JPH093303A - Phenolic resin composition, prepreg produced using same and laminate - Google Patents

Abstract

PURPOSE: To obtain a phenolic resin composition which contains a phosphorus compound, combines sufficient heat resistance and excellent flame retardancy, and is useful for producing prepregs for a laminate by incorporating specific ingredients. CONSTITUTION: This composition contains: a phosphorus compound flame retardant and a bromine compound flame retardant; at least one nitrogen compound selected from among melamine resins, urea resins, urethane resins, modifications of these resins, compounds containing any of these, dicyandiamide, and aniline; at least one radical-trapping agent selected from among organic peroxides and radical terminators; and a cyanurate compound represented by the formula (R1 , R2 , and R3 each is an alkyl). It has a bromine compound content of 1-8wt.% based on all solid resin components. It preferably has a phosphorus compound content and a cyanurate compound content of 0.5-3wt.% and 1-10wt.%, respectively.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a phenol resin composition,
Regarding the prepreg and the laminated board using the phenolic resin composition, for example, they are useful for a paper base laminated board to be mounted on electric equipment / electronic equipment, industrial equipment and the like.

[0002]

Brominated flame retardants are commonly used to impart flame retardancy to paper-based phenolic resin laminates mounted in electronic devices and the like. In recent years, as the flame retardancy level of the flame retardancy, for example, in the UL test method, the maximum combustion time is 3
It is required to improve the level of V-1 of 0 seconds or less to the level of V-0 of maximum burning time of 10 seconds or less. In order to realize this, a brominated flame retardant is added to the phenol resin composition. The content of the bromine component is 10% by weight or more based on the resin solid content. However, the use of the brominated flame retardant is required to reduce the amount of use because of pollution problems. In order to reduce the amount of brominated flame retardants used, phosphorus-based flame retardants have been studied as an alternative flame retardant, but phosphorus-based flame retardants have improved flame retardancy as the content increases, but heat resistance, especially There is a problem that solder heat resistance deteriorates. Therefore, there is a demand for a phenolic resin composition containing a phosphorus-based flame retardant, which has both good heat resistance and excellent flame retardancy.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above facts, and an object thereof is to reduce the amount of brominated flame retardant used and to maintain the heat resistance level. At the same time, it is to provide a phenol resin composition containing a phosphorus-based flame retardant having excellent flame retardancy, a prepreg using the phenol resin composition, and a laminate.

[0004]

The phenol resin composition according to claim 1 of the present invention is a phenol resin composition containing a phosphorus flame retardant and a bromine flame retardant, wherein the composition contains melamine. At least one selected from the group consisting of a resin, a urea resin, a urethane resin alone, a modified product thereof, a resin-containing compound thereof, and dicyandiamide and aniline.
One or more nitrogen-containing compounds, organic peroxides, at least one or more radical trapping agents among radical reaction terminators, and a cyanurate compound represented by the following structural formula [1] as components, and The content of the bromine component in the resin composition is 1 to 8% by weight based on the resin solid content.
It is characterized by being.

[0005]

Embedded image

[In the formula, R _1, R _{2 and} R ₃ represent an alkyl group. The phenol resin composition according to claim 2 of the present invention is characterized in that, in the phenol resin composition according to claim 1, the radical reaction terminator is hydroquinone.

In the prepreg according to claim 3 of the present invention, a substrate is impregnated with the phenol resin composition according to claim 1 or 2, and the resin of the impregnated phenol resin composition is in a semi-cured state. It is characterized by

The laminated plate according to a fourth aspect of the present invention is characterized in that the resin is completely cured by using the prepreg according to the third aspect.

Hereinafter, the present invention will be described in detail. As the phenol resin constituting the phenol resin composition of the present invention, various ones can be used, and a phenol resin alone, a modified product or a mixture thereof can be used.

As a constituent material of the phenol resin composition of the present invention, a phosphorus flame retardant and a bromine flame retardant are contained. Examples of the phosphorus-based flame retardant include triphenyl phosphate, tricresyl phosphate, xylenyl diphenyl phosphate, cresyl diphenyl phosphate, and derivatives thereof. The content of the phosphorus component of the phosphorus-based compound is appropriately determined by the solid content of the resin composition of the resulting laminate and the composition ratio of the base material, for example, the solid content of the resin composition in the laminate is When the amount is about 50% by weight, the content of the phosphorus component is preferably 0.5 to 3% by weight, and about 2% by weight is suitable for the solid amount of the resin composition. If the content of the phosphorus component in the phosphorus-based compound is small, the flame retardancy is poor, and if it is too large, the heat resistance is reduced.

