KR101411008B1 - Novel phosphorus compound, method for preparing thereof and flame retardant thermoplastic resin composition containing the same - Google Patents

Abstract

(상기 식에서, R은 수소, C₁-C₆의 알킬기, C₆ -C₁₂의 아릴기임).The present invention provides a phosphorus compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

(Wherein R is hydrogen, a C ₁ -C ₆ alkyl group, or a C ₆ -C ₁₂ aryl group).

Description

TECHNICAL FIELD [0001] The present invention relates to a novel phosphorus compound, a method for producing the phosphorus compound, and a flame retardant thermoplastic resin composition containing the same. BACKGROUND ART [0002]

The present invention relates to a novel phosphorus compound, a process for producing the same, and a flame retardant thermoplastic resin composition containing the same. More specifically, the present invention relates to a novel phosphorus compound capable of improving flame retardance, heat resistance and impact strength by containing phenol and hydroquinone linker having a tert-butyl group at a specific position, a process for producing the same, and a flame retardant thermoplastic resin composition containing the same will be.

Recently, the use of plastic polymer or synthetic resin has been diversified in vehicles, building materials, aircraft, railroad, household electric appliances, etc., and as the development of various functional additives is progressing rapidly, the application range thereof is explosively increasing. However, the plastic itself has characteristics that can easily burn up and is not resistant to fire. Therefore, plastic can easily burn by an external ignition source, and can play a role of spreading fire more. In view of this, the United States, Japan, and European countries are regulating the use of polymer resins that meet flame retardancy standards to ensure the safety of electronic products.

Examples of the flame retarding method of a polymer include a method of synthesizing a thermally stable resin through design or molecular structure design, a method of chemically improving conventional polymers (reaction type), a method of physically adding flame retardant by blending or compounding (Addition type), a method of coating or painting a flame retardant, and the like. One of the most widely used flame retardant methods is to add a flame retardant to the polymer resin. Additive flame retardants are classified into halogen-based, phosphorus-based, nitrogen-based, silicone-based, and inorganic flame retardants, depending on their constituents.

The halogen-based flame retardant plays a role in suppressing the chain reaction of the combustion process by reacting with the radicals generated on the gas during the combustion process of the polymer in the resin. As the halogen-based compounds, polybrominated diphenyl ether, tetrabromobisphenol A, bromine-substituted epoxy compounds and chlorinated polyethylene are mainly used, and as the antimony compounds, antimony trioxide and antimony pentoxide are mainly used. Brominated flame retardants are the most widely used in the electrical and electronics fields due to their unique properties, price and excellent flame retardancy, but there is a constant debate about environmental issues. As a result, RoHS (Restriction of the Use of Hazardous Substances in Electrical and Electronic Equipment) has become effective, and as a result, some of the general-purpose brominated flame retardants, also called deca, have been discontinued and their usage has been significantly reduced.

Phosphorous flame retardant is a recently demanded environmentally friendly flame retardant, and it stands out as a representative non-halogen flame retardant that can cope with environmental regulation. Such a phosphorus flame retardant exhibits an excellent flame retardant effect in a solid phase reaction, and is particularly effective for plastics containing a large amount of oxygen. Phosphorous flame retardants are classified into phosphates, phosphine oxides, phosphites, phosphonates and the like. In recent years, aromatic phosphoric esters such as resorcinol bisphenolphosphate and bisphenol bisdiphenylphosphate are mainly used.

When a phosphorus flame retardant is used, it has advantages such as improvement of flame retardancy and easiness of processing due to an increase of resin flow, but it tends to lower heat resistance of the resin itself.

Recently, the application range of synthetic resins is expanding to automobiles and aircrafts, and as electronic materials are highly integrated, resins with higher heat resistance are required. As a result, conventional phosphoric acid ester flame retardants cause problems such as gas generation, decomposition, and appearance problems during processing.

Japanese Patent Publication JP-A-1991-211293 discloses a structure in which resorcinol substituted with diphosphate is replaced with hydroquinone or biphenol. However, the improvement in thermal deformation temperature is insignificant and hydrolysis occurs.

