KR20180075095A - Thermoplastic flame retardant resin composition, method for preparing the resin composition and molding product comprising the resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic flame retardant resin composition, a manufacturing method thereof, and an injection molded product comprising the same. More specifically, the present invention provides a thermoplastic flame retardant resin composition with high quality, comprising a brominated epoxy resin in a specific content to impart flame retardancy to the thermoplastic resin composition, wherein the brominated epoxy resin has a structure in which hydroxyl groups (-OH) are substituted with an oxazolidone group or a urethane group, thereby having excellent flame retardancy, improving compatibility with the composition, mechanical strength such as impact strength, heat resistance such as a thermal deformation temperature or the like, and reducing a phenomenon in which a composition is carbonized during long time thermoforming.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic flame retardant resin composition, a method for producing the same, and an injection molded article comprising the thermoplastic flame retardant resin composition. BACKGROUND ART [0002]

The present invention relates to a thermoplastic flame retardant resin composition, a process for producing the same, and an injection-molded article containing the same, and more particularly, to a novel thermoplastic flame retardant resin composition containing a hydroxyl group (-OH) contained in a brominated epoxy resin substituted with an oxazolyl group or a urethane group Is a thermoplastic flame retardant resin composition containing a brominated epoxy resin as a flame retardant. The flame retardant composition of the present invention is excellent in flame retardancy, but also has improved heat resistance such as compatibility between compositions, mechanical properties such as impact strength and heat distortion temperature, To a thermoplastic flame retardant resin composition capable of providing a high-quality flame retardant resin composition with reduced carbonization, a method for producing the same, and an injection molded article containing the same.

ABS-based resin and the like are excellent in physical properties such as mechanical strength, moldability and heat resistance and are used in various fields. However, since they are weak in flame retardancy, they are required to have flame retardancy and weatherability Is required.

Usually, a flame retardant styrene resin composition is prepared by mixing a flame retardant and a flame retardant auxiliary to give flame retardancy to a styrenic copolymer, and mainly a halogen-based flame retardant and an antimony-containing inorganic flame retardant auxiliary are added. The halogen-based flame retardant has an advantage of excellent flame retardancy and does not significantly deteriorate the inherent properties of the styrene-based resin. However, the halogen-based flame retardant has a problem of discoloring due to heat or light or generating toxic gas such as hydrogen chloride.

In order to solve such a problem, a method using a brominated epoxy oligomer (BEO) as an example of a halogenated epoxy resin having an increased molecular weight by using an epoxy has been proposed. This method has an excellent flame retardant property of halogen, Has been improved to greatly reduce the generation of toxic gas during thermoforming and to improve the weather resistance, and thus it has been widely used.

However, since the terminal epoxy group and the hydroxy group present in the above-mentioned brominated epoxy oligomer structure are strong in adhesion to metals, there is a problem that they are carbonized when they stay in the molding machine for a long time during processing using an injection molding machine or the like. do.

However, full-capping BEO, in which half-capping BEO or end epoxy groups are completely encapsulated, in which part of the epoxy groups at the end of the brominated epoxy oligomer is encapsulated, has been proposed. However, this method has a problem of significantly reducing the weatherability of the brominated epoxy oligomer .

Therefore, there is a need to develop a technology capable of reducing the degree of carbonization during injection residence without significantly deteriorating the weatherability inherent to the brominated epoxy oligomer, even though the flame retardancy is excellent.

Korean Patent No. 10-0372804

In order to solve the problems of the prior art as described above, the present invention can improve the heat resistance such as compatibility of the compositions, mechanical properties such as impact strength, heat distortion temperature, etc., The present invention also provides a thermoplastic flame retardant resin composition which is improved in carbonization and a method for producing the same.

It is another object of the present invention to provide an injection molded product which is excellent in flame retardancy and which has improved flame retardancy and physical properties such as mechanical strength and heat resistance and which is improved in carbonization during a long time thermoforming, .

These and other objects of the present invention can be achieved by the present invention described below.

In order to attain the above object, the present invention provides a rubber composition comprising 100 parts by weight of a base resin comprising a rubber polymer-aromatic vinyl compound-vinyl cyan compound copolymer and an aromatic vinyl compound-vinyl cyan compound copolymer and 10 to 30 parts by weight of a brominated epoxy resin Wherein the brominated epoxy resin comprises a brominated epoxy resin containing an oxazolidin group or a urethane group.

