JPH0864961A - Metallic foil clad body, adhesive layer, and adhesive - Google Patents

Abstract

PURPOSE: To provide bonding technology for forming a metallic body to be bonded firmly in a minute printed circuit board with high-density pattern and realizing a printed circuit board with good strength between the metallic body and an adhesive layer. CONSTITUTION: In a production step, thermosetting resin and/or a homogeneous mixture of photosensitive resin and thermoplastic resin are used as a raw material and hardened to form a uniform resin complex with pseudo-uniform compatibility structure, co-continuity structure or spherical domain structure. The uniform resin complex can be used as a heat-resistant resin matrix in an adhesive layer. In this way, a strong resin matrix for an adhesive can be obtained without reducing heat resistance, electric insulation or chemical stability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal film adherend, an adhesive layer and an adhesive, and particularly to heat resistance, electrical insulation,
And a technique for providing an adhesive and an adhesive layer having excellent toughness without deteriorating the chemical stability and stably providing various metal film adherends having excellent adhesion to the coating metal. .

[0002]

2. Description of the Related Art In recent years, a wiring board for mounting a printed circuit board or an LSI is required to have a high density and a high reliability by a fine pattern corresponding to downsizing or speeding up of electronic equipment as the electronic industry advances. ing.

Therefore, recently, as a method of forming a conductor on a wiring board, an adhesive is applied to the surface of a substrate to form an adhesive layer, and the surface of the adhesive layer is roughened, followed by electroless plating. The additive method of applying a conductor to form a conductor is drawing attention. According to this method, since a conductor is formed by applying electroless plating after forming a resist, a wiring having a higher density and a higher pattern accuracy can be manufactured at a lower cost than an etched foil method (a subtractive method) in which a pattern is formed by etching. There is a feature that can be produced in.

In such an additive method, as a means for improving the adhesion between the conductor and the adhesive layer (hereinafter described as "peel strength"), conventionally, the adhesive layer is formed on the conductor forming surface side of the adhesive layer. A method of providing fine irregularities by chemical etching is known.

However, in a recent additive type printed wiring board which requires wiring with higher density and higher pattern accuracy, a fine pattern of resist is formed by surface roughening of the adhesive layer in order to accurately form the resist pattern. It is necessary to make the anchor smaller. for that reason,
The smaller the anchor, the smaller the fracture area,
There was a problem that the peel strength was significantly reduced.

On the other hand, fields related to automobiles and transportation equipment, electric machinery,
In the electronic parts, machinery related fields, household products related fields, civil engineering and construction fields, and medical fields, metal parts are being replaced by 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 polyacetal bearing can be used. Furthermore, gears made of ultra high molecular weight polyethylene have been developed.

However, in some cases, it has been necessary to coat the surface of these resin parts with a metal film in view 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, a method has been proposed in which an adhesive layer is provided on the surface of a resin substrate, the surface of the adhesive layer is roughened, and then a metal film is coated. For example, in JP-B-58-44709, an adhesive for electroless plating consisting of acrylonitrile butadiene rubber and epoxy resin is applied on the surface of an insulating substrate, and then the epoxy resin portion on the surface of the adhesive layer is dissolved and removed. A method for obtaining a metal film coated body by subjecting the surface to roughening and then performing electroless plating is disclosed. Further, in JP-A-61-276875, a substrate is coated with an adhesive for electroless plating in which a heat-resistant resin fine powder is dispersed in a heat-resistant resin matrix,
Then, a method is disclosed in which the heat-resistant resin fine powder is treated with an oxidizing agent to roughen the surface, and then electroless plating is performed.

However, an engineering plastic (base resin) coated with a metal film via an adhesive layer
Is, when a heat cycle occurs, cracks occur due to the difference in coefficient of thermal expansion between the base resin and the adhesive layer, or when stress occurs,
There was a problem that the adhesive layer itself had cracks.

In order to solve these various problems, there is a method of increasing the strength of the heat-resistant resin matrix forming the coating metal or the adhesive. However, according to the 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 forming an adhesive in the conventional technique. It was found that the peeling of the film was caused by the destruction of the heat resistant resin matrix. That is, it was found that the cause of the decrease in adhesion strength was insufficient strength of the heat-resistant resin matrix forming the adhesive. Further, it was also found that the cause of cracks generated during heat cycle and cracks generated during stress was insufficient strength on the side of the heat resistant resin matrix.

[0010]

Therefore, in order to solve the above-mentioned various problems of the prior art, the main object of the present invention is to reduce heat resistance, electrical insulation, and chemical stability. Another object of the present invention is to provide an adhesive layer having excellent adhesion to a coating metal, which is to toughen a heat-resistant resin matrix that constitutes the adhesive. Is to establish a technique capable of stably providing various metal film adherends for printed wiring boards and other industrial parts which are excellent in peel strength even in high-density wiring with high pattern accuracy.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted earnest researches for improving the strength of a heat-resistant resin matrix which constitutes an adhesive as a result of the achievement of the above object. As the uncured thermosetting resin containing a resin having a functional group partially substituted with a photosensitive group and / or a mixed resin of an uncured photosensitive resin and a thermoplastic resin, the resin is further cured. 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 formed by the roughening treatment is small by using the resin composite as described above as an adhesive layer. Heading into the invention.

That is, (1) the adhesive composition of the present invention has a structure in which an uncured heat-resistant resin matrix is dispersed with a particulate substance capable of being dissolved or removed by decomposition, The resin matrix is selected from an uncured thermosetting resin (hereinafter simply referred to as "uncured thermosetting resin") containing a resin in which a part of functional groups is substituted with a photosensitive group, and an uncured photosensitive resin. A resin mixture in which the compatibility of at least one or two resins with a thermoplastic resin is adjusted,
This resin mixture is preferably dissolved in a solvent to be in a compatible or incompatible state. When this resin mixture is in a compatible state, it is possible to obtain a pseudo-homogeneous compatible structure, a co-continuous structure, and a spherical domain structure described later by adjusting the phase separation rate and the curing rate when curing the resin mixture. it can. On the other hand, when this resin mixture is in an incompatible state, the spherical domain structure can be obtained by curing the resin mixture as it is. Here, at least one selected from the group consisting of inorganic particles, metal particles, elastomer particles, alkali-soluble resin particles and solvent-soluble resin particles may be used as the above-mentioned soluble and removable particulate substance. desirable. In addition, as the above-described particulate substance that can be decomposed and removed, it is desirable to use a suspension-polymerized amino resin having a low degree of crosslinking. In the present invention, "dissolving and removing" means to cause dissolution and decomposition of particulate matter by a chemical action using a roughening liquid such as acid, alkali, oxidizing agent, water and organic solvent. The term “decomposition / removal” means that the particulate matter is decomposed by adjusting the atmosphere such as heating, pressurization, and humidity adjustment without using the roughening liquid. Further, in the present invention, "a resin mixture of at least one or two resins selected from thermosetting resins and photosensitive resins and a thermoplastic resin"
And. A resin mixture of a thermosetting 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.

Another structure of the adhesive of the present invention is to disperse a resin liquid in an uncured heat-resistant resin matrix that is incompatible with the matrix before curing and can be dissolved and removed after curing. In the adhesive, the heat-resistant resin matrix adjusts the compatibility between the thermoplastic resin and at least one or two resins selected from uncured thermosetting resin and uncured photosensitive resin. It is characterized by comprising a resin mixture. Still another configuration of the adhesive of the present invention is to mix a resin liquid that is compatible with the uncured heat-resistant resin matrix with the matrix before curing and that is phase-separated after the curing and can be dissolved and removed. In the adhesive, the heat resistant resin matrix has compatibility with at least one or two resins selected from uncured thermosetting resin and uncured photosensitive resin and the thermoplastic resin. It is characterized by comprising an adjusted resin mixture.
When such a resin mixture is in a compatible state, when it is cured, a phase-separation rate and a curing rate are adjusted to obtain a pseudo-homogeneous compatible structure, a co-continuous structure, and a spherical domain structure described later. be able to. On the other hand, when such a resin mixture is in an incompatible state, the spherical domain structure can be obtained by curing the resin mixture as it is.

(2) The constitution of the adhesive layer of the present invention is an adhesive layer having a roughened surface formed on a substrate, and this layer contains a particulate substance which can be dissolved or removed by decomposition. At least one selected from a thermosetting resin (hereinafter simply referred to as "thermosetting resin") and a photosensitive resin which are cured and include a resin in which a part of functional groups are substituted with a photosensitive group, or The resin composite is characterized by being dispersed in a heat-resistant resin matrix composed of a resin composite of two kinds of resins and a thermoplastic resin. This resin composite has a pseudo-homogeneous compatible structure, a co-continuous structure or a spherical domain structure. Are preferably formed. Here, at least one selected from the group consisting of inorganic particles, metal particles, elastomer particles, alkali-soluble resin particles and solvent-soluble resin particles may be used as the above-mentioned soluble and removable particulate substance. desirable. In addition, as the above-described particulate substance that can be decomposed and removed, it is desirable to use a suspension-polymerized amino resin having a low degree of crosslinking.

Another structure of the adhesive layer of the present invention is an adhesive layer having a roughened surface formed on a substrate, in which the resin which can be dissolved and removed is a thermosetting resin and a photosensitive resin. Of a heat-resistant resin matrix, which has been cured and is made of a resin composite of a thermoplastic resin and at least one or two resins selected from a water-soluble resin, is dispersed in the sea in an island shape to form a sea-island structure. It is preferable that the resin composite has a pseudo-homogeneous compatible structure, a co-continuous structure, or a spherical domain structure. Here, the above-mentioned resin that can be dissolved and removed is incompatible with the uncured heat-resistant resin matrix before curing, and forms a “sea-island structure” in a non-uniform state with the resin matrix after curing. The resin that is compatible with the uncured heat-resistant resin matrix before curing, phase-separates from the resin matrix during the curing process, and after curing, is in a non-uniform state with the resin matrix and has a “sea-island structure”. It is desirable to use a resin that forms Phase separation during the hardening process means. Those that cause phase separation upon curing of the matrix resin ,. Those that cause phase separation due to curing of both the matrix and the resin to be dissolved and removed ,. There is one in which phase separation is caused by heat (temperature) applied during curing and the phase is fixed by curing. In addition,
In the present invention, the term "sea-island structure" means that the heat-resistant resin matrix is sea, and in this sea, a portion where the concentration of the resin that can be dissolved and removed is high exists in an island shape. It means the state, and the boundary between the sea and the island is unclear.
This island may be independent in the sea, or may be a series of comrades.

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

(3) The structure of the metal film adherend of the present invention has an adhesive layer having a roughened metal coating side on a substrate, and the roughened surface of the adhesive layer. In the case where a metal film is provided, the adhesive layer is thermally cured including a resin in which a particulate substance capable of being dissolved or removed by decomposition is subjected to a curing treatment and a functional group of which is partially substituted with a photosensitive group. Dispersed in a heat-resistant resin matrix composed of a resin composite of a thermoplastic resin and at least one or two resins selected from a photosensitive resin (hereinafter, simply referred to as "thermosetting resin") and a photosensitive resin. It is preferable that the resin composite has a quasi-homogeneous compatible structure, a co-continuous structure, or a spherical domain structure. Here, at least one selected from the group consisting of inorganic particles, metal particles, elastomer particles, alkali-soluble resin particles and solvent-soluble resin particles may be used as the above-mentioned soluble and removable particulate substance. desirable. In addition, as the above-described particulate substance that can be decomposed and removed, it is desirable to use a suspension-polymerized amino resin having a low degree of crosslinking.

Another structure of the metal film adherend of the present invention has an adhesive layer having a roughened metal coating side on a substrate, and the metal is provided on the roughened surface of the adhesive layer. In the case where the adhesive layer is provided with a film, the adhesive layer is formed by dissolving a resin capable of being dissolved and removed with at least one or two resins selected from thermosetting resins and photosensitive resins which have been subjected to a curing treatment. A heat-resistant resin matrix composed of a resin composite with a plastic resin is dispersed in the sea in an island shape to form a sea-island structure. This resin composite has a pseudo-homogeneous compatible structure. , It is preferable to form a co-continuous structure or a spherical domain structure. Here, the above-mentioned resin that can be dissolved and removed is incompatible with the uncured heat-resistant resin matrix before curing, and forms a “sea-island structure” in a non-uniform state with the resin matrix after curing. The resin that is compatible with the uncured heat-resistant resin matrix before curing, phase-separates from the resin matrix during the curing process, and after curing, is in a non-uniform state with the resin matrix and has a “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, a fiber, a rod, or a sphere, and various industrially usable shapes.

