a spherical domain structure.

(Example 16) Basically, it is the same as Example 4, and the following was used as an adhesive solution. After mixing a butadiene-acrylonitrile copolymer oligomer (CTBN) and a bisphenol A type epoxy resin, the mixture is heated at 160 ° C. for 2 hours to obtain an epoxy-modified CTBN. Shell, Epicoat 82
8) 65 parts by weight, polyether sulfone (PES) (IC
I, 35 parts by weight of Victrex) and 5 parts by weight of an imidazole-based curing agent (trade name: 2E4MZ-CN, manufactured by Shikoku Chemicals), and then mixed with dimethylformamide / butyl cellosolve (1)
/ 1) An adhesive solution obtained by adjusting the viscosity to 100 CPS with a homodisper stirrer while adding a mixed solvent, and then kneading with three rolls.

A cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Example 4 was etched in methylene chloride for dissolving PES, and subjected to SEM. Observed, average particle size
A continuous structure (co-continuous structure) of spherical objects considered to be rich in epoxy resin of 0.2 to 2 μm was observed. When this resin matrix was observed by SEM, an “island structure” of a butadiene-acrylonitrile copolymer rubber resin was observed in the sea of the resin matrix.

(Example 17) Basically, it is the same as Example 5, and the following was used as the adhesive solution. After mixing a butadiene-acrylonitrile copolymer oligomer (CTBN) and a bisphenol A type epoxy resin, the mixture is heated at 160 ° C. for 2 hours to obtain an epoxy-modified CTBN. Shell, Epicoat 82
8) 50 parts by weight of polyethersulfone (PES) (IC
I, 50 parts by weight of Victrex) and 5 parts by weight of an imidazole-based curing agent (trade name: 2E4MZ-CN, manufactured by Shikoku Chemicals Co.) Then, an adhesive solution obtained by kneading with three rolls.

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Example 5 was etched on the cross section with methylene chloride to dissolve PES, and then subjected to SEM. As a result of observation, a spherical product having an average particle size of about 2 to 5 μm, which is considered to be rich in epoxy resin, was observed. Moreover, the resin matrix had a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres floated on the PES-rich base (see FIG. 4). When this resin matrix was observed by SEM, an “island structure” of a butadiene-acrylonitrile copolymer rubber resin was observed in the sea of the resin matrix.

(Example 18) Basically, it is the same as Example 7, and the following was used as the adhesive solution. After mixing a butadiene-acrylonitrile copolymer oligomer (CTBN) and a bisphenol A type epoxy resin, the mixture was heated at 160 ° C. for 2 hours to obtain an epoxy-modified CTBN.
Epoxy oligomer (CNA25, molecular weight 4000), sensitized with 25% of the epoxy groups of the cresol novolak type epoxy resin dissolved in water, PES (molecular weight 17)
000), imidazole curing agent (Shikoku Chemicals, trade name; 2E)
4MZ-CN), an acrylated isothiocyanate that is a photosensitive monomer (trade name, manufactured by Toagosei Co., Ltd .; Aronix M215)
), A photoinitiator benzophenone (BP) (manufactured by Kanto Chemical), a photosensitizer Michler's ketone (manufactured by Kanto Chemical),
An adhesive solution obtained by mixing with NMP using the following composition, adjusting the viscosity to 120 CPS with a homodisper stirrer, and then kneading with three rolls. Resin composition: Photosensitized epoxy / PES / M215 / BP / imidazole = 75/25/10/5 / 0.5 / 5

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Example 7 was observed with a TEM in the same manner as in Example 1. Resin particles having a diameter of 0.1 μm or less were observed. A cured product obtained by curing a mixture of a resin composition not mixed with the rubber-based resin has a vibration frequency of 6.28 rad / sec,
When a viscoelasticity measurement test was performed under the condition of a temperature rising rate of 5 ° C./min, one peak of the glass transition temperature Tg was found. Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure (see FIG. 3). Further, when this resin matrix was observed by SEM, an “island structure” of a butadiene-acrylonitrile copolymer rubber resin was observed in the sea of the resin matrix.

