JP2003049051A - Flame-retardant resin composition and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition exhibiting sufficient flame-retardance without containing a halogen-based flame retardant and having excellent curing property and capable of providing laminates having good heat resistance in good productivity. SOLUTION: The flame-retardant resin composition is obtained by adding an organophosphorus compound which is a derivative of 9, 10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide and has two or more phenolic hydroxy groups and a phosphate-based compound selected from phosphates and condensed phosphates to a resin composition containing an epoxy resin and an amine-based curing agent so that a weight ratio of the organophosphorus compound to the phosphate-based compound is (2:8) to (7:3) and total of these weights is 5-30 wt.% based on total weight of the flame-retardant resin composition solid content.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant material which does not contain a halogen-based flame-retardant agent, exhibits sufficient flame retardancy, exhibits excellent curability, and is capable of obtaining a laminate having good heat resistance. It relates to a resin composition. The present invention also relates to a prepreg, a laminated board, and a printed wiring board, which are applications of the flame-retardant resin composition.

[0002]

2. Description of the Related Art In recent years, due to increasing environmental problems, electricity and
Prepregs, laminated boards and printed wiring boards used in electronic devices and the like are required not to emit harmful substances into the environment when they are discarded or incinerated. Therefore, in order to avoid the so-called dioxin problem during incineration, the number of products characterized by containing no halogen-based flame retardant is increasing. As the flame retardant which is an alternative to the halogen flame retardant, a metal hydroxide type, a phosphorus type, a melamine modified resin type or the like is used. Particularly, phosphorus-based flame retardants are useful because they can obtain a high flame-retardant effect even in a small amount, and among them, phosphoric acid esters are widely used because they are resistant to hydrolysis and generate little toxic gas (phosphine, etc.). ing. Furthermore, in recent years, flame retardants of reactive phosphorus compounds capable of easily reacting with an epoxy resin to form a chemical bond have been used. In that case, 9,10-dihydro-9-oxa-10 is used.
A compound having a -phosphaphenanthrene-10-oxide structure is used.

[0003]

However, as the phosphorus-based flame retardant, the above phosphoric acid esters and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 are used.
When a reactive phosphorus compound having an oxide structure is used, there is a problem that the curability of the resin changes. In particular, in a base material for a printed wiring board, an epoxy resin composition that uses dicyandiamide as an amine-based curing agent is often used. However, when phosphoric acid esters are added as a flame retardant to these resins, the resin composition Curing of the product is significantly hindered, which causes problems such as a decrease in productivity and a decrease in laminated plate properties. When a reactive phosphorus compound is added as a flame retardant, the reaction between the epoxy group and dicyandiamide, which is the original curing mechanism, and the reaction between the epoxy group and the reactive phosphorus compound compete with each other, so that the curing is very fast, and It becomes difficult to control. On the other hand, JP-A-4-11662 and JP-A-2
000-80251 discloses a method in which a reactive phosphorus compound as a flame retardant is reacted with a non-crosslinkable epoxy resin in advance to synthesize a phosphorus-modified epoxy resin, and then a composition is prepared. However, as a matter of course, the cost is increased in terms of equipment and processes, and the applicable applications are limited.

Further, in Japanese Patent Application Laid-Open No. 2001-49085, 9,1 which is a reactive phosphorus compound is used as a flame retardant.
An epoxy resin composition containing a combination of 0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof and phosphoric acid esters is disclosed. Kind, also
Depending on the weight ratio of the reactive phosphorus compound and the phosphoric acid ester to be added, the curability of the epoxy resin composition will be poor.

[0005]

Means for Solving the Problems The present inventors have sufficient flame retardancy and have sufficient flame retardance by simply adding additives such as halogen-free flame retardants and curing agents to resin compositions. As a result of various studies on a method capable of producing a flame-retardant resin composition having curability, the following invention has been found.

