JP3142424B2 - Resin composite for interlayer resin insulation of multilayer wiring boards - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel resin composite comprising a thermosetting resin and a thermoplastic resin, or a photosensitive resin and a thermoplastic resin, in which a part of the functional groups is substituted by a photosensitive group. In particular, the present invention proposes a resin composite that can be advantageously applied to an interlayer resin insulating material (adhesive for electroless plating) of a multilayer circuit board.

[0002]

2. Description of the Related Art Resins having so-called photosensitive properties, which can be cured by exposure, have a wide range of industrial uses. For example, they are used for photolithography, photoresists used in semiconductors and dense drawing of printed wiring boards, and the like. Have been. Particularly, in the field of printed wiring board manufacture, a resin having this photosensitive property is suitably used as an insulating material useful for forming a high-density conductive pattern.

However, a resin having the above-mentioned photosensitive characteristics has a problem in practical use because of its low toughness. Regarding such a problem, conventionally, as a technique for improving the toughness of a resin, a technique of mixing a thermosetting resin with a thermoplastic resin to form a composite has been proposed. For example, in a mixed system (PES-modified epoxy resin) of an epoxy resin and polyether sulfone (hereinafter, referred to as “PES”),
Due to the co-continuous structure formed by the epoxy resin and PES,
That is the technology that improves the toughness of epoxy resins (Keiz
o Yamanakaand Takasi Inoue, Polymer, 1989, vol. 30, p6
62).

[0004] Certainly, the PES-modified epoxy resin obtained by mixing two kinds of resins has improved toughness of the resin as compared with the epoxy resin alone. It is this PE
This is because the S-modified epoxy resin forms a structure in which epoxy spherical domains are connected to each other in the PES matrix and are regularly dispersed, that is, a so-called bicontinuous structure. This co-continuous structure, when mixed with an epoxy resin such as bisphenol A type epoxy resin and PES, when the epoxy resin is cured at a high temperature, the epoxy resin and PES do not completely dissolve (compatible state). However, it is formed because spinodal decomposition occurs and the thermosetting resin and the thermoplastic resin are mixed in a separated state (phase separated state).

[0005]

The above prior art, however, relates to a so-called composite technique of a thermosetting resin and a thermoplastic resin which forms a spherical domain structure or a co-continuous structure only by thermosetting. It is not a composite technology of resin with photosensitive characteristics. Therefore, even if a resin having poor toughness and photosensitive characteristics is used, a method for synthesizing a resin composite having excellent toughness has not yet been studied. That is, the fact is that the composite of a resin having photosensitive characteristics and a thermoplastic resin has not been put to practical use yet.

The object of the present invention has been made in view of such circumstances, and in particular, the physical properties of resins having photosensitive characteristics such as partially acrylated epoxy resins and acrylic resins, for example, heat resistance and photosensitive characteristics. It is an object of the present invention to establish a novel resin composite having excellent physical properties (excellent toughness) inherent to thermoplastic resins such as PES, and a technique for producing the same.

[0007]

The epoxy resin / P
In the ES mixed system, as shown in FIG. 1, the epoxy resin and PES are compatible at low temperature but separate into two phases at high temperature, so-called LCST type (Low Critical Solution Tempo).
erature) is known to show the phase diagram. But,
It has been found that when part of the epoxy group of the epoxy resin is replaced with an acrylic group, the epoxy resin and PES are hardly compatible with each other even at a low temperature, and the phase separation is easily caused. On the other hand, when part of the epoxy group of the epoxy resin is replaced with an acrylic group, it can be cured by exposure, so that the epoxy resin can be cured while maintaining the compatible state seen at low temperatures, Separation is suppressed. That is,
When using a thermosetting resin having a photosensitive group, after exposure,
Phase separation does not occur because molecular motion is frozen. This is because phase separation requires the movement and diffusion of molecules. As described above, the provision of the photosensitive group has both effects of promoting the phase separation and suppressing the phase separation.

The present inventors have conducted further studies focusing on such facts, and as a result, have found that a thermosetting resin in which a functional group is substituted with a photosensitive group or a photosensitive resin and a thermoplastic resin are appropriately used. The inventors have found that a clear bicontinuous structure or a spherical domain structure can be formed by performing phase separation, and the present invention has been completed.

