KR102141198B1 - Thermoplastic flame retardant resin composition, method for preparing the resin composition and molding product comprising the resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic flame-retardant resin composition, a method for manufacturing the same, and a molded article manufactured by including the same, more specifically, a thermoplastic flame-retardant resin composition comprising a styrene-based resin, a phosphorus-based flame retardant, an epoxy-based resin and a flame-retardant auxiliary agent, a flame-retardant auxiliary agent The present invention relates to a thermoplastic flame retardant resin composition and a method for manufacturing the same, wherein the zeolite and melamine polyphosphate or ammonium polyphosphate are used in a specific combination.
The molded article manufactured by including the thermoplastic flame-retardant resin composition according to the present invention has an excellent flame-retardant grade, but has a significant improvement in mechanical strength such as impact strength, thereby providing an excellent-quality molded article.

Description

Thermoplastic flame-retardant resin composition, method for manufacturing the same, and molded article manufactured by the same{THERMOPLASTIC FLAME RETARDANT RESIN COMPOSITION, METHOD FOR PREPARING THE RESIN COMPOSITION AND MOLDING PRODUCT COMPRISING THE RESIN COMPOSITION}

The present invention relates to a thermoplastic flame-retardant resin composition, a method for manufacturing the same, and a molded article manufactured by including the same, and more specifically, as a flame-retardant auxiliary agent, zeolite and melamine polyphosphate or ammonium polyphosphate are included in a specific combination to provide excellent flame-retardant grade and impact. The present invention relates to a thermoplastic flame-retardant resin composition capable of greatly improving mechanical strength, such as strength, and a molded article manufactured by including the same.

Styrene-based resins such as acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polystyrene, and high-impact polystyrene copolymer have advantages such as mechanical rigidity and ease of processing, and are used for various purposes.

Among them, acrylonitrile-butadiene-styrene (hereinafter referred to as ``ABS-based resin'')-based resins have excellent mechanical properties such as impact strength, chemical resistance, processability, and other properties, such as housings for electrical/electronic products, office equipment, It is widely used for applications such as automobile parts.

However, ABS-based resin has the characteristics of easy combustion and has little resistance to fire, so ABS-based resin used in electric/electronic products or office equipment must satisfy strict flame retardant standards to ensure stability against fire. .

Methods for imparting flame retardancy to ABS-based resins include polymerization by including flame retardant monomers in the manufacture of resins, and mixing flame retardants and flame retardants in the prepared resins. Examples of the flame retardants include halogen-based flame retardants, phosphorus and nitrogen Non-halogen-based flame retardants such as system and hydroxide, and antimony-based compounds, silicon-based compounds and zinc-based compounds are mainly used as the flame retardant.

The halogen-based flame retardant has a higher flame retardant efficiency than non-halogen-based flame retardants, and has the advantage of not significantly deteriorating the mechanical properties inherent in ABS resins, and is widely used as a flame retardant for styrene-based resins including ABS resins. Among the flame retardants, bromine-based flame retardants are particularly effective. However, in the case of manufacturing a thermoplastic resin composition including a bromine-based flame retardant, thermal stability is degraded due to high temperature and pressure applied during processing, and decomposition is caused. Corrosive toxic gas is generated, thereby adversely affecting the working environment and the human body. There was, and such a problem also occurs when the ABS-based resin product manufactured containing a bromine-based flame retardant is burned.

To solve this problem, a method using a non-halogen-based flame retardant has been proposed, and phosphorus-based flame retardants are most widely used. However, since this has a low flame retardant efficiency compared to a halogen-based flame retardant, an excessive amount is required, thereby causing a problem that the mechanical strength of the final molded product is lowered.

In addition, due to the principle of the phosphorus-based flame retardant system, in the case of a thermoplastic resin composition that does not produce char, it is difficult to sufficiently exhibit flame retardancy and there is a difficulty in satisfying the flame retardant standard. Accordingly, a method of mixing and using a phosphorus-based flame retardant with a flame retardant aid that can promote char formation, such as an antimony-based compound, has been proposed, but an antimony-based compound also requires a flame retardant aid that can replace it with a toxic substance.

For reference, there is a UL-94 vertical combustion test method as a flame retardant standard and flame retardant discrimination test method. This is a rule for determining flame resistance from internal ignition due to short circuit, short circuit, short circuit, etc. of a circuit board inside an electronic product finished product. Plastics used for electronic products distributed in the Americas must satisfy the above standards.

Korean Patent Publication No. 2013-0130320

In order to solve the problems of the prior art as described above, the present invention does not contain a compound that causes environmental problems, such as halogen-based flame retardants or antimony-based flame retardants, is environmentally friendly, maintains high flame retardancy even when reducing the flame retardant, impact strength, etc. An object of the present invention is to provide a thermoplastic flame-retardant resin composition and a method for manufacturing the same, which can greatly improve the mechanical stiffness.

