TWI450910B - A flame retardant styrene-based resin composition, and a molded article obtained - Google Patents

Description

Flame retardant styrene resin composition and molded article obtained therefrom

The invention relates to a material suitable for preparing plastic molded articles for electrical equipment, office equipment, automobile parts, household articles, etc., in particular to a rubber modified styrene resin, a bromine-based flame retardant and a bismuth-containing material. A flame retardant styrene resin composition of an oxide. The present invention also provides a molded article formed from the composition.

Most of the components contained in plastic molded articles for electrical equipment, household goods, and the like are rubber-modified styrene resins, polycarbonate resins (Polycarbonate Resin), and the like. Among them, the rubber modified styrene resin, such as Acrylonitrile-Butadiene-Styrene Resin (ABS), has high surface hardness, good chemical resistance, good electrical properties and easy molding. Such as excellent characteristics, and gradually applied to a variety of plastic molded products.

However, when the rubber-modified styrene-based resin is used in an environment in which flame retardancy is required, the flame retardant property is not good and the flame retardant effect cannot be achieved. Although the subsequent study adds flame retardant to improve its flame retardancy, the flame retardant of the flame retardant contained in the rubber modified styrene resin containing the flame retardant will gradually decrease under long-term storage. Therefore, considering the safety of the fire, the rubber-modified styrene resin is still required to maintain flame retardancy after being stored for a long period of time. Further, the rubber-modified styrene-based resin produces a foul smell during the high-temperature processing.

In view of the above, in addition to effectively improving the flame retardant properties and maintaining mechanical and processing properties, it is still necessary to develop a flame-retardant styrene-based resin composition which is formed after subsequent processing to form a molded article and stored for a long period of time. The product has better flame retardancy and aging, and the composition does not emit malodor during the processing and molding process to meet the needs of the industry.

Accordingly, a first object of the present invention is to provide a flame-retardant styrene-based resin composition which does not emit a foul smell during processing.

Thus, the flame retardant styrenic resin composition of the present invention comprises:

100 parts by weight of rubber modified styrene resin (A);

4 parts by weight to 40 parts by weight of a bromine-based flame retardant (B);

1 part by weight to 10 parts by weight of cerium-containing oxide (C);

Wherein the rubber-modified styrene resin (A) is composed of a continuous phase formed by a copolymer of 50% by weight to 90% by weight and a dispersed phase formed by 10% by weight to 50% by weight of rubber particles; The copolymer comprises 50% by weight to 90% by weight of styrene monomer units and 10% by weight to 50% by weight of nitrileated vinyl monomer units; the rubber particles have a non-occlusion structure; The content of the styrene monomer and the nitrile vinyl monomer in the flammable styrene resin composition is 100 parts by weight of the flame retardant styrene resin composition. Below 5,000 ppm.

A second object of the present invention is to provide a molded article having a flame retardant styrene resin composition which is preferably hardly flammable.

Then, the molded article of the flame-retardant styrene-based resin composition of the present invention is obtained by subjecting a flame-retardant styrene-based resin composition as described above to a kneading process.

The effect of the present invention is that the content of the dimeric or trimeric body derived from the styrene monomer and the nitrile vinyl monomer in the flame retardant styrene resin composition is 5,000 ppm or less, so that the content is 5,000 ppm or less. When the molded article formed from the composition is stored for a long period of time, the bromine-based flame retardant is not deposited on the surface of the molded article due to the presence of the dimeric or trimeric body, which in turn causes the molded article to be burned. The deterioration of the characteristics causes the molded article to have no better flame retardancy and the like; in addition, the flame retardant styrene resin composition does not give a foul smell during the subsequent high-temperature processing.

The flame retardant styrene resin composition of the present invention comprises: 100 parts by weight of a rubber-modified styrene resin (A); 4 parts by weight to 40 parts by weight of a bromine-based flame retardant (B); and 1 part by weight to 10 parts by weight a cerium-containing oxide (C); wherein the rubber-modified styrene resin (A) is a continuous phase composed of 50% by weight to 90% by weight of a copolymer and 10% by weight to 50% by weight of rubber particles The dispersed phase is formed; the copolymer comprises 50% by weight to 90% by weight of styrene monomer units and 10% by weight to 50% by weight of nitrile vinyl monomer units; the rubber particles have non-occluding The styrene-based monomer and the nitrile-based vinyl monomer in the flame-retardant styrene-based resin composition are all contained in the dimer or tri-dimer, and constitute the flame-retardant styrene resin composition. 100 parts by weight or less of 5,000 ppm or less.

Preferably, the styrene monomer and the nitrile vinyl monomer derived from the flame retardant styrene resin composition are all present in the dimer or triad body in an amount of the flame retardant styrene resin. The composition is 2,000 ppm or less in 100 parts by weight. More preferably, the total content of the dimeric or trimeric body derived from the styrene monomer and the nitrile vinyl monomer in the flame retardant styrene resin composition accounts for the flame retardant styrene resin. The composition is 1,500 ppm or less in 100 parts by weight.

Preferably, the rubber particles also have an occlusion.

Preferably, when the rubber particles further have a occluding structure, the styrene monomer and the nitrile vinyl monomer derived from the flame retardant styrene resin composition are di- or tri-dimeric The total content is 2,001 ppm to 5,000 ppm per 100 parts by weight of the flame retardant styrene resin composition. More preferably, the total content of the dimeric or trimeric body derived from the styrene monomer and the nitrile vinyl monomer in the flame retardant styrene resin composition accounts for the flame retardant styrene resin. The composition is 3,000 ppm to 4,500 ppm in 100 parts by weight.

Preferably, the flame retardant styrene resin composition comprises: 100 parts by weight of a rubber-modified styrene resin (A); 10 parts by weight to 30 parts by weight of a bromine-based flame retardant (B); and 2 parts by weight ～8 parts by weight of cerium-containing oxide (C).

The rubber-modified styrene resin (A) preferably has a rubber component content of 5 parts by weight to 40 parts by weight based on 100 parts by weight of the total amount of the rubber-modified styrene-based resin (A).

