KR20130031077A - Thermoplastic flame retardant resin composition having improved impact strength - Google Patents

Abstract

PURPOSE: A thermoplastic flame retardant resin composition is provided to have excellent impact resistance by comprising a polyfunctional epoxy resin or urethane-modified epoxy resin and N,N-bis-stearic amide. CONSTITUTION: A thermoplastic flame retardant resin composition comprises 100.0 parts by weight of a base resin, 1-30 parts by weight of a multi-functional epoxy resin or urethane-modified epoxy resin, 0.1-5 parts by weight of N,N-bis-stearic amide. The base resin is formed of 10-90 weight% of an acrylonitrile-butadiene-styrene copolymer and 10-90 weight% of a styrene-acrylonitrile copolymer.

Description

Thermoplastic flame retardant resin composition having improved impact strength

The present invention relates to a thermoplastic flame retardant ABS resin composition having excellent impact resistance, and more particularly, to a thermoplastic resin comprising an acrylonitrile-butadiene-styrene copolymer and a styrene-acrylonitrile copolymer, which is a phosphorus-based flame retardant and a char-forming material. The present invention relates to a thermoplastic flame-retardant ABS resin composition having an effect of very excellent impact resistance by adding a functional epoxy resin or a urethane-modified epoxy resin, and N, N-bis stearamide.

Generally, acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) resins are used in electrical, electronic and office equipment due to the stiffness and chemical resistance of acrylonitrile and the processability and mechanical strength of butadiene and styrene. It is widely used as exterior materials. ABS resins, however, have the characteristics that they can easily burn, and have little resistance to fire.

Due to these problems, ABS resins used in electrical, electronic products, and office equipment must satisfy the flame retardant specifications to ensure the fire safety of electrical and electronic products.

As a method of imparting flame retardancy, a method of including a flame-retardant monomer and polymerizing the rubber-modified styrene-based resin and a method of mixing a flame-retardant and a flame-retardant aid into the manufactured rubber-modified styrene-based resin include halogen-based flame retardants. There are non-halogen-based flame retardants such as phosphorus-based, nitrogen-based, and hydroxyl-based, and the flame retardant aids include antimony-based compounds, zinc-based compounds, silane-based compounds, and the like.

Since the halogen-based flame retardant has a higher flame retardant efficiency than the non-halogen-based flame retardant and can maintain the mechanical properties of the rubber-modified styrene-based resin, a method of using a halogen-based flame retardant is currently used to impart flame retardancy to the ABS resin. In general, bromine-based flame retardants are particularly effective. However, when the ABS resin is processed by adding a brominated flame retardant, the thermal stability is degraded due to the high temperature and pressure generated during processing, and thus, corrosive toxic gas is generated and thus adversely affects the working environment and the human body. have. This is a problem that occurs even when the ABS resin processed by adding the brominated flame retardant is burned.

There is a method of using a non-halogen flame retardant as a method of avoiding the above problems, and a method of using a phosphorus-based flame retardant among them is used a lot. However, since phosphorus flame retardants have a lower flame retardant efficiency than halogen flame retardants, an excessive amount of phosphorus flame retardants must be added, and in the case of a thermoplastic resin composition which does not generate char due to the principle of phosphorus flame retardant systems, flame retardancy is not sufficiently exhibited. The disadvantage is that it is difficult.

Therefore, there is a method of exhibiting flame retardancy by adding an additional material capable of generating char, but based on the ABS resin, since the phosphorus-based flame retardant and the char-generating material having different characteristics from the ABS resin are mixed in excess, the impact resistance is represented. It is inevitable that the mechanical properties of the ABS resin to be reduced.

Therefore, in order to commercialize and actualize the ABS resin, there is a need to compensate for the declining mechanical properties with maintaining the existing flame retardancy.

In order to solve the above problems of the prior art, the present inventors are polyfunctional epoxy resins or urethanes which are phosphorus-based flame retardants and char-generating materials in thermoplastic resins composed of acrylonitrile-butadiene-styrene copolymers and styrene-acrylonitrile copolymers. When the N, N-ethylene bis stearamide was added to the thermoplastic flame retardant resin composition made of a modified epoxy resin, it was confirmed that the impact resistance greatly increased, thereby completing the present invention.

An object of the present invention is to provide a flame retardant resin composition excellent in impact resistance.

These 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 (A) 10 to 90% by weight of acrylonitrile-butadiene-styrene copolymer (hereinafter referred to as ABS copolymer) and styrene-acrylonitrile copolymer (hereinafter referred to as SAN copolymer) 1 to 30 parts by weight of (B-1) polyfunctional epoxy resin or (B-2) urethane-modified epoxy resin with respect to 100 parts by weight of the base resin consisting of 10 to 90% by weight; (C) 1 to 30 parts by weight of a phosphorus flame retardant; And (D) 0.1 to 5 parts by weight of N, N- bis stearamide; provides a thermoplastic flame-retardant resin composition comprising a.

