KR100397366B1 - 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 thermoplastic resin, (B) 0.1-50 parts by weight of an epoxy derivative represented by formula (1), and (C) 1-50 parts by weight of a phosphorus compound:

Wherein X is an alkyl group between the C ₁ -C _34, an aryl group, the alkyl group is a substituted aryl group, an aralkyl group or an oxygen (O), the alkyl groups include nitrogen (N), phosphorous (P), sulfur (S) , An aryl group, or an aryl group in which an alkyl group is substituted.

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 thermoplastic resin composition having excellent flame retardancy regardless of the type of resin by using an epoxy derivative having excellent char generation ability in a thermoplastic resin together with a phosphorus compound flame retardant.

Background of the Invention

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

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. Although halo-based flame retardants exhibit excellent flame retardancy regardless of the resin type, they cause corrosion of processing equipment such as molds due to the generation of corrosive gas during processing, and toxic gases such as dioxins, furan, and hydrogen halide gas may be generated during combustion. There is a danger. 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 compound as a flame retardant. However, although phosphorus-based flame retardants have superior properties to halogen-based flame retardants in terms of generation of corrosive gases and toxic gases, there is a disadvantage in that the flame retardancy is relatively lower than that of halogen-based flame retardants. There exists a problem that the heat resistance of a resin composition falls. In addition, there is also a drawback that is applicable only to some thermoplastic resins having a large amount of char during combustion.

Most thermoplastic resins do not produce char when burned, and therefore, phosphorus-based flame retardants cannot be used to impart sufficient flame retardancy. In order to solve the disadvantage of the phosphorus-based flame retardant, a method of imparting flame retardancy by adding char having a large amount of char to a thermoplastic resin having a small char generation amount to form a char film upon combustion is being studied. The char film generated during combustion serves to provide flame retardancy by limiting the movement of oxygen, heat, and fuel gas necessary for the combustion to continue.

In contrast, the present inventors have developed a thermoplastic resin composition having excellent flame retardancy regardless of the type of resin by adding an epoxy derivative having a large amount of char generated to a resin composition composed of a thermoplastic resin and a phosphorus compound flame retardant. will be.

An object of the present invention is to provide a thermoplastic resin composition excellent in flame retardancy regardless of the type of thermoplastic resin used as the base resin.

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 comprises (A) 100 parts by weight of a thermoplastic resin, (B) 0.1-50 parts by weight of an epoxy derivative and (C) 1-50 parts by weight of a phosphorus compound, and the detailed description of each of these components As follows.

(A) thermoplastic resin

The type of thermoplastic resin used in the present invention is basically not limited. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene copolymer resin (ABS resin), rubber modified polystyrene resin (HIPS), acrylonitrile-styrene-acrylate copolymer resin (ASA resin), methyl methacrylate Butadiene-styrene resin copolymer resin (MBS resin), acrylonitrile-ethyl acrylate-styrene copolymer resin (AES resin), polycarbonate resin (PC), polyethylene (PE), polypropylene (PP), polyethylene tere Phthalates (PET), polybutylene terephthalate (PBT), polyvinyl chromide (PVC), polymethyl methacrylate (PMMA) and copolymers of these resins or mixed alloys.

(B) epoxy derivatives

The epoxy derivative of the present invention is represented by Formula 1, and is added to impart char forming ability to the base resin to improve flame retardancy:

[Formula 1]

Wherein X is an alkyl group between the C ₁ -C _34, an aryl group, the alkyl group is a substituted aryl group, an aralkyl group or an oxygen (O), the alkyl groups include nitrogen (N), phosphorous (P), sulfur (S) , An aryl group, or an aryl group in which an alkyl group is substituted.

The epoxy derivative is added to a thermoplastic resin having a small char generation amount to form a char film upon combustion. The char film generated during combustion serves to provide flame retardancy by limiting the movement of oxygen, heat, and fuel gas necessary for the combustion to continue.

