JP3172372B2 - Method for producing epoxy acrylate-PES resin composite - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an epoxy acrylate-PES-based resin composite, and more particularly to a method for providing a resin liquid having excellent coating strength and good workability to stably provide a pseudo-uniform structure. It is a proposal for an advantageous method by which a resin composite having the same can be produced.

[0002]

2. Description of the Related Art It is generally known that super engineering plastics such as PES (so-called super engineering plastics) have excellent properties such as toughness. However, this super engineering plastic is a thermoplastic resin,
When using it, a step of heating it to a melting point or higher is required as in injection molding, and a molding die is also required. Therefore, its use is considerably limited. On the other hand, thermosetting resins such as epoxy resins are widely used for applications such as paints and adhesives. This is because a thermosetting resin such as an epoxy resin can be used in a liquid state at normal temperature and has excellent workability. In recent years, research has been conducted on a compounding technique for introducing the properties of the super engineering plastic into a thermosetting resin having such excellent workability. For example, a mixed system (PE) of an epoxy resin and polyether sulfone (hereinafter, referred to as “PES”)
Epoxy resin and PES
This is a technique to improve the toughness of epoxy resin by the co-continuous structure formed by (Keizo Yamanakaand Takash
i Inoue, Polymer, vol. 30, P662 (1989)).

[0003] The above PES-modified epoxy resin obtained by mixing two kinds of resins is compared with the epoxy resin alone.
The toughness of the resin is improved. This is because the PES-modified epoxy resin forms a resin structure as described below. In other words, 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 PES do not completely dissolve (compatible state), but spinodal decomposition. Is caused and the epoxy resin and PES are mixed in a separated state (phase separated state). This is PE
In the matrix of S, epoxy spherical domains are connected to each other and are in a state of being regularly dispersed,
This is because a so-called co-continuous structure of epoxy resin and PES is formed.

However, the above-mentioned co-continuous structure is formed by the phase separation between the epoxy resin and PES, and the epoxy spherical domains generated by spinodal decomposition are simply dispersed in the PES matrix. It can be said that it is only a structure. 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
The glass transition temperature of the composite having a co-continuous structure was determined by dynamic viscoelasticity measurement. As a result, two peaks of the glass transition temperature were observed. This is probably because the interaction of The knowledge about the bicontinuous structure as described above was the same for the mixed system of an epoxy resin having a photosensitive group and PES.

In such an epoxy resin / PES mixed system, as shown in FIG.
It is compatible at low temperature but separates into two phases at high temperature.
The phase diagram of CST type (Low Critical Solution Temperature) is shown. On the other hand, when the epoxy resin is polymerized with the curing reaction and the glass transition temperature (T _g ) of the resin becomes higher than the curing temperature, the molecular motion is frozen at that temperature and the phase separation does not occur. This is because movement and diffusion of molecules are required for phase separation.

[0006] The inventors of the present invention have previously conducted intensive studies focusing on the above-mentioned facts, and as a result, have proposed a completely novel resin composite which is different from the known resin having the above-mentioned co-continuous structure (Japanese Patent Application No. 2002-287686). Hei 5-271192). In other words, this resin composite has a thermosetting resin and a thermoplastic resin forming a pseudo-homogeneous compatible structure, and has the unique physical properties of a thermosetting resin such as an epoxy resin or a photosensitive resin such as an acrylic resin. For example, it is a novel substance having heat resistance and photosensitive properties and exhibiting higher physical properties than the original physical properties of a thermoplastic resin such as PES. In the pseudo-homogeneous compatible structure, the particle diameter of the constituent resin particles is a transmission electron microscope (hereinafter, referred to as a transmission electron microscope).
It is characterized by having a measured value of 0.1 μm or less as measured by observation (indicated by “TEM”) and a single glass transition temperature peak value of the resin by dynamic viscoelasticity measurement. Here, the conditions of the dynamic viscoelasticity measurement are a vibration frequency of 6.28 rad / sec and a temperature rising rate of 5 ° C./min.

The resin composite having such a pseudo-homogeneous compatible structure can be freely processed or bored by exposure and development by imparting photosensitivity.
Therefore, it is desirable to use acrylated epoxy acrylate as the epoxy resin constituting the resin composite.