(Example 19) Basically, it is the same as Example 8, and the following was used as the adhesive solution. After mixing a butadiene-acrylonitrile copolymer oligomer (CTBN) and a bisphenol A type epoxy resin, the mixture was heated at 160 ° C. for 2 hours to obtain an epoxy-modified CTBN.
Epoxy oligomer (CNA25, molecular weight 4000), sensitized with 25% of the epoxy groups of the cresol novolak type epoxy resin dissolved in water, PES (molecular weight 17)
000), imidazole-based curing agent (Shikoku Chemicals, trade name;
2E4MZ-CN), a photosensitive monomer acrylated isothiocyanate (Toagosei Co., Ltd., trade name; ARONIX M215)
), Using a photoinitiator (Ciba Geigy, trade name; I-907), mixing with DMF with the following composition, adjusting the viscosity to 120 CPS with a homodisper stirrer, and kneading with a three-roll mill. Adhesive solution. Resin composition: Photosensitized epoxy / PES / M215 / I-907 / imidazole = 75/25/10/5/5

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Example 8 was etched with methylene chloride and its section was observed by SEM. A continuous structure (co-continuous structure) of spheres thought to be rich in epoxy resin having an average particle size of 0.2 to 2 μm was observed. In addition, this resin matrix is
Observed at M, in the sea of resin matrix,
An "island structure" of the butadiene-acrylonitrile copolymer rubber resin was observed.

(Example 20) Basically, it is the same as Example 9, and the following was used as the adhesive solution. After mixing a butadiene-acrylonitrile copolymer oligomer (CTBN) and a bisphenol A type epoxy resin, the mixture is heated at 160 ° C. for 2 hours to obtain an epoxy-modified CTBN. Epoxy oligomer with photosensitization (CNA2
5, molecular weight 4000), PES (molecular weight 17000), imidazole curing agent (Shikoku Chemicals, trade name; 2E4MZ-CN), photosensitive monomer acrylated isothiocyanate (Toa Gosei, trade name; Aronix M215), Using a photoinitiator (Ciba Geigy, trade name; I-907), D
Mix using MF, and homogenize with a homodisper stirrer.
An adhesive solution obtained by adjusting to PS and then kneading with three rolls. Resin composition: Photosensitized epoxy / PES / M215 / I-907 / imidazole = 75/25/10/5/5

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in the present embodiment in the same manner as in the ninth embodiment was subjected to SEM by etching the cross section with methylene chloride for dissolving PES. As a result of observation, spheres thought to be rich in epoxy resin having an average particle size of about 2 to 5 μm were found. Moreover, this matrix resin had a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres floated on the PSF-rich base. Also, when this resin matrix was observed by SEM,
An "island structure" of butadiene-acrylonitrile copolymer rubber resin was observed in the sea of the resin matrix.

(Example 21) Basically, it is the same as Example 7, and the following was used as the adhesive solution. Epoxy oligomer with photosensitization (CNA25, molecular weight 4000), in which 25% of epoxy groups of cresol novolac type epoxy resin are acrylated, PES
(Molecular weight 17000), imidazole curing agent (Shikoku Chemicals,
Trade name: 2E4MZ-CN), photosensitive monomer acrylated isothiocyanate (Toagosei, trade name; Aronix M215), photoinitiator (Chiba Geigy, trade name; I-90)
7), using DMF with the following composition and mixing, and further adding an epoxy group-terminated silicone resin to this mixture.
After mixing parts by weight, the viscosity is 120C with a homodisper stirrer.
It was adjusted to PS, and then kneaded with three rolls to obtain an adhesive solution. Resin composition: Photosensitized epoxy / PES / M215 / I-907 / imidazole = 70/30/10/5/5

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Example 7 was observed with a TEM in the same manner as in Example 1. Resin particles of 0.1 μm or less were observed. A cured product obtained by curing a mixture of a resin composition not mixed with the epoxy group-terminated silicone resin was subjected to a viscoelasticity measurement test under the conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min. However, there was one peak of the glass transition temperature Tg. Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure.