According to British Patent GB 2325933, it has been reported that by introducing 2,4-ditertbutylphenol, heat resistance and impact strength can be improved while maintaining flame retardancy. However, since the synthesis process is complicated, The effect of improving the flame retardancy and heat resistance is insignificant, the fluidity is deteriorated, and hydrolysis is also disadvantageous.

Accordingly, the present inventors have found that a novel phosphorous compound having excellent flame retardance, heat resistance, impact strength and fluidity and having no hydrolysis resistance, and a novel phosphorous compound having excellent flame retardancy and thermal shock resistance Resistant flame retardant thermoplastic resin composition which is excellent in strength and does not cause problems (gas generation, decomposition, appearance problems, etc.) during processing.

It is an object of the present invention to provide a novel phosphorus compound which improves the low thermal stability and hydrolytic properties of conventional aromatic phosphate esters.

Another object of the present invention is to provide a novel phosphorus compound which does not deteriorate flowability while exhibiting excellent flame retardancy, heat resistance and impact strength, and does not cause problems in processing such as gas generation, decomposition and appearance problems.

It is still another object of the present invention to provide an environmentally friendly phosphorus compound that does not emit halogenated gas causing environmental pollution during processing or combustion of resin.

Another object of the present invention is to provide a phosphorus compound having excellent hydrolysis resistance.

It is still another object of the present invention to provide a phosphorus compound capable of exhibiting excellent physical properties such as flame retardance, impact strength, heat resistance, flowability and hydrolysis resistance when applied to a thermoplastic resin.

Another object of the present invention is to provide a thermoplastic resin composition which is excellent in flame retardancy, heat resistance, hydrolysis resistance and impact strength by applying the phosphorus compound.

Another object of the present invention is to provide a high heat-resistant flame retardant thermoplastic resin composition which is excellent in flame retardancy, hydrolysis resistance and heat resistance and can be applied to molded articles such as electric / electronic and automobile / aircraft.

It is still another object of the present invention to provide a method for easily synthesizing the phosphorus flame retardant.

The technical objects to be achieved by the present invention are not limited to the above-mentioned technical problems, and other technical subjects which are not mentioned can be understood by those skilled in the art from the following description.

One aspect of the present invention relates to a phosphorus compound represented by the following formula

[Chemical Formula 1]

(Wherein R is hydrogen, a C ₁ -C ₆ alkyl group, or a C ₆ -C ₁₂ aryl group).

In a specific example, the phosphorus compound is dissolved in water to a concentration of 75%, and the acid value change is less than 0.5 mg KOH / g after stirring at 93 ^° C for 48 hours. The acid value change before and after 1 hour at 280 ^° C is 0.1 mg KOH / g. < / RTI >

The phosphorus compound may have a weight loss of less than 5.5% as measured by thermogravimetric analysis at 350 ^° C.

Another aspect of the present invention relates to a method for producing the phosphorus compound. In one embodiment, the compound can be prepared by reacting phosphorus oxychloride, a compound represented by the following formula 2, and hydroquinone. In another embodiment, phosphorus oxychloride and a compound of formula 2 are reacted; And reacting the reactant with hydroquinone.

(2)

(Wherein R is hydrogen, a C ₁ -C ₆ alkyl group, or a C ₆ -C ₁₂ aryl group).

The phosphorus compound exhibits excellent flame retardancy, heat resistance and impact strength and can be suitably used as a flame retardant for a thermoplastic resin.

Another aspect of the present invention relates to a flame retardant thermoplastic resin composition containing the phosphorus compound.

In an embodiment, the thermoplastic resin composition comprises 100 parts by weight of a thermoplastic resin; And 0.1 to 50 parts by weight of the phosphorus compound.

Styrene-acrylate copolymer resin (ASA resin), an acrylonitrile-butadiene-styrene copolymer resin (ABS resin), a rubber-modified polystyrene resin (HIPS) Styrene copolymer resin (SAN resin), a methyl methacrylate-butadiene-styrene copolymer resin (MBS resin), an acrylonitrile-ethyl acrylate-styrene copolymer resin (AES resin), a polycarbonate resin (PC), polyphenylene ether resin (PPE), polyphenylene sulfide resin (PPS), polyethylene resin (PE), polypropylene resin (PP), polyethylene terephthalate (PET), polybutylene terephthalate ), A poly (meth) acrylic resin, a polyamide (PA) resin, and the like.