[Rubber modified styrene resin (A)]

The rubber modified styrene resin (A) is produced by kneading the rubber graft copolymer (II), or 50% by weight to 90% by weight of the ethylene copolymer (I) and 10 5% by weight to 50% by weight of the rubber graft copolymer (II) is obtained by kneading; preferably, 60% by weight to 85% by weight of the ethylene-based copolymer (I) and 15% by weight to 40% by weight of the rubber The graft copolymer (II) is obtained by kneading; more preferably, from 65% by weight to 80% by weight of the ethylene-based copolymer (I) and from 20% by weight to 35% by weight of the rubber graft copolymer (II) Made by a mixed method.

The rubber graft copolymer (II) is selected from the group consisting of 50% by weight to 98% by weight of agglomerated or solution polymerized rubber graft copolymer (II-1) and 2% by weight to 50% by weight of an emulsion polymerized rubber graft copolymerization (II-2); preferably, 60% by weight to 95% by weight of the block or solution polymerized rubber graft copolymer (II-1) and 5% by weight to 40% by weight of the emulsion polymerized rubber graft copolymer ( II-2); more preferably, 70% by weight to 90% by weight of the block or solution polymerized rubber graft copolymer (II-1) and 10% by weight to 30% by weight of the emulsion polymerized rubber graft copolymer (II- 2), or a combination of these. The ethylene-based copolymer (I) is a suspension-polymerized ethylene-based copolymer.

Preferably, the rubber-modified styrene-based resin (A) is produced by kneading the emulsion-polymerized rubber graft copolymer (II-2) with a bulk or solution-polymerized rubber graft copolymer (II-1). The method is made by extruding. The rubber particles in the rubber-modified styrene-based resin (A) obtained include rubber particles having a absorbing structure and rubber particles having a non-occlusive structure; and the rubber particles having the absorbing structure are referred to as rubber components. The formed shell and the core formed by the copolymer, and the rubber particles having a non-occluded structure are formed of a rubber component. The rubber component is like the rubber component used in the rubber graft copolymer (II).

Preferably, the rubber-modified styrene-based resin (A) is produced by kneading the emulsion-polymerized rubber graft copolymer (II-2) and the ethylene-based copolymer (I) by kneading. The rubber particles in the rubber-modified styrene-based resin (A) obtained are rubber particles having a non-occlusive structure.

Hereinafter, the ethylene-based copolymer (I), the bulk or solution-polymerized rubber graft copolymer (II-1), and the emulsion-polymerized rubber graft copolymer (II-2) will be described in detail:

<ethylene copolymer (I)>

The ethylene-based copolymer (I) contains a styrene-based monomer (i-1) and a nitrile-vinyl monomer (i-2), and optionally other copolymerizable vinyl-based monomer (i) The first component of -3) is obtained by suspension polymerization.

The styrene monomer (i-1) may be used singly or in combination, and the styrene monomer (i-1) includes, but is not limited to, styrene, α-methylstyrene, p-tert-butylbenzene. Ethylene, p-methylstyrene, o-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, α-methyl-p-methylstyrene and Bromostyrene and the like. Preferably, the styrenic monomer (i-1) is selected from the group consisting of styrene, α-methylstyrene, or the like. Preferably, the content of the styrene monomer (i-1) is 50% by weight based on 100% by weight of the total of (i-1), (i-2), and (i-3). 90% by weight; more preferably, 55% by weight to 85% by weight; still more preferably, 58% by weight to 80% by weight.

The nitridinated vinyl monomer (i-2) may be used singly or in combination, and the nitrileated vinyl monomer (i-2) includes, but not limited to, acrylonitrile, α-methacrylonitrile, and the like. Preferably, the nitrileated vinyl monomer (i-2) is acrylonitrile. Preferably, the content of the nitridinated vinyl monomer (i-2) is 10% by weight based on 100% by weight of the total of (i-1), (i-2), (i-3) ～50% by weight; more preferably, 15% by weight to 45% by weight; still more preferably 20% by weight to 42% by weight.

The other copolymerizable vinyl monomer (i-3) may be used singly or in combination, and the other copolymerizable vinyl monomer (i-3) includes, but is not limited to, an acrylic monomer, a methacrylic acid system. Monomer, acrylate monomer, methacrylate monomer, monofunctional maleimide monomer, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1- Pentene, vinyl chloride, vinylidene chloride, tetrafluoroethylene, chlorotrifluoroethylene, butadiene, propenylamine, isobutenylamine, vinyl acetate, Ethyl vinyl ether, methyl vinyl ketone, triallyl isocyanate, anhydrous maleic acid, anhydrous methyl maleic acid ( Cis-methylbutenedioic acid), trans-methylbutenedioic acid, fumaric acid, itaconic acid, dimethylfumarate, itaconic acid Dibutyl itaconate and the like. Preferably, the content of the other copolymerizable vinyl monomer (i-3) is in the range of 100% by weight based on the total amount of (i-1), (i-2), (i-3) 0% by weight to 40% by weight; more preferably 1% by weight to 34% by weight; still more preferably 3 to 30% by weight.

The acrylic monomer includes, but is not limited to, acrylic acid or the like. The methacrylic monomer includes, but is not limited to, methacrylic acid or the like. The acrylate monomer includes, but is not limited to, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, and the like. Preferably, the acrylate monomer is butyl acrylate.

The methacrylate monomer includes, but is not limited to, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, and Cyclohexyl acrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, ethylene glycol Ethylene dimethacrylate, neopentyl dimethacrylate, and the like. Preferably, the methacrylate monomer is selected from methyl methacrylate or butyl methacrylate.

In the suspension polymerization, a suspension stabilizer may be optionally added. The suspension stabilizer may be used singly or in combination, and the suspension stabilizer includes, but is not limited to, (1) inorganic suspension stabilizer: clay, barium sulfate, magnesium hydroxide, etc.; (2) organic suspension stabilizer: polyvinyl alcohol (polyvinylalcohol, abbreviated as PVA), carboxymethylcellulose (CMC), polyacrylamide, methyl acrylate-acrylamide, and the like. Preferably, the suspension stabilizer is contained in an amount ranging from 1 ppm to 100 ppm based on 100 parts by weight of the total of (i-1), (i-2), and (i-3).

