JP3076607B2 - Flame retardant polyamide composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION It is an object of the present invention to provide a material suitable as a material for automobile parts including a material for electric and electronic parts.

[0002]

2. Description of the Related Art As flame retarding technology for polyamide, halogen-based, phosphorus-based, and nitrogen-based flame retardants are used. In the electrical and electronic field, each flame retardant has been used for its own advantages and disadvantages. However, in the automotive field, there is a trend toward flame retardancy, and flame-retardant polyamides have been demanded.When examining suitable materials, halogen-based flame retardants have a problem of metal corrosion, and phosphorus-based flame retardants have strong coloring. However, it turned out that there was a drawback that coloring could not be performed in various colors. In addition, among nitrogen-based flame retardants, melamine cyanurate (JP-A-53-31759) or an organic addition salt of triguanamine with cyanuric acid (JP-A-54-37145)
And organic addition salts of diguanamine and cyanuric acid (JP-A-54-37146), all of which have problems in moldability, heat resistance and the like. At first, it was not at a satisfactory level as a material for automobile parts.

[0003]

As described above, there has been a demand for a flame-retardant polyamide resin composition having excellent moldability and heat resistance for use as a material for electric and electronic parts and for automobile parts.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention relates to: Polyamide resin B. At least one of the compounds represented by chemical structural formulas (1) and (2)

[0005]

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And C.I. Compound represented by chemical structural formula (3)

[0007]

Embedded image A composition comprising:
The amount of component B is b weight%, and the amount of component C is c weight%
Where a + b + c = 100 1 ≦ b + c ≦ 40 1/9 ≦ b / c ≦ 9

In the present invention, the polyamide is a polymer having an amide bond, and comprises a polycondensation of an organic diamine and an organic dicarboxylic acid, a polycondensation of aminocaproic acid,
It is obtained by ring-opening polymerization of lactam and the like. Examples of the organic diamine include tetramethylene diamine, hexamethylene diamine, meta-xylylenediamine, and the like.Examples of the organic dicarboxylic acid include adipic acid, sebacic acid, dodecanoic acid, terephthalic acid, and isophthalic acid. .
Examples of aminocaproic acid include ε-caproic acid and 1
Examples of 1-aminoundecanoic acid and lactam include ε-
Caprolactam, ω-laurolactam and the like.
The polyamide may be a copolymer of these or a polymer blend. Among these polyamides, 6,6-nylon, a polyamide containing 6,6-nylon as a main component, and a copolymer of terephthalic acid, adipic acid, hexamethylenediamine, terephthalic acid, hexamethylenediamine, and ε-caprolactam Copolymers are particularly preferred in terms of heat resistance and mechanical properties. For example, a copolymer of 6,6-nylon and 6-nylon, a blend of 6,6-nylon and 6-nylon, a copolymer of 6T-nylon and 66-nylon (hereinafter, T indicates terephthalic acid), 6
T-nylon and 6-nylon copolymer, 6T-nylon, 66-nylon and 612-nylon terpolymer, and the like.

In the present invention, the compound used as a flame retardant is represented by the following chemical formulas (1), (2) and (3).

[0010]

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The method for producing these flame retardants is not particularly limited. For example, succinoguanamine, which is one of the compounds of formula (1), is prepared by heating dicyandiamide and succinonitrile in a solvent in the presence of an alkali catalyst. Are synthesized by Various compounds of the formula (1) can be obtained by using nitriles having different carbon numbers instead of succinonitrile.

The compound of the formula (2) can be obtained, for example, by a condensation reaction of melamine and formaldehyde. The compound of the chemical formula (3) is synthesized, for example, by heating dicyandiamide and trinitrile in a solvent in the presence of an alkali catalyst. Each compound is a white solid and is usually used after being ground. The finer the particle size of the powder, the finer the dispersed particle size in the polyamide when mixed with the polyamide, the more preferable in terms of flame retardancy and mechanical properties. However, the fineness is economically disadvantageous, and a material having an appropriate particle size is used. Preferably 0.1 to 15
μ, and more preferably 0.1 to 5 μ.

The total amount of the flame retardant, that is, b + c is 1 to 40% by weight. If it is less than 1% by weight, the expression of flame retardancy is insufficient, and if it exceeds 40% by weight, mechanical properties and
Molding fluidity and economic efficiency deteriorate. Preferably it is 1 to 20% by weight. It is difficult to exhibit a sufficient flame retardant effect by using the B component or the C component alone, but when the B component and the C component are used in combination, a sufficient flame retardant effect can be exhibited due to a synergistic effect. B / c, which is the ratio of the B component and the C component, is 1 /
9 to 9. Outside this range, a sufficient flame retardant effect cannot be exhibited. Preferably, from 3/7 to 7/3
It is.

It is preferable that the flame retardant is finely dispersed in the polyamide in terms of flame retardancy and mechanical properties. Even if the particle size of the flame retardant powder is reduced, secondary aggregation occurs at the time of blending with the polyamide. This is of course to be avoided as much as possible, and the average particle size of the dispersed particles in the polyamide is 0.1 to 30 μm, preferably 0.1 to 2 μm.
0 μ, more preferably 0.1 to 10 μ. Also, the maximum particle size becomes a problem. Preferably it is 100 μ or less, more preferably 50 μ or less.

