JP2003147051A - Resin composition, method for producing the same, and prepreg for printed wiring board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having excellent adhesive strength to a metal foil, especially a copper foil, and further having excellent heat resistance, moisture resistance and electrolytic corrosion resistance, and further to provide a method for producing the resin composition and a prepreg for a printed wiring board using the composition. SOLUTION: This resin composition consists essentially of (A) a condensate of a primary and/or secondary amine compound with an epoxy resin, (B) the epoxy resin and (C) a phenol resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to adhesiveness with a metal foil,
The present invention relates to a resin composition having excellent heat resistance and electric insulation, a method for producing the resin composition, and a prepreg for a printed wiring board using the resin composition.

[0002]

2. Description of the Related Art With the recent miniaturization and multi-functionalization of electronic equipment, printed wiring boards are becoming more dense and compact. Along with this, finer wiring is required for printed wiring boards. At this time, the resin composition forming the insulating layer is required to have high reliability in heat resistance, water absorption, and the like, as well as to have high adhesive strength with the copper foil forming the circuit. In addition, as circuits become finer,
The roughening treatment of the metal foil, which is performed to improve the adhesive force with the resin, tends to be finer. Therefore, it is desired that the resin forming the insulating layer further enhances the adhesive force with the metal foil forming the circuit. On the other hand, epoxy resins are currently mainly used for adhesive films and printed wiring boards. At this time, a curing agent such as an aromatic amine, a phenol resin, or dicyandiamide is also used from the viewpoint of the heat resistance of the resin and the adhesiveness with the copper foil. However, when a phenolic resin is used as the curing agent, the heat resistance is excellent, but the adhesive strength with the metal foil is poor.
On the other hand, when an amine-based curing agent such as dicyandiamide or an aromatic amine is used, there are problems in heat resistance, moisture resistance, electrolytic corrosion resistance and the like.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is a resin composition having excellent adhesive strength to metal foil, particularly copper foil, and also excellent heat resistance, moisture resistance and electrolytic corrosion resistance. The present invention also provides a method for producing the same, and a printed wiring board prepreg using the same.

[0004]

In order to solve the above-mentioned drawbacks, the present inventor has proposed a resin composition having excellent adhesiveness to a metal foil, heat resistance, moisture resistance, and electrolytic corrosion resistance, a method for producing the same, and a method for producing the same. The present invention has been achieved as a result of continuing intensive studies on the used prepreg for a printed wiring board.

The present invention relates to the following: (1) A resin composition containing (A) a condensation product of a primary and / or secondary amine compound and an epoxy resin (B) an epoxy resin (C) a phenol resin as an essential component. (2) The resin composition according to claim 1, wherein a condensate having a weight average molecular weight of 1000 or more in terms of standard polystyrene is used as a condensate of the primary and / or secondary amine compound and the epoxy resin. . (3) (D) Condensate of primary and / or secondary amine compound and epoxy resin 0.1 to 100 parts by weight (E) Epoxy resin 1 to 100 parts by weight (F) Phenolic resin 1-1
A resin composition containing 100 parts by weight as an essential component. (4) As the primary and / or secondary amine compound,
(1) characterized by using a diamine compound
The resin composition according to any one of (3). (5) A prepreg for a printed wiring board obtained by impregnating a substrate with the resin composition according to (1) to (4), followed by heating and drying. (6) (G) Primary and / or secondary amine compound (H) Epoxy resin (I) In the method for producing a resin composition containing a phenol resin, a primary and / or secondary amine compound and an epoxy resin are used. A method for producing a resin composition, which comprises performing a condensation reaction in advance.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a resin composition is obtained by mixing a phenol resin and an amine compound as a curing agent with an epoxy resin. At this time, we found that a resin composition having an excellent adhesive force to a metal conductor can be obtained by previously conducting a condensation reaction between an epoxy resin and an amine compound.

The resin composition in the present invention is a resin composition containing (A) a primary and / or secondary amine compound and an epoxy resin condensate (B) an epoxy resin (C) a phenol resin as essential components, It is a thermosetting resin that is excellent in adhesion to metal conductors, heat resistance, moisture resistance, and electrolytic corrosion resistance and has excellent properties as an electrical insulating material.