The present invention also provides a rubber composition comprising 100 parts by weight of a base resin comprising 20 to 50% by weight of a rubber polymer-aromatic vinyl compound-vinyl cyanide copolymer and 50 to 80% by weight of an aromatic vinyl compound-vinyl cyanide copolymer; And 10 to 30 parts by weight of a brominated epoxy resin containing an oxazolidinone group or a urethane group, and extruding the kneaded mixture.

The present invention also provides an injection molded article produced by injecting the thermoplastic flame retardant resin composition.

According to the present invention, it is possible to improve not only flame retardancy, but also heat resistance, such as compatibility between compositions, mechanical strength such as impact strength, heat resistance, and heat distortion temperature, as well as the use of a brominated epoxy resin having reduced affinity with metals as a flame retardant It is possible to effectively improve the phenomenon of carbonization of the composition at the time of long-term injection retention, thereby providing a high-quality molded article of flame retardant resin with high productivity.

The present inventors have found that when a flame retardant resin composition is prepared by using a novel brominated epoxy oligomer prepared by substituting a hydroxy group contained in an existing brominated epoxy oligomer (BEO) with an oxazolididone group or a urethane group as a flame retardant agent, And the heat resistance such as heat distortion temperature are improved and the phenomenon of carbonization of the resin composition during the injection residence for a long time is effectively reduced, and the present invention has been completed on the basis thereof.

The thermoplastic flame retardant resin composition of the present invention comprises 100 parts by weight of a base resin comprising a rubber polymer-aromatic vinyl compound-vinyl cyan compound copolymer and an aromatic vinyl compound-vinyl cyan compound copolymer and 10 to 30 parts by weight of a brominated epoxy resin , And the brominated epoxy resin may include an oxazolidinone group or a brominated epoxy resin containing a urethane group.

Hereinafter, the thermoplastic flame retardant resin composition of the present invention will be described in detail for each component.

A) Base resin

The base resin of the present invention comprises A1) a rubber polymer-aromatic vinyl compound-vinyl cyanide copolymer and A2) an aromatic vinyl compound-vinyl cyan compound.

For example, the base resin may include 20 to 50% by weight of a rubber polymer-aromatic vinyl compound-vinyl cyanide copolymer and 50 to 80% by weight of an aromatic vinyl compound-vinyl cyanide copolymer. In this case, Is excellent in mechanical properties and easy in processing and molding.

In another example, the base resin may include 30 to 50% by weight of the rubber polymer-aromatic vinyl compound-vinyl cyanide copolymer and 50 to 70% by weight of the aromatic vinyl compound-vinyl cyan compound, and within this range, , Processability, and the like.

As another example, the base resin may include 35 to 45% by weight of the rubber polymer-aromatic vinyl compound-vinyl cyan compound copolymer and 55 to 65% by weight of the aromatic vinyl compound-vinyl cyan compound, Excellent impact strength and excellent workability.

A1) Rubber polymer - aromatic vinyl compound - vinyl cyan compound copolymer

The rubber polymer-aromatic vinyl compound-vinyl cyan compound copolymer is not particularly limited in the case of a thermoplastic styrene type resin commonly used in the technical field of the present invention, and preferably an aromatic vinyl compound and a vinyl cyan compound May be copolymerized.

Specific examples of the rubber polymer-aromatic vinyl compound-vinyl cyan compound copolymer include an acrylic rubber polymer-aromatic vinyl compound-vinyl cyan compound copolymer (hereinafter referred to as 'ASA copolymer') and a diene rubber polymer- -Vinyl cyanide copolymer (hereinafter referred to as " ABS-based copolymer ").

In addition, the rubber polymer-aromatic vinyl compound-vinyl cyanide copolymer may include at least one kind of ASA-based copolymer, at least one kind of ABS-based copolymer, or all of them.

In the present invention, the ASA-based copolymer means a copolymer in which an aromatic vinyl compound and a vinyl cyanide compound are graft-polymerized to an acrylic rubber polymer. For example, the ASA-based copolymer contains 10 to 60% by weight of an acrylic rubber polymer, 30 to 65% by weight, and 10 to 40% by weight of a vinyl cyan compound may be used. In this range, excellent physical properties such as heat resistance, mechanical strength, workability and weather resistance can be obtained.

As another example, the ASA-based copolymer may be prepared by graft polymerization comprising 30 to 60% by weight of an acrylic rubber polymer, 30 to 55% by weight of an aromatic vinyl compound and 10 to 30% by weight of a vinyl cyanide compound, Within this range, properties such as heat resistance, fluidity and mechanical strength can be satisfied at the same time.