In the suspension polymerization, a salting-out agent may be optionally added. The salting-out agent may be used singly or in combination, and the salting-out agent includes, but not limited to, sodium sulfate, potassium sulfate, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, pyrosulfite, pyrosulfate, and Hydrosulfite, formaldehydesulfoxylate, thiosulfate, sulfoxylate. Preferably, the salting-out agent is selected from the group consisting of sodium hydrogen sulfite, sodium metabisulfite, sodium dithionite or sodium formaldehyde sulfoxylate. Preferably, the salting-out agent is contained in an amount ranging from 10 ppm to 1,000 ppm based on 100 parts by weight of the total of (i-1), (i-2), and (i-3).

In the suspension polymerization, water may be selectively added. Preferably, the content of the water is from 0.5 to 10 times the total amount of the monomers, based on 100 parts by weight of the total of (i-1), (i-2), and (i-3).

In the suspension polymerization, a polymerization initiator may be optionally added. The polymerization initiator is selected from a monofunctional polymerization initiator, a polyfunctional polymerization initiator, or a combination thereof. The monofunctional polymerization initiator may be used singly or in combination, and the monofunctional polymerization initiator includes, but is not limited to, benzoyl peroxide, dicumyl peroxide, T-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxybenzoate T-butyl-peroxy benzoate), bis-2-ethylhexyl peroxy dicarbonate, tert-butyl peroxy isopropyl carbonate BPIC), cyclohexanone peroxide, 2,2'-azo-bis-isobutyronitrile (AIBN), 1,1'-azobicyclo 1,1'-azo-biscyclohexane-1-carbonitrile, 2,2'-azo-bis-2-methylbutyronitrile (2,2'-azo-bis-2- Methyl butyronitrile) and the like. Among them, benzammonium peroxide and 2,2'-azo-bis-isobutyronitrile are preferred.

The polyfunctional polymerization initiator may be used singly or in combination, and the polyfunctional polymerization initiator includes, but is not limited to, 1,1-bis-tert-butylperoxycyclohexane (1,1-bis-t) -butyl peroxy cyclohexane (TX-22), 1,1-bis-tert-butylperoxide-3,3,5-trimethylcyclohexane (1,1-bis-t-butylperoxy-3,3 ,5-trimethyl cyclohexane, abbreviated as TX-29A), 2,5-dimethyl-2,5-bis-(2-ethylperoxyhexane)hexane [2,5-dimethyl-2,5-bis -(2-ethylhexanoxy peroxy)hexane], 4-(t-butylperoxycarbonyl)-3-hexyl-6-[7-(t-butylperoxycarbonyl)heptyl]cyclohexane {4-( T-butyl peroxy carbonyl)-3-hexyl-6-[7-(t-butyl peroxy carbonyl)heptyl]cyclohexane}, di-t-butyl-diperoxyazelate , 2,5-Dimethyl-2,5-bis(benzoquinone peroxy)hexane, 2,5-dimethyl-2,5-bis-(benzoyl peroxy)hexane, di-t-butyl Di-t-butyl peroxy-hexahydro-terephthalate (BPHTH), 2,2-bis(4,4-di-t-butylperoxy)cyclohexylpropane [ 2,2-bis-(4,4-di-t-butyl peroxy)cyclohexyl propane, referred to as PX -12] and so on.

In the suspension polymerization, a chain transfer agent may be selectively added. The chain transfer agent may be used singly or in combination, and the chain transfer agent includes, but is not limited to, n-dodecyl mercaptan (NDM), stearyl mercaptan, and third. - T-dodecyl mercaptan (TDM), n-propyl mercaptan, n-octyl mercaptan, tri-octyl mercaptan, tri-decyl mercaptan, and the like.

Preferably, the suspension polymerization reaction has an operating temperature in the range of from 30 ° C to 160 ° C; more preferably, the suspension polymerization has an operating temperature in the range of from 50 ° C to 120 ° C. Preferably, the ethylene-based copolymer (I) has a weight average molecular weight in the range of 200,000 or more.

<Rubber graft copolymer (II)> [Bulk or solution polymerized rubber graft copolymer (II-1)]

The block or solution polymerized rubber graft copolymer (II) is obtained by bulk or solution polymerization of a second component, wherein the second component comprises 50% by weight to 90% by weight of a styrene system. a monomer and 10% by weight to 50% by weight of a nitrileated vinyl monomer, and optionally 0% to 40% by weight of other copolymerizable vinyl monomer, and the total amount of the above monomers is 0.5 parts by weight to 25 parts by weight of the rubber component, based on 100 parts by weight. In the bulk or solution polymerization, an additive may be optionally added, and the additive includes, but is not limited to, a solvent, a polymerization initiator or a chain transfer agent, and the like.

Preferably, the rubber component is selected from a diene rubber, a polyacrylate rubber, or a polyoxyalkylene rubber.

Preferably, the diene rubber is obtained by polymerizing a diene monomer, and has a glass transition temperature of 0 ° C or lower. The diene rubber includes, but is not limited to, butadiene rubber, isoprene rubber, chloroprene rubber, ethylene propylene diene terpolymer (EPDM), styrene. - a diene rubber, an acrylonitrile-diene rubber, or the like. Wherein, the butadiene rubber comprises, but is not limited to, a high cis (Hi-Cis) content of butadiene rubber and a low cis (Low-Cis) content of butadiene rubber. The typical weight composition of cis (Cis)/vinyl (Vinyl) in the high cis content butadiene rubber is (94 to 99 wt%) / (0 to 5 wt%), and the rest of the composition is trans. (Trans) structure, and Mooney viscosity is between 20 and 120, and the molecular weight range is preferably from 100,000 to 800,000. The typical weight composition of cis/vinyl in the low cis content butadiene rubber ranges from (20 to 40 wt%) / (6 to 20 wt%), the balance is trans structure, and the Mooney viscosity is From 20 to 120, the molecular weight range is preferably from 100,000 to 800,000. The styrene-diene rubber includes, but is not limited to, styrene-butadiene rubber, styrene-isoprene rubber, and the like, and the styrene-diene rubber may be a block copolymer or a random copolymer. Or a composition in which the composition is tapered/tapered, wherein the styrene-butadiene rubber preferably has a weight ratio of styrene of 50% by weight or less, and preferably has a molecular weight of 50,000 to 600,000. Preferably, the styrene-diene rubber is a styrene-butadiene rubber.