In one embodiment, the thermoplastic resin is a polycarbonate resin and may include 1 to 10 parts by weight of the phosphorus compound per 100 parts by weight of the polycarbonate resin.

In another embodiment, the thermoplastic resin is a blend of a polycarbonate resin and a rubber modified aromatic vinyl polymer resin, and may include 10 to 25 parts by weight of the phosphorus compound relative to 100 parts by weight of the blend.

The thermoplastic resin composition may further contain additives such as a flame retardant, a flame retardant, a lubricant, a plasticizer, a heat stabilizer, a dripping inhibitor, an antioxidant, a compatibilizer, a light stabilizer, a pigment, a dye and an inorganic additive.

Disclosure of Invention Technical Problem [8] The present invention has been made in view of the above problems, and it is an object of the present invention to provide a novel aromatic phosphoric acid ester which is capable of improving the low thermal stability and hydrolyzability of a conventional aromatic phosphoric acid ester and exhibiting excellent flame retardancy, heat resistance and impact strength, And does not emit halogenated gas which causes environmental pollution during processing or combustion of resin. Therefore, it is environmentally friendly and has excellent hydrolysis resistance. When applied to thermoplastic resin, flame retardancy, impact strength, heat resistance, fluidity, hydrolysis resistance And a thermoplastic resin composition which is excellent in flame retardancy, hydrolysis resistance and heat resistance and can be applied to a molded article of materials such as electric / electronic and automobile / aircraft by using the phosphorus compound capable of exhibiting excellent physical properties balance of .

FIG. 1 is an H-NMR image of the phosphorus compound prepared in Example 1. FIG.

The phosphorus compound of the present invention can be represented by the following formula (1)

[Chemical Formula 1]

(Wherein R is hydrogen, a C ₁ -C ₆ alkyl group, or a C ₆ -C ₁₂ aryl group).

Preferably, R is hydrogen or a linear alkyl group, more preferably R is hydrogen, methyl or ethyl, and most preferably R is hydrogen.

The phosphorus compound of the present invention is characterized in that a tert-butyl group is introduced at the Ortho position and contains a hydroquinone linker. Thus, by introducing the tert-butyl group at the Ortho position, 2,4-, 2,6-, 2,4,6-, 2,3,5,6-, 3,5-, 4-, 4,5,6-, and the like, it is possible to impart superior flame retardancy, heat resistance and hydrolysis resistance to a tertiary butyl group. Preferably, the tert-butyl group is introduced only at the 2-position, as shown in Formula 1 above.

If other alkyl groups such as methyl, ethyl, propyl or n-butyl groups other than t-butyl groups are introduced to the Ortho position, sufficient flame retardance can not be achieved. Flame retardant may be volatilized during processing and hardly hydrolyzable.

The phosphorus compound has an acid value change of less than 0.5 mg KOH / g, preferably less than 0.3, for example, 0.01 to 0.25 mg KOH / g after 75% concentration by dissolving in water and stirring at 93 ^° C for 48 hours.

In the present invention, 0.5 to 20 g of the acid value in the present invention is measured by dissolving 0.5 g to 20 g of the sample in dimethylsulfoxide (50 ml), adding 1 to 2 ml of the BTB solution, and titrating with 0.1 N NaOH solution.

Acid value = ((0.1N-NaOH solution consumption ml) * (0.1N-NaOH solution Factor) * 5.61) / sample amount (g)

Also, the acid value change before and after leaving for 1 hour at 280 ^° C is less than 0.1 mg KOH / g, preferably less than 0.05, for example, 0 to 0.01 mg KOH / g.

The phosphorus compound may have a weight loss of less than 5.5%, preferably 0.1 to 5%, as measured by thermogravimetric analysis at 350 ^° C.

The phosphorus compound may be prepared by reacting phosphorus oxychloride, a 2-tertiary butylphenol compound represented by the following formula (2), and hydroquinone.

(2)

(Wherein R is hydrogen, a C ₁ -C ₆ alkyl group, or a C ₆ -C ₁₂ aryl group).

