KR101251333B1 - Flame retardant thermoplastic resin composition having good weatherability and impact resistance and molded article produced therefrom - Google Patents

Abstract

(A) 50 to 90% by weight of acrylonitrile-butadiene-styrene resin; And (B) 5 to 40 parts by weight of acrylonitrile-chlorinated polyethylene-styrene resin; and (C) 5 to 40 parts by weight of a brominated diphenylethane mixture with respect to 100 parts by weight of the base resin. It provides a flame retardant thermoplastic resin composition excellent in weatherability and impact resistance. The flame retardant thermoplastic resin composition according to the present invention has excellent weather resistance and high impact resistance due to high compatibility of diphenyl ethane brominated with acrylonitrile-butadiene-styrene resin and chlorinated polyethylene in acrylonitrile-chlorinated polyethylene-styrene resin. Characteristics.

Thermoplastic, Brominated Diphenylethane, Flame Retardant

Description

Flame retardant thermoplastic resin composition having good weatherability and impact resistance and molded article produced therefrom}

The present invention relates to a flame retardant thermoplastic resin composition excellent in weatherability and impact resistance, and a molded article prepared therefrom, and more particularly to a flame retardant thermoplastic resin composition comprising a brominated diphenylethane mixture and an excellent flame retardant thermoplastic resin composition and a molded article prepared therefrom. It is about.

Acrylonitrile-butadiene-styrene (ABS) flame retardant resins are used in a wide range of applications from everyday household goods to automotive interiors, office equipment, and display exteriors.

In particular, in case of flame-retardant ABS resin applied to exterior materials, due to the low weatherability due to the double bond of butadiene, which imparts impact resistance, the weathering stabilizer or titanium oxide is prescribed to compensate for the insufficient weather resistance, but the characteristics are limited to express satisfactory level. Was not.

Meanwhile, in the case of acrylonitrile-styrene-acrylate (ASA) resin having excellent weather resistance due to the absence of double bonds on the rubber to impart impact characteristics, it is difficult to realize flame retardancy, and thus it does not satisfy both flame retardancy and weather resistance.

In general, brominated diphenylethane-based flame retardants have been known as flame retardants suitable for thermoplastic resin compositions, thermosetting resin compositions, and the like, which are processed at high temperatures with excellent flame retardancy and good thermal stability. In particular, brominated diphenylethane-based flame retardants can be added in a small amount due to the high bromine content has been used in various products.

Decabromodiphenylethane having 10 bromine substitutions in a diphenylethane flame retardant is disclosed in US Pat. Nos. 5,008,477, 5302,768, 5,324,874, 5,401,890, 5,457,248 and 7,129,384. have. However, decabromodiphenylethane lowers the impact strength of the thermoplastic resin composition used due to the high melting temperature and low compatibility, and has a disadvantage in that the applicable polymer is limited by reducing the flowability.

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

Another object of the present invention is to provide a molded article prepared from a flame-retardant thermoplastic resin composition excellent in weather resistance and impact resistance.

All of the above and other purposes of the present invention may be achieved in accordance with the present invention as described in detail.

In order to achieve the above technical problem, the present invention (A) 50 to 90% by weight of acrylonitrile-butadiene-styrene resin; And (B) 5 to 40 parts by weight of acrylonitrile-chlorinated polyethylene-styrene resin; and (C) 5 to 40 parts by weight of a brominated diphenylethane mixture with respect to 100 parts by weight of the base resin. It provides a flame retardant thermoplastic resin composition excellent in weatherability and impact resistance.

The flame retardant thermoplastic resin composition excellent in weatherability and impact resistance may further comprise 1 to 6 parts by weight of (D) antimony trioxide based on 100 parts by weight of the base resin.

Specifically, the (A) acrylonitrile-butadiene-styrene resin may include 10 to 20 parts by weight of a diene rubber, 40 to 60 parts by weight of an aromatic vinyl compound, and 20 to 30 parts by weight of a vinyl cyanide compound.

The chlorine content of the (B) acrylonitrile-chlorinated polyethylene-styrene resin is preferably 10 to 20% by weight.

