JPH04202361A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition, excellent in mechanical properties, heat resistance, etc., remarkably improved in flame retardance and suitable in the electrical, electronic and mechanical fields, etc., by blending nylon 46 with a polyphenylene ether, a high-molecular weight halogenated flame retardant, etc., in specific amounts. CONSTITUTION:A resin composition is obtained by blending (A) 15-97wt.%, preferably 20-85wt.% nylon 46 with (B) 1-70wt.%, preferably 10-60wt.% polyphenylene ether [e.g. poly(2,6-dimethyl-1,4-phenylene) ether], (C) 1-40wt.%, preferably 3-40wt.% high-molecular weight halogenated flame retardant (e.g. a halogenated phenoxy resin) and (D) 1-40wt.%, preferably 3-30wt.% hydrotalcite.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention has excellent mechanical properties, heat resistance, chemical resistance, and flame retardancy, and changes in dimensions and physical properties due to water absorption are greatly suppressed. This invention relates to a novel resin composition that has excellent thermal stability during molding. For more details (A)
This invention relates to a resin composition comprising nylon 46, (B) polyarylate, (C) a high molecular weight/S halogenated non-flame retardant, and (D) hydrotalcite.

The resin composition of the present invention can be molded using various molding methods such as injection molding, extrusion molding, and blow molding, and due to its excellent properties, it is expected to be used in a wide range of fields such as electrical/electronic, machinery, and automobiles. It is something that

(Prior Art) Nylon 46, which is made of tetramethylene diamine, adipic acid, and functional derivatives thereof, is a well-known polyamide. For example, Japanese Patent Publications No. 60-8248 and Japanese Patent Publication No. 60-28843 disclose methods for manufacturing nylon 46 products. Nylon 46 is also known to have exceptional properties as an engineering plastic, particularly excellent heat resistance. For example, its melting point is 295°C, which is not only higher than the 260°C of nylon 66, but also the 28°C of polyphenylene sulfide.
It exceeds even 5°C. High crystallinity and crystallization rate, heat distortion temperature (4.5Kg/cm2 load) is 280
°C or higher, the highest value among engineering plastics. In addition, mechanical strength such as tensile strength and bending strength,
It also has excellent sliding properties and fatigue resistance.

However, nylon 46 has a higher concentration of amide groups than nylon 6 and nylon 66, so it has a problem of high water absorption. As a result, dimensional changes and physical property changes due to water absorption are large, and opportunities for application in a wide range of fields such as automobiles, electrical/electronic, and machinery have been limited.

As a method to improve this drawback, JP-A-62-15616
Publication No. 1 discloses a method of blending other polyamides having a melting point of 200°C or higher. Also, JP-A-60-24
No. 8775 discloses a resin composition of nylon 46 and nylon 12. However, in these cases, it was not possible to achieve a sufficient reduction in water absorption, and there was a problem in that the heat resistance, which is the most important feature of nylon 46, was significantly reduced, making it less valuable as a molding material.

Furthermore, when producing such resin compositions, the so-called balance effect often occurs, making compounding difficult. Further, JP-A-62-185724 discloses blending a styrene polymer modified with a functional group. In this case, the water absorption rate decreases, thereby suppressing dimensional changes, but nylon 4
The toughness, which is an excellent feature of No. 6, is greatly reduced, and the mechanical properties are also significantly reduced. Further, JP-A-64-318'66 discloses a resin composition of nylon 46, polyester, and polyolefin modified with a functional group.

In such a resin composition, the water absorption rate is lowered, thereby suppressing dimensional changes, but in this case as well, the heat resistance, which is the most important feature of nylon 46, is significantly lowered.

As mentioned above, many attempts have been made to reduce dimensional changes and changes in physical properties due to water absorption in nylon 46, but the effects are not sufficient, or the mechanical properties, heat resistance, or toughness, which are the characteristics of nylon 46, are significantly reduced. There were some problems.

Therefore, there has been a demand in a wide range of fields for a molding material that can greatly suppress changes in dimensions and physical properties due to water absorption without impairing the excellent mechanical properties, heat resistance, chemical resistance, etc. of nylon 46.

A proposal to meet such requests is JP-A-2-202.
No. 947 is known. Here, a resin composition comprising nylon 46, polyphenylene ether, and rubber is proposed.