As another example, the ASA-based copolymer may be prepared by graft polymerization including 45 to 55% by weight of an acrylic rubber polymer, 30 to 40% by weight of an aromatic vinyl compound and 10 to 20% by weight of a vinyl cyanide compound In this case, the resin composition has excellent physical properties such as heat resistance, fluidity and mechanical strength.

Wherein the acrylic rubber polymer is a rubber polymer prepared by incorporating at least one acrylic compound selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate , And preferably includes butyl acrylate.

The acrylic rubber polymer formed by the polymerization of the acrylic compound may preferably have an average particle diameter of 0.1 to 2 탆, 0.5 to 2 탆, or 0.5 to 1.4 탆, and the mechanical strength such as impact resistance There is an advantage in that it has excellent appearance characteristics such as glossiness and coloring property.

In the present description, the average particle diameter can be measured by a dynamic light skating method using a Nicomp 380 instrument.

In the present invention, the aromatic vinyl compound may be at least one selected from styrene, alpha-methylstyrene, alpha-ethylstyrene, para-methylstyrene, vinyltoluene and the like, .

In the present description, the vinyl cyan compound may be at least one kind selected from acrylonitrile, methacrylonitrile, and ethacrylonitrile, and preferably includes acrylonitrile, unless otherwise specified.

As a specific example, the ASA-based copolymer may be but is not limited to butyl acrylate rubber-styrene-acrylonitrile copolymer.

In the present description, the ABS-based copolymer means a copolymer in which an aromatic vinyl compound and a vinyl cyan compound are graft-polymerized to a diene-based rubber polymer.

For example, the ABS copolymer may be prepared by graft polymerization comprising 50 to 80 wt% of a diene rubber polymer, 5 to 30 wt% of an aromatic vinyl compound, and 10 to 40 wt% of a vinyl cyan compound, In this case, mechanical strength such as impact strength, heat resistance, workability and the like are excellent.

In another example, the ABS-based copolymer may be prepared by graft polymerization comprising 50 to 70 wt% of a diene rubber polymer, 5 to 20 wt% of an aromatic vinyl compound, and 20 to 40 wt% of a vinyl cyan compound , There is an advantage in that the physical properties such as fluidity, heat resistance and mechanical strength are excellent within the above-mentioned range.

As another example, the ABS-based copolymer may be prepared by graft polymerization comprising 55 to 65% by weight of a diene rubber polymer, 5 to 15% by weight of an aromatic vinyl compound and 25 to 35% by weight of a vinyl cyan compound And has an excellent mechanical strength within this range, and an excellent balance of physical properties such as fluidity, flexibility and heat resistance.

The diene rubber polymer may be at least one selected from a butadiene polymer, a butadiene-styrene copolymer, a butadiene-acrylonitrile copolymer, and an ethylene-propylene copolymer. Preferably a butadiene polymer.

The diene rubber polymer may preferably have an average particle diameter of 0.1 to 0.7 mu m, 0.2 to 0.5 mu m, or 0.2 to 0.4 mu m, for example. Within this range, it is preferable that the diene rubber polymer has excellent mechanical strength such as impact resistance, And appearance characteristics such as coloring property are excellent.

The aromatic vinyl compound and the vinyl cyan compound contained in the ABS-based copolymer may be the same compounds as those contained in the ASA-based copolymer.

For example, the ABS-based copolymer may include butadiene rubber-styrene-acrylonitrile copolymer.

Further, the rubber polymer-aromatic vinyl compound-vinyl cyan compound copolymer may be a (meth) acrylic acid ester compound such as methyl methacrylate or ethyl methacrylate, or an aromatic vinyl compound or vinyl cyan compound, Maleimide compounds such as N-phenylmaleimide, maleic anhydride, and the like.

The rubber polymer-aromatic vinyl compound-vinyl cyanide copolymer may have a weight average molecular weight of, for example, 30,000 to 200,000 g / mol, and more preferably 50,000 to 150,000 g / mol. Within this range, the resin composition of the present invention has excellent heat resistance and excellent processability and moldability.

In the present description, the weight average molecular weight can be measured by gel permeation chromatography after the polymer is dissolved in an organic solvent such as THF and pretreated.

In the present invention, the rubber polymer-aromatic vinyl compound-vinyl cyanide copolymer can be produced by the emulsion graft polymerization method, and the emulsion polymerization method and the conditions which are conventionally employed in the graft copolymerization of the monomer compound to the rubber polymer And there is no particular limitation in the case where the selection is made by absolute selection.

