JPH01146953A - Flame-retarding resin composition - Google Patents

Abstract

PURPOSE:To obtain a flame-retarding resin composition which can give a molding improved in appearance without detriment to the inherent properties of nylon 46, by adding a flame retardant to a mixture of nylon 46 with other aliphatic nylons. CONSTITUTION:This flame-retarding resin composition comprises a nylon (A) and a flame retardant (B), wherein a mixture of 80-99wt.% nylon 46 (C) with 1-20wt.% other aliphatic nylons (D) is used as said nylon (A). As said nylon (D), nylon 6 and nylon 66 are desirable. Examples of said flame retardant (B) include brominated polystyrene, brominated polyphenylene ether, brominated bisphenol epoxy polymers and brominated crosslinked aromatic polymers.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a flame retardant resin composition, and more particularly to a flame retardant nylon 46 resin composition.

The flame-retardant resin composition of the present invention can be expected to be applied in various fields due to its excellent heat resistance and flame retardancy, and is particularly suitable for parts in the electrical and electronic fields.

(Conventional technology) Nylon 46 is an already known polyamide.

For example, Japanese Patent Publication No. 60-8248 and Japanese Patent Publication No. 60-8248
JP-A-28843 discloses a method for producing nylon 46. It is also known that nylon 46 has excellent properties as an engineering plastic, particularly excellent heat resistance.

For example, its melting point is 295°C, which is similar to nylon 6.
220°C, which is not only higher than the 260°C of nylon 66, but also the 285'C of polyphenylene sulfide.
It even exceeds that. The degree of crystallinity is also high, and the non-reinforced heat distortion temperature (18,6Kg/c+fl load) is 220°
C, which is the highest value among engineering plastics.

It also has excellent sliding properties, fatigue resistance, and rigidity.

However, flame retardancy is not necessarily sufficient.

Particularly in applications in the electrical and electronic fields, high flame retardance is required, meeting, for example, American Underwriters Laboratories (UL) standards.

Nylon 46 as it is has a relatively low level of V-2, and cannot be used as it is for applications in the electrical and electronic fields. Methods of increasing the flame retardancy of polyamides are known. Among these, it is common to add a halide as a flame retardant, or a flame retardant aid typified by a halide Of and antimony dioxide.

Regarding nylon 46, a method of adding a brominated polymer is disclosed in JP-A-61-188463.

(Problems to be Solved by the Invention) However, when nylon 46 and a brominated polymer are blended, there is a drawback that the appearance of the molded product is poor.

(Means and effects for solving the problem) As a result of intensive research to develop a flame-retardant nylon 46 resin composition with improved appearance of molded products, the present inventors found that nylon 46
By blending other aliphatic nylons with nylon 46 in a flame-retardant resin composition consisting of nylon 46 and a brominated polymer, the appearance of the resulting molded product is improved without impairing the inherent properties of nylon 46. The present invention was based on this discovery.

That is, the present invention provides a flame retardant resin composition comprising (A) nylon and (B) an RLC flame retardant, in which the nylon (A) is composed of (C) 4680 to 99% by weight of nylon and (D
) A flame-retardant nylon resin composition characterized in that it is a mixture with 1 to 20% by weight of other aliphatic nylons.

Nylon 46 used in the present invention uses adipic acid or a functional derivative thereof as an acid component.

It is a linear polymeric polyamide obtained by a condensation reaction using tetramethylene diamine or its functional derivative as an amine component.

The method for producing nylon 46 used in the present invention is arbitrary. For example, Special Publication No. 60-28843, Special Publication No. Sho G
0-8248, JP-A-58-83029, JP-A-61-43631, etc., in other words, a prepolymer having a small amount of cyclic end groups is first produced under specific conditions, and then Particularly useful are those obtained by solid phase polymerization in a steam atmosphere to prepare high molecular weight nylon 46, or those obtained by heating in a polar organic solvent such as 2-pyrrolidone or N-methylpyrrolidone. preferable.

Although there is no particular restriction on the degree of polymerization of nylon 46 used in the present invention, the relative viscosity was determined using 96% sulfuric acid at a concentration of 1 g/
Nylon 46 having a dfi in the range of 1.5 to 5.5, and even 2.0 to 4.5, when measured at 25°C, is preferred. When nylon 46 having a relative viscosity exceeding 5.5 is used, not only the fluidity of the composition becomes poor.

This is not preferable because it increases the variation in mechanical and thermal properties. On the other hand, a relative viscosity lower than 1.5 has the disadvantage that the mechanical strength of the composition decreases.

Other aliphatic nylons used in the present invention include polymers obtained by condensing aliphatic dicarboxylic acids and aliphatic diamines, and polymers obtained by condensing aliphatic lactams and corresponding aliphatic aminocarboxylic acids. etc. can be given. These other aliphatic nylons may be used alone.

Further, mixtures and copolymers thereof may also be used.

