KR100394905B1 - Flame Retardant Thermoplastic Resin Composition - Google Patents

Abstract

The flame retardant thermoplastic resin composition of the present invention (A) 100 parts by weight of a thermoplastic resin; (B) (b ₁₎ an organic clay Clay 0.1-20% prepared by reaction with an organic cation represented by the general formulas (1) and (b ₂₎ an organic phosphoric ester treated with an organic clay consisting of 80-99.9% organic phosphoric acid ester compound 5-30 parts by weight of compound; (C) 0-20 parts by weight of the phosphorus compound; And (D) 0-5 parts by weight of the antidripping agent:

[Formula 1]

Wherein R ₁ , R ₂ , R ₃ , and R ₄ are the same as or independently of each other, an alkyl group of C ₁ -C ₃₀ , an aryl group of C ₆ -C ₃₀ , or an aryl group substituted with alkyl; Or a C ₁ -C ₃₀ alkyl group having a hydroxy group, an C ₆ -C ₃₀ aryl group; X is not limited to cationic ions but is often chloride, bromide, iodide, carbonate, nitrate, sulphate, persulfate, etosulphate, methyl carbonate, ethyl carbonate and mixtures thereof.

Description

Flame Retardant Thermoplastic Resin Composition

Field of invention

The present invention relates to a flame retardant thermoplastic resin composition. More specifically, the present invention relates to a flame retardant thermoplastic resin composition having excellent heat resistance and mechanical properties by using an organic phosphate ester compound treated with an organic clay and a phosphorus compound as a flame retardant.

Background of the Invention

The most well known method of imparting flame retardancy to thermoplastic resins is to impart flame retardancy by adding halogen-based flame retardants. U.S. Patent Nos. 4,983,658 and 4,883,835 disclose examples of using halogen containing compounds as flame retardants. Halogen-based flame retardants exhibit excellent flame retardancy regardless of the type of resin, but cause corrosion of processing equipment such as molds due to the generation of corrosive gas during processing, and may have a fatal effect on the human body due to hydrogen halide gas. In particular, polybrominated diphenyl ethers, which are mainly halogen-based flame retardants, have a high possibility of generating very toxic gases such as dioxins and furans during combustion. Therefore, the demand for resins that do not contain halogen-based flame retardants has recently been expanding rapidly.

A technique for imparting flame retardancy without using a halogen flame retardant is currently the most common is to use a phosphorus flame retardant. However, when the phosphorus-based flame retardant is used, it is superior to the halogen-based flame retardant in terms of generation of corrosive gas and toxic gas, which is environmentally friendly, but has a disadvantage of seriously impairing the heat resistance of the resin. Triphenylphosphate, the most commonly used phosphorus-based flame retardant, acts as a plasticizer in the resin when applied to the resin, which seriously degrades the heat resistance and mechanical properties of the resin.

Clay is a layer silicate mineral with an interlayer structure and contains metal cations between layers. When the interlayer metal compound of clay is replaced with an organic cation, the lipophilic property increases and the gap between the layers allows the polymer or organic molecules to be intercalated. In this way, it is known that dispersion of clay occurs in nano units by inserting polymers between layers, and consequently, physical and thermal properties of polymers can be increased.

On the other hand, the inventors of the present invention by inserting the phosphorus flame retardant to reduce the heat resistance between the organic layered clay layer in order to overcome the problems caused when using the halogen-based flame retardant and phosphorus flame retardant, heat resistance generated by the use of phosphorus flame retardant To solve the problem of lowering the degree and at the same time to develop a flame retardant thermoplastic resin composition with improved mechanical properties.

An object of the present invention is to provide a thermoplastic resin composition excellent in flame retardancy without deterioration in heat resistance and mechanical properties.

Another object of the present invention is to provide a thermoplastic resin composition which does not generate toxic gases such as dioxin, furan or hydrogen halide gas during processing and combustion.

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

The flame retardant thermoplastic resin composition of the present invention (A) 100 parts by weight of a thermoplastic resin; (B) 5-30 parts by weight of an organic clay-treated organic phosphate ester compound; (C) 0-20 parts by weight of the phosphorus compound; And (D) 0-5 parts by weight of the anti-dripping agent, the detailed description of each of these components are as follows.