A2) Aromatic vinyl compound-vinyl cyanide copolymer

The base resin of the present invention includes an aromatic vinyl compound-vinyl cyanide copolymer (hereinafter referred to as "SAN-based copolymer") as a matrix resin.

The SAN-based copolymer is not particularly limited when it is a SAN-based copolymer commonly used in the technical field of the present invention, and preferably includes 50 to 80% by weight of an aromatic vinyl compound and 20 to 50% by weight of a vinyl cyanide In this case, the resin composition is excellent in mechanical properties such as mechanical strength and heat resistance and excellent in processability and moldability.

The SAN-based copolymer may include, for example, 60 to 80% by weight of an aromatic vinyl compound and 20 to 40% by weight of a vinyl cyanide compound. Within this range, the SAN-based copolymer is excellent in physical properties such as mechanical strength, There is an advantage of this.

As another example, the SAN-based copolymer may include 70 to 80% by weight of an aromatic vinyl compound and 20 to 30% by weight of a vinyl cyanide compound. Within this range, the SAN-based copolymer may have an impact resistance such as impact strength, There is an advantage in that the heat resistance property is excellent and the processability is excellent.

The aromatic vinyl compound and the vinyl cyan compound may include the same compound as that contained in the ASA-based copolymer or the ABS-based copolymer.

The SAN-based copolymer may be produced by bulk polymerization, emulsion polymerization, or the like, but it may be preferable to use the one produced by bulk polymerization in view of production cost.

The SAN-based copolymer may preferably have a weight average molecular weight of 50,000 to 200,000 g / mol, 80,000 to 180,000 g / mol, or 100,000 to 150,000 g / mol, for example. And is excellent in fluidity and easy to process and form.

As a specific example, the SAN-based resin may be a styrene-acrylonitrile copolymer or an (alpha-methylstyrene) -acrylonitrile copolymer but is not limited thereto.

B) a brominated epoxy resin

The thermoplastic flame retardant resin composition of the present invention comprises a brominated epoxy resin as a flame retardant and the brominated epoxy resin may include at least one selected from an oxazolidin group or a brominated epoxy resin containing a urethane group , The flame retardancy of the resin composition is excellent, and the carbonization phenomenon at the time of injection molding is reduced.

In the present specification, the brominated epoxy resin containing an oxazolidinone group or a urethane group means a compound in which a part of the hydroxyl groups (-OH) contained in the brominated epoxy resin is substituted with an oxazolidinone group or a urethane group, and the affinity As the relatively strong hydroxyl groups are substituted with oxazolidinone groups or urethane groups, the phenomenon of carbonization of the composition is improved while the inherent weatherability of the brominated epoxy resin is not lowered during injection molding, and the physical properties such as mechanical strength, heat resistance, and productivity Can be improved.

The brominated epoxy resin may be contained in an amount of 10 to 30 parts by weight, and most preferably 20 to 30 parts by weight, based on 100 parts by weight of the base resin of the present invention. Within this range, there is an advantage that the flame retardant property is excellent, but the phenomenon of carbonization at the time of injection residence is effectively reduced, thereby improving physical properties such as mechanical strength and heat resistance of the final product.

The brominated epoxy resin may contain 30 to 100% by weight or 50 to 100% by weight (based on 100% by weight of a brominated epoxy resin) of at least one selected from the oxazolidinone group or urethane group-containing brominated epoxy resin, Within this range, the flame retardant properties of the final resin composition are excellent, the physical properties such as mechanical strength and heat resistance are maintained high, and the phenomenon of carbonization at the time of injection retention can be effectively reduced.

As a more preferred example, the brominated epoxy resin may contain the oxazolidin group-containing brominated epoxy resin alone; Or a brominated epoxy resin containing the urethane group alone; Or a mixture containing 40 to 60% by weight of the oxazolidin group-containing brominated epoxy resin and 40 to 60% by weight of the urethane group-containing brominated epoxy resin based on 100% by weight of the total of the brominated epoxy resin, The flame retardancy of the composition is excellent, and the physical properties such as mechanical strength and heat resistance property are maintained at a high level, thereby reducing the phenomenon of carbonization at the time of injection molding and improving the quality of the final molded article.

As a specific example, the brominated epoxy resin may include 10 to 15 parts by weight of the brominated epoxy resin containing the oxazolidinone group or the urethane group and 10 to 15 parts by weight of the oxazolidinone group or the brominated epoxy resin containing no urethane group In this case, the resin composition is excellent in flame retardancy and has the effect of reducing the phenomenon of carbonization at the time of injection residence.