The type of the styrene monomer, the nitrile vinyl monomer, the other copolymerizable vinyl monomer, the polymerization initiator, and the chain transfer agent is as described above for the preparation of the styrene series in the ethylene copolymer (I). The type of the (i-1), the nitrileated vinyl monomer (i-2), the other copolymerizable vinyl monomer (i-3), the polymerization initiator, and the chain transfer agent will not be described again.

The solvent may be used singly or in combination, and the solvent includes, but is not limited to, benzene, toluene, ethylbenzene, p-xylene, o-xylene, m-xylene, pentane, octane, cyclohexane, methyl ethyl ketone, acetone, and methyl ketone. Ketone, or a combination of these. Preferably, the content of the solvent is in the range of 0 parts by weight based on 100 parts by weight of the total of the rubber component, the styrene monomer, the nitrileated vinyl monomer, and the other copolymerizable vinyl monomer. 100 parts by weight; more preferably, the solvent is contained in an amount ranging from 0 part by weight to 60 parts by weight; more preferably, the solvent is contained in an amount ranging from 1 part by weight to 50 parts by weight.

Preferably, the content of the polymerization initiator is in the range of 100 parts by weight based on 100 parts by weight of the total of the rubber component, the styrene monomer, the nitrile vinyl monomer, and the other copolymerizable vinyl monomer. The parts by weight to 1 part by weight; more preferably, the polymerization initiator is contained in an amount ranging from 0.001 part by weight to 0.5 part by weight.

Preferably, the chain transfer agent is present in an amount ranging from 0 parts by weight based on 100 parts by weight of the total of the rubber component, the styrenic monomer, the nitrileated vinyl monomer, and the other copolymerizable vinyl monomer. Parts to 2 parts by weight; more preferably, the chain transfer agent is contained in an amount ranging from 0.001 part by weight to 1 part by weight.

The block or solution polymerization rubber graft copolymer (II-1) is prepared by using the above rubber component, styrene monomer, nitrile vinyl monomer, and other copolymerizable vinyl monomer. The starting material is continuously fed into the reactor. After the reaction reaches the desired conversion rate, the reacted solution is continuously taken out from the reaction device and introduced into a devolatilizer, and the devolatilizer is unreacted. The bulk material or the solution-polymerized rubber graft copolymer (II-1) of the present invention can be obtained by removing the starting material and the volatile component produced after the reaction, or further granulating. The final monomer conversion rate in the general polymerization reaction is 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more. In general, the devolatilizer can use a vacuum degassing tank device or a degasser. Thereafter, the unreacted monomer or volatile component is recovered by a condenser, and if necessary, the water in the recovered liquid can be removed and reused as a raw material solution.

The reactor includes, but is not limited to, a plug flow reactor (PFR), a continuous stirred-tank reactor (CSTR), or a reactor containing a static mixer (Static reactor) )Wait. The number of the reactors may be one, or two or more, preferably three or more, in combination. When more than two reactors are used, the first reactor is preferably a fully mixed reactor (CSTR), and the final reactor is preferably a columnar flow reactor (PFR).

Preferably, the operating temperature of the reactor ranges from 20 ° C to 300 ° C; more preferably, the operating temperature of the reactor ranges from 60 ° C to 250 ° C; more preferably, the operating temperature range of the reactor is 80 °C ~ 240 °C. Preferably, the operating pressure of the reactor ranges from 1 kg/cm ² to 10 kg/cm ² .

[Emulsified Polymer Rubber Graft Copolymer (II-2)]

The emulsion-polymerized rubber graft copolymer (II-2) is a third component comprising 40% by weight to 90% by weight of a rubber emulsion (solid content) and 10% by weight to 60% by weight of a functional monomer component. Obtained by emulsion polymerization, wherein the functional monomer component comprises 50% by weight to 90% by weight of styrene monomer, 10% by weight to 50% by weight of nitrile vinyl monomer, and 0 weight % to 40% by weight of other copolymerizable vinyl monomers. In the emulsion polymerization reaction, an additive may be optionally added, and the additive includes, but is not limited to, an emulsifier, a polymerization initiator or a chain transfer agent, and the like. After the emulsion polymerization reaction, it can be selectively subjected to steps such as coagulation, dehydration, and drying.

The rubber emulsion is obtained by emulsion polymerization of the rubber component, or further subjected to hypertrophy treatment after the emulsion polymerization reaction, and optionally adding other copolymerizable monomers to the emulsion polymerization reaction. The rubber component is the rubber component of the above-mentioned bulk or solution-polymerized rubber graft copolymer (II-1). The other copolymerizable monomers include, but are not limited to, styrene, acrylonitrile, (meth) acrylate, and the like.

The hypertrophy treatment can be carried out by a general method of freezing fertilizer, additive hypertrophy or mechanical hypertrophy. The additives used in the additive hypertrophy method include, but are not limited to, (1) acidic substances: acetic anhydride, hydrogen chloride, sulfuric acid, etc.; (2) salt-based substances: sodium chloride, potassium chloride, calcium chloride, etc.; A polymer aggregating agent containing a carboxylic acid group: a (meth)acrylic acid-(meth)acrylate copolymer (such as a methacrylic acid-butyl acrylate copolymer, a methacrylic acid-ethyl acrylate copolymer) or the like.

For example, the method for producing a diene rubber emulsion can be polymerized by an emulsion polymerization method using a diene monomer (for example, butadiene), or 50% by weight to 100% by weight of a diene monomer and 0% by weight. The monomer such as styrene and/or acrylonitrile of 50% by weight is polymerized by an emulsion polymerization method to obtain a diene rubber emulsion having a weight average particle diameter of 0.05 μm to 0.6 μm. A small particle size diene rubber emulsion having a weight average particle diameter of 0.05 μm to 0.20 μm may be obtained by an emulsion polymerization method, and then subjected to a fertilizer treatment to increase the weight of the small particle size diene rubber emulsion. A large particle size diene rubber emulsion having an average particle diameter of 0.22 μm to 0.6 μm.