The present invention provides a resin composition containing an epoxy resin and an amine-based curing agent, which has the formula (1):

[0007]

[Chemical 4]

(Wherein R ₁ is a group containing no halogen element and containing two or more phenolic hydroxyl groups), and at least one organic phosphorus compound represented by the formula (2):

[0009]

[Chemical 5]

(Wherein R ₂ , R ₃ and R ₄ are each independently phenyl, hydroxyphenyl, methylphenyl or dimethylphenyl) and the formula (3):

[0011]

[Chemical 6]

(In the formula, R ₅ is either phenylene, methylphenylene, dimethylphenylene or 2,2-propanediphenylene, and R ₆ , R ₇ , R ₈ and R ₉ are
Each independently phenyl, hydroxyphenyl, methylphenyl or dimethylphenyl;
n is an integer of 1 to 10), at least one phosphoric acid ester compound selected from condensed phosphoric acid esters represented by the formula (1) and the phosphoric acid ester compound. The ratio to the weight of the compound is from 2: 8
In the range of 7: 3, and the total weight of the organic phosphorus compound of the formula (1) and the phosphate compound is based on the total weight of the solid content of the flame-retardant resin composition excluding the organic solvent and the inorganic component. It is a flame-retardant resin composition obtained by adding 5 to 30% by weight.

Further, according to the present invention, an epoxy resin and an amine-based curing agent are reacted in an organic solvent at 80 to 140 ° C. to obtain a resin composition which is compatible with each other in the absence of the solvent. The flame-retardant resin composition is obtained by adding the organic phosphorus compound of the formula (1) and the phosphoric acid ester compound. Here, a resin composition that is compatible even in the absence of a solvent means that when the resin composition is magnified 100 times and observed in a solvent-free state, a precipitate of the amine-based curing agent is uniform. It means a resin composition which is not visually confirmed.

In the present invention, the epoxy resin contains at least one of a phenol novolac type epoxy resin and a cresol novolac type epoxy resin, and their weight is
30% by weight or more based on the total weight of the epoxy resin,
In the above flame-retardant resin composition, the amine-based curing agent is dicyandiamide, and the addition amount of the amine-based curing agent is 0.3 to 0.6 equivalents relative to 1 equivalent of epoxy groups of the epoxy resin. The present invention is the above flame-retardant resin composition containing aluminum hydroxide as an inorganic filler in an amount of 10 to 50% by weight based on the total weight of the solid content of the flame-retardant resin composition excluding the organic solvent. .

In the present invention, the organophosphorus compound of the formula (1) is 10- (2,5-dihydroxyphenyl) -9,
10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the phosphoric acid ester compound is a condensed phosphoric acid ester of formula (3), and R ₅
Is phenylene, which is the flame-retardant resin composition.

Furthermore, the present invention provides a prepreg obtained by impregnating a base material with the above-mentioned flame-retardant resin composition and drying the prepreg, a laminated plate in which a metal foil is laminated on at least one surface of the prepreg,
And a printed wiring board obtained by circuit-processing the metal foil of this laminate.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant resin composition of the present invention contains an epoxy resin. As the epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalenediol type epoxy resin,
Phenol novolac type epoxy resin, cresol novolac type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester resin, glycidyl amine resin, heterocyclic epoxy resin (triglycidyl isocyanurate, diglycidyl hindatoin, tetrakis (glycidyloxyphenyl) ethane Etc.) and epoxy resins obtained by modifying these with various reactive monomers. These epoxy resins can be used alone or in combination of two or more kinds. In particular, from the viewpoint of ensuring high heat resistance and reliability applicable to electrical and electronic materials, it contains at least one of phenol novolac type epoxy resin and cresol novolac type epoxy resin, and their total weight is 3 for total weight
It is preferably 0% by weight or more.

