JPS58117249A - Flame-retardant polyamide resin composition - Google Patents

Abstract

PURPOSE:To provide a non-blooming resin compsn., prepared by adding a small amount of modified polyolefin to a polyamide resin compsn. which contains a halogen-based flame retarder and a flame retarding auxiliary. CONSTITUTION:The resin compsn. is prepared by adding 0.3-5wt% modified polyolefin (B) 3-30wt% halogen-based flame retarder (C) (e.g. decabromodiphenyl ether) and a flame retarding auxiliary (D) (e.g. antimony trioxide) used in 5-100wt% of (C), to a polyamide resin (e.g. nylon 6, 66 or 12). Used as (B) are (1) modified polyolefin (or elastomer) to which alicyclic carboxylic acid (deriv.) having a cis double bond in the ring has been added, (2) ionomer resin and (3) ethylene/alpha,beta-ethylenically unsatd. carboxylic acid copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the prevention of blooming of flame-retardant polyamide $-+ fat composition molded articles, and more specifically, the present invention relates to prevention of blooming of flame-retardant polyamide $-+ fat composition molded articles, and more specifically, the present invention relates to prevention of blooming of flame-retardant polyamide $-+ fat composition molded articles. This is an anti-blooming agent for obtaining flame-retardant polyamide resin moldings that do not cause pluming on the molding surface.

Polyamide resin has excellent mechanical properties, heat resistance, and mechanical properties, so it is used in electrical parts and machinery products.

As engineering plastics such as automatic umbrella parts 1
For example, as the use of light-emitting materials as a substitute for ordinary materials progresses, even more advanced physical properties are required.

9 to improve the rigidity and thermal properties of polyand
It is well known that adding inorganic powder or glass fiber to polyamide usually has a remarkable effect.
Unfortunately, we cannot replace polyamide with organic powder or glass*
*For compositions fortified with.

Generally has poor flammability. Polyamide originally has self-extinguishing properties, but by adding inorganic powder or glass fiber,
It becomes flammable due to willow breakage, which is generally referred to as the wax wick effect.

Halogen compounds, phonemic compounds, phosphorus compounds, metal hydroxides, metal oxides, etc. are well known as flame retardants for polyamide, and by adding them, flame retardant polyamide resin compositions can be made. Obtainable. Among these,
In order to impart a high degree of flame retardance to a composition made of polyamide reinforced with inorganic powder or glass lII fibers, the combination of a halogenated flame retardant and a metal oxide is most suitable for k.

However, when a polyamide composition molded article containing a halogen-based saponifying agent is dry-heated at 110°C or higher, it produces a white powder (pluming), which makes it susceptible to foreign enemies. In addition, in some cases, there are problems such as stripes corroding the connected metal.

The inventors of the present invention have made extensive research in view of the above-mentioned problems, and have added a small amount of modified polyolefin to a polyamide resin promoter to which a halogenated I# flame agent and a flame retardant aid have been added. By doing so, we have arrived at the present invention, which is capable of preventing blooming.

Hereinafter, one aspect of the present invention will be explained in detail.

The polyamides in the present invention are homopolyamides and copolyamides obtained by polycondensation of a lactam, Ih-aminocarboxylic acid, and cyanamine dicarboxylic acid, and mixtures thereof. Specifically, examples include nylon 6, nylon 66, nylon 6/10. Nylon 6/12. Nylon 11. It is a nylon 12-life polymer, a copolymer or a mixture containing two or more of these components.

The halogen flame retardant used in the present invention may be one that is normally used as a flame retardant for polyamide. Examples include decabromodiphenyl ether, hexabromobenzene, decabromo biphenyl, tetrabromobisphenol A, and derivatives thereof. Antimony trioxide is effective as a flame retardant aid. The amount of the halogen flame retardant added to the polyamide resin is adjusted depending on the desired degree of flammability, but is in the range of 3 to 3031. #! The amount of combustion aid added is 5 to 1001i relative to the halogen flame retardant.
t%.

The polyolefin used is (1) a polyolefin or olefin elastomer containing at least one tank selected from the group consisting of an alicyclic carboxylic acid having a cis-type double bond in the ring, or such *PWs conductor. Modified polyolefin or qualitative olenic elastomer with added compound (2) Ethylene, α-β-ethylenically unsaturated carboxylic acid and gold of unsaturated carboxylic acid
A polyolefin copolymer consisting of a salt, so-called iono"-4lt%, (81 ethylene, a-β-ethylenically unsaturated carboxylic acid.

These include a polyolefin-based comonomer consisting of gold MW of unsaturated carboxylic acid and alkylnisdale unsaturated carboxylic acid. Specifically, 9 examples are (11 as an alicyclic carboxylic acid having one cis-type double bond within one sea).

Cis-4-cyclohexene-1,2 dicarboxylic acid.

Endo-bicyclo-[2,2,1]-5-heptene-2
゜3Dicarbonate is preferable, and functional derivatives include acid anhydrides, esters, and acid amides thereof.

Acid halogens and metal salts, etc. (examples of 2+ olefins, ethylene, propylene, butene-1, hexene-1
, Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, hexamaric acid, monoalkyl esters, and examples of anhydride ions include sodium, zinc, etc. (8) Examples of unsaturated carboxylic acid alkyl esters as, methyl acrylate, ethyl acrylate, n-
Examples include propyl acrylate, inglovir acrylate, methyl methacrylate, and n-butyl methacrylate.