In another example, the brominated epoxy resin may include 10 to 15 parts by weight of the brominated epoxy resin containing the oxazololidone group and 10 to 15 parts by weight of the brominated epoxy resin containing the urethane group. In this case, And the carbonization phenomenon at the time of injection residence is reduced, thereby providing a molded article of thermoplastic flame retardant resin of high quality.

As another example, the brominated epoxy resin may be 20 to 30 parts by weight of the oxazolidin group-containing brominated epoxy resin or 20 to 30 parts by weight of the urethane group-containing brominated epoxy resin. In this case, Thereby further reducing the carbonization phenomenon.

In the present invention, the brominated epoxy resin containing the oxazolidinone group or the urethane group is, for example, one in which the hydroxyl group (-OH) contained in the brominated epoxy resin represented by the following formula 2 is substituted with an oxazolyl group or a urethane group And the hydroxyl group having relatively high affinity with metals is substituted with an oxazolidin group or a urethane group, the weatherability of the brominated epoxy resin is not lowered at the time of injection molding, and the composition is carbonized to improve the mechanical strength, There is an effect that physical properties such as heat resistance and productivity are improved.

(2)

(Wherein n is an integer of 1 to 8, X is Br, and a and b are each independently an integer of 1 to 4.)

For example, the brominated epoxy resin containing the oxazolidinone group or the epoxy group may be a compound represented by the following general formula (1). In this case, the flame retardancy is excellent and the physical properties such as impact strength and heat resistance of the final product are improved, The phenomenon of carbonization of the composition during injection residence can be effectively reduced.

[Chemical Formula 1]

(Wherein Z is an oxazolyl group or a urethane group, n is an integer of 1 to 8, X is Br, and a and b are each independently an integer of 1 to 4.)

As a more specific example, the brominated epoxy resin containing the oxazolidinone group or the urethane group may be a compound represented by the following formula (1a) It is possible to improve the physical properties such as mechanical strength and heat resistance and productivity of the final product by improving the carbonization of the composition without deteriorating the weatherability inherent to the brominated epoxy resin at the time of injection residence.

[Formula 1a]

중에서 선택된다.)(Wherein, n is an integer of 1 to 8, X is Br, a and b are each independently an integer of 1 to 4, R1 is hydrogen or an alkyl group having 1 to 5 carbon atoms, R2 is a C1- R 3 is selected from alkylene or arylene having 1 to 10 carbon atoms, Y is a group derived from a brominated epoxy resin of the above formula (1a) or

.

In the case where Y in the formula (1a) is a brominated epoxy resin, for example, it may be represented by the following formula (B).

[Chemical Formula B]

(Wherein R, R ', R ₃ and n are the same as defined in the above formula (1a).)

The brominated epoxy resin containing the oxazolidone group may be prepared by reacting 2-oxazolidone with the brominated epoxy resin represented by the formula (2), but is not limited thereto.

The brominated epoxy resin containing the urethane group may be prepared by reacting phenyl isocyanate or hexamethylene diisocyanate with the brominated epoxy resin represented by the above formula (2), but is not limited thereto.

The brominated epoxy resin containing oxazolidinone group or urethane group may be one in which at least one epoxy terminal is capped with a compound containing bromine. In this case, the problem of lowering thermal stability due to epoxy group is improved, Physical properties, heat resistance, flame retardancy and the like are improved.

The compound containing bromine may be, for example, an aryl group substituted with at least one bromine atom, but is not limited thereto.

As a specific example, the brominated epoxy-based flame retardant encapsulated with a compound containing a bromine atom may be a half-capping epoxy resin in which some of the epoxy groups are encapsulated as shown in the following Chemical Formula 3.

(3)

(Wherein R, R ', Z and n are the same as defined above, and f is an integer of 1 to 5.)

As another example, the brominated epoxy resin sealed at the terminal with a compound containing bromine may be a full-capping type brominated epoxy resin in which epoxy groups at both ends are encapsulated as shown in the following chemical formula (4).

[Chemical Formula 4]

(Wherein R, R ', Z and n are the same as defined above, and d and e are independently an integer of 1 to 5.)

The brominated epoxy resin containing the oxazolidinone group or urethane group of the present invention may contain 3 to 20% by weight, preferably 3 to 15% by weight, of oxazolidinone group or urethane group, for example, Preferably 3 to 10% by weight. Within this range, there is an effect of improving the physical properties such as mechanical strength and heat resistance by effectively reducing the phenomenon of carbonization at the time of injection residence, while being excellent in flame retardance and thermal stability of the final product.