The flame-retardant resin composition of the present invention contains an amine curing agent. In the present invention, the amine curing agent also includes dicyandiamide and its derivatives. Examples of amine-based curing agents include linear aliphatic amines (ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropylamine, dicyandiamide, tetramethylguanidine, triethanolamine, etc.), cyclic fatty acids. Group amines (mensendiamine, isophoronediamine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, bis (4-amino-)
3-methyldicyclohexyl) methane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl)-
2,4,8,10-tetraoxaspiro [5.5] undecane and the like) and aromatic amines (xylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and the like). These may be used alone or in combination of two or more.
Among these, it is preferable to use dicyandiamide from the viewpoint of the properties of a cured product obtained by curing a curable and flame-retardant resin composition.

In the present invention, the blending amount of the amine-based curing agent is set in order to maintain good properties of the cured product obtained by curing the flame-retardant resin composition, particularly heat resistance, hygroscopicity, flame retardancy and the like. , 0.3 to 1 equivalent of epoxy group of epoxy resin
It is preferably in the range of to 0.6 equivalent. When the blending amount is within this range, the cross-linking density of the obtained cured product does not decrease, and the moisture absorption of the cured product increases. The problem of does not occur. A more preferable range of the compounding amount of the amine-based curing agent is 0.4 to 0.5 equivalent.

Here, 1 equivalent of the amine-based curing agent is the weight of the amine-based curing agent per 1 mol of active hydrogen bonded to the nitrogen atom present in the amine-based curing agent, and 1 equivalent of dicyandiamide is 1 The equivalent ratio is calculated as corresponding to a weight of / 4 mol.

The flame-retardant resin composition of the present invention comprises at least one organic phosphorus compound represented by the formula (1), a phosphoric ester represented by the formula (2) and a condensation represented by the formula (3). It contains at least one phosphoric acid ester compound selected from phosphoric acid esters.

In an epoxy resin composition, particularly an epoxy resin composition using dicyandiamide, which is frequently used as a base material for printed wiring boards, as an amine-based curing agent, an organic phosphorus compound of formula (1) and a phosphoric acid ester-based compound are added. When the compound is added, the organophosphorus compound of the formula (1) and the phosphoric acid ester compound have an adverse effect on the curability of the epoxy resin composition. That is, it is recognized that the organic phosphorus compound of the formula (1) accelerates the curing of the epoxy resin composition and the phosphate ester compound inhibits the curing. When the ratio of the weight of the organic phosphorus compound of formula (1) to the weight of the phosphoric acid ester compound is 2: 8 to 7: 3, When mixed and added to the resin composition, proper curability is maintained. When the amount of the organophosphorus compound of the formula (1) is more than this range, curing is too fast to control, and it becomes difficult to produce a printed wiring board using this flame-retardant resin composition. On the other hand, if the amount of the phosphoric acid ester compound is more than this range, the curing will be remarkably delayed, the productivity will be lowered in the production of the prepreg, and the laminate characteristics will be deteriorated due to the incomplete curing. A more preferable range of the ratio of the weight of the organic phosphorus compound of the formula (1) to the weight of the phosphoric acid ester compound is 3: 7 to 6: 4.

In the present invention, the total weight of the organophosphorus compound of formula (1) and the phosphate compound is
It is 5 to 30% by weight based on the solid content of the flame-retardant resin composition excluding the organic solvent and the inorganic components. When the weight of the organophosphorus compound of the formula (1) and the phosphoric acid ester compound is within this range, a sufficient flame retarding effect is obtained, and the organophosphorus compound of the formula (1) completely reacts in the molding and curing process. Sufficient laminated board properties can be obtained without being left in the cured product without being able to do so and causing the plasticizing action by the phosphate compound. The weight of the organophosphorus compound of the formula (1) is the total value of the weights of the organophosphorus compound of the formula (1) when there are two or more kinds. The weight of the phosphoric acid ester compound means that the phosphoric acid ester compound is 2
If more than one species, the total value of their weight shall be used.