The epoxy derivatives may be used alone or in combination. In the present invention, the epoxy derivative is used in an amount of 0.1-50 parts by weight based on 100 parts by weight of the thermoplastic resin (A) which is the base resin.

(C) phosphorus compounds

The phosphorus compound flame retardant used in the present invention is a phosphate ester compound, a phosphate ester morphide compound, a phosphazene compound, a phosphoramidate compound and the like, and these phosphorus compounds may be used alone or in combination. The phosphorus compound (C) is used in an amount of 1-50 parts by weight based on 100 parts by weight of the thermoplastic resin (A). A detailed description of each phosphorus compound is as follows.

Phosphoric Acid Ester and Phosphoamidate Compounds

Phosphoric acid esters and phosphoramidate compounds used in the present invention are represented by Formula 2:

Wherein R ₃ , R ₄ , R ₅ are independently of each other 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, bisphenol-S, etc .; Y is oxygen (O) or nitrogen (N); m is 0-4.

Among the phosphate esters and phosphoamidate compounds used in the present invention, when m is 0, triphenylphosphate, tricresylphosphate, trigylenylphosphate, tri (2,6-dimethylphenyl) phosphate, tri (2, 4,6-trimethylphenyl) phosphate, tri (2,4-dibutylbutylphenyl) phosphate, tri (2,6-dibutylbutylphenyl) phosphate, triphenyl phosphoramidate, and m is 1 Examples thereof include resorcinol bis (diphenyl) phosphate, resorcinol bis (2,6-dimethylphenyl) phosphate, resorcinol bis (2,4-dibutylbutylphenyl) phosphate, hydroquinol bis (2,6- Dimethylphenyl) phosphate, hydroquinolbis (2,4-dibutylbutylphenyl) phosphate, etc. are typical examples.

These phosphoric acid esters and phosphoramidate compounds can be used alone or in mixed form.

Phosphate Ester Morphoxide Compound

Phosphoric acid ester morphide compounds used in the present invention are represented by Formula 3:

In which x is 1 or 2; R ₁ is C ₆ -C ₂₀ aryl or an alkyl substituted C ₆ -C ₂₀ aryl group; R ₂ is C ₆ -C ₃₀ aryl or an alkyl substituted C ₆ -C ₃₀ aryl group derivative; n and m represent the number average polymerization degree, respectively, and the average value of n + m is 0-5.

In the formula, R ₁ is preferably 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, double phenyl group or methyl More preferred are phenyl groups substituted with ethyl, isopropyl or t-butyl groups. R ₂ is preferably resorcinol, hydroquinone or bisphenol-A.

These phosphoric acid ester morphide compounds may be used alone or in a mixed form.

Phosphazene compounds

The phosphazene compounds used in the present invention are linear phosphazene compounds represented by formula 4, cyclic phosphazene compounds represented by formula 5, and mixtures thereof:

In Formulas 4 and 5, R ₁ , R ₂ , and R ₃ are optionally substituted from C ₆ -C ₃₀ alkyl, aryl, alkyl substituted aryl, aralkyl, alkoxy, aryloxy, amino or hydroxy groups. Represents; k is an integer of 0-10. The expression of the alkoxy group or aryloxy group is an alkyl group, an aryl group, an amino group, a hydroxyl group, CN or NO _2; Or an aryl group having an OH group.

In addition to the above components, the thermoplastic resin composition of the present invention may be added with antidropping agents, impact modifiers, inorganic additives, thermal stabilizers, antioxidants, light stabilizers, pigments, and / or dyes. 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 the (A) thermoplastic resin, (B) epoxy derivative and (C) phosphorus compound used in the following Examples and Comparative Examples are as follows.

(A) thermoplastic resin

(a ₁ ) Rubber modified polystyrene copolymer (High Impact Polystyrene)

A rubber-modified polystyrene resin prepared by a conventional method, the rubber content is 9% by weight, the average rubber particle size is 1.5 ㎛, the weight average molecular weight (Mw) of the polystyrene was used 220,000.