Further, in order to produce such a resin composite having a quasi-homogeneous compatible structure from a liquid state at normal temperature, in the case of an epoxy acrylate / PES mixed system, epoxy acrylate and PES are uniformly mixed in a phase solvent. Mixed into
The mixture is dried and cured while controlling such that the mixture does not undergo phase separation in the phase solvent, thereby producing a composite. Therefore, in order to stably produce an epoxy acrylate-PES-based resin composite having a quasi-homogeneous compatible structure, the epoxy acrylate and PES may be mixed in the step of drying the mixed solvent of epoxy acrylate and PES.
It is important to select a phase solvent that does not cause phase separation.

Therefore, the inventors have found that the compatibility with PES is excellent, and the phase separation temperature between epoxy acrylate and PES is set to 80.
Attention was paid to normal methylpyrrolidone (hereinafter referred to as “NMP”) as a phase solvent that can be raised to about ° C.

Incidentally, epoxy acrylate requires a reaction solvent when synthesizing it, and the synthesized resin itself is usually obtained in a state of being dissolved in this reaction solvent. Therefore, in order to use the above NMP as a phase solvent, it is desirable to use NMP also as the above reaction solvent.
However, the epoxy resin has a problem that when NMP is used as a reaction solvent at the time of the synthesis reaction for acrylizing the epoxy group, the epoxy resin is gelled, and it is not possible to stably synthesize epoxy acrylate. On the other hand, there is a method in which epoxy acrylate synthesized using a solvent other than NMP as a reaction solvent is used for producing a resin composite using NMP as a phase solvent. However, in this method, a solvent other than NMP as a reaction solvent and NM as a phase solvent are used.
Compatibility with P has arisen as a new problem. In other words, if the compatibility between the reaction solvent and the compatibilizing agent is poor, they are easily separated from each other, resulting in a fatal problem that a resin composite having a pseudo-homogeneous compatible structure cannot be stably obtained.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to prepare an epoxy acrylate-PES resin composite having a quasi-homogeneous compatible structure as a phase solvent for uniformly mixing epoxy acrylate and PES. NMP
The object of the present invention is to solve the above-mentioned problem that occurs when using the method. That is, a solvent having excellent compatibility with NMP and suitable as a reaction solvent for epoxy acrylate was found,
It is an object of the present invention to establish a manufacturing technique capable of stably obtaining a resin composite having a quasi-homogeneous compatible structure.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies for realizing the above object, and as a result, diethylene glycol dimethyl ether (hereinafter, referred to as a solvent having excellent compatibility with NMP and being suitable as a reaction solvent for epoxy acrylate). "DMDG"), and conceived of the method of the present invention having the following content as a summary structure.

That is, the present invention relates to an epoxy acrylate resin solution synthesized using diethylene glycol dimethyl ether (DMDG) as a reaction solvent and a polyether sulfone (PES) resin solution using normal methylpyrrolidone (NMP) as a diluting solvent. Is mixed as a phase solvent, dried and cured to produce a resin composite having a pseudo-homogeneous compatible structure.

[0014]

The method of the present invention is characterized in that DMDG is used as a solvent which is excellent in compatibility with NMP which is a diluting solvent for PES and also a phase solvent for epoxy acrylate and PES, and which is suitable as a reaction solvent for epoxy acrylate. There are features.
As a result, NMP and DMDG are uniformly mixed with each other, so that the mixture of epoxy acrylate resin and PES can maintain a uniform mixed state without phase separation even at a high temperature of about 80 ° C. And D
Since MDG does not gel epoxy acrylate after the synthesis reaction, it is also excellent as a reaction solvent for epoxy acrylate resin. Therefore, according to the method of the present invention, it is possible to stably produce an epoxy acrylate-PES-based resin composite having a pseudo-homogeneous compatible structure.

[0015] The quasi-homogeneous compatible structure according to the present invention is, as described above, to uniformly mix epoxy acrylate and PES with NMP as a phase solvent, and then dry and increase the curing rate, and / or phase separation. It is formed by reducing the speed to make the particle diameter of the constituent resin particles 0.1 μm or less as measured by observation with a transmission electron microscope (hereinafter, referred to as “TEM”).