However, depending on the use of such resin compositions, it has become necessary to further improve flame retardancy. In particular, molded products in the electrical and electronic fields have become increasingly required to be more flame retardant due to heightened safety regulations. However, since the resin composition made of nylon 46 and polyphenylene ether has excellent heat resistance, it requires a correspondingly high molding temperature, and even if a high molecular weight halogenated flame retardant, which is generally said to have high heat resistance, is added. Decomposition and deterioration may occur during molding.
The original excellent properties of such resin compositions were often impaired. Therefore, there was a strong need for a solution.

(Problems to be Solved by the Invention) The problems to be solved by the present invention are to improve the mechanical properties, heat resistance, and
The objective is to improve flame retardancy while maintaining chemical resistance and the characteristics of less deterioration of dimensions and physical properties due to water absorption.

(Means for Solving the Problems) As a result of intensive research to solve the above problems, the present inventors found that (A) nylon 46 is 15 to 97% by weight and (B
) A resin composition comprising 1 to 70% by weight of polyphenylene ether, (C) 1 to 40% by weight of a high molecular weight halogenated flame retardant, and (D) 1 to 40% by weight of hydrotalcite is an object of the present invention. The present invention has been achieved by finding that the following requirements are satisfied.

The resin composition of the present invention contains a high molecular weight halogenated flame retardant, and despite the high molding temperature, there is almost no decomposition or deterioration during molding, and due to the combination of hydrotalcite, nylon 46 and polyphenylene ether It is quite surprising that the excellent properties of the resin composition consisting of

The nylon 46 used in the present invention is a polyamide whose main constituent units are polyamides composed of tetramethylene diamine, adipic acid, and functional derivatives thereof. It may also be replaced with other copolymer components.

The copolymerization component is not particularly limited, and known amide and l-forming components can be used.

Representative examples of copolymerized components include 6-aminocaproic acid, 1
Amino acids such as 1-aminoundecanoic acid, 12-aminododecanoic acid, para-aminomethylbenzoic acid, lactams such as ε-caprolactam and ω-lauryllactam, hexamethylenediamine, undecamethylenediamine, F-decamethylenediamine, 2,2. 4-/2, 4.4- 1-
Dimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, baraxylylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane,
-Amino-3-aminomethyl-3.5.5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2.2-his(4-aminocyclohexane) diamines such as xyl)propane, bis(aminopropyl)piperazine, bis(aminoethyl)piperazine,
sheric acid, azelaic acid, sebacic acid, dodecanoic acid,
Terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid,
Examples include dicarboxylic acids such as 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid.

The method for producing nylon 46 used in the present invention is arbitrary. For example, Japanese Patent Publication No. 6O-2B843, Japanese Patent Publication No. 6
0-8248, the method disclosed in JP-A-58-83029 and JP-A-61-43631,
In other words, first, a prepolymer with a small amount of cyclic end groups is produced under specific conditions, and then solid-phase polymerized in a steam atmosphere to prepare high-viscosity nylon 46, or 2-pyrrolidone or N-methyl Those obtained by heating in a polar organic solvent such as pyrrolidone can be used.

There is no particular restriction on the degree of polymerization of nylon 46 used in the present invention, but sulfuric acid with a relative viscosity of 96% is used, and a concentration of 1
g/dl, 1.5-5.5 when measured at 25°C
, more preferably nylon 46 in the range of 2.0 to 4.5. If the relative viscosity exceeds 5.5, excessive heat history is required when heating and melting it, which accelerates deterioration and increases variations in mechanical and thermal properties, which is not preferable. If the relative viscosity is lower than 1.5, the mechanical strength of the composition will be low.

The polyphenylene ether used in the present invention is known per se, for example, the general formula (where R, , R2, R3
and R4 is hydrogen, halogen, an alkyl group, an alkoxy group, or at least 2 atoms between the halogen atom and the phenyl ring.
represents a monovalent substituent selected from haloalkyl and haloalkoxy groups having 5 carbon atoms and containing no tertiary α-carbon, where n is an integer representing the degree of polymerization. ) is a general term for polymers represented by the above general formula, and may be a single type of polymer or a mixture of two or more types of polymers represented by the above general formula. It may also be a copolymer.

