KR100449881B1 - Flame Retardant Thermoplastic Resin Composition - Google Patents

Abstract

The flame-retardant thermoplastic resin composition of this invention consists of 100 weight part of (A) polycarbonate resins, 0.01-1 weight part of (B) perfluorinated alkane sulfonate salts, and 0.01-1 weight part of (C) sulfone sulfonate salts.

Description

Flame Retardant Thermoplastic Resin Composition

Field of invention

The present invention relates to a polycarbonate-based thermoplastic resin composition excellent in flame retardancy, heat resistance and mechanical strength. More specifically, the present invention relates to a flame retardant thermoplastic resin composition which exhibits excellent flame resistance as well as heat resistance and mechanical strength by adding perfluorinated alkane sulfonate salts and sulfone sulfonate salts to polycarbonate resins.

Background of the Invention

Polycarbonate resins have been widely used in office automation devices, electrical and electronic products as engineering plastics because of their excellent low temperature impact resistance, self-extinguishing, electrical properties, transparency, dimensional stability and thermal stability compared to other resins. However, polycarbonate resins have disadvantages of poor processability and notched impact strength, so they are used in combination with other types of resins to improve them. For example, a blend of polycarbonate / styrene-containing copolymer It is a resin mixture which improved workability while maintaining the notch impact strength.

Since polycarbonate-based blend resin compositions are usually applied to large heat dissipating materials such as computer housings or other office equipment, it is essential to maintain flame retardancy and high mechanical strength. In order to impart flame retardance to such a resin composition, a halogen-based flame retardant and an antimony compound have been conventionally used.

U.S. Patent Nos. 4,983,658 and 4,883,835 disclose examples of the use of halogen containing compounds as flame retardants. However, when using a halogen-based flame retardant, there is a problem of human health of the gas generated during combustion. Therefore, the demand for resins containing no halogen-based flame retardant has been rapidly expanded in recent years.

As a technique for imparting flame retardancy without using a halogen flame retardant, a perfluorinated alkane sulfonate salt may be used as a flame retardant.

U.S. Patent No. 3,775,367 discloses the use of perfluorinated alkane sulfonate salts as flame retardants in polycarbonate resins. However, when only the perfluoroalkane sulfonate salts are used in the polycarbonate resin alone, it is difficult to prevent the dropping of the spark generated during combustion.

In order to solve this problem, U.S. Patent No. 4,303,575 discloses a technique of adding bromine or chlorine aromatic carboxyl anhydride to the perfluorinated alkane sulfonate salts to prevent dropping during combustion and to improve flame retardancy. However, when using such bromine or chlorine-based aromatic carboxylic acid anhydride has the advantage of improving the flame retardancy, there is a fatal disadvantage that generates toxic gases during combustion.

On the other hand, the present inventors, in order to solve the above problems, by using a perfluoroalkane sulfonate salts and sulfone sulfonate salts in combination with a polycarbonate resin as a flame retardant, flame retardant thermoplastic resin having excellent heat resistance as well as flame retardancy and mechanical strength It is early to develop the composition.

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 excellent heat resistance.

Still another object of the present invention is to provide a thermoplastic resin composition having excellent mechanical properties.

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

The thermoplastic resin composition of this invention consists of 0.01-1 weight part of (B) perfluorinated alkane sulfonate salts, and 0.01-1 weight part of (C) sulfone sulfonate salts with respect to 100 weight part of (A) polycarbonate resins, These Detailed description of each component is as follows.

(A) polycarbonate resin

The polycarbonate resin according to the present invention is prepared by reacting diphenols represented by the following formula (1) with phosgene, halogen formate or carbonic acid diester:

[Formula 1]

Wherein, A is a single bond, a cycloalkylidene, S or SO ₂ in the alkylidene, C _5-6 alkylene, C _1-5 of C _1-5.

Examples of the diphenols represented by the above formula include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, and 2,4-bis- (4- Hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2 -Bis- (3,5-dichloro-4-hydroxyphenyl) -propane and the like. Among them, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 1,1-bis- (4- Bisphenols, such as hydroxyphenyl) -cyclohexane, are preferable, and 2,2-bis- (4-hydroxyphenyl) -propane also called bisphenol-A is the most preferable.