In the above-mentioned metal film adherend according to the present invention, a substrate is used as a substrate, and the coated metal is etched as required, or the metal is coated in a pattern shape to form a printed wiring board. . Such a printed wiring board has, for example, an adhesive layer in which a particulate substance that can be dissolved or removed by decomposition is dispersed in a hardened heat-resistant resin matrix on a substrate. A printed wiring board having a roughened surface formed on the conductor forming surface of the adhesive layer, and a conductor circuit provided on the roughened surface, wherein the heat-resistant resin matrix is A resin composite of at least one or two resins selected from a curable resin and a photosensitive resin and a thermoplastic resin. The resin composite has a pseudo-homogeneous compatible structure. , It is preferable to form a co-continuous structure or a spherical domain structure. Another configuration of the printed wiring board is a resin composite of a thermoplastic resin and a resin capable of being dissolved and removed on the substrate, at least one or two resins selected from thermosetting resins and photosensitive resins. An adhesive layer is formed in the sea of a heat-resistant resin matrix that has been cured to consist of islands and forms a sea-island structure, and the conductor forming surface of this adhesive layer is A roughened surface is formed, and a conductor circuit is provided on the roughened surface, and the heat-resistant resin matrix is a resin composite of a thermosetting resin or a photosensitive resin and a thermoplastic resin. The resin composite is preferably composed of a body, and it is preferable that the resin composite has a pseudo-homogeneous compatible structure, a co-continuous structure, or a spherical domain structure.

[0020]

[Action]

(1) The adhesive of the present invention is characterized in that, as an adhesive matrix, "an uncured thermosetting resin containing a resin in which a part of functional groups is substituted with a photosensitive group (hereinafter, simply referred to as" uncured thermosetting resin ") is used. And / or uncured photosensitive resin ”and / or a mixture of“ thermoplastic resin ”. In particular, the adhesive of the present invention is homogeneous in a resin mixture of at least one or two resins selected from uncured thermosetting resin and uncured photosensitive resin and a thermoplastic resin in a compatible state. It is desirable to be mixed with.
This makes it possible to strengthen the resin matrix of the adhesive without lowering the heat resistance, electrical insulation and chemical stability.

Here, the reason why the above-mentioned compatible resin mixture is used as the heat resistant resin matrix of the adhesive is at least one selected from thermosetting resins and photosensitive resins obtained by curing. Alternatively, the resin structure of the resin composite composed of the two kinds of resins and the thermoplastic resin can be easily controlled by the curing conditions.

As a method for homogeneously mixing and dispersing at least one or two kinds of resins selected from uncured thermosetting resins and uncured photosensitive resins and thermoplastic resins in a compatible state. Include a method of dissolving a resin in a solvent, a method of melting a thermoplastic resin by heating and then mixing a thermosetting resin or a photosensitive resin. Among them, the method of dissolving the resin in the solvent is preferably used. The reason is that the workability is good and the resin can be made compatible at a low temperature. Examples of the solvent include dimethylformamide (DMF), normal methylpyrrolidone (NMP), methylene chloride, diethylene glycol dimethyl ether (DMDG) and the like.

In the adhesive of the present invention, the heat-resistant resin matrix is at least one selected from uncured thermosetting resin and uncured photosensitive resin, or 2
The compounding ratio of the seed resin and the thermoplastic resin is preferably 15 to 50 wt% in terms of the content of the thermoplastic resin. The reason for this 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 wt%, it is difficult to apply and a smooth and uniform adhesive is obtained. This is because it becomes difficult to form a layer.

The viscosity of the adhesive of the present invention is preferably 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 deteriorates and a smooth adhesive surface cannot be obtained, while if it is less than 0.5 Pa · s, sedimentation of particulate matter that can be removed by dissolution or decomposition can occur. This is because a sufficiently roughened surface cannot be obtained and the adhesion with the coating metal is reduced.

(2) The adhesive layer of the present invention is characterized in that, as a resin matrix of the adhesive layer, a thermosetting resin containing a resin in which a part of functional groups is substituted with a photosensitive group (hereinafter, simply referred to as “thermosetting resin”). A resin composite of a thermoplastic resin and at least one or two resins selected from the group consisting of a "curable resin") and a photosensitive resin is used. This makes it possible to stably provide an adhesive layer having excellent adhesion to the coating metal.

The reason for using a resin composite of a thermoplastic resin and at least one or two resins selected from thermosetting resins and photosensitive resins as the heat resistant resin matrix of the adhesive layer is as follows. When made into a resin composite,
Unique physical properties of thermosetting resin or photosensitive resin,
Since it is possible to develop the toughness peculiar to the thermoplastic resin together, the toughness of the entire resin matrix can be achieved without lowering the heat resistance, elastic modulus, electrical insulating property and chemical stability. is there.

The surface of the adhesive layer of the present invention is roughened, but the roughened surface is dissolved by a particulate substance that can be dissolved and removed by decomposition, or a resin that can be dissolved and removed by dispersing in an island shape. It is formed by a so-called octopus-shaped recess formed by being decomposed and removed. Therefore, in this recess, a metal coating such as electroless plating is deposited to serve as an anchor, and since the resin matrix that constitutes this recess has large toughness and resin breakage does not easily occur, the metal coating forms an adhesive layer. It is possible to maintain high adhesion strength (peel strength) without peeling from the roughened surface. Further, since the heat-resistant resin matrix is excellent in toughness, the adhesive layer itself is not easily broken even when it is deformed, and can be used even when the substrate is deformed or stressed.

In the adhesive layer of the present invention, the resin composite preferably has a pseudo-homogeneous compatible structure, a co-continuous structure or a spherical domain structure. Here, (a). Quasi-homogeneous compatible structure means so-called LCST type (Low
In a resin composite of a thermosetting resin or a photosensitive resin showing a phase diagram of Critical Solution Temperature) and a thermoplastic resin, the particle diameter of the constituent resin particles is 0.1 μm or less as measured by a transmission electron microscope. , Means a state in which the glass transition temperature peak value of the resin measured by dynamic viscoelasticity is one. This state is close to the ideal mixed state of the resin, and is a new concept originally devised by the inventor. Here, the conditions of the dynamic viscoelasticity measurement in the present invention are: vibration frequency 6.28 rad / sec, temperature rising rate 5 ° C. /
Minutes. That is, this pseudo-homogeneous compatible structure maintains the physical properties peculiar to the thermosetting resin such as epoxy resin or the photosensitive resin such as acrylic resin, and exceeds the physical properties peculiar to the thermoplastic resin such as polyether sulfone (PES). It has a more homogeneous structure showing the introduction effect, and the interaction between the thermosetting resin or the photosensitive resin and the thermoplastic resin is extremely strong. It is understood that the structure of such a resin composite is uniform even if its fractured surface is etched using a solvent that dissolves the thermoplastic resin, and its surface state is almost unchanged from that before etching. The resin composite forming such a quasi-homogeneous compatible structure has higher breaking strength and tensile strength than those of the constituent resins alone.

The effect of the structure of such a resin composite is that the thermoplastic resin (eg PE
It becomes particularly remarkable when the content of S) is 15 to 50 wt% in terms of solid content. The reason is that the content of thermoplastic resin is 15 wt%
If less than, the effect of toughening is not sufficiently exerted because there are few thermoplastic resin molecules entangled in the mesh of the resin component, on the other hand,
This is because when the content of the thermoplastic resin exceeds 50 wt%, the interaction between the thermosetting resin or the photosensitive resin and the thermoplastic resin is reduced due to the reduction of the crosslinking points.

Such a quasi-homogeneous compatible structure has an uncured thermosetting resin or an uncured photosensitive resin and a thermoplastic resin, if necessary, dissolved in a solvent and uniformly mixed, and then cured. It is formed by increasing the speed and / or decreasing the phase separation speed so that the particle diameter of the constituent resin particles becomes 0.1 μm or less as measured by observation with a transmission electron microscope.

Specifically, as a first method, when a thermosetting resin is used, it is selected from the curing temperature of the thermosetting resin, the type of curing agent, and the presence or absence of photosensitivity.
With a curing rate exceeding the pseudo-homogeneous phase formation point determined by one or more factors, while when using a photosensitive resin, the photocuring factor of the photosensitive resin, such as an initiator, a sensitizer, or a photosensitivity There is a method of curing at a curing rate that exceeds the quasi-homogeneous phase formation point determined by the monomer and exposure conditions. The quasi-homogeneous phase formation point here means that the particle size of the resin particles forming 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, formation of a pseudo-homogeneous phase determined by one or more factors of the number of functional groups or the molecular weight in one molecule of uncured thermosetting resin or uncured photosensitive resin. There is a method of curing at a phase separation speed not exceeding the point. The quasi-homogeneous phase formation point here is the upper limit value of the phase separation rate that can obtain 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. Means

Further, as a third method, there is a method of curing at a curing rate exceeding the quasi-homogeneous phase forming point and at a phase separation rate not exceeding the quasi-homogeneous phase forming point. This means a method in which the factors that determine the curing rate and the phase separation rate influence each other.

Next, the interrelationship of the above-mentioned various factors that determine the curing rate or the phase separation rate will be described. First, regarding the factors that determine the curing rate, the curing rate increases as the curing temperature of the thermosetting resin increases, assuming that other factor conditions are constant. Therefore, when the thermosetting resin is cured below the lower limit of the curing temperature required to obtain a curing rate exceeding the pseudo-homogeneous phase formation point, the structure of the obtained resin composite becomes a pseudo-homogeneous compatible structure. A curing agent having a shorter gel time has a higher curing speed. Therefore, when the thermosetting resin is cured with a curing agent that does not exceed the upper limit of the gelling time required to obtain a curing rate that exceeds the pseudo-homogeneous phase formation point, the structure of the resin composite obtained is pseudo. It has a uniform compatible structure. The higher the photosensitivity, the faster the curing speed. Therefore,
In a combination in which other factor conditions form a quasi-homogeneous compatible structure, by imparting photosensitivity to the resin, the obtained resin composite has a more homogeneous quasi-homogeneous compatible structure. In addition, as a method of imparting photosensitivity, there are a method of introducing a photosensitive group into a thermosetting resin or a thermoplastic resin, and a method of blending a photosensitive monomer. You may mix | blend. 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 the pseudo-homogeneous phase formation point determined by the photocuring factor such as an initiator, a sensitizer, a photosensitive monomer and exposure conditions. However, when imparting photosensitivity to the thermosetting resin or when imparting a photosensitive monomer in order to improve the resolution of development, it is selected from an uncured thermosetting resin and an uncured photosensitive resin. The compatibility between at least one or two of the above resins and the thermoplastic resin decreases, and phase separation occurs even at a relatively low temperature (see FIGS. 10 to 12). Therefore, when imparting photosensitivity to the thermosetting resin or imparting a photosensitive monomer, the adhesive is vacuum dried at low temperature (30 to 60 ° C), if necessary, and then exposed and cured. , Then heat curing (80 ~
By performing the treatment at 200 ° C, a pseudo-homogeneous compatible structure can be obtained.

Considering these facts, when the thermosetting resin or the photosensitive resin and the thermoplastic resin are compounded, if the above-mentioned variation factor is one, the value of the factor corresponding to the pseudo-homogeneous phase formation point is One point is decided. Therefore, when the above-mentioned fluctuation factors are two or more, various combinations of the values of the factors corresponding to the pseudo-homogeneous phase formation point are conceivable. That is, the particle size of the constituent resin particles is a value measured by TEM observation.
It is possible to select a combination that exhibits a curing rate of 0.1 μm or less.

Next, regarding the factors that determine the phase separation rate, if the other factor conditions are constant, the greater the number of functional groups in one molecule of the uncured thermosetting resin or the uncured photosensitive resin, the more phase separation will occur. Difficult to occur (phase separation speed slows down). Therefore, 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 pseudo-homogeneous phase formation point. When cured with
The resulting resin composite has a pseudo-homogeneous compatible structure. The larger the molecular weight of the uncured thermosetting resin or the uncured photosensitive resin, the less likely phase separation occurs (the phase separation speed becomes slower). Therefore, when the uncured thermosetting resin or the 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 quasi-homogeneous phase formation point is used for curing, the resulting resin composite is obtained. The body structure becomes a pseudo-homogeneous compatible structure.

Considering these facts, in the case where the thermosetting resin or the photosensitive resin and the thermoplastic resin are compounded, if the above-mentioned variation factor is one, the value of the factor corresponding to the pseudo-homogeneous phase forming point is One point is decided. Therefore, when the above-mentioned variation factors are two types, various combinations of the values of the factors corresponding to the pseudo-homogeneous phase formation points are possible. That is, the particle size of the constituent resin particles is a value measured by TEM observation.
It is possible to select a combination showing a phase separation rate of 0.1 μm or less.