(A) thermoplastic resin

The thermoplastic resin used in the preparation of the flame retardant thermoplastic resin composition according to the present invention comprises at least one thermoplastic resin described below. Examples of the thermoplastic resin include polycarbonate resins; Polyarylene ether resins; Polyolefin resins such as polyethylene or polypropylene; Thermoplastic resins composed of vinyl carboxylic acid or derivatives thereof such as polyalkyl acrylate, polyalkyl methacrylate, polyacrylamide, polyacrylonitrile or polyacrylic acid; Polystyrene-based vinyl aromatic resins; Diene resins such as polybutadiene, polyisoprene and the like; Polyamide resins such as nylon-6, nylon-6,6 and the like; And polyester resins such as polyethylene terephthalate and polybutylene terephthalate.

The thermoplastic resin used in the present invention includes both a homopolymer and a copolymer, and in the case of a copolymer, includes a random, block or graft copolymer. For example, in the case of polystyrene-based resins, high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene graft copolymer (ABS), and the like are all included.

Thermoplastic resins used in the preparation of the resin composition of the present invention include polycarbonate, polyphenylene ether, polyester, styrene polymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene air among the thermoplastic resins. Coalescence and the like are preferred. These can be used alone or in blends, including polyphenylene ether / styrene polymers (including HIPS), polyphenylene ether / acrylonitrile-butadiene-styrene copolymers (including styrene-acrylonitrile copolymers), polycarbonates / Especially preferred are acrylonitrile-butadiene-styrene copolymers (including styrene-acrylonitrile copolymers), polycarbonate / polyester blends, and the like.

(B) organophosphate ester compounds treated with organoclays

(b ₁ ) organoclay

Clays that can be used in the present invention are mica-like layer silicates belonging to the smectite group, and include montmorillonite, saponite, hectorite, bentonite, bayderite, stevensite, and the like. It can be used as a compound of species or more. Clays used are platy clay minerals with a cationic substitution capacity of 50-200 milliequivalents per 100 grams.

The clay is reacted with an organic cation (quaternary ammonium salt) represented by Formula 1 to prepare an organoclay:

[Formula 1]

Wherein R ₁ , R ₂ , R ₃ , R ₄ are the same as or independently of each other an alkyl group of C ₁ -C ₃₀ , an aryl group of C ₆ -C ₃₀ or an alkyl substituted aryl group; Or a C ₁ -C ₃₀ alkyl group having a hydroxy group, or an C ₆ -C ₃₀ aryl group. X is not limited to cationic ions, but is often chloride, bromide, iodide, carbonate, nitrate, sulphate, persulfate, etosulphate, methyl carbonate, ethyl carbonate and mixtures thereof.

When the interlayer metal compound of clay is substituted with the organic cation as described above, the lipophilic property is increased and the interlayer is separated, thereby allowing the polymer or organic molecules to be intercalated.

(b ₂ ) Organophosphate ester compound

The organophosphorous ester compound of the present invention is represented by Formula 2:

[Formula 2]

Wherein R ₃ , R ₄ and R ₅ are each independently hydrogen or an alkyl group of C ₁ -C ₄ , and X is a C ₆ -C ₂₀ aryl group or a C ₆ -C ₂₀ aryl group substituted with an alkyl group. It is derived from dialcohols such as socinol, hydroquinol and bisphenol-A. M ranges from 0 to 4.

Examples of the compound corresponding to the above formula include triphenylphosphate, tricresylphosphate, trigyrenylphosphate, tri (2,6-dimethylphenyl) phosphate and tri (2,4,6-trimethylphenyl) phosphate when m is 0. , Tri (2,4-dibutylbutylphenyl) phosphate, tri (2,6-dibutylbutylphenyl) phosphate, and the like, when m is 1, resorcinol bis (diphenyl) phosphate, resorcinol bis; (2,6-dimethylphenyl) phosphate, resorcinolbis (2,4-dibutylbutylphenyl) phosphate, hydroquinolbis (2,6-dimethylphenyl) phosphate, hydroquinolbis (2,4-dibutylbutyl) Phenyl) phosphate and the like are representative examples. The phosphate ester compounds may be used alone or in mixtures of each.

