JPS58179263A - Flame retardant polyamide composition - Google Patents

Abstract

PURPOSE:To provide the titled composition obtained by compounding a specific melamine derivative in combination with melamine cyanurate to a polyamide, having high flame-retardance and remarkably diminished defects of a polyamide composition containing only one of the above additives, and giving a molded article having excellent appearance and physical properties. CONSTITUTION:A polyamide is compounded with (A) a melamine derivative of formula I (R<1> is 1-15C hydrocarbon residue) (e.g. methylene dimelamine) and/or formula II (R<2> is 1-15C hydrocarbon residue; n is integer of 1-5) (e.g. diethylene trimelamine) and (B) melamine cyanurate. The sum of (A) and (B) is 1-50wt%, especially 2-30wt%, based on the polyamide, and the weight ratio of (A):(B) is preferably 95:5-5:95.

Description

[Detailed description of the invention] FIELD OF THE INVENTION This invention relates to flame retardant polyamide compositions.

More specifically, the present invention relates to a flame-retardant polyamide composition that has a high degree of flame retardancy and can produce molded articles with good appearance and physical properties.

It is known to add flame retardants such as melamine, anuric acid, isocyanuric acid, etc. to polyamide in order to impart flame retardancy to polyamide (for example, Japanese Patent Publication No. 47-4
1745, Japanese Patent Application Laid-open No. 1745, etc.)
. Furthermore, it is said that cyanuric acid, isocyanuric acid, etc. have a greater flame retardant effect than melamine. In polyamide compositions containing these known flame retardants, the flame retardant may sublimate during molding and contaminate the mold, or the flame retardant may be released in small amounts when the resulting molded product absorbs moisture or during use. In the form of powder, it has the drawback of precipitating (bleeding out) on the surface of molded products and impairing the aesthetic appearance of molded products. When cyanuric acid, in/anuric acid, etc. are used as flame retardants,
In addition to the above-mentioned drawbacks, there is a drawback that /anuric acid, iso/anuric acid, etc. decompose during molding, resulting in partially foamed molded products.

In order to improve this deficiency caused by melamine, cyanuric acid, iso/yunuric acid, etc., melamine and/or
Equimolar reaction product with bunuric acid, i.e. melamine/
It has been proposed to use annulate as a flame retardant.
(Japanese Unexamined Patent Publication No. 53-31759). When using melamine/americate &: f: , r) 1J
Although the drawbacks of melamine, anuric acid, incyanuric acid, etc. mentioned above can be improved to a considerable extent, they are still not fully satisfactory in order to impart a higher degree of flame retardancy required for electrical component materials. It cannot be said that it is possible, and there is room for improvement. In the present invention, the authors used melamine/gamma nurate as a flame retardant, but found that the flame retardant effect of melamine was lower than that of melamine and gamma nuric acid. .

For example, Nye "2/6 is 80 tons and melamine is 2.0"
The composition consisting of the tun M part meets the UL flame retardant standards (U, L-9
4) Clear vo. Nao.

To clear V-O, a combustion test is conducted on five test pieces, and (1) the average burning time is 5 seconds or less.

(2) Maximum burning time is 10 seconds or less; (3) Absorbent cotton placed 1″2 inches below the tip of the test piece will not burn due to the drippings (even 1 out of 5 cotton wool should not burn).

All slow conditions must be met. However,
80 parts by weight of nylon 6 and 20 parts by weight of melamine annulate
parts by weight, the average burning time and the maximum burning time satisfy the aforementioned conditions.

Regarding absorbent cotton ignition due to drippings, even if the same test was repeated several times, the drops always burned the absorbent cotton in 1 to 2 out of 5 test pieces, and the ■-0 condition was not fully satisfied.

Furthermore, in order to improve the drawbacks of conventional melamine, anuric acid, isocyanuric acid, etc., it has been proposed to use melamine derivatives such as methylene dimelamine and ethylene dimelamine as flame retardants for polyamide (Japanese Patent Application Laid-open No. 53-47451, JP-A-56-22347, etc.). However, according to research by Honkomei et al., the flame retardant f-・1 effect of these melamine derivatives is +
Is it? [71
However, when the ratio of 11" to Ny[)/6 is increased to 10 ton[i], the V-0 condition is not fully satisfied, and there is still room for significant improvement.