In such a quasi-homogeneous compatible structure of the resin composite, an epoxy resin can be used as the thermosetting resin, but the epoxy resin has an epoxy equivalent of 100 to 100.
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 when it exceeds 1000, it is difficult to mix with a thermoplastic resin such as PES, and moreover, the Tg point is lowered, so that the curing This is because phase separation easily occurs during heating and it is difficult to obtain a pseudo-homogeneous compatible structure. The molecular weight of this epoxy resin is preferably 200 to 10,000.
The reason for this is that if the molecular weight of the epoxy resin is less than 200, a sufficient reaction rate cannot be obtained, and even if it is cured, the cured product will be too hard and brittle, while if it exceeds 10,000, it will not be compatible with the thermoplastic resin. This is because the compatibility decreases. Although PES can be used as the thermoplastic resin, the molecular weight of this PES is preferably 3,000 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 quasi-homogeneous compatible structure cannot be obtained, while if it exceeds 100000, a compatible state with thermosetting resin or photosensitive resin cannot be formed. Because.

As described above, the resin composite having a quasi-homogeneous compatible structure has the unique physical properties of thermosetting resin such as epoxy resin or the unique physical properties of photosensitive resin such as acrylic resin. At the same time, it is possible to exhibit physical properties higher than the original physical properties of the thermoplastic resin such as PES. That is, the PES-modified epoxy resin and PES-modified acrylic resin according to the present invention have higher resin strength than that of PES alone, and have an unprecedented toughening effect on epoxy resin or acrylic resin.

(B). A co-continuous structure means a composite structure in which a thermosetting resin-rich spherical particles such as an epoxy resin which are interconnected are present in a thermoplastic resin-rich matrix such as PES. (Takashi Inoue et al., POLYMER, 30, p662
(1989)). The structure of such a resin composite is such that when the fracture surface thereof is etched using a solvent that dissolves the thermoplastic resin, the thermoplastic resin-rich matrix portion is dissolved, and only spherical particles such as linked epoxy resin are observed. I understand from that. The resin composite forming such a co-continuous structure has a toughness thermoplastic resin as a continuous phase, and thus is tougher than a thermosetting resin alone such as an epoxy resin.

(C). The spherical domain structure mainly means a structure in which spherical domains consisting of a thermosetting resin or a photosensitive resin are uniformly dispersed independently of each other in a resin matrix of a thermoplastic resin. Point to. The structure of such a resin composite has a structure in which when a fracture surface of the resin composite is etched using a solvent that dissolves a thermoplastic resin, a thermoplastic resin-rich matrix portion is melted and dispersed independently and uniformly. It can be seen from the fact that only spherical particles of are observed.
The resin composite forming such a spherical domain structure is
Since spherical particles of the thermosetting resin are dispersed in the "sea" of the thermoplastic resin, the resin is tougher than the thermosetting resin alone.

The effect of the co-continuous structure or spherical domain structure of such a resin composite is that the content of the thermoplastic resin (for example, PES) in the composite is 15 to 50 wt% in terms of solid content.
It becomes especially remarkable when it is%. The reason for this is that if the content of the thermoplastic resin is less than 15 wt%, the toughening effect is not sufficiently exerted because the number of thermoplastic resin molecules entangled in the resin component network is small, while the content of the thermoplastic resin is 50 wt%. If it exceeds%, the interaction between the thermosetting resin or the photosensitive resin and the thermoplastic resin is reduced due to the reduction of the cross-linking points.

In such a resin composite, it is desirable that the average particle diameter of the spherical particles constituting the co-continuous structure or the spherical domain structure is 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 co-continuous structure or spherical domain structure, while if it exceeds 5 μm,
This is because it is not possible to improve the toughness and the photosensitivity and heat resistance are also reduced.

The above-mentioned co-continuous structure or spherical domain structure controls the substitution ratio of the functional group involved in thermosetting of the thermosetting resin with the photosensitive group, or adjusts the type and molecular weight of the photosensitive resin. By mixing the uncured thermosetting resin or the uncured photosensitive resin with the thermoplastic resin in a compatible or incompatible state, and then adjusting the drying conditions and curing conditions, It is formed by setting the average particle diameter of the spherical particles to exceed 0.1 μm and 5 μm or less. Further, as the resin matrix, at least one kind or two kinds of resins selected from thermosetting resins and photosensitive resins may be used, and a thermoplastic resin may be used as a resin forming spherical domains connected or independent to each other. Good.

As described above, the adhesive layer of the present invention preferably has a quasi-homogeneous compatible structure, a co-continuous structure or a spherical domain structure. Among them, the quasi-homogeneous compatible structure is formed. Since it is possible to obtain higher resin strength than forming a co-continuous structure or a spherical domain structure, forming a quasi-homogeneous compatible structure is more suitable as the resin matrix of the adhesive layer.

The thickness of the adhesive layer of the present invention is
It is preferably 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) will decrease, while if it exceeds 200 μm, it will be difficult to remove the solvent in the adhesive and it will be dried and cured. Because it is difficult.

(3) The metal film adherend according to the present invention is characterized in that it has a roughened adhesive layer on the surface of a substrate, and that a metal film is provided on the roughened surface of the adhesive layer. In the metal film adherend, the thermosetting resin matrix of the adhesive layer contains a resin in which a part of functional groups is replaced with a photosensitive group (hereinafter, simply referred to as "thermosetting resin"). And a resin composite of at least one or two resins selected from photosensitive resins and a thermoplastic resin. Here, it is preferable that the resin composite has a pseudo-homogeneous compatible structure, a co-continuous structure, or a spherical domain structure.

The surface of the adhesive layer in the metal film adherend of the present invention is roughened, and the roughened surface is a particulate substance that can be dissolved and removed, decomposed and removed, or a dissolved substance that is dispersed in an island shape. It is formed by a so-called octopus-shaped recess formed by dissolving and decomposing the removable resin. Therefore,
In this recess, a coating metal such as electroless plating is deposited to serve as an anchor, and since the resin matrix forming this recess has large toughness and does not easily break the resin, the metal coating is used as a rough surface of the adhesive layer. It is possible to maintain high adhesion strength (peel strength) without peeling off.

In the metal film adherend according to the present invention, a printed wiring board can be obtained by using a substrate as a substrate and etching or coating the coating metal in a pattern. Further, such a printed wiring board can be multi-layered. In this case, the roughened surface preferably has R _max = 1 to 20 μm.
The reason for this is that when the thickness is less than 1 μm, the adhesion strength between the coating metal and the adhesive layer decreases, and when it exceeds 20 μm, the pattern spacing is 10
This is because it becomes difficult to manufacture a printed wiring board having a fine pattern of 0 μm or less.

According to such a printed wiring board, the heat-resistant resin matrix forming the adhesive can be toughened without lowering the heat resistance, elastic modulus, chemical stability and electrical insulation. Therefore, it is possible to stably provide a wiring board having a higher 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 is an amino resin such as phenol resin, melamine resin or urea resin. , Epoxy resin, epoxy modified polyimide resin, unsaturated polyester resin, polyimide resin, urethane resin, diallyl phthalate resin and the like can be used. The reason for this is that these resins have excellent thermal and electrical characteristics. As this thermosetting resin, a resin in which a functional group partially contributing to thermosetting is partially substituted with a photosensitive group can be used, and for example, an acrylic compound of 5 to 70% of an epoxy resin is suitable.

As the thermoplastic resin used for the heat resistant resin matrix, polyether sulfone (PES), polysulfone (PSF), phenoxy resin, polyetherimide (PEI), polystyrene, polyethylene, polyarylate, polyamideimide, polyphenylene sulfide, Polyether ether ketone, polyoxybenzoate, polyvinyl chloride, polyvinyl acetate, polyacetal, polycarbonate and the like can be used. The reason for this is
These thermoplastic resins have high heat resistance and are tough,
Moreover, it is possible to be compatible with the thermosetting resin by using the solvent.

Among them, 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 can be mixed and dispersed in a solvent such as methylene chloride or dimethylformamide to easily form a pseudo-homogeneous compatible structure, co-continuous structure, or spherical domain structure. is there. Moreover,
When a mixed system of epoxy resin and PES is used, the PES-modified epoxy resin forms a quasi-homogeneous compatible structure, whereby the matrix becomes tougher, and both the tensile strength and the tensile elongation are higher than those of the epoxy resin alone.
It turned out to be improved more than 1.5 times. Further, 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 only the epoxy resin as the resin matrix. The inventors have confirmed that it is higher than when it is used.

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

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, those having 1 to several unsaturated double bonds such as acryloyl group, methacryloyl group, allyl group and vinyl group in the molecule can be used,
Epoxy acrylate, polyester acrylate, polyether acrylate, silcon acrylate, polybutadiene acrylate, polystytyl ethyl methacrylate, vinyl / acrylic oligomer Copolymerized and then reacted with an acrylic monomer), polyethylene / thiol (copolymer of olefin and mercaptan) and the like are preferably used.

Here, as the photoinitiator important as a photocuring factor for the photosensitive resin, benzoisobutyl ether, benzyl dimethyl ketal, diethoxyacetophenone, acyloxime ester, chlorinated acetophenone, hydroxyacetophenone, etc. Bond cleavage type,
Benzophenone, Michler's ketone, dibenzosuberone,
Any one or more of intramolecular hydrogen abstraction type such as 2-ethylanthraquinone and isobutylthioxanthone are preferably used.

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

As the sensitizer, Michler's ketone, Irgacure 651, isopropylthioxanthone, etc. are suitable, and among the above photoinitiators, some 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 / 100 parts by weight of the photosensitive resin.
Weight parts Irgacure 907 / isopropyl thioxanthone = 5 weight parts / 0.5 weight parts are preferred.

Epoxy acrylate, epoxy methacrylate, urethane acrylate, polyester acrylate, polystyryl methacrylate, etc. are preferably used as the photosensitive monomer or photosensitive oligomer constituting the photosensitive resin.

Further, as the curing agent for the resin matrix of the present invention, when an epoxy resin is used as the thermosetting resin, an imidazole type curing agent, diamine, polyamine, polyamide, anhydrous organic acid, vinylphenol or the like can be used. On the other hand, when a thermosetting resin other than the epoxy resin is used, a known curing agent can be used.

Next, the particulate substance which can be dissolved or removed by decomposition in the present invention and the resin which can be dissolved and removed by being dispersed in the sea of the heat resistant resin matrix in the form of islands will be described in detail. ． Examples of such substances that can be dissolved and removed include "curing-treated heat-resistant resin powder soluble in acid or oxidizing agent" or "inorganic particles, metal particles, elastomer particles, alkali-soluble resin particles and It is possible to use at least one or more types of particulate matter capable of being dissolved and removed, selected from resin particles soluble in a solvent. (a). Regarding "heat-resistant resin powder that is soluble in an acid or an oxidant and has been cured," the reason for using such a heat-resistant resin powder is that this heat-resistant resin powder is
Since the thermosetting resin, the photosensitive resin, and the thermoplastic resin are insoluble in a diluent solvent that dissolves the resin, the viscosity of the resin solution is reduced by the diluent solvent, so that the heat-resistant resin powder that has been cured is This is because they are uniformly dispersed in the solution. Further, when a resin composite having a pseudo-homogeneous compatible structure is obtained, a solvent is used to mix the thermosetting resin or the photosensitive resin with the thermoplastic resin in a compatible state. Since the above-mentioned heat-resistant resin powder of (3) does not dissolve in the solvent, a clear anchor can be formed. The reason why it is desirable to be soluble in acids and oxidants is that the oxidant has a strong decomposing power, can form a clear anchor in a short time, is excellent in productivity, and is formed by this oxidant. This is because the adhesive layer having the formed anchor hardly dissolves or deteriorates in a normal use environment. On the other hand, the acid is
It is economical because it does not require the neutralization treatment found in oxidizers, and it is easier to treat waste liquid than oxidizers, and the equipment is simpler, and it has excellent safety. Because there is. As the heat resistant resin powder, epoxy resin, amino resin (melamine resin, urea resin, guanamine resin), polyester resin, bismaleidotriazine resin, etc. can be used. (b). "Inorganic particles, metal particles, elastomer particles, resin particles soluble in alkali and resin particles soluble in a solvent," As, silica, alumina, zirconia, zinc oxide, magnesia, cordierite, titania and other oxides, silicon carbide, boron carbide and other carbides, aluminum nitride, boron nitride, silicon nitride and other nitrides, calcium carbonate, sodium carbonate It is possible to use a carbonate such as, a sulfate such as barium sulfate, or talc. The reason for using such inorganic particles is that they have the effect of reducing the coefficient of thermal expansion of the heat resistant resin matrix (resin composite) and can improve the heat cycle resistance. In particular, the use of high thermal conductivity inorganic particles such as silicon carbide or aluminum nitride can improve the thermal conductivity of the adhesive layer. Aluminum, nickel, magnesium, copper, zinc, iron or the like can be used as the metal particles. The reason for using such metal particles is that electromagnetic properties can be imparted to the adhesive layer itself. Examples of the elastomer particles include rubber resins such as polybutadiene rubber, butadiene styrene rubber, butadiene acrylonitrile rubber, polychloroprene rubber, polyisoprene rubber, acrylic rubber, polysulfuric synthetic rubber, urethane rubber, fluoro rubber, silicone rubber and ABS resin. An elastomer such as a polyester elastomer, a polystyrene-polybutadiene-polystyrene (SBS) thermoplastic elastomer, a polyolefin-based thermoplastic elastomer (TPO), or a polyvinyl chloride-based thermoplastic elastomer can be used. The reason for using such elastomer particles is that they are non-heat resistant particles, are relatively low in price, and are effective for cost reduction. 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 the neutralization treatment as seen in an oxidizer is not required, it is economical, and the waste liquid treatment is easier than the oxidizer etc. It is also easy and safe. As the resin particles soluble in the above solvent (particularly organic solvent), thermoplastic resin powder such as styrene resin, vinyl chloride resin, vinyl acetate resin, etc. can be used. 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 there is no need to neutralize the waste liquid, This is because the cost can be reduced. Since the above-mentioned inorganic particles and metal particles are insoluble in a diluent solvent that dissolves the thermosetting resin, the photosensitive resin, and the thermoplastic resin, the viscosity of the resin solution is reduced by the diluent solvent, and thus the inorganic particles Metal particles are uniformly dispersed in this resin solution. Further, when obtaining a resin composite having a quasi-homogeneous compatible structure,
A solvent is used to mix the thermosetting resin or the photosensitive resin with the thermoplastic resin in a compatible state.However, even in such a case, the inorganic particles and the metal particles do not dissolve in the solvent, so it is clear. Anchors can be formed.