The method of blending the flame retardant with the polyamide is not particularly limited. At the time of polymerization of polyamide, a method of adding,
There are a method in which the polyamide pellet or powder is simply mixed with the flame retardant powder and then melt-kneading with a twin screw extruder, a method in which the polyamide pellet and the flame retardant powder are simply mixed and directly subjected to injection molding. In the composition of the present invention, a heat-resistant agent is preferably added as necessary.

Typical heat-resistant agents include (a) copper compounds such as copper acetate, copper iodide, and copper bromide. The amount of addition is 0.001 to 5% by weight, preferably 0.001 to 2% by weight, based on the polyamide resin (component A). (B) Alkali metal halides such as potassium iodide and potassium bromide. The amount of addition is 0.01 to 5% by weight, preferably 0.1 to 2.5% by weight, based on the polyamide resin (component A), and it is preferable to use it together with the copper compound.

(C) Hindered phenol compounds such as N, N'-hexamethylenebis (3,5-di-
Tert-butyl-4-hydroxy-hydrocyanamide), 4,4'-butylidenebis (3-methyl-6-tert-butyl-phenol), pentaerythrityl-
Tetrakis [3- (3,5-di-tert-butyl-4)
-Hydroxyphenyl) propionate].

(D) amine compounds, for example,

[0019]

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(E) Phosphorus compounds, for example,

[0021]

Embedded image And the like.

It is also preferable to add a lubricant and a release agent. Examples of these include calcium stearate, aluminum stearate, calcium montanate, fatty acid metal salts such as sodium montanate, ethylenebisstearylamide, amide compounds such as methylenebisstearylamide,
Examples include ester compounds of montanic acid and stearic acid with alcohol.

The addition amount is 0.01 to 0.5% by weight, preferably 0.05%, based on the components (A) + (B) + (C).
~ 0.2% by weight. Other additives for polyamide are also suitably used. Glass fiber, potassium titanate, carbon fiber and the like can be added as a fibrous reinforcing material, and wollastonite, kaolin, calcined kaolin, mica, talc, montmorillonite, glass beads and the like can be added as an inorganic filler. Component (A) + (B) +
Usually, 1 to 40% by weight is added to (C).

The composition of the present invention is used for electric and electronic parts and automobile parts. Examples of components include connectors, fasteners, cable ties, junction boxes, corrugated tubes, and the like. The substances used in the examples, their abbreviations, evaluation methods, and the like are as follows. Nylon 66 (Ny66); number average molecular weight 15,000 Succinoguanamine (SG)

[0025]

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Ethylene dimelamine (ED)

[0027]

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Triguanamine (TG)

[0029]

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Melamine cyanurate (MC)

[0031]

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Ethylene dimelamine cyanurate (ED
C) 5: 1 organic addition salt of ethylene dimelamine and cyanuric acid Triguanamine cyanurate (TGC) 5: 1 organic addition salt of triguanamine and cyanuric acid Melamine (M)

[0033]

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(Evaluation Method) A test piece having a 1/32 inch thickness was evaluated in accordance with the flame retardancy @ UL94 V test. Mold Deposits When molding test specimens for combustion tests with a 3.9 oz injection molding machine, the mold during molding was observed to determine the presence or absence of mold deposits.

[0035]

Examples 1 to 4 85% by weight of Ny66 and 15% by weight of a flame retardant powder (SG, ED, TG) were blended and melt-kneaded using a twin-screw extruder to obtain composition pellets. The composition pellets were injection molded to prepare test specimens and the flame retardancy was evaluated.

[0036]

Comparative Examples 1 to 6 SG, ED, TG, T
A composition was prepared and evaluated in the same manner as in Examples 1 and 2, except that GC, MC, and M were used. Example 1
Table 1 shows the results of Comparative Example 4 and Comparative Examples 1 to 6. SG, ED,
Although TG cannot secure UL94 V-0 by itself, it can be seen that V-0 can be achieved by using SG and TG or ED and TG together.

From the viewpoint of thermal stability, when the foaming status of the strands is compared, TGC and MC have foaming,
It can be seen that the combination of SG, TG, and ED has excellent thermal stability without foaming. Also in comparison of mold deposits, it can be seen that no mold deposit is observed in the combination of SG, TG and ED.

[0038]

[Table 1]

[0039]

The composition of the present invention has excellent moldability and heat resistance, and is effective as electrical and electronic parts such as connectors, fasteners, binding bands, jean cushion boxes, corrugated tubes, and automobile parts.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 77/00-77/12 C08K 5/00-5/59 CA (STN)

Claims (1)

(57) [Claims] 1. A. First Embodiment Polyamide resin B. At least one of the compounds represented by chemical structural formulas (1) and (2) And C.I. Compound represented by chemical structural formula (3) A composition comprising:
The amount of component B is b weight%, and the amount of component C is c weight%
Where, a + b + c = 100 1 ≦ b + c ≦ 40 1/9 ≦ b / c ≦ 9