That is, the present invention firstly provides a resin composite comprising a thermoplastic resin and a thermosetting resin in which a part of a functional group is substituted by a photosensitive group, The resin and the thermoplastic resin are a resin composite for an interlayer resin insulating material of a multilayer wiring board formed by forming a dispersed state of a co-continuous structure, and the thermosetting resin has a functional group of 5 to 70. % Is desirably substituted with a photosensitive group. Second, a resin composite comprising a photosensitive resin and a thermoplastic resin, wherein the photosensitive resin and the thermoplastic resin form a co-continuous structure and form a dispersed state, thereby forming an interlayer resin insulation of a multilayer wiring board. It is a resin composite suitable for use as a material layer (electroless plating adhesive layer). Here, in these resin composites, it is desirable that the average particle diameter of the spherical particles constituting the bicontinuous structure is more than 0.1 μm and 5 μm or less, and in these resin composites, thermosetting resin Alternatively, the mixing ratio of the photosensitive resin and the thermoplastic resin is 15% by the content of the thermoplastic resin.
It is desirably about 50% by weight. The method for producing a resin composite according to the present invention includes, first, a method of forming a composite of a thermosetting resin and a thermoplastic resin by curing a thermosetting resin mixed with the thermoplastic resin; A part of the thermosetting resin and the thermoplastic resin, which are substituted with a photosensitive group, are mixed and dispersed in an incompatible state, and then, this is exposed and cured by heating, and the thermosetting resin and This is a method characterized by forming a bicontinuous structure with a thermoplastic resin. Second, in a method of combining the photosensitive resin and the thermoplastic resin by curing the photosensitive resin mixed with the thermoplastic resin, the photosensitive resin and the thermoplastic resin are mixed and dispersed in an incompatible state. Then, this is cured by exposing it to form a co-continuous structure of a photosensitive resin and a thermoplastic resin. Here, as the thermosetting resin, it is desirable to use a resin in which 5 to 70% of the functional groups are substituted with a photosensitive group, and a thermosetting resin or a mixture of a photosensitive resin and a thermoplastic resin. The ratio is desirably 15 to 50% by weight in terms of the content of the thermoplastic resin.

[0010]

The resin composite for an interlayer resin insulation material of the multilayer wiring board according to the present invention is characterized in that a thermosetting resin whose functional group is partially substituted by a photosensitive group and a thermoplastic resin are both used. The point is that a dispersed state having a continuous structure is formed, and the photosensitive resin and the thermoplastic resin form a dispersed state having a co-continuous structure. By forming such a structure,
While maintaining the heat resistance and chemical resistance of the thermosetting resin, the photosensitive properties of the photosensitive resin, etc., the properties of the thermoplastic resin can be imparted, so that high toughness, high strength, low dielectric constant and low thermal expansion coefficient can be obtained. A resin composite can be obtained. Therefore,
When the resin composite having such a co-continuous structure is applied to an interlayer resin insulating layer of a multilayer wiring board, particularly to a resin matrix of an adhesive for electroless plating, heat resistance, chemical resistance,
Since the toughness and strength are greatly improved while maintaining the photosensitive characteristics, the irregularities formed in the adhesive layer by the roughening treatment can be reliably retained, and as a result, the more complex irregularities are formed. Even on the roughened surface, the adhesion to the electroless plating film formed thereon can be greatly improved. Specifically, the resin composite of the present invention has a structure shown in a scanning electron microscope (hereinafter, referred to as “SEM”) photograph of FIG. 2 (co-continuous structure). Such an effect due to the structure of the resin composite is particularly remarkable when the content of the thermoplastic resin (for example, PES) in the composite is 15 to 50 wt% in solid content. The reason is that if the content of the thermoplastic resin is less than 15 wt%, the effect of toughening is not sufficiently exhibited because the number of thermoplastic resin molecules entangled in the network of the resin component is small, while the content of the thermoplastic resin is 50 wt%. %, The interaction between the thermosetting resin and the thermoplastic resin decreases due to the decrease in the number of crosslinking points.

In the present invention, the globular domain structure is
In a resin matrix mainly composed of a thermoplastic resin, spherical domains of a thermosetting resin or a resin mainly composed of a photosensitive resin in which a part of functional groups are substituted with a photosensitive group are independent of each other, or a part thereof is Refers to the structure in a state of being linked and dispersed, and the bicontinuous structure is a thermosetting resin in which some of the functional groups are replaced with photosensitive groups in a resin matrix mainly composed of thermoplastic resin. It refers to a structure in which spherical domains composed of a resin or a resin mainly composed of a photosensitive resin are connected to each other and are regularly dispersed.