(a ₂ ) SAN graft copolymer resin

36 parts by weight of styrene, 14 parts by weight of acrylonitrile and 150 parts by weight of deionized water were added to 50 parts by weight of butadiene rubber latex solid, 1.0 parts by weight of potassium oleate, 0.4 parts by weight of cumene hydroperoxide, and mercaptan-based chain transfer agent. 0.2 parts by weight, 0.4 parts by weight of glucose, 0.01 parts by weight of iron sulfate hydrate, and 0.3 parts by weight of pyrophosphate sodium salt were added and reacted while maintaining at 75 ° C. for 5 hours to prepare an ABS graft latex. Sulfuric acid was added to the resulting polymer latex by 0.4 parts by weight based on the solid content of the resin, and coagulated to prepare a graft copolymer resin (g-ABS) powder.

(a ₃ ) Styrene-containing copolymer resin

Styrene 75 parts by weight, acrylonitrile 25 parts by weight 120 parts by weight of deionized water, 0.15 parts by weight of azobisisobutyronitrile, 0.4 parts by weight of tricalcium phosphate, 0.2 parts by weight of mercaptan-based chain transfer agent and 90 to 80 ℃ After the temperature was raised for minutes, the temperature was maintained at this temperature for 180 minutes to prepare a SAN copolymer resin. The prepared copolymer was washed with water, dehydrated and dried to use a powdery SAN copolymer resin.

(a ₄ ) polycarbonate resin

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

(B) epoxy derivatives

Epoxy derivative (trade name: KDT4400) of Kukdo Chemical Co., Ltd. represented by Formula 6 was used:

(C) phosphorus compounds

(c ₁ ) Triphenylphosphate (TPP) having a melting point of 48 ° C. was used.

(c ₂ ) A resorcinol diphosphate (RDP) oligomer was used as a viscous liquid at room temperature.

(c ₃ ) Triphenyl morpholido resorcinol diphosphate represented by Formula 7 was used:

(c ₄ ) P-3800 manufactured by Japanese Soda Industries, Inc. was used.

Example 1-7

As shown in Table 1, each component was charged and extruded at the temperature of 200-280 degreeC using the conventional twin screw extruder, and the extrudate was manufactured in pellet form.

The prepared pellets were dried at 80 ° C. for 3 hours and then injected at a condition of molding temperature of 220-280 ° C. and mold temperature of 40-80 ° C. in a 6 Oz injection machine to prepare specimens for measuring a limited oxygen index (LOI). The limit oxygen index was measured according to the standard of ASTM D2863.

Comparative Example 1-3

In Comparative Example 1-3, no epoxy derivative (B) was used. Specimens were prepared in the same manner as in Example 1-7 except that each component was changed as described in Table 1.

Example Comparative Example One 2 3 4 5 6 7 One 2 3 ingredient (A) Thermoplastic (a ₁ ) 100 100 100 100 100 - - 100 - - (a ₂ ) - - - - - 70 42 - 70 42 (a ₃ ) - - - - - 30 18 - 30 18 (a ₄ ) - - - - - - 40 - - 40 (B) epoxy derivatives 5 10 5 5 5 5 5 - - - (C) phosphorus compounds (c ₁ ) 15 15 - - - 15 15 15 15 15 (c ₂ ) - - 15 - - - - - - - (c ₃ ) - - - 15 - - - - - - (c ₄ ) - - - - 15 - - - - - Calculating Asset Index (LOI) 31 39 34 33 33 34 37 21 23 26

The limit oxygen indexes of the resins prepared in Examples 1-7 and Comparative Examples 1-3 are shown in Table 1 above. The limit oxygen index indicates that the larger the number, the higher the amount of oxygen required for the combustion to continue, and that it has excellent flame retardancy. Example 1-7 is a case where the epoxy derivative (B) according to the present invention is used together with a phosphorus compound flame retardant (C), and Comparative Example 1-3 is a phosphorus compound flame retardant (C) without using an epoxy derivative (B). Only used.