.. Particle substances that can be decomposed and removed include such substances as emulsion-polymerized low-crosslinking amino resins (melamine resin, urea resin, guanamine resin).
Can be used. The reason for using such a decomposable and removable particulate substance is that, for example, emulsion-polymerized melamine resin particles having a low degree of crosslinking decompose under high humidity, high temperature and high pressure conditions to form formalin and a melamine monomer. Therefore, there is no need to specially immerse the adhesive layer in the roughening liquid for roughening the surface of the adhesive layer, and the production facility becomes simple, which is advantageous.

.. The resin that can be dissolved and removed by being dispersed in the sea of the heat-resistant resin matrix in the form of an island is such a resin that is not compatible with the uncured heat-resistant resin matrix before curing, and is not compatible with the resin matrix after curing. The resin that forms the "sea-island structure" in a non-uniform state is compatible with the uncured heat-resistant resin matrix before curing, but after curing it is phase-separated from the resin matrix and non-uniform with the resin matrix. The resin that forms the “sea-island structure” can be used. Examples of the former resin include an epoxy group-terminated silicone resin. Examples of the latter resin include rubber resins such as butadiene and ABS resin described above, and thermoplastic resins such as polyester elastomer. For example,
The rubber-based resin dissolves in the compatibilizing solvent of the uncured heat-resistant resin matrix, but is incompatible with the uncured heat-resistant resin matrix itself, and the region (island) where the concentration of rubber-based resin is high is uncured heat-resistant. It is formed in the resin matrix (sea) and has a non-uniform concentration state (sea-island structure). It is difficult to control the size of the “islands” and the quality of the resin liquid that forms the “sea-island structure” is difficult to control. In this respect, it is disadvantageous in mass production as compared with a resin such as pre-cured resin and inorganic or metal particles which does not require a curing treatment, in which the particle diameter can be controlled by classification or the like and the quality can be easily controlled. Furthermore, in order to make the uncured heat-resistant resin matrix have a pseudo-homogeneous compatible structure, the curing conditions must be adjusted. Also in this respect, the presence of the uncured resin liquid as described above is disadvantageous because the curing conditions of the resin liquid must be adjusted. However, since the resin liquid forming the "sea-island structure" does not contain solid components such as pre-cured resin, inorganic particles, and metal particles, the kneading time is short and the adhesive solution It is excellent in that it can be easily prepared. Further, since it is easy to reduce the viscosity, the smoothness and leveling property of the coating film are excellent.

In the present invention, as the particulate matter, various shapes such as spherical shape, hollow shape and crushed piece shape can be used. Particularly, (1) particles having an average particle diameter of 10 μm or less, (2) average particle diameter of 2 μm Aggregated particles obtained by aggregating the following powders to have an average particle size of 2 to 10 μm, (3) a mixture of powder having an average particle size of 2 to 10 μm and powder having an average particle size of 2 μm or less, (4) average particle size 2
It is preferable to select from pseudo particles formed by adhering at least one of powder having an average particle diameter of 2 μm or less and inorganic powder having an average particle diameter of 2 μm or less on the surface of the powder having a particle diameter of ˜10 μm. The reason 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 agglomerated particles of (2) above, the mixture of (3) or (4) above. The reason why the pseudo-particles are preferable is that a complex anchor can be formed and the peel strength can be improved. In order to prevent agglomeration, it is desirable that the surface of the particulate matter be coated with silica sol or the like. The mixing amount of this particulate material is the resin solid content of the heat resistant resin matrix.
It is desirable that the weight ratio is 5 to 100 with respect to 100. The reason for this is that if the weight ratio is less than 5, the anchor cannot be formed, and if it exceeds 100, the 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 is reduced.

In the present invention, an epoxy resin is used as a thermosetting resin component constituting a heat-resistant resin matrix insoluble in a roughening liquid such as an acid or an oxidizing agent, while a roughening liquid such as an acid or an oxidizing agent is used. Epoxy resin powder can be used as the soluble heat-resistant resin powder. This point will be described below by taking solubility in an oxidizing agent as an example. The physical properties of the epoxy resin can be varied greatly by controlling the type of prepolymer (a relatively low molecular weight polymer having a molecular weight of about 300 to 10,000), the type of curing agent, and the crosslinking density. This difference in physical properties is
The solubility in an oxidizing agent is not an exception, 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. , Is the main factor, and is used secondarily. Regarding the skeleton structure of the monomer, the aliphatic epoxy generally has the highest solubility, and the glycidyl amine type and the glycidyl ether type generally have the lowest solubility. Regarding the cross-linking structure, for example, a hydroxy ether structure obtained by a reaction of an epoxide and an amine has a particularly high solubility, and an ether structure obtained by reacting an epoxide with imidazole as a curing catalyst has a particularly low solubility. The crosslink density decreases as the epoxy equivalent increases, resulting in higher solubility. The decrease in solubility is achieved by polyfunctionalizing the epoxy monomer, and in the phenol novolac type, the solubility decreases as the repeating unit n of the monomer increases sequentially from 0 to 1, 2. Therefore, based on the solubility difference with respect to the oxidizing agent, for example, as the "oxidizing agent-soluble epoxy resin" that constitutes the heat-resistant resin powder, (A) "Aliphatic epoxy is used as an epoxy prepolymer and a fat is used as a curing agent. A mildly cross-linked epoxy resin having an epoxy equivalent of about 265 using a group amine curing agent is used. On the other hand, as the "epoxy resin which is hardly soluble (including insoluble) in the oxidizing agent" which is the thermosetting resin component of the heat resistant resin matrix, (B) "bisphenol A type epoxy resin is used as the epoxy prepolymer , Using an aromatic diamine-based curing agent as a curing agent,
"Epoxy resin with an epoxy equivalent of around 170" and (C) "Phenolic novolac type epoxy resin is used as an epoxy prepolymer, an imidazole curing agent is used as a curing agent, and the epoxy equivalent is about 136, which has lower solubility. "Epoxy resin" is used. Further, the epoxy resin (B) can also be used as an “oxidizer-soluble epoxy resin”. In this case,
The epoxy resin (C) is used as “epoxy resin which is hardly soluble in an oxidizing agent”.

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

[0067]

[Table 1]

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

In the present invention, a thermosetting resin such as an epoxy resin is used as the heat-resistant resin matrix in PES.
A mixture of a thermoplastic resin such as the above is used, and the inclusion of the thermoplastic resin in this way has a tendency to decrease the solubility in an acid or an oxidizing agent. In particular,
When a resin composite having a quasi-homogeneous compatible structure was used as the heat resistant resin matrix, the decrease in solubility was remarkable.

Next, a method of manufacturing the metal film adherend of the present application will be described. ． First, a resin mixture of at least one or two resins selected from the adhesive of the present invention, a so-called uncured thermosetting resin and an uncured photosensitive resin, and a resin mixture of a thermoplastic resin is mainly provided on a substrate. An adhesive layer is provided by applying the constituted adhesive, or by 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.

Here, as the above-mentioned substrate, the following metals, resins, and papers can be used, which are molded into a predetermined shape. (Magnetic medium) Polyethylene terephthalate film, hard magnetic disk (Electromagnetic shield) Filter paper (Automobile) Disc brake body, disc brake piston, clutch hub, oil pump cam, mission gear shaft (industrial machinery) screw, bearing (electrical / electronic industry) Printed wiring boards, substrates for mounting semiconductors (building materials) Phenolic resin impregnated core paper

.. Next, at least a part of the removable particulate matter or the island-shaped resin in the sea-island structure dispersed on the surface of the adhesive layer is treated with an acid, an oxidizing agent, an alkali,
It is dissolved and removed using a roughening liquid such as water or an organic solvent, or decomposed and removed under conditions of high temperature, high humidity and high pressure. As a method using the above-mentioned roughening liquid, it is possible to carry out by immersing the substrate on which the adhesive layer is formed in the roughening liquid, or by spraying the roughening liquid on the substrate. As a result, the surface of the adhesive layer can be roughened. Chromic acid, chromate salts, permanganate, ozone, etc. are preferable as the oxidizer, and hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, organic acids, etc. are preferable as the acid. As the alkali,
Sodium hydroxide, sodium carbonate, potassium hydroxide,
Ammonia is good. As the organic solvent, 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 preferable.

The relationship between the particulate matter or the island-like resin in the sea-island structure and the roughening liquid for removing them will be described. For heat-resistant resin particles that are soluble in acid or oxidant, oxidizers such as chromic acid, chromate salts, permanganate, ozone, hydrochloric acid, nitric acid, hydrofluoric acid and sulfuric acid,
Acids such as organic acids are preferred. In particular, amino resins can use wastewater-free hydrochloric acid as a roughening liquid, so that waste liquid treatment is easy and practical. For elastomers such as rubber resins, chromic acid, a mixture of chromic acid and sulfuric acid,
Oxidizing agents such as chromate, permanganate and ozone are suitable as the roughening liquid. Of the inorganic powders, hydrofluoric acid is suitable for silica and alumina, hydrochloric acid for carbonates such as calcium carbonate and sodium carbonate, and water for aluminum nitride that decomposes with water. Is. Since aluminum nitride is decomposed by water and gradually oxidized by oxygen in the air, it is necessary to seal a metal film adherend using aluminum nitride with nitrogen or argon before use. Of the particulate substances (thermoplastic resins) that can be dissolved and removed with an organic solvent, styrene resins include methyl ethyl ketone, benzene, toluene, dioxane, acetone, trichloroethylene, ethylene dichloride,
Carbon disulfide, ethyl acetate and butyl acetate are suitable as the roughening liquid for the vinyl chloride type, and organic solvents such as tetrahydrofuran, cyclohexanone, nitroethane and pyridine.

.. Next, the surface roughened adhesive layer on the substrate is coated with a metal film. As a method for coating the metal film, there are methods such as electroless plating, electrolytic plating and sputtering. As this electroless plating, for example, electroless copper plating, electroless nickel plating, electroless tin plating,
Examples of the electroless gold plating and electroless silver plating include electroless copper plating, electroless nickel plating and electroless gold plating, electroless cobalt-nickel-phosphorus plating, electroless copper-nickel-phosphorus plating. It is preferable that at least one of them is used. In addition, it is also possible to further perform different types of electroless plating or electroplating on the above electroless plating, or to coat solder. During electroless plating, various patterns can be drawn by plating by forming a plating resist or the like. Alternatively, the entire surface may be electroless plated and then etched. Furthermore, as the metal to be deposited by a method such as sputtering, Cu, Ni,
There are Cr, Ti, Mo, Au or alloys thereof.

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 transportation pipe and a gear in the field of the automobile industry, the electric / electronic industry. In the field, lead frames, hermetic seals, ceramic packages, connectors, capacitors, resistors, solar electrodes,
It can be applied to hard disks and the like, and in the industrial machinery industry field, it can be applied to pumps, valves, heat exchangers, filters, screws, dies, bearings and the like.

Next, a method of manufacturing a printed wiring board as this metal film adherend will be described. ． First, a substrate is used as a base, and the adhesive of the present invention, a so-called uncured thermosetting resin and / or
Alternatively, an adhesive mainly composed of a resin mixture of an uncured photosensitive resin and a thermoplastic resin is applied, or the adhesive itself is semi-cured to form a film, or the substrate itself is laminated. A layer of an adhesive is provided by forming 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 a pseudo-homogeneous compatible structure, a co-continuous structure or a spherical domain structure.

