KR20120060687A - Hallogen-free resin composite having flame retardancy - Google Patents

Abstract

PURPOSE: A halogen-free flame-retardant resin composition is provided to satisfies flame retardancy standard, to have excellent physical properties like impact resistance, and not to use halogen based compound, thereby capable of manufacturing an environment-friendly product. CONSTITUTION: A halogen-free flame-retardant resin composition comprises 100.0 parts by weight of acrylonitrile-butadiene-styrene copolymer of which average particle diameter is 3-10 micron, and 10-25 parts by weight of metal phosphinate compound of which average particle diameter is 10 micron or less. The acrylonitrile-butadiene-styrene copolymer comprises a vinyl aromatic compound, a vinyl cyanide compound, and rubber containing one or more selected from a group consisting of butadiene based rubber, and styrene-butadiene based rubber.

Description

Halogen-free resin composite having flame retardancy

The present invention relates to a resin composition excellent in flame retardancy without using a halogen compound.

ABS resin is a typical resin having both functionality and versatility, and has excellent properties such as impact strength, tensile strength, and elastic modulus, and is widely used for automobile parts and various electric / electronic parts. However, since ABS resins are easy to burn, they are often restricted when used in electrical or electronic products that generate heat. In order to overcome this limitation, many studies have been conducted to impart flame retardancy to ABS resins.

In general, the flame retardancy of ABS resin uses the international flame retardant standard called UL94, and is mainly classified into flame retardant grades of V-2, V-1, and V-0. In the above flame retardant grade, the cause of fire was focused on internal ignition. Recently, discussions on the stability of external ignition of fire continued, so that IEC / 60095, the safety standard of Audio / Video, and IEC 60950, the safety standard of IT products, Incorporated, a new safety standard called IEC 62368 has resulted in the establishment of a new flame retardant standard called 'Candle Flame' that verifies the safety of fires caused by external ignition. In particular, in the TV industry in which ABS is widely used for exterior housing, products exported to Europe from July 2010 have to use a resin satisfying the candle flame retardant specification for exterior housing.

Up to now, it is known that the use of a halogen-based compound as a flame retardant together with a flame retardant aid as a flame retardant method of ABS resin to satisfy the flame retardant specification. However, when manufacturing ABS resin processed products using halogen-based compounds, there is a problem of corroding molds and releasing harmful gases that threaten workers' health, and regulations on their use are expanding around Europe. .

In addition, the antimony compound used as a flame retardant aid is also classified as a toxic substance and its use is limited.

In addition, rubber-modified styrene resins using phosphate ester compounds that do not use halogen compounds as flame retardants are widely used in OA equipment such as copiers and printers. Phosphate ester compounds have a low melting point and are easily decomposed at resin processing temperatures. The resin composition using the ester compound has a problem of mold deposit when it is processed for a long time, leaving gas marks on the surface of the product due to decomposition gas, and thus the appearance of the product is poor. By applying a phosphate ester compound to the ABS resin alone, Candle flame retardant standards do not meet the situation.

As a result of studying the method of improving the flame retardancy of ABS resin without using halogen, the inventors have found that using the phosphinic acid metal salt represented by a specific chemical formula can improve the flame retardancy of ABS resin. When the ABS copolymer alone is used, it was found that the difference in impact strength is large depending on the average particle diameter of the phosphinic acid metal salt and the ABS copolymer, thereby completing the present invention. That is, an object of the present invention is to provide a halogen-free flame retardant resin composition satisfying the candle flame retardant standard and the ABS resin processed product using the same.

The present invention for solving the above problems relates to a halogen-free flame retardant resin composition,

100 parts by weight of an acrylonitrile-butadiene-styrene (ABS) copolymer having an average particle diameter of 3 μm to 10 μm; And

10 to 25 parts by weight of a phosphinic acid metal salt compound having an average particle diameter of 10 μm or less,

The ABS copolymer,

Aromatic vinyl compounds; Vinyl cyanide compounds; And a rubber containing at least one selected from the group consisting of butadiene rubber and styrene-butadiene rubber.

In addition, the present invention is another feature of the ABS resin processed article comprising the halogen-free flame retardant resin composition.

The halogen-free flame retardant resin composition of the present invention can not only satisfy the flame retardant standard, but also have excellent impact characteristics and can be manufactured in an environment-friendly product because it does not use a halogen-based compound.

The term "halogen-free" used in the present invention means that no halogen-based compound is used as a flame retardant additive, and the "resin processed product" means all molded articles produced by processing the flame retardant resin of the present invention. In addition, "ABS copolymer" means a copolymer of acrylonitrile-butadiene-styrene, and the term "extended diameter ABS copolymer" used in the present invention is a continuous or batch dosage form. Mean an ABS copolymer having an average particle diameter of 1 μm or more prepared by the bulk polymerization method.