In a specific example, the reaction may be performed by first reacting phosphorous oxychloride and the 2-tertiary butylphenol compound represented by the formula 2, and then reacting the reaction product with hydroquinone.

For example, by reacting phosphorus oxychloride with 2-tertiary butylphenol to prepare di-2-tert-butylphenylphenylchlorophosphate; And reacting the di-2-tert-butylphenyl chlorophosphate with hydroquinone.

In an embodiment, the reaction of the phosphorus chloride-based compound with tertiary butylphenol may be carried out using a Lewis acid catalyst or a base catalyst.

As the Lewis acid catalyst, a metal chloride or a metal oxide may be used, and metal chlorides such as magnesium chloride, aluminum chloride and calcium chloride may be used, but not always limited thereto. The amount used is 0.1-10 mol%. The reaction rate is excellent in the above range and is advantageous for catalyst removal after the reaction. It is preferably 0.5 to 5 mol%, more preferably 1 to 2 mol%.

As the base catalyst, an organic amine compound is used. Preferably, an aromatic amine such as pyridine or lutidine, a tallowamine of trialkylamines, or the like can be used. Of these, pyridine or triethylamine is preferable. The amount of the base catalyst to be used at this time is 1-3 equivalents, preferably 1.1-2 equivalents, more preferably 1.2-1.5 equivalents to the amount of chlorine element of the raw material used. In this range, the completeness of the reaction can be enhanced and by-products can be minimized.

Usable solvents are aprotic organic solvents with a boiling point of 110-200 ° C and no hydroxy. Preferably, the aromatic compound is toluene, xylene, chlorobenzene, dichlorobenzene, and more preferably toluene, xylene, and chlorobenzene. The reaction proceeds very slowly in a solvent having a boiling point lower than 110 캜 and a solvent having a boiling point higher than 200 캜 is difficult to completely dry after the reaction and the color of the product is deteriorated. These solvents may be used alone or in combination of two or more.

The reaction temperature of the phosphorus chloride-based compound and the tertiary butylphenol-based compound is 80-170 캜, preferably 100-160 캜.

When the phosphorus chloride-based compound and the tertiary butylphenol-based compound are reacted, a tertiary butylphenylchlorophosphate-based compound is obtained as an intermediate. Then, hydroquinone is added to the intermediate to react. At this time, it is preferable to react 0.5 to 2 equivalents of hydroquinone with respect to 1 equivalent of the phosphoryl chloride compound. When applied at the above equivalence ratio, the completeness of the reaction can be enhanced and by-products can be minimized.

The phosphorus compound exhibits excellent flame retardancy, hydrolysis resistance, heat resistance and impact strength and can be suitably used as a flame retardant for a thermoplastic resin. And can be suitably applied to thermoplastic resins containing oxygen in particular.

Another aspect of the present invention relates to a flame retardant thermoplastic resin composition containing the phosphorus compound. Wherein the thermoplastic resin composition comprises 100 parts by weight of a thermoplastic resin; And 0.1 to 50 parts by weight of a phosphorus compound. The thermoplastic resin composition has a flame retardancy of V-1 or V-0 according to UL-94 vertical at a thickness of 1.5 mm and a heat distortion temperature of 90 ° C or higher, preferably 90.5-135 ° C.

The thermoplastic resin may be an aromatic vinyl resin, a (meth) acrylate resin, a polyolefin resin, a polyester resin, a polyamide resin, a polyvinyl chloride resin, a polyether resin or a polycarbonate resin . In an embodiment, the thermoplastic resin is at least one selected from the group consisting of a polystyrene resin (PS resin), an acrylonitrile-butadiene-styrene copolymer resin (ABS resin), a rubber modified polystyrene resin (HIPS), an acrylonitrile-styrene- Styrene copolymer resin (AES resin), acrylonitrile-styrene copolymer resin (SAN resin), methyl methacrylate-butadiene-styrene copolymer resin (MBS resin) (PC), polyphenylene ether resin (PPE), polyphenylene sulfide resin (PPS), polyethylene resin (PE), polypropylene resin (PP), polyethylene terephthalate (PET) Terephthalate (PBT), poly (meth) acrylic resin, polyamide (PA) resin, and the like. These may be used alone or in combination of two or more.

