KR100405198B1 - Flame Retardant Thermoplastic Resin Composition - Google Patents

Abstract

The flame retardant thermoplastic resin composition of the present invention comprises (A) 100 parts by weight of a polyphenylene ether resin or a polyphenylene ether resin comprising a mixture of polyphenylene ether and a vinyl aromatic polymer; (B) 1-30 parts by weight of an organophosphorous compound consisting of 5-90% by weight of (B ₁ ) phosphazene compound and 95-10% by weight of (B ₂ ) phosphate ester morphide compound; And (C) 0.05-5 parts by weight of a fluorinated polyolefin resin having an average particle size of 0.05-1000 μm and a density of 1.2-2.3 g / cm ³ , and optionally (D) 40 parts by weight or less of a styrene-based impact modifier. It may further include.

Description

Flame Retardant Thermoplastic Resin Composition

Field of invention

The present invention relates to a flame retardant polyphenylene ether-based thermoplastic resin composition. More specifically, the present invention is composed of a thermoplastic polyphenylene ether resin, a phosphazene compound, a phosphate ester morphide compound, a fluorinated polyolefin resin and a styrene impact reinforcing material exhibits excellent flame retardancy, heat resistance and mechanical strength The present invention relates to a flame-retardant thermoplastic resin composition excellent in impact resistance, heat stability, workability and appearance characteristics.

Background of the Invention

Polyphenylene ether (PPE or PPO) resins or mixtures of polyphenylene ether and vinyl aromatic polymers (MPPO resins) have excellent mechanical and electrical properties and are widely used in various fields such as automobile parts, electrical parts, and electronic parts. However, molded articles made of such polyphenylene ether-based resins have various physical properties such as impact strength, tensile strength, heat resistance, etc., but generally have a disadvantage in that they are combustible. Since the products molded from the polyphenylene ether resin composition are generally applied to large heat-dissipating materials such as electrical and electronic products, especially computer housings or other office equipment, flame retardancy is essential in combination with mechanical strength. do.

The technique of imparting flame retardancy to a resin composition has been studied so far, and generally, a method of imparting flame retardancy to a resin composition by adding a compound including antimony, halogen, phosphorus, or nitrogen is known and used.

U.S. Patent No. 3,639,506 discloses a technique of using a monomeric aromatic phosphate ester compound such as triphenylphosphate or a mixture of this compound and a halogen compound as a flame retardant in a polyphenylene ether resin composition. However, the use of a monomeric aromatic phosphate ester compound may exhibit excellent flame retardancy and mechanical properties. However, the flame retardant migrates to the surface of the molded part during molding, causing a problem of juices and deterioration in the heat resistance of the resin composition. It has a disadvantage.

U.S. Patent No. 4,154,775 discloses a technique of applying a cyclic phosphate compound to a polyphenylene ether resin composition as a flame retardant to improve flame retardancy without deteriorating physical properties such as impact strength. It is known to decompose or cause decomposition, and has the disadvantage of lowering the inherent physical properties of the high heat-resistant polyphenylene ether resin.

Japanese Patent Laid-Open No. 59-202,240 discloses a technique of applying an aryl phosphate oligomer in the form of a condensed phosphate ester to a polyphenylene ether resin as a flame retardant. However, the application of a flame retardant in the form of a condensed phosphate ester to a polyphenylene ether resin has the advantage of less occurrence of juice phenomenon and improved heat resistance compared to the case of using a monomeric phosphate ester compound, but when a flame retardant of the same weight is used. Because of the disadvantage of lowering the flame retardancy, a higher amount of flame retardant must be added to secure an equivalent level of flame retardancy, and since a certain amount of the monomeric phosphate ester compound is included, It did not completely prevent the juice from moving.

Japanese Patent Laid-Open No. 2-187,456 discloses a phosphorus compound in the form of a condensed phosphate ester, but the examples in which the phosphorus compound is applied are not limited to monomolecular phosphorus compounds having improved thermal properties, and the above composition is flame retardant. In view of the efficiency has a disadvantage that the dropping phenomenon occurs during combustion depending on the composition.