In addition, the brominated epoxy resin of the present invention may preferably have a bromine content of 45 to 70% by weight, more preferably 50 to 60% by weight. Within this range, there is an effect that the weather resistance inherent to the brominated epoxy resin is not largely lowered but the thermal stability and the flame retardancy are excellent.

The brominated epoxy resin of the present invention may preferably have an epoxy equivalent of 150 to 800 g / eq or 200 to 450 g / eq. In this case, the thermal stability of the flame retardant is improved, and the weather resistance of the final product is excellent .

In the present specification, the epoxy equivalent means a value obtained by dividing the weight average molecular weight of the epoxy resin by the number of epoxy groups per molecule.

The number of epoxy groups in the present description can be determined by end-of-term analysis.

The brominated epoxy resin of the present invention may preferably have a weight average molecular weight of 1,000 to 15,000 g / mol or 1,000 to 10,000 g / mol, and within this range, excellent properties such as workability and flame retardancy are exhibited.

C) Additive

The thermoplastic flame retardant resin composition of the present invention may optionally contain additives as required. The additives are not particularly limited as long as they are commonly used in the art to which the present invention belongs, and can be appropriately selected and used.

The additive may be at least one selected from the group consisting of a flame retarder, a lubricant, an antioxidant, a heat stabilizer, a light stabilizer, an antistatic agent, an antistatic agent and a colorant, Or 1 to 10 parts by weight. Within the above-mentioned range, the effect of the additive can be exhibited without deteriorating the physical properties, the moldability, and the appearance quality of the final product.

The flame retarding auxiliary may be, for example, an antimony-based inorganic material such as antimony trioxide and antimony pentoxide, which can synergize with the brominated epoxy-based flame retardant to further improve the flame retardancy.

Hereinafter, the method for producing the thermoplastic flame retardant resin composition of the present invention will be described.

The thermoplastic flame retardant resin composition of the present invention is, for example, 100 parts by weight of a base resin comprising 20 to 50% by weight of a rubber polymer-aromatic vinyl compound-vinyl cyanide copolymer and 50 to 80% by weight of an aromatic vinyl compound- part; And 10 to 30 parts by weight of a brominated epoxy resin; and wherein the brominated epoxy resin comprises an oxazolidin group or a brominated epoxy resin containing a urethane group can do.

During the kneading, optional additives such as a flame retardant additive, a lubricant, an antioxidant, a heat stabilizer, a light stabilizer, an antistatic agent, an antistatic agent and a coloring agent may be added.

The kneading and extruding may be carried out, for example, at 100 to 300 rpm, 100 to 200 rpm or 150 to 300 rpm; And 210 to 230 占 폚, 210 to 220 占 폚, or 220 to 230 占 폚. Within this range, excellent workability can be obtained.

Further, the thermoplastic flame retardant resin composition of the present invention may be produced as an injection molded product through an injection process, and the injection may be performed at 200 to 230 ° C, 200 to 210 ° C or 220 to 230 ° C, for example. And 60 to 100 bar or 60 to 80 bar; Lt; / RTI >

The injection molded article has an advantage that the impact strength as measured by ASTM D256 is 16 kgcm / cm or more, 16 to 24 kg / cm or 19 to 24 kg / cm, and excellent mechanical strength.

Further, the injection molded product has an advantage of excellent heat resistance characteristics at 81.5 ° C or higher, 81.5 ° C to 90 ° C, or 82 ° C to 85 ° C as measured at a heat distortion temperature (load 18.6 kg / cm ² ) measured according to ASTM D648.

Other conditions that are not specifically described in the description of the thermoplastic resin composition, production method thereof, and injection molded article of the present invention are not particularly limited when they are within the range usually practiced in the technical field of the present invention, have.

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

The materials used in the following examples and comparative examples are as follows.

A) Base resin

A1) ABS resin

-Butyl acrylate rubber-styrene-acrylonitrile copolymer, DP270 (containing 55% by weight of butadiene rubber) was used.

A2) SAN resin

- styrene-acrylonitrile copolymer was used.

B) a brominated epoxy resin

BEO 1) Non-capped BEO substituted with oxazolidone represented by the following Formula A was prepared by reacting 100 parts by weight of the brominated epoxy resin represented by Formula 2 and 10 parts by weight of 2-oxazolidone .

(A)

(In the formula (A), n is an integer of 1 to 8.)

BEO 2) Non-capped BEO substituted with a urethane group represented by the following formula (B) was prepared by reacting 100 parts by weight of the brominated epoxy resin represented by the formula (2) and 10 parts by weight of hexamethylene diisocyanate.