According to the present invention, there is an effect of providing a flame-retardant resin composition excellent in impact resistance by injecting a polyfunctional epoxy resin or a urethane-modified epoxy resin and N, N-bis stearamide together.

In order to solve the problems of the prior art as described above, the present invention provides (A) a multi-pipe (B-1) based on 100 parts by weight of the base resin consisting of 10 to 90% by weight ABS copolymer and 10 to 90% by weight SAN copolymer 1 to 30 parts by weight of a functional epoxy resin or (B-2) urethane-modified epoxy resin; (C) 1 to 30 parts by weight of a phosphorus flame retardant; And (D) 0.1 to 5 parts by weight of N, N- bis stearamide; provides a thermoplastic flame-retardant resin composition comprising a.

Hereinafter, the present invention will be described in detail.

The thermoplastic flame-retardant resin composition of the present invention (A) is based on 100 parts by weight of the base resin consisting of 10 to 90% by weight of acrylonitrile-butadiene-styrene copolymer and 10 to 90% by weight of styrene-acrylonitrile copolymer (B- 1) 1 to 30 parts by weight of a polyfunctional epoxy resin or (B-2) urethane-modified epoxy resin; (C) 1 to 30 parts by weight of a phosphorus flame retardant; And (D) 0.1 to 5 parts by weight of N, N-bisstearic amide.

Each component which comprises the said thermoplastic flame-retardant resin composition is demonstrated in detail.

(A) Base Resin

In the thermoplastic flame retardant resin composition of the present invention, the base resin is composed of 10 to 90% by weight of acrylonitrile-butadiene-styrene copolymer and 10 to 90% by weight of styrene-acrylonitrile copolymer.

Although the acrylonitrile-butadiene-styrene copolymer is not particularly limited, butadiene rubber, acrylonitrile monomer and styrene monomer may be prepared in a powder state by emulsifying graft polymerization, then agglomeration, dehydration and drying, and average It is preferable that butadiene-based rubber having a particle diameter of 0.1 to 0.5 mu m is usually included in a high percentage by weight.

The emulsion graft polymerization is 50 to 70 parts by weight of butadiene rubber, 0.6 to 2 parts by weight of emulsifier, 0.2 to 1 part by weight of molecular weight regulator, based on 100 parts by weight of the total monomer content of the acrylonitrile-butadiene-styrene copolymer, And a monomer mixture consisting of 5 to 40 parts by weight of acrylonitrile and 20 to 65 parts by weight of styrene in a mixed solution composed of 0.05 to 0.5 parts by weight of a polymerization initiator.

The styrene-acrylonitrile copolymer has a weight average molecular weight of 50,000 to 150,000, preferably an acrylonitrile monomer content of 20 to 40% by weight, and may be used singly or in mixture of two or more kinds.

The ABS copolymer used to form the base resin in the present invention is preferably 10 to 90% by weight and SAN copolymer is in the range of 10 to 90% by weight, considering the mechanical properties of the resin, ABS copolymer 10 to 50 It is preferably in weight percent and in the range of 50 to 90 weight percent of SAN copolymer.

(B-1) Multifunctional  Epoxy Resin or (B-2) Urethane Modified Epoxy Resin

In the thermoplastic flame retardant resin composition of the present invention, the multifunctional epoxy resin may be represented by the following Chemical Formula 1.

In Formula 1 n is a natural number of 1 to 100.

In addition, the urethane-modified epoxy resin may be represented by the following formula (2).

를 갖는 에폭시 기이며, R₂는 말단부가 이소시아네이트기로 치환된 작용기이며, R₃ 및 R₄는 독립적으로 수소 원자 혹은 탄소수 1 내지 20의 알킬 또는 아릴기이고, n₁ 및 n₂는 1 내지 100인 자연수이다.
In Formula 2, R ₁ is a structure

R ₂ is a functional group in which the terminal is substituted with an isocyanate group, R ₃ and R ₄ are independently a hydrogen atom or an alkyl or aryl group having 1 to 20 carbon atoms, and n ₁ and n ₂ are 1 to 100 It is a natural number.

Preferably, the polyfunctional epoxy resin or urethane-modified epoxy resin is included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the base resin, and the thermoplastic resin composition prepared within this range generates char and does not require excessive use of a phosphorus-based flame retardant. It is because it is preferable for expressing excellent flame-retardant performance.

(C) take over Flame retardant

In the thermoplastic flame retardant resin composition of the present invention, the phosphorus-based flame retardant is preferably included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the base resin, and the thermoplastic resin composition prepared within this range does not significantly reduce mechanical strength and thermal stability. There is an effect having excellent fluidity and gloss.

