KR101419574B1 - Hallogen-free resin composite having flame retardancy - Google Patents
Hallogen-free resin composite having flame retardancy Download PDFInfo
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Abstract
The present invention relates to a halogen-free flame retardant resin composition, and more particularly, to a flame retardant resin composition comprising an ABS copolymer and a phosphinic acid metal salt compound represented by a specific formula. INDUSTRIAL APPLICABILITY The present invention relates to an ABS resin which is not only environmentally friendly but also has excellent mechanical properties such as impact strength and the like, and in particular, a resin finished product satisfying the candle flame flame retardant specification because it does not use halogen compounds, antimony compounds, .
Description
The present invention relates to a resin composition which is excellent in flame retardancy without using a halogen compound.
ABS resin has excellent properties such as impact strength, tensile strength and elastic modulus, and is widely used for use in automobile parts and various electric / electronic parts. However, since the ABS resin is easy to burn, it is highly restricted when it is used in electric and electronic products in which heat is generated. In order to overcome these limitations, many studies have been made to impart flame retardancy to ABS resins.
In general, the flame retardancy of ABS resin uses an international flame retardant standard called UL94, and it is divided into flame retardant grades of V-2, V-1 and V-0. IEC 60095, which is a safety standard for audio / video, and IEC 60950, a safety standard for IT products, have been recently discussed in the above flame retardancy grade, As a new safety standard called IEC 62368 was introduced, a new flame retardant specification called 'Candle Flame' was established to verify the stability of fire caused by external ignition. Especially, in the TV industry where ABS is used for exterior housing, the products that are exported to Europe from July 2010 must use resin that meets the candle flame flame retardant specification for exterior housing.
Up to now, it has been known that it is most effective to use a halogen-based compound as a flame retardant together with a flame-retardant adjuvant as an anti-flammability method for an ABS resin to satisfy the flame retardancy standard. However, there is a problem that corrosive molds are corroded when halogenated compounds are used to produce ABS resin processed products, and harmful gas which threatens the health of workers is released, and regulations on the use thereof are spreading in Europe .
In addition, antimony compounds used as flame retardant adjuvants are also classified as toxic substances and their use is limited.
A rubber-modified styrenic resin using a phosphoric acid ester-free compound as a flame retardant agent that does not use a halogen compound is widely used in OA equipment such as copying machines and printers. Phosphoric ester compounds have low melting points and are easily decomposed at a resin processing temperature, The resin composition using an ester compound has a problem of mold depot phenomenon at the time of processing for a long time and gas marks are left on the surface of the product due to decomposition gas, resulting in poor appearance of the product. Phosphoric ester compounds are applied to the ABS resin alone The flame retardancy of candle flame is not satisfied.
The present inventors have studied a method for improving the flame retardancy of an ABS resin without using a halogen. As a result, it has been found that the use of a phosphinic acid metal salt represented by a specific formula can improve the flame retardancy of the ABS resin. When the ABS copolymer was used alone, it was found that the impact strength varied greatly depending on the average particle diameter of the phosphinic acid metal salt and the ABS copolymer, thereby completing the present invention. That is, the object of the present invention is to provide a halogen-free flame-retardant resin composition satisfying the candle flame retardant standard and an ABS resin finished 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 탆 to 10 탆; And
10 to 25 parts by weight of a phosphinic acid metal salt compound having an average particle diameter of 10 mu m or less,
The ABS copolymer is a copolymer
Aromatic vinyl compounds; Vinyl cyanide compounds; And a rubber containing at least one member selected from the group consisting of butadiene rubber and styrene-butadiene rubber.
Further, the present invention is further characterized by an ABS resin processed product comprising the halogen-free flame retardant resin composition.
The halogen-free flame-retardant resin composition of the present invention not only satisfies the flame retardancy standard but also has excellent impact properties and does not use a halogen-based compound, so that an environment-friendly product can be produced.
The term " halogen-free " used in the present invention means that a halogen-based compound is not used as a flame retardant additive, and " resin processed product " means all molded products produced by processing the flame- The term " ABS copolymer " means a copolymer of acrylonitrile-butadiene-styrene, and the term " high-caliber ABS copolymer " Means an ABS copolymer having an average particle diameter of 1 占 퐉 or more prepared by a bulk polymerization method.
Hereinafter, the present invention will be described in more detail.
100 parts by weight of an ABS copolymer having an average particle diameter of 3 占 퐉 to 10 占 퐉; And 10 to 25 parts by weight of a phosphinic acid metal salt compound having an average particle diameter of 10 m or less.
