JP3142425B2 - Resin composite having pseudo-homogeneous compatible structure - 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, and more particularly to a resin comprising an epoxy resin and a polyether sulfone. Complex, so-called PES
It is a proposal for a modified epoxy resin or a resin composite composed of an acrylic resin and polyethersulfone, a so-called PES-modified acrylic resin, and a method for producing them.

[0002]

2. Description of the Related Art A typical technique for a resin composite is to improve the physical properties of a thermosetting resin by mixing a thermosetting resin with a thermoplastic resin to form a composite. For example, epoxy resin and polyether sulfone (hereinafter, referred to as
A technique for improving the toughness of the epoxy resin by a co-continuous structure formed by the epoxy resin and the PES in a mixed system (shown by "PES") (Keizo Yamanaka and Takashi Inoue, Polyme)
r, vol. 30, p. 662 (1989)).

[0003] The above PES-modified epoxy resin obtained by mixing two kinds of resins has improved toughness of the resin as compared with the epoxy resin alone. This is because the PES-modified epoxy resin forms a resin structure as described below. That is, in a mixed system of an epoxy resin such as a bisphenol A type epoxy resin and PES, when the epoxy resin is cured at a high temperature, the epoxy resin and the PES do not completely dissolve (compatibility state) but spinodal decomposition. Is caused and the epoxy resin and PES are mixed in a separated state (phase separated state). Such a phase-separated state depends on the degree of incompatibility in the initial dispersion state of the resin to be mixed, and when the degree of incompatibility is large, a spherical domain structure is formed, and the degree of incompatibility is small. In such a case, a bicontinuous structure is formed. The "spherical domain structure" refers to a state in which spherical domains composed of a resin mainly composed of an epoxy resin are independent of each other in a resin matrix mainly composed of PES, or a part of them is connected and dispersed. The term "co-continuous structure" refers to a structure in which spherical domains composed of a resin mainly composed of an epoxy resin are connected to each other and regularly dispersed in a resin matrix mainly composed of PES. . That is, in such a structure, each of the constituent resins is not completely separated, but the PES also contains the epoxy resin, and the ratio is overwhelmingly high in PES, while Has a structure in which the ratio of epoxy resin is high, and each resin is not completely phase-separated but partially compatible with each other.

[0004]

However, the above-mentioned co-continuous structure is formed when the epoxy resin and PES are in a phase-separated state, and the epoxy spherical domains generated by spinodal decomposition are simply contained in the PES matrix. It is a structure that is only dispersed in Therefore, although there is an effect of dispersing and introducing PES into the epoxy resin, it cannot be made higher than the original physical properties of PES. The reason for this is that when the glass transition temperature of the composite having a bicontinuous structure was measured by dynamic viscoelasticity measurement, it was confirmed that the number of peaks of the glass transition temperature was two. It is considered that the interaction with is weak. The knowledge about the co-continuous structure as described above was the same for a mixed system of a photosensitive resin and a thermoplastic resin, for example, a mixed system of an acrylic resin and polyether sulfone (PES-modified acrylic resin).

[0005] An object of the present invention is to provide a thermosetting resin such as an epoxy resin or a photosensitive resin such as an acrylic resin having specific physical properties such as heat resistance and photosensitive characteristics, and a thermoplastic resin such as PES. It is an object of the present invention to provide a novel resin composite exhibiting higher physical properties than the original physical properties shown, and a production technique therefor.

[0006]

Means for Solving the Problems In order to achieve the above object, the inventors first studied a system of a thermosetting resin and a thermoplastic resin, which is one mixed system of a resin composite.
In a mixed system of a thermosetting resin and a thermoplastic resin, for example, an epoxy resin / PES mixed system,
As shown in FIG. 1, S is compatible at low temperature but separates into two phases at high temperature, so-called LCST type (Low Critical Sol.
ution Temperature). However, when the epoxy resin is polymerized with the curing reaction and the glass transition temperature (T _g ) of the resin increases and becomes higher than the curing temperature, the molecular motion is frozen at that temperature and the phase cannot be separated. This is because phase separation requires the movement and diffusion of molecules.

The present invention has been completed as a result of intensive studies focusing on such a fact, and a clear co-continuous structure is obtained by phase separation between a thermosetting resin and a thermoplastic resin.
The above object can be achieved by controlling the phase separation rate and the curing rate so as to cure and composite the resin so as not to form a structure or a spherical domain structure .

That is, the present invention relates to a resin composite comprising a thermosetting resin and a thermoplastic resin, or a resin composite comprising a thermosetting resin and a thermoplastic resin and provided with photosensitivity. A resin composite characterized in that the thermosetting resin and the thermoplastic resin form a pseudo-homogeneous compatible structure, wherein the particle diameter of the constituent resin particles forming the pseudo-homogeneous compatible structure is transmitted. Type electron microscope (hereinafter, "TEM")
(Measured value by observation) is 0.1 μm or less, and the number of peaks of the glass transition temperature of the resin by dynamic viscoelasticity measurement is one. Here, the condition of the dynamic viscoelasticity measurement in the present invention is that the vibration frequency is 6.28 rad /.
sec, heating rate 5 ° C./min.

On the other hand, the present inventors have studied on a system of a photosensitive resin and a thermoplastic resin, which is another mixed system of a resin composite, in order to achieve the above object. As a result, basically, like a mixed system of thermosetting resin and thermoplastic resin,
By forming a clear co-continuous structure or a spherical domain structure by phase separation between the photosensitive resin and the thermoplastic resin, by controlling the phase separation rate and the curing rate to cure and composite the resin, The inventors have found that the object can be achieved and completed the present invention.

That is, the present invention provides a resin composite comprising a photosensitive resin and a thermoplastic resin, wherein the photosensitive resin and the thermoplastic resin form a pseudo-homogeneous compatible structure. In the pseudo-homogeneous compatible structure, the particle diameter of the constituent resin particles is 0.1 μm or less as measured by TEM observation, and the peak number of the glass transition temperature of the resin by dynamic viscoelasticity measurement is 1 It is characterized by one. Here, the conditions of the dynamic viscoelasticity measurement in the present invention are a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min.