In the present invention, the organophosphorus compound of the formula (1) is a derivative of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which is 2
It has one or more phenolic hydroxyl groups. The organophosphorus compound of the formula (1) according to the present invention has 9,10-dihydro-9-oxa-10 due to the presence of the phenolic hydroxyl group.
-Compared to phosphaphenanthrene-10-oxide,
It has excellent reactivity with epoxy resin and has an excellent effect of accelerating the curing of the resin composition, so it can be effectively cured when used in combination with a phosphoric acid ester compound (which has the function of inhibiting curing as described above). The inhibitory effect can be supplemented.

Examples of the organic phosphorus compound of the formula (1) of the present invention include 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-phospha Phenanthrene-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- Examples thereof include oxides. Since excellent flame retardancy is obtained, 1
0- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-
10-oxide is preferred. These may be used alone or in combination of two or more.

In the present invention, the phosphoric acid ester compound is selected from the phosphoric acid ester represented by the formula (2) and the condensed phosphoric acid ester represented by the formula (3). Formula (2)
Examples of the phosphoric acid ester represented by are triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, dicresyl phenyl phosphate, cresyl diphenyl phosphate, tris (hydroxyphenyl) phosphate, and the like.

Further, the compound represented by the formula (3) (in the present specification, referred to as condensed phosphoric acid ester),
1,3-Bis (diphenylphosphoryl) benzene [Resorcinol bis (diphenyl phosphate) is designated as a common name. The same shall apply hereinafter], resorcinol bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (dixylenyl phosphate), and the like.

Of these phosphate compounds,
From the viewpoint of high melting point and hydrolysis resistance, the condensed phosphoric acid ester of the formula (3) is preferable, and the condensed phosphoric acid ester of the formula (3) in which R ₅ is phenylene is more preferable. In particular, resorcinol bis (dixylenyl phosphate) is more preferable in terms of solvent solubility and cost. The phosphoric acid ester compounds may be used alone or in combination of two or more. Commercially available phosphoric acid ester of formula (2) is TPP, TCP, CDP, PX-110 manufactured by Daihachi Chemical Industry Co., Ltd., and condensed phosphoric acid ester of formula (3) is large. CR- manufactured by Hachika Kogyo Co., Ltd.
733S, PX-200, RDP manufactured by Ajinomoto Co., Inc., and the like.

In the present invention, the flame-retardant resin composition comprises
Inorganic fillers other than halogen compounds can be included for the purpose of further improving flame retardancy, high rigidity, and low thermal expansion. For example, silica, talc, mica, aluminum hydroxide, magnesium carbonate, barium carbonate, etc. ,
Aluminum hydroxide having a function of improving flame retardancy is particularly preferable. These inorganic fillers are contained in an amount of 10 to 50 relative to the total weight of the solid content of the flame retardant resin composition excluding the organic solvent.
It is preferred to add in the amount of wt%. If the amount added is in this range, the inorganic filler can achieve its purpose and does not deteriorate the adhesiveness or workability of the laminate or printed wiring board produced from the flame-retardant resin composition. .

In the present invention, additives other than these, such as flame retardants and pigments, adhesion aids, antioxidants, curing accelerators and organic solvents, can be added to the flame retardant resin composition. However, known substances can be used, respectively, and there is no particular limitation as long as they are substances other than the halogen compound as long as they do not deteriorate the properties of the laminate and the printed wiring board.

In the present invention, an organic solvent can be used. Regarding the kind and amount thereof, the epoxy resin and the amine-based curing agent constituting the flame-retardant resin composition are uniformly dissolved to prepare a prepreg. There is no particular limitation as long as it has a viscosity and volatility suitable for From the viewpoint of price, handleability, and safety, methyl ethyl ketone, 2-methoxyethanol, 2-methoxypropanol, 1-methoxy-2
-Propanol and the like are preferable, and it is preferable to use about 10 to 50% by weight based on the total weight of the flame-retardant resin composition.

