KR20150067691A - Composition of thermoplastic resin comprising waste polyester resin - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition comprising a waste polyester resin and a thermoplastic resin prepared from the same, wherein the thermoplastic resin composition is prepared by the recycling of a waste polyester resin and has excellent impact strength and melting index (moldability) as well as high gloss. Accordingly, the thermoplastic resin prepared from the thermoplastic resin composition by adding a compound represented by the [Formula 1] and an organic nucleating agent has excellent impact strength, a tensile elongation and melting index (moldability) as well as high gloss.

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition comprising a waste polyester resin,

The present invention relates to a thermoplastic resin composition having excellent impact strength and melt index (moldability), as well as excellent gloss, by recycling a waste polyester resin, and a thermoplastic resin produced therefrom.

As the development of technology and the consumption of packaging containers are rapidly increased, the amount of glass bottles used mainly as packaging containers is reduced, and a polyester resin, particularly polyethylene terephthalate (PET) resin Is being replaced.

In addition, polyester resin including polyethylene terephthalate resin is a resin balanced in mechanical strength, heat resistance, chemical resistance, electrical properties, precision moldability and abrasion resistance among engineering plastics, and it is preferable to add glass fiber, inorganic filler, flame retardant and various additives By mixing with other resins, automotive parts, electricity; Electronic parts, general industrial materials, and other fields requiring high functionality.

On the other hand, as the utilization of polyester resin such as polyethylene terephthalate (PET) resin has come to be developed, the production amount has been rapidly increased, and the amount of waste polyester resin has been increased to an enormous amount. However, It is true. The disposable polyester resins are collectively collected and then recycled into packaging containers or recycled for use as fibers or packaging materials. However, they are more realistic in terms of high added value, economical efficiency and practicality It is imperative to find concrete recycling plans.

Accordingly, a polyester resin having improved impact strength is prepared by adding an impact modifier and a compatibilizing agent to a waste polyester resin having a low molecular weight and having a low impact strength, as one of methods for treating waste polyester resin effectively and environmentally. However, in order to obtain the desired effect, a large amount of a compatibilizing agent must be added, and the heat resistance may be lowered to lower the thermal stability, and the economical efficiency may decrease. Therefore, there is a need for a method capable of producing a polyester resin having excellent physical properties while being able to recycle waste polyester resin environmentally.

Under the above background, the inventors of the present invention have been studying a method of producing a polyester resin having excellent physical properties while being able to recycle the waste polyester resin environmentally and recycling waste polyester resin, styrenic copolymer and core- Butadiene-styrene type impact modifier, the polyester resin prepared from the thermoplastic resin composition to which the compound represented by the general formula (1) and the organic nucleating agent are added has excellent impact strength, tensile elongation and melt index As well as the improvement of the gloss.

An object of the present invention is to provide a thermoplastic resin composition which is excellent in impact strength and melt index (moldability) as well as in gloss when recycled waste polyester resin is used.

Another object of the present invention is to provide a thermoplastic resin composition produced from the thermoplastic resin composition.

In order to solve the above problems, the present invention provides a resin composition comprising 0.1 to 5 parts by weight of a compound represented by the following formula (1) and 0.1 to 1 part by weight of an organic nucleating agent based on 100 parts by weight of a base resin composition; Wherein the base resin composition comprises: a) from 25% to 50% by weight of waste polyester resin; b) 20% to 45% by weight of a styrenic copolymer; And c) 20 to 40% by weight of an acrylonitrile-butadiene-styrene graft copolymer.

[Chemical Formula 1]

Wherein R, R _1, R _2, R _3, R ₄ and R ₅ are each other at the same time or independently H, CH _3, higher alkyl, and R ₆ is an alkyl group, x, y, z is an integer from 1 to 20, respectively to be.

The present invention also provides a thermoplastic resin produced from the above thermoplastic resin composition and having excellent impact strength, tensile elongation and melt index (moldability) as well as excellent gloss by recycling the waste polyester resin.