The method for producing the resin composite of the present invention as described above firstly comprises curing a thermosetting resin or a photosensitive resin mixed with a thermoplastic resin to form a thermosetting resin or a photosensitive resin. When complexing a thermoplastic resin and a thermoplastic resin, in the case of a thermosetting resin and a thermoplastic resin, the curing temperature of the thermosetting resin, the type of curing agent, and the presence or absence of photosensitivity are selected. In the case of one or more factors, on the other hand, in the case of a photosensitive resin and a thermoplastic resin, the resin is cured at a curing speed exceeding a quasi-uniform phase formation point determined by a photocuring factor of the photosensitive resin. I do. Second, when a thermosetting resin or a photosensitive resin mixed with a thermoplastic resin is cured to form a composite of the thermosetting resin or the photosensitive resin and the thermoplastic resin, an uncured thermosetting resin or an uncured resin is used. The cured photosensitive resin is cured at a phase separation rate not exceeding a quasi-homogeneous phase formation point determined by one or more factors of a crosslinking density or a molecular weight. Third, when the thermosetting resin or the photosensitive resin mixed with the thermoplastic resin is cured to form a composite of the thermosetting resin or the photosensitive resin and the thermoplastic resin, the temperature exceeds the pseudo-homogeneous phase formation point. It is characterized in that the composition is cured at a curing rate and at a phase separation rate not exceeding the pseudo-homogeneous phase formation point. Here, it is desirable that the blending ratio between the thermosetting resin or the photosensitive resin and the thermoplastic resin is 15 to 50% by weight in terms of the content of the thermoplastic resin.

[0012]

The feature of the resin composite of the present invention comprising a thermosetting resin or a photosensitive resin and a thermoplastic resin is that the thermosetting resin or the photosensitive resin and the thermoplastic resin form a pseudo-homogeneous compatible structure. It is in the point. This quasi-homogeneous compatible structure is a new concept devised by the inventors and refers to a structure described below. That is, the quasi-homogeneous compatible structure has the unique physical properties of a thermosetting resin such as an epoxy resin or the specific properties of a photosensitive resin such as an acrylic resin, and the original physical properties of a thermoplastic resin such as PES. A higher homogeneity structure with higher physical property values. One glass transition temperature peak value by dynamic viscoelasticity measurement.
The interaction between the thermosetting resin or the photosensitive resin and the thermoplastic resin is extremely strong. Therefore, the resin composite of the present invention is obtained by using a scanning electron microscope (hereinafter, referred to as a scanning electron microscope) shown in FIG.
Indicated by “SEM”. 2) It has a structure as shown in the photograph, which is clearly different from the conventional bicontinuous grain structure shown in the SEM photograph of FIG. 2 (b). In addition, the resin composite has a more uniform particle diameter of the constituent resin particles of 0.1 μm or less as observed by TEM observation (see FIG. 2 (c)). Because of such a homogeneous resin composite,
The thermoplastic resin is hardly eluted by the solvent, etc.
Excellent in nature. With the co-continuous structure described in the prior art
Means that PES is eluted by methylene chloride and the surface is uneven
(See FIG. 2 (b), a substitute photograph for the drawing).
Dissolution of thermoplastic resin such as PES by methylene chloride
The output is small and no irregularities are generated on the surface.

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

Such a pseudo-homogeneous compatible structure of a thermosetting resin or a photosensitive resin and a thermoplastic resin is formed by the following method of the present invention. That is,
The quasi-homogeneous compatible structure according to the present invention, a thermosetting resin or a photosensitive resin and a thermoplastic resin are dissolved in a solvent as necessary and uniformly mixed, and thereafter, the curing speed is increased,
It is formed by reducing the phase separation speed and / or the particle diameter of the constituent resin particles to 0.1 μm or less as measured by TEM observation.

Specifically, in the method of the present invention, first, when a thermosetting resin is used, the thermosetting resin is selected from the curing temperature of the thermosetting resin, the type of the curing agent, and the presence or absence of photosensitivity. At a curing rate exceeding the quasi-homogeneous phase formation point determined by one or more factors, on the other hand, when a photosensitive resin is used, photocuring factors of the photosensitive resin, such as an initiator, a sensitizer, It is characterized in that it is cured at a curing speed exceeding a quasi-uniform phase formation point determined by a reactive monomer, exposure conditions and the like. Here, the quasi-homogeneous phase formation point is a value obtained by measuring the particle size of the resin particles constituting the composite by TEM observation.
It means the lower limit of the curing rate at which a quasi-homogeneous compatible structure of 0.1 μm or less can be obtained.

Second, the method of the present invention may further comprise the step of exceeding the quasi-homogeneous phase formation point determined by at least one of the crosslinking density and the molecular weight of the uncured thermosetting resin or uncured photosensitive resin. It is characterized in that it cures at a phase separation speed that is not high. Here, the quasi-homogeneous phase formation point means that the particle size of the resin particles constituting the composite is 0.1% as measured by TEM observation.
a quasi-homogeneous compatible structure of not more than μm can be obtained,
It means the upper limit of the phase separation rate.

Thirdly, the method of the present invention is characterized in that curing is performed at a curing rate exceeding the above-mentioned pseudo-homogeneous phase formation point and at a phase separation rate not exceeding the above-mentioned pseudo-homogeneous phase formation point. This means a method in which the factors determining the curing rate and the phase separation rate interact.