[Chemical Formula B]

Wherein R and R 'are as defined in the above formula (A), R ₃ is - (CH ₂ ) ₆ -, and n is an integer of 1 to 8.

(For reference, in the case of reacting 20 parts by weight or more of isocyanate or oxazolidone with respect to 100 parts by weight of the brominated epoxy resin represented by the general formula (2), the resin is preferably used in an amount of less than 20 parts by weight, Most preferably 10 parts by weight or less.)

BEO 3) LFR 1350E manufactured by BAKELITE KOREA (containing oxazolidone or urethane groups)

BEO 4) LFR 1460C manufactured by BAKELITE KOREA (containing oxazolidone or urethane groups)

C) Additive

- 5 parts by weight of antimony trioxide having an average particle diameter of 0.35 μm as a flame retardant auxiliary, 1 part by weight of a stearamide base lubricant, EBA, 0.3 part by weight of an antioxidant, 0.3 part by weight of a heat stabilizer, 0.1 part by weight of an inhibitor were used.

[Example]

Example  1 to 6, Reference example  1 to 2 and Comparative Example  1 to 4

The mixture containing the components and contents of Tables 1 and 2 was homogeneously mixed using a Henschel mixer, and then the mixture was fed into a twin-screw extruder and melt-kneaded and extruded at 220 ° C and 250 rpm to prepare a resin composition in the form of a pellet.

The resin composition was dried in a hot air drier at 80 ° C for 2 to 3 hours to remove water and then injection molded at 210 ° C and 80 bar to prepare specimens for physical property measurement.

division Example Reference example One 2 3 4 5 6 One 2 ABS resin 30 30 30 30 30 30 - - SAN resin 70 70 70 70 70 70 - - BEO 1 20 10 10 10 30 - 20 20 BEO 2 - 10 - - - 20 10 - BEO 3 - - 10 - - - - 10 BEO 4 - - - 10 - - - -

(ABS resin and SAN resin are weight%, BEO is ABS resin and 100 parts by weight of SAN resin are parts by weight)

division Comparative Example 3 4 8 9 ABS resin 30 30 30 30 SAN resin 70 70 70 70 BEO 1 - BEO 2 BEO 3 20 - 30 - BEO 4 - 20 - 30

(ABS resin and SAN resin are% by weight, and BEO is parts by weight with respect to 100 parts by weight of ABS resin and SAN resin).

[Test Example]

The properties of the specimens prepared in the above Examples, Reference Examples and Comparative Examples were measured by the following methods, and the results are shown in Tables 3 and 4 below.

1) Izod Impact Strength (kgcm / cm): Impact strength was measured using a 1/8 "thick specimen according to ASTM D256.

2) Heat deformation temperature (占 폚): Measured according to ASTM D648 using a 1/4 "thick specimen at a load of 18.6 kg / cm ² .

3) Flame Retardancy: The flame retardancy was evaluated by using a bar type specimen having a thickness of 1/8 "in accordance with the flame retardancy grade UL-94-VB.

4) Evaluation of the degree of carbonization at the time of injection residence: The degree of carbonization was evaluated by the number of black spots formed on the specimen after injection residence at 230 ° C for 30 minutes. The smaller the number of black spots, the lower the degree of carbonization.

division Example Reference example One 2 3 4 5 6 One 2 Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Impact strength 22.1 21.7 19.5 21.1 20.4 21.1 18.9 17.8 Heat resistance 84.8 83.2 82.6 83.5 83.7 82.5 83.5 82.9 Black score <3 <10 <17 <13 <10 <12 <22 <32

division Comparative Example One 2 3 4 Flame retardancy V-1 V-1 V-0 V-0 Impact strength 17.5 18.6 15.0 16.4 Heat resistance 81.1 82.2 80.4 81.6 Black score <41 <21 <52 <32

As shown in Tables 3 and 4, the specimens of Examples 1 to 6 satisfied the V-0 of the flame retardancy grade while the impact strength and the heat resistance were maintained at a high level, and the number of black spots was significantly smaller than those of Comparative Examples 1 to 4, It was confirmed that the carbonization phenomenon was greatly reduced.

Examples 3 and 4 in which oxazolidin-containing brominated epoxy resin as a flame retardant and a conventional brominated epoxy resin (not containing oxazolidinone) were mixed and applied were found to have a large number of black spots as compared with Examples 1 to 2 and 5 to 6 .

Also, as shown in Table 4, it was confirmed that the specimens of Comparative Examples 1 and 2 had a low flame retardancy grade compared with the comparative example in which the flame retardant was contained in an equivalent amount.