Hereinafter, the present invention will be described in more detail.

The present invention is 100 parts by weight of the ABS copolymer having an average particle diameter of 3 ㎛ to 10 ㎛; And 10 to 25 parts by weight of the phosphinic acid metal salt compound having an average particle diameter of 10 μm or less.

In addition, the ABS copolymer has an average particle diameter of 3 μm to 10 μm, more preferably 3.5 μm to 9.5 μm, and when less than 3 μm, it is difficult to expect an effect of improving tensile strength and impact resistance, 10 If the thickness exceeds the mechanical properties such as tensile strength and impact resistance increases but there is a problem that the gloss of the final product is reduced.

In addition, the phosphinic acid metal salt has an average particle diameter of 10 μm or less, preferably 5 μm or less, more preferably 1 to 5 μm, and wherein the average particle diameter of the phosphinic acid metal salt exceeds 10 μm, the impact strength Since it falls sharply, it is good to use what has an average particle diameter within the said range.

The halogen-free flame retardant resin composition of the present invention is characterized in that it contains 10 to 25 parts by weight of the phosphinic acid metal salt with respect to 100 parts by weight of the ABS copolymer, wherein the phosphinic acid metal salt is less than 10 parts by weight to improve flame retardancy. The effect is not seen, if used in excess of 25 parts by weight, the flame retardancy is improved, but the impact strength is sharply reduced.

The ABS copolymer which is one of the halogen-free flame retardant resin compositions of the present invention comprises an aromatic vinyl compound; Vinyl cyanide compounds; And a polymer prepared by polymerizing a rubber containing at least one selected from the group consisting of butadiene-based rubber and styrene-butadiene-based rubber, and further polymerizing by using an additive such as an organic oxide initiator and a molecular weight regulator. can do. The polymerization method is not particularly limited, but is preferably a bulk polymer obtained by bulk polymerization in view of mechanical strength, in particular, impact strength.

The amount of the aromatic vinyl compound used is 60 to 80 parts by weight based on 100 parts by weight of the ABS copolymer, preferably 65 to 75 parts by weight. The aromatic vinyl compound may be an aromatic vinyl compound generally used in the art, but is not particularly limited in the present invention, and preferably, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, and t- It is preferable to use at least one selected from butyl styrene, and more preferably styrene.

The amount of the vinyl cyanide compound to be used is 15 to 30 parts by weight with respect to 100 parts by weight of the ABS copolymer, preferably 20 to 25 parts by weight. The vinyl cyanide compound may be one or more selected from acronitrile, methacrylonitrile, and ethacrylonitrile, and more preferably acrylonitrile.

The rubber is preferably used 5 to 20 parts by weight, more preferably 10 to 20 parts by weight based on 100 parts by weight of the total ABS copolymer.

The organic oxide initiator is preferably 0.01 to 1 parts by weight, more preferably 0.05 to 0.5 parts by weight based on 100 parts by weight of the total ABS copolymer. In addition, an initiator generally used in the art may be used, and the present invention is not particularly limited, but preferably 1,1-bis (t-butylperoxy) -3,3,5-trimethyl cyclohexane, 1 , 1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -2-methyl cyclohexane and 2,2-bis (4,4-di-t-butylperoxy It is preferable to use at least one organic oxide initiator selected from cyclohexyl) propane.

The molecular weight modifier is preferably 0.01 to 1 parts by weight, more preferably 0.1 to 0.7 parts by weight based on 100 parts by weight of the total ABS copolymer. In addition, an initiator generally used in the art may be used, and is not particularly limited in the present invention. Preferably, a thiol-based molecular weight regulator is selected from t-dodecyl mercaptan and n-octyl mercaptan. It is preferable to use one or more thiol type molecular weight regulators.

The phosphinic acid metal salt compound, which is one of the components of the present invention, is represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1, R ¹ and R ² are the same as or different from each other, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and M is Al, Zn, Mg or Ca and n is 2-3. Preferably, R ¹ and R ² are the same as each other, an alkyl group having 1 to 3 carbon atoms, M is Al, n is preferably 3, more preferably R ¹ and R ² are the same as each other, an ethyl group , M is Al, and n is preferably 3. Herein, the carbon number of the alkyl group, the cycloalkyl group, and the aryl group may be within the above range, respectively, in terms of flame retardant effect.

The halogen-free flame-retardant resin composition of the present invention described above may further include an additive in addition to the ABS copolymer and the phosphinic acid metal salt within a range in which flame retardancy and mechanical properties are not impaired, and the additive may include lubricant, heat stabilizer, and oxidation. Inhibitor, light stabilizer, hydrolysis stabilizer, release agent, pigment, antistatic agent, conductivity imparting agent, EMI shielding agent, magnetic imparting agent, mineral filler, crosslinking agent, antimicrobial agent, processing aid, metal deactivator, depressant, fluorine-based anti-dropping agent, anti-friction It may include one or more selected from abrasion resistant and coupling agents.