In the present invention, the molecular weight is increased by previously reacting an amine compound with an epoxy resin. As a result, the amine can be efficiently introduced into the epoxy resin, and the resin composition having high adhesive strength to the metal conductor can be obtained.

At this time, the amine compound to be used is not particularly limited, but it is preferable to use a primary amine or a secondary amine, or a mixture thereof, because it is necessary to react with an epoxy resin to increase the molecular weight. In addition, since it is easy to increase the molecular weight and the reaction is easily controlled,
A compound (diamine compound) having two amino groups in the molecule is preferable, and a diamine compound having two primary amino groups is particularly preferable. Such amine compounds include m-phenylenediamine, p-phenylenediamine, m-toluylenediamine, m-xylylenediamine, 4,4′-diaminobenzanilide (hereinafter,
DABZ), 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (hereinafter abbreviated as DMDB), 2,2'-bis [4- (4
In addition to aromatic diamines such as -aminophenoxy) phenylpropane], aliphatic diamines such as ethylenediamine and hexamethylenediamine, and urea can be exemplified. Further, as the amine compound, an oligomer or polymer whose both ends are aminated can also be used. For example, both-end aminated polyethylene terephthalate, both-end aminated polypropylene, both-end aminated dimethylpolysiloxane, both-end aminated polyamide and the like can be used. Among these, aromatic diamines are more preferable in terms of heat resistance, and among them, DMDP and DABZ are particularly preferable over other diamines in terms of the property balance of the resulting resin composition.

There is no limitation on the epoxy resin that undergoes the condensation reaction with the amine compound, and for example, bisphenol type epoxy resin such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin. Epoxy resin, novolak type epoxy resin such as bisphenol A novolac type epoxy resin, dicyclopentadiene type epoxy resin and the like can be used. Among them, the bisphenol type epoxy resin is preferable because the reaction is easily controlled and the adhesive strength of the obtained resin composition to the metal conductor is high, and the bisphenol A type epoxy resin is particularly preferable for the same reason.

In the present invention, the amine compound and the epoxy resin are reacted in advance to synthesize a condensate. On this occasion,
The molecular weight of the product obtained is important. If the molecular weight of the obtained product is too low, the effect of improving the adhesive strength to the metal conductor is low. Therefore, the molecular weight of the condensate is preferably 300 or more, and particularly preferably 1000 or more in terms of standard polystyrene equivalent weight average molecular weight. Further, in consideration of compatibility and the like when blended into a varnish, the weight average molecular weight is preferably 300,000 or less, and particularly preferably 100,000 or less.

The reaction temperature and reaction time vary depending on the type and molar ratio of the amine and epoxy resin used, but are usually 0 to 1.
3 at a temperature of 50 ° C., preferably room temperature to 100 ° C.
It is preferable to react for 0 minutes or more. In addition, the above reaction is
For example, it is preferably carried out in a solvent such as acetone, methyl ethyl ketone, toluene, xylene, ethyl acetate, dimethylformamide, dimethylacetamide. The reaction concentration is not particularly limited, but if it is high, the produced polymer is difficult to dissolve, and if it is low, the reaction is difficult to proceed.
1 to 90% is preferable. In addition, dimethylacetamide is preferable because the resulting polymer has high solubility. Further, it is preferable to carry out the reaction in a nitrogen atmosphere because side reactions do not occur.

By blending the thus obtained amine compound-epoxy condensate with a thermosetting resin, it is possible to obtain a thermosetting resin having excellent adhesion to a metal conductor, especially a copper foil. .

Examples of the thermosetting resin to be used include polyimide resin, bismaleimide resin, epoxy resin, phenol resin and the like, but epoxy resin is particularly preferable from the viewpoint of cost and property balance. The type of epoxy resin used at this time is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and dicyclopentadiene type epoxy resin. Can be used. Further, it is necessary to blend a phenol resin as a curing agent in order to improve the heat resistance of the resin. Examples of the phenol resin used include phenol novolac, cresol novolac, and bisphenol A novolac. Of these, phenol novolac is preferred from the viewpoint of cost and property balance.