Next, the interrelation of the above-mentioned various factors for determining the curing rate or the phase separation rate will be described. First, as for the factors that determine the curing speed, assuming that other factor conditions are constant, the higher the curing temperature of the thermosetting resin, the faster the curing speed. Therefore, when the thermosetting resin is cured beyond the lower limit of the curing temperature required to obtain a curing speed exceeding the quasi-homogeneous phase formation point, the structure of the obtained resin composite becomes a quasi-homogeneous compatible structure. The shorter the gelling time, the faster the curing speed. Therefore, when the thermosetting resin is cured using a curing agent that does not exceed the upper limit of the gelation time necessary to obtain a curing rate exceeding the quasi-homogeneous phase formation point, the structure of the obtained resin composite becomes pseudo- A homogeneous compatible structure results. The curing speed increases as the photosensitivity increases. Therefore, in a combination in which another factor condition forms a pseudo-homogeneous compatible structure, by imparting photosensitivity to the resin, the obtained resin composite has a more homogeneous pseudo-homogeneous compatible structure. The method of imparting photosensitivity includes a method of introducing a photosensitive group into a thermosetting resin or a thermoplastic resin, and a method of blending a photosensitive monomer. If necessary, a photoinitiator and a photosensitizer may be used. May be blended. Further, a photosensitive resin such as an acrylic resin can be used instead of the thermosetting resin. In this case, it is necessary to cure the photosensitive resin at a curing rate exceeding a pseudo-homogeneous phase formation point determined by a photocuring factor such as an initiator, a sensitizer, a photosensitive monomer, and exposure conditions.

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

Next, as for the factors that determine the phase separation rate, if the other factor conditions are kept constant, the higher the crosslinking density of the uncured thermosetting resin or uncured photosensitive resin, the less the phase separation occurs (phase Separation speed decreases). Therefore, when cured using an uncured thermosetting resin or uncured photosensitive resin having a crosslinking density exceeding the lower limit of the crosslinking density required to obtain a phase separation rate not exceeding the pseudo-homogeneous phase formation point, it is obtained. The structure of the resin composite is a pseudo-homogeneous compatible structure. As the molecular weight of the uncured thermosetting resin or uncured photosensitive resin increases, phase separation is less likely to occur (the phase separation speed decreases). Therefore, when cured using an uncured thermosetting resin or uncured photosensitive resin having a molecular weight exceeding the lower limit of the molecular weight required to obtain a phase separation rate not exceeding the quasi-homogeneous phase formation point, the resulting resin composite The body structure is a quasi-homogeneous compatible structure.

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

The resin composite obtained by the method of the present invention as described above has not only the specific properties of a thermosetting resin such as an epoxy resin, but also the specific properties of a photosensitive resin such as an acrylic resin. , PES and the like can exhibit higher physical property values than the original physical properties. That is, the PES-modified epoxy resin and the PES-modified acrylic resin according to the present invention have a higher strength than the resin strength of PES alone, and have a toughening effect of an epoxy resin or an acrylic resin that has not existed conventionally.

In the present invention, as described above, prior to compounding the thermosetting resin or the photosensitive resin with the thermoplastic resin, the thermosetting resin or the photosensitive resin and the thermoplastic resin may be used as required. And dissolve in a solvent to mix uniformly. Examples of such a solvent include dimethylformamide (DMF), methylene chloride, dimethylsulfoxide (DMSO), and normal methylpyrrolidone (NM
P) can be used. In addition, below the phase separation start temperature,
At a temperature lower than the curing start temperature, the thermosetting resin or the photosensitive resin and the thermoplastic resin can be mixed by heating and melting.

In the present invention, as the thermosetting resin, phenol resin, amino resin such as melamine resin and urea resin, epoxy resin, epoxy modified polyimide resin, unsaturated polyester resin, polyimide resin, urethane resin,
A diallyl phthalate resin or the like can be used. As the thermosetting resin, a resin in which a part of a functional group that partially contributes to thermosetting is substituted with a photosensitive group can be used. For example, a 20 to 50% acrylate of an epoxy resin is preferable.

In the present invention, as the thermoplastic resin, phenoxy resin, polyether sulfone, polysulfone,
Engineering plastics such as polyphenylene sulfide, polyetheretherketone, polyacetal, polycarbonate, and polyetherimide, polystyrene, polyethylene, polyarylate, polyamideimide, polyoxybenzoate, polyvinyl chloride, polyvinyl acetate, and the like can be used.

In the present invention, the photosensitive resin is preferably an acrylic resin such as poly (methyl methacrylate) or a thermosetting resin in which 100% of the functional group is acrylated.
Here, a photoinitiator which is important as a photocuring factor of the photosensitive resin includes intramolecular bond cleavage type such as benzoisobutyl ether, benzyldimethyl ketal, diethoxyacetophenone, acyloxymester, chlorinated acetophenone, and hydroxyacetophenone. One or more of intramolecular hydrogen abstraction types such as benzophenone, Michler's ketone, dibenzosuberone, 2-ethylanthraquinone, and isobutylthioxanson are preferably used. Examples of photoinitiator include triethanolamine, Michler's ketone, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy) ethyl, Any one or more of isoamyl-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and polymerizable tertiary amine are used. Suitable sensitizers include Michler's ketone, Irgacure 651, isopropylthioxanthone, and the like. Some of the above photoinitiators act as sensitizers. The composition ratio of the photoinitiator and the sensitizer is, for example, benzophenone / Michler's ketone = 5 parts by weight / 0.5 parts by weight based on 100 parts by weight of the photosensitive resin. Irgacure 184 / Irgacure 651 = 5 parts by weight / 0.5.
Parts by weight Irgacure 907 / isopropylthioxanthone = 5 parts by weight / 0.5 parts by weight is preferred. Further, as a photosensitive monomer or a photosensitive oligomer constituting the photosensitive resin, epoxy acrylate, epoxy methacrylate, urethane acrylate, polyester acrylate, polystyryl methacrylate and the like are preferably used.

In the present invention, as the curing agent when an epoxy resin is used as the thermosetting resin, an imidazole curing agent, a diamine, a polyamine, a polyamide, an organic acid 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.

In addition to the physical properties inherent to a thermosetting resin such as an epoxy resin, or the physical properties inherent to a photosensitive resin such as an acrylic resin, the physical properties inherent to a thermoplastic resin such as PES to be compounded are even higher. Indicates physical property value,
The resin composite of the present invention includes an adhesive for electroless plating such as an adhesive for a printed wiring board, a substrate material, a resist material and a prepreg material used for a printed wiring board, a sealing material for a semiconductor package, and a fiber-reinforced composite. It is expected to be used in various applications such as base materials for materials, injection molding materials, and compression molding materials.