The phosphorus-based flame retardant is not particularly limited as long as it is usually used in thermoplastic resins, and specific examples thereof include triphenyl phosphate, tricresyl phosphate, tri (2,6-dimethylphenyl) phosphate, and tri (2,4,6-trimethylphenyl) phosphate. Phosphate-based compounds such as phosphate-based compounds, tetra-phenyl-resinolol diphosphate, tetra-creslesinolol diphosphate, tetra (2,6-dimethylphenyl) resorcinol-diphosphate, tetra-phenyl bisphenol A diphosphate, such as diphosphate-based compounds, 3 Organic phosphorus flame retardants such as polyphosphate compounds, phosphonate compounds or phosphinate compounds having two or more phosphate groups may be used alone or in combination of two or more thereof.

(D) N, N- Ethylene bis stearamide

In the thermoplastic flame retardant resin composition of the present invention, the N, N-ethylene bis stearamide is a general-purpose material used as a lubricant in the resin as well as the thermoplastic resin. It is also a general fact that when the general lubricants containing the above-mentioned N, N-ethylene bis stearamide are used for resin processing, the Izod impact property is slightly increased than when not used.

However, in the case of the present invention, when the N, N- ethylene bis stearamide is used together with the polyfunctional epoxy resin or the urethane-modified epoxy resin described above, it can be confirmed that the Izod impact of the resin is significantly increased than usual.

The thermoplastic flame-retardant resin composition may further include one or more additives selected from the group consisting of impact modifiers, thermal stabilizers, anti-drip agents, antioxidants, light stabilizers, ultraviolet light blocking step, pigments and inorganic fillers.

The method for preparing a thermoplastic flame retardant resin composition having excellent flame retardancy of the present invention may include the steps of adding the components A) to D) into an extruder, mixing and extruding at a barrel temperature of 220 to 250 ° C., but the extruder is not particularly limited. However, twin screw extruders can be used.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Example  One

25 parts by weight of ABS copolymer (55% by weight of butadiene rubber) prepared by LG Chem by emulsion graft polymerization using butadiene rubber latex having an average particle diameter of 0.3 μm, acrylonitrile content of 25% by weight, and weight average molecular weight 100 parts by weight of a basic resin consisting of 75 parts by weight of a styrene-acrylonitrile copolymer (SAN copolymer) of 120,000, 10 parts by weight of a polyfunctional epoxy resin (product name: DNTH), tetra (2) of Japan DAIHACHI KAGAKU KOHGYO Co., Ltd. , 6-dimethylphenyl) resosocinol diphosphate (product name: PX-200) 10 parts by weight, and N, N- bis stearamide as the N, N-bis stearamide (product name: sunroof (EBA)) 1 The parts by weight were added and mixed uniformly using a Henschel mixer to prepare a thermoplastic resin composition in pellet form through a twin screw extruder.

The pellet-type thermoplastic resin composition was prepared by injection molding into 1/4 "specimens and 1/8" specimens in accordance with ASTM-256. Specimens produced Notch according to ASTM D-256.

In addition, it was prepared by injection molding into a flame retardant test specimen of 10 centimeters wide, 10 centimeters long, and 3 millimeters thick.

Example  2

The same method as in Example 1 was carried out except that 10 parts by weight of a urethane-modified epoxy resin was added instead of the polyfunctional epoxy resin in Example 1.

Comparative example  One

Except that N, N- bis stearamide was not added in Example 1 was carried out in the same manner as in Example 1.

Comparative example  2

Except that N, N- bis stearamide was not added in Example 2 was carried out in the same manner as in Example 2.

Comparative example  3

Except that the polyfunctional epoxy resin was not added in Example 1 was carried out in the same manner as in Example 1.

Comparative example  4

Example 1 was carried out in the same manner as in Example 1, except that neither the multifunctional epoxy resin nor N, N-bis stearamide was added.

Comparative example  5

Example 1 was carried out in the same manner as in Example 1, except that 10 parts by weight of an epoxy derivative was added instead of the multifunctional epoxy resin.

Epoxy derivatives are shown in the following formula (3).

In Formula 3, X is an alkyl or aryl group having 1 to 30 carbon atoms, and may optionally include oxygen or nitrogen.

Comparative example  6

Except that N, N- bis stearamide was not added in Comparative Example 5 was carried out in the same manner as in Comparative Example 5.

[Test Example]

Using the thermoplastic flame retardant resin composition specimens prepared in Examples 1 to 2 and Comparative Examples 1 to 6, impact strength and external candle flame ignition flame retardancy were measured and the results are shown in Table 1 below. .

Notched Izod Impact Strength: Measured according to ASTM D-256 using 1/4 "and 1/8" thick specimens.