In addition, an object of the present invention is to provide an injection molded article having high flame retardancy and excellent mechanical strength such as impact strength, including the thermoplastic flame retardant resin composition.

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

In order to achieve the above object, the present invention is a thermoplastic flame-retardant resin composition comprising 100 parts by weight of styrene-based resin, 1 to 30 parts by weight of phosphorus-based flame retardant, 1 to 30 parts by weight of epoxy-based resin and 1 to 10 parts by weight of flame retardant, The flame retardant aid is not the same as the phosphorus-based flame retardant, zeolite 20 to 60% by weight; And 40 to 80% by weight of at least one polyphosphate selected from melamine polyphosphate or ammonium polyphosphate; and the flame retardant resin composition provides a flame retardant resin composition characterized by having an impact strength of 12 kgcm/cm or more.

In addition, the present invention comprises the steps of kneading and extruding 100 parts by weight of a styrene-based resin, 1 to 30 parts by weight of a phosphorus-based flame retardant, 1 to 30 parts by weight of an epoxy-based resin and 1 to 10 parts by weight of a flame-retardant auxiliary agent, wherein the flame-retardant auxiliary agent is the phosphorus-based Not equal to a flame retardant, 20-60% by weight of zeolite; And 40 to 80% by weight of at least one polyphosphate selected from melamine polyphosphate or ammonium polyphosphate; provides a method for producing a thermoplastic flame-retardant resin composition comprising a.

In addition, the present invention provides an injection molded article characterized by being manufactured by injecting the thermoplastic flame retardant resin composition.

According to the present invention, it does not contain a compound that causes environmental problems, such as halogen-based flame retardants or antimony-based flame retardants, and is environmentally friendly, has excellent flame retardant properties, and has the advantage of requiring less flame retardant by using a specific combination of flame retardants. , Mechanical strength such as impact strength of the final molded product is greatly improved.

Hereinafter, the thermoplastic flame-retardant resin composition of the present description will be described in detail.

When the present inventors use a combination of zeolite and melamine polyphosphate or ammonium polyphosphate as a flame retardant aid, it is confirmed that the mechanical rigidity such as impact strength is greatly improved even if the amount of flame retardant used is reduced, and mechanical rigidity such as impact strength is greatly improved. Sold out to complete the present invention.

The thermoplastic flame-retardant resin composition of the present invention includes, for example, 100 parts by weight of a styrene-based resin, 1 to 30 parts by weight of a phosphorus-based flame retardant, 1 to 30 parts by weight of an epoxy-based resin, and 1 to 10 parts by weight of a flame-retardant auxiliary agent, wherein the flame-retardant auxiliary agent is the Not the same as phosphorus-based flame retardants, zeolite 20-60% by weight; And 40 to 80% by weight of at least one polyphosphate selected from melamine polyphosphate or ammonium polyphosphate.

The thermoplastic flame-retardant resin composition of the present invention may be characterized by having high mechanical stiffness with an impact strength of 12 kgcm/cm or more using a specific combination of flame-retardant aids as described above.

Hereinafter, the thermoplastic flame-retardant resin composition of the present description will be described in detail for each component.

A) Styrene resin

The styrene-based resin is not particularly limited as long as it is a styrene-based resin generally meaning in the technical field to which the present invention pertains, preferably a vinyl cyan compound-diene rubber-aromatic vinyl compound copolymer, an aromatic vinyl compound-vinyl cyan compound, It may be one or more selected from polystyrene (PS), high-impact polystyrene (HIPS) copolymers and polymers derived therefrom.

The polymer derived from the present description means a polymer prepared by polymerization of a polymer of another monomer compound or a polymer copolymerized with a polymer or a derivative of a monomer compound not originally included in the polymer.

In the present description, a derivative means a compound in which the hydrogen atom or atomic group of the original compound is substituted with another atom or atomic group, for example, a halogen or alkyl group.

For example, the styrene-based resin is 10 to 90% by weight of a vinyl cyan compound-diene rubber-aromatic vinyl compound copolymer (ABS-based resin) and 10 to 90% by weight of an aromatic vinyl compound-vinyl cyan compound (SAN-based resin). In this case, in this case, while having excellent mechanical properties such as impact strength of the final molded product, it has the advantage of excellent physical properties such as chemical resistance and workability.

In another example, the styrene resin is 15 to 60% by weight of a vinyl cyan compound-diene rubber-aromatic vinyl compound copolymer (ABS resin) and 40 to 85% by weight of an aromatic vinyl compound-vinyl cyan compound (SAN resin). It may include, excellent mechanical strength, such as impact strength of the final molded product within this range, there is an effect that is excellent in physical properties such as chemical resistance, workability.