The flame-retardant resin composition of the present invention contains the above-mentioned epoxy resin and an amine-based curing agent, and the organic phosphorus compound of formula (1) and the phosphate ester are mixed in the above-mentioned weight ratio and amount ranges. It can be produced by adding a system compound and, if necessary, the above-mentioned inorganic filler or additive.

However, depending on the types of the epoxy resin and the amine-based curing agent, simply mixing these components may cause phase separation of the organic-based solvent and volatilization of the amine-based curing agent after volatilization of the organic solvent during prepreg production. There is a case. In such a case, there is a high possibility that a uniform cured product cannot be produced even if molding and curing are carried out as they are. Therefore, it is preferable to react the epoxy resin and the amine-based curing agent in an organic solvent at 80 to 140 ° C. before mixing the components in advance. The reaction time is usually 1 to 6 hours. By this reaction, the epoxy resin and the amine-based curing agent can be made into a resin composition that is compatible even in the absence of a solvent, and a flame-retardant resin composition that gives a uniform cured product in the subsequent steps. Because you can get things.

Here, in the reaction between the epoxy resin and the amine-based curing agent, a bond is partially formed between the epoxy group of the epoxy resin and the amino group of the amine-based curing agent, and this acts as a compatibilizing agent for both. Conceivable. If the reaction temperature is lower than 80 ° C, the reaction is very slow and the productivity is lowered, while if it is higher than 140 ° C, the reaction rate cannot be controlled. Further, in this step, a reaction accelerator can be added appropriately.

Furthermore, the flame-retardant resin composition of the present invention can be made into a prepreg by impregnating and drying a base material such as glass cloth. Furthermore, by laminating a metal foil on this prepreg and heating and pressurizing the prepreg to laminate and integrate them, a laminated plate can be manufactured. A printed wiring board can also be manufactured by etching away unnecessary portions of the metal foil of this laminated board. In the production of these prepregs, laminated boards, and printed wiring boards, the usual coating, laminating, and circuit processing steps in the industry can be applied, whereby high heat resistance, high flame retardancy, high reliability, and A laminated board and a printed wiring board containing no halogen-based flame retardant can be obtained.

[0036]

The present invention will be described in more detail below with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.

In the examples and comparative examples, the following were used for the epoxy resin, amine curing agent, organic phosphorus compound of formula (1), phosphate ester compound and other special materials. Regarding other organic solvents, additives, general-purpose inorganic fillers and glass cloth, copper foil, etc. constituting laminates / prepregs, raw materials generally used in the chemical industry and the electronic industry field, except for those specifically mentioned. Was used. -Epoxy resin 1: Bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.), trade name 828
(Epoxy equivalent 188) -Epoxy resin 2: Cresol novolac type epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc.), trade name N-6
73 (epoxy equivalent 210) -amine curing agent: dicyandiamide (manufactured by Nippon Carbide Co., Ltd.)-Organophosphorus compound of formula (1): 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd.) Trade name HCA-HQ-phosphate ester compound: Condensed phosphate ester (trade name PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.)-Curing Accelerator: 2-Ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd.) Product name 2E4MZ

Example 1 Epoxy resins 1 and 2, dicyandiamide (amine curing agent), 2E4MZ (curing accelerator), an organophosphorus compound of formula (1) and a phosphate ester compound were compounded in the composition shown in Table 1. Then, a flame-retardant resin composition for laminated boards was produced. A glass cloth (thickness 0.2
mm, weighing 0.021 g / cm ² ) and impregnating at 160 ° C for 4
After drying for a minute, a prepreg was obtained. Four sheets of this prepreg were overlaid, and copper foil of 18 μm was overlaid on both sides thereof, heated and pressed at 185 ° C. and a pressure of 4 MPa for 80 minutes, and molded to a thickness of 0.
An 8-mm double-sided copper clad laminate was prepared. Circuit formation (test pattern) was performed on the surface of this double-sided copper clad laminate by the subtractive method. Further, the surfaces of the two prepared double-sided copper clad laminates with a circuit were subjected to oxidative roughening treatment to improve the adhesiveness, and two prepregs similar to the above were sandwiched between them, and the prepregs were laminated on the outside. 2 sheets and 18μ
m copper foil was overlaid and laminated and pressed in the same manner as above to produce a 6-layer printed wiring board with an inner layer circuit. This printed wiring board was subjected to outer layer circuit processing, through hole formation, resist ink printing, and component mounting by a conventional method.

