JP2002302529A - Dicyandiamide-added phosphorus-modified epoxy resin- containing resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition exhibiting sufficient flame retardancy without containing any halogen-based flame retardant and having good curabili ty, and capable of giving highly heat-resistant laminated boards in high produc tivity. SOLUTION: This dicyandiamide-added phosphorus-modified epoxy resin- containing resin composition is obtained by partially adding dicyandiamide to a phosphorus-modified epoxy resin which is obtained by reaction of an epoxy resin with an organophosphorus compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing a dicyandiamide-added phosphorus-modified epoxy resin and a method for producing the same. In particular, the present invention shows sufficient flame retardancy without containing a halogen-based flame retardant and has excellent curability. And a resin composition capable of obtaining a laminate having good productivity and good heat resistance. The present invention also relates to a prepreg, a laminate, and a printed wiring board using the resin composition.

2. Description of the Related Art In recent years, environmental problems have been increasing, and prepregs, laminated boards, and printed wiring boards used for electric and electronic devices have been required not to emit harmful substances into the environment when they are discarded or incinerated. I have. Therefore, in order to prevent harmful substances such as dioxins from being generated at the time of combustion, products characterized by not containing a halogen-based flame retardant are increasing. As a flame retardant which can be used in place of a halogen-based flame retardant, a metal hydroxide-based, phosphorus-based, melamine-modified resin-based flame retardant or the like is used. is there. However, red phosphorus, phosphates, phosphate esters, etc., which have been put into practical use as phosphorus-based flame retardants, emit toxic phosphine gas when burned, or have heat resistance and heat resistance of laminated boards and printed wiring boards by hydrolysis. There is a disadvantage that the chemical property is reduced.

On the other hand, JP-A-4-11662 and JP-A-2000-80251 disclose a phenolic hydroxyl group having a structure different from that of a phosphate ester and capable of easily reacting with an epoxy resin. A reaction product of an organophosphorus compound and an epoxy resin having a non-halogenated flame retardant containing no halogen-based flame retardant without deteriorating heat resistance or chemical resistance. It is disclosed that the composition can be manufactured. However, in general, when the epoxy resin and the organic phosphorus compound are simply reacted, the epoxy group decreases due to this reaction, the crosslink density of the epoxy resin decreases, and the curability deteriorates. Productivity decreases during production. When the amount of the curing accelerator or the like is increased to compensate for this, there has been a problem that the hygroscopicity and heat resistance of the obtained laminated board and the like are reduced.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a laminated board which shows sufficient flame retardancy without containing a halogen-based flame retardant, has excellent curability, has good productivity and good heat resistance. An object of the present invention is to provide a dicyandiamide-added phosphorus-modified epoxy resin-containing resin composition which can be used, and a method for producing the same. Another object of the present invention is to provide a prepreg, a laminated board, and a printed wiring board using the resin composition.

[0005]

According to the present invention, an epoxy resin is represented by the following general formula (1):

[0006]

Embedded image

(Wherein R is a group containing two or more phenolic hydroxyl groups) and a dicyandiamide-added phosphorus obtained by adding dicyandiamide to a phosphorus-modified epoxy resin obtained by reacting with an organic phosphorus compound represented by the following formula: In the modified epoxy resin-containing resin composition, (epoxy resin equivalent / organic phosphorus compound equivalent of formula (1)) in the phosphorus modification step is in the range of 2 to 5, and dicyandiamide equivalent is:

[0008]

(Equation 2)

(Wherein the epoxy resin equivalent includes the equivalent of the epoxy resin additionally added after the phosphorus modification step), and the addition reaction rate of dicyandiamide is 0.5.
It is a resin composition characterized by being 15%. Here, one equivalent of the epoxy resin is defined as the weight of the epoxy resin per mole of the epoxy group, and one equivalent of the organic phosphorus compound of the formula (1) is defined as the weight of the organic phosphorus compound per mole of the phenolic hydroxyl group. Assuming that one equivalent of dicyandiamide corresponds to 1/4 mol of dicyandiamide, the equivalent ratio is calculated. The present invention also relates to the resin composition, wherein the organic phosphorus compound of the formula (1) is 10-
(2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10
An oxide, wherein 50 to 90% by weight of the epoxy resin is a bisphenol F type epoxy resin.