In another example, the styrene-based resin is 20 to 40% by weight of a vinyl cyan compound-diene rubber-aromatic vinyl compound copolymer (ABS resin) and 60 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound (SAN resin). % May be included, and within this range, there is an advantage in that the balance of physical properties such as mechanical strength and workability of the final product is excellent.

The ABS-based resin may be, for example, a diene-based rubber content of 30 to 70% by weight, 40 to 60% by weight or 50 to 60% by weight of an emulsified graft polymer, and within this range, mechanical strength such as impact strength of the final product Has an excellent advantage.

In addition, the diene-based rubber may have an average particle diameter of 0.1 to 0.6 μm, 0.2 to 0.5 μm, or 0.2 to 0.4 μm as an example, and within this range, the impact resistance of the final product is excellent, while the appearance quality such as glossiness is excellent. There is this.

In the present description, the diene-based rubber may be, for example, at least one selected from butadiene polymers, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, and ethylene-propylene copolymers, and preferably includes butadiene polymers.

Aromatic vinyl compounds in the present disclosure may be one or more selected from styrene, alpha-methylstyrene, alpha-ethylstyrene, para-methylstyrene, vinyltoluene, and the like, unless otherwise specified. To include.

In the present description, the vinyl cyan compound may be one or more selected from acrylonitrile, methacrylonitrile, and ethacrylonitrile, unless otherwise specified, and preferably includes acrylonitrile.

As a specific example, the ABS-based resin may be acrylonitrile-butadiene rubber-styrene copolymer, but is not limited thereto.

The SAN-based resin may be, for example, a bulk polymer containing 50 to 95% by weight of an aromatic vinyl compound and 5 to 50% by weight of a vinyl cyan compound, and has excellent effects in processability and moldability of the resin composition within this range.

In another example, the SAN-based resin may be a bulk polymer containing 60 to 80% by weight of an aromatic vinyl compound and 20 to 40% by weight of a vinyl cyan compound, and within this range, properties such as processability and moldability of the resin composition may be obtained. It has an excellent advantage.

In another example, the SAN-based resin may be a bulk polymer containing 70 to 80% by weight of an aromatic vinyl compound and 20 to 30% by weight of a vinyl cyan compound, and does not significantly reduce the mechanical strength of the final resin composition within this range. It has the effect of being excellent in physical properties such as processability and moldability.

The aromatic vinyl compound and the vinyl cyan compound may be the same compound as the compound included in the ABS resin.

Further, the SAN-based resin may preferably have a weight average molecular weight of 50,000 to 150,000 g/mol, 100,000 to 150,000 g/mol, or 120,000 to 140,000 g/mol, for example, mechanical strength of the final product within this range. There is an effect that workability is improved without lowering the physical properties.

As a specific example, the SAN-based resin may be a styrene-acrylonitrile copolymer having a weight average molecular weight of 120,000 to 150,000 g/mol, but is not limited thereto.

In the present description, the weight average molecular weight can be measured by gel permeation chromatography by dissolving the resin in a solvent such as tetrahydrofuran.

B) phosphorus flame retardant

The phosphorus flame retardant may be, for example, one or more selected from the group consisting of phosphate-based compounds, diphosphate-based compounds, polyphosphate-based compounds, phosphonate-based compounds, and phosphinate-based compounds.

As a specific example, the phosphorus-based flame retardant is a phosphate-based compound such as triphenyl phosphate, tricresyl phosphate, tri(2,6-dimethylphenyl)phosphate, tri(2,4,6-trimethylphenyl)phosphate, tetraphenylresoci Diphosphate-based compounds such as noldiphosphate, tetracresylsolecinoldiphosphate, tetra(2,6-dimethylphenyl)resorcinoldiphosphate, tetraphenylbisphenol A diphosphate, polyphosphate-based compounds having three or more phosphate groups, phospho It may be one selected from nate-based compounds, phosphinate-based compounds, and the like.

The phosphorus flame retardant may be preferably included as 1 to 30 parts by weight, 5 to 20 parts by weight or 10 to 20 parts by weight, and most preferably 12 to 15 parts by weight based on 100 parts by weight of the styrene-based resin. Within the above-described range, while having excellent flame retardant properties, mechanical properties such as impact strength of the final product are excellent.

C) Epoxy resin

The epoxy-based resin is not particularly limited as long as it is compatible with the styrene-based resin and can form char when the processed thermoplastic resin is burned.