.. Next, at least a part of the removable particulate matter or the island-shaped resin in the sea-island structure dispersed on the surface of the adhesive layer is treated with an acid, an oxidizing agent, an alkali,
It is dissolved and removed using a roughening liquid such as water or an organic solvent, or decomposed and removed under conditions of high temperature, high humidity and high pressure. As a method of using the above-mentioned roughening liquid, the same roughening liquid as that described above is used to immerse the substrate on which the adhesive layer is formed in the solution or to spray the roughening liquid on the substrate. And the like, and as a result, the surface of the adhesive layer can be roughened.

.. Next, the surface-roughened adhesive layer on the substrate is subjected to electroless plating. For this electroless plating,
For example, electroless copper plating, electroless nickel plating, electroless tin plating, electroless gold plating, electroless silver plating, etc. can be mentioned, and in particular, electroless copper plating, electroless nickel plating or electroless gold plating It is preferable that it is at least one kind. In addition, it is also possible to further perform different types of electroless plating or electroplating on the above electroless plating, or to coat solder. In addition to the electroless plating, a method such as electrolytic plating or sputtering may be used to provide the metal adhesion layer. As the metal to be deposited, Cu, Ni, Cr, T
i, Mo, Au, alloys of these, and the like.

In electroless plating, a wiring pattern can be directly drawn by plating by forming a plating resist or the like. Alternatively, electroless plating may be applied to the entire surface and then etching may be performed to draw a conductor circuit.

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

[0081]

【Example】

(Example 1) (1) Cresol novolac 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 (manufactured by Shikoku Kasei, product name: 2E4MZ-CN)
5 parts by weight and rubber-based resin fine powder (made by Japan Synthetic Rubber) having an average particle size of 5.5 μm, 20 parts by weight, 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), and subsequently kneaded with a three-roll mill to obtain an adhesive solution. At this time, the viscosity at room temperature is 2-5 Pa.
・ It was s. (2) Using a roller coater (made by Thermatronics Trading Co., Ltd.), this adhesive solution was applied on a glass epoxy insulating plate (made by Toshiba Chemical Co., Ltd.) on which no copper foil was adhered, and then at 80 ° C. for 2 hours. 5 hours at 120 ℃, 2 hours at 150 ℃,
It was dried and cured to form an adhesive layer having a thickness of 20 μm. (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 then a neutralizing solution (made by Shipley) is used. ) And then washed with water. Roughened surface is JIS-B-0601 R _max = 10μ
It was 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, and then a plating resist is provided according to a conventional method, and then shown in Table 2. For electroless plating solution with additive composition
After immersion for 11 hours, electroless copper plating with a plating film thickness of 25 μm was performed to manufacture 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-mentioned conditions was observed by TEM to find resin particles with an average particle size of 0.1 μm or less. Was given. The cured product obtained by curing the resin composition mixture containing no 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 only 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 quasi-homogeneous compatible structure (see FIG. 3).

Example 2 (1) 70 parts by weight of cresol novolac type epoxy resin (Nippon Kayaku, trade name; EOCN-103S), polyether sulfone (PES) (ICI, trade name; Victrex) 30 parts by weight Part, imidazole-based curing agent (Shikoku Kasei, trade name: 2PHZ
-CN) 10 parts by weight and spherical silica fine powder (manufactured by Nippon Shokubai Kogyo Co., Ltd.) having an average particle size of 5.5 μm, 20 parts by weight, 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 kneading with a three-roll mill to obtain an adhesive solution. (2) Using a roller coater (made by Thermatronics Trading Co., Ltd.), this adhesive solution is applied on a glass epoxy insulating plate (made by Toshiba Chemical) on which no copper foil is adhered, and then at 80 ° C. for 3 hours. 120 ℃ for 3 hours, 150 ℃ for 5 hours,
It was dried and cured to form an adhesive layer having a thickness of 20 μm. (3) The above substrate on which the adhesive layer was formed was treated with hydrofluoric acid at 70 ° C for 15 minutes.
The surface of the adhesive layer was roughened by immersion for a minute, 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, and then a plating resist is provided according to a conventional method, and then shown in Table 2. For electroless plating solution with additive composition
After immersion for 11 hours, electroless copper plating with a plating film thickness of 25 μm was performed to manufacture 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 by TEM in the same manner as in Example 1 to find that the average particle size was 0.05 μm. The following resin particles were seen. Further, the cured product obtained by curing the mixture of the resin composition in which the fine silica powder is not mixed 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 quasi-homogeneous compatible structure.

Example 3 (1) A butadiene-acrylonitrile copolymer oligomer (CTBN) and a bisphenol A type epoxy resin were mixed and then heated at 160 ° C. for 2 hours to obtain an epoxy-modified CTBN.
I got (2) Bisphenol A type epoxy resin (made by Yuka Shell,
Trade name: Epicoat 828, Epoxy equivalent 190, Molecular weight 380
) 70 parts by weight, polyether sulfone (PES) (IC
I, product name; Victrex) 30 parts by weight, imidazole-based curing agent (manufactured by Shikoku Kasei, product name: 2E4MZ-CN) 10 parts by weight and the epoxy modified CTBN 30 parts by weight, and then N
Viscosity with a homodisper stirrer while adding MP solvent
The pressure was adjusted to 120 CPS, followed by kneading with a triple roll to obtain an adhesive solution. (3) Using a roller coater (made by Thermatronics Trading Co., Ltd.), this adhesive solution is applied on a glass epoxy insulating plate (made by Toshiba Chemical) on which no copper foil is adhered, and then at 80 ° C. for 1 hour. 2 hours at 120 ℃, 4 hours at 150 ℃,
It was dried and cured to form an adhesive layer having a thickness of 20 μm. (4) The above-mentioned substrate on which the adhesive layer was formed was 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 then a neutralizing solution (made by Shipley) was used. ) And then 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, and then a plating resist is provided according to a conventional method, and then shown in Table 2. A printed wiring board was manufactured by immersing in an electroless plating solution for additive having the composition for 11 hours and performing electroless copper plating having a plating film thickness of 25 μm.

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 in Example 1 to find that the average particle size was 0.1 μm. The following resin particles were seen. Further, the cured product obtained by curing the mixture of the resin composition in which the rubber resin is not mixed was subjected to a viscoelasticity measurement test under conditions of a vibration frequency of 6.28 rad / sec and a temperature rising 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 quasi-homogeneous compatible structure. Furthermore, when the resin matrix was observed by SEM, the "island structure" of the butadiene-acrylonitrile copolymer resin could be observed in the sea of the resin matrix after curing. That is, when the surface of the adhesive layer is treated with an oxidizing agent, the island structure portion is dissolved and removed, and the surface is roughened.

Example 4 Basically the same as in Example 1, the following adhesive solution was used. Bisphenol A type epoxy resin (made by Yuka Shell, Epicoat 82
8) 65 parts by weight, polyether sulfone (PES) (IC
I, product name: Victrex) 35 parts by weight, imidazole-based curing agent (manufactured by Shikoku Kasei, product name: 2E4MZ-CN) 5 parts by weight, and rubber-based resin fine powder (manufactured by Japan Synthetic Rubber) with an average particle diameter of 5.5 μ.
After mixing 20 parts by weight of m and 10 parts by weight of 0.5 μm in average particle size, the viscosity was adjusted to 100 CPS with a homodisper stirrer while adding a dimethylformamide / butyl cellosolve (1/1) mixed solvent, Subsequently, an adhesive solution obtained by kneading with a three-roll mill.

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 subjected to SEM by etching the cross section with methylene chloride which dissolves PES. Observed, average particle size
A continuous structure (co-continuous structure) of spheres considered to be 0.2 to 2 μm rich in epoxy resin was observed.

(Example 5) Basically the same as in Example 1, and the following adhesive solution was used. Bisphenol A type epoxy resin (made by Yuka Shell, Epicoat 82
8) 50 parts by weight, polyether sulfone (PES) (IC
I, product name; Victrex) 50 parts by weight, imidazole type curing agent (manufactured by Shikoku Kasei, product name; 2E4MZ-CN) 5 parts by weight and rubber resin fine powder (manufactured by Japan Synthetic Rubber) average particle size 5.5 μ
20 parts by weight of m and 10 parts by weight of particles having an average particle size of 0.5 μm were mixed, and the viscosity was adjusted to 100 CPS with a homodisper stirrer while adding DMF (dimethylformamide). An adhesive solution obtained by kneading with a roll.

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 subjected to SEM by etching the cross section with methylene chloride which dissolves PES. As a result of observation, spheres having an average particle size of about 2 to 5 μm and considered to be rich in epoxy resin were found. Moreover, this resin matrix had a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres were floated on the PES-rich base (see FIG. 4).

Example 6 (1) A photosensitive dry film (made by DuPont) was laminated on a glass epoxy copper clad laminate (made by Toshiba Chemical),
An image was printed by exposing it to ultraviolet light through a mask film on which a desired conductor circuit pattern was drawn. Then 1,1,
After development with 1-trichloroethane and removal of copper in the non-conductor portion using a cupric chloride etching solution, the dry film was peeled off with methylene chloride. Thus, a wiring board having a first-layer conductor circuit composed of a plurality of conductor patterns on the substrate was prepared. (2) 200 g of alumina particles (manufactured by Nippon Light Metal Co., Ltd .; trade name; AX34, average particle size 3.9 μm) were dispersed in 5 l of acetone into an alumina particle suspension obtained while stirring in a Henschel mixer, Alumina powder (manufactured by Nippon Light Metals, trade name; AX3) in an acetone solution prepared by dissolving 30 g of epoxy resin (manufactured by Mitsui Petrochemical Co., Ltd.) in 1 liter of acetone.
(4, average particle size 0.5 μm) 300g of dispersed dispersion was added dropwise to adhere the alumina powder to the surface of the alumina particles, and then the acetone was removed, and then heated to 150 ° C. 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 the range of ± 2 μm centering on the average particle size. (3) 70 parts by weight of 50% acrylate of cresol novolac type epoxy resin (Okaka Shell, epoxy equivalent 210, molecular weight 2000), 30 parts by weight of polyether sulfone (PES), 15 parts by weight of diallyl terephthalate, 2-methyl -1-
4 parts by weight of [4- (methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba Geigy), 4 parts by weight of imidazole-based curing agent (manufactured by Shikoku Kasei, trade name; 2E4MZ-CN), and the above. After mixing 50 parts by weight of the alumina pseudo particles prepared in (2), while adding butyl cellosolve, adjust the viscosity to 250 cps with a homodisper stirrer, and then knead with a three-roll to form a photosensitive adhesive solution. Prepared. (4) Apply this photosensitive adhesive solution onto the wiring board prepared in (1) above using a roll coater and keep it horizontal.
After standing 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 having a 100 μmφ black circle printed thereon was brought into close contact with the wiring board subjected to the treatment of (4), and 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 a 100 μmφ via hole on the wiring board. Further, the wiring board was exposed with an ultra-high pressure mercury lamp at about 3000 mj / cm ² and exposed at 100 ° C. for 1 hour.
By heat treatment for 5 hours at 150 ° C., an adhesive layer having openings having excellent dimensional accuracy equivalent to a photomask film was formed. (6) The wiring board treated in (5) above was treated with hydrofluoric acid and then treated with potassium permanganate (KMnO ₄ , 500 g / l).
Roughen the surface of the adhesive layer by dipping it at 15 ° C for 15 minutes, then
It was immersed in a neutralization solution (made by Shipley) and then washed with water. (7) A palladium catalyst (manufactured by Shipley) is applied to the substrate with the surface of the adhesive layer roughened to activate the surface of the adhesive layer, and then the electroless plating solution for additive having the composition shown in Table 2 is used. After immersion for a period of time, electroless copper plating having a plating film thickness of 25 μm was performed. (8) After repeating steps (4) to (7) twice,
Further, by carrying out 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 has its cross section etched with methylene chloride to obtain SE.
Observation of M shows a continuous structure (co-continuous structure) of spheres that are considered to be rich in epoxy resin with an average particle size of 0.2 to 2 μm.
Was observed (see FIG. 6). Further, the cured product obtained by curing the mixture of the resin compositions in which the alumina pseudo particles were not mixed 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 co-continuous structure.