The polycarbonate resin (A) of the present invention has a weight average molecular weight (M _w ) of 10,000 to 200,000, preferably 15,000 to 80,000.

The polycarbonate resin of the present invention may be branched chain, preferably 0.05-2 mol% of tri- or more polyfunctional compounds, such as trivalent or more, based on the total amount of diphenols used for polymerization. It can be prepared by adding a compound having a phenol group.

The polycarbonate (PC) used in the preparation of the resin composition of the present invention may be used in the form of a homopolymer, a copolymer, or a mixture thereof. In addition, the polycarbonate resin (A) may be used in part or in whole by an aromatic polyester-carbonate resin obtained by polymerizing in the presence of an ester precursor, such as a bifunctional carboxylic acid.

(B) perfluorinated alkane sulfonate salts

In the present invention, the perfluorinated alkane sulfonate salt is used as a flame retardant, and is used in an amount of 0.01-1 part by weight based on 100 parts by weight of the polycarbonate resin (A) which is the base resin.

The perfluorinated alkane sulfonate salts of the present invention include perfluoromethane sulfonate, perfluoroethane sulfonate, perfluorinated propane sulfonate, perfluorinated butane sulfonate, perfluorinated methyl butane sulfonate, perfluorinated hexane sulfonate, perfluorinated Sodium or potassium salts of heptane sulfonate, octane perfluoride sulfonate; Tetraethylammonium perfluorinated butane sulfonate, tetraethylammonium perfluorinated methylbutane sulfonate, and the like. These can be used independently from each other, or can use together 2 or more types different from each other.

(C) sulfone sulfonate salts

As the sulfone sulfonate salts used in the present invention, one or more mixtures may be used as the mono or polymer aromatic sulfonsulfonate salts. Practically alkali metal salts or alkaline earth metal salts are used. As the metal, sodium, lithium, potassium, rubidium, cesium, baryllium, magnesium, calcium, strodium and barium can be used.

The mono-type aromatic sulfone sulfonate salts can be represented by the following formula (2).

[Formula 2]

R '(SO ₂ ) _l R "(SO ₃ M) _m X _n

Wherein l is an integer of 1-2, m is an integer of 1-6, n is an integer of 0-11, X is an electron withdrawing radical, M is an alkali or alkaline earth metal, And R 'and R "are aryl radicals of 1 to 2 aromatic rings or aliphatic radicals having 1 to 6 carbon elements, and may be the same or different from each other. They may be used independently of each other, It may be used in combination.

The sulfone sulfonate salts are used in an amount of 0.01-1 part by weight based on 100 parts by weight of the polycarbonate resin (A) which is the base resin.

In addition to the above components, 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 additive pigments, or dyes according to their respective uses. The added inorganic additive may be used in the range of 0-20 parts by weight, preferably 1-10 parts by weight, based on 100 parts by weight of the base resin component (A).

The resin composition of this invention can be manufactured by the well-known method of manufacturing 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 flame retardant thermoplastic resin composition of the present invention can be used for molding various products, and is particularly suitable for the manufacture of housings of electrical and electronic products such as computer housings that require flame retardancy and high impact 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) polycarbonate resin, (B) perfluorinated alkane sulfonate salts, and (C) sulfone sulfonate salts used in the following examples and comparative examples are as follows.

(A) polycarbonate resin

A polycarbonate of bisphenol-A type having a weight average molecular weight (Mw) of 25,000 was used.

(B) perfluorinated alkane sulfonate salts

FR-2025, a commercially available product of 3M potassium perfluorobutane sulfonate, was used.

(C) sulfone sulfonate salts

Potassium diphenylsulfone-3- sulfonate and dipotassium diphenyl sulfone-3,3'-disulfonate are about 75:25 weight ratio. It was used as a main component, mixed with a small amount of diphenylsulfonate (diphenylsulfonate).

Example 1-4

Each component of the composition shown in Table 1, antioxidant, and heat stabilizer were added, mixed in a conventional mixer, and introduced into a twin screw extruder having L / D = 29 and Φ = 45 mm. The mixture was prepared into a resin composition in pellet form through an extruder, and a specimen for evaluation of physical properties and flame retardancy at an injection temperature of 300 ° C. was prepared using a 10 oz injection machine.