The ABS copolymer preferably has an average particle diameter of 3 to 10 탆, more preferably 3.5 to 9.5 탆. When the average particle diameter is less than 3 탆, it is difficult to expect an improvement in tensile strength and impact resistance. If it is more than 탆, the mechanical properties such as tensile strength and impact resistance are increased but the gloss of the final product is decreased.
Preferably, the phosphinate acid metal salt has an average particle diameter of 10 m or less, preferably 5 m or less, more preferably 1 to 5 m, and when the average particle diameter of the phosphinic acid metal salt exceeds 10 m, It is preferable to use one having an average particle diameter within the above range.
The halogen-free flame retardant resin composition of the present invention is characterized by containing 10 to 25 parts by weight of the above phosphonic acid metal salt per 100 parts by weight of the ABS copolymer. When the amount of the phosphinic acid metal salt is less than 10 parts by weight, If it is used in an amount exceeding 25 parts by weight, the flame retardancy is improved but the impact strength is drastically reduced.
The ABS copolymer, which is one of the halogen-free flame retardant resin compositions of the present invention, is an aromatic vinyl compound; Vinyl cyanide compounds; And a rubber containing at least one member selected from the group consisting of a butadiene rubber and a styrene-butadiene rubber, and further, an additive such as an organic oxide initiator and a molecular weight adjuster is additionally used for polymerization reaction can do. The polymerization method is not particularly limited, but a bulk polymer obtained by bulk polymerization is preferable in terms of mechanical strength, particularly impact strength.
The amount of the aromatic vinyl compound to be used is preferably 60 to 80 parts by weight, preferably 65 to 75 parts by weight, based on 100 parts by weight of the ABS copolymer. The aromatic vinyl compound may be an aromatic vinyl compound generally used in the art, and is not particularly limited in the present invention. Preferably, styrene,? -Methylstyrene, p-methylstyrene, vinyltoluene, Butylstyrene, and styrene. It is more preferable to use styrene.
The amount of the vinyl cyanide compound to be used is preferably 15 to 30 parts by weight, preferably 20 to 25 parts by weight, based on 100 parts by weight of the ABS copolymer. The vinyl cyanide compound is preferably at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, and more preferably acrylonitrile.
The rubber is preferably used in an amount of 5 to 20 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the ABS copolymer.
The organic oxide initiator is preferably used in an amount of 0.01 to 1 part by weight, more preferably 0.05 to 0.5 part by weight based on 100 parts by weight of the entire ABS copolymer. In addition, initiators generally used in the art can be used, and although not particularly limited in the present invention, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1 (Tert-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane and 2,2- Cyclohexyl) propane is preferably used as the initiator.
The molecular weight modifier is preferably used in an amount of 0.01 to 1 part by weight, more preferably 0.1 to 0.7 part by weight based on 100 parts by weight of the total amount of the ABS copolymer. The initiator generally used in the art can be used, and although not particularly limited in the present invention, it is preferable to use a thiol-based molecular weight modifier, more preferably, t-dodecyl mercaptan and n-octyl mercaptan It is advisable to use at least one thiol-type molecular weight modifier.
The phosphinic acid metal salt compound as one of the components of the present invention is characterized by being represented by the following general formula (1).
[Chemical Formula 1]
In Formula 1, R 1 and R 2 are the same or different and each is 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, M is Al, Zn, Mg, Ca, and n is 2 to 3. Preferably, R 1 and R 2 are the same and are an alkyl group having 1 to 3 carbon atoms, M is Al and n is 3, more preferably R 1 and R 2 are the same and are an ethyl group , M is Al, and n is 3. If the number of carbon atoms in the alkyl group, cycloalkyl group and aryl group is within the above range, the flame retardant effect may be deteriorated.
The halogen-free flame retardant resin composition of the present invention may additionally contain an additive in addition to the ABS copolymer and the phosphonic acid metal salt within a range that does not impair flame retardancy and mechanical properties. The additive may be a lubricant, a heat stabilizer, An antistatic agent, a conductive agent, an EMI shielding agent, a magnetic property-imparting agent, a mineral filler, a crosslinking agent, an antimicrobial agent, a processing aid, a metal deactivating agent, a suppressing agent, a fluorine- An anti-wear agent and a coupling agent.