Example 22 (1) Cresol novolak type epoxy resin (manufactured by Nippon Kayaku, trade name; EOCN-104S, epoxy equivalent 220, molecular weight 50)
00) 65 parts by weight, polyether sulfone (PES) (IC
I, product name: Victrex, molecular weight 17000) 40 parts by weight, imidazole-based curing agent (Shikoku Chemicals, trade name: 2E4MZ-CN)
5 parts by weight and low cross-linking melamine resin powder average particle size
20 parts by weight of 5.5 μm and 0.5 μm average particle size
After mixing 10 parts by weight, the viscosity was adjusted to 120 CPS with a homodisper stirrer while adding NMP, and then kneaded with three rolls to obtain an adhesive solution. At this time, the viscosity at room temperature was 2 to 5 Pa · s. (2) Apply the adhesive solution to both sides of the glass epoxy board, leave it in a horizontal state for 20 minutes, and dry at 60 ° C.
1 hour at 150 ° C and 5 hours at 150 ° C to a thickness of about 50
A μm resin adhesive layer was formed. (3) The substrate having the double-sided adhesive layer is heated at 121 ° C. and 2 atm.
It was left in saturated steam for 2 hours to decompose and remove the melamine resin powder on the surface of the adhesive layer. FIGS. 13 and 14 show electron microscope (SEM) photographs before and after the decomposition and removal. As is clear from these photographs, the melamine resin is reduced due to the decomposition. (4) A palladium catalyst (manufactured by Shipley Co., Ltd.) is applied to the substrate having the surface of the resin insulating layer roughened to activate the surface of the insulating layer. Then, the substrate is immersed in an electroless copper plating solution for 11 hours to form a plating film. Electroless copper plating having a thickness of 25 μm was performed to obtain a double-sided copper-clad laminate. (5) Through holes were made in this double-sided copper-clad laminate. (6) After applying a palladium nucleus (manufactured by Shipley), a photoresist was stuck, exposed and developed to form a plating resist. (7) According to a conventional method, electroless copper plating was performed, and further, electrolytic copper plating was performed to form a conductor circuit portion. (8) After the plating resist was stripped off, etching was performed with ferric chloride to remove the copper film between the patterns to produce a printed wiring board.

A cured product obtained by thermosetting only the resin corresponding to the resin matrix of the adhesive used in this example under the above conditions was observed by TEM in the same manner as in Example 1.
Resin particles having an average particle size of 0.1 μm or less were observed. The cured product obtained by curing the mixture of the resin composition without mixing the melamine resin powder has a vibration frequency of 6.28 rad / sec,
When a viscoelasticity measurement test was conducted under the condition of a temperature rising rate of 5 ° C./min, one peak of the glass transition temperature Tg was found. Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure (see FIG. 3).

(Example 23) Basically, it is the same as Example 7, and the following was used as the adhesive solution. A sensitizing epoxy oligomer (CNA 25, molecular weight 4,000), PES (molecular weight 17,000), imidazole-based curing agent (trade name, manufactured by Shikoku Chemicals) in which 25% of epoxy groups of a cresol novolac type epoxy resin dissolved in DMDG are acrylated. 2E4MZ-CN), an acrylated isothiocyanate that is a photosensitive monomer (manufactured by Toa Gosei,
Trade name: Aronix M215), photoinitiator benzophenone (BP) (Kanto Chemical), photosensitizer Michler's ketone (Kanto Chemical), and further powdered cellulose acetate butyrate, mixed with NMP with the following composition An adhesive solution obtained by adjusting the viscosity to 120 CPS with a homodisper stirrer and then kneading with three rolls. Resin composition: photosensitized epoxy / PES / M215 / BP / imidazole = 75/25/10/5 / 0.5 / 5 The roughening conditions in this example are as follows. The reaction was performed by hydrolyzing cellulose acetate butyrate.

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Example 7 was observed with a TEM in the same manner as in Example 1. Resin particles of 0.1 μm or less were observed. A cured product obtained by curing a mixture of a resin composition not mixed with the rubber resin was subjected to a viscoelasticity measurement test under the conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min. There was one peak of the transition temperature Tg. Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure.

The peel strength of the electroless copper plating film on the printed wiring boards manufactured in Examples 1 to 23, the insulation resistance of the interlayer resin insulating layer, and the glass transition temperature _Tg were measured. Further, a heat cycle test of -65 ° C × 30 min to 125 ° C. × 30 min was performed. Table 3 shows the results. As is clear from the results shown in this table, the quasi-homogeneous phase dissolution structure,
Printed wiring with significantly improved adhesive strength, insulation, heat resistance and heat cycle characteristics by using the adhesive of the present invention using a resin composite of a resin composite exhibiting a bicontinuous structure and a spherical domain structure as compared with the conventional one. Boards can be manufactured.

