JPH01131274A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain a flame-retardant resin composition, consisting or nylon prepared by copolymerizing a nylon 46 component with a nylon 6 component having flame retardance imparted thereto and improved impact resistance without impairing original characteristics and capable of providing molded products having excellent appearance. CONSTITUTION:A flame retardant resin composition consisting of (A)preferably 60-97wt.% nylon prepared by copolymerizing 80-99wt.%, preferably 90-99wt.% nylon 46 component with 1-20wt.%, preferably 1-10wt.% nylon 6 component and having 1.5-5.5, preferably 2-4.5 intrinsic viscosity(measured by using 96% sulfuric acid in 1g/dl concentration at 25 deg.C) and (B)preferably 3-30wt.% flame retardant, e.g., brominated polystyrene expressed by formula I(x is 1-5, preferably 2-3; n is >=2), brominated polyphenylene ether expressed by formula II(n is >=2), brominated bisphenol type epoxy based polymer, brominated crosslinked aromatic polymer, etc.

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 has excellent heat resistance.

Due to its flame retardancy, it can be expected to be applied in various fields, but it 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.
It is not only higher than 220°C of nylon 66 and 260°C of nylon 66, but also higher than 285°C of polyphenylene sulfide. It also has a high degree of crystallinity, and its unreinforced heat distortion temperature (18.6 kg/c load) is 220°C, 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 (TLL) 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 to add a halide and a flame retardant aid typified by antimodium trioxide. 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 using nylon 46 copolymerized with ε-caprolactam in a flame retardant resin composition comprising 6 and a brominated polymer.

The inventors have discovered that the appearance of the resulting molded product is improved without impairing the inherent properties of nylon 46, and that the impact resistance represented by the Izot impact strength is surprisingly improved, leading to the present invention.

That is, the present invention provides a flame retardant resin composition comprising (A) nylon and (B) a flame retardant, in which the nylon (A) contains 40 to 49.5% by weight of diaminobutane and 40 to 40% by weight of adipic acid. 49.5% by weight and ε-caprolactam 1-2
The invention relates to a flame retardant resin composition characterized in that it is a nylon obtained by copolymerizing 0% by weight of brominated polystyrene, and the flame retardant is brominated polystyrene.

Brominated polyphenylene ether, brominated bisphenol type epoxy polymer or brominated crosslinked aromatic polymer.

The method for producing the copolymerized nylon used in the present invention is arbitrary. For example, Japanese Patent Publication No. 60-28843.

Japanese Patent Publication No. 60-8248, Japanese Patent Publication No. 58-83029
Methods disclosed in Japanese Patent Application Publication No. 61-43631 and the like.

In other words, a prepolymer with a small amount of cyclic terminal groups is first produced under specific conditions, and then this is solid-phase polymerized in a steam atmosphere to prepare a high molecular weight nylon copolymer, or a 2-pyrrolidone copolymer. It is particularly preferable to use polar compounds such as N-methylpyrrolidone and N-methylpyrrolidone obtained by heating in an organic solvent.

There is no particular restriction on the degree of polymerization of the copolymerized nylon used in the present invention, but the relative viscosity was determined using 96% sulfuric acid at a concentration of 1 g.
/di, preferably a copolymerized nylon in the range of 1.5 to 5.5, more preferably 2.0 to 4.5, when measured at 25°C. If a copolymerized nylon having a relative viscosity exceeding 5.5 is used, the fluidity of the composition will not only deteriorate, but also the mechanical and thermal properties will vary widely, which is not preferable. On the other hand, if the relative viscosity is lower than 1.5, the mechanical strength of the composition will be low.

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.

The brominated polystyrene used in the present invention is designated by 2 (I).

x: an integer of 1≦X≦5 n: an integer of 2 or more The bromine-containing bromine content of the brominated polystyrene is preferably 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 amount of brominated polystyrene added to the copolymerized nylon must be increased.

This is undesirable because it reduces the heat resistance of the resin composition. Moreover, when X exceeds 3, the compatibility between the brominated polystyrene and the copolymerized nylon decreases, 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 10 to 500.
Preferably.

The brominated polyphenylene ether used in the present invention is represented by Formula 1 (II).

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

1,500 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).

(I[I)

A group selected from an ether group, a thioether group, and a sulfone group n: an integer from pal to 4, an integer necessary to make the epoxy equivalent 2.500 or more.The epoxy equivalent here means the molecular weight per 11 epoxy groups.

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 becomes too large, n becomes too large and the compatibility with the resin to be blended decreases. ,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 is pulverized to about 0.1 to 30 μm and then blended into the resin to be made flame retardant.