The organic phosphate ester compound treated with the organic clay may be prepared by reacting the organic clay (b ₁ ) with the organic phosphate ester compound (b ₂ ). The liquid organic phosphate ester can be reacted with an organic clay or dissolved in an organic solvent and then added with an organic clay. The reaction temperature is between 50 ° C. and 100 ° C., and the reaction can be carried out for 10 minutes to one day to completely react. Let's do it. After the reaction, the XRD peak of the organic clay disappears, thereby confirming that the organic phosphate ester is inserted between the layers of the organic clay. The organic solvent that can be used is not limited but benzene, toluene, acetone, methylene chloride, chloroform, tetrahydrofuran and the like are most suitable.

By inserting the organic phosphate ester between the layers as described above, the dispersion of clay occurs in nano units, and as a result, it is possible to increase the physical and thermal properties of the polymer.

The organophosphate ester compound treated with the organoclay of the present invention is composed of (b ₁ ) 0.1-20% organoclay and (b ₂ ) organophosphate ester compound 99.9-80%. The organophosphorous ester compound (B) treated with the organic clay is used in an amount of 5 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin (A).

(C) phosphorus compounds

The thermoplastic resin composition of the present invention may further include a phosphorus compound (C) in addition to the essential components (A) and (B). The phosphorus compound flame retardant used in the present invention is a conventional phosphorus flame retardant without treatment with organic clay, unlike the organic phosphate ester compound (B) treated with the organic clay, and is an organic phosphate ester compound represented by the formula (2). .

When the phosphorus-based compound is used alone as a flame retardant, it acts as a plasticizer in the resin to lower the heat resistance and mechanical properties of the resin. However, in the present invention, the phosphorus-based compound is mixed with the organic phosphate ester compound (B) treated with an organic clay. By using the composition to form a resin composition having improved heat resistance and mechanical properties than when used alone.

In the present invention, the phosphorus compound (C) may be used alone or in combination, and may be used in an amount of 20 parts by weight or less based on 100 parts by weight of the thermoplastic resin (A).

(D) anti-dripping agent

The flame retardant thermoplastic resin composition of the present invention may further include an anti-dripping agent in addition to the essential components (A) and (B). The anti-dripping agent is added to prevent the molten resin from dropping down during combustion, and is mainly used as a fluorine-based resin. Fluorine resins include polytetrafluoroethylene, polyvinylidene fluoride, copolymers of tetrafluoroethylene and vinylidene fluoride, copolymers of tetrafluoroethylene and fluoroalkyl vinyl ether, and tetrafluoroethylene and hexafluoro Propylene copolymers. These may be used independently from each other, or a mixture of two or more different from each other may be used.

Fluorine-based resins form a fibrillar network in the resin when mixed and extruded together with the thermoplastic resin to reduce the flow viscosity and increase the shrinkage rate of the resin during combustion, thereby preventing dripping of the resin. The fluorine-based resin that may be preferably used may be polytetrafluoroethylene, and may be used in an amount of 5.0 parts by weight or less based on 100 parts by weight of the basic resin (A) of the present invention.

In addition to the above components, the thermoplastic resin composition of the present invention may be added with an impact modifier, an inorganic additive, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, and a dye. The inorganic additives to be added include asbestos, glass fibers, talc, ceramics, sulfates, etc., which may be used in the range of 0 to 50 parts by weight based on 100 parts by weight of the base resin (A) of the present invention.

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) thermoplastic resin, (B) phosphorus flame retardant treated with organic clay, (C) phosphorus compound and (D) antidropping agent used in the following Examples and Comparative Examples are as follows.

(A) thermoplastic resin

(a ₁ ) Rubber modified polystyrene copolymer (High Impact Polystyrene): Rubber modified polystyrene resin prepared by a conventional method, the rubber content is 9% by weight, the size of the average rubber particles is 1.5 ㎛, the weight average molecular weight of polystyrene A Mw of 220,000 was used.