[0125]

[Table 3]

The above-described peel strength, insulation resistance, glass transition temperature Tg and heat cycle test method or evaluation method will be described. (1) Peel strength JIS-C-6481 (2) An interlayer insulating layer was formed on an insulation resistance substrate, and after roughening, a catalyst was applied, and then a plating resist was formed to form a resist pattern. Thereafter, electroless plating was performed, and the insulation resistance between the patterns was measured. The insulation between patterns is
L / S = 75 ° C / 85% /
The value after 24 hours and 1000 hours was measured. (3) Glass transition temperature Tg Measured by dynamic viscoelasticity measurement. (4) Heat cycle test A heat cycle test was performed at −65 ° C. × 30 min to 125 ° C. × 30 min to check for the occurrence of cracks and peeling of the interlayer insulating layer.

(Example 24): Metallic melamine decorative board In Examples 1 to 23, the embodiments relating to the printed wiring board were described, but this embodiment is an application example of the present invention to a decorative board. (1) Wood pulp fiber paper with a basis weight of 10 to 80 g / m ²
Impregnated with melamine resin, dried it, thickness 100
μm impregnated paper. (2) Cresol novolak type epoxy resin (manufactured by Nippon Kayaku, trade name: EOCN-104S, epoxy equivalent 220, molecular weight 50)
00) 65 parts by weight, polyether sulfone (PES) (IC
I, product name: Victrex, molecular weight 17000) 40 parts by weight, imidazole-based curing agent (Shikoku Chemicals, trade name: 2E4MZ-CN)
5 parts by weight and fine calcium carbonate powder with an average particle size of 5.5 μm
After mixing 20 parts by weight of m and 10 parts by weight of an average particle diameter of 0.5 μm, the mixture was adjusted to a viscosity of 120 CPS with a homodisper stirrer while adding a mixed solvent of dimethylformamide / butyl cellosolve (1/1). Subsequently, the mixture was kneaded with three rolls to obtain an adhesive solution. At this time, the viscosity at room temperature is
It was 2 to 5 Pa · s. (3) The adhesive obtained in the above (2) is applied to the surface of the plywood board, and then dried in vacuum at 30 ° C, and then dried at 80 ° C for 2 hours.
5 hours at 150 ° C, 2 hours at 150 ° C, cured to 20μm
Was formed. (4) The adhesive layer was immersed in 6N hydrochloric acid at 70 ° C. for 15 minutes to roughen the surface of the adhesive layer, and then immersed in a neutralizing solution (manufactured by Shipley), washed with water, and R _max = 10 ± An adhesive layer of 5 μm was obtained. (5) Apply a palladium catalyst (manufactured by Shipley) to the substrate whose surface has been roughened to activate the surface of the adhesive layer. 60
A μm silver layer was formed. (6) On the surface of the silver layer, the melamine resin impregnated paper obtained in the above (1) was laminated as an overlay paper. (7) Further, a shaping plate provided with irregularities of 1 to 60 μm is laminated on the overlay paper, and thermocompression-bonded at 130 to 170 ° C. under a pressure of 30 to 80 kg / cm ² , to thereby form the overlay paper. And embossing the surface to obtain a melamine decorative plate having a metallic luster.

Since the melamine decorative board thus obtained is formed of a melamine resin layer having a light-transmitting and uneven surface, the unevenness serves as a lens to lift the lower silver layer. The silver luster was shining and the design was excellent. Moreover, for this decorative board, -65
When a heat cycle test was carried out at 30 ° C. × 30 min to 125 ° C. × 30 min, neither crack nor peeling was observed.

The cured product obtained by thermosetting only the resin corresponding to the resin matrix of the adhesive used in this example under the above conditions was observed with a TEM in the same manner as in Example 1. Resin particles of 0.1 μm or less were observed. The cured product obtained by curing the mixture of the resin composition without mixing the calcium carbonate fine powder has a vibration frequency of 6.28 r.
When a viscoelasticity measurement test was performed under the conditions of ad / sec and a heating rate of 5 ° C./min, one peak of the glass transition temperature Tg was found. Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure.