Preferably, the sum of the Cheng penta bromo diphenyl ethane, the hepta bromo diphenyl ethane and the nona bromo diphenyl ethane compound in the “brominated diphenyl ethane mixture is 10 to 25% by weight, and the content of hexa bromo diphenyl ethane. It is 55-85 weight% of brominated diphenyl ethane compounds.

Further, preferably, the average brominated number of the above-brominated diphenylethane mixture is 5.5 to 7.7.

The flame retardant thermoplastic resin composition excellent in weatherability and impact resistance may further include one or more additives selected from the group consisting of heat stabilizers, dyes, pigments, lubricants, weather stabilizers, mold release agents, anti-dropping agents, dispersants, inorganic fillers and inorganic fibers. .

In order to achieve the above another technical problem, the present invention provides a molded article prepared from a flame-retardant thermoplastic resin composition excellent in weather resistance and impact resistance.

The flame retardant thermoplastic resin composition according to the present invention has excellent weather resistance and high impact resistance due to high compatibility of diphenyl ethane brominated with acrylonitrile-butadiene-styrene resin and chlorinated polyethylene in acrylonitrile-chlorinated polyethylene-styrene resin. Characteristics.

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

The present invention (A) 50 to 90% by weight of acrylonitrile-butadiene-styrene resin; And (B) 5 to 40% by weight of acrylonitrile-chlorinated polyethylene-styrene resin; (C) 5 to 40 parts by weight of the brominated diphenylethane mixture, based on 100 parts by weight of the base resin; It provides a flame retardant thermoplastic resin composition excellent in weatherability and impact resistance comprising a.

While researching to solve the problem of poor weather resistance in ABS resins and difficulty in implementing flame retardance in ACS resins, (A) acrylonitrile-butadiene-styrene resin and (B) acrylonitrile-chlorinated polyethylene-styrene system By blending the resin (C) brominated diphenyl ethane mixture in an optimum content ratio with the resin as the base resin, it was confirmed that a thermoplastic resin composition excellent in impact properties while satisfying weather resistance and flame retardancy at the same time can be obtained, and based on the present invention, It was completed.

In particular, (A) acrylonitrile-butadiene-styrene resin was applied to (B) acrylonitrile-chlorinated polyethylene-styrene resin without double bond for weather resistance and flame retardancy, and also produced by bromination of diphenyl ethane. Bromine diphenyl ethane in the bromine diphenyl ethane compound, which is a reaction product obtained through the process of adding 5.5 to 7.7 bromines in diphenyl ethane and recovering brominated diphenyl ethane from the reactant as an admixture. Brominated dibromine with a total of 10 to 25% by weight of the substituted pentabromo diphenyl ethane, hepta bromo diphenyl ethane, and nona bromo diphenyl ethane compound and a content of hexa bromo diphenyl ethane By applying a phenyl ethane compound to the ABS / ACS mixed resin as a flame retardant, a flame-retardant thermoplastic resin having both excellent weatherability and impact resistance characteristics It can be prepared for the holy.

The brominated diphenyl ethane mixture is prepared by adding bromine to diphenylethane. For example, the brominated diphenyl ethane mixture may be prepared by adding bromine to a reactor filled with diphenylethane, a solvent, and a catalyst and reacting for 0.5 to 3 hours by maintaining the reactor temperature at -10 to 35 ° C.

The catalyst may be a metal such as aluminum or antimony, bromide or chloride, or a mixture thereof. Examples thereof include Al, Sb, Fe, Ti, Sn, Be, Cd, Zn, B, Bi, Zr, AlCl ₃ , SbCl ₃ , SbCl ₅ , SbBr ₃ , SbClBr ₄ , SbBrCl ₄ , FeCl ₃ , FeBr ₃ , TiCl ₄ , TiBr ₄ , SnCl ₂ , SnBr ₃ , SnCl ₄ , AlBr ₃ , BeCl ₂ , CdCl ₂ , ZnCl ₂ , BF ₄ , BCl ₃ , BBr ₃ , BiCl ₃ , ZrCl ₄ and the like can be used, and diphenylethane 0.01 to 3 moles per mole may be used. In one embodiment of the present invention can be used in 0.01 to 1.5 moles per mole of diphenylethane.