From the results of Table 1, it can be seen that the addition of epoxy derivatives increases the char (char) production amount of the resin during combustion, so that the threshold oxygen index is sharply higher than that without adding the epoxy derivatives, and thus has excellent flame retardancy.

That is, excellent flame retardancy can be imparted to the thermoplastic resin composition by using an epoxy derivative having a large amount of char generated during combustion regardless of the type of the thermoplastic resin used as the base resin. In particular, when the epoxy derivative is applied to a resin having little or no char generation ability in the thermoplastic resin, an excellent effect can be obtained.

The present invention has excellent flame retardancy regardless of the type of thermoplastic resin used as a base resin by using an epoxy derivative having a large amount of char generated during combustion together with a phosphorus compound flame retardant, and has a dioxin, furan or hydrogen halide gas during processing and combustion. It has the effect of providing a thermoplastic resin composition that does not generate toxic gases such as.

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 (5)

(A) 100 parts by weight of thermoplastic resin; (B) 0.1-50 parts by weight of the epoxy derivative represented by Formula 1; And [Formula 1] Wherein X is an alkyl group between the C ₁ -C _34, an aryl group, the alkyl group is a substituted aryl group, an aralkyl group or an oxygen (O), the alkyl groups include nitrogen (N), phosphorous (P), sulfur (S) , Aryl group, alkyl group substituted aryl group. (C) 1-50 parts by weight of the phosphorus compound; Flame-retardant thermoplastic resin composition, characterized in that consisting of. The method of claim 1, wherein the thermoplastic resin (A) is acrylonitrile-butadiene-styrene copolymer resin (ABS resin), rubber modified polystyrene resin (HIPS), acrylonitrile-styrene-acrylate copolymer resin (ASA resin) ), Methyl methacrylate-butadiene-styrene resin copolymer resin (MBS resin), acrylonitrile-ethyl acrylate-styrene copolymer resin (AES resin), polycarbonate resin (PC), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), copolymers of the above resins and mixtures thereof Flame retardant thermoplastic resin composition characterized in that. The flame-retardant thermoplastic according to claim 1, wherein the phosphorus compound (C) is selected from the group consisting of a phosphate ester compound, a phosphamidate compound, a phosphate ester morphide compound, a phosphazene compound and mixtures thereof. Resin composition. The flame retardant thermoplastic resin composition of claim 1, wherein the phosphorus compound (C) is at least one compound selected from compounds having the structures of Formulas 2, 3, 4, and 5 below: [Formula 2] Wherein R ₃ , R ₄ , R ₅ are independently of each other 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, bisphenol-S, etc .; Y is oxygen (O) or nitrogen (N); m is 0-4; [Formula 3] In which x is 1 or 2; R ₁ is C ₆ -C ₂₀ aryl or an alkyl substituted C ₆ -C ₂₀ aryl group; R ₂ is C ₆ -C ₃₀ aryl or an alkyl substituted C ₆ -C ₃₀ aryl group derivative; n and m represent the number average degree of polymerization, respectively, and the average value of n + m is 0 to 5; And [Formula 4] [Formula 5] In Formulas 4 and 5, R ₁ , R ₂ , and R ₃ are optionally substituted from C ₆ -C ₃₀ alkyl, aryl, alkyl substituted aryl, aralkyl, alkoxy, aryloxy, amino or hydroxy groups. Represents; k is an integer from 0 to 10; The alkoxy group or the aryloxy group is an alkyl group, an aryl group, an amino group, a hydroxyl group, CN or NO ₂ ; Or an aryl group having an OH group. The anti-dripping agent according to claim 1, wherein the resin composition is based on 100 parts by weight of the thermoplastic resin (A). Flame retardant thermoplastic resin composition further comprises 0-50 parts by weight of at least one additive selected from plasticizers, heat stabilizers, antioxidants, light stabilizers, compatibilizers, pigments and / or dyes, inorganic additives.