The copolymerization ratio of the nylon component in the flame-retardant resin composition of the present invention is based on the total nylon (A).

40-49.5% by weight of diaminobutane and 4% by weight of adipic acid
0 to 49.5% by weight and 1 to 20% by weight of ε-caprolactam are preferred. In particular, diaminobutane 45-49.5
% by weight, 45-49.5% by weight of adipic acid and 1-10% by weight of ε-caprolactam. If the copolymerization ratio of ε-caprolactam is less than 1% by weight, the effect of improving 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 preferred.

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 the amount is less than 30% by weight, the effect of flame retardation is small, and if it is added more than 30% by weight, the inherent properties of the nylon resin will be impaired, which is disadvantageous.

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 antimony dioxide, antimony pentoxide, antimony tartrate, zinc borate, barium metaborate,
Examples include hydrated alumina, zirconium oxide, ammonium polyphosphate, and organic peroxides, among which antimony compounds, especially 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, plasticizers, lubricants, colorants, etc. may be added.

The fl flammable resin composition of the present invention is made into a powder, pellet, or other shape, and is press-molded using this product.

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

The present invention will be explained 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: 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 bubble, etc. The results are shown with the following symbols.

○: Good △: Fairly bad ×: Bad ■Izo impact strength: ASTM D-256, notched ■Bending test: ASTM D-790 ■Heat distortion temperature: ASTM D-648 Example 1.2 ε-caprolactam in Table 1 Nylon 46 (relative viscosity 3.6) copolymerized with the composition shown in Table 1, brominated polystyrene (manufactured by Nissan Ferro Organic Chemical ■, Pyrocheck 68PB, bromine content 66% by weight) and antimony trioxide are blended in the composition shown in Table 1. did. 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. On this occasion,
A combustion piece 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 with relative viscosity 3.5 and Pyrocheck 68P
B and antimony trioxide were blended in the composition shown in Table 1, treated in the same manner as in Example 1 to produce pellets and test pieces, and evaluated. The results are shown in Table 1.

Example 3.4 Instead of the brominated polystyrene used in Example 1, brominated polyphenylene ether (PO-
Pellets and test pieces were prepared and evaluated in the same manner as in Example 1 except that 64P (bromine content: 62% by weight) was used. The results are shown in Table 1.

Comparative Example 3 Nylon 46 used in Comparative Example 2, PO-64P, and antimony trioxide were blended in the composition shown in Table 1, and treated in the same manner as in Example 1 to produce pellets and test pieces, and evaluated. . The results are shown in Table 1.

Examples 5 and 6 Instead of the brominated polystyrene used in Example 1, a brominated bisphenol type epoxy polymer (manufactured by Matsunaga Kagaku ■,
Pellets and test pieces were prepared and evaluated in the same manner as in Example 1 except that EBR-101 (bromine content: 52% by weight) was used. The results are shown in Table 1.

Comparative Example 4 Nylon 46 used in Comparative Example 2, EBR-101, and antimony trioxide were blended in the composition shown in Table 1, and treated in the same manner as in Example 1 to produce pellets and test pieces, and evaluated. . The results are shown in Table 1.

Examples 7 and 8 Instead of the brominated polystyrene used in Example 1, a brominated crosslinked aromatic polymer (manufactured by Matsunaga Kagaku ■, EBR-370P) was used.
Pellets and test pieces were prepared and evaluated in the same manner as in Example 1 except that K, bromine content 68 weight per particle size 10 to 30 μm) were used.

The results are shown in Table 1.

Comparative Example 5 Nylon 46 used in Comparative Example 2, EBR-370PK, and antimony dioxide were blended in the composition shown in Table 1, and treated in the same manner as in Example 1 to produce pellets and test pieces, and evaluated. . The results are shown in Table 1.

(Effects of the invention) From these, the flame retardant resin composition consisting of nylon 46 copolymerized with ε-caprolactam and a flame retardant is imparted with flame retardancy without impairing the characteristics of nylon 46.
It can be seen that the impact resistance is improved and the appearance of the molded product is improved.

Patent applicant: Unitika Co., Ltd. Draft by Teki Watafu (spontaneous) March 9, 1986

Claims (2)

[Claims] (1) In a flame retardant resin composition consisting of (A) nylon and (B) a flame retardant, the nylon (A) contains 40 to 49.5% by weight of diaminobutane and 40 to 49% by weight of adipic acid.
．． A flame-retardant resin composition characterized in that it is nylon obtained by copolymerizing 5% by weight of ε-caprolactam and 1 to 20% by weight of ε-caprolactam. (2) The flame retardant 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. Flammable resin composition.