Examples of the brominated flame retardant include tetrabromobisphenol A and tetrabromobisphenol A.
Diglycidyl ether, 2-2-propane-bis [4-
(3-Polybromophenyloxy-2-hydroxypropyl) oxy-3,5-dibromophenol and the like can be mentioned. The content of the brominated flame retardant is such that the content of the brominated component in the phenol resin composition is 1 to the resin solid content.
8% by weight. If the content of the above-mentioned brom component is small, the flame retardancy is poor, and if it is too large, the effect of reducing the amount used is not achieved.

The phenol resin composition of the present invention contains, as its characteristic constituent materials, a nitrogen-containing compound, a radical trapping agent, and a cyanurate compound represented by the above structural formula [1] as components. The nitrogen-containing compound, the radical trapping agent, and the cyanurate compound function as a flame retardant auxiliary agent, and when these three components are contained, even if the content of the phosphorus-containing compound is small, the flame retardancy is high. Further, since the content of the phosphorus-containing compound is small, the level of heat resistance is not lowered.

In the phenol resin composition of the present invention, the nitrogen-containing compound is selected from the group consisting of melamine resin, urea resin, urethane resin alone and modified, these resin-containing compounds, and dicyandiamide and aniline. At least one selected from the above is included. The nitrogen-containing compound functions as a flame retardant aid.

The phenol resin composition of the present invention contains, as a radical trapping agent, at least one of organic peroxides and radical reaction terminators. Examples of the organic peroxide include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, 1,4-bis (t-butylperoxyisopropyl) benzene, 1,3-bis (t-butylperoxy). Isopropyl) benzene, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-dibenzoylperoxyhexane and the like can be mentioned. Examples of the radical reaction terminator include hydroquinone, 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2, t-di-t-butyl-4-ethylphenol, and 2,2. '-Methylene-bis- (4-methyl-6-t
-Butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, and the like. Among them, hydroquinone alone,
Alternatively, when used in combination, in the steps up to the production of the laminated plate, it reacts with the formaldehyde remaining during the production of the phenol resin to reduce combustibles or increase the crosslink density to suppress the thermal decomposition of the laminated plate. It is preferable because it is expensive.

When one or more of the above organic peroxides and radical reaction terminators are contained together with the phosphorus-based flame retardant, the phosphorus-based flame retardant serves to block oxygen by the formation of polyphosphoric acid and synergize with the phosphorus-based flame retardant. It has the effect of stopping the combustion reaction. Generally, the function of the flame retardant is presumed to be due to the function of generating gas or the like to block oxygen during combustion and the function of stopping the combustion reaction. Although the phosphorus-based flame retardant has a function of blocking oxygen by the generation of polyphosphoric acid, it has almost no function of stopping the combustion reaction. Had to increase. However, in the phenol resin composition of the present invention, by containing at least one of the organic peroxide and the radical reaction terminator together with the phosphorus-based flame retardant, it is possible to have a function of stopping the combustion reaction. result,
The flame retardancy can be improved and the heat resistance can be favorably maintained without increasing the amount of the phosphorus-based flame retardant.

The cyanurate compound is represented by the above structural formula [1]. R ₁ , R ₂ , R ₃ in the formula
Represents an alkyl group, and all may be the same alkyl group or different alkyl groups. When the above cyanurate compound is contained, not only flame retardancy but also heat resistance is improved. The content of the cyanurate compound is preferably 1 to 10% by weight, more preferably 3 to 5% by weight, based on the solid amount of the resin composition.
The degree is suitable.

Since the phenol resin composition of the present invention contains the above-mentioned components, it imparts a high level of flame retardancy even if the content of the phosphorus compound is small. Since the content of the phosphorus-based compound is small, it is also effective from the viewpoint of preventing deterioration of heat resistance. Further, the cyanurate compound has an effect of improving heat resistance.

The above-mentioned phenol resin composition may be optionally combined with other flame retardants such as antimony. Further, an inorganic or organic filler, a solvent, and other additives such as water may be appropriately blended.

In the production of a prepreg using the above-mentioned phenol resin composition, examples of the substrate include kraft paper, linter paper, and other kraft paper or linter paper mixed with an inorganic or organic material. These substrates are impregnated with the above-mentioned phenol resin composition and the resin is semi-cured to obtain a prepreg. In the case of a laminated board having a high degree of electrical characteristics, since it is necessary to contain a large amount of resin, when impregnated, a primary impregnation treatment using the above-mentioned phenol resin composition or a resin composition different from the phenol resin composition. It is effective to carry out a secondary impregnation treatment using the above-mentioned phenol resin composition. In general, the resin composition for primary impregnation used has a low viscosity diluted with a solvent or water.