As the solvent, any solvent may be used as long as it dissolves diphenyl ethane well and is inert to metal, metal salt Lewis acid, bromine and bromine chloride. Solvents that can be used include methylene chloride, chloroform, carbon tetrachloride, 1-2-dichloroethane, 1,1,1-trichloroethane, 1,1,2, 2-tetra chloro ethane, methylene bromide, methyl bromide, tetrabromomethane, 1-2-dibromoethane, 1,1,1 Tribromoethane, 1,1,2,2-tetra bromo ethane, and the like. The said chlorine organic solvent may be used individually or in mixture. Chlorine- or bromine-based organic solvents include chlorobenzene, o, m, p-dichlorobenzene (o, m, p-dichlorobenzene), bromobenzene, o, m, p-dibromobenzene (o Aromatic solvents such as (m, p-dibromobenzene) are not preferred because bromine is substituted in the aromatic nucleus.

The bromine may be added in an amount of 5 to 9 mol, preferably 6.0 to 8.5 mol, and most preferably 6.2 to 8.3 mol per mol of diphenylethane so that 6.5 to 8.5 hydrogens in diphenylethane are replaced with Br. .

After the reaction is completed, the organic phase may be washed with an alkaline aqueous solution or an alkaline sulfate to remove the metal salt Lewis acid catalyst, bromine or bromine chloride remaining in the organic phase. If metal is used as a catalyst, it can be removed by washing with acidic aqueous solution. In addition, when a small amount of halogen remains a problem, the unreacted halogen can be adsorbed and removed by passing the washed organic phase through the activated carbon layer or adding granular activated carbon in the organic phase. Then, the precipitate is separated from the precipitate and the organic phase by filtration or centrifugation, and the separated organic phase is introduced into a large amount of non-commercial solvent such as methanol to separate the precipitate, and the precipitate separated in each step is dried and brominated. Recover dimethyl ethane. This recovery method is not limited to the above method, and can be used also by other known methods.

The flame retardant thermoplastic resin composition excellent in weatherability and impact resistance according to the present invention may further include an auxiliary flame retardant. In one embodiment of the present invention, 1 to 6 parts by weight of antimony trioxide (D) more than 100 parts by weight of the base resin.

More specifically, the (A) acrylonitrile-butadiene-styrene resin may include those containing 10 to 20 parts by weight of a diene rubber, 40 to 60 parts by weight of an aromatic vinyl compound and 20 to 30 parts by weight of a vinyl cyanide compound. have.

The rubber may be a diene rubber such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), or the like; Saturated rubber hydrogenated to the diene rubber; Isoprene rubber; Alkyl acrylate rubbers; Ethylene-propylene-diene terpolymers (EPDM), ethylene-propylene rubber, and the like can be used. Among them, polybutadiene, poly (styrene-butadiene), isoprene and alkyl acrylate rubbers are preferable. The rubber may be used alone or a mixture of two or more thereof.

As the aromatic vinyl compound, a styrene-based monomer may be preferably used. Examples include, but are not limited to, styrene, α-methyl styrene, o-, m-, p-methyl styrene, ethyl styrene, isobutyl styrene, tert-butyl styrene, and the like. Of these, styrene is most preferred.

The vinyl cyanide compound may be acrylonitrile.

The (A) acrylonitrile-butadiene-styrene resin may be prepared by a conventional method using a bulk polymerization, suspension polymerization, emulsion polymerization or a mixture thereof, and among these polymerization methods, the bulk polymerization method is preferable. Can be used.

The aromatic vinyl resin (A) may be polymerized by thermal polymerization without using an initiator or polymerized in the presence of an initiator. Polymerization initiators that can be used include one or more selected from peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, cumenehydro peroxide, and azo initiators such as azobis isobutyronitrile. Can be.

In another embodiment of the present invention, the (B) acrylonitrile-chlorinated polyethylene-styrene resin is 20 to 30 parts by weight of acrylonitrile monomer, 20 to 30 parts by weight of styrene monomer and 40 to 60 parts by weight of chlorinated polyethylene monomer It is a copolymer superposed | polymerized by content ratio.