As a preferred example, the epoxy-based resin, a phenoxy resin comprising a urethane-modified end group represented by the following formula (1) and an epoxy end group represented by the following formula (2); A polyfunctional phenoxy resin comprising an epoxy end group represented by Formula 2 below; And it may be at least one selected from the group consisting of a tetrafunctional resin containing an epoxy terminal group represented by the following formula (2), in this case, without reducing the properties of the styrene-based resin has excellent flame retardant properties.

[Formula 1]

(In Formula 1, X and Y are the same as or different from each other, and are independently selected from alkylene having 1 to 20 carbon atoms or arylene having 6 to 20 carbon atoms, and may include oxygen or nitrogen.)

[Formula 2]

As a specific example, the epoxy-based resin may be at least one of a phenoxy clock compound represented by the following formula A, a multifunctional phenoxy clock compound represented by the following formula B, and a tetrafunctional resin represented by the following formula C, in this case The compatibility with the styrene-based resin is excellent, so that it is easy to process and mold, and forms a char during combustion, thereby providing excellent flame retardant properties.

[Formula A]

(In Formula A, R ₁ is a urethane-modified end group represented by Formula 1; R ₂ is an epoxy end group represented by Formula 2; R ₃ and R ₄ are the same as or different from each other, and independently carbon atoms Selected from 1 to 20 alkylene or arylene having 6 to 20 carbon atoms, and may include oxygen or nitrogen; n ₁ and n ₂ may be the same or different from each other and are independently an integer from 1 to 100; a And b can be the same or different from each other and are independently an integer from 1 to 3.)

[Formula B]

(In Formula B, R ₂ is an epoxy end group represented by Formula 2; R ₅ and R ₆ are the same as or different from each other, and independently of alkylene having 1 to 20 carbons or arylene having 6 to 20 carbons Selected, may contain oxygen or nitrogen; n ₃ is an integer from 1 to 100; c and d may be the same or different from each other and independently an integer from 1 to 3.)

[Chemical Formula C]

(In Formula C, R ₂ is an epoxy end group represented by Formula 2)

In addition, the socks ends of the formulas A and B do not affect the flame retardancy of the resin composition, and the structure having an epoxy group is not particularly limited, and may be selected from the following formulas a and b.

[Formula a]

[Formula b]

The epoxy-based resin may be preferably included as 1 to 30 parts by weight, 5 to 20 parts by weight, or 15 to 20 parts by weight based on 100 parts by weight of the styrene-based resin, and impact resistance of the final molded product within this range, It has excellent physical properties such as workability and glossiness, and has excellent flame retardant properties.

D) Flame retardant supplements

In the present invention, the flame retardant adjuvant does not contain the same compound as the phosphorus-based flame retardant, and includes zeolite and melamine or ammonium polyphosphate which further improve flame retardant properties by promoting char formation.

In one example, the flame retardant aid is 20 to 60% by weight of zeolite; And 40 to 80% by weight of at least one polyphosphate selected from melamine polyphosphate or ammonium polyphosphate; and exhibits a high level of flame retardant properties even by reducing the flame retardant within this range, and mechanical rigidity such as impact strength of the final product. This has the effect of improving.

In another example, the flame retardant aid is 40 to 60% by weight of zeolite; And 40 to 60% by weight of at least one polyphosphate selected from melamine polyphosphate or ammonium polyphosphate; and has excellent flame retardant properties within this range, but has an effect of greatly improving mechanical strength such as impact strength of the final molded product. .

In another example, the flame retardant aid is 45 to 55% by weight of zeolite; And 45 to 55% by weight of at least one polyphosphate selected from melamine polyphosphate or ammonium polyphosphate; and has excellent flame retardant properties within this range, but has an effect of significantly improving mechanical strength such as impact strength of the final molded product. .

In a specific example, the flame retardant aid is 40 to 60% by weight of zeolite; Melamine polyphosphate 10-35 wt%; And ammonium polyphosphate 10 to 35% by weight; may include, excellent flame retardant properties within this range, even if the phosphorus-based flame retardant is reduced, excellent flame retardancy of the final molded product, the effect of mechanical properties such as impact strength is greatly improved There is.

In addition, the flame retardant aid may preferably include 1 to 10 parts by weight, 1 to 5 parts by weight, or 1 to 3 parts by weight as an example based on 100 parts by weight of the styrene-based resin, and the desired flame retardant grade within this range. It can have, and has an excellent impact resistance of the final molded product.

As a specific example, the zeolite may include 0.5 to 5 parts by weight or 1 to 3 parts by weight based on 100 parts by weight of the styrene-based resin, and within this range, char formation is promoted during combustion of the thermoplastic resin composition to have high flame retardant properties. Can.