I\Komyouna et al. have been working diligently to overcome the drawbacks of conventionally known flame retardants, including melamine.
As a result of repeated research, we surprisingly found that melamine soanurate, which was mentioned above, was used as a flame retardant for polyamide.

It was discovered that when J7 is used in combination with specific melamine derivatives such as methylene/melamine and ethylene dimelamine, it has a flame retardant effect that is more immediate than could be predicted when J7 is used alone, leading to the present invention. It was.

The present invention is directed to poly-F mid.

(A) Formula (1) (In the formula, R' represents a hydrocarbon residue having 1 to 15 carbon atoms.)
Melamine derivatives and/or (wherein R2
represents a hydrocarbon residue having 1 to 15 carbon atoms.

n is an integer from 1 to 5. ) and a melamine derivative represented by

(B) This relates to a flame-retardant polyamide composition blended with melamine noanurate.

The flame-retardant polyamide composition of the present invention not only has (1) an unprecedented feature of exhibiting a high degree of flame retardancy with a small amount of flame retardant, but also (2) contains a flame retardant. Since fewer needles are needed, there is no need to worry about adverse effects on the excellent physical properties inherent to polyamide.

(3) The mold will not be contaminated during molding (II), (4) The molded product will not foam, and (5) The flame retardant will not bleed out onto the surface of the molded product. be. Also, according to the flame retardant polyamide composition of the invention 1/+
The disadvantages of combining the melamine derivative (Δ) in +jiJ and the melamine cyanurate (B) alone in No. 1 are the following: ,,',Sa7Lru.

Specific examples of polyamides used in the present invention include nylon 6, nylon 11. Polylactams such as nylon 12, nylon 66, nylon m1) 610.
From nocarboxylic acids such as nylon 612 and diamino
(Examples include boria, amide, copolyamides such as nylon 6/66, nylon 76/66/610, mixtures of these 7L, etc.).

Formula (1) of the above (A) blended into polyamide in the present invention
Typical specific examples of melamine derivatives represented by C1. methylene dimelamine, ethylene dimelamine,
trimethyleneft melamine, tetramethylene/melamine,
・＼Kizamethylene dimelamine, Tecamethylene 7/Melamine, Trimethylene dimelamine.

113-/ta11-\gi/leno/melane, p-phenylene//melami/, p-quinolinenedimelamine.

Examples include 4.4'-methylene dimelamine. Typical specific examples of the melamine derivatives represented by the formula (n) in (A) above include diethylene trimelamine, triethylene tetramelamine, tetraethylene pentamelamine, hexaethylene hebutamelamine, and the like.

These melamine derivatives are a combination of multiple types It's okay to do that.

In the present invention, the melamine cyanurate (B) that is blended together with the melamine derivative (A) in the polyamide is an equimolar reaction product of melamine and anuric acid. Other substituents 2 such as methyl group, phenyl group, carboxy/
Notyl group, 2-carboxy/ethyl group, anomethyl group,
It is acceptable even if it is substituted with a 2-cyanethyl group or the like.

Furthermore, the melamine derivative (A) and the melamine cyanurate (B) that are blended into the polyamide in the present invention do not necessarily have to be of high purity.

It may be possible to use unreacted starting materials or impurities that have been mixed in for one month to produce CO2.

1. Uninvented. -The melamine derivative of (A) and (
13) The blending of melamine cyanurate is such that the total amount of (A) and (B) is 1 to 50 tons (6%
(//It should be 2 to 30% by weight as soon as possible.) If the blending ratio is too low, the flame retardance will be 1 minute per -t' mil-41. f・] cannot be given.

If the weight is too high, 1'1, which is inherent in polyamide, will be reduced to 1. (A):(B')=99-1:1-99. Preferably, the ratio is 95-5:5-95.

In the present invention, there is no particular restriction on the method of blending the melamine derivative (A) and the melamine cyanurate ()3) into the polyamide, and a known blending method may be used, for example, by tribrazing the polyamide and the above compound.・1 method, method of melt-kneading polyamide and the above-mentioned compound using an extruder, etc. can be adopted as appropriate.