In addition, after mixing the ABS copolymer, the phosphinic acid metal salt, and the additive, which are the composition of the halogen-free flame retardant resin composition of the present invention, various compound processing equipment such as a single screw extruder, a twin screw extruder, a roll mill, a kneader or a half-barrier mixer, etc. It is possible to obtain pellets after melting and kneading using a pellet or the like, and the processed product can be obtained by injection molding the pellets.

Hereinafter, the present invention will be described in more detail with reference to examples of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

[ Example ]

Example  One

(1) super-diameter ABS copolymer

The super-diameter ABS copolymer (product name: MA221, average particle diameter of 3.5 μm) manufactured by LG Chem through bulk polymerization was used as it is without purification.

(2) phosphinic acid metal salt compounds

Clariant's diethyl phosphinic acid aluminum salt (product name: OP935, average particle diameter: 4.5 mu m) was used.

(3) Preparation of halogen free flame retardant ABS resin

15 parts by weight of the diethyl phosphinate aluminum salt, 1 part by weight of lubricant (ethylene bis stearamide, EBA), and a heat stabilizer (distearyl pentaeryl diphosphite, Distearyl pentaeryl based on 100 parts by weight of the super-diameter ABS copolymer After mixing 0.3 parts by weight of diphosphite), a halogen-free flame-retardant resin in pellet form was prepared using a twin screw extruder at 220 ° C.

Example  2 to 3

In the same manner as in Example 1 To prepare a pellet-free halogen-free flame retardant ABS resin, Example 2 and Example 3 was carried out by varying the amount and type of the ABS copolymer and the phosphinic acid metal salt compound, respectively, as shown in Table 1 below.

Comparative example  One

In the same manner as in Example 1 To prepare a halogen-free flame-retardant ABS resin in pellet form, Comparative Example 1 was carried out using less than 10 parts by weight of diethyl phosphinic acid aluminum salt as shown in Table 1.

Comparative example  2

In the same manner as in Example 1 To prepare a halogen-free flame-retardant ABS resin in the form of pellets, Comparative Example 2 was carried out using 30 parts by weight of more than 25 parts by weight of diethyl phosphinic acid aluminum salt as shown in Table 1.

Comparative example  3

In the same manner as in Example 1 Comparative Example 3 was prepared using a diethyl phosphinic acid aluminum salt having a pellet-type halogen-free flame retardant ABS resin having an average particle diameter of more than 10 μm.

Comparative example  4

In the same manner as in Example 1 A halogen-free flame retardant ABS resin in the form of pellets was prepared, but Comparative Example 4 was carried out using a phosphoric acid ester compound instead of diethyl phosphinic acid salt as a flame retardant.

Comparative example  5

28 parts by weight of grafted ABS copolymer (product name DP270, LG Chem) and styrene acrylonitrile, which were carried out in the same manner as in Example 1, but manufactured by emulsion polymerization instead of the super-diameter ABS copolymer prepared by bulk polymerization. (SAN, product name 92HR, LG Chemical) Comparative Example 5 was carried out using 72 parts by weight.

division Example Comparative example One 2 3 One 2 3 4 5 ABS
Copolymer A ^(One) 100 100 0 100 100 100 100 - B ⁽²⁾ - - 100 - - - - - Graft
ABS C ⁽³⁾ - - - - - - - 28 SAN ⁽⁴⁾ - - - - - - - 72 Phosphinic acid
Metal salt D ⁽⁵⁾ 15 22 15 5 30 - - 15 E ⁽⁶⁾ - - - - - 15 - - Phosphate Ester Compound ⁽⁷⁾ - - - - - - 15 - (1) ABS copolymer (A): average particle diameter of 3.5 ㎛, trade name MA221 of LG Chemical
(2) ABS copolymer (B): average particle diameter of 9 ㎛, trade name MA220 of LG Chem
(3) Grafted ABS copolymer (C): 0.3 ㎛ average particle diameter, DP270 brand name of LG Chemicals
(4) Styrene acrylonitrile (SAN): Product name 92HR of LG Chem.
(5) Phosphate metal salt (D): average particle diameter of 4.5 µm, trade name OP935 of Clariant
(6) Phosphate metal salt (E): 20 µm in average particle diameter, trade name OP1240 from Clariant
(7) Phosphate ester compound: The brand name PX200 of Daihachi Corporation, Japan

Manufacturing example  1 to 3 and Comparative Production Example  1 to 5

Preparation of specimens (molded products) by injection molding each of the pellet-type halogen-free flame retardant ABS resin prepared in Examples and Comparative Examples using a 150MT injection machine having a nozzle temperature of 220 ° C. and a mold temperature of 50 ° C. Production Examples 1 to 5 were carried out.