The styrene monomer, the nitrile vinyl monomer, the other copolymerizable vinyl monomer, the polymerization initiator, and the chain transfer agent in the functional monomer component are prepared as described above for the vinyl copolymer ( Styrene monomer (i-1), nitrile vinyl monomer (i-2), other copolymerizable vinyl monomer (i-3), polymerization initiator and chain transfer agent in I) The type, so no longer repeat them.

[Bromide-based flame retardant (B)]

The bromine-based flame retardant (B) may be used singly or in combination. Preferably, the bromine-based flame retardant (B) is selected from a bromine-based bisphenol compound and a derivative thereof, and a bromine-based alicyclic hydrocarbon compound. , bromine aromatic hydrocarbon compounds, brominated phenyl ether compounds, brominated trimeric isocyanate compounds, tetrabromophthalic anhydride, brominated polycarbonate, brominated epoxy resin, poly(pentabromobenzyl carbonate) Ester), ethyl bis(tetrabromoimine), or a combination thereof.

The bromine bisphenol compounds and derivatives thereof include, but are not limited to, tetrabromobisphenol A (TBBA), tetrabromo bisphenol S, tetrabromobisphenol F, tetrabromobisphenol Tetrabromobisphenol A bis (dibromopropyl ether), tetrabromobisphenol S bis(2,3-dibromopropyl) ether (octabromobisphenol S, TBSBPE for short), tetrabromo Bisphenol F bis(2,3-dibromopropyl)ether, tetrabromobisphenol A bis(2,3-dibromoisobutyl)ether, tetrabromobisphenol S bis(2,3-dibromopyridinium) Ether, tetrabromobisphenol F bis(2,3-dibromoisobutyl)ether, 2,2',6,6'-Tetrabromobisphenol A diallyl ether, Tetrabromobisphenol S diallyl ether, tetrabromobisphenol F diallyl ether, tetrabromobisphenol A dimethallyl ether, tetrabromobisphenol S dimethallyl ether, tetrabromo Bisphenol F dimethallyl ether and the like.

The bromoalicyclic hydrocarbon compound includes, but is not limited to, hexabromocyclododecane, tetrabromocyclooctane, monochloropentabromocyclohexane, and the like.

The bromine-based aromatic hydrocarbon compound includes, but is not limited to, pentabromotoluene, hexabromotoluene, pentabromophenyl ethane, brominated polystyrene (BPS). , octabromodimethyl indane, etc.

The bromine phenyl ether compound includes, but is not limited to, decabromodiphenyl ether, octabromodiphenyl ether (hereinafter referred to as OBDPE), hexabromobiphenyl ether, 1,2-bis(2,4,6-tribromophenoxy)ethane [1,2-bis(2,4,6-tribromophenoxy)ethane], 1,2-bis(pentabromophenoxy) Ethane [1,2-bis (pentabromophenoxy) ethane, abbreviated as BPBPE], poly(oxidized 2,6-dibrominated phenyl) and the like.

The bromine trimeric isocyanate compound includes, but is not limited to, tris(2,3-dibromopropyl) 1,3,5-isocyanate [tris(2,3-dibromoisopropyl)-1,3,5 -isocyanurate], tris(2,3-dibromoisobutyl) 1,3,5-isobromoisobutyl-1,3,5-isocyanurate) and the like.

[锑-containing oxide (C)]

The cerium-containing oxide (C) may be used singly or in combination. Preferably, the cerium-containing oxide (C) is selected from antimony trioxide, antimony trioxide (hereinafter referred to as Sb ₂ O ₃ ), Bismuth tetraoxide, antimony pentoxide, or a combination of these.

Preferably, the weight ratio of the bromine content in the bromine-based flame retardant to the cerium content in the cerium-containing oxide (C) is from 1 to 10.

In the flame retardant styrene resin composition of the present invention, various additives such as an antioxidant, a lubricant, an ultraviolet absorber, a UV stabilizer, a charge preventive agent, a colorant, and a polymerizable flame retardant auxiliary may be added as necessary. Wait. The content of the additive is in the range of 6 parts by weight or less based on 100 parts by weight of the total of the flame retardant styrene resin composition.

The polymeric flame retardant auxiliary may be used singly or in combination, and the polymeric flame retardant auxiliary includes but is not limited to polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/all A fluoroalkyl vinyl ether copolymer, a tetrafluoroethylene/ethylene copolymer, a hexafluoropropylene/propylene copolymer, a polyvinylidene fluoride, a vinylidene fluoride/ethylene copolymer, or the like.

The flame retardant styrene resin composition of the present invention can be mixed with various polymers as necessary. The polymer may be used singly or in combination, and the polymer includes, but is not limited to, acrylonitrile-butadiene-α-methylstyrene resin, acrylonitrile-styrene-methyl methacrylate resin, acrylonitrile-styrene -nitro-phenylmaleimide resin, styrene-anhydrous maleic acid resin, styrene-nitrogen-phenyl maleimide resin, polymethyl methacrylate, polycarbonate resin, styrene - Methacrylic resin, methacrylic acid-butadiene-styrene resin, acrylonitrile-butadiene-nitrogen-phenylmaleimide-styrene resin, polyamide resin, polyester resin, polyphenylene ether Resin, acrylonitrile-acrylate rubber-styrene resin, acrylonitrile-(ethylene-propylene diene rubber)-styrene resin, acrylonitrile-ruthenium-styrene resin, and other resins. The content of the polymer is 80 parts by weight or less based on 100 parts by weight of the total of the flame retardant styrene resin composition.

The flame retardant styrene resin composition can be prepared by a general mixing method, and the rubber modified styrene resin (A), the bromine-based flame retardant (B), and the cerium-containing oxide (C) are placed in a stirring manner. The mixture is stirred and uniformly mixed, and if necessary, an additive or a polymer may be added to obtain a flame-retardant styrene-based resin composition of the present invention.

The molded article of the flame-retardant styrene-based resin composition of the present invention is obtained by subjecting a flame-retardant styrene-based resin composition as described above to a kneading process.