[0029]

【Example】

(Example 1: Influence of curing agent) (1) In the epoxy resin / PES system, curing agents having different gelling times (curing speeds) are used, and the type of the curing agent of the epoxy resin is the resin structure and physical properties of the above-mentioned mixed system. Was examined for its effect on (2) As the curing agents having different gelling times, several kinds of imidazole-based curing agents (manufactured by Shikoku Chemicals) shown in Table 1 were used. (3) In order to investigate the effect of the curing agent, a bisphenol A type epoxy resin (manufactured by Yuka Shell, trade name: Epicoat 828) was used as the epoxy resin.
The mixing ratio of PES was 70/30, PES was dissolved in twice the amount of dimethylformamide (DMF), a predetermined amount of epoxy resin and a curing agent were mixed and cured, and the epoxy equivalent of the epoxy resin was 184 to 184. 194, and the curing conditions were fixed at 120 ° C. × 5 hours + 150 ° C. × 2 hours.

FIG. 3 and Table 1 show the results of examining the structure and physical properties of the obtained cured resin. FIGS. 3 (a) to 3 (d)
FIG. 2 is an SEM photograph showing the structure of a cured resin obtained using the imidazole-based curing agent shown in Table 1, wherein (a) 2PHZ-CN,
(b) 2PZ-OK, (c) 2E4MZ-CN, (d) 1B2MZ. As is clear from these photographs and the results shown in Table 1, it was found that when a curing agent having a low curing rate was used, a spherical domain structure was formed due to progress of phase separation, and the strength and elongation of the resin were low. On the other hand, when the epoxy resin and PES are cured with a curing agent having a curing speed exceeding the pseudo-homogeneous phase formation point, the epoxy resin and PES form a pseudo-homogeneous compatible structure, and both the strength and the elongation of the cured product are greatly improved. It turns out.

FIG. 4 is a graph showing the relationship between the particle size of the resin obtained by SEM observation of the cured resin and the gelation time of the curing agent. As is clear from the results shown in this figure, 12
When the gelation time at 0 ° C. became about 5 minutes or less, it was found that the particle size of the resin sharply decreased, and the spherical domain structure became a pseudo-homogeneous compatible structure. That is, under the conditions of this example, it can be seen that the quasi-homogeneous phase formation point determined by the gel time of the curing agent exists at a point where the gel time is about 5 minutes.

[0032]

[Table 1]

(Example 2: Influence of curing temperature) (1) In an epoxy resin / PES system, by curing under curing conditions having different curing temperatures, the curing temperature of the epoxy resin is changed to the resin of the obtained cured resin. The effect on the structure was investigated. (2) The curing conditions with different curing temperatures are as follows:
The conditions were implemented. a. 6 hours at 80 ° C b. 6 hours at 100 ° C. c. 5 hours at 120 ° C. d. 4 hours at 150 ° C (3) When the curing temperature is lower and the quasi-homogeneous compatible structure is formed by the curing agent From the knowledge that the higher the curing temperature, the quasi-homogeneous compatible structure may be formed, As the agent, an amine-based curing agent (manufactured by Sumitomo Chemical Co., trade name: DDM) and an imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E4MZ-CN) were used. (Four)
In order to investigate the effect of the curing temperature, bisphenol A type epoxy resin (manufactured by Yuka Shell,
Product name: Epicoat 828), epoxy resin / PE
The compounding ratio of S / curing agent is 70/30/20 for amine-based curing agent (DDM), 70/30/5 for imidazole-based curing agent (2E4MZ-CN), and twice the amount of PES. The resin was dissolved in dimethylformamide (DMF), a predetermined amount of an epoxy resin and a curing agent were mixed and cured, and the epoxy equivalent of the epoxy resin was kept constant at 184 to 194.

The results of examining the structure of the obtained cured resin are shown in FIGS. 5 and 6. 5 (a) to 5 (d) and FIG. 6 (a)
To (d) relate to an amine-based curing agent and an imidazole-based curing agent, respectively, each of which is a SEM showing the structure of the cured resin obtained at the various curing temperatures described above.
(A) 80 ° C, (b) 100 ° C, (c) 120 ° C, (d) 15
Shows the case of 0 ° C. When a type of amine-based curing agent (DDM) was used as the curing agent, as shown in the photograph of FIG. 5, the resin structure formed a pseudo-homogeneous compatible structure when the curing temperature was 80 ° C. At a temperature of 100 ° C. or higher, a spherical domain structure is formed, and the particle size of the spherical domain is 0.
It was found to be 2 μm or more. On the other hand, when a type of imidazole-based curing agent (2E4MZ-CN) is used as the curing agent, as shown in the photograph of FIG. 6, the resin structure has a pseudo-homogeneous compatible structure at a curing temperature of 100 ° C. or higher. It was found that when the curing temperature was 80 ° C., a spherical domain structure having a particle size of about 0.3 μm was formed.

FIGS. 7 and 8 show the relationship between the particle size of the resin obtained by SEM observation and the curing temperature of the epoxy resin for the above two types of curing agents. As is clear from the results shown in these figures, in the case of the type amine-based curing agent, when the curing temperature is 90 ° C. or lower, the spherical domain structure changes to a pseudo-homogeneous compatible structure, while
Curing temperature of 90 ° C for imidazole type curing agents
From the above, it was found that a quasi-homogeneous compatible structure was obtained from the spherical domain structure. That is, under the conditions of this example,
It can be seen that the quasi-homogeneous phase formation point determined by the curing temperature of the epoxy resin exists at a curing temperature of about 90 ° C.

Example 3 Influence of Crosslink Density (1) In an epoxy resin / PES system, by curing epoxy resins having the same skeletal structure and different epoxy equivalents, the epoxy equivalent of the epoxy resin can be reduced. The effect on the resin structure of the cured product was examined, and the effect of the crosslink density of the resin was examined. (2) As epoxy resins having different epoxy equivalents, see Table 2
The following two types of bisphenol A type epoxy resins were used. (3) In order to investigate the effect of the epoxy equivalent, an imidazole-based curing agent (Shikoku Chemicals, trade name: 2E) was used as a curing agent.
Using 4MZ-CN), the mixing ratio of epoxy resin / PES / hardener is 70/30/5, PES is dissolved in twice the amount of dimethylformamide (DMF), and a predetermined amount of epoxy resin and hardener are mixed The curing conditions were 80 ° C. for 1 hour, 100 ° C. for 1 hour, 120 ° C. for 1 hour, and 150 ° C. for 3 hours.