Further, the present invention provides a method for producing the above resin composition, wherein the reaction of the organic phosphorus compound of the formula (1) to the epoxy resin and the addition of dicyandiamide to the epoxy resin are carried out in a one-step method. And a reaction between the epoxy resin and the organic phosphorus compound of the formula (1), and then an addition reaction of dicyandiamide to the reaction product is carried out. Still further, the present invention provides a method for performing the above reaction and the addition reaction in an organic solvent at a temperature of 100 to 160 ° C. in these production methods,
The above reaction and the addition reaction were carried out by adding triphenylphosphine as a reaction catalyst in an amount of 0.0
It is performed by adding 5 to 2.00 parts by weight.

[0011] The present invention also provides a prepreg obtained by impregnating a base material with the above resin composition and drying, a laminated plate in which a metal foil is laminated on at least one surface of the prepreg, and a circuit processing of the metal foil of the laminated plate. Printed wiring board.

BEST MODE FOR CARRYING OUT THE INVENTION

The epoxy resin used in the present invention includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene diol type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin. Epoxy resin, cycloaliphatic epoxy resin,
Glycidyl ester resin, glycidylamine resin, heterocyclic epoxy resin (triglycidyl isocyanurate,
Diglycidyl hydantoin, tetrakis (glycidyloxyphenyl) ethane, etc.), and modified epoxy resins obtained by modifying these with various reactive monomers. Also, two or more of these epoxy resins can be used in combination. As the epoxy resin has higher functionality, a cured product having a higher crosslinking density can be produced. However, since both dicyandiamide and the organic phosphorus compound of the formula (1) are bifunctional or trifunctional or higher, the epoxy resin The higher the functionality, the thicker or gelled during the production of the resin composition of the present invention, and the more difficult it is to handle. Therefore, the epoxy resin preferably contains a bifunctional epoxy resin, and it is particularly preferable to use a bisphenol F-type resin in an amount of 50 to 90% by weight of the epoxy resin.

The organic phosphorus compound of the formula (1) used in the present invention is 10- (2,5-dihydroxyphenyl)-
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxy-3-methylphenyl) -9,10-dihydro-
9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxy-4-methylphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 − (2,
5-dihydroxy-6-methylphenyl) -9,10-
Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (1,4-dihydroxy-2
-Naphthyl) -9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide and the like. Because particularly excellent flame retardancy is obtained, 10-
(2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10
-Oxides are preferred.

In the resin composition of the present invention, the compounding amount of the epoxy resin and the organic phosphorus compound of the formula (1) is such that (epoxy resin equivalent / organic phosphorus compound equivalent of the formula (1)) in the phosphorus modification step is 2 to 5; Range. When the compounding amounts of the epoxy resin and the organic phosphorus compound are within the above range in terms of the equivalent ratio, sufficient flame retardancy is exhibited, and there is no problem in handling in terms of viscosity.

In order to adjust the phosphorus content and the like, an additional epoxy resin can be added after the phosphorus modification step of reacting the epoxy resin with the organic phosphorus compound of the formula (1). In this case, no direct reaction occurs between the additionally added epoxy resin and the organophosphorus compound of the formula (1), so that there is no restriction on the mixing ratio.

In the resin composition of the present invention, the compounding amount of dicyandiamide is as follows.

[0017]

(Equation 3)

(Wherein the epoxy resin equivalent includes the equivalent of the epoxy resin additionally added after the phosphorus modification step). When the equivalent of dicyandiamide is in this range, the crosslink density of the cured product does not decrease, the moisture absorption of the cured product increases, and blistering or interlayer of the metal foil for forming a circuit in a printed wiring board manufacturing process using this resin composition. There is no problem such as peeling.

In the resin composition of the present invention, the reaction rate of dicyandiamide that has undergone an addition reaction to the epoxy resin is 0.1.
It is in the range of 5 to 15%. When the addition reaction rate of dicyandiamide is in this range, the resin composition of the present invention does not gel during the production, so that there is no problem in handling and the curability is good, so that the resin composition is produced in the production stage of a laminated board or the like. Nature can also be secured.

The resin composition may contain a halogen compound such as silica, talc, mica, aluminum oxide, magnesium carbonate, barium carbonate, etc. for the purpose of further increasing the flame retardancy, increasing the rigidity, and reducing the thermal expansion. Other inorganic fillers can be used. From the viewpoint of improving the flame retardancy, aluminum hydroxide is particularly preferable, and it is preferable to add 10 to 50% by weight based on the total solid content of the resin composition. In addition, other flame retardants, pigments, adhesion aids, antioxidants, curing accelerators and the like can be added to the resin composition of the present invention. Each of these can be a known substance, and is not particularly limited as long as it is a substance other than the halogen compound that does not deteriorate the properties of the laminate and the printed wiring board.