In another example, the zeolite may include 0.5 to 1.5 parts by weight of zeolite based on 100 parts by weight of the styrene-based resin, 0.3 to 1.5 parts by weight or 0.3 to 1 part by weight of at least one polyphosphate selected from melamine polyphosphate or ammonium polyphosphate. In this range, the mechanical strength of the final processed product is excellent, while the flame retardant properties are excellent.

The zeolite may include, for example, a natural zeolite or a synthetic zeolite comprising at least one metal selected from Group I, Group II, and Group IV metal elements of the periodic table.

In another example, the zeolite is an A-type zeolite containing an alkali metal, Mg-substituted zeolite, Ca-substituted zeolite, Zn-substituted zeolite, Sr-substituted zeolite, Ba-substituted zeolite, Zr-substituted zeolite, and Sn-substituted zeolite It may be one or more selected, preferably containing calcium (Ca).

The melamine or ammonium polyphosphate may be included in an amount of 0.5 to 5 parts by weight or 1 to 3 parts by weight as an example based on 100 parts by weight of the styrene-based resin, in which case the impact of the final molded product while maintaining high flame retardant properties even by reducing the phosphorus-based flame retardant It has an effect of greatly improving strength and the like.

The thermoplastic flame-retardant resin composition of the present invention may be characterized by exhibiting excellent flame-retardant properties by excluding antimony-based compounds and zinc-based compounds used as flame-retardant aids using a specific combination of flame-retardant aids as described above.

E) Additive

The thermoplastic flame-retardant resin composition may optionally further include at least one additive selected from the group consisting of impact modifiers, heat stabilizers, dripping inhibitors, antioxidants, light stabilizers, sunscreens, pigments and inorganic fillers.

The additive may be preferably included in an amount of 0.01 to 10 parts by weight or 0.05 to 5 parts by weight as an example based on 100 parts by weight of the styrene-based resin, and within this range, the effect of the additive without lowering the physical properties of the final resin composition Can be implemented.

The thermoplastic flame-retardant resin composition of the base material can greatly improve the impact strength of the final molded product by using a specific combination of flame-retardant aids. For example, the thermoplastic flame-retardant resin composition of the base material is uniformly kneaded, then extruded and injected. The sheet may be characterized by having excellent mechanical strength with an impact strength of 12 kgcm/cm or more, 12 to 20 kgcm/cm, or 15 to 20 kgcm/cm measured according to ASTM D256.

Hereinafter, a method of manufacturing the thermoplastic flame-retardant resin composition of the present substrate will be described.

The method of manufacturing the thermoplastic flame-retardant resin composition of the present disclosure is, for example, kneading and extruding 100 parts by weight of a styrene-based resin, 1 to 20 parts by weight of a phosphorus-based flame retardant, 1 to 30 parts by weight of an epoxy-based resin, and 1 to 10 parts by weight of a flame-retardant auxiliary agent Included, the flame retardant aid is 40 to 60% by weight of zeolite; And 40 to 60% by weight of at least one polyphosphate selected from melamine or ammonium polyphosphate.

The kneading may further include at least one additive selected from impact modifiers, heat stabilizers, dripping inhibitors, antioxidants, light stabilizers, sunscreens, pigments and inorganic fillers.

The kneading and extrusion may be, for example, a device such as a banbury mixer (banbury mixer), a Henschel mixer, a single screw extruder, a twin screw extruder, and a bus kneader, but is not limited thereto.

In addition, the kneading and extrusion may be carried out under conditions of, for example, 180 to 240°C and 100 to 350 rpm or 190 to 230°C and 200 to 300 rpm, but is not limited thereto.

Other conditions not specifically specified in the description of the thermoplastic flame-retardant resin composition of the present disclosure and a method for manufacturing the same are not particularly limited and may be appropriately selected and carried out within a range generally practiced in the technical field to which the present invention pertains.

Furthermore, the thermoplastic flame-retardant resin composition according to the present invention may be manufactured as an injection molded article including an injection process, and the injection is, for example, 170 to 250°C or 180 to 230°C and 30 to 110 bar or 50 to 90 bar. It can be carried out, but is not limited thereto.

As described above, the injection molded article according to the present disclosure is characterized by having excellent mechanical strength, such as impact strength measured in accordance with ASTM D256 of 12 kgcm/cm or more, 12 to 20 kgcm/cm, or 15 to 20 kgcm/cm. can do.

In addition, the injection molded article according to the present disclosure may be characterized by having excellent flame retardant properties, such as a flame retardant grade of V-1 or higher measured according to the test method UL-94 standard.

Hereinafter, a preferred embodiment is provided to help the understanding of the present invention, but the following examples are only illustrative of the present invention, and it is apparent to those skilled in the art that various changes and modifications are possible within the scope and technical scope of the present invention. It is no wonder that such variations and modifications fall within the scope of the appended claims.