(Example 7) (1) A photosensitive dry film (made by DuPont) was laminated on a glass epoxy copper clad laminate (made by Toshiba Chemical),
An image was printed by exposing it to ultraviolet light through a mask film on which a desired conductor circuit pattern was drawn. Then 1,1,
After development with 1-trichloroethane and removal of copper in the non-conductor portion using a cupric chloride etching solution, the dry film was peeled off with methylene chloride. Thus, a wiring board having a first-layer conductor circuit composed of a plurality of conductor patterns on the substrate was prepared. (2) Photosensitized epoxy oligomer (CNA25, molecular weight 4000), PES (molecular weight 17,000), imidazole type curing agent (cresol novolac type epoxy resin dissolved in DMDG (diethylene glycol dimethyl ether)) Shikoku Kasei, trade name; 2E4MZ-CN), acrylated isothiocyanate as a photosensitive monomer (Toagosei, trade name; Aronix M
215), photoinitiator (Ciba-Geigy, trade name: I-907)
The following composition was mixed with an NMP solvent, and a rubber-based resin fine powder (manufactured by Japan Synthetic Rubber) having an average particle size of 5.5 μm was added to the mixture in an amount of 20 parts by weight, and an average particle size of 0.1.
After mixing 10 parts by weight of 5 μm, the viscosity was adjusted to 120 CPS with a homodisper stirrer and subsequently kneaded with a three-roll mill to obtain a photosensitive adhesive solution. Resin composition: Photosensitized epoxy / PES / M215 / I-907 / imidazole = 75/25/10/5/5/5 (3) Apply this photosensitive adhesive solution to the wiring board prepared in (1) above. , Using a roll coater, in a horizontal state
After leaving it for 20 minutes, it was dried at 60 ° C. (4) A photomask film having a 100 μmφ black circle printed thereon was brought into close contact with the wiring board subjected to the treatment of (3), and exposed with an ultrahigh pressure mercury lamp of 500 mj / cm ² . By ultrasonically developing this with DMDG solution, 100 μm on the wiring board
An opening to be a φ via hole was formed. Further, the wiring board is exposed by an ultra-high pressure mercury lamp at about 3000 mj / cm ² ,
By heat-treating at 100 ° C. for 1 hour and at 150 ° C. for 5 hours, an adhesive layer having a thickness of 50 μm and having an opening excellent in dimensional accuracy corresponding to a photomask film was formed. (5) The wiring board treated in (4) above is immersed in potassium permanganate (KMnO ₄ , 500g / l) at 70 ℃ for 15 minutes to roughen the surface of the adhesive layer and then neutralize it. It was immersed in a solution (made by Shipley) and 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, and then the electroless plating solution for additive having the composition shown in Table 2 is used. After immersion for a period of time, electroless copper plating having a plating film thickness of 25 μm was performed. (7) After repeating the steps (3) to (6) twice,
Further, by carrying out 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, and
The cured product obtained by heat curing was TEM as in Example 1.
Upon observation, resin particles having an average particle size of 0.1 μm or less were found. Further, the cured product obtained by curing a mixture of resin compositions in which the rubber-based resin fine powder is not mixed has a vibration frequency
When a viscoelasticity measurement test was conducted under the conditions of 6.28 rad / sec and a heating rate of 5 ° C./min, the peak of the glass transition temperature Tg was 1
It was one. Therefore, it is considered that the resin matrix of the adhesive used in this example has a quasi-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 the same as in Example 7, and the following adhesive solution was used. Photosensitizing epoxy oligomer (CNA2) in which 25% of the epoxy groups of cresol novolac type epoxy resin are acrylated.
5, molecular weight 4000), PES (molecular weight 17,000), imidazole-based curing agent (manufactured by Shikoku Kasei, trade name: 2E4MZ-CN), acrylated isothiocyanate as a photosensitive monomer (manufactured by Toagosei, trade name: Aronix M215), Using a photoinitiator (Ciba Geigy, trade name: I-907), N with the following composition
Mix using MP (dimethylformamide), and further mix 20 parts by weight of rubber resin fine powder (manufactured by Japan Synthetic Rubber) having an average particle size of 5.5 μm with an average particle size of 0.
A photosensitive adhesive solution obtained by mixing 10 parts by weight of 5 μm, adjusting the viscosity to 120 CPS with a homodisper stirrer, and subsequently kneading with three rolls. Resin composition: Photosensitized epoxy / PES / M215 / I-907 /
Imidazole = 75/25/10/5/5 The adhesive was cured by drying at 80 ° C., UV-curing it, and then heat-curing it.

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 subjected to SEM observation by etching the cross section thereof with methylene chloride. A continuous structure (co-continuous structure) of spherical objects having a diameter of 0.2 to 2 μm and considered to be rich in epoxy resin was observed.

Example 9 Basically the same as in Example 7, the following adhesive solution was used. Photosensitizing epoxy oligomer (CNA2) in which 25% of the epoxy groups of cresol novolac type epoxy resin are acrylated.
5, molecular weight 4000), PES (molecular weight 17,000), imidazole-based curing agent (manufactured by Shikoku Kasei, trade name; 2E4MZ-CN), acrylated isothiocyanate as a photosensitive monomer (manufactured by Toagosei, trade name; Aronix M215), Using a photoinitiator (Ciba Geigy, trade name: I-907), N with the following composition
Mix using MP, and further mix 20 parts by weight of the rubber-based resin fine powder having an average particle size of 5.5 μm and 10 parts by weight of an average particle size of 0.5 μm with this mixture, and then use a homodisper stirrer. The viscosity of the photosensitive adhesive solution was adjusted to 120 CPS with, and then kneaded with a three-roll mill. Resin composition: Photosensitized epoxy / PES / M215 / I-907 / imidazole = 75/25/10/5/5 The adhesive is cured by drying at 100 ° C and 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 this example under the above conditions was subjected to SEM observation by etching the cross section with methylene chloride that dissolves PES. However, the average particle size is 2
Spherical particles considered to be rich in epoxy resin having a size of about 5 μm were observed. Moreover, this resin matrix had a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres were floated on a PSF-rich base.

As in Examples 7 to 9 above, by changing the drying conditions, it is possible to obtain a cured product having a pseudo-homogeneous phase dissolution structure, a co-continuous structure, and a spherical domain structure 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 cured rapidly by photocuring, so that phase separation due to subsequent heat curing is relatively unlikely to occur. For reference, the phase diagrams are shown in FIGS. These phase diagrams are different from those of Examples 7 to 9 in that the preparation conditions of the adhesive are different, and the photosensitized epoxy / PES / TMPTA / I-907 / imidazole = 75/25/20/5/5. .

Example 10 Basically the same as in Example 7, the following adhesive solution was used. Cresol novolac type epoxy resin (made by Yuka Shell) 100% acrylated photosensitive epoxy oligomer, PES, imidazole type curing agent (Shikoku Kasei, trade name: 2E4MZ-CN), acrylic as a photosensitive monomer Isothiocyanate (manufactured by Toagosei, trade name; Aronix M
215), photoinitiator (Ciba-Geigy, trade name; I-907)
The following composition was used to mix with NMP, and 20 parts by weight of a rubber-based resin fine powder (made by Japan Synthetic Rubber) having an average particle size of 5.5 μm and an average particle size of 0.5 μm were mixed with this mixture.
A photosensitive adhesive solution obtained by mixing 10 parts by weight of the product, adjusting the viscosity to 120 CPS with a homodisper stirrer, and subsequently kneading with a three-roll mill. 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 by TEM in the same manner as in Example 1.
Resin particles having an average particle size of 0.1 μm or less were found. Further, a cured product obtained by curing a resin composition mixture in which the rubber-based resin fine powder is not mixed has a vibration frequency of 6.28 rad / sec,
When the viscoelasticity measurement test was conducted under the condition of the temperature rising 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 quasi-homogeneous compatible structure (see FIG. 3).

(Example 11) Basically the same as in Example 7, the following adhesive solution was used. Cresol novolac type epoxy resin (made by Yuka Shell) 100% acrylated photosensitive epoxy oligomer, phenoxy resin, imidazole type curing agent (Shikoku Kasei, trade name: 2E4MZ-CN), photosensitive monomer Acrylated isothiocyanate (Toagosei, trade name; Aronix M215), photoinitiator (Ciba Geigy, trade name;
I-907) and mixed with DMF in the following composition, and further to this mixture, an agglomerated rubber-based resin fine powder having an average particle size of 3.5 μm (manufacturing method in Example 1 of JP-A-1-301775). Is added, and the viscosity is adjusted to 120 CPS with a homodisper stirrer while adding a DMF solvent, followed by kneading with a three-roll mill to obtain a photosensitive adhesive. Agent solution. Resin composition: Photosensitized epoxy / phenoxy / M215 / I-90
7 / imidazole = 79/30/10/5/5

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 7 has a cross section in which the phenoxy resin is dissolved.
As a result of SEM observation after etching with butanone, a continuous structure (co-continuous structure) of spherical objects having an average particle diameter of 0.2 to 2 μm and considered to be rich in epoxy resin was observed.

Example 12 Basically the same as in Example 7, the following adhesive solution was used. Cresol novolac type epoxy resin (made by Yuka Shell) 100% acrylated photosensitive epoxy oligomer, PSF, imidazole type curing agent (manufactured by Shikoku Kasei, trade name: 2E4MZ-CN), acrylic as a photosensitive monomer Isothiocyanate (manufactured by Toagosei, trade name; Aronix M
215), photoinitiator (Ciba-Geigy, trade name; I-907)
And mixed with DMF with the following composition, and further to this mixture, an agglomerated rubber-based resin fine powder having an average particle size of 3.5 μm is disclosed (Example 1 of JP-A-1-301775 discloses a manufacturing method. 30 parts by weight, and then DM
While adding F solvent, use a homodisper agitator to obtain a viscosity of 12
A photosensitive adhesive solution obtained by adjusting to 0 CPS and then kneading with a three-roll mill. Resin composition: Photosensitized epoxy / PSF / M215 / I-907 / imidazole = 60/40/10/5/5

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 7 was subjected to SEM by etching the cross section with methylene chloride which dissolves PSF. As a result of observation, spheres having an average particle size of about 2 to 5 μm and considered to be rich in epoxy resin were found. Moreover, this resin matrix had a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres were floated on a PSF-rich base.

(Example 13) Basically the same as in Example 5, except that the rubber-based resin fine powder was zirconia (manufactured by Nippon Shokubai Kagaku Kogyo, trade name; NS-OY-S) and the roughening solution was a fluorine solution. Acid. The resin structure of the resin matrix of the adhesive used in this example was a spherical domain structure. (Example 14) Basically the same as in Example 8, except that the rubber-based resin fine powder was magnesia (manufactured by Iwatani Chemical Co., Ltd., trade name: MT
K-30) and the roughening 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 the same as in Example 9, except that the rubber resin fine powder was aluminum hydroxide (manufactured by Nippon Light Industry Co., Ltd., trade name: B103.T) and the roughening liquid 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 the same as in Example 4, the following was used as the adhesive solution. Butadiene-acrylonitrile copolymer oligomer (CTBN)
After mixing bisphenol A type epoxy resin with 160
By heating at ℃ for 2 hours to obtain epoxy modified CTBN, 30 parts by weight of this resin solution, 65 parts by weight of bisphenol A type epoxy resin (Eikaka Shell, Epicoat 828), polyether sulfone (PES) (ICI, product Name; Victrex) 35
Parts by weight, imidazole-based curing agent (Shikoku Kasei, trade name;
2E4MZ-CN) 5 parts by weight, and then a dimethylformamide / butyl cellosolve (1/1) mixed solvent was added, the viscosity was adjusted to 100 CPS with a homodisper stirrer, and subsequently obtained by kneading with three rolls. 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 4 was subjected to SEM by etching the cross section with methylene chloride which dissolves PES. Observed, average particle size
A continuous structure (co-continuous structure) of spheres considered to be 0.2 to 2 μm rich in epoxy resin was observed. When this resin matrix was observed by SEM, the "island structure" of the butadiene-acrylonitrile copolymer rubber resin was observed in the sea of the resin matrix.

Example 17 Basically the same as Example 5, the following adhesive solution was used. Butadiene-acrylonitrile copolymer oligomer (CTBN)
After mixing bisphenol A type epoxy resin with 160
After heating at ℃ for 2 hours to obtain epoxy modified CTBN, 30 parts by weight of this resin solution, 50 parts by weight of bisphenol A type epoxy resin (Eikaka Shell, Epicoat 828), polyether sulfone (PES) (ICI, product First name; Victrex) 50
Parts by weight, imidazole-based curing agent (Shikoku Kasei, trade name;
2E4MZ-CN) 5 parts by weight, and then added with DMF, adjusted to a viscosity of 100 CPS with a homodisper stirrer, and subsequently kneaded 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 5 was subjected to SEM by etching the cross section with methylene chloride which dissolves PES. As a result of observation, spheres having an average particle size of about 2 to 5 μm and considered to be rich in epoxy resin were found. Moreover, this resin matrix had a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres were floated on the PES-rich base (see FIG. 4). When this resin matrix was observed by SEM, the "island structure" of the butadiene-acrylonitrile copolymer rubber resin was observed in the sea of the resin matrix.