In one embodiment, the thermoplastic resin may be a polycarbonate resin. When the polycarbonate resin is used as the base resin, it may contain 1 to 10 parts by weight, preferably 3 to 6 parts by weight, of the phosphorus compound per 100 parts by weight of the polycarbonate resin.

In another embodiment, the thermoplastic resin may be a blend of a polycarbonate resin and a rubber modified aromatic vinyl polymer resin. When the blend is used as a base resin, 10 to 25 parts by weight, preferably 10 to 20 parts by weight, of the phosphorus compound may be contained per 100 parts by weight of the blend of the polycarbonate resin and the rubber-modified aromatic vinyl polymer resin.

The thermoplastic resin composition may further contain additives according to the respective applications. Examples of the additive include flame retardants, flame retardants, lubricants, plasticizers, heat stabilizers, anti-dripping agents, antioxidants, compatibilizers, light stabilizers, pigments, dyes and inorganic additives. These may be used alone or in combination of two or more. Preferable examples of the inorganic additive include asbestos, glass fiber, talc, ceramic or sulfate. The additive may be used in an amount of 30 parts by weight or less based on 100 parts by weight of the base resin. Further, in order to improve the flame retardancy, generally used flame retardants and flame-retardant adjuvants such as halogen-containing organic compounds, cyanurate compounds, metal salts, and fluorinated polyolefins may be further added to the phosphorus compounds described above.

The metal salts which can be used as the flame retarding auxiliary agent include commonly known sulfonic acid metal salts and sulfonic acid metal salts. Examples of the fluorinated polyolefin resins usable as the anti-drip agent include polytetrafluoroethylene, polyvinylidene fluoride, tetra Fluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, and ethylene / tetrafluoroethylene copolymer, and the like. These may be used independently of each other, or two or more different types may be used in combination.

The flame retardant thermoplastic resin composition according to 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 simultaneously mixed and then melt-extruded in an extruder to produce pellets or chips.

Since the thermoplastic resin composition of the present invention has excellent flame retardancy and excellent physical properties such as heat resistance, the thermoplastic resin composition of the present invention can be used in a variety of applications such as TV, audio, cellular phone, digital camera, navigation, washing machine, And can be widely used in the production of office automation equipment and other large-sized injection molding products.

There is no particular limitation on the method of molding a plastic molded article using the thermoplastic resin composition according to the present invention, and for example, extrusion, injection molding, or casting molding methods can be applied. Such molding can be easily carried out by a person having ordinary skill in the art to which the present invention belongs.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example

Example 1

2 equivalents of phosphorus oxychloride (Aldrich), 4 equivalents of 2-t-butylphenol (Aldrich) and 4.4 equivalents of triethylamine were added to toluene (10 times the amount of phosphorus oxychloride), and the mixture was heated to 130 ^° C and stirred for 10 hours or more. After the reaction was completed, the temperature was lowered to room temperature and toluene (manufactured by Samchun) was added at a rate of one half of the initial charge with one equivalent of hydroquinone (manufactured by Samchun) and 2.2 equivalents of triethylamine (manufactured by Samchun). The reactor was heated to 130 ^° C and then stirred for 10 hours or more. After completion of the reaction, the temperature was lowered to room temperature, and water (half of the total amount of toluene) was added thereto and washed three times. The water layer was discarded and the organic layer was removed under reduced pressure. Methanol was added and the temperature was raised to 70 ^° C, and the mixture was completely dissolved. The mixture was heated to below 0 ^° C and recrystallized. The phosphorus compound obtained after filtration had a white solid property and was obtained in a yield of 97%. H-NMR photograph (Bruker 300 MHz) is shown in FIG. 1, and the structure of the following formula 1-1 was confirmed.

[Formula 1-1]

The hydrolysis resistance and heat resistance of the prepared compound were measured by the following methods.

(1) Hydrolysis resistance: 25 g of distilled water was dissolved in 75 g of phosgene compound, and then the acid value was compared after stirring at 93 ^° C. × 48 h. The acid value (mg KOH / g) was obtained by dissolving 0.5 to 20 g of the sample in dimethylsulfoxide (50 ml), adding 1 to 2 ml of the BTB solution, titrating with 0.1 N NaOH solution and measuring it.