Example 2 Of the formulations shown in Table 1, epoxy resins 1 and 2, dicyandiamide (amine curing agent), 2E4MZ (curing accelerator) and 2-methoxyethanol (organic solvent) were mixed,
After dissolution, the mixture was stirred at 100 ° C. for 2 hours as a preliminary reaction. Then, it cooled to room temperature, Then, the organic phosphorus compound of Formula (1), a phosphoric acid ester type compound, and aluminum hydroxide were mix | blended, and the flame-retardant resin composition for laminated boards was produced. A glass cloth (thickness 0.2
mm, weighing 0.021 g / cm ² ) and impregnating at 160 ° C for 4
After drying for a minute, a prepreg was obtained. Using this prepreg, a double-sided copper clad laminate was produced in the same manner as in Example 1. Using this double-sided copper-clad laminate, a 6-layer printed wiring board with an inner layer circuit was prepared in the same manner as in Example 1, and an outer layer circuit processing, through-hole formation, resist ink printing and Parts were mounted.

Comparative Example 1 In the same manner as in Example 2, a flame-retardant resin composition was prepared by the formulation shown in Table 1 and the method shown in Example 2. Using this flame-retardant resin composition, a prepreg was prepared in the same manner as in Example 1, but it was necessary to dry it at 160 ° C. for 12 minutes in order to obtain a prepreg having proper fluidity. Using this prepreg, a double-sided copper clad laminate was produced in the same manner as in Example 1.

Comparative Example 2 In the same manner as in Example 2, a flame-retardant resin composition was prepared by the formulation shown in Table 1 and the method shown in Example 2. A prepreg was prepared by drying at 160 ° C. for 3 minutes, but the gel time was too short to cure the prepreg, and a prepreg having proper fluidity could not be obtained. Using this prepreg, a double-sided copper clad laminate was produced in the same manner as in Example 1. In addition,
If the heating time is less than 3 minutes, the solvent cannot be sufficiently volatilized and the drying becomes insufficient.

COMPARATIVE EXAMPLE 3 By the formulation shown in Table 1 and the method shown in Example 2, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was used instead of the organophosphorus compound of the formula (1). A flame-retardant resin composition was prepared using (manufactured by Sanko Co., Ltd., trade name HCA). Using this flame-retardant resin composition, a prepreg was prepared in the same manner as in Example 1, but it was necessary to dry at 160 ° C. for 10 minutes in order to obtain a prepreg having proper fluidity. Using this prepreg, a double-sided copper clad laminate was produced in the same manner as in Example 1.

Comparative Examples 4 to 6 Flame-retardant resin compositions were prepared by the formulations shown in Table 1 and the method shown in Example 2. Glass flame (thickness 0.2 mm, weight 0.021 g / c)
m ² ), and dried at 160 ° C. for 4 minutes to obtain 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 gelation times of the flame-retardant resin compositions of Examples 1 and 2 and Comparative Examples 1 to 6, the compatibility of the epoxy resin and the amine-based curing agent in the absence of solvent, and the laminates. Show the characteristics.