In contrast, the present inventors use a phosphazene compound and an oligomeric phosphate ester morphide compound together as a flame retardant, and apply a fluorinated polyolefin resin and a styrene impact modifier to a polyphenylene ether resin to overcome the above problems. It is to develop a flame retardant thermoplastic resin composition exhibiting excellent flame retardancy, heat resistance and mechanical strength, and excellent balance of physical properties such as impact resistance, thermal stability, workability and appearance characteristics.

An object of the present invention is to provide a thermoplastic resin composition excellent in flame retardancy.

Another object of the present invention is to provide a thermoplastic resin composition having an excellent balance of physical properties such as impact resistance, thermal stability, heat resistance, workability and appearance.

The above and other objects of the present invention can be achieved by the present invention described below.

The thermoplastic resin composition of the present invention is an organophosphorous compound 1- consisting of (A) 100 parts by weight of a polyphenylene ether resin, (B) 5-90% by weight of a phosphazene compound and 95-10% by weight of a phosphate ester morphide compound. 30 parts by weight, (C) fluorinated polyolefin resin 0.05-5 parts by weight, and optionally (D) styrene-based impact modifier 0-40 parts by weight, the detailed description of each of these components is as follows.

(A) polyphenylene ether resin

The polyphenylene ether resin according to the present invention may be a polyphenylene ether resin alone or a mixture of a polyphenylene ether resin and a vinyl aromatic polymer.

Specific examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6) -Dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether , Poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4- Copolymer of phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3, Copolymers of 6-triethyl-1,4-phenylene) ether and the like can be used, and double poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl- It is preferable to use a copolymer of 1,4-phenylene) ether or poly (2,6-dimethyl-1,4-phenylene) ether, and poly (2,6-dimethyl-1,4-phenylene) Most preferably, ether is used.

The degree of polymerization of the polyphenylene ether resin used in the preparation of the resin composition of the present invention is not particularly limited, but considering the thermal stability and workability of the resin composition, the intrinsic viscosity when measured in a chloroform solvent at 25 ° C is measured. It is preferable that it is 0.2-0.8. It is also possible to use the above polyphenylene ether resins alone or to use two or more thereof in an appropriate ratio.

The above polyphenylene ether resins exhibit very good compatibility with vinyl aromatic polymers, in particular styrene-based polymers. As the vinyl aromatic polymer used in the component (A) of the present invention, polystyrene, high impact polystyrene (HIPS), polychlorostyrene, polyα-methylstyrene, polyt-butylstyrene and the like and copolymers thereof alone are used. Or a mixture of two or more thereof, and it is preferable to use double polystyrene or high impact polystyrene.

The molecular weight of the vinyl aromatic copolymer is not particularly limited either, but considering the thermal stability and workability of the resin composition, the weight average molecular weight is preferably 20,000 to 500,000.

(B) Organophosphorus Compound

In the present invention, the organophosphorus compound is used as a flame retardant and consists of 5-90 wt% of phosphazene compound (B ₁ ) and 95-10 wt% of phosphate ester morphide compound (B ₂ ). The organophosphorus compound of the present invention is used in 1-30 parts by weight based on 100 parts by weight of polyphenylene ether resin, and more preferably in the range of 1.5-25 parts by weight.

(B _One Phosphazene compounds

The phosphazene compound of the present invention is a linear phosphazene compound represented by the following general formula (1) or a cyclic phosphazene compound represented by the following general formula (2).

[Formula 1]

[Formula 2]

Wherein R is selected from the group consisting of alkyl group, aryl group, alkyl substituted aryl group, arylalkyl group, alkoxy group, aryloxy group, amino group or hydroxy group, k is an integer of 0-10. The alkoxy group or aryloxy group may be substituted with an alkyl group, an aryl group, an amino group, a hydroxyl group, or the like.

(B ₂ ) Phosphate ester morphide compound

The phosphate ester morphide compound of the present invention is a phosphate ester morphide compound represented by the following formula (3) or a mixture thereof.

[Formula 3]

Wherein x is 1 or 2, R ₁ is a C _6-20 aryl or alkyl substituted C _6-20 aryl group, R ₂ is a C _6-30 aryl or alkyl substituted C _6-30 aryl group derivative. In the above formula, n and m each represent a number average degree of polymerization, and the average value of n + m is 0-5.