The amount of polyolefin added to the polyamide composition is 0.3
~6% by weight, more preferably 0.5~5wt%
It is. Q: If the amount is less than 3 wt%, a sufficient pluming prevention effect cannot be expected. In addition, 3O
Even if NIk% is added, the ability to prevent bleeding is sufficient with the addition of 6-fold polyolefin, and K added beyond this level is not as good.

In the present invention, the method of mixing the additives into the polyamide is not particularly limited, as long as the additives are uniformly dispersed. Specifically, additives may be added to pellets of polymerized polyamide, blended uniformly in a tumbler or Henshil mixer, and then pelletized and molded in an extruder.

The polyamide composition of the present invention includes inorganic powder, glass fiber,
1 candidate agent 1 dispersant, ? v-agent, plasticizer, pigment.

Dye 9, a foaming agent, etc. can be used in combination.

As stated above, the present invention is a flammable polyamide composition containing an organic halogen-based flammable agent and an oxidized oxide, and a specific violet polyolefin. The present invention provides a polyamide acid product.

Below, the present invention will be explained more clearly with examples. ,
For clarity, the present invention is not limited to these.

Incidentally, the combustion properties and pluming properties shown in the examples were evaluated by the following side foot method.

1. Flammability: Test specimens were prepared with a length of 5 inches, width of 1 part of 2 inches, thickness of 1 part of 32 inches, 1 part of 16 inches, and 1 part of 8 inches.
TER8 LABORATORIES)
Measured according to the method.

2. Pluming property...100φ, 0.2 thickness @
A test piece was prepared and placed in a constant temperature bath at 120°C for 500 hours.

Check the surface condition visually.

Examples 1 to 7 Part of nylon 6651, part of cMp*Hm 102 (difficult polyolefin manufactured by Tonen Petrochemical) 53Nlll.

Tecafromodiphenyl ether (DBDE) 20
N ionization, antimony trioxide (5b203) 10]
] i'iliM - 65 praises blended with a tumbler
The mixture was mixed using an extruder to ensure uniform dispersion, pelletized, and dried. The temperature of this pellet in the cylinder is 240℃#C
Each of the test pieces described above was molded using the set injection molding machine.

Further, test pieces were molded in the same manner by changing the addition ratio of the two compositions. The performance of the above test pieces was measured using the test method described above. The results are shown in Table-1.

Also, instead of CMPo/HA102, Kobolen■-Q
D580 (ionomer resin manufactured by Asahi Dow@).

Alternatively, a test piece was prepared in the same manner using Surlyn@-17O6 (ionomer resin manufactured by Debatabon, USA).
The performance of the aircraft was given an acid level. The results are shown in Table 1.

Comparative Examples 1 to 3 Parts of nylon 67011IL, 1 part of DBDE201 and 1 part of Bb20s 10N were blended in a tumbler and pelletized in the same machine as Example 1 to obtain the above test piece.

Performance was measured using the test method described in SaJ. Table the results.
Show IK.

Moreover, in addition to CMPo-HA102 of Example 1, Kaete and Sumirikisen Co., Ltd.-L211. (Polyethylene manufactured by Sumitomo Chemical) was used to obtain test pieces in the same manner, and the performance was measured.

The results are shown in Table-1.

Examples 7 to 9 Nylon 655m[-1 part, DBDE15]Lz part, Sbz□5151 part and glass fiber (10 μΦ, length 4-1 part) were blended in a tumbler and pelletized in the same manner as in Example 1. A test piece described in HIJ was obtained, and its performance was measured using the test method described above.

In addition, instead of glass fiber, wollastonite (mineral powder whose main component is calcium silicate) and Merck (mineral powder whose main component is magnesium silicate) were added in different amounts and pelletized into the same machine. - pieces were obtained and performance measured. The results are shown in Table-2.

Table 1 Table 2 However, in Table 2, ○ indicates no pluming, × indicates Blue 11-mink presence, and XX indicates significant pluming.

Claims (1)

[Claims] 1. Polyamide resin 20-80% by weight, polyolefin 0.3-6% by weight, halogen flame retardant 3-301% by weight,
111 A polyamide resin composition free from pluming, comprising 5 to 100 parts by weight of a flame retardant and a flame retardant. 2. The halogen flame retardant is an organic bromine compound. The polyamide resin composition according to claim 1, wherein the flame retardant aid is antimony trioxide. 3. The polyolefin is (1) a modified polyolefin or olefin yarn elastomer with at least one compound selected from the group consisting of alicyclic carboxylic acids having a cis-type double bond or functional derivatives thereof; Olefin-based elastom "f-, (
21 ethylene. Claim #V1 Item t! It is a polyolefin comonomer consisting of a/β-ethylenically unsaturated carboxylic acid and a gold JIi salt of the unsaturated carboxylic acid, a so-called ionomer resin! Koshiki's polyamide resin composition'a
A patent claim containing at least one of the following: ll,, (Jll x tyrene, a.l. - polyolefin comonomer consisting of an ethylenically unsaturated carboxylic acid, an unsaturated carboxylic acid metal salt, and an unsaturated carboxylic acid alkyl ester) The polyamide resin gauze according to item 1.