FIG. 9 and Table 2 show the results of examining the structure of the obtained cured resin. FIGS. 9 (a) to 9 (d) are SEM photographs showing the structure of the cured resin obtained using the epoxy resins having the various epoxy equivalents described above.
828, (b) epicoat 1001, (c) epicoat 1004, (d) epicoat 1007. As is clear from these photographs and the results shown in Table 2, the epoxy equivalent was large,
In other words, it was found that the lower the crosslink density, the easier the phase separation was, while the lower the epoxy equivalent, in other words, the higher the crosslink density, the more the resin structure became a quasi-homogeneous compatible structure. That is, under the conditions of this example, it can be seen that the quasi-homogeneous phase formation point determined by the epoxy equivalent (or crosslink density) of the epoxy resin exists at a point where the epoxy equivalent is around 300.

[0038]

[Table 2]

Example 4: Influence of photosensitive monomer introduction (1) In the epoxy resin / PES system, by introducing a photosensitive monomer, what effect is exerted on the resin structure and physical properties of the obtained cured resin. To find out
Thus, the effect of the photosensitivity was considered. (2) As the photosensitive monomer, as shown in Table 3, dipentaerythritol hexaacrylate (DPE-6A, manufactured by Kyoeisha Yushi) and neopentyl glycol-modified trimethylolpropane diacrylate (R-604, manufactured by Nippon Kayaku)
Benzophenone (BP, manufactured by Kanto Chemical) as a photoinitiator, and Michler's ketone (MK, manufactured by Kanto Chemical) as a promoter
And a resin cured product was obtained under the following curing conditions. [Light curing condition] 3 J / cm ² [Thermal curing condition] 80 ° C for 1 hour, 100 ° C for 1 hour, 120 ° C
For 1 hour and 150 ° C for 3 hours. (3) To investigate the effect of introducing the photosensitive monomer,
As the epoxy resin, bisphenol A type epoxy resin (manufactured by Yuka Shell, trade name: Epicoat 828), and as the curing agent, an imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E)
4MZ-CN) and the mixing ratio of epoxy resin / PES is 70 /
30 and the PES in double the amount of dimethylformamide (DMF
), And a predetermined amount of epoxy resin and a curing agent are mixed and cured, and the epoxy equivalent of the epoxy resin is adjusted to 18
4-194, and fixed conditions.

Table 3 shows the results of examining the structure and physical properties of the obtained cured resin. As is evident from the results shown in Table 3, the epoxy resin and PES are homogeneously mixed at a low temperature and cured using a photoreaction, and then thermally cured to form a pseudo-homogeneous phase having a smaller particle size. As a result of forming a melt structure, it was found that the strength and elongation of the cured product were further improved.

[0041]

[Table 3]

Further, the obtained cured resin was observed by TEM under the following conditions. As a result, the particle diameter of the resin constituting the cured resin was 0.1 μm or less. [Observation conditions] Using a microtome, cut the sample into 70 nm slices. The cut slice is immersed in a methanol solution of osmium tetroxide (OsO ₄ ) for 24 hours. Observation is performed with an acceleration voltage of 80 kV during TEM observation. Further, the glass transition temperature _Tg was measured by dynamic viscoelasticity. As a result, as shown in FIG. 10, there was only one _Tg peak, which proved to be homogeneous in physical properties. As a result, it is assumed that the physical properties such as tensile strength and elongation become higher than those of the constituent resin component alone.

Example 5 Influence of PES Blending Amount (1) In the epoxy resin / PES system, how the PES blending amount is variously changed affects the physical properties of the obtained cured resin. Examined. (2) The amount of PES was varied from 0 wt% to 60%. (3) In order to investigate the effect of the PES content, a cresol novolac epoxy resin (manufactured by Nippon Kayaku, trade name: EOCN-103S) was used as the epoxy resin, and an imidazole-based curing agent (manufactured by Shikoku Chemicals) was used as the curing agent. , Product name: 2E4MZ-C
N) and double the amount of PES with dimethylformamide (D
MF) to dissolve, mix a predetermined amount of epoxy resin and curing agent and cure, and adjust the epoxy equivalent of epoxy resin.
210 to 230, curing condition of epoxy resin at 80 ° C for 1 hour,
The conditions were fixed at 100 ° C. for 1 hour, 120 ° C. for 1 hour, and 150 ° C. for 3 hours.

FIG. 11 shows the result of examining the change in physical properties of the resin cured product thus obtained. As is clear from the results shown in this figure, the strength of the resin increased as the amount of PES increased, showed a maximum value at 30% PES, and thereafter the resin strength decreased. Especially 30% PES
The cured resin is not only epoxy resin but also PES
Higher strength than alone. Under the conditions of this example,
The obtained cured resin had a pseudo-homogeneous compatible structure in all the compounding compositions. Thus, from the results of this example, it was found that in the epoxy resin / PES system, the blending amount of PES is desirably 15 to 50% by weight, more preferably 20 to 40% by weight.

Example 6 (1) In the epoxy resin / PES system, a bisphenol A type epoxy resin having an epoxy equivalent of 184 to 194 (manufactured by Yuka Shell, trade name: Epicoat 828) is used as the epoxy resin.
), Using an imidazole-based curing agent (Shikoku Chemicals, trade name: 2E4MZ-CN) as a curing agent, mixing the resin with DMF with the following composition, and curing at 120 ° C for 5 hours and 150 ° C for 2 hours. To obtain a cured resin having a pseudo-homogeneous compatible structure. The gel time of the curing agent at 120 ° C. was 3 minutes. Resin composition: Epicoat 828 / PES / 2E4MZ-CN = 70/30 /
5

With respect to the cured resin obtained as described above,
As a result of TEM observation in the same manner as in Example 4, the resin particle size was 0.1 μm or less. Further, as a result of measuring the glass transition temperature T _g by dynamic viscoelasticity measurement, the peak value of T _g was one as in Example 4.