Preferred examples of R ₁ are a phenyl group or a phenyl group substituted with an alkyl group such as methyl, ethyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, isoamyl, t-amyl, double phenyl group or methyl, ethyl Most preferred is a phenyl group substituted with an isopropyl or t-butyl group. R ₂ is preferably derived from resorcinol, hydroquinone or bisphenol-A.

The oligomeric phosphate ester morphide-based compound reacts aryl morpholino chlorophosphate by reacting morpholine with an aromatic alcohol having R ₁ group in phosphorus oxychloride (POCl ₃ ) in a presence of a suitable catalyst at a temperature of 50 ° C-200 ° C. The aryl morpholino chlorophosphate and the hydroxy aryl compound having an R ₂ group can be obtained and reacted at a temperature of 70 ° C.-220 ° C. using an appropriate catalyst. At this time, a solution polymerization method or a melt polymerization method can be used as a polymerization method.

Catalysts that can be used to prepare an oligomeric phosphate ester morphide compound such as Chemical Formula 3 according to the present invention include aluminum chloride (AlCl ₃ ), magnesium chloride (MgCl ₂ ) or zinc chloride (ZnCl ₂ ). There is a metal chloride, it is also preferred to add a trivalent amine such as triethylamine to remove the hydrogen chloride (HCl) produced by the reaction.

The phosphate ester morphide compound prepared by the above method is monophosphate having both 0 and n values when morpholine is reacted with phosphorus oxychloride (POCl ₃ ) in an excess of aromatic alcohol having R ₁ group and morpholine. Only esters may be prepared, and depending on the reaction process, it is possible to control the amount of the compound having a value of 0 for both n and m. In addition, the produced composite can be used as it is or as a purified compound.

(C) fluorinated polyolefin resin

The fluorinated polyolefin resin (C) used in the preparation of the flame retardant thermoplastic resin composition of the present invention may be prepared using a known polymerization method, for example, a pressure of 7-71 kg / cm ² and a temperature of 0-200 ° C. , Preferably at 20-100 ° C., in an aqueous medium containing free radical forming catalysts such as sodium, potassium or ammonium peroxydisulfate.

Preferable specific examples of the fluorinated polyolefin resin (C) include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer And ethylene / tetrafluoroethylene copolymers. Of these, polytetrafluoroethylene having a particle size of 0.05-1,000 μm and specific gravity of 1.2-2.3 g / cm ³ is most preferred. These may be used independently from each other, and two or more different types may be used together.

When the fluorinated polyolefin resin is mixed with other component resins of the present invention and extruded, a fluorinated polyolefin-based resin forms a fibrillar network in the resin, thereby lowering the flow viscosity of the resin during combustion and increasing the shrinkage rate, thereby dropping the resin. It is to prevent the phenomenon.

The fluorinated polyolefin resin may be used in an emulsion state or a powder state. When the fluorinated polyolefin resin in an emulsion state is used, the dispersibility in the entire resin composition is good, but the manufacturing process is complicated. Therefore, even if it is powder state, if it can disperse | distribute suitably in the whole resin composition and can form a fibrous network, it is preferable to use it in powder state.

The content of the fluorinated polyolefin resin used in the production of the resin composition of the present invention is used at 0.05-5 parts by weight based on 100 parts by weight of the polyphenylene ether resin (A).

(D) Styrene Shock Reinforcement

The styrenic impact modifier used in the present invention is derived from a vinyl aromatic monomer, and may be a block or a radial tere block copolymer in the form of AB or ABA.

The AB or ABA type block or radial block copolymer is a copolymer composed of a vinyl aromatic monomer and a block of hydrogenated, partially hydrogenated or unhydrogenated unsaturated diene, and examples of the AB diblock type block copolymer include Polystyrene-polybutadiene, polystyrene-polyisoprene, polyalphamethylstyrene-polybutadiene copolymers, and hydrogenated forms thereof.

Such AB diblock type copolymers are widely known commercially, and representative examples include Solprene, K-resin, and Kraton D and Kraton G from Phillips.