In the present invention, as an epoxy acrylate curing agent, an imidazole curing agent, a diamine, a polyamine, a polyamide, an organic acid anhydride, a vinyl phenol, or the like can be used.

The interrelationship between various factors that determine the curing speed or the phase separation speed will be described. First, the factors that determine the curing speed will be described. With the other conditions constant,. The higher the curing temperature of the epoxy acrylate, the faster the curing speed. Therefore, in the method of the present invention, the curing temperature is set so that the curing speed is such that a pseudo-homogeneous compatible structure is formed. . The shorter the gel time, the faster the curing rate. Therefore, in the method of the present invention, the epoxy resin is cured using a curing agent whose gel time has been adjusted so that the curing speed is such that a pseudo-homogeneous compatible structure is formed. . The curing speed increases as the photosensitivity increases. Therefore, in the method of the present invention, since the epoxy resin is provided with photosensitivity, the obtained resin composite has a more homogeneous pseudo-homogeneous compatible structure.

Next, factors that determine the phase separation speed will be described. . As the number of functional groups in one molecule of the uncured epoxy acrylate increases, phase separation is less likely to occur (the phase separation speed decreases). Therefore, in the method of the present invention, an uncured epoxy acrylate in which the number of functional groups in one molecule is adjusted so as to have a phase separation rate that forms a pseudo-homogeneous compatible structure is used. . The larger the molecular weight of the uncured epoxy acrylate, the less the phase separation occurs (the lower the phase separation rate). Therefore, in the method of the present invention, an uncured epoxy acrylate whose molecular weight has been adjusted so as to have a phase separation rate that forms a pseudo-homogeneous compatible structure is used.

The PES-modified epoxy resin obtained by the method of the present invention as described above has a higher resin strength than that of PES alone, and has an unprecedented toughening effect of the epoxy resin.

Accordingly, the resin composite obtained by the method 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 and the like.
It is expected to be used in various applications such as resist materials and prepreg materials, base materials for fiber-reinforced composite materials, injection molding materials, and compression molding materials.

[0021]

【Example】

(Example 1) (1) A photosensitive dry film (manufactured by DuPont) was laminated on a glass epoxy copper-clad laminate (manufactured by Toshiba Chemical),
The image was printed by exposing to ultraviolet light through a mask film on which a desired conductive circuit pattern was drawn. Then, 1,1,
After developing with 1-trichloroethane and removing copper in the non-conductive portion using a cupric chloride etching solution, the dry film was peeled off with methylene chloride. As a result, a wiring board having a first-layer conductive circuit including a plurality of conductive patterns on the substrate was prepared. (2) Epoxy resin particles (Toray, average particle size 3.9 μm) 20
In an epoxy resin particle suspension obtained by dispersing 0 g in 5 l of acetone, 30 g of epoxy resin (manufactured by Mitsui Petrochemical) was dissolved in 1 l of acetone while stirring in a Henschel mixer. A suspension obtained by dispersing 300 g of an epoxy resin powder (manufactured by Toray, average particle size 0.5 μm) in an acetone solution was dropped, and the epoxy resin powder was allowed to adhere to the surface of the epoxy resin particles. The acetone was removed and then heated to 150 ° C. to produce pseudo particles. These pseudo particles have an average particle size of about 4.3 μm
And about 75% by weight is ± 2 μm around the average particle size.
Existed in the range. (3) In a DMDG solvent, methacrylic acid is added to an epoxy group of a cresol novolak type epoxy resin (trade name: EOCN-103S, manufactured by Nippon Kayaku) to give a 25% acrylated cresol novolak type epoxy resin. Epoxy acrylate was synthesized. 70 parts by weight of epoxy acrylate in 30 parts by weight of DMDG synthesized in this way, polyether sulfone (PES, manufactured by BASF, trade name: Ultrason E-1010)
) 30 parts by weight of NMP were added to 70 parts by weight of NMP, and the mixture was stirred at room temperature and dissolved to prepare a resin solution of PES; caprolactone-modified tris (acryloxyethyl) isocyanurate as a photosensitive monomer (trade name, manufactured by Toagosei; Aronix M
325) 10 parts by weight, 5 parts by weight of benzophenone as a photoinitiator, 0.5 parts by weight of a photosensitizer Michler's ketone, 5 parts by weight of an imidazole-based curing agent (trade name: 2P4MZ-CN, manufactured by Shikoku Chemicals), and (2) After mixing 40 parts by weight of the pseudo particles prepared in the above, the viscosity was adjusted to 250 cps with a homodisper stirrer while adding NMP as a phase solvent, and then kneaded with three rolls to obtain a photosensitive resin composition (adhesive). ) 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 60 ° C. About 50μ
m of the photosensitive resin insulating layer (adhesive layer). (5) A photomask film on which a black circle of 100 μmφ was printed was brought into close contact with the wiring board subjected to the treatment of (4), and was exposed with an ultrahigh pressure mercury lamp of 500 mj / cm ² . This was subjected to ultrasonic development with diethylene glycol diethylene ether (DMDG) to form an opening serving as a 100 μmφ via hole on the wiring board. Further, the wiring board was exposed at about 3000 mj / cm ² by an ultra-high pressure mercury lamp, and was exposed at 80 ° C. for 30 minutes.
By performing a heat treatment at 100 ° C. for 1 hour and then at 150 ° C. for 2 hours, a resin insulating layer (adhesive layer) having openings having excellent dimensional accuracy corresponding to a photomask film was formed. (6) The wiring board subjected to the treatment of (5) is immersed in potassium permanganate (KMnO ₄ , 500 g / l) at 70 ° C. for 15 minutes to roughen the surface of the interlayer resin insulating layer. After being immersed in a Japanese solution (made by Shipley), it was 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) After repeating the steps (4) to (7) twice,
Further, by performing the step (1), a build-up multilayer wiring board having four wiring layers was manufactured.