Preferably, the chlorine content of the (B) acrylonitrile-chlorinated polyethylene-styrene resin is 10 to 20% by weight. When the chlorine content is less than 10% by weight, the impact strength reinforcing effect may be limited, and when it exceeds 20% by weight, thermal stability may be deteriorated.

The (B) acrylonitrile-chlorinated polyethylene-styrene resin may have a low Tg basically to act as a rubber.

The flame-retardant thermoplastic resin composition excellent in weatherability and impact resistance according to the present invention is selected from the group consisting of heat stabilizers, dyes, pigments, lubricants, weather stabilizers, mold release agents, anti-dropping agents, dispersants, inorganic fillers and inorganic fibers according to the use of the final structural material It may further comprise one or more additives.

In another embodiment of the invention, 10 to 20 parts by weight of graft copolymer resin (g-ABS) and 60 to 70 parts by weight of styrene / acrylonitrile copolymer resin (SAN), acrylonitrile-chlorinated polyethylene-styrene Provided is a thermoplastic resin composition containing 10 to 30 parts by weight of brominated diphenyl ethane having a bromine content of 55 to 85% as a flame retardant in 10 to 30 parts by weight of the system resin (ACS).

The method for producing a thermoplastic resin composition according to the present invention comprises reacting bromine with diphenylethane to synthesize a brominated diphenyl ethane mixture; And mixing and extruding the thermoplastic resin in the brominated diphenyl ethane mixture.

After the resin composition of the present invention is mixed with the above components and other additives simultaneously, it can be melt-extruded in an extruder and prepared in pellet form. The prepared pellets may be manufactured into various molded articles through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding.

The present invention also provides a molded article prepared from the flame-retardant thermoplastic resin composition excellent in weatherability and impact resistance of the present invention. The molded article is excellent in impact resistance, weather resistance, flame retardancy, etc., and can be widely applied to automobile interior parts or electronic product cases.

This invention may be better understood than by the following embodiments, which are intended to illustrate the purposes of the present invention and are not intended to limit the scope of protection as defined in the appended claims.

Example

Hereinafter, the specifications of each component and additives used in Examples and Comparative Examples are as follows.

(A) resin

(A1) acrylonitrile-butadiene-styrene (ABS) resin

Graft copolymer resin (g-ABS) and styrene / acrylonitrile copolymer resin (SAN) were each prepared and used as follows.

50 parts by weight of butadiene rubber latex, 36 parts by weight of styrene, 14 parts by weight of graft copolymerizable monomer acrylonitrile, and 150 parts by weight of deionized water in a mixture of 1.0 parts by weight of potassium oleate and cumenehydr 0.4 parts by weight of loper oxide, 0.2 parts by weight of mercaptan-based chain transfer agent, 0.4 parts by weight of glucose, 0.01 parts by weight of iron sulfate hydrate, and 0.3 parts by weight of pyrophosphate sodium salt were added, and the reaction was completed by maintaining the temperature at 75 ° C. for 5 hours. Copolymer (g-ABS) latex was prepared. 0.4 parts by weight of sulfuric acid was added to the resulting resin composition solids and solidified to prepare a graft copolymer resin (g-ABS) in powder form.

Room temperature was added by adding 75 parts by weight of styrene, 25 parts by weight of acrylonitrile, 120 parts by weight of deionized water, 0.2 parts by weight of azobisisobutyronitrile, 0.4 parts by weight of tricalcium phosphate, and 0.2 parts by weight of mercaptan-based chain transfer agent. After raising the temperature to 80 ° C. for 90 minutes and maintaining the temperature at this temperature for 180 minutes to prepare a styrene / acrylonitrile copolymer resin (SAN), the water was washed with water, dehydrated and dried to obtain a powder.

(A2) Acrylonitrile-chlorinated polyethylene-styrene (ACS) resin

ACS resin with a chlorine content of 15% (chlorine content can be measured by ion chromatography) was used.