That is, the resin forming each of the above structures is:
Rather than being completely separated from each other, the thermoplastic resin contains a thermosetting resin or a photosensitive resin in which some of the functional groups are replaced with a photosensitive group, and the ratio is overwhelming. Thermoplastic resin is high in terms of thermosetting resin, while thermoplastic resin is contained in thermosetting resin or photosensitive resin in which a part of functional group is substituted by photosensitive group, and the ratio is thermosetting resin. High resin or photosensitive resin. That is, the respective resins are not completely phase-separated but are slightly compatible. Note that a resin mainly composed of a thermoplastic resin may be dispersed in a resin matrix mainly composed of a thermosetting resin or a photosensitive resin in which a part of the functional groups is substituted by a photosensitive group.

The above-mentioned co-continuous structure or spherical domain structure is obtained by dissolving a thermoplastic resin in a solvent such as dimethylformamide (DMF), methylene chloride, dimethylsulfoxide (DMSO), or normal methylpyrrolidone (NMP), and subjecting the surface to SEM. Can be confirmed by observation.

In the present invention, the thermosetting resin preferably has 5-70% of the functional groups substituted by photosensitive groups. The reason for this is that if it is less than 5%, photosensitivity cannot be obtained, and if it exceeds 70%, compatibility with the thermoplastic resin becomes difficult.

In the resin composite of the present invention, the spherical particles constituting the bicontinuous structure or the spherical domain structure have an average particle diameter of:
It is preferable that each of them exceeds 0.1 μm and is 5 μm or less. The reason is that it is difficult to uniformly dissolve the thermosetting resin or the photosensitive resin and the thermoplastic resin in which a part of the functional group is substituted with the photosensitive group.
Adjustment to less than 0.1 μm is difficult, while 5 μm
If it exceeds m, the toughness cannot be improved, and the photosensitive characteristics and heat resistance also decrease. The average particle size of the resin composite is mainly measured by SEM observation.

Next, a method for producing the resin composite of the present invention will be described. A first method for forming a composite of a thermoplastic resin and a thermosetting resin in which a part of a functional group is substituted with a photosensitive group includes, for example, a functional group involved in thermosetting of the thermosetting resin and a photosensitive group. Is controlled by controlling the substitution ratio with the thermoplastic resin, thereby changing the compatibility with the thermoplastic resin to be mixed, adjusting the degree of incompatibility, and exposing it to heat and curing it. A second method of compounding the photosensitive resin and the thermoplastic resin is to change the compatibility with the thermoplastic resin to be mixed, for example, by adjusting the type and molecular weight of the photosensitive resin, and to adjust the degree of incompatibility. Is adjusted, and this is exposed and cured. In this way, a bicontinuous structure or a spherical domain structure can be formed. Hereinafter, a specific manufacturing method thereof will be described.

In the first method, first, a thermosetting resin in which a part of functional groups is substituted by a photosensitive group and a thermoplastic resin are mixed and dispersed in a solvent, if necessary, to obtain a non-phased resin. Make into a molten state. The thermosetting resin in which a part of the functional group is substituted by the photosensitive group is hardly compatible with the thermoplastic resin, and becomes a dispersed state in an incompatible state. Next, when a solvent is used, the solvent is removed by drying, and then the photosensitive group in the thermosetting resin is cured by exposing it to light. Thereafter, the thermosetting resin remaining in the thermosetting resin is cured. By heating and reacting the functional groups of the mold, they are completely cured to form a co-continuous structure or a spherical domain structure of the thermosetting resin and the thermoplastic resin. Here, at the time of performing the thermal curing, the motion of the molecular chain is already frozen by the reaction of the photosensitive group, so that phase separation due to the thermal curing hardly occurs. Therefore, a thermosetting resin and a thermoplastic resin in which a part of the functional group is substituted by a photosensitive group are:
In the initial dispersion state, if the degree of incompatibility is large, a spherical domain structure is formed, and if the degree of incompatibility is small, a bicontinuous structure is formed. The degree of incompatibility varies depending on the type and molecular weight of the thermoplastic resin and the thermosetting resin, but if the type and molecular weight of the resin are the same, the functional group of the thermosetting resin is replaced with a photosensitive group. Thus, it can be controlled by the replacement rate. In addition, by performing a curing reaction of the thermosetting functional group remaining in the thermosetting resin, the antioxidant properties are improved, so that the thermosetting resin in which a part of the functional groups is substituted with a photosensitive group is used. A resin composite having a co-continuous structure or a spherical domain structure with a thermoplastic resin is suitable for application to a resin matrix of an adhesive for electroless plating.