(Embodiment 25); Plating Gear This embodiment is an application of the present invention to a plating gear. (1) A gear-shaped molded body was produced by using a polyimide according to a conventional method. (2) Photosensitizing epoxy oligomer (CNA25, molecular weight 4000) in which 25% of epoxy groups of cresol novolac type epoxy resin dissolved in DMDG are acrylated, P
ES (molecular weight 17000), imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E4MZ-CN), caprolactone-modified tris isocyanurate as a photosensitive monomer (manufactured by Toa Gosei,
Product name: Aronix M315), photoinitiator benzophenone (BP), photosensitizer Michler's ketone, mixed with NMP with the following composition, and in addition, rubber filler (manufactured by Nippon Gosei) was added. After mixing 30 parts by weight of 5.0 μm, the viscosity was adjusted to 1000 CPS with a homodisper stirrer and then kneaded with three rolls to obtain an adhesive solution. Resin composition: photosensitized epoxy / PES / M315 / BP / imidazole = 70/30/10/5 / 0.5 / 5 (3) The gear-shaped molded body prepared in (1) above was added to (2)
After applying the adhesive prepared in the above, vacuum drying was performed at 25 ° C., this was UV-cured, and further heat-cured to form an adhesive layer composed of a resin matrix having a pseudo-homogeneous compatible structure. (4) Then, the solution was added to chromic acid aqueous solution (CrO ₃ , 500 g / l)
The surface of the adhesive layer was roughened by immersion for 15 minutes, immersed in a neutralizing solution (made by Shipley), and then washed with water. The roughened surface is JIS-B-
[0601] R _max = 10 µm. (5) After activating the surface of the adhesive layer by applying a palladium catalyst (manufactured by Shipley) to the substrate having the surface of the adhesive layer roughened, nickel-phosphorus plating is performed according to a conventional method to obtain a metallic luster. Made gear with.

The gear thus obtained was resistant to chemicals such as acid, and had excellent abrasion resistance due to its hard surface. The use of the gear did not cause the nickel layer on the surface to peel off. Moreover, cracks did not occur in the adhesive layer due to the stress caused by the use of the gear, and the nickel plating did not peel off.

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example under the above conditions was observed with a TEM in the same manner as in Example 1. Resin particles of μm or less were observed. The cured product obtained by curing the mixture of the resin composition without mixing the rubber filler has a vibration frequency of 6.28 rad / sec.
When a viscoelasticity measurement test was conducted under the condition of a temperature rising rate of 5 ° C./min, one peak of the glass transition temperature Tg was found.
Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure.

(Embodiment 26): Semiconductor mounting board with heat sink This embodiment is an application example of the present invention to a semiconductor mounting board with heat sink. (1) A photosensitized epoxy oligomer (CNA2) in which 25% of the epoxy groups of a cresol novolak type epoxy resin dissolved in DMDG is acrylated.
5, molecular weight 4000), PES (molecular weight 17000), imidazole curing agent (Shikoku Chemicals, trade name: 2E4MZ-CN), caprolactone-modified tris isocyanurate as a photosensitive monomer (Toagosei, trade name; ARONIX M315) ,
Using a photoinitiator benzophenone (BP) and a photosensitizer Michler's ketone, mixing using NMP with the following composition and further adding aluminum nitride powder with an average particle size of 5.0 μm
After mixing 30 parts by weight of the above, the viscosity was adjusted to 1000 CPS with a homodisper stirrer, followed by kneading with three rolls to obtain an adhesive solution. Resin composition: photosensitized epoxy / PES / M315 / BP / imidazole = 70/30/10/5 / 0.5 / 5 (2) The base material of the semiconductor mounting substrate composed of an aluminum substrate and a lead frame was subjected to the above-mentioned (1). Apply the adhesive solution, perform vacuum drying at 25 ° C, and after UV curing,
The aluminum substrate was covered with an adhesive layer by thermosetting, and at the same time, the aluminum substrate and the lead frame were integrated to form an adhesive layer made of a resin matrix having a pseudo-homogeneous compatible structure. (3) The substrate for mounting a semiconductor having the adhesive layer formed thereon was immersed in water to dissolve and remove the aluminum nitride powder present on the surface of the adhesive layer to roughen the adhesive layer. (4) Attach a plating resist film, expose and develop a plating resist to form a plating resist, perform electroless copper plating, form a conductor circuit on the surface, and make an electrical connection with the lead frame using the conductor circuit. Was. (5) After mounting the IC chip, the package was sealed with a resin by potting and then casingd to produce a semiconductor mounting substrate with a heat sink.