Further, the tensile strength and tensile elongation of the obtained cured resin were 835 kg / cm ² 8.0%, respectively, which was higher than that of the resin component alone. The tensile strength and tensile elongation of a cured product made of only epoxy resin prepared under the same curing agent and curing conditions are about 500 kg each.
/ cm ² , 4.8%.

The above-mentioned results were similarly obtained when an imidazole-based curing agent (trade name: 1B2MZ, manufactured by Shikoku Chemicals) was used as the curing agent. In this case, the gel time of the curing agent at 120 ° C. was 44 seconds.

(Example 7) (1) In an epoxy resin / PES system, a bisphenol A type epoxy resin having an epoxy equivalent of 184 to 194 (trade name: Epicoat 828, manufactured by Shikoku Chemicals Co., Ltd.)
Using imidazole-based curing agent (manufactured by Yuka Shell, trade name: 2E4MZ-CN) as the curing agent, and mixing the resin with DMF with the following composition, set the curing conditions at 80 ° C x 1 hour + 150 ° C x 4 hours. To obtain a cured resin having a pseudo-homogeneous compatible structure. This embodiment is different from the sixth embodiment only in the curing temperature of the epoxy resin. Resin composition: Epicoat 828 / PE
S / 2E4MZ-CN = 70/30/5

With respect to the cured resin obtained as described above,
As a result of TEM observation in the same manner as in Example 4, the resin particle size was 0.1 μm or less. Further, as a result of measuring the glass transition temperature T _g by dynamic viscoelasticity measurement, there was one T _g peak as in Example 4.

Further, the tensile strength and tensile elongation of the obtained cured resin were 835 kg / cm ² 9.1%, respectively, which was higher than that of the resin component alone. The tensile strength and tensile elongation of a cured product made of only epoxy resin prepared under the same curing agent and curing conditions are about 500 kg each.
/ cm ² , 4.5%.

Example 8 (1) In an epoxy resin / PES system, a bisphenol A type epoxy resin having an epoxy equivalent of 184 to 194 (manufactured by Yuka Shell, trade name: Epicoat 828) is used as the epoxy resin.
), Using an amine-based curing agent (Sumitomo Chemical Co., trade name: DDM) as the curing agent, mixing the resin with DMF with the following composition, and curing at 80 ° C for 6 hours and 150 ° C for 2 hours. The resin was cured to obtain a cured resin having a pseudo-homogeneous compatible structure. Resin composition: Epicoat 828 / PES / DDM = 70/30/18

With respect to the resin cured product thus obtained,
As a result of TEM observation in the same manner as in Example 4, the resin particle size was 0.1 μm or less. As a result of measurement of a glass transition temperature T _g in the dynamic viscoelasticity, in the same manner as in Example 4 T _g
Had one peak.

Further, the tensile strength and the tensile elongation of the obtained cured resin were 860 kg / cm ² and 8.6%, respectively, which were confirmed to be higher than those of the resin component alone. The tensile strength and tensile elongation of a cured product made of only epoxy resin produced under the same curing agent and curing conditions are about 500 kg /
cm ² , 5%.

(Example 9) In an epoxy resin / PES system, a cresol novolak type epoxy resin having an epoxy equivalent of 210 to 230 (Nippon Kayaku Co., Ltd., trade name: EOCN-103S) as an epoxy resin, and an imidazole-based curing agent as a curing agent Mix the resin with the following composition using DMF using the agent (Shikoku Chemicals, trade name: 2E4MZ-CN), and cure at 80 ° C for 1 hour and at 150 ° C for 4 hours to obtain a pseudo-homogeneous phase. A cured product having a molten structure was obtained. Resin composition: EOCN-103S / PES / 2E4MZ-CN = 70/30/5

With respect to the cured resin obtained as described above,
As a result of TEM observation in the same manner as in Example 4, the resin particle size was 0.1 μm or less. Further, as a result of measuring the glass transition temperature T _g by dynamic viscoelasticity measurement, as in Example 4, there was one peak at the T _g point.

Further, the tensile strength and tensile elongation of the obtained cured resin were 990 kg / cm ² and 6.5%, respectively, which were confirmed to be higher than those of the resin component alone. The tensile strength and tensile elongation of a cured product made of only epoxy resin prepared under the same curing agent and curing conditions are about 550 kg each.
/ Cm ² , 2.8%.

Example 10: Application to an adhesive for an additive wiring board (1) 70 parts by weight of a cresol novolak type epoxy resin (manufactured by Nippon Kayaku), polyether sulfone (PES, ICI)
30 parts by weight), 5 parts by weight of an imidazole-based curing agent (manufactured by Shikoku Chemicals, trade name: 2E4MZ-CN), and 25 parts by weight of an epoxy resin fine powder (manufactured by Toray) having an average particle size of 5.5 μm and an average particle size of 25 parts by weight After mixing 10 parts by weight of a particle having a diameter of 0.5 μm, the mixture is adjusted to a viscosity of 120 cps with a homodisper stirrer while adding a dimethylformamide / butyl cellosolve (1/1) mixed solvent, and then kneaded with a three-roll mill. An adhesive solution was obtained. (2) This adhesive solution is applied on a glass epoxy insulating plate (manufactured by Toshiba Chemical) to which no copper foil is stuck, using a roller coater, and then at 80 ° C. for 1 hour and at 100 ° C. for 1 hour. After drying and curing at 120 ° C. for 1 hour and at 150 ° C. for 3 hours, an adhesive layer having a thickness of 20 μm was formed. (3) The substrate on which the adhesive layer is formed is immersed in a chromic acid aqueous solution (CrO ₃ , 500 g / l) at 70 ° C. for 15 minutes to roughen the surface of the adhesive layer, and then a neutralizing solution (manufactured by Shipley) And then washed with water. (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. After immersion for an hour, electroless copper plating with a plating film thickness of 25 μm was performed.