In the second method, first, a photosensitive resin and a thermoplastic resin are mixed and dispersed in a solvent, if necessary, to make them incompatible. The photosensitive resin and the thermoplastic resin are
It is hardly compatible and becomes an individual dispersion state in an incompatible state. Next, in the case of using a solvent, after removing the solvent by drying, the photosensitive resin is cured by exposing it,
A co-continuous structure or a spherical domain structure of the photosensitive resin and the thermoplastic resin is formed. In the initial dispersion state, the photosensitive resin and the thermoplastic resin have a spherical domain structure if the degree of incompatibility is large, and have a bicontinuous structure if the degree of incompatibility is small. The degree of this incompatibility can be controlled by the type and molecular weight of the thermoplastic resin and the photosensitive resin. In this method, since curing is performed by exposure, phase separation during curing can be suppressed, and the initial dispersion state is directly reflected on the cured product.

The solvent which can be used in the method of the present invention as described above includes, for example, dimethylformamide (DM
F), methylene chloride, dimethyl sulfoxide (DMSO),
Normal methylpyrrolidone (NMP) is preferred.
As the thermosetting resin, an amino resin such as a phenol resin melamine and a urea resin, an epoxy resin, an epoxy-modified polyimide resin, an unsaturated polyester resin, a polyimide resin, a urethane resin, and a diallyl phthalate resin are preferable. In the present invention, a part, preferably 5 to 70%, of these functional groups involved in curing is substituted with a functional group such as an acrylic group for use. As the thermoplastic resin, polyether sulfone, polysulfone, phenoxy resin,
Preferred are polyetherimide, polystyrene, polyethylene, polyarylate, polyamideimide, polyphenylene sulfide, polyetheretherketone, polyoxybenzoate, polyvinyl chloride, polyvinyl acetate, polyacetal, polycarbonate and the like. In the present invention, the blending amount of these thermoplastic resins is 15 to 50%,
It is compounded with the above-mentioned thermosetting resin or photosensitive resin. As the photosensitive resin, an acrylic resin or a thermosetting resin in which the functional group is acrylated to 100% can be suitably used. As the curing agent, when an epoxy resin is used as the thermosetting resin, an imidazole-based curing agent, a diamine, a polyamine, a polyamide, an organic anhydride, a vinyl phenol, 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. The first
In the method (2), a curing agent may be provided together with the thermosetting resin. In the second method, a photosensitizer or a photoinitiator may be added together with the photosensitive resin.

According to the resin composite of the present invention as described above, physical properties specific to a thermosetting resin such as a partially acrylated epoxy resin or physical properties specific to a photosensitive resin such as an acrylic resin are provided. It can also have excellent physical properties (excellent toughness) inherent to a thermoplastic resin such as PES. That is, the PES according to the present invention
The modified partially acrylated epoxy resin or PES-modified acrylic resin does not lower the photosensitive properties, and enables toughness, a low dielectric constant, and a low thermal expansion coefficient of epoxy resins and acrylic resins which have not been conventionally available.

The resin composite of the present invention can be used as an adhesive for electroless plating such as an adhesive for printed wiring boards, a substrate material used for printed wiring boards, a resist material and a prepreg material, and a semiconductor package. It is expected to be used in various applications such as materials, base materials of fiber-reinforced composite materials, injection molding materials, and compression molding materials.

[0022]

【Example】

(Example 1: co-continuous structure) (1) 70% of 25% acrylate of phenol novolak type epoxy resin (made by Yuka Shell)
Parts by weight, 30 parts by weight of polyether sulfone (PES), 15 parts by weight of diallyl terephthalate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba-Geigy) 4 Parts by weight and 4 parts by weight of an imidazole-based curing agent (trade name: 2E4MZ-CN, manufactured by Shikoku Chemicals Co., Ltd.) were mixed in DMF, and then the obtained mixture was dried at 80 ° C. for 1 hour to remove the solvent. After the removal, the resin was UV-cured under the condition of ³ J / cm ² , and further heat-cured at 80 ° C. for 6 hours and 150 ° C. for 2 hours to obtain a cured resin having a bicontinuous structure.