The resin composition of the present invention can be produced by the following method. That is, it can be produced by a method in which an epoxy group of an epoxy resin is reacted with a phenolic hydroxyl group of an organic phosphorus compound represented by the formula (1), and dicyandiamide is added to the epoxy resin.
These reactions may be performed by mixing an epoxy resin, an organic phosphorus compound and dicyandiamide (referred to as a one-step method), or by a two-step method, ie, by reacting the epoxy resin with the organic phosphorus compound and then forming the reaction. The reaction may be performed in a sequential reaction in which dicyandiamide is added to the product.

The compounding amount of the epoxy resin and the organic phosphorus compound of the formula (1) used in the above reaction is such that (epoxy resin equivalent / equivalent of the organic phosphorus compound of the formula (1)) in the phosphorus modification step is in the range of 2 to 5. It is. Note that an additional epoxy resin can be added to adjust the phosphorus content and the like, but there is no limitation on the mixing ratio between the additionally added epoxy resin and the organic phosphorus compound. On the other hand, the dicyandiamide equivalent used in the above addition reaction is

[0023]

(Equation 4)

(Wherein, the epoxy resin equivalent includes the equivalent of the epoxy resin additionally added after the phosphorus modification step).

In the production method of the present invention, the reaction between the phenolic hydroxyl group of the organic phosphorus compound of the formula (1) and the epoxy group of the epoxy resin is completed while the flame retardancy is ensured. It is necessary to keep the addition reaction within a range necessary for enhancing the curability in order to prevent the addition reaction from proceeding excessively and making the handling difficult due to thickening or gelling. In the production method of the present invention, the addition reaction rate of dicyandiamide is set to 0.1 by setting conditions such as a solvent and a reaction temperature by utilizing the large difference in the reaction rate between the former reaction and the latter addition reaction.
Keep in the range of 5-15%.

That is, in the production method of the present invention, the above reaction and the addition reaction are preferably performed in an organic solvent. Regarding the type and amount of the organic solvent, the epoxy resin, dicyandiamide, the organic phosphorus compound of the formula (1), and the reaction product thereof are uniformly dissolved and have a viscosity and volatility suitable for preparing a prepreg. If it is, there is no particular limitation. In terms of price, handling, and safety, 2-
Methoxyethanol, 2-methoxypropanol, 1-
It is preferable to use methoxy-2-propanol or the like in an amount of 10 to 50% by weight based on the total amount of the resin composition.

In the production method of the present invention, the above-mentioned reaction and addition reaction complete the reaction between the epoxy resin and the organophosphorus compound of the formula (1) and ensure an appropriate addition reaction rate of dicyandiamide. , Usually 70-200
C., preferably 100 to 160.degree. C., particularly preferably 120 to 150.degree. Further, triphenylphosphine is used as a catalyst in epoxy resin 10
By adding 0.05 to 2.00 parts by weight to 0 parts, the reaction time can be shortened.

Further, a prepreg can be obtained by impregnating and drying the resin composition of the present invention on a glass cloth, a glass nonwoven fabric or a paper substrate. Also, overlay a metal foil on at least one side of this prepreg,
A laminated plate can be obtained by laminating and integrating by heating and pressing. Further, a printed wiring board can be obtained by processing a circuit of the metal foil of the laminated board. In the production of these prepregs, laminated boards, and printed wiring boards, ordinary coating, laminating, and circuit processing steps in the relevant industry can be applied.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below based on embodiments of the present invention, but the present invention is not limited thereto.

In the examples and comparative examples, the following epoxy resins, organic phosphorus compounds of the formula (1) and other special materials were used. For other organic solvents, additives, general-purpose inorganic fillers and glass cloth, copper foil, etc. constituting laminates / prepregs, raw materials generally used in the chemical and electronic industries except for those specifically described. Using.

