JP2002284850A - Phosphorus and nitrogen modified flame retardant epoxy resin composition, prepreg and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphorus- and nitrogen-containing epoxy resin which does not contain halogen, is excellent in heat resistance and moisture resistance and can impart flame retardancy, and a prepreg and a laminate using the epoxy resin. It is in. SOLUTION: An epoxy resin and a compound of the formula (I): (Where A is a phenyl group or a -N <group, and when A is a phenyl group, s is 1 to 4, t is 4, and A is -N <
Where s is 1 to 6, t is 6, and X is of the formula (I
I) wherein R ^{1 to} R ³ are hydrogen, an alkyl or cycloalkyl group having 1 to 4 carbon atoms, a cycloalkyl group or a phenyl group). Resin composition, prepreg and laminate using the epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphorus- and nitrogen-modified flame-retardant epoxy resin composition containing an epoxy resin, a phosphorus- and nitrogen-containing compound and a curing agent, and a prepreg and a laminate using the epoxy resin.

[0002]

2. Description of the Related Art Conventionally, as a method of making an epoxy resin flame-retardant, an organic halogen compound is mainly used as a flame retardant. In particular, in order to maintain electrical characteristics, flame retardant treatment is performed by reacting tetrabromobisphenol A with an epoxy resin. In addition, antimony trioxide is essential as a synergist for improving the flame retardancy.

There is also a method using red phosphorus, a phosphoric acid ester, or a condensed phosphoric acid ester as a phosphorus-based flame retardant.

[0004] However, these high molecular compounds containing halogen and antimony trioxide are generally incinerated after finishing their intended use. At that time, it is known that hydrogen bromide gas, phosphine gas and polybrominated dioxins which are harmful to the human body are generated, and their effects on the environment are being pointed out.

[0005] An epoxy resin using a phosphoric acid ester or a condensed phosphoric acid ester containing no halogen is described in Japanese Patent Application Laid-Open No. 10-265654. At
It is known that hydrolysis easily occurs and the physical properties of the epoxy resin are significantly reduced.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, without containing halogen or red phosphorus, without deteriorating the physical properties of the epoxy resin,
An object of the present invention is to provide an epoxy resin having good flame retardancy.

Another object of the present invention is to provide an epoxy resin which does not generate phosgene at all even when incinerated by the above-described resin using dioxins or red phosphorus, and a prepreg using the epoxy resin. It is to provide a laminate.

[0008]

According to the present invention, an epoxy resin and a compound of general formula (I)

[0009]

Embedded image [In the formula, A is a phenyl group or a -N <group. When A is a phenyl group, s is an integer of 1 to 4, t is 4, and when A is -N <, s is s. Is an integer of 1 to 6, t is 6, and X is a group represented by the general formula (II)

[0010]

Embedded image (Wherein, R ¹ , R ² , and R ³ are each hydrogen, and have 1 to 4 carbon atoms.
Which is an alkyl group, a cycloalkyl group or a phenyl group)]], a phosphorus- and nitrogen-modified flame-retardant epoxy resin composition characterized by being a reaction product with an organic phosphorus compound represented by the formula:

Further, according to the present invention, there are provided a prepreg and a laminate using the above-mentioned phosphorus- and nitrogen-modified flame-retardant epoxy resin composition.

[0012]

Embodiments of the present invention will be described below in detail.

The present invention is a novel phosphorus and nitrogen containing epoxy resin obtained by reacting an epoxy group of an epoxy resin with a primary amine group of a phosphorus and nitrogen containing compound represented by the formula (I).

The resin obtained by the present invention can impart heat resistance and flame retardancy to various synthetic resin molded articles, and can improve the performance as molded articles.

The phosphorus and nitrogen-containing compounds used in the present invention are disclosed in JP-B-59-6318 and JP-B-58-1.
No. 531 discloses its production method. Further, JP-A-53-5253 discloses a pophenylene ether, JP-A-53-5249 discloses a polyamide resin, and JP-B-55-9436 discloses a polycarbonate resin. It is disclosed as a compound capable of imparting flame retardancy to a compound.

However, there is no description about the epoxy resin, and as a result of intensive studies, we have been able to provide an epoxy resin composition which is excellent in heat resistance, moisture resistance and flame retardancy without containing halogen. It has become possible.

The phosphorus and nitrogen-containing epoxy resin obtained in the present invention is obtained by reacting an organic phosphorus compound with benzoguanamine or melamine to form a phosphorus compound having a functional group represented by the formula (I), and then reacting with an epoxy group. Phosphorus content 0.
An epoxy resin containing 1 to 5% by weight of nitrogen and 0.1 to 5% by weight of nitrogen and phosphorus and nitrogen.