With respect to the resin cured product thus obtained,
After the fractured surface was polished, it was etched with methylene chloride and observed by SEM. As a result, a spherical continuous structure having an average particle diameter of the spherical resin particles of about 2 μm was observed. In addition,
Since only the PES portion is etched with methylene chloride, it is estimated that the spherical continuous structure is an epoxy-rich region and the matrix is a PES-rich region.

The tensile strength and tensile elongation of the obtained cured resin were 700 kg / cm ² and 6.0%, respectively, and were intermediate values between the epoxy resin and PES. The same curing agent,
Tensile strength and tensile elongation of a cured product made of only epoxy resin produced under curing conditions are about 500 kg / cm ² and 5%, respectively.
Met.

Example 2 Spherical Domain Structure (1) 80% by weight of 50% acrylate of phenol novolak type epoxy resin (manufactured by Yuka Shell), 20 parts by weight of polyether sulfone (PES), 15 parts by weight of diallyl terephthalate Parts, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba-Geigy), 4 parts by weight, and an imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E4M)
4 parts by weight of Z-CN) in DMF, and then drying the resulting mixture at 80 ° C. for 1 hour to remove the solvent, followed by UV curing under the condition of ³ J / cm ^2. , And 80 ° C
For 6 hours and at 150 ° C. for 2 hours to obtain a cured resin having a spherical domain structure.

With respect to the resin cured product thus obtained,
After the fractured surface was polished, it was etched with methylene chloride and observed by SEM. As a result, a spherical continuous structure having an average particle diameter of the spherical resin particles of about 2 μm was observed. In addition,
Since only the PES portion is etched with methylene chloride, it is estimated that the spherical continuous structure is an epoxy-rich region and the matrix is a PES-rich region.

The tensile strength and tensile elongation of the obtained cured resin were 650 kg / cm ² and 5.8%, respectively, which were intermediate values between the epoxy resin and PES. The same curing agent,
Tensile strength and tensile elongation of a cured product made of only epoxy resin produced under curing conditions are about 500 kg / cm ² and 5%, respectively.
Met.

Example 3 Application of Multilayer Wiring Board to Interlayer Insulating Material (1) A photosensitive dry film (manufactured by DuPont) was laminated on a glass epoxy copper-clad laminate (manufactured by Toshiba Chemical).
The image was printed by exposing to ultraviolet light through a mask film on which a desired conductive circuit pattern was drawn. Then, 1,1,1-
After developing with trichloroethane and removing the copper in the non-conductive portion using a cupric chloride etching solution, the dry film was peeled off with methylene chloride. As a result, a wiring board having a first-layer conductive circuit including a plurality of conductive patterns on the substrate was prepared. (2) Epoxy resin particles (Toray, average particle size: 3.9 μm)
A suspension of epoxy resin particles obtained by dispersing 200 g in 5 l of acetone was stirred in a Henschel mixer.
An epoxy resin powder (manufactured by Toray, average particle size: 0.5 μm) was dissolved in an acetone solution in which 30 g of an epoxy resin (manufactured by Mitsui Petrochemical) was dissolved in 1 liter of acetone in this suspension.
m) The suspension obtained by dispersing 300 g was dropped, so that the epoxy resin powder was attached to the surface of the epoxy resin particles, the acetone was removed, and then 150 ° C.
To produce pseudo particles. The pseudo particles had an average particle size of about 4.3 μm, and about 75% by weight was in a range of ± 2 μm around the average particle size. (3) 70% by weight of a 30% acrylate of cresol novolac type epoxy resin (manufactured by Yuka Shell), polysulfone (P
SF) 30 parts by weight, diallyl terephthalate 15 parts by weight, 2-
4 parts by weight of methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba-Geigy), 4 parts by weight of imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E4MZ-CN) And 50 parts by weight of the pseudo particles prepared in the above (2), and the mixture was adjusted to a viscosity of 250 cps with a homodisper stirrer while adding butyl cellosolve, followed by kneading with three rolls to form a photosensitive resin composition. Was prepared. (4) The solution of the photosensitive resin composition is applied to the wiring board prepared in the above (1) using a knife coater, left in a horizontal state for 20 minutes, and dried at 70 ° C. to obtain a thickness. About 50μm
Was formed. (5) A photomask film on which a black circle of 100 μmφ was printed was brought into close contact with the wiring board subjected to the treatment of (4), and was exposed with an ultrahigh pressure mercury lamp of 500 mj / cm ² . This is subjected to ultrasonic development with a chlorocene solution to form a 100 μm
An opening to be a via hole of φ was formed. Further, the wiring board was exposed at about 3000 mj / cm by an ultra-high pressure mercury lamp,
A heat treatment was performed at 1 ° C. for 1 hour and then at 150 ° C. for 10 hours to form a resin insulating layer having openings having excellent dimensional accuracy corresponding to a photomask film. (6) The wiring board subjected to the treatment of (5) is immersed in a chromic acid aqueous solution (CrO ₃ , 500 g / l) at 70 for 15 minutes to roughen the surface of the resin insulating layer. (Made by Shipley) and washed with water. (7) A palladium catalyst (manufactured by Shipley) is applied to the substrate having the surface of the resin insulating layer roughened to activate the surface of the insulating layer,
Thereafter, the substrate was immersed in an electroless plating solution for additive having the composition shown in Table 1 for 11 hours to perform electroless copper plating with a plating film thickness of 25 μm. (8) The above steps (4) to (7) were further repeated twice to produce a build-up multilayer wiring board having four wiring layers.