Epoxy resin A: Bisphenol F type epoxy resin (Epicoat 806, manufactured by Japan Epoxy Resin Co., Ltd.) (epoxy equivalent: 167) Epoxy resin B: Cresol novolac type epoxy resin (Dai Nippon Ink Chemical Industry Co., Ltd.) , N-673) (epoxy equivalent 210) Organophosphorus compound A: 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Sanko Co., Ltd.) Organophosphorus compound B: triphenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd.) 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., 2E4MZ)

Example 1 In a 1,000 ml flask, 334.0 g of epoxy resin A was added.
(2.00 equivalents), 12.6 g of dicyandiamide (0.
60 equivalents), 108.1 g (0.67) of organic phosphorus compound A
Eq), triphenylphosphine 1.00 g, 2E4M
Z 0.018 g, 2-methoxyethanol 224.4 g
And heated to 120 ° C. in 30 minutes with stirring.
After holding for 0 minutes, it was cooled to room temperature. White when heated
The heterogeneous reaction solution gradually became a viscous homogeneous solution. After that, when the product was analyzed by high performance liquid chromatography, the reaction rate of the organic phosphorus compound A was 98.6.
% And the reaction rate of dicyandiamide was 7.3%. The gel time of this solution at 160 ° C. was 210 seconds. The resin composition thus obtained is impregnated into a glass cloth (nominal thickness 0.2 mm, basis weight 210 g / m ² ),
It dried at 4 degreeC for 4 minutes, and obtained the prepreg. An 18 μm copper foil is placed on both sides of the four prepregs.
It was heated and pressed at 85 ° C. under a pressure of 4 MPa for 80 minutes to form a double-sided copper-clad laminate having a thickness of 0.8 mm. Table 1 shows the characteristics of the laminate.

Example 2 In a 1,000 ml flask, 334.0 g of epoxy resin A was added.
(2.00 equivalents), 108.1 g of organic phosphorus compound A
(0.67 equivalent), triphenylphosphine 1.00
g, 224.4 g of 2-methoxyethanol, and the mixture was heated to 140 ° C. in 30 minutes with stirring and maintained for 60 minutes.
Cooled to 100 ° C. and kept at that temperature. There, 12.6 g (0.60 equivalent) of dicyandiamide, 2E4M
0.018 g of Z was added, and the mixture was kept at 100 ° C. for 120 minutes and then cooled to room temperature. Thereafter, when the product was analyzed by high performance liquid chromatography, the conversion of the organic phosphorus compound A was 99.5%, and the conversion of dicyandiamide was 11.8%. The gel time of this solution at 160 ° C. was 202 seconds. Using the resin composition thus obtained, a prepreg and a double-sided copper-clad laminate were prepared in the same manner as in Example 1. Table 1 shows the characteristics of the laminate.

Example 3 334.0 g of epoxy resin A was placed in a 2,000 ml flask.
(2.00 equivalents), 108.1 g of organic phosphorus compound A
(0.67 equivalent), triphenylphosphine 1.00
g, 224.4 g of 2-methoxyethanol, and the mixture was heated to 140 ° C. in 30 minutes with stirring and maintained for 60 minutes.
Cooled to 100 ° C. and kept at that temperature. There, 219.9 g (1.05 equivalents) of epoxy resin B, 28.8 g (1.37 equivalents) of dicyandiamide, 2E4MZ 0.2 g.
After adding 040 g and keeping at 100 ° C. for 120 minutes,
Cooled to room temperature. Then, the product was analyzed by high performance liquid chromatography.
%Met. The gel time of this solution at 160 ° C. was 196 seconds. 296.5 g of aluminum hydroxide powder and methyl ethyl ketone 26 were further added to this solution.
2.4 g was added, and the mixture was stirred at room temperature to be uniformly dispersed.
A prepreg and a double-sided copper-clad laminate were prepared in the same manner as in Example 1 using the resin composition thus obtained. Table 1 shows the characteristics of the laminate.

Comparative Example 1 334.0 g of epoxy resin A was placed in a 1,000 ml flask.
(2.00 equivalents), 108.1 g of organic phosphorus compound A
(0.67 equivalent), triphenylphosphine 1.00
g, 224.4 g of 2-methoxyethanol, and the mixture was heated to 140 ° C. in 30 minutes with stirring and maintained for 60 minutes.
Cooled to room temperature. The reaction solution, which was white and non-uniform at the time of heating, gradually became a viscous homogeneous solution. After cooling, 12.6 g (0.60 equivalents) of dicyandiamide, 2E4M
When 0.018 g of Z was added and the product was analyzed by high performance liquid chromatography, the conversion of organic phosphorus compound A was 99.6%, and the conversion of dicyandiamide was 0.1%. The gel time of this solution at 160 ° C. is 703.
Seconds. Using the resin composition thus obtained, a prepreg was prepared in the same manner as in Example 1. However, Example 1
In order to obtain a prepreg having the same moldability (flow) as above, it was necessary to dry at 160 ° C. for 11 minutes. Further, using this prepreg, a double-sided copper-clad laminate was produced in the same manner as in Example 1. Table 1 shows the characteristics of the laminate.

