JPS63223060A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition outstanding in heat resistance, flame retardancy and thermal stability, suitable for parts in electrical and electronic industries, etc., by blending nylon 46, an aromatic halide and hydrotalcite in specified amounts, respectively. CONSTITUTION:The objective composition can be obtained by blending (A) 90-40wt.% of nylon 46 with a relative viscosity 2-6, (B) 40-5wt.% of an aromatic halide (e.g., hexabromobenzene) and (C) 40-0.01wt.% of a hydrotalcite of formula (M is Mg, Mn, Fe, etc.; M' is Al, Fe, Cr, etc.; A is OH, F, etc.; m is positive number; 0<x<=0.5; n is number of anion value of A).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a stabilized flame-retardant resin composition, more specifically a flame-retardant nylon 46 resin composition stabilized by hydrotalcites. It is related to.

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

(Prior Art) Nylon 46 is already known as boria≧do. for example,
JP-A-56-149429 discloses a method for manufacturing nylon 46 products. 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℃, which is 20℃ for nylon 60.
The temperature is not only higher than that of nylon 660 at 260°C, but also higher than that of polyphenylene sulfide at 285°C. The degree of crystallinity is also high.

Non-reinforced heat distortion temperature (18,6kf/d load) is 220"
C, which is the highest value among engineering plastics. It also has excellent sliding properties, fatigue resistance, and rigidity.

However, the Sa flammability is not necessarily sufficient. Particularly in applications in the electrical and electronic fields, high flame retardance is required, such as meeting the American Underwriters Laboratories (UL) standards.

Nylon 46 as it is has a relatively low level of HB.

Methods of increasing the flame retardancy of polyamides are known.

Among them, the presence of halides as flame retardants,
Alternatively, it is common to include a halide and a flame retardant aid represented by antimony trioxide. Regarding nylon 46, JP-A-61-188463 discloses a method of making a brominated compound exist.

However, the heat stability of halides used as flame retardants, especially during hot melt molding processing, is not always sufficient, especially in cases such as nylon 46, which has a high melting point and therefore requires a high heat melting temperature. However, in many cases, only resin compositions that were subject to thermal deterioration, discolored, or had deteriorated physical properties were obtained.

(Problems to be Solved by the Present Invention) In view of the above circumstances, the present invention provides a flame retardant resin composition with improved heat resistance stability, more specifically, an S-flammable nylon 46 resin with improved heat resistance stability. The purpose is to obtain a composition.

(Means and effects for solving the problem) As a result of intensive research for this purpose, the present inventors found that by making hydrotalcites exist in a resin composition consisting of nylon 46 and an aromatic norogenide, , 'H〈We have found that the heat resistance stability is significantly improved without impairing its physical properties, especially its flame retardancy, heat resistance (1) bending strength, and mechanical properties such as Izot impact dust resistance (2) The present invention has been reached.

That is, the present invention is characterized in that it consists of (A) nylon 4690 to 40 prk%, (B) aromatic halide 40 to 5 prk%, and (0 hydride a talside 40 to 0.0 IMM%). This is a stabilized flame-retardant resin composition.

Nylon 46 used in the present invention includes polytetramethylene adipamide obtained from tetramethylene diamine and adipic acid, a copolyamide having tetramethylene adipamide units as a main constituent unit, and a mixed polyamide. The copolymerization component or mixed component is not particularly limited, and known amide-forming components can be used. Representative examples of copolymerized components include 6-aminocaproic acid, 11
-Amino acids such as aminoundecanoic acid, 12-aminododecanoic acid, para-aminomethylbenzoic acid, ε-caprolactam, ω-lauryl lactam, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine? 2.2.4-72.4.4-Trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1.3-bis(aminomethyl)cyclohexane,
1.4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-)limethylcyclohexane, bis(3-methyl-4-aminocyclohexyl)methane, 2.2-bis( Diamines such as 4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, aminoethylpiperazine and adipic acid, speric acid, azelaic acid, sebacic acid, dodeca/diacid,
Terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylinphthalic acid,
Examples include dicarboxylic acids such as 5-sodium sulfoiphthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid.

Further, examples of the mixed polyamide include polyamides made of these components.

The method of applying nylon 46 used in the present invention is arbitrary. For example, JP-A-56-149430.

JP-A-56-149431, JP-A-58-830
29 and JP-A No. 61-43631, etc., first, a prepolymer with a small amount of cyclic terminal groups is produced under specific conditions, and then this is solid-phase polymerized in a steam atmosphere. It is particularly preferable to use one obtained by a method of preparing high-viscosity nylon 46 or one obtained by a method of heating in a polar organic solvent such as 2-pyrrolidone or N-methylpyrrolidone. There are no restrictions on the degree of polymerization of nylon 460.

Nylon 46, which typically has a relative viscosity within the range of 2.0 to 6.0, can be arbitrarily selected.

What is the aromatic halide used in the present invention?

It contains an aromatic ring in its molecule and some or all of the hydrogen atoms in the aromatic ring are replaced with halogen atoms, and exhibits a substantial flame retardant effect.

Moreover, two or more kinds of these flame retardants can also be used simultaneously.

Specific examples of such aromatic halides include:

Hexabromobenzene, hexachlorobenzene.

pentabromotoluene, pentabromoethylbenzene,
Thecabromodiphenyl ether, decabromodiphenyl sulfone, decabromodiphenyl.