Materials used in the following examples and comparative examples are as follows.

1) Styrene resin

-ABS resin: DP270, manufactured by emulsion chemical polymerization using butadiene rubber latex having an average particle diameter of 0.3 µm, was used.

-SAN resin: a styrene-acrylonitrile copolymer having an acrylonitrile content of 25% by weight and a weight average molecular weight of 120,000 was used.

2) Phosphorus-based flame retardant: Tetra(2,6-dimethylphenyl)resorcinol diphosphate (trade name: PX-200) from DAIHACHI, Japan, was used.

3) Epoxy resin

-Epoxy (A): KD-1090 of Kukdo Chemical was used as the compound represented by Chemical Formula A.

-Epoxy (B): KD-1065 of Kukdo Chemical was used as the compound represented by Chemical Formula B.

4) Flame retardant supplements

-Zeolite: APS-30 (zeolite (A)) and APSC-20 (zeolite (B)) of Aekyung Materials were used.

-Ammonium polyphosphate (APP): APP1011 of SL Chem was used.

-Melamine polyphosphate (MPP): MPS of SL Chem was used.

[Example]

Example One

100 parts by weight of styrene-based resin comprising 25 parts by weight of ABS resin and 75 parts by weight of SAN resin, 20 parts by weight of epoxy (A) as an epoxy resin, 13 parts by weight of phosphorus-based flame retardant, 1 part by weight of zeolite as flame retardant and melamine phosphate 1 After mixing the parts by weight and uniformly mixing using a Henschel mixer, a thermoplastic flame-retardant resin composition in the form of pellets was prepared through a twin-screw extruder (220°C).

The pellet-shaped thermoplastic flame-retardant resin composition was injection molded (210° C., 80 bar) to prepare a specimen for measuring physical properties.

Example 2

In Example 1, except for using epoxy (B) instead of epoxy (A), it was carried out in the same manner as in Example 1.

Example 3

It was carried out in the same manner as in Example 1, except for using ammonium phosphate instead of melamine phosphate in Example 1.

Example 4

In Example 2, it was carried out in the same manner as in Example 2, except that ammonium phosphate was used instead of melamine phosphate.

Example 5

In Example 1, the epoxy resin was used in the same manner as in Example 1, except that 10 parts by weight of epoxy (A) and 10 parts by weight of epoxy (B) were used instead of 20 parts by weight of epoxy (A). .

Example 6

In Example 3, the epoxy resin was used in the same manner as in Example 1, except that 10 parts by weight of epoxy (A) and 10 parts by weight of epoxy (B) were used instead of 20 parts by weight of epoxy (B). .

Example 7

It was carried out in the same manner as in Example 1, except that 0.5 parts by weight of melamine phosphate and 0.5 parts by weight of ammonium phosphate were used instead of 1 part by weight of melamine phosphate in Example 1.

Example 8

In Example 1, the zeolite was used in the same manner as in Example 1, except that 0.5 parts by weight instead of 1 part by weight and melamine phosphate was used in 1.5 parts by weight instead of 1 part by weight.

Example 9

It was carried out in the same manner as in Example 1, except that 0.3 parts by weight of melamine phosphate and 0.7 parts by weight of ammonium phosphate were used instead of 1 part by weight of melamine phosphate in Example 1.

Example 10

In Example 1, it was carried out in the same manner as in Example 1, except that 0.7 parts by weight of melamine phosphate and 0.3 parts by weight of ammonium phosphate were used instead of 1 part by weight of melamine phosphate.

Example 11

In Example 1, the zeolite APS-30 was used in the same manner as in Example 1, except that APSC-20 manufactured by the same company was used.

Comparative example One

In Example 1, the phosphorus-based flame retardant was used as 15 parts by weight instead of 13 parts by weight, as a flame retardant auxiliary, used as 4 parts by weight instead of 1 part by weight of zeolite, and was carried out in the same manner as in Example 1, except that the injection of melamine phosphate was omitted. Did.

Comparative example 2

In Example 2, the phosphorus-based flame retardant was used as 15 parts by weight instead of 13 parts by weight, and as a flame retardant auxiliary, used as 4 parts by weight instead of 1 part by weight of zeolite, and was carried out in the same manner as in Example 2, except that the injection of melamine phosphate was omitted. Did.

Comparative example 3

In Example 1, the phosphorus-based flame retardant was used as 15 parts by weight instead of 13 parts by weight, as a flame retardant auxiliary, used as 2 parts by weight instead of 1 part by weight of zeolite, and was carried out in the same manner as in Example 1, except that the injection of melamine phosphate was omitted. Did.