Among these aliphatic nylons, it is preferable that the ratio K of the number of amide bonds (-NHCO-) to methylene groups (-C1,-) in one molecule is 11 or less, that is, the latter. Furthermore, 4≦ and ≦8 are preferable. If K exceeds 11, the compatibility with nylon 46 decreases, which is not preferable. Preferred nylons include nylon 6 and nylon 66.

The flame retardant used in the present invention is a brominated polymer that exhibits a substantial flame retardant effect when blended with nylon, specifically brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy Examples include polymers, brominated crosslinked aromatic polymers, and the like.

Brominated polystyrene used in the present invention is represented by formula 2 (1).

n: an integer of 2 or more The brominated polystyrene preferably has a nitrogen content of 55 to 75% by weight. In terms of X, 2 to 3 are preferable. If X is less than 2, the flame retardant effect will be reduced, so the blending amount of brominated polystyrene relative to nylon 46 must be increased. This is undesirable because it reduces the heat resistance of the resin composition. Moreover, if X exceeds 3, the compatibility between brominated polystyrene and nylon 46 will decrease, which is not preferable.

The molecular weight of such brominated polystyrene is 3,000 to 20
0,000 is preferred. In terms of n, it is lO ~ 500
Preferably.

The brominated polyphenylene ether used in the present invention is represented by Formula 7 (II).

n: integer greater than or equal to 2 The molecular weight of such brominated polyphenylene ether is:

L 500 to 25,000 is preferred. In terms of n, 5 to 100 is preferable.

The brominated bisphenol-type epoxy polymer used in the present invention is represented by general formula (III).

(III) X: Bromine atom Y: Group selected from hydrogen, glycidyl group, alkyl group, phenyl group, benzyl group, and derivatives thereof R: Direct bond, alkylene group, carbonyl group.

Group selected from ether group, thioether group, and sulfone group n: Epoxy Integer necessary to make 592,500 or more p: An integer from 1 to 4 Here, epoxy equivalent means the amount per molecule of epoxy group, i.e. .

represents.

-C In formula (III), the epoxy equivalent is 2,500
If the epoxy equivalent is smaller, that is, if the amount of epoxy groups in the molecule increases, gels may occur during the production of the resin composition of the present invention, making it difficult to operate. desirable. Furthermore, if the epoxy equivalent is too large, n becomes too large and the compatibility with the resin to be blended decreases. 3,500 to 30,000 is preferred.

The brominated crosslinked aromatic polymer used in the present invention is.

It has a three-dimensional structure, is substantially insoluble and infusible, and has a bromine content of 30 to 70% by weight.

Among such brominated crosslinked aromatic polymers, a brominated crosslinked aromatic polymer obtained by copolymerization of polystyrene and divinylbenzene is preferred.

Such a brominated crosslinked aromatic polymer has a molecular weight of 0.1 to 30 Jim.
After being crushed to a certain degree, it is blended into the resin that is intended to be flame retardant.

The mixing ratio of the nylon components in the flame-retardant resin composition of the present invention is 4680 to 99% by weight of nylon (C) to the entire nylon (A), and 1 to 20% by weight of other aliphatic nylon (D). % by weight is preferred. Especially (C) nylon 4
690-99% by weight and other aliphatic nylon 1 of (D)
~10% is preferred. If the amount of other aliphatic/neurons (D) is less than 1% by weight, the reforming effect on the appearance of the molded product will be small, and if it exceeds 20% by weight, the heat resistance and mechanical properties of the resin composition will deteriorate, which is not preferable.

The blending ratio of nylon and flame retardant in the flame retardant resin composition of the present invention can be selected from a wide range depending on the purpose of use, but if the balance between flame retardance, mechanical properties and heat resistance stability is taken into consideration, the overall against.

The amount of nylon (A) is preferably 60 to 97% by weight, and the amount of flame retardant (B) is preferably 3 to 30% by weight. Addition amount of flame retardant is 3
If it is less than 30% by weight, the effect of flame retardation is small, and if it is added more than 30% by weight, it is disadvantageous because it will actually impair the inherent properties of the nylon resin.

A flame retardant aid may be added to the flame retardant resin composition of the present invention, if necessary. As flame retardant aids, antimony compounds such as andimony trioxide, antimony pentoxide, and antimony tartrate, zinc borate, barium metaborate,
Examples include hydrated alumina, zirconium oxide, ammonium polyphosphate, and aqueous peroxide, among which antimony compounds, particularly antimony trioxide, are preferred.

The flame retardant resin composition of the present invention may optionally include glass fiber, carbon fiber, aramid fiber, calcium carbonate, talc, mica, potassium titanate, boron nitride, inorganic silicate, silica gel, hydrotalcite, Additives such as reinforcing fillers such as cristobalite, clay, heat stabilizers, light stabilizers, antioxidants, desensitizers, lubricants, colorants, etc. may be added.