[0045]

[Table 1]

The characteristic evaluation of the laminated board and the printed wiring board is as follows.
The procedure was as follows. -The flame retardancy is evaluated by the burning time by the UV-94 vertical method, the average burning time is 5 seconds or less and the maximum burning time is 1.
V-0 for 0 seconds or less, V-1 for average burning time of 10 seconds or less and maximum burning time of 30 seconds or less, and H for burning more than that.
Classified as B. -Other laminated plate properties (copper foil peeling strength, glass transition temperature, insulation resistance, moisture absorption solder heat resistance, chemical resistance) were evaluated based on JIS C6481. -The evaluation of the heat resistance of the moisture-absorbing solder was evaluated by ◯: no change, Δ: occurrence of measling or eye bleeding, and ×: occurrence of blister. The treatment conditions are as follows: Moisture absorption solder heat resistance (1) is 4 hours treatment with a pressure cooker, and solder dipping is performed at 260 ° C for 20 seconds. Moisture absorption solder heat resistance (2) is 2 hours with a pressure cooker. After the treatment, solder immersion was performed at 288 ° C. for 20 seconds. -The curability of the varnish was evaluated by dropping 0.5 ml of the varnish on a hot plate at 160 ° C., stirring with a rod having a diameter of 1 mm, and the time until gelling (gelling time). -Compatibility of the epoxy resin and the amine-based curing agent in the absence of a solvent, unless otherwise specified, at the time of compounding the flame-retardant resin composition, an epoxy resin, an amine-based curing agent, a curing accelerator,
At the time of mixing only the solvent (after the reaction for the preliminary reaction), about 0.1 ml was taken, dropped on a transparent glass plate and dried at 160 ° C for 10 minutes to volatilize the organic solvent. Was observed with an optical microscope at a magnification of 100 times, and the presence or absence of precipitate was visually confirmed.

From Table 1, in the illustrated Examples 1 and 2, since the necessary amount of phosphorus-based flame retardant was contained and the gel time of the flame-retardant resin composition was appropriate, the productivity and moldability were excellent. A laminate having sufficient flame retardancy was obtained. In addition,
In Example 2, the compatibility of the epoxy resin and the amine curing agent in the absence of a solvent was confirmed before the addition of the organic phosphorus compound of formula (1) and the phosphate compound and before heating. , Acicular crystals of dicyandiamide were deposited, but became uniform after heating, that is, after the preliminary reaction, and compatibility was confirmed.

Further, outer layer circuit processing, through hole formation, resist ink printing, and component mounting were performed on the printed wiring boards manufactured in Examples 1 and 2 by a conventional method, but they were manufactured without problems in a normal printed wiring board manufacturing process. It was confirmed that it was possible.

On the other hand, in Comparative Examples 1 and 2, the ratio of the weight of the organic phosphorus compound of the formula (1) to the weight of the phosphoric acid ester compound is out of the range of the present invention, and therefore, the appropriate curability is obtained. As a result, sufficient laminated plate properties are not obtained due to defective molding. In Comparative Example 3, 9,10-dihydro-9-oxa-10- having no phenolic hydroxyl group was used instead of the organophosphorus compound of the formula (1).
Since phosphaphenanthrene-10-oxide was used, proper curability could not be obtained, and the laminated plate properties such as moisture absorption solder heat resistance and chemical resistance were inferior. In addition, Comparative Example 4
In ~ 6, by reducing the total amount of compounds containing phosphorus,
Even if the ratio of the weight of the organic phosphorus compound of the formula (1) to the weight of the phosphoric acid ester compound is out of the range of the present invention, proper curability is obtained. However, the flame retardancy is lowered because the total amount of the compound containing phosphorus, which is a flame retardant, is insufficient. Due to these, only the flame-retardant resin composition having the combination and compounding amount of the compound of the present invention has proper curability, and by using these flame-retardant resin compositions, sufficiently good properties can be obtained. It is obvious that the laminated plate and the like shown can be obtained.