The laminated plate of the present invention comprises several prepregs obtained by the above-mentioned manufacturing method, and if necessary, copper, aluminum,
When metal foils such as nickel are superposed and heated and pressed, the resin in the base material is completely cured and is produced. Since the above-mentioned phenol resin composition is used, a laminate having good heat resistance such as solder heat resistance and improved flame retardancy can be obtained. Since the amount of the brominated flame retardant used is reduced, the above laminated plate is also excellent in terms of pollution prevention.

[0021]

【Example】

Example 1 The resin composition for primary impregnation and the primary impregnation were performed as follows. Resol type phenol reaction product A was obtained by reacting 100 parts by weight of phenol (hereinafter referred to as “part”) and 70 parts of 37% by weight (hereinafter referred to as “%”) formalin. Also,
Melamine 100 parts, formalin (solid content 37%) 100
Parts were reacted to obtain a melamine reaction product B. A mixture of 50 parts of this resol type phenol reaction product A and 50 parts of melamine reaction product B was diluted with an aqueous methanol solution in which water and methanol were mixed in a ratio of 1: 1 to obtain a resin composition for primary impregnation with a solid content of 15%. It was Weight of base material 126g / m ²
This kraft paper was first impregnated with the above resin composition for primary impregnation. Then, it was dried for 30 seconds in a dryer at 135 ° C. to obtain a primary prepreg A in which the resin was semi-cured. In this primary prepreg A, the resin content of the primary varnish A was 15% based on the kraft paper.

The phenol resin composition used for the secondary impregnation was prepared as follows. 100 parts of phenol, 80 parts of 37% formalin and 30 parts of tung oil were reacted to produce a tung oil-modified resol type phenol resin. To 100 parts of this tung oil-modified resol type phenolic resin, 10 parts of tetrabromobisphenol A diglycidyl ether as a bromine flame retardant, 10 parts of triphenyl phosphate as a phosphorus flame retardant, and the above melamine reaction product B as a nitrogen-containing compound. 15 parts of R ₁ , R ₂ and R in the structural formula [1]
₃ is ethylene (-CH ₂ CH ₂ -) 1 parts cyanurate compound represented by hydroquinone were mixed 5 parts of a radical reaction inhibitor, to produce a phenolic resin composition.

The secondary impregnation treatment was performed as follows. The primary prepreg A is impregnated with the phenol resin composition, and 1
The resultant was treated with a drier at 55 ° C. for 100 seconds to produce prepreg B in which the resin was in a semi-cured state. This prepreg B
The content of the resin therein was 50%.

Next, eight prepregs B were stacked, a copper foil having a thickness of 0.035 mm was arranged on the uppermost layer through an adhesive, and this was molded at a pressure of 100 kg / cm ² and a temperature of 160 ° C. for 60 minutes. Thus, a 1.6 mm thick laminated plate in which the resin was completely cured was obtained.

The phosphorus content of the phosphorus flame retardant is 1% by weight based on the solid amount of the resin composition of both the primary impregnation and the secondary impregnation, and the bromine component of the bromine flame retardant is 1% by weight. Was 7% by weight, and the cyanurate compound was 1% by weight.

Example 2 A primary prepreg A and a prepreg B were prepared in the same manner as in Example 1 except that 1 part of hydroquinone was added in the formulation of the phenol resin composition used for the secondary impregnation, and the laminated plate was prepared. Obtained.

Example 3 A primary prepreg A and a prepreg B were prepared in the same manner as in Example 1 except that 10 parts of hydroquinone was used in the compounding of the phenol resin composition used for the secondary impregnation, and the laminated plate was prepared. Obtained.

Example 4 In the formulation of the phenol resin composition used for the secondary impregnation, 1,4 as an organic peroxide was used instead of hydroquinone.
-Preparation and lamination of primary prepreg A and prepreg B were carried out in the same manner as in Example 1 except that bis (t-butylperoxyisopropyl) benzene (Perbutyl P manufactured by NOF CORPORATION) was changed to 0.5 part. I got a plate.

Example 5 In the formulation of the phenolic resin composition used for the secondary impregnation, 1,4-bis (t-butylperoxyisopropyl) benzene (Perbutyl P manufactured by NOF Corporation) was used as 1 part. A primary prepreg A and a prepreg B were produced in the same manner as in Example 4 to obtain a laminated plate.

Example 6 In the formulation of the phenol resin composition used for the secondary impregnation, 2 parts of 1,4-bis (t-butylperoxyisopropyl) benzene (produced by NOF CORPORATION, perbutyl P) were used. A primary prepreg A and a prepreg B were produced in the same manner as in Example 4 to obtain a laminated plate.