Examples of ABA triblock type block copolymers include polystyrene-polybutadiene-polystyrene, polystyrene-polyisoprene-polystyrene, polyalphamethylstyrene-polybutadiene-polyalphamethylstyrene, polyalphamethylstyrene-polyisoprene-polyalphamethylstyrene Copolymers such as these and hydrogenated forms thereof. Such ABA triblock type copolymers are also widely known commercially, and are representative of Shell Cariflex, Kraton D, Kraton G and Kuraray Septon.

Styrene-based impact modifiers used in the preparation of the resin composition of the present invention are optionally added, and 0-40 parts by weight based on 100 parts by weight of the polyphenylene ether (A).

The flame retardant thermoplastic resin composition of the present invention may include general additives such as flame retardant aids, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, reinforcing agents, inorganic additives, pigments or dyes according to the respective applications in addition to the above components, The added inorganic additive may be used in the range of 0-60 parts by weight, preferably 1-40 parts by weight, based on 100 parts by weight of the polyphenylene ether (A).

The resin composition of the present invention can be produced by a known method for producing a resin composition. For example, the components of the present invention and other additives may be mixed simultaneously, then melt extruded in an extruder and prepared in pellet form.

The compositions of the present invention can be used for molding a variety of products, and are particularly suitable for the manufacture of housings and interiors of electrical and electronic products, such as computer housings, which require high flame resistance and high flame resistance while being injected at high temperatures.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

The specifications of (A) polyphenylene ether resin, (B) organophosphorus compound, (C) fluorinated polyolefin resin, and (D) styrene impact modifier used in the following Examples and Comparative Examples are as follows.

(A) polyphenylene ether resin

(A ₁ ) PPE P401 from Asahi Kasei of Japan was used.

(A ₂ ) High-impact polystyrene (HI-1190F, manufactured by Cheil Industries, Ltd., Korea) was used as the vinyl aromatic polymer mixed with polyphenylene ether.

(B) Organophosphorus Compound

(B ₁ ) phosphazene compound

As the cyclic phosphazene represented by the following structural formula, a mixture of one wherein R is a phenoxy group and the values of k are 1 and 2 was used.

(B ₂ ) Phosphate ester morphide compound

(B ₂₁ ) It obtained by making phenol and morpholine react with phosphorus oxychloride. The compound has 9% by weight of triphenylphosphate; 86% by weight of the compound of Formula 3, wherein R ₁ is a phenyl group, x is 1, and both n and m are 0; 5% by weight of a compound in which R ₁ is a phenyl group, x is 2, and the values of n and m are both 0; A mixture of the included mono phosphate ester morphide compounds was used.

(B ₂₂ ) Resorcinol and phenylmorpholino chlorophosphate were reacted. In Formula 3, R ₁ was a phenyl group and R ₂ was a resorcinol derivative. Wherein n and m are both 0 and x is 1, 1.5 wt% of the phosphate ester morpholide compound, 68.4 wt% of the compound of which x is 1 and the value of n + m is 1, and x is 1 and n + m of A mixture of an oligomeric phosphate ester morpholide compound containing 30.1% by weight of a compound having a value of 2 or more was used.

(C) fluorinated polyolefin resin

Teflon (trade name) 7AJ of Du Pont, USA was used.

(D) Styrene Shock Reinforcement

Kraton G 1651 from Shell, USA was used.

Example 1-5

Each component of the composition shown in Table 1, antioxidants and heat stabilizers were added, mixed in a conventional mixer, and extruded at a temperature of 240-270 ° C. using a twin screw extruder having L / D = 35 and Φ = 45 mm. The extrudate was prepared in pellet form. Specimens for physical property measurement and flame retardancy evaluation were prepared using a 10 oz injection machine at an injection temperature of 240-270 ° C. These specimens were measured for 48 hours at 23 ° C. and 50% relative humidity, and then measured for physical properties according to ASTM standards.

Comparative Example 1-4

In Comparative Examples 1 and 2, specimens were prepared in the same manner as in Example 1-3 except that only phosphazene compounds or phosphate ester morphide compounds were used as flame retardants, respectively. Comparative Examples 3 and 4 were prepared in the same manner as in Example 4, except that only phosphazene compounds or oligomeric phosphate ester morphide compounds were used as flame retardants, respectively.

The physical properties of the specimens molded in Examples and Comparative Examples were measured by the following method.

(1) Flame retardancy was evaluated using a 1.6 mm thick specimen in accordance with UL-94.