Comparative Example 2 To the resin composition of Comparative Example 1, 3.08 g of 2E4MZ was added in order to obtain appropriate curability. The gel time after the addition was 231 seconds. Using the resin composition thus obtained, it was dried at 160 ° C. for 4 minutes in the same manner as in Example 1 to produce a prepreg. Further, using this prepreg, a double-sided copper-clad laminate was produced in the same manner as in Example 1. Table 1 shows the characteristics of the laminate.

Comparative Example 3 An organic phosphorus compound B was used in place of the organic phosphorus compound A of Example 1. Epoxy resin A3 in 1000ml flask
34.0 g (2.00 equivalents), dicyandiamide
9 g (0.90 equivalents), organophosphorus compound B 111.3
g, 0.018 g of 2E4MZ, and 228.6 g of 2-methoxyethanol, and stirred at 120 ° C. for 30 minutes.
And kept for 30 minutes, then cooled to room temperature. After cooling, the product was analyzed by high performance liquid chromatography. As a result, the conversion of organic phosphorus compound B was 0.1%, and the conversion of dicyandiamide was 5.4%. 16 of this solution
The gel time at 0 ° C. was 460 seconds. The resin composition obtained in this manner is applied to a glass cloth (nominal thickness 0.2 m).
m, basis weight 210 g / m ² ) and dried at 160 ° C. for 7 minutes to prepare a prepreg. Using this prepreg,
A double-sided copper-clad laminate was produced in the same manner as in Example 1. Table 1 shows the characteristics of the laminate.

Comparative Example 4 A reaction was carried out in the same manner as in Example 2 to obtain a resin composition. However, the temperature at the time of adding dicyandiamide and 2E4MZ was set to 80 ° C., and after these additions, the temperature was maintained at 80 ° C. for 6 hours and then cooled to room temperature. Then, when the product was analyzed by high performance liquid chromatography, the reaction rate of dicyandiamide was 0.3%. The gel time of this solution at 160 ° C. was 602 seconds. Using the resin composition thus obtained, a prepreg was prepared in the same manner as in Example 1. However, in order to obtain a prepreg having the same moldability (flow) as in Example 1, it was necessary to dry at 160 ° C. for 11 minutes. there were.

[0039]

[Table 1]

The characteristics of the laminated board and the printed wiring board were evaluated by the following methods. UL-94 for flame retardancy
V-0 when the average burning time is 5 seconds or less and the maximum burning time is 10 seconds or less, and V-1 when the average burning time is 10 seconds or less and the maximum burning time is 30 seconds or less. Were classified by HB. Other laminate characteristics (copper foil peeling strength, glass transition temperature, insulation resistance, moisture absorption solder heat resistance) are described in JIS C6481.
It evaluated based on. The glass transition temperature is determined by the inflection point of the thermal expansion line of the thermomechanical property evaluation device (TMA), and the evaluation of the moisture resistance of the moisture-absorbing solder is made by ○: no change, Δ: occurrence of measling or bleeding, ×: occurrence of blistering. did. The curability of the varnish was evaluated by dropping 0.5 ml of the varnish onto a hot plate at 160 ° C., stirring the mixture with a rod having a diameter of 1 mm and gelling (gelation time). The reactivity of the organic phosphorus compound and dicyandiamide in the varnish was determined by high performance liquid chromatography using a column: ODS-2 type reverse phase column manufactured by GL Sciences, a developing solution: a water / tetrahydrofuran (70/30) mixed solution, and detection. Apparatus: Under the condition of an ultraviolet absorption spectrophotometer of 280 nm, the reduction rate of the peak area with respect to before the reaction was determined by an internal standard method, and this was evaluated as the reaction rate.

From Table 1, it can be seen that in all of the illustrated examples, while maintaining sufficient flame retardancy, laminates having good properties such as moisture absorption solder heat resistance, copper foil peeling strength, glass transition temperature, and insulation resistance were obtained. It was confirmed that a plate could be obtained. On the other hand, in Comparative Example 1, the reaction rate of dicyandiamide was 0.1%, and the curability was reduced due to the decrease in the number of epoxy groups due to the reaction of the epoxy resin A and the organic phosphorus compound A. In order to obtain moldability (flow), additional drying time is required, and thus productivity is reduced. Also,
In Comparative Example 2, the apparent gel time was shortened by increasing the amount of the curing accelerator, but the water absorption increased due to the effect of the increased curing accelerator, and a laminate having sufficient properties was not obtained. Furthermore, in Comparative Example 3, the organic phosphorus compound B that does not react with the epoxy resin is used, and the curability and the laminate characteristics are reduced due to the plasticizer effect. In Comparative Example 4, although the reaction rate of dicyandiamide is 0.3%, additional drying time is required in order to obtain the same moldability (flow) as in the example, and the productivity also decreases. From these results, the advantage of the present invention is clear.