(A3) Acrylonitrile-styrene-acrylate (ASA) resin

Cheil Industries' WR-9100 was used.

(B) Flame retardant

A brominated diphenyl ethane compound having a bromine content of 74.7 wt% was used.

Composition analysis using GC / MS of the synthesized flame retardant was performed after diluting a given sample in toluene with Dilution Factor = 2000 (0.5 mg / mL) and completely dissolving it. Agilent 7683 injector-GC Agilent 7890N-MSD agilent 5975C was used as a measuring instrument. Measurement condition is Inlet temperature 320 ℃, split ratio is splitless, column is DB-5HT, column flow is 1.0 ml / min, Oven temperature program is 40 ℃ (2 min)-40 ℃ / min → 200 ℃-10 ℃ / min → 260 ° C.-20 ° C./min → 340 ° C. (2 min) and the MS interface temperature is set at 280 ° C. Qualitative analysis was performed by injecting 1 μl into GC / MSD using an autosampler. Each measured composition was used based on area. The analysis of Br content was carried out using IC, and the sample was burned by injecting excess oxygen, and then measured using an IC-500.

Furtherance Area ratio (%) Flame Retardant B Br5 0.8 Br6 66.2 Br7 14.8 Br8 13.1 Br9 5.2 Br content 74.7%

(C) flame retardant supplements

Ilsan antimony trioxide antimony trioxide ANTIS-W was used.

(D) UV stabilizer

(D1) TINUVIN 770DF from CIBA-GEIGY was used.

(D2) TINUVIN P of CIBA-GEIGY was used.

(E) titanium oxide

Tiona RCL 188 from Millennium Inorganic Chemical was used.

Examples 1-8

The ingredients were added according to the amounts in Table 1 below, followed by uniform mixing for 3-10 minutes in a Henschel mixer. The mixture was extruded in a conventional twin screw extruder at an extrusion temperature of 180 to 210 ° C., a screw rotational speed of 150 to 300 rpm, and a composition feed rate of 30 to 60 kg / hr. The prepared pellets were dried at 100 ° C. for 4 ° C. and then injected into a 6 Oz injection machine under conditions of a molding temperature of 180 to 210 ° C. and a mold temperature of 40 to 80 ° C. to prepare a specimen. The prepared specimens were measured for physical properties, flame retardancy and fluidity by the following method.

(1) Melt Flow Index: measured at 200 ° C./5kg according to ASTM D-1238.

(2) Impact Strength: Izod impact strength (1/8 ″ notch, kgf · cm / cm) was measured according to ASTM D-256.

(3) Flame retardancy: Flame retardancy was measured at a thickness of 2.5 mm according to the UL 94 flame retardant regulations.

(4) Weather resistance: After 300 hours exposure to Xenon-Arc lamp according to ASTM D4459, the color difference (dE) of the 3.2 mm thick specimen was measured by CCM instrument.

Comparative Examples 1 to 6

Except that the specimen was prepared according to the composition as shown in Table 2, all the same procedure as in the above Example, and the results are shown in Table 2 together.

Ingredients Product name and unit Example 1 Example 2 Example 3 Example 4 Example
5 Example 6 Example 7 Example 8 ABS resin g-ABS 10 10 10 10 10 20 20 20 SAN 80 75 70 65 60 70 60 50 ACS Resin ACS 10 15 20 25 30 10 20 30 Flame retardant B 15 15 15 15 15 20 20 20 Flame Retardant Supplements Sb2O3 4 4 4 4 4 4 4 4 Titanium oxide TIONA 5 5 5 5 5 5 5 5 Impact strength (kgcm / cm) 5.9 8.4 12.8 15.3 16.9 14.7 16.8 18.4 Flammability 2.5mm V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Weatherability dE 12.4 10.1 9.9 8.5 7.8 15.4 13.8 11.7