[0029]

[Table 1]

(Comparative Example 1: Application to interlayer insulating material of multilayer wiring board) (1) Except for the resin composition shown below,
A solution of a photosensitive resin composition containing pseudo particles comprising an epoxy resin is prepared, and on a wiring board having a first layer conductive circuit,
Approximately 50μm interlayer resin insulation layer and plating film thickness of 25μ
m of electroless copper plating films were alternately formed to produce a build-up multilayer wiring board having four wiring layers. [Resin composition] 30% acrylate of cresol novolak type epoxy resin (manufactured by Yuka Shell): 60 parts by weight Bisphenol A type epoxy resin (manufactured by Yuka Shell): 40 parts by weight Diallyl terephthalate: 15 parts by weight 2-methyl-1 -[4- (methylthio) phenyl] -2-morpholino propanone-1 (manufactured by Ciba-Geigy): 4 parts by weight Imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2P4MHZ): 4 parts by weight

The measured peel strength of the electroless copper plated film in the build-up multilayer wiring board produced, and the insulation resistance and glass transition point T _g of the interlayer resin insulating layer in Example 3 and Comparative Example 1. Furthermore, -65 ℃ × 30min ~ 125 ℃ ×
A 30 minute heat cycle test was performed. Table 2 shows the results.
Shown in As is clear from the results shown in this table, by applying the resin composite of the present invention to the resin insulating layer of the build-up multilayer wiring board, the adhesive strength, insulating property, heat resistance and heat cycle characteristics of the conventional one ( (Only the thermosetting resin is used as the resin insulating layer).

[0032]

[Table 2]

Example 4: Resin other than Epoxy Substituted with Photosensitive Group and Thermoplastic Resin In an epoxy-modified polyimide resin / PSF system, an epoxy-modified polyimide resin (manufactured by Mitsui Petrochemical Industries, trade name: TA-1800) )) And a photosensitizing oligomer in which 30% of the epoxy groups are acrylated and P
SF, imidazole-based curing agent (Shikoku Chemicals, trade name: 2E
4MZ-CN), trimethyltriacrylate (TMPTA) as a photosensitive monomer, I-907 (manufactured by Ciba-Geigy) as a photoinitiator, and a resin mixed with DMF with the following composition,
Next, the obtained mixture was dried at 80 ° C. for 30 minutes to remove the solvent, and then UV-cured under the condition of ³ J / cm ² and further heat-cured at 150 ° C. for 5 hours. A cured product was obtained. Resin composition: TA-1800 / PSF / TMPTA / I-907 / imidazole-based curing agent = 70/30/10/5/5

The cured resin obtained had a tensile strength and a tensile elongation of 750 kg / cm ² and 6.2%, respectively. The tensile strength and tensile elongation of a cured product made of only the 30% acrylated epoxy resin prepared under the same curing agent and curing conditions were 550 kg / cm ² and 4.3%, respectively.