Acid value = ((0.1N NaOH solution consumption ml) * (0.1N NaOH solution Factor) * 5.61) / sample amount (g)

(2) Heat resistance:

(a) 10 g of the phosphorus compound was compared with the acid value before and after standing at 280 ^° C × 1 h. Acid value was obtained in the same manner as in the above method.

(b) Weight loss (%) was determined by thermogravimetric analysis (TGA) at 200 ^° C, 250 ^° C, 300 ^° C and 350 ^° C.

Comparative Example  One

Hydrolysis resistance and heat resistance were evaluated in the same manner as above using bisphenol bisdiphenyl phosphate (China Yoke BDP) instead of the phosphorus compound prepared in Example 1.

Comparative Example  2

Hydrolysis resistance and heat resistance were evaluated in the same manner as above using PX-200 (trade name) of Daihachi Co., Ltd. instead of the phosphorus compound prepared in Example 1. [

Example 1 Comparative Example 1 Comparative Example 2 I hydrolyse
(Acid value change: mg KOH / g) 0.24 0.91 2.20 Heat resistance
(Acid value change: mg KOH / g) 0.00 0.89 1.19 Weight loss (%) 200 ^o C 0.6 1.0 0.4 250 ^o C 0.6 1.6 0.7 300 ^o C 1.3 4.1 4.2 350 ^o C 4.9 17.6 19.5

Example  2

5 parts by weight of the phosphorus compound (1-1) prepared in Example 1 and 5 parts by weight of bisphenol-A type polycarbonate (PANLITE L-1250W, manufactured by Teijin Ltd.) having a weight average molecular weight of 25,000 g / And extruded using a conventional twin-screw extruder. The extrudate was then pelletized, and the pellet was dried at 80 ° C. for 2 hours, and then molded at a temperature of 200 to 280 ° C. and a mold temperature of 40 to 80 ° C. Specimens were prepared using 10 oz injection machine.

Comparative Example 3

The procedure of Example 2 was repeated, except that PX-200 (trade name) (A ') of Daihachi Co., Ltd. was used instead of the phosphorus compound used in Example 2.

Example 2 Comparative Example 3 Flammability (UL94, 1/8 ") V-0 V-1 Heat resistance (VST, ^o C) 130.4 128.1 IZOD (1/8 ", kgf · cm / cm) 13.2 11.4

Vicat softening temperature (VST) was measured in accordance with ISO R 306. The weight of the weight was 5 kg

* IZOD: Measured according to ASTM D-256 standard at 1/8 "thickness (kgf · cm / cm).

As shown in Table 2, it was found that the phosphorus compound of the present invention significantly improved flame retardancy, heat resistance and impact strength as compared with Comparative Example 3 using the conventional compound PX-200.

Example  3 to 6

A bisphenol-A type polycarbonate (PANLITE L-1250W, manufactured by Teijin Company) having a weight average molecular weight of 25,000 g / mol was added to the phosphorus compound (1-1) prepared in Example 1, And CHT, a rubber-reinforced styrene resin of Cheil Industries, Ltd., were used in the amounts shown in Table 3 below.

Example 3 4 5 6 Polycarbonate resin 80 80 80 80 Rubber modified aromatic vinyl polymer 20 20 20 20 Phosphorus compound (Formula 1-1) 12 14 16 18 Flammability (UL94, 2mm) V-0 V-0 V-0 V-0 Flammability (UL94, 1.5mm) V-1 V-0 V-0 V-0 Heat resistance (HDT, ^o C) 96.2 93.2 91.2 90.6

Comparative Example  4 to 7

The procedure of Example 3 to 6 was repeated except that bisphenol bisdiphenyl phosphate (China Yoke BDP) was used in place of the phosphorus compound (Formula 1-1) used in Examples 3 to 6. The results are shown in Table 4.