The semiconductor mounting substrate with a heat sink thus obtained had good heat dissipation because of the high thermal conductivity of aluminum nitride. In addition, the resin matrix of the present example is such that the terminal functional group is decomposed to generate organic acids such as acetic acid and formic acid under high temperature, high humidity and high pressure conditions, while aluminum nitride forms ammonia under the above conditions. The acid is decomposed while generating, so that the acid can be neutralized and the corrosion of the adhered metal can be suppressed.

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example under the above conditions was observed with a TEM in the same manner as in Example 1. Resin particles of μm or less were observed. The cured product obtained by curing the mixture of the resin composition not mixed with aluminum nitride has a vibration frequency of 6.28 rad /
When a viscoelasticity measurement test was conducted under the conditions of sec and a heating rate of 5 ° C./min, there was one peak of the glass transition temperature Tg. Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure.

(Embodiment 27) Electromagnetic Interference (EMI) Plating Shield This embodiment is an application of the present invention to an electromagnetic interference (EMI) plating shield. (1) Cresol novolak type epoxy resin (manufactured by Nippon Kayaku, trade name: EOCN-104S, epoxy equivalent 220, molecular weight 50)
00) 65 parts by weight, polyether sulfone (PES) (IC
I, product name: Victrex, molecular weight 17000) 40 parts by weight, imidazole-based curing agent (Shikoku Chemicals, trade name: 2E4MZ-CN)
After mixing 5 parts by weight and 20 parts by weight of nickel fine powder having an average particle size of 5.5 μm and 10 parts by weight having an average particle size of 0.5 μm, a mixed solvent of dimethylformamide / butyl cellosolve (1/1) was added. While adjusting the viscosity to 120 CPS with a homodisper stirrer, the mixture was kneaded with three rolls to obtain an adhesive solution. At this time, the viscosity at room temperature is 2 to
It was 5 Pa · s. (2) This adhesive solution was applied to filter paper using a roller coater (manufactured by Thermotronics Trading), and then dried and cured at 80 ° C for 2 hours, 120 ° C for 5 hours, and 150 ° C for 2 hours. An adhesive layer having a thickness of 20 μm was formed. (3) The filter paper on which the adhesive layer was formed was immersed in hydrochloric acid at 70 ° C. for 15 minutes to roughen the surface of the adhesive layer, and then immersed in a neutralizing solution (manufactured by Shipley) and then washed with water. The rough surface is JI
SB-0601 R _max = 10 μm. (4) A palladium catalyst (manufactured by Shipley) was applied to the substrate whose surface was roughened to activate the surface of the adhesive layer, and then nickel plating was performed according to a conventional method.

The thus obtained electromagnetic interference wave (EM
I) The shielding material also contains nickel in the adhesive itself, has a shielding effect on the plating film, and has a multi-layered structure, so that it has excellent shielding characteristics. Moreover, even if the shield material is bent, no crack is generated in the adhesive layer, and the processing of the shield material is facilitated.

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example under the above conditions was observed with a TEM in the same manner as in Example 1. Resin particles of μm or less were observed. A cured product obtained by curing a mixture of a resin composition not mixed with the nickel fine powder has a vibration frequency of 6.28 rad / se.
c) When a viscoelasticity measurement test was conducted under the condition of a temperature rising rate of 5 ° C./min, there was one peak of the glass transition temperature Tg.
Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure.

Example 28: Screw (1) A screw-shaped substrate was formed from polycarbonate. (2) Cresol novolak type epoxy resin (manufactured by Nippon Kayaku, trade name: EOCN-104S, epoxy equivalent 220, molecular weight 500)
0) 65 parts by weight, polyether sulfone (PES) (IC
I, product name: Victrex, molecular weight 17000) 40 parts by weight, imidazole-based curing agent (Shikoku Chemicals, trade name: 2E4MZ-CN)
5 parts by weight and vinyl chloride resin powder with an average particle size of 5.5 μm
After mixing 20 parts by weight and 10 parts by weight of an average particle size of 0.5 μm, the mixture was stirred with a homodisper stirrer.
The mixture was kneaded with three rolls to obtain an adhesive solution. (3) The screw-shaped substrate of the above (1) is immersed in the adhesive solution, and then at 80 ° C. for 2 hours and at 120 ° C. for 5 hours.
It was dried and cured at 150 ° C. for 2 hours to form an adhesive layer having a thickness of 20 μm. The cured adhesive layer had a spherical domain structure as a result of etching the fractured surface with methylene chloride and performing SEM observation. (4) Next, the surface of the adhesive layer was roughened by dissolving and removing the vinyl chloride resin powder on the surface of the adhesive layer by immersion in acetone. (5) A palladium catalyst (manufactured by Shipley) was applied to the surface of the adhesive layer to activate the surface of the adhesive layer, and then electroless silver plating was performed according to a conventional method to produce a screw.