Unit: parts by weight

Ingredients Product name and unit Comparative Example 1 Comparative Example 2 Comparative Example
3 Comparative Example 4 Comparative Example 5 Comparative Example 6 ABS resin g-ABS 20 20 30 30 30 - SAN 80 80 70 70 70 - ASA resin WR-9100 - - - - - 100 Flame retardant B 15 15 15 15 15 15 Flame Retardant Supplements Sb ₂ O ₃ 4 4 4 4 4 4 Titanium oxide TIONA 5 5 5 5 5 5 UV stabilizer D1 - 0.4 0.4 - 0.4 - D2 - - - 0.4 0.4 - Impact strength (kgcm / cm) 13.7 13.6 23.4 22.6 22.8 20.1 Flammability 2.5mm V-0 V-0 V-0 V-0 V-0 Fail Weatherability dE 23.4 21.7 23.1 18.9 19.7 0.9

Unit: parts by weight

Comparative Example 1 in which only ABS resin is used, and Comparative Examples 2 to 5 in which UV protection agent is used in ABS resin are compared with Examples 1 to 8 in which ACS resin is used in ABS resin, Comparative Example 1 Shows that the weather resistance was significantly lowered, and the weather resistance was improved compared to Comparative Example 1 by reinforcing the sunscreen in Comparative Examples 2 to 5, but the weatherability and impact strength balance of Examples 1 to 8 were not obtained.

In addition, when ACS resin and ABS resin are used together, weather resistance is expected to be significantly lower than that of Comparative Example 6 using only ASA, but Examples 1 to 8 are flame retardant while maintaining some satisfactory weather resistance compared to Comparative Example 6. It also shows that it can be secured excellently.

Claims (9)

(A) 60 to 90% by weight of acrylonitrile-butadiene-styrene resin; And (B) 10 to 40% by weight of acrylonitrile-chlorinated polyethylene-styrene resin; with respect to 100 parts by weight of the base resin, (C) 5 to 40 parts by weight of a brominated diphenylethane mixture, In the above-brominated diphenyl ethane mixture (C), the total amount of pentane bromo diphenyl ethane, hepta bromo diphenyl ethane and nona bromo diphenyl ethane compound is 10 to 25% by weight, and the content of hexabromo diphenyl ethane is A flame-retardant thermoplastic resin composition excellent in weatherability and impact resistance, characterized by a brominated diphenyl ethane mixture of 55 to 85% by weight. The flame-retardant thermoplastic resin composition of claim 1, further comprising 1 to 6 parts by weight of antimony trioxide (D), based on 100 parts by weight of the base resin. The acrylonitrile-butadiene-styrene resin (A) according to claim 1, wherein the acrylonitrile-butadiene-styrene resin comprises 10 to 20 parts by weight of a diene rubber, 40 to 60 parts by weight of an aromatic vinyl compound and 20 to 30 parts by weight of a vinyl cyanide compound. Flame retardant thermoplastic resin composition excellent in weatherability and impact resistance. The flame retardant thermoplastic excellent in weatherability and impact resistance according to claim 1, wherein the chlorine content of the acrylonitrile-chlorinated polyethylene-styrene resin (B) is 10 to 20% by weight based on ion chromatography. Resin composition. The acrylonitrile-chlorinated polyethylene-styrene resin according to claim 1 or 4, wherein the acrylonitrile-chlorinated polyethylene-styrene resin is 20 to 30 parts by weight of the acrylonitrile monomer, 20 to 30 parts by weight of the styrene monomer and 40 to 60 parts by weight of the chlorinated polyethylene monomer. A flame-retardant thermoplastic resin composition excellent in weatherability and impact resistance, characterized in that the copolymer copolymerized in a content ratio of parts. delete The flame-retardant thermoplastic resin composition excellent in weatherability and impact resistance according to claim 1, wherein the brominated diphenylethane mixture has an average brominated number of 5.5 to 7.7. The weathering and impact resistance according to claim 1, further comprising at least one additive selected from the group consisting of a heat stabilizer, a dye, a pigment, a lubricant, a weather stabilizer, a mold release agent, an antidropping agent, a dispersant, an inorganic filler, and an inorganic fiber. This excellent flame retardant thermoplastic resin composition. A molded article prepared from a flame-retardant thermoplastic resin composition excellent in weatherability and impact resistance according to any one of claims 1 to 4.