In preferred embodiments, R1 and R2 have 1 to 4 carbon atoms.
is an alkyl group, and R3 and R4 are hydrogen or an alkyl group having 1 to 4 carbon atoms.

For example, poly(2,6-cymethyl-1,4-phenylene)
Ether, poly(2-diethyl-1,4-phenylene)
Ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-broby-1,4-phenylene) ether, poly(2,6-diprobyl-L4-phenylene) ether, etc. can be mentioned. Particularly preferred P and PE are poly(2,6-dimethyl-1.4-phenylene) ether.

Examples of the polyphenylene ether copolymer include copolymers containing a portion of alkyl trisubstituted phenol, such as 2,3.6-)limethylphenol, in the polyphenylene ether repeating unit. It may also be a copolymer in which a styrene compound is grafted onto these polyphenylene ethers. Styrene compound grafted polyphenylene ether is a copolymer obtained by graft polymerizing styrene compounds such as styrene, α-methylstyrene, vinyltoluene, and chlorostyrene.

Specific examples of the high molecular weight halogenated flame retardant used in the present invention include halogenated phenoxy resin, halogenated polystyrene, halogenated polyphenylene ether, and Dechlorane Plus (trade name, manufactured by Hooker Chemical Co., Ltd.). ), but are not limited to these.

The hydrotalcite used in the present invention has the general formula (I)
It is expressed as

Ml-x M' x (OH) z A xy,・m
H20 (1) where M is Mg, Mn, Fe, Co, N
i,Cu.

and Zn, M゛ is A1゜Fe
, Cr, Co and In, A is OH, F,
Selected from CI, Br, NO3, Cox, Fe(CN)6 and CH, Coo. m is a positive number and X is O
A number in the range <x≦0.5, where n is equal to the anion valence of A. There are natural and artificial types of such no-λ hydrotalcite, and both can be used in the present invention. The hydrotalcite used in the present invention may be an alkali metal salt of a higher fatty acid such as an alkali metal salt of stearic acid or oleic acid, or an alkali metal salt of an organic sulfonic acid such as an alkali metal salt of dodecylbenzenesulfonic acid. Surface treatment may be applied.

The blending amount of nylon 46 as component (A) of the resin composition of the present invention is 15 to 97% by weight, more preferably 20 to 97% by weight.
It is 85% by weight. The content of nylon 46 is 15% by weight.
If it is less than 10%, mechanical strength and chemical resistance decrease. On the other hand, if the amount of nylon 46 exceeds 97% by weight, the heat resistance will decrease and the changes in dimensions and physical properties due to water absorption will increase.

The blending amount of polyphenylene ether as component (B) in the resin composition of the present invention is 1 to 70% by weight, more preferably 10 to 60% by weight. If the amount of polyphenylene ether blended is less than 1% by weight, heat resistance will be low and changes in dimensions and physical properties due to water absorption will be large. On the other hand, when the amount of polyphenylene ether blended exceeds 70% by weight, chemical resistance decreases.

The blending amount of the high molecular weight halogenated flame retardant as component (C') in the resin composition of the present invention is 1 to 40% by weight, more preferably 3 to 40% by weight. If the amount of the high molecular weight halogenated flame retardant is less than 1% by weight, the flame retardancy of the resin composition will decrease. On the other hand, if the blending amount exceeds 40% by weight, the heat resistance and mechanical properties will deteriorate, which is not preferable.

The amount of hydrotalcite as component (D) in the resin composition of the present invention is 1 to 40% by weight, more preferably 3% by weight.
~30% by weight. The amount of hydrotalcite is 1
If the amount is less than % by weight, the thermal stability of the resin composition during molding will decrease. On the other hand, if the blending amount exceeds 40% by weight, the mechanical properties will deteriorate, which is not preferable.

The resin composition of the present invention contains flame retardant aids such as antimony trioxide, zinc borate, barium metaborate, hydrated alumina, zirconium oxide, ammonium polyphosphate, and organic peroxide to further improve flame retardancy. Can be added.

In the resin composition of the present invention, other polymers may be blended as necessary, as long as the properties thereof are not significantly impaired.