The screw thus obtained has a silver surface, so that it is difficult for algae or the like to adhere due to the sterilizing effect of silver. Further, since the substrate is integrally formed of polycarbonate, the screw is rotated by centrifugal force. Hard to break. Moreover,
A normal screw is cut out from a metal lump by cutting, so that the cost is increased. However, the screw of the present embodiment can be integrally molded with resin, so that the cost can be reduced. Further, since the adhesive layer has toughness, no crack is generated by distortion due to rotation.

[0141]

As described above, the adhesive of the present invention is a thermosetting resin and / or a resin mixture of a photosensitive resin and a thermoplastic resin as its heat-resistant resin matrix. Use a resin complex whose state of compatibility is adjusted so as to form a resin composite having a resin structure of either a homogeneous compatible structure, a co-continuous structure or a spherical domain structure, and decompose into a resin mixture. Dissolvable particulate material comprising at least one selected from the group consisting of particulate matter, inorganic particles, metal particles, elastomer particles, alkali-soluble resin particles and solvent-soluble resin particles, or dissolvable resin The adhesive is cured under appropriate curing conditions to form a sea-island structure, a quasi-homogeneous compatible structure, and a co-continuous structure. Alternatively, it is possible to form a resin composite having a resin structure of any one of a spherical domain structure, so that the resin matrix is toughened without lowering heat resistance, electrical insulation and chemical stability, and the adhesive layer and Adhesion with the coated metal can be significantly improved. This makes it possible to stably provide various types of metal film adherends for printed wiring boards and other industrial components that are excellent in peel strength even in wiring with higher density and higher pattern accuracy. In other words, not only for printed wiring boards, but also in the automotive industry, application to various parts such as disc brake bodies, clutch hubs, fuel injection nozzles, fuel transport pipes, gears, and in the electrical and electronic industries, lead frames, hermetic seals , Ceramic package, connector, capacitor, resistor, solar electrode,
Application to hard disks, etc., in the industrial machinery industry, it is possible to apply to building materials such as pumps, valves, heat exchangers, filters, screws, dies, bearings, decorative boards, etc. It can be applied to various structural materials and parts, and is industrially useful.

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram showing one embodiment of a printed wiring board according to the present invention.

FIG. 2 is a view showing the results of dynamic viscoelasticity measurement of a resin composite having a pseudo-homogeneous compatible structure according to the present invention.

FIG. 3 is a TEM photograph of a crystal structure showing a quasi-homogeneous compatible structure of the resin composite according to the present invention.

FIG. 4 is an SEM photograph of a crystal structure showing a spherical domain structure of a resin composite according to the present invention.

FIG. 5 is another manufacturing process diagram showing one embodiment of the printed wiring board according to the present invention.

FIG. 6 is an SEM photograph of a crystal structure showing a bicontinuous structure of the resin composite according to the present invention.

FIG. 7 is a view showing the results of dynamic viscoelasticity measurement of a resin composite having a bicontinuous structure according to the present invention.

FIG. 8 shows a crystal structure of a cross section of the adhesive layer before drying and before curing.
It is a SEM photograph.

FIG. 9 is an SEM photograph showing a crystal structure of a cross section of an adhesive layer after curing.

FIG. 10 is a phase diagram showing the relationship between the drying temperature of the CNA25 / PES / TMPTA-based mixture and the state of the cured resin composite.

FIG. 11 is a phase diagram showing the relationship between the drying temperature of a CNA25 / PES-based mixture and the state of the resin composite after curing.

FIG. 12 is a phase diagram showing the relationship between the drying temperature of the epoxy / PES-based mixture and the state of the resin composite after curing.

FIG. 13 is a SEM showing a crystal structure of a cross section of an adhesive layer showing a state before decomposition of decomposable particles (melamine resin having a low degree of polymerization).
It is a photograph.