(a ₂ ) Polyphenylene ether resin (PPE): Poly (2,6-dimethyl-1,4-phenylene) ether (trade name: P-402) of Asahi Kasei, Japan, was used.

(a ₃ ) SAN graft copolymer resin: 36 parts by weight of styrene, 14 parts by weight of acrylonitrile and 150 parts by weight of deionized water are added to 50 parts by weight of butadiene rubber latex solids, 1.0 part by weight of potassium oleate and cumene relative to the total solids Graft ABS latex was prepared by adding 0.4 parts by weight of hydroperoxide, 0.2 parts by weight of mercaptan-based chain transfer agent, 0.4 parts by weight of glucose, 0.01 parts by weight of iron sulfate hydrate, and 0.3 parts by weight of sodium pyrophosphate, and maintaining the temperature at 75 ° C. for 5 hours. It was. 0.4 parts by weight of sulfuric acid was added to the resulting polymer latex and solidified, thereby preparing a graft copolymer resin (g-ABS) powder.

(a ₄ ) Styrene-containing copolymer resin (SAN): 75 parts by weight of styrene, 25 parts by weight of acrylonitrile, 120 parts by weight of deionized water, 0.15 parts by weight of azobisisobutyronitrile, 0.4 parts by weight of tricalcium phosphate and mercaptan-based 0.2 parts by weight of a chain transfer agent was added and the temperature was raised from room temperature to 80 ° C. for 90 minutes, and then maintained at this temperature for 180 minutes to prepare a copolymer resin (SAN). The copolymer was washed with water, dehydrated and dried to use a powdery SAN.

(a ₅ ) Polycarbonate resin (PC): A linear bisphenol-A polycarbonate having a weight average molecular weight (Mw) of 25,000 was used.

(B) organophosphate ester compounds treated with organoclays

(b ₁ ) Organoclay: As an organoclay, benzyldimethyl octadecyl ammonium-modified montmorillonite from Nanocor was used.

(b ₂ ) Organophosphate ester compound: Triphenylphosphate (TPP) was used as the organophosphate ester compound.

The organic phosphate ester compound was treated with the organic clay to use an organic phosphate ester compound treated with an organic clay composed of 5% organic clay and 95% organic phosphate ester compound.

(C) phosphorus compounds

Triphenylphosphate (TPP) with a melting point of 48 ° C. was used.

(D) anti-dripping agent

The brand name Teflon 7AJ of Mitsui Dupont, Japan was used.

(A) When rubber modified polystyrene resin and polyphenylene ether are used as basic resin : Example 1-2 and Comparative Example 1-2

Example 1-2

Each component is added to rubber-modified polystyrene resin and polyphenylene ether, which are basic resins, as shown in Table 1, and extruded at a temperature range of 200-280 ° C. using a conventional twin screw extruder. Was prepared.

The prepared pellets were dried at 80 ° C. for 3 hours and then injected into a 6 Oz injection machine under conditions of a molding temperature of 220-280 ° C. and a mold temperature of 40-80 ° C. to prepare a physical specimen. The prepared specimens were measured for flame retardancy according to the UL 94 VB flame retardant regulation, the heat deformation temperature was measured at 5 kgf load according to ASTM D1525, and the tensile strength was measured according to ASTM D638.

In Example 1, only the organic phosphate ester compound (B) treated with an organic clay was used as a flame retardant. In Example 2, an organic phosphate ester compound (B) and a phosphorus-based compound (C) treated with an organic clay were used.

Comparative Example 1-2

In Comparative Example 1, only the phosphorus-based compound (C) was used as a flame retardant without using the organic phosphate ester compound (B) treated with an organic clay, and in Comparative Example 2, instead of the organic phosphate ester compound (B) treated with an organic clay The organoclay and the phosphorus compound (C) were simply mixed and used. The organic clay used in the comparative example was the same as the organic clay (b ₁ ) used when preparing the organic phosphate ester compound (B) treated with the organic clay used in the example. Specimens were prepared in the same manner as in Example 1-2 except for varying each component as described in Table 1.