The flame-retardant resin composition of the present invention is made into powder, solid, 1, and other shapes, and is press-molded using this composition.

Various useful products can be made using commonly known plastic molding methods such as injection molding and extrusion molding.

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited thereto.

(Example) Physical property measurements described in Examples and Comparative Examples were performed according to the following method.

■Flame retardancy test 2 Compliant with UL-94 ■Appearance of molded product: A test piece was injection molded, and the surface of the molded product was observed for rough skin, one color of bubbles, etc. The results are shown with the following symbols.

○: Good Δ: Fairly bad ×: Bad ■Izo impact strength: ASTM D-256, notched ■Bending test: ASTM D-790 ■Heat distortion temperature: ASTM D-648 Examples 1 to 6 Relative viscosity of 3.5 Nylon 46. Nylon 6 (Unideka Nylon 6 A1030BRF) or Nylon 66 (
Maranyl A146), brominated polystyrene (manufactured by Nissan Ferro Organic Chemical 91, Pyrocheck 68PB, bromine content 66% by weight), and antimony trioxide were blended in the composition shown in Table 1. This blend was extruded at 290°C using a twin-screw extruder to obtain pellets.

Using this pellet, injection molding was performed at a cylinder temperature of 300°C, an injection time of 6 seconds, and a cooling time of 6 seconds.
Inch and 1732 inch specimens were obtained.

At this time, a combustion single-sided mold specified by UL94 was used.

A flammability test was conducted using these test pieces. The results are shown in Table 1.

Separately, a test piece with a thickness of 178 inches was injection molded under the same conditions and subjected to a physical property test. The results are shown in Table 1.

Comparative Example 1 Nylon 46 used in Example 1 was treated in the same manner as in Example 1 without adding flame retardant and antimony trioxide to produce pellets and test pieces, and a flammability test was conducted. The results are shown in Table 1.

Comparative Example 2 Nylon 46 and Pyrodiec 68P with relative viscosity 3.5
B and antimony trioxide were blended in the composition shown in Table 1 and treated in the same manner as in Example 1 to prepare Perene I and test pieces, and evaluations were performed. The results are shown in Table 1.

Examples 7 to 9 Brominated polyphenylene ether (PO-
Pellets 1- and test pieces were prepared and evaluated in the same manner as in Example 1 except that 64P (bromine content: 62 weight) was used. The results are shown in Table 2.

Comparative Example 3 Nylon 46 with a relative viscosity of 3.5, PO-64P, and antimony trioxide were blended in the composition shown in Table 2, and treated in the same manner as in Example 1 to produce pellets and test pieces.

We conducted an evaluation. The results are shown in Table 2.

Examples 10 to 12 Instead of the brominated polystyrene used in Example 1, a brominated bisphenol type epoxy polymer (manufactured by Matsunaga Kagaku ■,
Pereso 1~ and test pieces were prepared and evaluated in the same manner as in Example 1 except that EBR-101 (bromine content: 52 weight) was used. The results are shown in Table 2.

Ratio 1 Example 4 Nylon 46 with a relative viscosity of 3.5, EIIR-101 and antimony trioxide 7 were blended in the composition shown in Table 2, and Example 1
Pellets and test pieces were prepared and evaluated in the same manner as above. The results are shown in Table 2.

Examples 13 to 15 Instead of the brominated polystyrene used in Example 1, a brominated crosslinked aromatic polymer (manufactured by Matsunaga Chemical ■, IEBI?-37) was used.
0PK, bromine content 68% by weight, particle size 1o~30μm)
Pellets and test pieces were prepared and evaluated in the same manner as in Example 1, except that .

The results are shown in Table 2.

Comparative Example 5 Nylon 46 and IEBR-370FK with relative viscosity of 3.5
and antimony dioxide in the composition shown in Table 2, and processed in the same manner as in Example 1 to prepare pellets and test pieces.
We conducted an evaluation. The results are shown in Table 2.

(Effect of the invention) From these, nylon 4 blended with other aliphatic nylons
The flame-retardant resin composition consisting of 6 and a flame retardant is imparted with flame retardancy without impairing the inherent properties of nylon 46, particularly heat resistance and mechanical properties, and has an improved appearance of the molded product. I understand.

Patent applicant: Unitika Co., Ltd.

Claims (3)

[Claims] (1) In a flame retardant resin composition consisting of (A) nylon and (B) a flame retardant, (A) nylon is (C) 80 to 99% by weight of nylon 46 and (D) other fat. A flame-retardant nylon resin composition characterized in that it is a mixture with 1 to 20% by weight of a group nylon. (2) The resin according to claim 1, wherein the flame retardant (B) is brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, or brominated crosslinked aromatic polymer. Composition. (3) The resin composition according to claim 1, wherein the other aliphatic nylon (D) is nylon 6 or nylon 66.