FIG. 14 is an SEM showing a crystal structure of a cross section of an adhesive layer showing a state after decomposition of decomposable particles (melamine resin having a low degree of polymerization).
It is a photograph.

[Explanation of symbols]

1 substrate 2 adhesive layer 3 Resist 31 Dry film 4, 6, 8, 10 conductors 5 Via Hole

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-5-25650 (JP, A) JP-A-5-29761 (JP, A) JP-A-4-325590 (JP, A) JP-A-61-1 34085 (JP, A) JP-A-5-214548 (JP, A) JP-A-5-5066691 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H05K 3/38 C09J 4 / 00 C09J 201/00 C23C 18/20 H05K 1/03

Claims (5)

(57) [Claims] (1)If the surface to be coated with metal has a rough surface
Having a roughened adhesive layer, and the roughening of the adhesive layer
In a metal film adherend having a metal film provided on a surface, The adhesive layer may include a thermosetting resin and / or a photosensitive resin.
Uncured heat resistance consisting of a resin mixture of fat and thermoplastic resin
Particulate matter that can be decomposed and removed in the conductive resin matrix
Formed by curing the dispersed adhesive
The roughened surface is present on the surface of the cured adhesive layer.
Decomposing and removing the particulate matter that can be decomposed and removed.
Thus formed, The resin mixture has a pseudo-homogeneous compatible structure by a curing treatment,
One of co-continuous structure or globular domain structure
In order to form a resin composite having a resin structure,
A metal film adherend characterized in that solubility is adjusted. . (2)If the surface to be coated with metal has a rough surface
Having a roughened adhesive layer, and the roughening of the adhesive layer
In a metal film adherend having a metal film provided on a surface, The adhesive layer may include a thermosetting resin and / or a photosensitive resin.
Uncured heat resistance consisting of a resin mixture of fat and thermoplastic resin
Inorganic particles, metal particles, elas
For tomer particles, alkali-soluble resin particles and solvents
At least one kind of dissolution removal selected from soluble resin particles
Cures an adhesive made of dispersible particulate matter
Formed by Before the roughened surface is present on the surface of the cured adhesive layer
Dissolving and removing particulate matter that can be dissolved and removed
Formed The resin mixture has a pseudo-homogeneous compatible structure by a curing treatment,
One of co-continuous structure or globular domain structure
In order to form a resin composite having a resin structure,
A metal film adherend characterized in that solubility is adjusted. (3)If the surface to be coated with metal has a rough surface
Having a roughened adhesive layer, and the roughening of the adhesive layer
In a metal film adherend having a metal film provided on a surface, The adhesive layer may include a thermosetting resin and / or a photosensitive resin.
Between fat and thermoplastic resin Uncured heat resistance consisting of resin mixture
Before curing, the heat-resistant resin matrix
Wood that is incompatible with
By curing the adhesive made by dispersing the fat liquid
Formed, The resin mixture forms a resin composite by a curing treatment.
And the resin which can be dissolved and removed is cured.
Island in the sea of heat resistant resin matrix composed of resin composite
To form a sea-island structure
Has been adjusted, Before the roughened surface is present on the surface of the cured adhesive layer
By dissolving and removing the island-like dissolvable resin
Metal film adherend characterized by being formed by . (4)If the surface to be coated with metal has a rough surface
Having a roughened adhesive layer, and the roughening of the adhesive layer
In a metal film adherend having a metal film provided on a surface, The adhesive layer may include a thermosetting resin and / or a photosensitive resin.
Uncured heat resistance consisting of a resin mixture of fat and thermoplastic resin
Before curing, the heat-resistant resin matrix
And heat-resistant resin matrix after curing
And a resin solution that can be separated and dissolved and removed
Formed by hardening the adhesive, The resin mixture forms a resin composite by a curing treatment.
And the resin which can be dissolved and removed is cured.
Island in the sea of heat resistant resin matrix composed of resin composite
To form a sea-island structure
Has been adjusted, Before the roughened surface is present on the surface of the cured adhesive layer
By dissolving and removing the island-like dissolvable resin
Metal film adherend characterized by being formed by . 5. The photosensitive resin according to claim 1, wherein said photosensitive resin is a functional compound of a thermosetting resin.
Characterized in that it is a resin in which some of the groups have been replaced with photosensitive groups.
The metal film adherend according to claim 1.