[0059]

[Table 4]

Comparative Example 1: Application to Adhesive for Additive Wiring Board (1) An adhesive solution containing fine epoxy resin powder was prepared in the same manner as in Example 10 except for the following conditions, and a copper foil was prepared. Glass epoxy insulation board without sticker (manufactured by Toshiba Chemical)
On top, a 20μm thick adhesive layer and a 25μm thick plating film
An electroless copper plating film was formed. [Resin composition] Phenol novolak epoxy resin: 100 parts by weight imidazole-based curing agent (Shikoku Chemicals, trade name: 2P4MH
Z): 4 parts by weight [Conditions for curing the adhesive layer] 1 hour at 100 ° C, 5 hours at 150 ° C

The peel strength of the electroless copper plating films formed in Example 10 and Comparative Example 1, the insulation resistance of the adhesive layer and the glass transition point T _g were measured. Table 5 shows the results. As is clear from the results shown in this table, by applying the PES-modified epoxy resin according to the present invention which forms a pseudo-homogeneous compatible structure to the adhesive for wiring boards, the adhesive strength,
It was found that the heat resistance and the electrical insulation were significantly improved as compared with the conventional one.

[0062]

[Table 5]

Example 11 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 parts by weight of a 50% acrylated cresol novolak type epoxy resin (manufactured by Yuka Shell), 30 parts by weight of polyether sulfone (PES), 15 parts by weight of diallyl terephthalate, 2-methyl-1- [4- ( 4 parts by weight of methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba-Geigy)
Imidazole-based curing agent (Shikoku Chemicals, trade name: 2E4MZ-C
N) After mixing 4 parts by weight and 50 parts by weight of the pseudo particles prepared in (2) above, while adding butyl cellosolve,
Adjust the viscosity to 250 cps with a homodisper stirrer, then
The mixture was kneaded with three rolls to prepare a solution of the photosensitive resin composition. (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) for 70 minutes to roughen the surface of the resin insulating layer. ) 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,
Then, it was immersed in an electroless plating solution for additive having the composition shown in Table 4 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.

(Comparative Example 2: 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] 50% 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

[0065] was 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 11 and Comparative Example 2. Furthermore, -65 ℃ × 30min ~ 125 ℃ ×
A 30 minute heat cycle test was performed. Table 6 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, insulation, heat resistance and heat cycle characteristics are reduced to those of the conventional one. It was found to be significantly improved.

[0066]

[Table 6]

Example 12: Epoxy resin / PES-based epoxy resin / PES-based epoxy equivalent of 210 to
230 parts by weight of cresol novolak type epoxy resin (manufactured by Nippon Kayaku, trade name: ECON-103S), 30 parts by weight of polyether sulfone (PES, ICI) and imidazole-based curing agent (trade name: 2E4MZ) -CN) was mixed with DMF using DMF, and then the mixture was added at 80 ° C for 1 hour for 15 hours.
The composition was cured at 0 ° C. for 5 hours to obtain a cured product having a pseudo-homogeneous compatible structure.

With respect to the resin cured product thus obtained,
As a result of TEM observation in the same manner as in Example 4, the resin particle size was 0.1 μm or less. Further, as a result of measuring the glass transition temperature T _g by dynamic viscoelasticity measurement, as in Example 4, there was one peak at the T _g point.

Further, the tensile strength and the tensile elongation of the cured resin obtained were 995 kg / cm ² and 6.4%, respectively, which were higher than those of the resin component alone. In addition,
Tensile strength and tensile elongation of a cured product consisting only of epoxy resin prepared under the same curing agent and curing conditions are about 550 each.
kg / cm ² , 3.0%.

(Example 13: Epoxy resin / PSF type) In an epoxy resin / polysulfone (PSF) type, a bisphenol A type epoxy resin (manufactured by Yuka Shell, trade name: Epicoat 828) as an epoxy resin and an imidazole type as a curing agent Curing agent (Shikoku Chemicals, trade name: 2E4MZ-CN)
The resin was mixed with DMF having the following composition and cured at 80 ° C. for 1 hour and at 150 ° C. for 5 hours to obtain a cured product having a pseudo-homogeneous compatible structure. Resin composition: Epicoat 828 / PSF / imidazole-based curing agent = 70/30/5

With respect to the resin cured product thus obtained,
As a result of TEM observation in the same manner as in Example 4, the resin particle size was 0.1 μm or less. Further, as a result of measuring the glass transition temperature T _g by dynamic viscoelasticity measurement, as in Example 4, there was one peak at the T _g point.

Further, the tensile strength and tensile elongation of the obtained cured resin were 800 kg / cm ² and 7.8%, respectively, which were higher than those of the resin component alone. In addition,
Tensile strength and tensile elongation of a cured product made of only epoxy resin prepared under the same curing agent and curing conditions are about 500 respectively.
kg / cm ² , 4.5%. The resin obtained in Example 13 had a dielectric constant of 4.0 and a coefficient of thermal expansion of 5.5 × 10 ^-5 /
° C, and can be used as a sealing resin for a semiconductor package by mixing with silica powder or the like.

(Example 14: Epoxy-modified polyimide resin / PSF system) In an epoxy-modified polyimide resin / polysulfone (PSF) system, an epoxy-modified polyimide resin (manufactured by Mitsui Petrochemical Industries, trade name: TA-1800) and imidazole-based curing A resin (Shikoku Chemicals, trade name: 2E4MZ-CN), and a resin mixed with DMF having the following composition,
Curing was performed for 5 hours at 150 ° C. for 5 hours to obtain a cured product having a pseudo-homogeneous compatible structure. Resin composition: TA-1800 / PSF / imidazole-based curing agent = 75
/ 25/5

With respect to the resin cured product thus obtained,
As a result of TEM observation in the same manner as in Example 4, the resin particle size was 0.1 μm or less. Further, as a result of measuring the glass transition temperature T _g by dynamic viscoelasticity measurement, as in Example 4, there was one peak at the T _g point.

Further, the tensile strength and tensile elongation of the cured resin obtained were 980 kg / cm ² and 9.0%, respectively, which were confirmed to be higher than those of the resin component alone. In addition,
Tensile strength and tensile elongation of a cured product consisting only of epoxy resin prepared under the same curing agent and curing conditions are about 700 each.
kg / cm ² , 6.0%.