Comparative example 4

In Example 2, the phosphorus-based flame retardant was used as 15 parts by weight instead of 13 parts by weight, and as a flame retardant auxiliary, it was used as 2 parts by weight instead of 1 part by weight of zeolite, and was carried out in the same manner as in Example 2, except that the injection of melamine phosphate was omitted. Did.

[Test Example]

The properties of the specimens prepared in Examples and Comparative Examples were measured by the following methods, and the results are shown in Tables 1 and 2 below.

1) Izod impact strength (kgcm/cm): Izod impact strength was measured using a specimen having a thickness of 1/8" according to ASTM D256.

2) Flame retardancy: After preparing a specimen of size 125mm X 125mm X 1.5mm according to the flame retardant grade standard UL-94, the flame retardancy was evaluated by recording the primary and secondary combustion times and glowing time.

For example, in the UL-94 determination method based on the primary and secondary combustion times and glowing time, the primary combustion time and the secondary combustion time are each less than 30 seconds, and the sum of the combustion times of all five specimens is 250 If it is within seconds and there is no ignition of the lower cotton wool, it is evaluated as V-1.

Example One 2 3 4 5 6 7 8 9 10 11 ABS 25 25 25 25 25 25 25 25 25 25 25 SAN 75 75 75 75 75 75 75 75 75 75 75 Phosphorous flame retardant 13 13 13 13 13 13 13 13 13 13 13 Epoxy (A) 20 - 20 - 10 10 20 20 20 20 20 Epoxy (B) - 20 - 20 10 10 - - - - - Zeolite (A) One One One One One One One 0.5 One One - Zeolite (B) - - - - - - - - - - One MPP One One - - One - 0.5 1.5 0.3 0.7 One APP - - One One - One 0.5 - 0.7 0.3 - Flame retardancy (V-1) PASS PASS PASS PASS PASS PASS PASS PASS PASS PASS PASS Impact strength
(kgcm/cm) 13 17 12 15 14 13 13 15 12 13 16

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 ABS 25 25 25 25 SAN 75 75 75 75 Phosphorous flame retardant 15 15 15 15 Epoxy (A) 20 - 20 - Epoxy (B) - 20 - 20 Zeolite (A) 4 4 2 2 Flame retardancy (V-1) PASS PASS FAIL FAIL Impact strength
(kgcm/cm) 6 8 8 10

As shown in Table 1, in the case of Examples 1 to 11 containing zeolite and MPP or APP in a specific combination as a flame retardant adjuvant, UL-94 even though it contains less phosphorus-based flame retardant than Comparative Examples 1 to 4 not according to the present invention It was confirmed that the flame retardancy of the V-1 grade was satisfied.

In addition, it was confirmed that the specimens of Examples 1 to 11 according to the present invention have high mechanical stiffness with an impact strength of 12 kgcm/cm or more.

On the other hand, as shown in Table 2, the specimens of Comparative Examples 1 to 4 containing only zeolite as a flame retardant aid had an impact strength of 10 kgcm/cm or less, which was confirmed to be poor compared to Examples 1 to 11 according to the present invention. Comparative Examples 3 and 4, which were added in 2 parts by weight, were found to not satisfy the flame retardant grade UL-94 V-1 due to the delay in char generation even though a large amount of phosphorus flame retardant was added compared to the Examples.

Summarizing the above results, the combination of zeolite and MPP or APP as a flame retardant adjuvant can promote char production, and as a result, even though the phosphorus-based flame retardant is reduced, it can satisfy the flame retardancy of UL-94 V-1 grade, The impact strength can be greatly improved.

Claims (16)