That is, the phosphorus and nitrogen-modified epoxy resin composition is used in an amount of 1 to 100 parts by weight of the epoxy resin.
100 parts by weight of a compound of formula (I), preferably 10-5
It contains 0 parts by weight of the compound of formula (I). At that time, a curing agent may be added to the epoxy resin and the phosphorus- and nitrogen-containing compound represented by the formula (I). However, the compound represented by the formula (I) also has a primary amino group. It also has some function as a curing agent.

When a curing agent is added, the amount is 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on the epoxy resin. Also, from the gist of the present invention, it is preferable that a halogen compound is not contained.

Further, the modified epoxy resin containing phosphorus and nitrogen preferably contains a curing accelerator.

In order to impart flame retardancy, the phosphorus and nitrogen containing modified epoxy resin contains 0.1 to 10% by weight of phosphorus, preferably in the range of 0.5 to 5% by weight.
Further, the content of nitrogen imparted to the flame retardancy is inevitably generated from the chemical structural formula of this compound. The amount contains 0.1 to 10% by weight of nitrogen, preferably 0.1 to 10% by weight.
It is in the range of 5-5% by weight.

The specific structural formula of the modified epoxy resin containing phosphorus and nitrogen is shown below, but is not limited thereto.

[0023]

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[0024]

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[0025]

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These phosphorus and nitrogen-containing modified epoxy resins are used in the form of one kind or a mixture of two or more kinds.

In the production of the modified epoxy resin containing phosphorus and nitrogen according to the present invention, the compounds represented by the formulas (III) to (V), the epoxy resin, the curing agent and the reaction accelerator are used in the conventional manner. be able to.

As the polyepoxide compound used in the present invention, a compound having at least two epoxy groups in one molecule is used, and the epoxy equivalent is 100 to 4000.
Is preferred, and particularly preferably 150 to 500. As the epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin,
Bisphenol S type epoxy resin, novolak type epoxy resin, polyglycidyl ether of polyhydric alcohol and the like can be mentioned. These resins are not particularly limited, but bisphenol A type epoxy resins and novolak type epoxy resins which are liquid at room temperature are preferred. For example, shrimp coat 828
(Trade name of Yuka Shell Epoxy).

Examples of the curing agent used in the present invention include amine compounds, acid anhydride compounds, amide compounds and phenol compounds.

Specific examples thereof include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, dicyandiamide, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, phenol novolak, modified products thereof, and imidazole. However, the present invention is not limited to these. These may be used alone or in combination of two or more.

The curing accelerator used in the present invention includes:
For example, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, 2- (diaminomethyl) phenol, 1,8-diaza-bicyclo (5,
Tertiary amines such as (4,0) undecene-7; phosphines such as triphenylphosphine; and metal compounds such as tin octylate.

The production of the epoxy resin according to the present invention can be carried out without solvent or in a solvent.

When used in a solvent, aprotic polar solvents are preferred, and specific examples thereof include N-methylpyrrolidone, dimethylformaldehyde, dimethylacetamide, tetrahydrofuran, dioxane, dialkyl ether and glycol ether, and acetone, Ketones such as methyl isobutyl ketone, methyl isopropyl ketone and methyl ethyl ketone; and aliphatic or aromatic hydrocarbons such as hexane, cyclohexane, toluene, xylene and benzene. Preferred are methyl ethyl ketone and methoxypropanol.

The epoxy resin composition thus obtained is preferably reinforced with glass cloth or glass fiber. Further, a filler, for example, silica, talc, lime powder, aluminum oxide hydrate, aluminum hydroxide, magnesium hydroxide, or the like can be filled as an inorganic filler.

The thus obtained epoxy resin composition according to the present invention can also be used as a prepreg, a copper foil or laminate of a printed wiring board for electronic components, a sealing material, a molding material, a paint and an adhesive.

[0036]

The present invention will be described below in more detail with reference to specific examples.

Example 1 A phosphorus and nitrogen-containing compound 2,4 represented by the general formula (III) was placed in a 1-liter flask.
-Bis {[6H-dibenzo- <c, e> (1,2) -oxaphospholin-6-yl] -methylamino} -6
-Phenyl-1,3,5-triazine 100 g, bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co.) 380 g, dicyandiamide 19
g, benzyldimethylamine 0.9 g, 150 g
Heated at 0 ° C for 1 hour.

Further, the liquid material was sandwiched between iron plates provided with 2 mm spacers, and heated at 170 ° C. for 70 minutes at a pressure of 30 kg / cm ² to obtain a cured product. The obtained resin is
It contained 2.0% by weight of phosphorus and 1.9% by weight of nitrogen.