(Example 15: Photosensitive resin / PES system) (1) In the photosensitive resin / PES system, a phenol novolak type epoxy resin (manufactured by Yuka Shell) was used as the photosensitive resin.
100% acrylate, dipentaerythritol hexaacrylate (manufactured by Kyoeisha Oil & Fats) and neopentyl glycol-modified trimethylolpropane diacrylate (manufactured by Nippon Kayaku) as a photosensitive monomer, benzophenone (manufactured by Kanto Chemical) as a photoinitiator, accelerator A cured resin was obtained using Michler's ketone (manufactured by Kanto Chemical) under the following composition and curing conditions. [Resin composition] 100% acrylated cresol novolak type epoxy resin: 70 parts by weight PES: 30 parts by weight Dipentaerythritol hexaacrylate: 10 parts by weight Neopentyl glycol modified trimethylolpropane diacrylate: 5 parts by weight Benzophenone: 5 parts by weight Michler's ketone: 0.5 parts by weight [curing conditions] drying: 80 ° C. × 1 hour photocurable: 3J / cm ² after curing: 0.99 ° C. × 2 hours

The tensile strength and tensile elongation of the resin cured product thus obtained were 865 kg / cm ² and 6.8%, respectively, which were higher than those of the resin component alone.
In addition, the tensile strength and tensile elongation of a cured product made of only a photosensitive resin prepared under the same curing conditions are approximately 560 kg /
cm ² , 3.1%.

The above-described 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
L / S = 80/85 with comb pattern of 75/75 μm
% / 24V, the value after 1000 hours was 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.

[0079]

As described above, according to the present invention, a thermosetting resin such as an epoxy resin exhibits specific physical properties, such as heat resistance, and the original physical properties of a thermoplastic resin such as PES to be compounded. Thus, a novel resin composite exhibiting even higher physical property values can be reliably provided. In addition, a novel resin composite having the same properties as the photosensitive resin and exhibiting properties higher than the intrinsic properties of the thermoplastic resin such as PES can be obtained. Furthermore, it has excellent chemical resistance.

[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 (a) SEM photograph of a crystal structure showing a pseudo-homogeneous compatible structure of a resin composite according to the present invention, and (b) SEM of a crystal structure showing a co-continuous particle structure of a resin composite according to the prior art.
FIG. 2 is a photograph and (c) a TEM photograph of a crystal structure showing a pseudo-homogeneous compatible structure of the resin composite according to the present invention.

Fig. 3 Various imidazole curing agents (a) 2PHZ-CN, (b) 2PZ
5 is an SEM photograph showing the crystal structure of a cured resin obtained using -OK, (c) 2E4MZ-CN, and (d) 1B2MZ.

FIG. 4 is a diagram showing the relationship between the gelation time of a curing agent and the particle size of a resin constituting a composite.

FIG. 5 shows various curing temperatures (a) for amine-based curing agents.
4 is an SEM photograph showing a crystal structure of a cured resin obtained at 100 ° C., (b) 100 ° C., (c) 120 ° C., and (d) 150 ° C.

FIG. 6 shows various curing temperatures for imidazole-based curing agents
It is a SEM photograph which shows the crystal structure of the cured resin obtained at (a) 80 ° C, (b) 100 ° C, (c) 120 ° C, and (d) 150 ° C.

FIG. 7 is a diagram showing the relationship between the curing temperature of the resin and the particle size of the resin constituting the composite (in the case of an amine-based curing agent).

FIG. 8 is a diagram showing the relationship between the curing temperature of the resin and the particle size of the resin constituting the composite (in the case of an imidazole-based curing agent).

Fig. 9 Epoxy resin of various epoxy equivalents (a) Epicoat 828, (b) Epicoat 1001, (c) Epicoat 1004, (d)
4 is an SEM photograph showing a crystal structure of a cured resin obtained using Epicoat 1007.

FIG. 10 is a diagram showing the results of measuring dynamic viscoelasticity of the resin composite according to the present invention.

FIG. 11 is a diagram showing (a) tensile strength and (b) tensile elongation in the strength test measurement results of the resin composite according to the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08G 59/14

Claims (6)

(57) [Claims] 1. A thermosetting resin and a thermoplastic resin.
A cured resin composite, in which a thermosetting resin and a thermoplastic resin have a pseudo-homogeneous compatible structure,
The structure is such that the particle size of the resin particles constituting the composite is
0.1 μm or less measured with a scanning electron microscope
And the temperature rise rate is 5 ° C./min, and the vibration frequency is 6.28 ra
of resin by dynamic viscoelasticity measurement at d / s
Lath transition temperature with one peak
Resin composite, characterized in that it. 2. A resin composite comprising a thermosetting resin and a thermoplastic resin and provided with photosensitivity,
Thermosetting resin and thermoplastic resin have pseudo-homogeneous compatible structure
And the quasi-homogeneous compatible structure is
The particle size of the fat particles is the value measured by observation with a transmission electron microscope.
0.1 μm or less, heating rate 5 ° C./min, vibration
Dynamic viscoelasticity measured at a frequency of 6.28 rad / sec
The number of peaks of the glass transition temperature of the resin is one
A resin composite characterized by exhibiting the following characteristics . 3. A resin composite comprising a photosensitive resin and a thermoplastic resin, wherein the photosensitive resin and the thermoplastic resin are simulated.
It has a homogeneous compatible structure, and its pseudo-homogeneous compatible structure is
The particle size of the resin particles composing the coalescence is determined by transmission electron microscopy.
0.1 μm or less as measured by observation and the rate of temperature rise
Measured at 5 ° C / min and vibration frequency 6.28 rad / sec.
Of the glass transition temperature of the resin by a defined dynamic viscoelasticity measurement.
A resin composite having the characteristic of having a single peak. 4. A compounding ratio of the thermosetting resin or photosensitive resin and the thermoplastic resin in the resin complex is any one of claims 1 to 3 is 15～50Wt% in the content of the thermoplastic resin 3. The resin composite according to item 1. 5. The thermosetting resin is an epoxy resin, according to claim 1 the thermoplastic resin is a polyether sulfone
Or the resin composite according to any one of 4 . 6. The photosensitive resin is an acrylic resin, according to claim 3 also the thermoplastic resin is a polyether sulfone
Is the resin composite according to 4 .