Circuits (test patterns) were formed on the front and back surfaces of each of the two double-sided copper-clad laminates prepared in Examples 1 to 3 by a subtractive method. Furthermore, in order to improve the adhesiveness of the surface, the surface was subjected to an oxidation roughening treatment, and two prepregs produced using the resin compositions obtained in Examples 1 to 3 were sandwiched therebetween. The copper foil was overlaid and laminated and pressed in the same manner as in Examples 1 to 3 to produce a six-layer printed wiring board with an internal circuit. Outer layer circuit processing, through-hole formation, resist ink printing, and component mounting were performed on this printed wiring board by ordinary methods used in the industry, but it was confirmed that no problems occurred in the normal printed wiring board manufacturing process. .

[0043]

The resin composition of the present invention has sufficient flame retardancy without containing a halogen-based flame retardant and has excellent curability. By using this resin composition, prepregs, laminated boards, and printed wiring boards having good flame retardancy and heat resistance properties and capable of meeting the requirements for environmental friendliness can be produced with high productivity. .

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yoshiyuki Takeda 1500 Oji Ogawa, Shimodate City, Ibaraki Pref.Hitachi Chemical Industry Co., Ltd. Inside Shimodate Office (72) Inventor Shinichi Kamoshida 1500 Odai Ogawa, Shimodate City, Ibaraki Prefecture Inside Shimodate Office Hitachi Chemical Co., Ltd. (72) Inventor Minoru Kakitani 1500 Oji Ogawa Shimodate City in Ibaraki Prefecture 72) Inventor Norihiro Abe 1500 Ogawa, Shimodate-shi, Ibaraki F-term in Shimodate Works of Hitachi Chemical Co., Ltd.

Claims (10)

[Claims] An epoxy resin and a compound represented by the general formula (1): (Wherein R is a group containing two or more phenolic hydroxyl groups), and a dicyandiamide-added phosphorus-modified epoxy resin obtained by adding dicyandiamide to a phosphorus-modified epoxy resin obtained by reacting with an organic phosphorus compound represented by the following formula: In the resin composition, (epoxy resin equivalent / organic phosphorus compound equivalent of formula (1)) in the phosphorus modification step is in the range of 2 to 5, and dicyandiamide equivalent is represented by the following formula. (Wherein the epoxy resin equivalent includes the equivalent of the epoxy resin additionally added after the phosphorus modification step), and the addition reaction rate of dicyandiamide is 0.5 to 15%. Composition. 2. The method according to claim 1, wherein the organic phosphorus compound of the formula (1) is 10-
(2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10
The resin composition according to claim 1, which is an oxide. 3. The resin composition according to claim 1, wherein 50 to 90% by weight of the epoxy resin is a bisphenol F type epoxy resin. 4. The method according to claim 1, wherein the reaction of the organic phosphorus compound of the formula (1) with the epoxy resin and the addition of dicyandiamide to the epoxy resin are carried out in a one-step method. A method for producing a resin composition containing a dicyandiamide-added phosphorus-modified epoxy resin. 5. The dicyandiamide-added phosphorus-modified epoxy resin according to claim 1, wherein the epoxy resin is reacted with the organic phosphorus compound of the formula (1), and then dicyandiamide is added to the reaction product. Method for producing resin-containing resin composition. 6. The resin composition according to claim 4, wherein the reaction of the epoxy resin with the organic phosphorus compound of the formula (1) and the addition reaction of dicyandiamide are carried out in an organic solvent at a temperature of 100 to 160 ° C. Manufacturing method. 7. The reaction of an epoxy resin with an organophosphorus compound of the formula (1) and an addition reaction of dicyandiamide, wherein triphenylphosphine is used as a reaction catalyst.
The method for producing a resin composition according to claim 4 or 5, wherein the method is performed by adding 0.05 to 2.00 parts by weight to 00 parts. 8. A prepreg, wherein a substrate is impregnated with the resin composition according to claim 1 and dried. 9. A laminate in which a metal foil is laminated on at least one surface of the prepreg according to claim 8. 10. A printed wiring board obtained by circuit-processing the metal foil of the laminate according to claim 9.