Example Comparative Example One 2 One 2 Furtherance (A) Thermoplastic (a ₁ ) 60 60 60 60 (a ₂ ) 40 40 40 40 (B) organophosphate ester compounds treated with organoclays 12 8 - - (C) phosphorus compounds - 4 11.4 11.4 (D) anti-dripping agent 0.1 0.1 0.1 0.1 Organoclay - - - 0.6 Properties VST (℃) 92 87 83 84 Tensile Strength (kg / ㎠) 430 410 380 390 UL 94 (2.0mm) V-1 V-1 V-1 V-1

Physical properties of the resins prepared in Example 1-2 and Comparative Example 1-2 are shown in Table 1 above. From the results in Table 1, it can be seen that when using the organic phosphate ester (B) treated with an organic clay as a flame retardant, the heat resistance and tensile strength is superior to Comparative Example 1-2 while maintaining the flame retardancy. That is, when only the phosphorus-based compound (C) not treated with an organic clay as Comparative Example 1 is used as a flame retardant, the heat resistance and tensile strength are lowered, and by simply mixing the organic clay and the organic phosphate ester (C) as in Comparative Example 2 Even when added, the heat resistance and tensile strength do not increase. On the contrary, when using the phosphorus-based flame retardant (B) treated with organic clay as in Example 1-2, it can be seen that the heat resistance and tensile strength are increased. It can be seen that the clay used is dispersed evenly as nanoparticles in the resin, so that the heat resistance and tensile strength are excellent.

(B) When acrylonitrile-butadiene-styrene / SAN / polycarbonate / (ABS / SAN / PC) alloy is used as the base resin: Example 3 and Comparative Example 3-4

Example 3

The same process as in Example 1 was carried out except that ABS / SAN / PC alloy was used as the base resin.

Comparative Example 3-4

Except for using the ABS / SAN / PC alloy as a base resin it was carried out in the same manner as in Comparative Example 1-2.

Example Comparative Example 3 3 4 Furtherance (A) Thermoplastic (a ₃ ) 10 10 10 (a ₄ ) 15 15 15 (a ₅ ) 75 75 75 (B) organophosphate ester compounds treated with organoclays 13 - - (C) phosphorus compounds - 12.4 12.4 (D) anti-dripping agent 0.1 0.1 0.1 Organoclay - - 0.6 Properties VST (℃) 93 86 88 Tensile Strength (kg / ㎠) 600 550 560 UL 94 (2.0mm) V-0 V-0 V-0

From the results in Table 2, in the case of Example 3 using the phosphorus-based flame retardant (B) treated with an organic clay, Comparative Example 3 using a phosphorus-based compound (C) not treated with an organic clay as a flame retardant and simply organic clay and organic phosphoric acid It can be seen that the heat resistance and tensile strength are greatly increased compared to Comparative Example 4, in which the ester (C) is mixed.

(C) When acrylonitrile-butadiene-styrene (ABS) copolymer is used as the base resin: Example 4 and Comparative Example 5-6

Example 4

Except that the ABS copolymer was used as the base resin was carried out in the same manner as in Example 1.

Comparative Example 5-6

Except that the ABS copolymer was used as the base resin was carried out in the same manner as in Comparative Example 1-2.

Example Comparative Example 4 5 6 Furtherance (A) Thermoplastic (a ₁ ) 28 28 28 (a ₂ ) 42 42 42 (a ₃ ) 30 30 30 (B) organophosphate ester compounds treated with organoclays 12 - - (C) phosphorus compounds - 11.4 11.4 Organoclay - - 0.6 Properties VST (℃) 92 83 84 Tensile Strength (kg / ㎠) 480 395 410 UL 94 (2.0mm) V-1 V-1 V-1

From the results in Table 3 above, in the case of Example 4 using the organic phosphate ester (B) treated with organic clay even when ABS was used as the base resin, Comparative Example using the phosphorus-based compound (C) not treated with the organic clay as a flame retardant It can be seen that heat resistance and tensile strength are superior to Example 5 and Comparative Example 6, which simply uses an organic clay and an organic phosphate ester (C).