The ABS copolymer, the phosphonic acid metal salt, and the additive, which are the constituent materials of the halogen-free flame retardant resin composition of the present invention, are mixed and then subjected to various mixing and processing equipments such as a single screw extruder, a twin screw extruder, a roll mill, Or the like, and then the pellets can be obtained. Further, the pellets can be injection-processed to obtain a work product.
Hereinafter, the present invention will be described in more detail with reference to Examples of the present invention. However, the following Examples are intended to illustrate the present invention, but the scope of the present invention is not limited by the following Examples.
[ Example ]
Example One
(1) the first caliber ABS copolymer
The bulk-diameter ABS copolymer (product name: MA221, average particle diameter 3.5 mu m) manufactured by LG Chemical Co. through mass polymerization was used without purification.
(2) Phosphinic acid metal salt compound
A diethylphosphinic acid aluminum salt (product name: OP935, average particle size 4.5 mu m) manufactured by Clariant was used.
(3) Manufacture of halogen-free flame retardant ABS resin
15 parts by weight of the diethylphosphinic acid aluminum salt, 1 part by weight of a lubricant (ethylene bis stearamide, EBA), 1 part by weight of a heat stabilizer (distearyl pentaerythritol, distearyl pentaerythritol, diphosphite), and then pelletized halogen-free flame-retardant resin was prepared at 220 ° C using a twin-screw extruder.
Example 2 to 3
In the same manner as in Example 1, Free flame-retardant ABS resin in the form of a pellet was prepared in the same manner as in Example 1 except that the amount and type of the ABS copolymer used and the phosphinate acid metal salt compound were changed as shown in Table 1 below.
Comparative Example One
In the same manner as in Example 1, Comparative Example 1 was carried out using 5 parts by weight of a halogen-free flame-retardant ABS resin in the form of pellets, which was less than 10 parts by weight of diethylphosphinic acid aluminum salt as shown in Table 1 below.
Comparative Example 2
In the same manner as in Example 1, A halogen-free flame-retardant ABS resin in the form of pellets was prepared, and Comparative Example 2 was carried out using 30 parts by weight of more than 25 parts by weight of diethylphosphinic acid aluminum salt as shown in Table 1 below.
Comparative Example 3
In the same manner as in Example 1, Comparative Example 3 was carried out using a diethylphosphinic acid aluminum salt having an average particle size exceeding 10 mu m while producing a pellet-type halogen-free flame-retardant ABS resin.
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, and Comparative Example 4 was carried out using phosphoric acid ester compound instead of diethylphosphinic acid aluminum salt as a flame retardant.
Comparative Example 5
Except that 28 parts by weight of grafted ABS copolymer (product name: DP270, manufactured by LG Chemical) having an average particle diameter of 0.3 탆 prepared by emulsion polymerization instead of the high-porosity ABS copolymer produced by bulk polymerization, and 28 parts by weight of styrene-acrylonitrile (SAN, product name: 92HR, manufactured by LG Chemical Co., Ltd.) (72 parts by weight).
Copolymer
ABS
Metal salt
(2) ABS copolymer (B): average particle diameter: 9 占 퐉; trade name: MA220
(3) Grafted ABS copolymer (C): average particle diameter 0.3 탆, product name of DP Chemie, DP270
(4) Styrene acrylonitrile (SAN): 92HR manufactured by LG Chemical Co.
(5) Phosphinic acid metal salt (D): average particle diameter 4.5 占 퐉, trade name OP935 manufactured by Clariant
(6) Phosphinic acid metal salt (E): average particle size of 20 탆, trade name OP1240 from Clariant
(7) Phosphoric ester compound: Product name of PX200
Manufacturing example 1 to 3 and Comparative Manufacturing Example 1-5
Each of the pellet type halogen-free flame-retardant ABS resins prepared in the above Examples and Comparative Examples was injected using a 150MT extruder having a nozzle temperature of 220 ° C and a mold temperature of 50 ° C to prepare specimens (molded articles) Production Examples 1 to 5 were carried out.
Experimental Example
The impact strength and the candle flame test of the specimens prepared in the above Production Examples and Comparative Production Examples were performed, 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 is an experiment simulating a 150 mm length candle with a diameter of 20 mm. The concrete method is as follows.
① Sample preprocessing
The specimens were pretreated for at least 24 hours in a conditioning chamber at 23 ± 2 ° C and 50 ± 5% relative humidity, and candle flame evaluation was performed in a laboratory with 25 ° C and 58% relative humidity within 1 hour.