A thermoplastic flame-retardant resin composition comprising 100 parts by weight of a styrene-based resin, 12 to 15 parts by weight of a phosphorus-based flame retardant, 15 to 20 parts by weight of an epoxy-based resin and 1 to 2.5 parts by weight of a flame retardant,
The flame retardant aid is not the same as the phosphorus-based flame retardant, zeolite 20 to 60% by weight; And 40 to 80% by weight of melamine polyphosphate;
The zeolite is 0.5 to 1 part by weight, the melamine polyphosphate is 1 to 1.5 parts by weight,
The flame-retardant resin composition is characterized in that the impact strength is 12 kgcm / cm or more
Thermoplastic flame-retardant resin composition. According to claim 1,
The styrene-based resin is at least one selected from the group consisting of vinyl cyan compound-diene rubber-aromatic vinyl compound copolymer, aromatic vinyl compound-vinyl cyan compound copolymer, polystyrene (PS) and high impact polystyrene (HIPS) copolymer Characterized by comprising
Thermoplastic flame-retardant resin composition. According to claim 2,
The styrene-based resin is characterized in that it comprises 10 to 90% by weight of a vinyl cyan compound-diene rubber-aromatic vinyl compound copolymer and 10 to 90% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer
Thermoplastic flame-retardant resin composition. According to claim 3,
The vinyl cyan compound-diene rubber-aromatic vinyl compound copolymer is an emulsion graft polymer having a diene rubber content of 30 to 70% by weight.
Thermoplastic flame-retardant resin composition. The method of claim 4,
The diene-based rubber is characterized in that the average particle size is 0.1 to 0.6㎛
Thermoplastic flame-retardant resin composition. According to claim 3,
The aromatic vinyl compound-vinyl cyan compound copolymer is a bulk polymer comprising 50 to 95% by weight of an aromatic vinyl compound and 5 to 50% by weight of a vinyl cyan compound.
Thermoplastic flame-retardant resin composition. The method of claim 6,
The aromatic vinyl compound-vinyl cyan compound copolymer is characterized in that the weight average molecular weight is 50,000 to 150,000 g/mol
Thermoplastic flame-retardant resin composition. According to claim 1,
The phosphorus flame retardant is characterized in that it comprises at least one selected from the group consisting of phosphate-based compounds, diphosphate-based compounds, polyphosphate-based compounds, phosphonate-based compounds and phosphinate-based compounds
Thermoplastic flame-retardant resin composition. According to claim 1,
The epoxy-based resin, a phenoxy resin comprising a urethane-modified end group represented by the following formula (1) and an epoxy end group represented by the following formula (2); A polyfunctional phenoxy resin comprising an epoxy end group represented by Formula 2 below; And characterized in that at least one member selected from the group consisting of a tetrafunctional resin comprising an epoxy end group represented by the formula (2)
Thermoplastic flame-retardant resin composition.
[Formula 1]

(In Formula 1, X and Y are the same as or different from each other, and are independently selected from alkylene having 1 to 20 carbon atoms or arylene having 6 to 20 carbon atoms, and may include oxygen or nitrogen.)
[Formula 2]

The method of claim 9,
The epoxy resin is characterized in that at least one of the compounds represented by the following formula A and formula B
Thermoplastic flame-retardant resin composition.
[Formula A]

(In Formula A, R ₁ is a urethane-modified end group represented by Formula 1; R ₂ is an epoxy end group represented by Formula 2; R ₃ and R ₄ are the same as or different from each other, and independently carbon atoms Selected from 1 to 20 alkyl or aryl having 6 to 20 carbon atoms, and may include oxygen or nitrogen; n ₁ and n ₂ may be the same as or different from each other, and are independently an integer from 1 to 100; a and b Can be the same or different from each other and are independently integers from 1 to 3.)
[Formula B]

(In Formula B, R ₂ is an epoxy end group represented by Formula 2; R ₅ and R ₆ are the same as or different from each other, and independently selected from alkyl having 1 to 20 carbons or aryl having 6 to 20 carbons, , May include oxygen or nitrogen; n ₃ is an integer from 1 to 100; c and d may be the same or different from each other and independently an integer from 1 to 3.) According to claim 1,
The zeolite is characterized in that it comprises a natural zeolite or synthetic zeolite comprising at least one metal selected from Group I, Group II and Group IV metal elements of the periodic table.
Thermoplastic flame-retardant resin composition. According to claim 1,
The zeolite is one type selected from A-type zeolites containing alkali metals, Mg-substituted zeolites, Ca-substituted zeolites, Zn-substituted zeolites, Sr-substituted zeolites, Ba-substituted zeolites, Zr-substituted zeolites and Sn-substituted zeolites Characterized by the above
Thermoplastic flame-retardant resin composition. According to claim 1,
The thermoplastic flame-retardant resin composition is characterized in that it further comprises at least one additive selected from the group consisting of impact modifiers, heat stabilizers, dripping inhibitors, antioxidants, light stabilizers, sunscreens, pigments and inorganic fillers
Thermoplastic flame-retardant resin composition. Kneading and extruding 100 parts by weight of styrene-based resin, 12 to 15 parts by weight of phosphorus-based flame retardant, 15 to 20 parts by weight of epoxy-based resin and 1 to 2.5 parts by weight of flame retardant aid,
The flame retardant aid is not the same as the phosphorus-based flame retardant, zeolite 20 to 60% by weight; And 40 to 80% by weight of melamine polyphosphate;
The zeolite is 0.5 to 1 part by weight, the melamine polyphosphate is characterized in that 1 to 1.5 parts by weight
Method for producing a thermoplastic flame-retardant resin composition. It characterized in that it is produced by injecting the thermoplastic flame-retardant resin composition according to any one of claims 1 to 13
Injection molded products. The method of claim 15,
The injection molded article is characterized in that the flame retardant grade V-1 according to the test method UL-94 standard
Injection molded products.