In this case, the blending amount is preferably 30% by weight or less. Such other polymers include polyarylate, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polycaprolactone, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyetherimide, polyphenylene sulfide, ABS, PMMA.

Examples include polypropylene, polyethylene, phenoxy resin, and rubbery polymers.

Furthermore, pigments, heat stabilizers, antioxidants, weathering agents, flame retardants, plasticizers, mold release agents, reinforcing agents, etc. may be added to the resin composition of the present invention as long as they do not impair its moldability and physical properties. is possible. Examples of reinforcing materials include fiber reinforcing materials such as glass fibers, metal fibers, potassium titanate whiskers, carbon fibers, and aramid fibers, and filler-based reinforcing materials such as talc, calcium carbonate, mica, glass flakes, and metal flakes. In particular, glass fibers having a diameter of 3 to 20 μm are preferred because they further improve the strength, elastic modulus, and heat resistance of the resin composition.

The method for producing the resin composition of the present invention or the method for obtaining various molded articles from the resin composition of the present invention is arbitrary. For example, the components of the resin composition of the present invention are mixed using a Banbury mixer, tumbler mixer, or other method, and this is directly molded by methods such as injection molding, extrusion molding, and blow molding to form various molded products. be able to.

In addition, each component is mixed using a Banbury mixer, tumbler mixer, or other method, and this is melt-kneaded using an extruder, etc., and cut into pellets, which are then processed by methods such as injection molding, extrusion molding, and blow molding. It can also be molded into various molded products.

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these. The measurement methods and raw materials used in Examples and Comparative Examples are as follows.

(1) Tensile strength and elongation at break ASTM D638.1 Danher (2) Eye impact strength ASTM D256.3.2mm thickness, notched (3) Heat distortion temperature ASTM D64B, load 4.5Kg/cm2 (4)
Water absorption treatment was carried out for 165 hours at 65°C x 95% RH.

(5) Dimensional change after water absorption treatment: length 12.5cm, width 1.25cm, thickness 0.32cm
The dimensional change in the length direction of the test piece of m was measured.

(6) Flame retardancy The test was conducted based on the UL94 flame retardancy test using a test piece with a thickness of 0.8 mm.

(7) Chemical resistance 16 Danher No. 1 in toluene at room temperature The samples were immersed for 5 hours and weight changes were examined.

(8) Raw materials used Nylon 46: Manufactured by Unitika, F5000 Polyphenylene ether: Manufactured by GE Plastics Japan, PPO
534J High molecular weight halogenated flame retardant Brominated polystyrene: Manufactured by Kaguchi Fellows, Vyrothiencro 8PB Brominated polyphenylene oxide = Made by Great Lakes, PO64P Brominated phenoxy resin: Mana, Ri, EB Hydrotalcite: Kyowa Chemical Industry, Alcamizer 2 Examples 1 to 6, Comparative Example 1.2 After mixing each raw material in a tumbler at the blending ratio shown in Table 1, vacuum drying was performed at 90'C for 16 hours. Then, using a twin screw extruder (manufactured by Ikegai Tekko Co., Ltd., PCM45),
The resin composition was melt-kneaded at a temperature of 0.000°C and cut into pellets of the resin composition. This pellet was molded at a temperature of 300''C by injection molding m (J100S manufactured by Kuchinsha Co., Ltd.) to obtain a test piece.The test piece was subjected to various physical property measurements.

Table 1 shows the results of physical property measurements. As specifically shown in Table 1, the resin compositions of the examples have significantly improved flame retardancy compared to the resin compositions of nylon 46 and polyphenylene ether, and still retain their excellent properties.

(Effects of the Invention) As specifically shown in the examples, the resin composition of the present invention has significantly improved flame retardancy compared to the resin composition of nylon 46 and polyphenylene ether, and has excellent properties. In other words, it retains its excellent mechanical properties, heat resistance, chemical resistance, and minimal deterioration of dimensions and physical properties due to water absorption.

Patent applicant: Unitika Co., Ltd.

Claims (1)

[Claims] (1) (A) 15 to 97% by weight of nylon 46 and (B)
A resin composition comprising 1 to 70% by weight of polyphenylene ether, 1 to 40% by weight of (C) a high molecular weight halogenated flame retardant, and 1 to 40% by weight of (D) hydrotalcite.