Claims (17)

100 parts by weight of a base resin comprising a rubber polymer-aromatic vinyl compound-vinyl cyan compound copolymer and an aromatic vinyl compound-vinyl cyan compound copolymer and 10 to 30 parts by weight of a brominated epoxy resin,
Wherein the brominated epoxy resin comprises an oxazolidin group or a brominated epoxy resin containing a urethane group
Thermoplastic flame retardant resin composition. The method according to claim 1,
The brominated epoxy resin containing oxazolidinone group or urethane group is a compound represented by the following formula (1a)
Thermoplastic flame retardant resin composition.
[Formula 1a]

(Wherein, n is an integer of 1 to 8, X is Br, a and b are each independently an integer of 1 to 4, R1 is hydrogen or an alkyl group having 1 to 5 carbon atoms, R2 is a C1- R 3 is selected from alkylene or arylene having 1 to 10 carbon atoms, Y is a group derived from a brominated epoxy resin of the above formula (1a) or

/ RTI &gt; 3. The method of claim 2,
Wherein the brominated epoxy resin is characterized in that at least one epoxy end is capped with a compound containing bromine
Thermoplastic flame retardant resin composition. The method of claim 3,
Wherein the compound containing bromine is an aryl group substituted with at least one bromine atom.
Thermoplastic flame retardant resin composition. The method according to claim 1,
The brominated epoxy resin containing an oxazolidinone group or a urethane group is characterized by containing an oxazolidinone group or a urethane group in an amount of 3 to 20% by weight
Thermoplastic flame retardant resin composition. The method according to claim 1,
Wherein the brominated epoxy resin has a bromine content of 45 to 70% by weight
Thermoplastic flame retardant resin composition. The method according to claim 1,
Wherein the brominated epoxy resin has an epoxy equivalent of 150 to 800 g / eq
Thermoplastic flame retardant resin composition. The method according to claim 1,
Wherein the brominated epoxy resin has a weight average molecular weight of 1,000 to 15,000 g / mol
Thermoplastic flame retardant resin composition. The method according to claim 1,
Wherein the base resin comprises 20 to 50% by weight of a rubber polymer-aromatic vinyl compound-vinyl cyanide copolymer and 50 to 80% by weight of an aromatic vinyl compound-vinyl cyanide copolymer
Thermoplastic flame retardant resin composition. The method according to claim 1,
Wherein the rubber polymer-aromatic vinyl compound-vinyl cyan compound copolymer comprises at least one member selected from the group consisting of an acrylic rubber polymer-aromatic vinyl compound-vinyl cyan compound copolymer and a diene rubber polymer-aromatic vinyl compound-vinyl cyan compound copolymer Characterized by
Thermoplastic flame retardant resin composition. 11. The method of claim 10,
The acrylic rubber polymer-aromatic vinyl compound-vinyl cyanide copolymer is prepared by graft polymerization comprising 10 to 60% by weight of an acrylic rubber polymer, 30 to 65% by weight of an aromatic vinyl compound and 10 to 40% by weight of a vinyl cyan compound Characterized by
Thermoplastic flame retardant resin composition. 11. The method of claim 10,
The diene rubber polymer-aromatic vinyl compound-vinyl cyanide copolymer is graft-polymerized, comprising 50 to 80 wt% of a diene rubber polymer, 5 to 30 wt% of an aromatic vinyl monomer, and 10 to 40 wt% of a vinyl cyan compound Characterized in that
Thermoplastic flame retardant resin composition. The method according to claim 1,
Wherein the thermoplastic flame retardant resin composition further comprises at least one additive selected from a flame retarder, a lubricant, an antioxidant, a heat stabilizer, a light stabilizer, an antistatic agent, an antistatic agent and a colorant
Thermoplastic flame retardant resin composition. 100 parts by weight of a base resin comprising 20 to 50% by weight of a rubber polymer-aromatic vinyl compound-vinyl cyan compound copolymer and 50 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; And 10 to 30 parts by weight of a brominated epoxy resin containing an oxazolidin group or a urethane group, and extruding the kneaded mixture
A method for producing a thermoplastic flame retardant resin composition. A flame retardant resin composition according to any one of claims 1 to 13,
Injection molded article. 16. The method of claim 15,
The molded article has an impact strength of 15 kgcm / cm or more as measured by ASTM D256
Injection molded article. 16. The method of claim 15,
The molded article has a heat distortion temperature (load 18.6 kg / cm ² ) measured according to ASTM D648 of 82 ° C or higher
Injection molded article.