Example 7 A primary resin was prepared in the same manner as in Example 1 except that 15 parts of the melamine reaction product B and 0.2 part of aniline were used as the nitrogen-containing compound of the phenol resin composition used for the secondary impregnation. A prepreg A and a prepreg B were produced to obtain a laminated board.

Example 8 Urea resin C was obtained by reacting 100 parts of urea with 100 parts of formalin (37% solid content). A primary prepreg A and a prepreg B were produced in the same manner as in Example 1 except that 15 parts of the above urea resin C was used as the nitrogen-containing compound of the phenol resin composition used for the secondary impregnation to obtain a laminated plate.

Example 9 Methylenebisparaphenylene diisocyanate (MD
I: manufactured by Mitsui Toatsu Chemicals, Inc.) 100 parts and bisphenol A 100 parts were reacted to obtain urethane resin D. Example 1 except that 15 parts of the urethane resin D was used as the nitrogen-containing compound of the phenol resin composition used for the secondary impregnation.
A primary prepreg A and a prepreg B were prepared in the same manner as in 1. to obtain a laminated plate.

Example 10 Preparation of primary prepreg A and prepreg B was carried out in the same manner as in Example 1 except that 20 parts of cresyl diphenyl phosphate was used as the phosphorus-based flame retardant of the phenol resin composition used for the secondary impregnation. Then, a laminated plate was obtained. In addition, the content of the phosphorus component of the phosphorus compound was 2% by weight based on the solid amount of the resin composition in both the primary impregnation and the secondary impregnation.

Comparative Example 1 The phenol resin composition used for secondary impregnation was prepared as follows. Phenol 100 parts, 37% formalin 8
0 part and 30 parts of tung oil were reacted to prepare a tung oil-modified resol type phenol resin. To 100 parts of this tung oil-modified resol type phenolic resin, 10 parts of tetrabromobisphenol A diglycidyl ether as a bromine flame retardant and 10 parts of triphenyl phosphate as a phosphorus flame retardant,
The melamine reaction product B as a nitrogen-containing compound
Parts were mixed to prepare a phenol resin composition. A primary prepreg A and a prepreg B were produced in the same manner as in Example 1 except that this phenol resin composition was used.
A laminated board was obtained.

The flame retardancy and heat resistance of the obtained laminated plates of Examples 1 to 10 and Comparative Example 1 were evaluated. Flame retardance is U
Ten extinction times were measured based on the L test method, and an average value and a maximum value were obtained. For heat resistance, solder heat resistance and oven heat resistance were measured. The solder heat resistance was measured by floating the solder at 260 ° C. and measuring the time until the occurrence of blistering. Regarding the above-mentioned oven heat resistance, after leaving it in an oven having a predetermined atmosphere temperature for 30 minutes, the appearance was visually observed, and those with blisters were rejected, those without blisters were accepted, and the limit temperature at which they passed was determined.

The results are shown in Table 1, Examples 1 to 1
In all 0, the flame retardancy was high and the maximum combustion time was 10 seconds or less, and the heat resistance was good. Comparative Example 1 was inferior in flame retardancy.

[0038]

[Table 1]

[0039]

When the phenol resin composition according to claim 1 or 2 of the present invention is used, the heat resistance is good and the flame retardancy is improved even if the amount of the bromine flame retardant used is reduced. A laminate is obtained.

Since the prepreg according to claim 3 of the present invention uses the above-mentioned phenol resin composition, the laminated board using this prepreg has good heat resistance and improved flame retardancy.

Since the laminated board according to claim 4 of the present invention uses the prepreg, the amount of the brominated flame retardant used can be reduced, and the heat resistance is excellent and the flame retardancy is excellent.

Claims (4)

[Claims] 1. A phenolic resin composition containing a phosphorus-based flame retardant and a bromine-based flame retardant, wherein a melamine resin, a urea resin, a urethane resin alone or a modified product thereof, a resin-containing compound thereof, And dicyandiamide,
At least one nitrogen-containing compound selected from the group consisting of aniline, at least one radical trapping agent among organic peroxides and radical reaction terminators, and cyanurate represented by the following structural formula [1] A phenol resin composition comprising a compound as a component, and the content of the bromine component in the resin composition is 1 to 8% by weight based on the resin solid content. Embedded image [In the formula, R _1, R _{2 and} R ₃ represent an alkyl group. ] 2. The phenolic resin composition according to claim 1, wherein the radical reaction terminator is hydroquinone. 3. A prepreg characterized in that a substrate is impregnated with the phenol resin composition according to claim 1 or 2, and the resin of the impregnated phenol resin composition is in a semi-cured state. 4. A laminate comprising the prepreg according to claim 3 and a resin in a completely cured state.