Comparative Example 4 5 6 7 Polycarbonate resin 80 80 80 80 Rubber modified aromatic vinyl polymer 20 20 20 20 Phosphorus compound (BDP) 12 14 16 18 Flammability (UL94, 2mm) V-0 V-0 V-0 V-0 Flammability (UL94, 1.5mm) V-2 V-1 V-0 V-0 Heat resistance (HDT, ^o C) 92.5 87.7 84.2 81.5

Comparative Example  8 ~ 11

Except that PX-200 (trade name) of Daihachi Co., Ltd. was used in place of the phosphorus compound (1-1) used in Examples 3 to 6. The results are shown in Table 5.

Comparative Example 8 9 10 11 Polycarbonate resin 80 80 80 80 Rubber modified aromatic vinyl polymer 20 20 20 20 Phosphorus compound (BDP) 12 14 16 18 Flammability (UL94, 2mm) V-0 V-0 V-0 V-0 Flammability (UL94, 1.5mm) V-1 V-0 V-0 V-0 Heat resistance (HDT, ^o C) 90.6 87.2 85.2 83.2

As shown in Tables 3 to 5, the composition of the present invention also has excellent heat resistance and flame retardancy as compared with Comparative Examples 4 to 11 even in a composition using a rubber-modified aromatic vinyl polymer.

Property evaluation method

(1) Flammability: For specimens 2mm and 1.5mm thick The flame retardancy was measured according to the UL-94 vertical flame retardance specification.

(2) Heat resistance: HDT (Heat Distortion Temperature) was measured according to ASTM D648 (1/4 ", 18.5 kgf / cm 2, 120 ° C / hr)

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims (10)

(1)
Wherein the acid value change is less than 0.5 mg KOH / g and the acid value change before and after standing at 280 ° C for less than 0.1 mg KOH / g after stirring at 93 ° C for 48 hours at 75%
[Chemical Formula 1]

(Wherein R is hydrogen).
delete The phosphorus compound according to claim 1, wherein the phosphorus compound has a weight loss of not more than 5.5% as measured by thermogravimetric analysis at 350 ^° C.
Phosphorus oxychloride and a compound represented by the following formula (2); And
Reacting the reactant with hydroquinone;
(1), comprising the steps of:
[Chemical Formula 1]

(Wherein R is hydrogen);
(2)

(Wherein R is hydrogen).
A flame retardant thermoplastic resin composition comprising the phosphorus compound of any one of claims 1 to 3.
6. The thermoplastic resin composition according to claim 5, wherein the thermoplastic resin composition comprises 100 parts by weight of a thermoplastic resin; And 0.1 to 50 parts by weight of the phosphorus compound.
The thermoplastic resin composition according to claim 5, wherein the thermoplastic resin is selected from the group consisting of a polystyrene resin (PS resin), an acrylonitrile-butadiene-styrene copolymer resin (ABS resin), a rubber modified polystyrene resin (HIPS), an acrylonitrile- Butadiene-styrene copolymer resin (MBS resin), acrylonitrile-ethyl acrylate-styrene copolymer resin (AES), acrylonitrile-styrene copolymer resin (SAN resin) (PC), polyphenylene ether resin (PPE), polyphenylene sulfide resin (PPS), polyethylene resin (PE), polypropylene resin (PP), polyethylene terephthalate (PET) Wherein the flame retardant thermoplastic resin composition comprises at least one member selected from the group consisting of butylene terephthalate (PBT), poly (meth) acrylic resin and polyamide (PA) resin.
The flame-retardant thermoplastic resin composition according to claim 5, wherein the thermoplastic resin is a polycarbonate resin and comprises 1 to 10 parts by weight of the phosphorus compound per 100 parts by weight of the polycarbonate resin.
The flame-retardant thermoplastic resin composition according to claim 5, wherein the thermoplastic resin is a blend of a polycarbonate resin and a rubber-modified aromatic vinyl-based polymer resin and comprises 10 to 25 parts by weight of the phosphorus compound per 100 parts by weight of the blend Composition.
The thermoplastic resin composition according to claim 5, wherein the thermoplastic resin composition comprises at least one additive selected from the group consisting of a flame retardant, a flame retardant aid, a lubricant, a plasticizer, a heat stabilizer, an antistatic agent, an antioxidant, a compatibilizer, a light stabilizer, a pigment, The flame retardant thermoplastic resin composition according to claim 1,

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