(2) The heat deflection temperature was measured at 18.6 kgf load in accordance with ASTM D648.

(3) Flexural strength was evaluated according to ASTM D790.

(4) The melt flow index was evaluated according to ASTM D1238 and evaluated under the condition of 250 ° C / 10kg load.

The composition and physical properties of the resin prepared in Example 1-5 and Comparative Example 1-4 are shown in Table 1 below.

Example Example Comparative Example One 2 3 4 5 One 2 3 4 PPE Resin (A) (A ₁ ) 50 50 50 75 60 50 50 75 75 (A ₂ ) 50 50 50 25 40 50 50 25 25 Organophosphorus compound (B) (B ₁ ) 2 5 8 3 3 14 - 10 - (B ₂₁ ) 12 9 6 - - - 14 - - (B ₂₂ ) - - - 7 9 - - - 10 Fluorinated Polyolefin Resin (C) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Styrene Shock Reinforcement (D) - - - 0.5 5 - - 0.5 0.5 UL94 flame retardant (1/16 ″) V-0 V-0 V-0 V-0 V-0 V-1 V-1 V-1 V-2 Heat deflection temperature 87 86 85 126 106 88 82 127 125 Flexural strength 26000 25500 25500 28500 25500 24000 24500 26500 27000 Melt flow index 37 36 34 6 15 30 38 5 6

From the results in Table 1, when a mixture of a phosphazene compound and a phosphate ester morphide-based compound is used as a flame retardant, the flame retardancy and flexural strength are not lowered as compared with the case where each of them is used alone. It can be seen that a synergistic effect is observed in.

The present invention uses a mixture of a phosphazene compound and a phosphate ester morphide compound as a flame retardant, so that the balance of flame retardancy, heat resistance, and mechanical strength is excellent, thereby producing an injection molding of a computer monitor or other office equipment. It has the effect of providing a thermoplastic resin composition useful for.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (5)

(A) 100 weight part of polyphenylene ether resin which consists of polyphenylene ether resin or the mixture of polyphenylene ether and a vinyl aromatic polymer; (B) 1-30 parts by weight of an organophosphorous compound consisting of 5-90% by weight of a (B ₁ ) phosphazene compound and (B ₂ ) 95-10% by weight of a phosphate ester morphide compound represented by the following Formula 3; And (C) 0.05-5 parts by weight of a fluorinated polyolefin resin having an average particle size of 0.05-1000 μm and a density of 1.2-2.3 g / cm ³ ; The phosphazene compound (B ₁ ) is a flame-retardant thermoplastic resin, characterized in that the linear phosphazene represented by the formula ( ₁ ), and / or a cyclic phosphazene compound represented by the formula (2) Composition. [Formula 1] [Formula 2] Wherein R is selected from the group consisting of alkyl group, aryl group, alkyl substituted aryl group, arylalkyl group, alkoxy group, aryloxy group, amino group or hydroxy group, k is an integer of 0-10. The oxy group may be substituted with an alkyl group, an aryl group, an amino group, or a hydroxyl group.) [Formula 3] Wherein x is 1 or 2, R ₁ is a C _6-20 aryl or alkyl substituted C _6-20 aryl group, and R ₂ is a C _6-30 aryl or alkyl substituted C _6-30 aryl group derivative n and m represent the number average degree of polymerization, respectively, and the average value of n + m is 0-5). The flame retardant thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition further comprises (D) styrene-based impact modifier at 40 parts by weight or less based on 100 parts by weight of polyphenylene ether resin. The flame retardant of claim 1, wherein the vinyl aromatic polymer is selected from the group consisting of polystyrene, high impact polystyrene (HIPS), polychlorostyrene, polyα-methylstyrene, polyt-butylstyrene, and mixtures thereof. Thermoplastic resin composition. The flame retardant thermoplastic resin composition according to claim 1, wherein the phosphazene compound (B ₁ ) is phenoxy phosphazene. The method according to claim 1, wherein R ₁ is a phenyl group or a phenyl group substituted with an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, isoamyl, t-amyl, R ₂ is a resorcinol, hydroquinone or bisphenol-A derivative, characterized in that the flame-retardant thermoplastic resin composition.