Comparative Example 1-3

A specimen was prepared in the same manner as in Example 1-4 except for a flame retardant. Comparative Examples 1 and 2 use only perfluorinated alkane sulfonate salts (B) as flame retardants, and Comparative Example 3 uses only sulfonsulfonate salts (C) as flame retardants.

Property measurement

These specimens were measured for 48 hours at 23 ° C. and 50% relative humidity, and then measured for physical properties according to ASTM standards.

(1) Flame retardancy was evaluated using a 2.5mm thick specimen in accordance with UL-94.

(2) The total combustion time is the sum of both primary and secondary combustion times when five specimens were evaluated.

(3) Heat deflection temperature is measured according to ASTM D648.

(4) Notched Izod impact strength (1/8 ") is measured according to ASTM D256.

Using the above-mentioned components, the same resin compositions as those shown in Examples 1-4 and Comparative Examples 1-3 of Table 1 were prepared, and their physical properties are also shown in Table 1.

Example Comparative Example One 2 3 4 One 2 3 (A) polycarbonate resin 100 100 100 100 100 100 100 (B) Perfluoroalkane sulfonate salts 0.1 0.3 0.3 1.0 0.1 0.3 - (C) sulfone sulfonate salts 0.1 0.1 0.3 1.0 - - - UL94 flame retardant (2.5 mm) V-0 V-0 V-0 V-0 V-2 (drip) V-2 (drip) V-2 (drip) Total combustion time 40 35 25 25 30 25 35 Heat deflection temperature 130 130 130 130 130 130 130 Izod impact strength (1/8 ^〃 ) 60 60 60 50 60 60 60

From the results of Table 1, when the perfluoroalkane sulfonate salts and the sulfone sulfonate salts are added to the polycarbonate base resin in parallel, the synergistic effect in the flame retardancy compared to the use of the perfluoroalkane sulfonate salts alone. ) Can be seen.

The present invention uses a mixture of perfluorinated alkane sulfonate salts and sulfone sulfonate salts as a flame retardant, so that the physical properties such as flame retardancy, heat resistance, and mechanical strength are 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 making.

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 parts by weight of polycarbonate resin; (B) 0.01-1 part by weight of perfluorinated alkane sulfonate salts; And (C) 0.01-1 part by weight of sulfone sulfonate salts; Flame-retardant thermoplastic resin composition, characterized in that consisting of. The perfluoroalkane sulfonate salt (B) is a perfluoromethane sulfonate, a perfluoroethane sulfonate, a perfluorinated propane sulfonate, a perfluorinated butane sulfonate, a perfluorinated methyl butane sulfonate, or a perfluorinated compound. Sodium or potassium salts of hexane sulfonate, perfluorinated heptane sulfonate, octane perfluoride sulfonate; A flame retardant thermoplastic resin composition, characterized in that it is selected from the group consisting of tetraethylammonium perfluorinated butane sulfonate, tetraethylammonium perfluorinated methylbutane sulfonate and mixtures thereof. The flame retardant thermoplastic resin composition according to claim 1, wherein the sulfone sulfonate salt (C) is represented by the following Chemical Formula 2. [Formula 2] R '(SO ₂ ) _l R "(SO ₃ M) _m X _n Wherein L is an integer of 1-2, m is an integer of 1-6, n is an integer of 0-11, X is an electron withdrawing radical, and M is an alkali or alkaline earth metal And R 'and R "are aryl radicals of 1-2 aromatic rings or aliphatic radicals having 1-6 carbon elements, each of which may be the same or different.) The flame retardant thermoplastic resin composition according to claim 1, wherein the sulfone sulfonate salts (C) are one or more mixtures of mono-type or polymer-type aromatic sulfone sulfonate salts. According to claim 1, wherein the perfluorinated alkane sulfonate salt (B) is potassium perfluorinated butane sulfonate, the sulfonsulfonate salt (C) is potassium diphenylsulfone-3-sulfonate (potassium diphenylsulfone-3-sulfonate ): Dipotsulum diphenylsulfone-3,3'-disulfonate (dipotassium diphenylsulfone-3,3'-disulfonate) in a mixture of 75: 25, by mixing diphenylsulfonate (diphenylsulfonate) prepared by mixing Flame retardant thermoplastic resin composition characterized in that.