The kneading processing and molding process can be carried out in a conventional manner, and therefore will not be described again.

The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.

<Example> [Synthesis Example 1] Suspension polymerization of ethylene-based copolymer (I-1)

70% by weight of styrene monomer, 30% by weight of nitrileated vinyl monomer, and the amount of 2,2'-azo-bis-isobutyronitrile used is 40% by weight based on 100 parts by weight of all monomers. Ppm, and the amount of the third-dodecyl mercaptan used was 15 ppm mixed uniformly to form the first component.

100 parts by weight of 10 ppm of polyvinyl alcohol, 100 ppm of sodium sulfate, and 1.5 times of ion-exchanged water were uniformly mixed with respect to 100 parts by weight of all monomers to form a second component. The first component and the second component were poured into a 50 liter reactor equipped with a stirrer and stirred for 15 minutes. The temperature in the reactor was raised to 70 ° C, and the reaction was taken for 4 hours, and the copolymer was separated, washed, and dried. The final polymerization rate was 95%, and a suspension-polymerized ethylene-based copolymer (I-1) having a weight average molecular weight of 250,000 was obtained.

[Synthesis Example 2] Thermally polymerized ethylene-based copolymer (I-2)

60 wt% of styrene and 40 wt% of acrylonitrile were placed at a rate of 12 kg/hr in a fully mixed reactor equipped with a stirrer maintained at 150 ° C and a capacity of 45 liters. And reacting, further adding ethylene distearylamine and tert-dodecyl mercaptan to the reaction at a rate of 3.0 g / hr, after the reaction, a reaction liquid having a solid content of 55% can be obtained, After the volatile matter was removed by a devolatilization apparatus, a pellet of the thermally polymerizable ethylene-based copolymer (I-2) having an acrylonitrile content of 28% by weight was obtained.

While obtaining the particles of the thermally polymerizable ethylene-based copolymer (I-2), the removed volatile components can be condensed by a condenser as a recovery liquid, and continuously added to the reaction for use.

[Synthesis Example 3] Catalyst polymerization of ethylene-based copolymer (I-3)

Mixing 68% by weight of styrene and 32% by weight of acrylonitrile at a rate of 12 kg/hr at a temperature of 130 ° C and a capacity of 45 liters in a fully mixed reactor with a stirrer for mixing And reacting, further adding ethylene distearylamine, 2,2'-azo-bis-isobutyronitrile and third-dodecyl mercaptan to the reaction at a rate of 3.0 g / hr, after the reaction A reaction liquid having a solid content of 55% was obtained, and the volatile liquid was removed by a devolatilization apparatus to obtain a catalyst-polymerized ethylene-based copolymer (I-3) having an acrylonitrile content of 28% by weight.

While obtaining the catalyst-polymerized ethylene-based copolymer (I-3), the removed volatile component can be condensed by a condenser as a recovery liquid, and continuously added to the reaction for reuse.

[Synthesis Example 4] Bulk or solution polymerization rubber graft copolymer (II-1)

103.2 parts by weight of styrene, 15 parts by weight of styrene/butadiene rubber (styrene/butadiene content = 25% by weight / 75% by weight, Mw = 130,000), 45.4 parts by weight of ethylbenzene, 31.4 Parts by weight of acrylonitrile, 3.9 parts by weight of butyl acrylate, 0.08 parts by weight of n-dodecyl mercaptan, 0.063 parts by weight of 3,5-bis(1,1-dimethylethyl)-4- Octadecyl hydroxyphenylpropionate and 0.063 parts by weight of ethylenedistearylamine were mixed to form a mixture.

100 parts by weight of styrene, 3.0 parts by weight of 1,1-bis-tert-butylperoxycyclohexane, and 1.8 parts by weight of diphenylguanidinium peroxide were used to form a polymerization initiator solution.

The above mixture was pumped at a flow rate of 61 kg/hour, and the above polymerization initiator solution was continuously supplied to the first reactor at a flow rate of 1.3 kg/hour to carry out a reaction, and the polymer solution after the reaction was further reacted. The reaction proceeds to the second reactor, the third reactor, and the fourth reactor. The first, second, third, and fourth reactors are sequentially connected in series, and the reactors are all columnar flow reactors having a capacity of 100 liters. The first reactor reaction temperature is 75 ° C ~ 90 ° C, stirring at 110 rpm, the second reactor reaction temperature is 95 ~ 105 ° C, stirring at 80 rpm, the third reactor reaction temperature 110 ~ 125 ° C, at 60 rpm Stirring, the fourth reactor reaction temperature was 135-150 ° C, and the mixture was stirred at a rotation speed of 5 rpm, and finally the polymer solid content was 62.5%. After the reaction is completed, the unreacted monomer and solvent are removed by a devolatilization device for recycling, and then the strip is extruded through a die, and then cooled or pelletized to obtain a block or solution polymerized rubber graft copolymer. (II-1).

[Synthesis Example 5] Emulsion Polymerized Rubber Graft Copolymer (II-2)

95.0 parts by weight of 1,3-butadiene, 5.0 parts by weight of acrylonitrile, 15.0 parts by weight of potassium persulfate solution, 3.0 parts by weight of sodium pyrophosphate, 1.5 parts by weight of potassium oleate, and 140.0 parts by weight of distilled water And 0.2 part by weight of the third-dodecyl mercaptan was reacted at a reaction temperature of 65 ° C for 12 hours to obtain a rubber emulsion having a conversion of 94%, a solid content of about 40% and a weight average particle diameter of 0.1 μm.

85.0 parts by weight of ethyl acrylate, 15.0 parts by weight of acrylic acid, 0.3 parts by weight of thirteen-dodecyl mercaptan, 2.0 parts by weight of potassium oleate, 1.0 part by weight of sodium dioctylsulfosuccinate, 0.4 The parts by weight of isopropylbenzene hydrogen peroxide, 0.3 parts by weight of sodium formaldehyde sulfoxylate and 200.0 parts by weight of distilled water are reacted at a reaction temperature of 75 ° C for 5 hours to obtain a conversion of 95% and a pH of 6.0. A polymer aggregating agent containing a carboxylic acid group.