[0039]

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Example 2 Phosphorus and nitrogen-containing compound represented by general formula (IV) 2-amino-4-{[6H-dibenzo- <c, e> (1,2)-
Oxaphospholin-6-yl] -methylamino｝-
100 g of 6-phenyl-1,3,5-triazine, 273 g of bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy), dicyandiamide 1
3.6 g and 0.7 g of benzyldimethylamine were charged,
Heated at 150 ° C. for 1 hour.

Further, the liquid material was sandwiched between iron plates provided with 2 mm spacers, and pressed at 170 ° C. under a pressure of 30 kg / cm ^2.
After heating for 0 minutes, the desired cured product was obtained. The resulting resin contained 2.0% by weight phosphorus and 4.5% by weight nitrogen.

[0042]

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Example 3 100 g of a mixture containing 70% by weight and 30% by weight of the general formulas (III) and (IV), respectively, and a bisphenol A type epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) 347
g, dicyandiamide 17.9 g, and benzyldimethylamine 0.9 g were charged and heated at 150 ° C. for 1 hour.

Further, the liquid material was sandwiched between iron plates provided with 2 mm spacers, and pressed at 170 ° C. under a pressure of 30 kg / cm ^2.
After heating for 0 minutes, the desired cured product was obtained. The resulting resin contained 2.0% by weight of phosphorus and 2.8% by weight of nitrogen.

Example 4 A phosphorus- and nitrogen-containing compound represented by the general formula (V) 6-amino-2,4-bis {[6H-dibenzo- <c, e> (1,
2) -oxaphospholin-6-yl] methylamino} -1,3,5-triazine 100 g, bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy) 431 g, dicyandiamide 21.5 g,
1.1 g of benzyldimethylamine was charged and heated at 150 ° C. for 1 hour. The liquid material is sandwiched between iron plates provided with 2 mm spacers and pressed at 170 ° C. under a pressure of 30 kg / cm ^2.
After heating for a minute, the desired cured product was obtained.

[0046]

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Example 5 130 g of the compound represented by the general formula (III), 500 g of a bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.), 25 g of dicyandiamide, and benzyldimethylamine were placed in a 1-liter flask. 3 g, N, N-dimethylformamide 80 g, and methyl ethyl ketone 300 g were charged.
After stirring at 70 ° C. for 4 hours, the mixture was cooled to obtain an epoxy resin varnish. Repeatedly applied to glass woven fabric, impregnated,
It dried at 170 degreeC and prepreg was manufactured.

Eight sheets were stacked, heated and pressed at 170 ° C. under a pressure of 40 kg / cm ² for 70 minutes to obtain a target glass epoxy laminate.

Comparative Example 1 500 g of bisphenol A type epoxy resin (Epicoat 828, manufactured by Yuka Shell Epoxy) and dicyandiamide 20 were placed in a 1 liter flask.
g, benzyldimethylamine 1.0 g, 150 g
Heated at 0 ° C. for 1 hour.

Further, the liquid material was sandwiched between iron plates provided with 2 mm spacers, and pressed at 170 ° C. under a pressure of 30 kg / cm ^2.
After heating for 0 minutes, the desired cured product was obtained.

The heat resistance and solder heat resistance of the resin plate obtained by the above method were evaluated. Table 1 shows the results.

[0052]

[Table 1]

[0053]

As described above, the phosphorus and nitrogen-containing epoxy resin obtained by reacting the compound represented by the formula (I) with the epoxy resin of the present invention contains no halogen and has excellent heat resistance and moisture resistance. It is possible to provide a prepreg and a laminate using the epoxy resin.

Claims (4)

[Claims] 1. An epoxy resin and a compound of the general formula (I) [In the formula, A is a phenyl group or a -N <group. When A is a phenyl group, s is an integer of 1 to 4, t is 4, and when A is -N <, s is s. Is an integer of 1 to 6, t is 6, and X is a group represented by the general formula (II). (Wherein, R ¹ , R ² , and R ³ are each hydrogen, and have 1 to 4 carbon atoms.
A phosphorus- and nitrogen-modified flame-retardant epoxy resin composition, characterized in that it is a reaction product with an organic phosphorus compound represented by the formula: 2. The epoxy resin is a bisphenol A type epoxy resin or a novolak type epoxy resin.
The phosphorus and nitrogen-modified flame-retardant epoxy resin composition according to 1. 3. A prepreg obtained by impregnating a substrate with the phosphorus and nitrogen-modified flame-retardant epoxy resin according to claim 1 or 2. 4. A laminate comprising a stack of one or more prepregs according to claim 3, which is heated and pressed.