Experimental Example

The impact strength and the candle flame test of the specimens prepared in Preparation Examples and Comparative Preparation Examples were conducted, and the results are shown in Table 2 below.

(1) impact strength test

Impact strength (IMP, 1/8 ") was tested according to ASTM D256.

(2) candle Flame  Evaluation experiment

The candle flame experiment simulates a 150 mm long candle having a diameter of 20 mm and a specific method is as follows.

① Sample pretreatment

The specimens were pretreated at least 24 hours in a conditioning chamber at 23 ± 2 ° C., 50 ± 5% relative humidity, and then candle flame evaluation was performed in a laboratory at 25 ° C. and 58% relative humidity within 1 hour.

② burner and flame

Butane gas having 95% purity was used as a fuel, and needle burners having a length of at least 50 mm, a diameter of 0.5 ± 0.1 mm, and a flame of 12 mm ± 1 mm were used.

③ Evaluation method of flame persistence

The tip of the burner was brought about 5 ± 0.5 mm from the surface of the specimen, the horizontal axis of the burner tube was kept within ± 5 °, and the center line of the burner tube did not deviate from 10 to 150 mm in the specimen. When burner flame was continued for 3 minutes and then removed even if shrinkage and greening of material occurred, it was considered suitable if the flame did not last for 3 minutes. And the result was shown to the following Table 2, and the suitable thing was represented by (circle) and the inappropriate thing was represented by x.

division Manufacturing example Comparative Production Example One 2 3 One 2 3 4 5 Impact strength
(kgfcm / cm) 25.2 18.9 20.4 35.2 9.1 2.3 22.3 2.1 Flame retardant
(candle flame) ○ ○ ○ × ○ ○ ○ ×

Looking at the Table 2, Examples 1 to 3 of the present invention all pass the candle flame test to satisfy the candle flame standard, it can be seen that the impact strength is also very good. However, Comparative Example 1 using less phosphinic acid metal salt compound (diethyl phosphinate aluminum salt) and Comparative Example 4 using phosphate ester compound had excellent impact strength, but did not pass the candle flame test. In addition, Comparative Example 2 using more than the phosphinic acid metal salt compound, Comparative Example 3 using the phosphinic acid metal salt compound having an average particle diameter of more than 10 ㎛ and Comparative Example 5 using the mixed copolymer passed the flame flame test, but the impact strength We can see that there is a problem that comes out very low.

By using the halogen-free flame retardant ABS resin composition of the present invention through the above examples and experimental examples, not only the mechanical properties such as impact strength are excellent, but also satisfy the candle flame flame retardant specification even when the ABS copolymer is used alone. It can be confirmed that the ABS resin can be provided.

Claims (8)

100 parts by weight of an acrylonitrile-butadiene-styrene (ABS) copolymer having an average particle diameter of 3 μm to 10 μm; And
10 to 25 parts by weight of a phosphinic acid metal salt compound having an average particle diameter of 10 μm or less,
The ABS copolymer,
Aromatic vinyl compounds;
Vinyl cyanide compounds; And
A halogen-free flame retardant resin composition comprising a rubber containing at least one selected from the group consisting of butadiene rubber and styrene-butadiene rubber.
The halogen-free flame retardant resin composition according to claim 1, wherein the phosphinic acid metal salt compound is represented by the following Chemical Formula 1;
[Formula 1]

In the above formula, R ¹ and R ² are the same as or different from each other, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and M is Al, Zn, Mg, or Ca And n is 2 to 3.
The halogen-free flame retardant resin composition according to claim 2, wherein R ¹ and R ² are the same as each other, an alkyl group having 1 to 3 carbon atoms, M is Al, and n is 3.
The method of claim 1, wherein the ABS copolymer
60 to 80 parts by weight of the aromatic vinyl compound;
15 to 30 parts by weight of a vinyl cyanide compound; And
5 to 20 parts by weight of rubber containing at least one selected from the group consisting of butadiene rubber and styrene-butadiene rubber
Halogen-free flame retardant resin composition comprising a in a polymerized form.
The halogen-free flame retardant resin composition according to claim 1, wherein the polymer is a bulk polymer.
The method of claim 4 wherein the aromatic vinyl compound
Halogen-free flame-retardant resin composition which is at least 1 type selected from styrene, (alpha) -methylstyrene, p-methylstyrene, vinyltoluene, and t-butylstyrene.
The compound of claim 4, wherein the vinyl cyanide compound is
At least one halogen-free flame retardant resin composition selected from acrylonitrile, methacrylonitrile and ethacrylonitrile.
The resin processed product containing the halogen-free flame retardant resin composition of any one of Claims 1-7.