Next, 3 parts by weight of the above-mentioned carboxylic acid group-containing polymer flocculant (dry weight) is used to ferment 100 parts by weight of the above rubber emulsion (dry weight), and the obtained enlarged rubber emulsion has a pH of 8.5 and an average weight of particles. The diameter is 0.30 μm. Thereafter, 100.0 parts by weight of the above-mentioned enlarged rubber emulsion (dry weight), 25.0 parts by weight of styrene, 8.3 parts by weight of acrylonitrile, 1.2 parts by weight of potassium oleate, and 0.2 parts by weight of a third-dodecyl group Mercaptan, 0.5 parts by weight of cumene hydroperoxide, 3.0 parts by weight of ferrous sulfate solution (concentration: 0.2 wt%), 3.0 parts by weight of sodium formaldehyde sulfoxylate solution (concentration: 10 wt%), 20.0 parts by weight Ethylenediamine tetraacetic acid solution (concentration: 0.25 wt%) and 200.0 parts by weight of distilled water are mixed and reacted, wherein the styrene and acrylonitrile are added to the reaction system for polymerization within 5 hours by continuous addition, followed by chlorine After the calcium (CaCl ₂ ) is coagulated, dehydrated, and then dried to a moisture content of 2% or less, the emulsion polymerized rubber graft copolymer (II-2) required by the present invention can be obtained, and the rubber component content is 75. The weight %, and the weight average particle diameter of the rubber particles was 0.31 μm.

[Preparation Example 1] Rubber-modified styrene resin (A-1)

88% by weight of the block or solution polymerized rubber graft copolymer (II-1) of the above Synthesis Example 4 was kneaded with 12% by weight of the emulsion polymerized rubber graft copolymer (II-2) of the above Synthesis Example 5, that is, A rubber-modified styrene resin (A-1) can be obtained.

[Preparation Example 2] Rubber-modified styrene resin (A-2)

76% by weight of the thermally polymerizable ethylene-based copolymer (I-2) of the above Synthesis Example 2 and 24% by weight of the emulsion-polymerized rubber graft copolymer (II-2) of the above Synthesis Example 5 were kneaded to obtain a rubber modification. A styrene resin (A-2).

[Preparation Example 3] Rubber-modified styrene resin (A-3)

76% by weight of the catalyst-polymerizable ethylene-based copolymer (I-3) of the above Synthesis Example 3 and 24% by weight of the emulsion-polymerized rubber graft copolymer (II-2) of the above Synthesis Example 5 were kneaded to obtain a rubber. The styrene resin (A-3) was modified.

[Preparation Example 4] Rubber-modified styrene resin (A-4)

76% by weight of the suspension-polymerized ethylene-based copolymer (I-1) of the above Synthesis Example 1 and 24% by weight of the emulsion-polymerized rubber graft copolymer (II-2) of the above Synthesis Example 5 were kneaded to obtain a rubber modification. A styrene resin (A-4).

The amounts of the ethylene-based copolymer (I) and the rubber-graft copolymer (II) used in the above Preparation Examples 1 to 4 were summarized in Table 1 below.

[Examples 1 to 7 and Comparative Examples 1 to 7] Flame-retardant styrene-based resin composition and molded article thereof

The rubber-modified styrene resin (A), the bromine-based flame retardant (B), and the cerium-containing oxide (C) are dry-mixed in the ratios of Tables 2 and 3 to obtain flame-retardant styrene. The resin composition was mixed and granulated by an extruder, and then a molded article of a flame-retardant styrene-based resin composition was obtained. The analysis and physical property evaluation results are shown in Table 2 and Table 3.

【Test items】 1. Impact strength evaluation (Izod) measurement:

The flame retardant styrene resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7 were injected, and standard test pieces were prepared in accordance with the standard method of ASTM D-256, and then tested in accordance with ASTM D-256 ( Unit: Kg-cm/cm).

2. Odour determination:

According to the standard method of Q/JLY J711061-2009, 11 g of the flame retardant styrene resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7 were placed in a serum bottle and allowed to stand at room temperature for 24 hours. The odor level is determined by an expert odor tester.

Odor index 1 means odorless;

Odor index 2 to 3 indicates a weak feeling of odor;

The odor index 4 indicates a stinky smell;

Odor index 5 to 6 indicates a strong feeling of odor;

The odor index 7 indicates a very strong smell.

3. Determination of the content of dimers and trimers in the flame retardant styrenic resin composition:

One gram of each of the flame retardant styrene resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7 was dissolved in acetone, and then methanol was added to cause aggregation of the high molecular weight polymer, and the supernatant liquid was taken and Hewlett Packard was used. A gas chromatograph with a flame ion detector attached to company number 5890A for quantitative analysis.

4. Flame retardant time-testing:

The molded articles of the flame retardant styrene resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7 were prepared into test pieces according to UL standard specifications, and placed at 60 ° C for 10 days, 20 days, and 30 days, respectively. Perform a burn test.

From the results of Table 2, the flame retardant styrene resin compositions of Examples 1 to 4 and Examples 5 to 7 were obtained by using a styrene monomer and a nitrile vinyl monomer. The total content of the triads is 3,909 ppm to 3,958 ppm and 471 ppm to 495 ppm, respectively. When the molded article formed by the compositions is stored for a long period of time, the halogen flame retardant does not precipitate on the surface of the molded article due to the presence of the dimeric or triamed body, and the burning property of the molded article is deteriorated. Further, the molded article has a better flame retardancy (grade: V0); and the flame retardant styrene resin composition does not cause a foul smell during the subsequent high-temperature processing of the molded article.

As is clear from the results of Table 3, the flame retardant styrene resin compositions of Comparative Examples 1 to 4, the total content of the dimeric or trimeric bodies derived from the styrene monomer and the nitrile vinyl monomer. It is 5,469 ppm to 9,484 ppm. When the molded article formed by the composition is stored for a long period of time, the halogen flame retardant is precipitated on the surface of the molded article due to the presence of a high content of a dimeric or trimeric body, and the burning property of the molded article is deteriorated. Further, the molded article does not have a preferable flame retardancy withstandability; in addition, the flame retardant styrene resin composition generates a malodorous taste during the subsequent high-temperature processing of the molded article.