The present invention has excellent flame retardancy without deterioration of heat resistance and mechanical properties by using organic phosphate esters treated with organic clay as a flame retardant, and does not cause dripping during combustion, while dioxins, furans or It has the effect of providing a thermoplastic resin composition which does not generate toxic gases such as hydrogen halide gas.

Simple modifications and variations of the present invention can be easily made 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 (9)

(A) 100 parts by weight of thermoplastic resin; And (B) 5-30 parts by weight of an organophosphoric ester compound treated with an organoclay composed of (b ₁ ) 0.1-20% organoclay and (b ₂ ) 80-99.9% organophosphate ester compound; Flame-retardant thermoplastic resin composition, characterized in that consisting of. The method of claim 1, wherein the thermoplastic resin (A) is polyacrylonitrile-butadiene-styrene copolymer resin (ABS resin), rubber modified polystyrene resin (HIPS), polyphenylene ether resin (PPE), acrylonitrile- Styrene-acrylate copolymer resin (ASA resin), methyl methacrylate-butadiene-styrene resin copolymer resin (MBS resin), acrylonitrile-ethylacrylate-styrene copolymer resin (AES resin), polycarbonate resin ( PC), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), polyamide resin (PA), a copolymer of the above resins and mixtures thereof. According to claim 1, wherein the organic clay (b ₁ ) is a mica-like layered compound belonging to the smectite group montmorillonite, saponite, hectorite, bentonite, vaderite, stevensite and the like 50- 100 grams A flame retardant thermoplastic resin composition characterized in that the clay is a plated clay mineral having a cation substitution capacity of 200 milliquivalents, organically treated by ion exchange reaction with an organic cation of Formula 1 below: [Formula 1] Wherein R ₁ , R ₂ , R ₃ , and R ₄ are the same as or independently of each other, an alkyl group of C ₁ -C ₃₀ , an aryl group of C ₆ -C ₃₀ , or an aryl group substituted with alkyl; Or a C ₁ -C ₃₀ alkyl group and C ₆ -C ₃₀ aryl group having 1-5 hydroxy groups; X is not limited to cationic ions but is often chloride, bromide, iodide, carbonate, nitrate, sulphate, persulfate, etosulphate, methyl carbonate, ethyl carbonate and mixtures thereof. The flame retardant thermoplastic resin composition according to claim 1, wherein the organic phosphate ester compound (b ₂ ) is a compound having a structure of Formula 2 or a mixture thereof: [Formula 2] Wherein R ₃ , R ₄ and R ₅ are each independently hydrogen or an alkyl group of C ₁ -C ₄ ; X is a C ₆ -C ₂₀ aryl group which is substituted with a C ₆ -C ₂₀ aryl group or an alkyl group and is derived from dialcohols such as resorcinol, hydroquinol, bisphenol-A and the like; m ranges from 0 to 4. The flame retardant thermoplastic resin composition according to claim 1, wherein the resin composition further comprises 20 parts by weight or less of the phosphorus compound (C) based on 100 parts by weight of the thermoplastic resin (A). The flame retardant thermoplastic resin composition according to claim 5, wherein the phosphorus-based compound (C) is a compound having a structure of Formula 2 or a mixture thereof: [Formula 2] Wherein R ₃ , R ₄ and R ₅ are each independently hydrogen or an alkyl group of C ₁ -C ₄ ; X is a C ₆ -C ₂₀ aryl group which is substituted with a C ₆ -C ₂₀ aryl group or an alkyl group and is derived from dialcohols such as resorcinol, hydroquinol, bisphenol-A and the like; m ranges from 0 to 4. The flame retardant thermoplastic resin composition according to claim 1, wherein the resin composition further comprises an antidripping agent (D) of 5 parts by weight or less based on 100 parts by weight of the thermoplastic resin (A). The flame retardant thermoplastic resin composition according to claim 7, wherein the anti-dripping agent (D) is a fluorine resin. The method of claim 1, wherein the resin composition further comprises up to 50 parts by weight of a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a compatibilizer, a pigment and / or a dye, an inorganic additive based on 100 parts by weight of the thermoplastic resin (A). Flame retardant thermoplastic resin composition, characterized in that.