The amount of the compound is not particularly limited, but if the amount of the amine compound-epoxy condensate is too small, the adhesive force to the metal conductor will be insufficient, and if it is too large, the heat resistance and moisture resistance will tend to be poor. Therefore, epoxy resin 100
It is preferable to add 0.1 to 100 parts by weight, preferably 1 to 30 parts by weight, of the condensate to the parts by weight. If the amount of the phenol resin is too small, the heat resistance is not sufficient, and if it is too large, the adhesion with the metal conductor deteriorates.
It is preferable to add 1 part by weight, preferably 1 to 100 parts by weight. Needless to say, a curing accelerator such as an imidazole derivative, an inorganic filler such as talc, silica, aluminum hydroxide or antimony oxide, or other components can be added as necessary. After mixing these components, it is preferable to stir at room temperature for 30 minutes or more. The resin composition thus obtained can be used as it is as a varnish.

The obtained resin composition can be used as it is as a varnish, but it is applied to a metal foil such as a copper foil or a supporting film such as polyethylene terephthalate, polyimide or aramid and dried by heating to form an adhesive film. You can also do it. It is also possible to impregnate a resin composition into a substrate made of glass fiber, paper, or organic fiber and then heat-dry it to obtain a prepreg for a printed wiring board. These adhesive films and prepregs for printed wiring boards can be manufactured by pressurizing and heating together with a metal foil or the like by a press or the like to produce a printed wiring board.

[0017]

[Embodiment] (Epoxy resin / phenolic resin mixture) Into a 1-liter flask equipped with a stirrer, each component was added according to the following formulation, and well stirred for 1 hour. The obtained varnish was left standing for 12 hours or more to remove it, and then used. Brominated bisphenol A type epoxy resin 30 parts by weight (ESB400T manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent 400) Orthocresol novolac type epoxy resin 70 parts by weight (ESCN-195 manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent 195) Phenol novolac 100 Parts by weight (HP-850 manufactured by Hitachi Chemical Co., Ltd., hydroxyl equivalent 106) 2-ethyl-4-methylimidazole 0.5 parts by weight dimethylformamide 134 parts by weight

(Synthesis of amine / epoxy condensate) A predetermined amount of 2,2'-dimethyl-4,4'-diaminobiphenyl ( Wakayama Seika Co., Ltd. m-TBHG
(Trade name), hereinafter abbreviated as DMDB), bisphenol A type epoxy resin (YD-8125 manufactured by Tohto Kasei Co., Ltd.)
(Trade name), epoxy equivalent 172, and below, bis-A-
20% with dimethylacetamide.
After diluting with, the reaction was carried out at 70 ° C. for 2 hours in a nitrogen atmosphere. 50 mg of the obtained varnish was collected, and dimethylformamide / tetrahydrofuran = 1/1 (volume ratio, phosphoric acid 0.06 M, lithium bromide 0.03 M contained).
The solution was added with 5 ml and measured by GPC, and the molecular weight of the polymer was calculated by converting it to standard polystyrene. DMD used
The amounts of B and bis-A-EP and the molecular weight of the obtained polymer are shown in Table 1.

[0019]

[Table 1] Table 1

(Examples 1 to 5) 500 ml with a stirrer
100 g of the above epoxy / phenolic resin in a flask
(Solid content) and No. 1 to 5 amine / epoxy condensate 5
g (solid content) was added, and the mixture was stirred for 30 minutes, and then degassed by standing for 12 hours or more to obtain varnishes of Examples 1 to 5. These varnishes were applied to a 18 μm thick copper foil (GTS-18, Furukawa Circuit Foil Co., Ltd.) and dried at 160 ° C. for 7 minutes to obtain a copper foil with an adhesive. Two copper foils with an adhesive were laminated with the resin surface inside and pressed at a pressure of 2.5 MPa and 175 ° C. for 1 hour to obtain a double-sided copper-clad adhesive film. This double-sided copper-clad adhesive film is cut into a width of 10 mm, fixed on a glass plate having a thickness of 10 mm with an adhesive (Araldite, manufactured by Ciba-Geigy Co., Ltd.), and then the interface between the resin and the copper foil is peeled off,
The 90 degree peel strength was measured. The results are shown in Table 2. Further, a double-sided copper-clad film was prepared in the same manner, and then the resin film obtained by etching the copper foil was subjected to t by a DVE wide range dynamic viscoelasticity measuring device (measurement frequency 10 Hz).
The glass transition temperature was measured from the maximum value of an δ. The results are shown in Table 2.