The thermoplastic resin composition of the present invention can not only control the molecular weight of the waste polyester resin but also improve the crystallinity and crystallinity by adding the compound represented by the formula (1) and the organic nucleating agent to the base resin composition containing the waste polyester resin Not only a thermoplastic resin having excellent impact strength, tensile elongation, melt index (moldability) and gloss can be produced, but also the waste polyester resin can be effectively reused.

Accordingly, the thermoplastic resin composition and the thermoplastic resin according to the present invention can be easily applied to industries requiring the same, and can also provide a method of reusing the waste polyester resin.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The present invention relates to a resin composition comprising a waste polyester resin, a styrene-based copolymer and an acrylonitrile-butadiene-styrene graft copolymer base resin composition, (Moldability) and glossiness of the thermoplastic resin composition.

Polyester resins are used in various industries including packaging containers because they are easy to handle, have a low cost, and have a strong shock resistance. Accordingly, waste polyester resins are increasingly in need, and a method for efficiently processing them is needed.

As a method for reusing the waste polyester resin as one of the methods for treating the waste polyester resin effectively and environmentally friendly, there have been studied, for example, an impact modifier and a compatibilizer for the waste polyester resin, Is added to produce a polyester resin having an improved impact strength. However, in order to obtain the desired effect, a large amount of a compatibilizing agent must be added, and the heat resistance may be lowered to lower the thermal stability, and the economical efficiency may decrease.

Therefore, there is a need for a method capable of recycling the waste polyester resin in an environmentally friendly manner, and capable of producing a polyester resin having excellent physical properties such as impact strength, moldability and gloss.

Accordingly, the present invention relates to a resin composition comprising a base resin composition comprising a waste polyester resin, a styrenic copolymer and an acrylonitrile-butadiene-styrene graft copolymer having a core-shell structure, (Impact strength), a tensile elongation, a melt index (moldability), and a gloss of the thermoplastic resin composition.

The thermoplastic resin composition according to an embodiment of the present invention comprises 0.1 to 5 parts by weight of a compound represented by the following formula (1) and 0.1 to 1 part by weight of an organic nucleating agent, based on 100 parts by weight of the base resin composition and; Wherein the base resin composition comprises: c) 25 to 50% by weight of waste polyester resin; d) 20% to 45% by weight of a styrenic copolymer; And e) 20% to 40% by weight of an acrylonitrile-butadiene-styrene graft copolymer.

[Chemical Formula 1]

Wherein R, R _1, R _2, R _3, R ₄ and R ₅ are each other at the same time or independently H, CH _3, higher alkyl, and R ₆ is an alkyl group, x, y, z is an integer from 1 to 20, respectively to be.

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

a) a compound represented by the formula (1)

The compound represented by the formula (1) according to an embodiment of the present invention is an epoxy group-containing vinyl copolymer, and can control the molecular weight of the polyester resin to be described later, thereby realizing the stable physical properties of the thermoplastic resin composition of the present invention . The waste polyester resin to be described later may have a reduced molecular weight due to moisture and heat history in the processing step, which may significantly deteriorate the physical properties. In order to reuse the waste polyester resin, it is necessary to compensate for the reduced physical properties. The compound represented by the general formula (1) of the present invention can act as a chain extender in the thermoplastic resin composition to increase the molecular weight of the waste polyester resin, thereby realizing stable physical properties.

Specifically, the compound represented by the following formula (1) may be prepared by polymerizing a monomer mixture containing an epoxy group-containing unsaturated epoxy compound, a vinyl compound and an acrylate compound so that an unsaturated epoxy group is present in the vinyl copolymer.

[Chemical Formula 1]

Wherein R, R _1, R _2, R _3, R ₄ and R ₅ are each other at the same time or independently H, CH _3, higher alkyl, and R ₆ is an alkyl group, x, y, z is an integer from 1 to 20, respectively to be.

The epoxy compound is not particularly limited, and examples thereof include epoxyalkyl acrylate, allyl glycidyl ester, aryl glycidyl ester, glycidyl methacrylate, glycidyl acrylate, butadiene monoxide, vinyl glycidyl ether , Glycidyl itaconate, and the like, preferably glycidyl methacrylate.