External Candle Flame Ignition: Measured according to IEC TS 62441, using specimens made from 10 centimeters wide, 10 centimeters long and 3 millimeters thick. According to the regulations, if the flame ignited on the flame-retardant resin composition specimens is extinguished within 3 minutes (= 180 seconds) as specified in the regulations, it is PASS, otherwise it is FAIL. Approximate time (unit: second) until completion is described.

division Example Comparative example One 2 One 2 3 4 5 6 Emulsion polymerization ABS 25 25 25 25 25 25 25 25 SAN 75 75 75 75 25 25 25 25 Epoxy resin Multifunctional Epoxy Resin 10 10 - - - - - Urethane Modified Epoxy Resin - 10 - 10 - - - - Epoxy derivatives - - - - - - 10 10 Phosphorus flame retardant 10 10 10 10 10 10 10 10 N, N-bisstearic amide One One - - One - One - External Candle Flame Ignition Test Result 60 seconds 90 seconds 60 seconds 90 seconds 180 seconds or more 180 seconds or more 120 seconds 120 seconds Impact Strength (1/4 "Thickness) 15.2 10.4 8.5 4.6 21.0 20.1 8.7 8.2 Impact Strength (1/8 "Thickness) 16.4 10.8 14.1 10.6 22.3 21.2 13.4 12.7

In Example 1 in which the multifunctional epoxy resin and N, N- bis stearamide were simultaneously added through Table 1 and in the case of Example 2 in which the urethane-modified epoxy resin and N, N-bis stearamide were simultaneously added, N, N -Compared with the case of Comparative Example 1 and Comparative Example 2 not added bis stearamide was confirmed that the impact strength significantly increased. In particular, it could be seen that the impact strength of the 1/4 "specimen was significantly increased.

On the other hand, in the case of Comparative Example 3, in which N, N-bisstearic acid was added but not the polyfunctional epoxy resin, the increase in impact strength was only slightly increased compared to the case of Comparative Example 4, in which neither of them was added. there was.

In addition, in Comparative Examples 5 and 6 using epoxy derivatives instead of polyfunctional epoxy resins, Comparative Example 5 using N, N-bisstearic amide also showed a slight increase in impact strength even when compared to Comparative Example 6 which was not. there was.

Therefore, it was confirmed that the thermoplastic flame-retardant resin composition of the present invention significantly improved the impact resistance by using a polyfunctional epoxy resin or a urethane-modified epoxy resin and N, N-bis stearamide simultaneously.

Claims (7)

(A) To 100 parts by weight of base resin consisting of 10 to 90% by weight of acrylonitrile-butadiene-styrene copolymer and 10 to 90% by weight of styrene-acrylonitrile copolymer
1 to 30 parts by weight of (B-1) a polyfunctional epoxy resin or (B-2) urethane-modified epoxy resin;
(C) 1 to 30 parts by weight of a phosphorus flame retardant; And
(D) 0.1 to 5 parts by weight of N, N-bis stearamide; thermoplastic flame-retardant resin composition comprising a. The method of claim 1,
The (B-1) polyfunctional epoxy resin is a thermoplastic flame-retardant resin composition, characterized in that represented by the following formula (1).
[Formula 1]

In Formula 1 n is a natural number of 1 to 100. The method of claim 1,
The urethane-modified epoxy resin (B-2) is a thermoplastic flame-retardant resin composition, characterized in that represented by the following formula (2).
(2)

In Formula 2, R ₁ is a structure

R ₂ is a functional group in which the terminal is substituted with an isocyanate group, R ₃ and R ₄ are independently a hydrogen atom or an alkyl or aryl group having 1 to 20 carbon atoms, and n ₁ and n ₂ are 1 to 100 It is a natural number. The method of claim 1,
The phosphorus-based flame retardant of (C) is at least one member selected from the group consisting of phosphate compounds, diphosphate compounds, polyphosphate compounds having three or more phosphate groups, phosphonate compounds and phosphinate compounds. Thermoplastic flame retardant resin composition. The method of claim 1,
The acrylonitrile-butadiene-styrene copolymer of the base resin (A) is 50 to 70% by weight of butadiene-based rubber, thermoplastic flame retardant resin composition, characterized in that prepared by emulsion graft polymerization. The method of claim 1,
In the (A) base resin, the styrene-acrylonitrile copolymer has a weight average molecular weight of 50,000 to 150,000 and an acrylonitrile monomer in 20 to 40% by weight, characterized in that the thermoplastic flame retardant resin composition. The method of claim 1,
The thermoplastic flame retardant resin composition further comprises at least one additive selected from the group consisting of impact modifiers, heat stabilizers, anti-drip agents, antioxidants, light stabilizers, ultraviolet light-blocking steps, pigments and inorganic fillers. Composition.