(Comparative Example 1) As a comparative example of Examples 1 to 5, a double-sided copper-clad adhesive film was prepared in the same manner as in Example 1 using an epoxy / phenolic resin containing no amine / epoxy condensate. The 90 degree peel strength and the glass transition temperature were measured. The results are shown in Table 2.

(Comparative Example 2) As a comparative example of Example 1, the above epoxy / phenol resin was used, and DADB and bis-A-EP in the same amount as used in Example 1 were compounded without precondensation. Then, a resin composition was obtained. With this,
A double-sided copper-clad adhesive film was prepared in the same manner as in Example 1, and the 90-degree peel strength and glass transition temperature were measured. The results are shown in Table 2.

Comparative Example 3 As a comparative example of Examples 1 to 5, 5 g (solid content) of the above amine / epoxy condensate and 30 g of brominated bisphenol A type epoxy resin (ESB400T manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent). 40
0), orthocresol novolac type epoxy resin 7
0 g (ESCN-195 manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent 195), 0.5 g of 2-ethyl-4-methylimidazole and 134 g of dimethylformamide were blended, and the same method as in Example 1 was used without using a phenol resin. Then, a double-sided copper-clad adhesive film was produced, and 90-degree peel strength and glass transition temperature were measured. The results are shown in Table 2.

[0024]

[Table 2] Table 2

Examples 1 to 7 in Table 2 all use the resin composition obtained by the present invention, and all have a high glass transition temperature and a high 90-degree peel strength. On the other hand, in both Comparative Example 1 in which the amine / epoxy condensate was not used and Comparative Example 2 in which the amine and the epoxy were not condensed in advance, the 90-degree peel strength was low and the adhesive strength was insufficient. Further, Comparative Example 3 in which the phenol resin was not used had a low glass transition temperature and had insufficient heat resistance.

[0026]

INDUSTRIAL APPLICABILITY The present invention is a resin composition having excellent adhesion to a metal conductor, especially a copper foil, and has high reliability as an insulating resin. Therefore, it is not only optimal as an insulating resin for a printed wiring board, but also applicable to an insulating resin for mounting, an adhesive, a sealing material, etc., and has a wide range of applications.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C08L 63:00 C08L 63:00 (72) Inventor Yasuyuki Mizuno 1500 Ogawa Ogawa, Shimodate-shi, Ibaraki Hitachi Chemical Industrial Research Institute, Research Institute F-term (reference) 4F072 AA07 AB02 AB03 AB09 AD23 AD31 AE01 AG03 AG19 AH21 AK05 AL13 4J036 AA01 AA05 AD01 AD08 AF01 AF06 AJ08 DC02 DC03 DC04 DC06 DC10 FB07 JA08 JA11

Claims (6)

[Claims] 1. A condensation product of (A) a primary and / or secondary amine compound and an epoxy resin (B) an epoxy resin (C)
A resin composition containing a phenol resin as an essential component. 2. The resin according to claim 1, wherein a condensate having a weight average molecular weight of 1000 or more in terms of standard polystyrene is used as a condensate of a primary and / or secondary amine compound and an epoxy resin. Composition. 3. (D) Condensate of primary and / or secondary amine compound and epoxy resin 0.1 to 100 parts by weight (E) Epoxy resin 1 to 100 parts by weight (F) Phenolic resin 1 to 100 parts by weight A resin composition containing as an essential component. 4. The resin composition according to claim 1, wherein a diamine compound is used as the primary and / or secondary amine compound. 5. A prepreg for a printed wiring board, which is obtained by impregnating a base material with the resin composition according to any one of claims 1 to 4 and then heating and drying it. 6. A method for producing a resin composition comprising (G) a primary and / or secondary amine compound (H) epoxy resin (I) phenol resin, and a primary and / or secondary amine compound. A method for producing a resin composition, which comprises subjecting an epoxy resin to a condensation reaction in advance.