(Example 18) Basically the same as in Example 7, the following adhesive solution was used. Butadiene-acrylonitrile copolymer oligomer (CTBN)
After mixing bisphenol A type epoxy resin with 160
After heating for 2 hours at ℃, epoxy modified CTBN was obtained, and 30 parts by weight of this resin solution was acrylated with 25% of the epoxy groups of the cresol novolac type epoxy resin dissolved in DMDG to give a photosensitizing epoxy oligomer (CNA25, molecular weight).
4000), PES (molecular weight 17,000), imidazole curing agent (manufactured by Shikoku Kasei, trade name; 2E4MZ-CN), acrylated isothiocyanate as a photosensitive monomer (manufactured by Toagosei, trade name; Aronix M215), photoinitiator benzophenone (BP) (manufactured by Kanto Kagaku) and photosensitizer Michler Ketone (manufactured by Kanto Kagaku) were mixed with NMP with the following composition and adjusted to a viscosity of 120 CPS with a homodisper stirrer, and then 3
An adhesive solution obtained by kneading with this roll. 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 by TEM in the same manner as in Example 1 and found to have an average particle size of Resin particles having a diameter of 0.1 μm or less were found. A cured product obtained by curing a mixture of resin compositions containing no rubber-based resin has a vibration frequency of 6.28 rad / sec.
When the viscoelasticity measurement test was conducted under the condition of the temperature rising 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 quasi-homogeneous compatible structure (see FIG. 3). Furthermore, when the resin matrix was observed by SEM, the "island structure" of the butadiene-acrylonitrile copolymer rubber resin was observed in the sea of the resin matrix.

Example 19 Basically the same as in Example 8, the following adhesive solution was used. Butadiene-acrylonitrile copolymer oligomer (CTBN)
After mixing bisphenol A type epoxy resin with 160
After heating for 2 hours at ℃, epoxy modified CTBN was obtained, and 30 parts by weight of this resin solution was acrylated with 25% of the epoxy groups of the cresol novolac type epoxy resin dissolved in DMDG to give a photosensitizing epoxy oligomer (CNA25, molecular weight).
4000), PES (molecular weight 17,000), imidazole curing agent (Shikoku Kasei, trade name; 2E4MZ-CN), photosensitive isothiocyanate acrylate (Toagosei, trade name; Aronix M215), photoinitiator (Made by Ciba Geigy, trade name: I-907), mixed with DMF with the following composition, adjusted to a viscosity of 120 CPS with a homodisper stirrer, and subsequently kneaded with a three-roll mill to obtain an 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 subjected to SEM observation by etching the cross section with methylene chloride. A continuous structure (co-continuous structure) of spherical objects having an average particle size of 0.2 to 2 μm and considered to be rich in epoxy resin was observed. In addition, this resin matrix is SE
When observed with M, in the sea of resin matrix,
The "island structure" of the butadiene-acrylonitrile copolymer rubber resin was observed.

Example 20 Basically the same as in Example 9, the following adhesive solution was used. Butadiene-acrylonitrile copolymer oligomer (CTBN)
After mixing bisphenol A type epoxy resin with 160
After heating at ℃ for 2 hours, epoxy modified CTBN was obtained, and 30 parts by weight of this resin solution was acrylated with 25% of the epoxy groups of cresol novolac type epoxy resin to give a photosensitizing epoxy oligomer (CNA25, molecular weight 4000), PES. (Molecular weight 17,000), imidazole-based curing agent (Shikoku Kasei, trade name; 2E4MZ-CN), photosensitive monomer acrylated isothiocyanate (Toagosei, trade name; Aronix M215), photoinitiator (Ciba Geigy, Product name; I-907
) Is mixed with DMF with the following composition, the viscosity is adjusted to 120 CPS with a homodisper stirrer, and then the mixture is kneaded with three rolls to obtain an adhesive solution. Resin composition: Photosensitized epoxy / PES / M215 / I-907 / imidazole = 75/25/10/5/5

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 9 was subjected to SEM by etching the cross section with methylene chloride which dissolves PES. As a result of observation, spheres having an average particle size of about 2 to 5 μm and considered to be rich in epoxy resin were found. Moreover, this matrix resin had a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres were floated on the PSF-rich base. Moreover, when this resin matrix was observed by SEM,
The "island structure" of the butadiene-acrylonitrile copolymer rubber resin was observed in the sea of the resin matrix.

(Example 21) Basically the same as in Example 7, and the following adhesive solution was used. Photosensitizing epoxy oligomer (CNA2) in which 25% of the epoxy groups of cresol novolac type epoxy resin are acrylated.
5, molecular weight 4000), PES (molecular weight 17000), imidazole curing agent (manufactured by Shikoku Kasei, trade name; 2E4MZ-CN), acrylated isothiocyanate which is a photosensitive monomer (manufactured by Toagosei, trade name; Aronix M215), light DM with the following composition using an initiator (Ciba Geigy, trade name: I-907)
After mixing with F, 25 parts by weight of epoxy group-terminated silicone resin was further mixed with this mixture, the viscosity was adjusted to 120 CPS with a homodisper stirrer, and then the mixture was kneaded with three rolls to obtain an adhesive solution. Got 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 subjected to TEM observation in the same manner as in Example 1 and found to have an average particle size. Resin particles of 0.1 μm or less were found. A cured product obtained by curing a mixture of resin compositions not mixed with the epoxy group-terminated silicone resin was subjected to a viscoelasticity measurement test under conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min. However, there was only 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 quasi-homogeneous compatible structure.

Example 22 (1) Cresol novolac 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 (manufactured by Shikoku Kasei, product name: 2E4MZ-CN)
5 parts by weight and low cross-linking degree of melamine resin powder were added to the average particle size.
20 parts by weight of 5.5 μm, average particle size of 0.5 μm
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 on both sides of the glass epoxy board, leave it horizontal for 20 minutes, then dry at 60 ° C and
About 1 hour at ℃, 5 hours at 150 ℃, heat cured to a thickness of about 50
A μm resin adhesive layer was formed. (3) Apply the substrate with this double-sided adhesive layer to 121 ° C, 2 atmospheres,
It was left for 2 hours in saturated steam to decompose and remove the melamine resin powder on the surface of the adhesive layer. Electron microscope (SEM) photographs before and after the decomposition and removal are shown in FIGS. As is clear from these photographs, the melamine resin has become smaller due to the decomposition. (4) Activate the surface of the insulating layer by applying a palladium catalyst (made by Shipley) to the substrate with the surface of the resin insulating layer roughened, and then immersing it in an electroless copper plating solution for 11 hours to remove the plating film. A 25 μm-thick electroless copper plating was applied to obtain a double-sided copper-clad laminate. (5) A through hole was opened in this double-sided copper-clad laminate. (6) After applying a palladium nucleus (manufactured by Shipley), a photoresist was attached, exposed and developed to form a plating resist. (7) Electroless copper plating was performed and electrolytic copper plating was further performed according to a conventional method to form a conductor circuit portion. (8) After removing the plating resist, it was etched with ferric chloride to remove the copper film between the patterns 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 by TEM in the same manner as in Example 1,
Resin particles having an average particle diameter of 0.1 μm or less were found. Further, a cured product obtained by curing a mixture of resin compositions in which the melamine resin powder is not mixed has a vibration frequency of 6.28 rad / sec,
When the viscoelasticity measurement test was conducted under the condition of the temperature rising 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 quasi-homogeneous compatible structure (see FIG. 3).

Example 23 Basically the same as in Example 7, the following adhesive solution was used. DMDG
Photosensitized epoxy oligomer (CNA25, molecular weight 4000), which is obtained by acrylating 25% of epoxy groups of cresol novolac type epoxy resin dissolved in
000), imidazole-based curing agent (Shikoku Kasei, trade name;
2E4MZ-CN), acrylated isothiocyanate as a photosensitive monomer (Toagosei, trade name; Aronix M215
), Photoinitiator benzophenone (BP) (manufactured by Kanto Kagaku),
Using a photosensitizer Michler's ketone (manufactured by Kanto Kagaku), further adding cellulose acetate butyrate powder, mixing with NMP with the following composition and adjusting the viscosity to 120 CPS with a homodisper stirrer, followed by kneading with a three-roll mill The obtained adhesive solution. Resin composition: Photosensitized epoxy / PES / M215 / BP / imidazole = 75/25/10/5 / 0.5 / 5 Further, the roughening condition of this example is that it is immersed in a 1M sodium hydroxide aqueous solution at 80 ° C. It 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 subjected to TEM observation in the same manner as in Example 1 and found to have an average particle size. Resin particles of 0.1 μm or less were found. Further, the cured product obtained by curing the mixture of the resin compositions 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 at the transition temperature Tg. Therefore, it is considered that the resin matrix of the adhesive used in this example has a quasi-homogeneous compatible structure.

The peel strength of the electroless copper-plated film, the insulation resistance of the interlayer resin insulation layer, and the glass transition temperature T _g of the printed wiring boards manufactured in Examples 1 to 23 were measured. Further, a heat cycle test was conducted at -65 ° C x 30 min to 125 ° C x 30 min. Table 3 shows the results. As is clear from the results shown in this table, the pseudo-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 having a resin matrix having a co-continuous structure and a spherical domain structure as a resin matrix. Plates can be manufactured.

[0125]

[Table 3]

The 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) Insulation resistance An interlayer insulation layer was formed on a substrate, roughened and then catalyst was applied, and then a plating resist was formed to form a resist pattern. Then, electroless plating was performed and the insulation resistance between patterns was measured. The insulation between the patterns is
L / S = 75 / 75μm comb pattern, 80 ℃ / 85% /
The value after 1000 hours at 24V was measured. (3) Glass transition temperature Tg It was measured by dynamic viscoelasticity measurement. (4) Heat Cycle Test A heat cycle test of −65 ° C. × 30 min to 125 ° C. × 30 min was performed to examine the occurrence of cracks and the peeling of the interlayer insulating layer, and evaluate the durability cycle number.

(Example 24): Metallic melamine decorative board In Examples 1 to 25, an example relating to a printed wiring board was described, but this example is an application example of the present invention to a decorative board. (1) For wood pulp fiber paper having a basis weight of 10 to 80 g / m ² ,
Impregnate it with melamine resin and dry it to a thickness of 100
The impregnated paper of μm was used. (2) Cresol novolac type epoxy resin (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 (manufactured by Shikoku Kasei, product name: 2E4MZ-CN)
5 parts by weight and calcium carbonate fine powder were added to an average particle size of 5.5 μ.
After mixing 20 parts by weight of m and 10 parts by weight of 0.5 μm in average particle size, the viscosity was adjusted to 120 CPS with a homodisper stirrer while adding a dimethylformamide / butyl cellosolve (1/1) mixed solvent, Then, 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) Apply the adhesive obtained in (2) above to the surface of the plywood board, then vacuum dry at 30 ° C, and then at 80 ° C for 2 hours for 120 hours.
5 hours at ℃, 2 hours at 150 ℃, heat cured to a thickness of 20 μm
The adhesive layer of was formed. (4) This adhesive layer was immersed in 6N hydrochloric acid at 70 ° C. for 15 minutes to roughen the surface of the adhesive layer, then immersed in a neutralizing solution (made by Shipley) and washed with water to obtain R _max = 10 ± An adhesive layer of 5 μm was obtained. (5) Applying a palladium catalyst (made by Shipley) to the surface of the roughened adhesive layer to activate the surface of the adhesive layer, and perform electroless silver plating according to a conventional method to obtain a thickness on the surface. 60
A μm silver layer was formed. (6) The melamine resin-impregnated paper obtained in (1) above was laminated on the surface of this silver layer as an overlay paper. (7) Furthermore, by laminating a patterning plate having irregularities of 1 to 60 μm on this overlay paper and thermocompressing it at 130 to 170 ° C. under a pressure of 30 to 80 kg / cm ² , overlay paper is obtained. And the surface was embossed to obtain a melamine decorative board having metallic luster.

Since the melamine decorative board thus obtained is formed of a melamine resin layer whose surface is transparent and has irregularities, the irregularities serve as a lens to raise the lower silver layer, The luster of silver was excellent, and the design was excellent. Moreover, -65
When a heat cycle test was conducted at a temperature of 30 ° C for 30 minutes to 125 ° C for 30 minutes, 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 by TEM in the same manner as in Example 1. Resin particles of 0.1 μm or less were found. The cured product obtained by curing the resin composition mixture containing no calcium carbonate fine powder has a vibration frequency of 6.28 r.
When a viscoelasticity measurement test was conducted under the conditions of ad / sec and a temperature rising rate of 5 ° C./minute, 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 quasi-homogeneous compatible structure.