(Example 5: Photosensitive resin / PES type) (1) In the photosensitive resin / PES type, 100% acrylated cresol novolak type epoxy resin as a photosensitive resin and dipentaerythritol hexaacrylate as a photosensitive monomer (Manufactured by Kyoeisha Oil & Fats) and neopentyl glycol modified trimethylolpropane diacrylate (manufactured by Nippon Kayaku), benzophenone (manufactured by Kanto Kagaku) as a photoinitiator, and Michler's ketone (manufactured by Kanto Kagaku) as an accelerator
And a resin cured product was obtained under the following composition and curing conditions. [Resin composition] 100% acrylated cresol novolak type epoxy resin (manufactured by Yuka Shell): 70 parts by weight PES: 30 parts by weight Dipentaerythritol hexaacrylate (manufactured by Kyoeisha Oil & Fats): 10 parts by weight Neopentyl glycol modified trimethylolpropane Diacrylate (Nippon Kayaku): 5 parts by weight Benzophenone: 5 parts by weight Michler's ketone: 0.5 parts by weight [Curing conditions] Drying: 80 ° C, 1 hour Light curing: 3 J / cm ² Thermal curing: 150 ° C, 2 hours

The tensile strength and tensile elongation of the obtained cured resin were 750 kg / cm ² and 5.0%, respectively, and were intermediate values between the epoxy resin and PES. The same curing agent,
Tensile strength and tensile elongation of a cured product made of only photosensitive resin prepared under curing conditions are about 560 kg / cm ² and 3.1%, respectively.
Met.

The peel strength, insulation resistance, glass transition point _Tg and heat cycle test method or evaluation method will be described. (1) Peel strength JIS-C-6481 (2) Insulation resistance An interlayer insulating layer was formed on a substrate, and after roughening, a catalyst was applied, and then a plating resist was formed to form a resist pattern. Thereafter, electroless plating was performed, and the insulation resistance between the patterns was measured. The insulation between patterns is
80 ° C / 85% / 24 with comb pattern of L / S = 75/75 μm
V and the value after 1000 hours were measured. (3) was measured by the glass transition point T _g dynamic viscoelasticity measurement. (4) Heat cycle test A heat cycle test was performed at −65 ° C. × 30 min to 125 ° C. × 30 min, and the occurrence of cracks and the presence or absence of peeling of the interlayer insulating layer were examined.

[0038]

As described above, according to the present invention, physical properties specific to a thermosetting resin such as a partially acrylated epoxy resin or physical properties specific to a photosensitive resin such as an acrylic resin,
For example, it is possible to provide a novel resin composite having not only heat resistance and photosensitive properties but also excellent physical properties inherent to a thermoplastic resin such as PES.

[Brief description of the drawings]

FIG. 1 is a diagram showing a phase diagram of a mixed system of a thermoplastic resin and a thermosetting resin.

FIG. 2 is an SEM photograph of a structure showing a co-continuous particle structure of a resin composite according to the present invention.

Continuation of the front page (56) References JP-A-5-310931 (JP, A) JP-A-7-82482 (JP, A) JP-A-2-279710 (JP, A) JP-A-4-353516 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 H05K 1/03 H05K 3/46

Claims (5)

(57) [Claims] 1. A part of the functional group is a resin composite comprising a thermosetting resin substituted with photosensitive groups and a thermoplastic resin, and the above-described thermosetting resin and thermoplastic resin, co Continuous structure
Interlayer resin of multilayer wiring board formed in a dispersed state
Resin composite for insulating material . 2. A resin composite comprising a photosensitive resin and a thermoplastic resin, and a photosensitive resin and a thermoplastic resin, a co
Layers of a multilayer wiring board formed in a dispersed state that is a continuous structure
A resin composite for inter-resin insulation . 3. The thermosetting resin has five to five functional groups.
The multilayer according to claim 1, wherein 70% is substituted with a photosensitive group.
Resin composite for interlayer resin insulation of wiring boards . 4. The resin composite according to claim 1, wherein the spherical particles constituting the bicontinuous structure have an average particle diameter of more than 0.1 μm and 5 μm or less. A resin composite for an interlayer resin insulating material of the multilayer wiring board according to the above. 5. The compounding ratio of the thermosetting resin or photosensitive resin and the thermoplastic resin in the resin complex is any one of claims 1 to 4 is 15～50Wt% in the content of the thermoplastic resin The resin composite for an interlayer resin insulating material of the multilayer wiring board according to the above.