[0050]

The flame-retardant resin composition of the present invention does not contain a halogen-based flame retardant, has sufficient flame retardancy, and is excellent in curability. By using this flame-retardant resin composition, a prepreg, a laminated board and a printed wiring board having good flame-retardant and heat-resistant properties and capable of meeting environmental requirements can be produced with high productivity. be able to.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 1/03 610 H05K 1/03 610L (72) Inventor Yoshiyuki Takeda 1500 Ogawa, Shimodate, Ibaraki Hitachi Chemical industrial Co., Ltd. Shimodate workplace F-term (reference) 4F072 AA04 AA05 AA07 AB09 AB27 AD24 AD27 AE04 AE07 AF03 AF28 AF30 AG03 AG19 AK05 AK14 AL13 4J002 CD001 CD021 CD041 CD051 CD061 CD081 CD131 CD141 DE148 EN009 ET009 EW047 EW116 EW136 FD136 FD137 FD138 FD149 GQ01 GQ05 4J036 AA01 AB07 AC01 AD01 AD07 AD08 AD21 AF06 AG00 AH00 AJ08 AJ18 DC02 DC31 FA01 FA12 JA07

Claims (11)

[Claims] 1. A resin composition containing an epoxy resin and an amine-based curing agent, wherein a resin composition represented by the formula (1): (Wherein R ₁ is a group containing no halogen element and containing two or more phenolic hydroxyl groups), and at least one organic phosphorus compound represented by the formula (2): (In the formula, R ₂ , R ₃ and R ₄ are each independently phenyl, hydroxyphenyl, methylphenyl or dimethylphenyl) and a phosphoric ester represented by the formula (3): ] (In the formula, R ₅ is any one of phenylene, methylphenylene, dimethylphenylene, and 2,2-propanediphenylene, and R ₆ , R ₇ , R ₈ and R ₉ are each independently phenyl and hydroxy. Either phenyl, methylphenyl or dimethylphenyl, n is 1 to 1
Is an integer of 0), at least one phosphoric ester compound selected from condensed phosphoric ester represented by
The ratio of the weight of the organic phosphorus compound of the formula (1) to the weight of the phosphate compound is in the range of 2: 8 to 7: 3,
Moreover, the total weight of the organic phosphorus compound of the formula (1) and the phosphate compound is 5 to 3 with respect to the total weight of the solid content of the flame-retardant resin composition excluding the organic solvent and the inorganic component.
A flame-retardant resin composition obtained by adding in the range of 0% by weight. 2. An epoxy resin and an amine-based curing agent are reacted in an organic solvent at 80 to 140 ° C. to obtain a resin composition which is compatible with each other in the absence of a solvent, and then the above-mentioned formula is used. The flame-retardant resin composition according to claim 1, which is obtained by adding the organic phosphorus compound (1) and the phosphate compound. 3. The epoxy resin contains at least one of a phenol novolac type epoxy resin and a cresol novolac type epoxy resin, and their weight is 30% by weight or more based on the total weight of the epoxy resin. The flame-retardant resin composition according to item 2. 4. The flame-retardant resin composition according to claim 1, wherein the amine curing agent is dicyandiamide. 5. The organophosphorus compound of the formula (1) is 10
-(2,5-Dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-1
The flame-retardant resin composition according to any one of claims 1 to 4, which is 0-oxide. 6. The flame-retardant resin according to claim 1, wherein the phosphoric acid ester compound is a condensed phosphoric acid ester of the formula (3), and R ₅ is phenylene. Composition. 7. The aluminum filler as an inorganic filler is contained in an amount of 10 to 50% by weight based on the total weight of the solid content of the flame-retardant resin composition excluding the organic solvent. The flame-retardant resin composition according to the item. 8. The flame-retardant property according to claim 1, wherein the addition amount of the amine-based curing agent is 0.3 to 0.6 equivalent with respect to 1 equivalent of the epoxy group of the epoxy resin. Resin composition. 9. A prepreg obtained by impregnating a base material with the flame-retardant resin composition according to claim 1 and drying the base material. 10. A laminated board in which a metal foil is laminated on at least one surface of the prepreg according to claim 9. 11. A printed wiring board obtained by circuit-processing the metal foil of the laminated board according to claim 10.