(Embodiment 25): Plating-covered gear This embodiment is an application example of the present invention to a plating-covered gear. (1) Using polyimide, a gear-shaped molded body was produced according to a conventional method. (2) A photosensitizing epoxy oligomer (CNA25, molecular weight 4000) in which 25% of the epoxy groups of the cresol novolac type epoxy resin dissolved in DMDG are acrylated, P
ES (molecular weight 17,000), imidazole-based curing agent (manufactured by Shikoku Kasei, trade name; 2E4MZ-CN), caprolactone-modified tris isocyanurate as a photosensitive monomer (manufactured by Toagosei,
Trade name: Aronix M315), photoinitiator benzophenone (BP), photosensitizer Michler ketone, and mixed with NMP with the following composition, and in addition to this, rubber filler (Nippon Gosei) average particle size After mixing 30 parts by weight of 5.0 μm, the viscosity was adjusted to 1000 CPS with a homodisper stirrer and subsequently kneaded with a three-roll mill to obtain an adhesive solution. Resin composition: Photosensitized epoxy / PES / M315 / BP / imidazole = 70/30/10/5/5 / 0.5 / 5 (3) The gear-shaped molded body prepared in (1) above, the above (2)
After applying the adhesive prepared in (1), it was vacuum dried at 25 ° C., UV-cured, and then heat-cured to form an adhesive layer composed of a resin matrix showing a pseudo-homogeneous compatible structure. (4) Then, add chromic acid solution (CrO ₃ , 500g / l) at 70 ℃.
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. 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 with the surface of the adhesive layer roughened, nickel-phosphorus plating is performed according to a conventional method to give a metallic luster. Produced a gear that has.

The gear thus obtained was resistant to chemicals such as acids, and had a hard surface, so that it was excellent in wear resistance, and the nickel layer on the surface was not peeled off when the gear was used. Moreover, the adhesive layer did not crack and the nickel plating did not peel off due to the stress associated with the use of the gear.

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 by TEM as in Example 1 to find that the average particle size was 0.1. Resin particles having a size of μm or less were observed. A cured product obtained by curing a resin composition mixture containing no rubber filler has a vibration frequency of 6.28 rad / sec.
When the viscoelasticity measurement test was conducted under the conditions of a temperature rising 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 quasi-homogeneous compatible structure.

(Embodiment 26); Semiconductor mounting board with heat sink This embodiment is an example of application of the present invention to a semiconductor mounting board with a heat sink. (1) A photosensitizing epoxy oligomer (CNA25, molecular weight 4000) in which 25% of the epoxy groups of a cresol novolac type epoxy resin dissolved in DMDG are acrylated, P
ES (molecular weight 17,000), imidazole-based curing agent (manufactured by Shikoku Kasei, trade name; 2E4MZ-CN), caprolactone-modified tris isocyanurate as a photosensitive monomer (manufactured by Toagosei,
Trade name: Aronix M315), photoinitiator benzophenone (BP), photosensitizer Michler ketone, and mixed with NMP in the following composition. In addition, aluminum nitride powder with an average particle size of 5.0 μm Was mixed with 30 parts by weight, and the viscosity was adjusted to 1000 CPS with a homodisper stirrer, followed by kneading with a three-roll mill to obtain an adhesive solution. Resin composition: Photosensitized epoxy / PES / M315 / BP / Imidazole = 70/30/10/5/5 / 0.5 / 5 (2) The base material of the semiconductor mounting substrate consisting of an aluminum substrate and a lead frame, as described in (1) above After applying the adhesive solution and vacuum drying at 25 ° C and UV curing this,
The aluminum substrate was heat-cured to cover the aluminum substrate with an adhesive layer, and at the same time, the aluminum substrate and the lead frame were integrated to form an adhesive layer made of a resin matrix showing a pseudo-homogeneous compatible structure. (3) The semiconductor mounting substrate having the adhesive layer formed thereon was dipped in water to dissolve and remove the aluminum nitride powder present on the surface of the adhesive layer to roughen the adhesive layer. (4) A plating resist film is attached, exposed and developed to form a plating resist, electroless copper plating is performed, a conductor circuit is formed on the surface, and the conductor circuit electrically connects to the lead frame. It was (5) After mounting the IC chip, the resin was sealed by potting, and the casing was mounted to manufacture 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. Moreover, the resin matrix of the present example, under high temperature, high humidity and high pressure conditions, the terminal functional groups decompose to generate organic acids such as acetic acid and formic acid, while aluminum nitride does not react with ammonia under the above conditions. Since it decomposes while generating, it is possible to neutralize the acid and suppress corrosion of the adherend metal.

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 by TEM as in Example 1 to find that the average particle size was 0.1. Resin particles having a size of μm or less were observed. The cured product obtained by curing the resin composition mixture containing no aluminum nitride had a vibration frequency of 6.28 rad /
When a viscoelasticity measurement test was conducted under the conditions of sec and a temperature rising 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 quasi-homogeneous compatible structure.

(Embodiment 27); Electromagnetic interference (EMI) plating film shield This embodiment is an application example of the present invention to an electromagnetic interference (EMI) plating film shield. (1) Cresol novolac type epoxy resin (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 (manufactured by Shikoku Kasei, product 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 of an average particle size of 0.5 μm, a dimethylformamide / butyl cellosolve (1/1) mixed solvent was added. Meanwhile, the viscosity was adjusted to 120 CPS with a homodisper stirrer and subsequently 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) Apply this adhesive solution to filter paper using a roller coater (Thermatronics Trading Co., Ltd.), and then dry cure at 80 ° C for 2 hours, 120 ° C for 5 hours, and 150 ° C for 2 hours to obtain a thick film. A 20 μm thick adhesive layer was formed. (3) The filter paper having the adhesive layer formed thereon 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 (made by Shipley) and then washed with water. Roughened surface is JI
SB-0601 R _max = 10 μm. (4) A palladium catalyst (manufactured by Shipley) was applied to the substrate having the surface of the adhesive layer roughened to activate the surface of the adhesive layer, and then nickel plating was performed according to a conventional method.

The electromagnetic interference wave (EM
I) In the shield material, the adhesive itself also contains nickel, the plating film also has a shield effect, and since these have a multiple structure, they have excellent shield characteristics. Moreover, even if the shield material is bent, cracks do not occur in the adhesive layer, and the shield material can be easily processed.

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 by TEM as in Example 1 to find that the average particle size was 0.1. Resin particles having a size of μm or less were observed. A cured product obtained by curing a resin composition mixture containing no nickel fine powder has a vibration frequency of 6.28 rad / se.
When the viscoelasticity measurement test was conducted under the conditions of temperature increase 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 quasi-homogeneous compatible structure.

(Example 28); Screw (1) A screw-shaped substrate was molded with polycarbonate. (2) Cresol novolac type epoxy resin (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 (manufactured by Shikoku Kasei, product name: 2E4MZ-CN)
5 parts by weight and vinyl chloride resin powder with an average particle size of 5.5 μm
20 parts by weight and 10 parts by weight of an average particle size of 0.5 μm were mixed, and then stirred with a homodisper stirrer, followed by
An adhesive solution was obtained by kneading with three rolls. (3) Immerse the screw-shaped substrate of (1) in this 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 SEM observation of the fracture surface etched with methylene chloride. (4) Next, the surface of the adhesive layer was roughened by immersing it in acetone to dissolve and remove the vinyl chloride resin powder on the surface of the adhesive layer. (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.

Since the surface of the screw thus obtained is silver, algae and the like are unlikely to adhere due to the sterilizing action of silver, and since the base body is integrally formed of polycarbonate, it is not affected by the centrifugal force of rotation. Hard to break. Moreover,
Since a normal screw is cut out from a metal lump by cutting, the cost is high, but the screw of the present embodiment can be integrally molded with resin, so the cost can be reduced. Further, since the adhesive layer has toughness, cracks do not occur due to strain due to rotation.

[0141]

As described above, according to the present invention,
As a heat-resistant resin matrix of the adhesive, heat resistance is obtained by using a resin composite in which a thermoplastic resin is combined with a thermosetting resin or a photosensitive resin to form a pseudo-homogeneous compatible structure, a co-continuous structure or a spherical domain structure. The resin matrix can be toughened and the adhesiveness between the adhesive layer and the coating metal can be remarkably improved without deteriorating the properties, electrical insulation and chemical stability. This makes it possible to stably provide various metal film adherends for printed wiring boards and other industrial parts that are excellent in peel strength even in wiring having higher density and higher pattern accuracy. That is, not only in printed wiring boards, but in the automobile industry field,
Application to various parts such as disc brake bodies, clutch hubs, fuel injection nozzles, fuel transportation pipes, gears, etc.In the electrical and electronic industry field, lead frames, hermetic seals, ceramic packages, connectors, capacitors, resistors, solar electrodes, It can be applied to hard disks, etc., and in the industrial machinery industry field, it can be applied to construction materials such as pumps, valves, heat exchangers, filters, screws, dies, bearings, decorative plates, etc. It can be applied to various structural materials and parts, and is industrially useful.

[Brief description of drawings]

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

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

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

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

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

FIG. 7 is a diagram showing the results of dynamic viscoelasticity measurement of a resin composite having a co-continuous structure according to the present invention.

FIG. 8: SE of crystal structure of cross section of adhesive layer after drying and before curing
It is an M photograph.

FIG. 9 is a SEM photograph of 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 a CNA 25 / PES / TMPTA system mixture and the state of the resin composite after curing.

FIG. 11 is a phase diagram showing the relationship between the drying temperature of the CNA 25 / PES 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 mixture and the state of the resin composite after curing.

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

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

[Explanation of symbols]

 1 substrate 2 adhesive layer 3 resist 4, 6, 8, 10 conductor 5 via hole

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location H05K 1/03 610 Q7511-4E

Claims (10)

[Claims] 1. A metal film adherend having an adhesive layer on the surface of a substrate, and a metal film provided on the adhesive layer, wherein the adhesive layer is a removable particulate substance, At least one selected from thermosetting resins and photosensitive resins
A metal film adherend characterized by being dispersed in a heat-resistant resin matrix which has been cured and is made of a resin composite of one or two kinds of resins and a thermoplastic resin. 2. An adhesive layer having a roughened surface formed on a substrate, in which the decomposable and removable particulate substance is at least one selected from thermosetting resins and photosensitive resins. An adhesive layer characterized by being dispersed in a heat-resistant resin matrix which has been cured and is made of a resin composite of one or two kinds of resins and a thermoplastic resin. 3. An adhesive layer having a roughened surface formed on a substrate, the layer comprising inorganic particles, metal particles, elastomer particles, alkali-soluble resin particles and solvent-soluble resin particles. At least one or more kinds of the removable particulate matter selected from the group consisting of a resin composite of a thermoplastic resin and at least one or two kinds of resins selected from thermosetting resins and photosensitive resins. An adhesive layer characterized by being dispersed in a heat-resistant resin matrix that has been cured. 4. An adhesive layer having a roughened surface formed on a substrate, in which the resin capable of being dissolved and removed is at least one selected from thermosetting resins and photosensitive resins. Alternatively, a cured heat-resistant resin matrix composed of a resin composite of two kinds of resins and a thermoplastic resin is dispersed in the sea like islands to form a sea-island structure. Adhesive layer. 5. The adhesive layer according to claim 2, wherein the photosensitive resin is a resin in which a part of functional groups of a thermosetting resin is replaced with a photosensitive group. 6. The resin composite, wherein the thermosetting resin or the photosensitive resin and the thermoplastic resin form any one of a pseudo-homogeneous compatible structure, a co-continuous structure and a spherical domain structure. The adhesive layer according to any one of 2 to 4. 7. In an uncured heat-resistant resin matrix,
In an adhesive agent in which a decomposable and removable particulate material is dispersed, the heat-resistant resin matrix is at least one selected from thermosetting resins and photosensitive resins or 2
An adhesive comprising a resin mixture of a seed resin and a thermoplastic resin. 8. In an uncured heat-resistant resin matrix,
In an adhesive obtained by dispersing at least one or more kinds of soluble and removable particulate matter selected from inorganic particles, metal particles, elastomer particles, resin particles soluble in alkali and resin particles soluble in a solvent, The resin matrix is at least one or two selected from thermosetting resins and photosensitive resins.
An adhesive comprising a resin mixture of a seed resin and a thermoplastic resin. 9. In an uncured heat-resistant resin matrix,
In an adhesive that is incompatible with the heat-resistant resin matrix before curing and is dispersed by a resin liquid that can be dissolved and removed after curing, the heat-resistant resin matrix is composed of a thermosetting resin and a photosensitive resin. At least one or two selected
An adhesive comprising a resin mixture of a seed resin and a thermoplastic resin. 10. In an uncured heat-resistant resin matrix,
In an adhesive agent that is compatible with the heat-resistant resin matrix before curing, and is mixed with a resin solution that is phase-separated from the heat-resistant resin matrix after curing and can be dissolved and removed, the heat-resistant resin matrix is At least one selected from curable resin and photosensitive resin or 2
An adhesive comprising a resin mixture of a seed resin and a thermoplastic resin.