Octabromodiphenyl, 2,2-(4-hydroxy-
3,5-cyfuromophenyl)furon(n), 2,2-4-
Examples include, but are not limited to, hydroxy-3,5-dichlorophenyl)furopane, brominated phenoxy resin, brominated polycarbonate, brominated polyphenylene ether, and a condensate of tetrabisphenol A and glycidyl ether.

The hydrotalnides used in the present invention have the general formula (
1), M M (OH)2 A ”/n - mH20 (
1) 1-4K (however, 9M is Mg, Mn, Fe, Co,
2M' selected from the group consisting of Ni, Cu and Zn
is selected from the group consisting of At, Fe, Cr*Co and In, and A is OH, F.

CI, Br t NO3, CO31SO4, Fe(
CN) 6 and CH3COO from the Naro group.

m is a positive number.

! is 0 (a number in the range z≦0.5, n is equal to the anion valence of A), and natural and synthetic ones are used.

In the present invention, hydrotalcites are surface-treated with a higher fatty acid alkali metal salt such as stearic acid or oleic acid alkali metal salt, or an organic sulfonic acid alkali metal salt such as dodecylbenzenesulfonic acid alkali metal salt. It can be used as

The blending ratio of each component in the flame retardant resin composition of the present invention can be selected from a wide range depending on the purpose of use, but f
a) Considering the balance of flammability, mechanical properties, and heat resistance stability, (A) Nylon 46 is 90 to 40% by weight, CB)
Aromatic halides preferably have a weight of 40 to 5, and hydrotalcites preferably have a weight of 40 to 0.01.

The resin composition of the present invention may optionally contain a combustion aid 9 such as antimony trioxide, zinc borate, barium metaborate, hydrated alumina, zirconium oxide, ammonium polyphosphate, organic)(-oxide, etc.). Also, if necessary, glass fiber, inorganic silicate, silica obtained by evaporation of silica gel, quartz, silica gel, carbon fiber, cristobalite, asbestos, clay.

Reinforcing fillers such as Merck and the like may also be included.

The resin composition of the present invention can be made into powder, chips, or other shapes, and can be used to make various useful products by press molding, injection molding, or extrusion molding by commonly known plastic molding methods. .

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

Comparative example 1. Examples 1-4 Nylon 46 with a relative viscosity of 4.0, decabromodiphenyl ether, and noidorotalside Mg 0.70 AI
O,30(OH)2 (CO3) 0.150.57
H20 was blended and mixed according to the composition shown in Table 1. Next, each mixture was dried under reduced pressure at 0.1 Torr at 110° C. for 8 hours, and then extruded at 300° C. by twin-screw extrusion to obtain pellets. Using this pellet, injection molding was performed at a cylinder temperature of 300''C and a body temperature of 315℃ to obtain a test piece.The molding cycle was 90 seconds in each case.Using the obtained test piece, 1/8 inch The Izot impact strength with thick notches and the appearance of the test pieces were observed.The results are also listed in Table-1.

As is clear from Table 1, in Comparative Example 1, the molding at 300° C. had already turned brown, and the Izot impact strength had also decreased. This deterioration behavior during molding is particularly remarkable when molded at 315°C. On the other hand, in Examples containing hydrotalcite, these deterioration behaviors were not observed, and the deterioration prevention effect was remarkable. When the flame retardance was evaluated using the test pieces of Comparative Example 1 and Examples 1 to 4, it was found to be UL94V-2 at 1/16 inch thickness.

Comparative example 2. Examples 5 to 9 Nylon 46 with a relative viscosity of 3,800, brominated polyphenylene ether (bromine 75 wt%), and several types of hydrotalcite were blended and mixed in the composition shown in Table 2. Next.

Each mixture was dried at 110° C. for 8 hours under reduced pressure at 0.1 Torr, and then extruded at 300° C. using a twin-screw extruder to obtain pellets. Injection molding is performed using this pellet,
A test piece was obtained, and a UL flame retardant test was performed and the appearance of the molded product was observed. The cylinder temperature during injection molding was carried out at two levels: 300°C and 315°C. The results are shown in Table 2.

In Comparative Example 2, which does not contain hydrotalcite, the deterioration during injection and molding is significant, whereas in the Examples, the deterioration prevention effect is extremely remarkable.

(Effects of the invention) By further mixing hydrotalcites into the combustibility-improving composition containing nylon 46 and aromatic halides, the molded product becomes white and the Izot impact strength is greatly improved, making it an excellent engineering material. It has great industrial advantages as a plastic.

Patent Applicant: Unitika Co., Ltd. Procedural Report 1 Issue) July 6, 1985 1, Indication of Case Patent Application No. 1982-57612 2, Name of Invention Flame Retardant Resin Composition 3, Person Making Amendment Relationship to the incident Patent applicant address 1-50 Higashihonmachi, Amagasaki City, Hyogo Prefecture Name (45
0) Yu-Tei Riki Co., Ltd. 541 Address 4-68 Kitakyutabe-cho, Kii-ku, Osaka Name Yu-tei
Teiriki Co., Ltd. Patent Department 5, Contents of Amendment (1) "Tetrabisphenol A" on page 7, lines 11-12 of the specification is corrected to "brominated polystyrene, tetrabromobisphenol A."

Claims (1)

[Claims] A flame-retardant resin comprising (A) 90-40% by weight of nylon 46, (B) 40-5% by weight of aromatic halides, and (C) 40-0.01% by weight of hydrotalsides. Composition.