The cured product obtained by curing only the resin corresponding to the matrix of the adhesive used in the present embodiment under the above conditions was etched with methylene chloride on its cross section, and subjected to SEM.
Upon observation, resin particles having an average particle size of 0.1 μm or less were observed. A cured product obtained by curing a mixture of a resin composition not mixed with the epoxy resin fine powder was subjected to a viscoelasticity measurement test under the conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min. And one glass transition temperature Tg. Therefore, it is considered that the adhesive matrix used in this example has a pseudo-homogeneous compatible structure. That is, according to the production method of the present invention, it can be seen that a pseudo-homogeneous compatible structure can be stably formed without phase separation even when dried and cured at a high temperature.

(Example 2, Comparative Example) As a reaction solvent used for synthesizing a 25% acrylate of a cresol novolac type epoxy resin, a diluting solvent for PES, and a phase solvent for epoxy acrylate and PES, a solvent shown in Table 1 is used. A resin insulating layer (adhesive layer) was formed under the same conditions as in Example 1 except for using. As a result, for the comparative examples other than the combination of the reaction solvent, the diluting solvent, and the phase solvent according to the method of the present invention, gelation occurs during synthesis of epoxy acrylate, or phase separation occurs during mixing of epoxy acrylate and PES, With the drying and curing at 80 ° C., an adhesive layer comprising a matrix of a resin composite having a pseudo-homogeneous compatible structure cannot be easily obtained. In this regard, for a suitable example of a combination of a reaction solvent, a diluting solvent, and a phase solvent according to the method of the present invention, an adhesive comprising a matrix of a resin composite having a pseudo-homogeneous compatible structure even at a high temperature of about 80 ° C. when dried and cured. It has been found that the layers can be obtained easily.

[0024]

[Table 1]

[0025]

As described above, the method of the present invention can be applied to PE
Since DMDG is used as a solvent suitable for the reaction solvent of epoxy acrylate, which has excellent compatibility with NMP, which is a diluting solvent for S and is also a phase solvent for uniformly mixing the epoxy resin and PES, An epoxy acrylate-PES-based resin composite having a quasi-homogeneous compatible structure can be stably obtained.

[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.

Claims (1)

(57) [Claims] 1. A resin solution of epoxy acrylate synthesized using diethylene glycol dimethyl ether (DMDG) as a reaction solvent, and normal methylpyrrolidone (NM
Polyethersulfone (PES) using P) as a diluent solvent
A method for producing an epoxy acrylate-PES-based resin composite, comprising mixing the resin liquid of (1) with NMP as a phase solvent, drying and curing the mixture to produce a resin composite having a pseudo-homogeneous compatible structure.