The flame-retardant boriat composition of the present invention can contain known additives such as an oxidation inhibitor, a lubricant, and an inorganic filler.

Next, Examples and Comparative Examples will be shown.

On the valley side, the flame retardancy of the molded article and the bleed-out of the flame retardant onto the surface of the molded article were evaluated as follows.

1 Flame retardancy (a) UL standard 5ubjeCt 94 (UL-94) specified by Underwriters Laboratories, Inc. in the United States for a test piece with a length of 5 inches, a width of 1/2 inch, and a thickness of 1/2 inch.
A combustion test was conducted according to the following.

(b) Limiting oxygen index (L, 0.cm,) A test piece of 5 inches in length, 1/4 inch in width, and 1/16 inch in thickness was tested using a candle method combustion tester manufactured by Toyo Seiki. According to D2863, O,1,
was measured.

2. From a blend of bleed-out flame-retardant polyamide composition and carbon black for 0.5 h; lengthwise and widthwise, 80 rirrn each.

Form the board of Susa 2 Dragon 2. This board was heated to a relative humidity of 95 degrees.
The specimen was left in air at a temperature of 40°C for 10 days, and the bleed-out of the flame retardant on the surface of the molded product (test piece) was observed with the naked eye.

In each case below, parts mean parts by weight.

Examples 1 to 5 90 parts of nylon 6 pellets with a number average molecular t=- of 13.00.0 were mixed with ethylene dimelamine and melamine cyanuride-1 so that the total number of stitches was 10 parts. :h
The mixture described by the first person was blended and pelletized using an extruder. Test pieces for combustion tests were prepared from the pellets by hot press molding (molding temperature 200°C). , the above nylon 6p L' y to 90
Bread 0.5 parts of the black and carbon black listed in Table 1 so that the total amount of ethylene dimelamine and melamine/amelate is 10 parts, and make pellets using an extruder. ! It's +. A test piece for a bleed-out test was prepared from this pellet by hot press molding (molding temperature: 2° C.).

The test results are shown in Table 1.

Comparative Examples 1 to 2 Example 1 except that 10 parts of each of ethylene dimelamine and melamine/amerate of Example 1 were blended alone.
Test pieces for each test were prepared in the same manner as above.

The test results are shown in Table 1.

Example 6 Same as Example 1 except that nylon 6 pellets with a number average molecular weight of 11,000 were used, and 95 parts of nylon 6 pellets were mixed with ethyle, 2.5 parts of ndimelamine, and 2.5 parts of melamine cyanurate. Test pieces for each test were prepared.

The test results are shown in Table 1.

Table 1 From this Table 1, it is clear that the flame retardant polyamide composition of the present invention is extremely effective even with a small amount of flame retardant/flame retardant.
It can be seen that the material has excellent flame retardancy.

Examples 7 to 9 Number average outer f, kf is i'5. Melamine derivative 5 listed in Table 2 was added to 90 parts of nylon 6 pellets of o o o.
and 5 parts of mejiminocyanurate.

-C pellets were obtained using an extruder. A test piece for a general combustion test was prepared from this pellet by heat molding (molding temperature 2°C). On the other hand, to 90 parts of the above nylon 6 pellets, 5 parts of the melamine derivative listed in Table 2,
5 parts of melamine 7 anurate and 0.0 parts of carbon black.
5 parts were blended and pellets were obtained using an extruder. A test piece for a bleed-out test was prepared from this pellet by hot press molding (molding temperature: 230°C).

The test results are shown in Table 2.

Comparative Examples 3 to 5 The melamine cyanurate of Examples 7 to 9 was not blended, and the second
Test pieces for each test were prepared in the same manner as in Examples 7 to 9, except that 10 parts of the melamine derivative listed in the table was added alone.

The test results are shown in Table 2.

Table 2 4゜

Claims (1)

[Claims] To polyamide. (A) Formula (1) (In the formula, R' represents a hydrocarbon residue having 1 to 15 carbon atoms.)
A melamine derivative represented by and/or a melamine derivative represented by formula (11) (wherein R2 represents a hydrocarbon residue having 1 to 15 carbon atoms, and l] is an integer of 1 to 5. B) A flame-retardant polyamide composition containing melamine/amelate.