② Burner and flame
A butane gas burner having a length of at least 50 mm and a diameter of 0.5 ± 0.1 mm and a flame of 12 mm ± 1 mm was used as a butane gas having 95% purity.
③ Flame persistence evaluation method
The end of the burner was brought to 5 ± 0.5 mm from the specimen surface, the horizontal axis of the burner tube was kept within ± 5 °, and the center line of the burner tube was not deviated from 10 to 150 mm in the specimen. Also, even if shrinkage and recording of the material occurred, it was considered appropriate if the burner flame was kept for 3 minutes and then removed and the flame did not last for 3 minutes. The results are shown in Table 2 below, and those that are suitable are marked with " "
(kgf · cm / cm)
(candle flame)
As shown in Table 2, all of Examples 1 to 3 of the present invention passed the candle flame test to satisfy not only the candle flame standard, but also excellent impact strength. However, Comparative Example 1 using a less amount of a phosphinate acid metal salt compound (diethylphosphinic acid aluminum salt) and Comparative Example 4 using a phosphoric acid ester compound showed excellent impact strength but failed to pass the candle flame test. Comparative Example 2 using a phosphinate acid metal salt compound and Comparative Example 3 using a phosphinate acid metal salt compound having an average particle diameter exceeding 10 탆 and Comparative Example 5 using a mixed copolymer passed the test of the candle flame, Is very low.
Using the halogen-free flame-retardant ABS resin composition of the present invention, the ABS copolymer alone has excellent mechanical properties such as impact strength, and satisfies the candle flame retardant standard It is possible to provide an ABS resin-finished product.
Claims (8)
And 10 to 25 parts by weight of a phosphinic acid metal salt compound having an average particle diameter of 1 탆 to 5 탆,
The copolymer may be a copolymer,
Aromatic vinyl compounds;
Vinyl cyanide compounds; And
Free flame retardant resin composition comprising a rubber containing at least one member selected from the group consisting of a butadiene rubber and a styrene-butadiene rubber.
[Chemical Formula 1]
In the above formulas, R 1 and R 2 are the same or different and each is 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, M is Al, Zn, Mg or Ca And n is 2 to 3.
60 to 80 parts by weight of an aromatic vinyl compound;
15 to 30 parts by weight of a vinyl cyanide compound; And
5 to 20 parts by weight of a rubber containing at least one member selected from the group consisting of a butadiene rubber and a styrene-butadiene rubber
Free flame retardant resin composition.
Styrene,? -Methylstyrene, p-methylstyrene, vinyltoluene, and t-butylstyrene.
Acrylonitrile, methacrylonitrile, and ethacrylonitrile. The halogen-free flame-retardant resin composition according to claim 1,
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100122308A KR101419574B1 (en) | 2010-12-02 | 2010-12-02 | Hallogen-free resin composite having flame retardancy |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020100122308A KR101419574B1 (en) | 2010-12-02 | 2010-12-02 | Hallogen-free resin composite having flame retardancy |
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| KR101419574B1 true KR101419574B1 (en) | 2014-07-14 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000219772A (en) * | 1999-01-30 | 2000-08-08 | Clariant Gmbh | Flame retardant combination for thermoplastic polymer |
| JP2002161211A (en) * | 2000-11-24 | 2002-06-04 | Daicel Chem Ind Ltd | Flame-retardant resin composition |
| JP2005113146A (en) * | 2003-10-07 | 2005-04-28 | Clariant Gmbh | Phosphorus-containing flame-retardant aggregate |
| KR20080062201A (en) * | 2006-12-29 | 2008-07-03 | 주식회사 엘지화학 | Styrenic themoplastic resin compositions with good mechanical properties and low gloss |
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- 2010-12-02 KR KR1020100122308A patent/KR101419574B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000219772A (en) * | 1999-01-30 | 2000-08-08 | Clariant Gmbh | Flame retardant combination for thermoplastic polymer |
| JP2002161211A (en) * | 2000-11-24 | 2002-06-04 | Daicel Chem Ind Ltd | Flame-retardant resin composition |
| JP2005113146A (en) * | 2003-10-07 | 2005-04-28 | Clariant Gmbh | Phosphorus-containing flame-retardant aggregate |
| KR20080062201A (en) * | 2006-12-29 | 2008-07-03 | 주식회사 엘지화학 | Styrenic themoplastic resin compositions with good mechanical properties and low gloss |
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| KR20120060687A (en) | 2012-06-12 |
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