In the flame retardant styrene resin compositions of Comparative Examples 5 to 6, the content of the dimeric or trimeric bodies contained therein was 5,871 ppm and 9,957 ppm, respectively, and the phosphorus-containing flame retardant was used to make the composition. The formed molded article has poor flame retardancy (grade: HB) when stored for a long period of time, and the flame retardant styrene resin composition generates a malodorous taste during subsequent high-temperature processing.

In the flame retardant styrene resin composition of Comparative Example 7, although the content of the dimer or triad is 4,173 ppm, the use of the phosphorus-containing flame retardant may cause the storage under a long period of time. The molded article formed by the composition has poor flame retardancy (grade: V2).

In summary, the content of the dimeric or trimeric body derived from the styrene monomer and the nitrile vinyl monomer in the flame retardant styrene resin composition is 5,000 ppm or less, so that When the molded article formed by the composition is stored for a long period of time, the halogen-containing flame retardant is not deposited on the surface of the molded article due to the presence of the dimeric or triamed body, which in turn causes the burning property of the molded article. The deterioration causes the molded article to have no better flame retardancy; and the flame retardant styrene resin composition does not produce a foul smell during the subsequent high-temperature processing, so that the present invention can be achieved. The purpose.

The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.

Claims (13)

A flame retardant styrene resin composition comprising: 100 parts by weight of a rubber-modified styrene resin (A); 4 parts by weight to 40 parts by weight of a bromine-based flame retardant (B); and 1 part by weight to 10 parts by weight a cerium-containing oxide (C); wherein the rubber-modified styrene resin (A) is a continuous phase formed by a copolymer of 50% by weight to 90% by weight and a rubber particle of 10% by weight to 50% by weight a dispersed phase formed; the copolymer comprises 50% by weight to 90% by weight of styrene monomer units and 10% by weight to 50% by weight of a nitrile vinyl monomer unit; the rubber particles have non-occluding The styrene-based monomer and the nitrile-based vinyl monomer in the flame-retardant styrene-based resin composition are all contained in the dimer or tri-dimer, and constitute the flame-retardant styrene resin composition. 100 parts by weight or less of 2,000 ppm or less. The flame retardant styrene resin composition according to the first aspect of the invention, wherein the styrene monomer and the nitrile vinyl monomer in the flame retardant styrene resin composition are derived from The total content of the volume or the triad is 1,500 ppm or less based on 100 parts by weight of the flame retardant styrene resin composition. The flame-retardant styrene-based resin composition according to the first aspect of the invention, wherein the rubber-modified styrene-based resin (A) is composed of 10% by weight to 50% by weight of a rubber graft copolymer and 50 The weight % to 90% by weight of the ethylene-based copolymer is obtained by kneading. The flame retardant styrene resin group according to item 3 of the patent application scope The product wherein the ethylene-based copolymer is a suspension-polymerized ethylene-based copolymer. The flame-retardant styrene-based resin composition according to claim 3, wherein the rubber-graft copolymer is an emulsion-polymerized rubber graft copolymer. A flame retardant styrene resin composition comprising: 100 parts by weight of a rubber-modified styrene resin (A); 4 parts by weight to 40 parts by weight of a bromine-based flame retardant (B); and 1 part by weight to 10 parts by weight a cerium-containing oxide (C); wherein the rubber-modified styrene resin (A) is a continuous phase formed by a copolymer of 50% by weight to 90% by weight and a rubber particle of 10% by weight to 50% by weight a dispersed phase formed; the copolymer comprises 50% by weight to 90% by weight of styrene monomer units and 10% by weight to 50% by weight of a nitrile vinyl monomer unit; the rubber particles have non-occluding Structure and occlusion structure; the total content of the styrene monomer and the nitrile vinyl monomer derived from the flame retardant styrene resin composition is the flammable styrene The resin composition is 2,001 ppm to 5,000 ppm in 100 parts by weight. The flame retardant styrene resin composition according to the sixth aspect of the invention, wherein the styrene monomer and the nitrile vinyl monomer in the flame retardant styrene resin composition are derived from The total content of the volume or the triad is 3,000 ppm to 4,500 ppm per 100 parts by weight of the flame retardant styrene resin composition. The flame retardant styrene resin group according to item 6 of the patent application scope The rubber modified styrene resin (A) is obtained by kneading a rubber graft copolymer, and the rubber graft copolymer comprises 2% by weight to 50% by weight of emulsion polymerization. A rubber graft copolymer and a 50% to 98% by weight of a bulk or solution polymerized rubber graft copolymer. The flame retardant styrene resin composition according to the first or sixth aspect of the patent application includes: 100 parts by weight of a rubber-modified styrene resin (A); and 10 parts by weight to 30 parts by weight of a bromine-based flame retardant The agent (B); and 2 parts by weight to 8 parts by weight of the cerium-containing oxide (C). The flame retardant styrene resin composition according to the first or sixth aspect of the invention, wherein the rubber modified styrene resin (A) is 100 parts by weight based on the total amount of the rubber modified The content of the rubber component in the styrene-based resin (A) is in the range of 5 parts by weight to 40 parts by weight. The flame retardant styrene resin composition according to the first or sixth aspect of the invention, wherein the bromine-based flame retardant (B) is selected from the group consisting of a bromine bisphenol compound and a derivative thereof, a bromine alicyclic hydrocarbon compound, a bromine aromatic hydrocarbon compound, a bromine phenyl ether compound, a bromine trimeric isocyanate compound, a tetrabromophthalic anhydride, a brominated polycarbonate, a brominated epoxy resin, Poly(pentabromobenzyl carbonate), ethyl bis(tetrabromoimide), or a combination thereof. The flame retardant styrene resin composition according to the first or sixth aspect of the invention, wherein the cerium-containing oxide (C) is selected from the group consisting of antimony trioxide, antimony trioxide, and antimony tetraoxide. , bismuth pentoxide, or a combination of these. A molded article of a flame-retardant styrene-based resin composition obtained by subjecting a flame-retardant styrene-based resin composition as described in claim 1 or 6 to a kneading process.