The vinyl-based compound may be an aromatic vinyl-based compound such as styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dibromostyrene , Vinyl naphthalene, and the like, preferably styrene.

The acrylate compound may be ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate and the like.

As mentioned above, an epoxy group-containing vinyl copolymer prepared by polymerizing a monomer mixture containing an unsaturated epoxy compound, a vinyl compound and an acrylate compound is a compound represented by the formula 1 according to one embodiment of the present invention May have a number average molecular weight (Mn) of 3000 or less, and may have 4 or more epoxy groups per chain. The compound represented by Formula 1 may have an epoxy equivalent weight (EEW) of 270 g / mol to 300 g / mol.

The compound represented by Formula 1 may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the base resin composition. If the amount of the compound represented by the formula (1) is less than 0.1 parts by weight, the amount of the compound represented by the formula (1) is too small to sufficiently perform its function and the tensile strength may be reduced. , The melt viscosity of the thermoplastic resin composition containing the thermoplastic resin composition is greatly increased when the thermoplastic resin composition is extruded, resulting in difficulty in extrusion processing.

b) Organic nucleating agent

The organic nucleating agent according to an embodiment of the present invention can improve the crystallization speed and crystallinity of the thermoplastic resin composition of the present invention, thereby shortening the molding cycle time and improving the mechanical rigidity.

The organic nucleating agent may be sodium benzoate, sodium laurate, dibenzylidene sorbitol (DBS) or a mixture thereof.

The organic nucleating agent may be included in an amount of 0.1 part by weight to 1 part by weight based on 100 parts by weight of the base resin composition. If the organic nucleating agent is contained in an amount of less than 0.1 part by weight, the action as a nucleating agent can not be performed properly, so that the tensile strength can be reduced. If the amount is more than 1 part by weight, the tensile elongation can be reduced.

c) Waste polyester resin

The waste polyester resin according to an embodiment of the present invention can be obtained in various products such as a packaging container, a polyester film, a polyester fiber, and the like, but is not limited to, a polyester resin having a melt temperature of 255 캜 to 265 캜, g to 1.0 dl / g, and a moisture content of 0.15% to 0.25%.

If the average polyester resin has an average intrinsic viscosity of less than 0.45 dl / g, the mechanical properties of the thermoplastic resin composition containing the polyester resin may be deteriorated. If the polyester resin has a viscosity higher than 1.0 dl / g, the fluidity of the thermoplastic resin composition The problem may be degraded. If the moisture content of the polyester resin is out of the above range, extrusion processability and physical properties of the thermoplastic resin composition containing the polyester resin may be deteriorated.

The waste polyester resin may be at least one selected from the group consisting of waste polyethylene terephthalate, waste polybutylene terephthalate, waste polyethylene naphthalate, waste polybutylene terephthalate and waste polypropylene terephthalate. It is not.

On the other hand, the waste polyester resin may be preferably used after being washed and pulverized, and may be processed into pellets through extrusion if necessary.

The waste polyester resin according to an embodiment of the present invention may be contained in the base resin composition in an amount of 25 wt% to 50 wt%. If the waste polyester resin is contained in an amount of less than 25% by weight, the solidification speed of the thermoplastic resin composition containing the thermoplastic resin composition may be accelerated to degrade the surface properties of the molded article. If the amount exceeds 50% by weight, The speed is too slow, the productivity drops, and the post-warpage may be relatively large.

d) a styrenic copolymer

The styrenic copolymer according to an embodiment of the present invention is a graft copolymer of a styrenic monomer and an acrylonitrile monomer, preferably 60 to 80% by weight of a styrenic monomer and 20 to 20% by weight of an acrylonitrile monomer To 40% by weight of styrene-acrylonitrile copolymer (SAN).

The styrenic copolymer according to an embodiment of the present invention may be included in the base resin composition in an amount of 20% by weight to 45% by weight. Preferably 20% to 45% by weight. If the styrenic copolymer is contained in an amount of less than 20% by weight, the flowability of the thermoplastic resin composition containing the styrenic copolymer may be decreased to decrease moldability. If the styrenic copolymer is contained in an amount exceeding 45% by weight, The impact strength and heat resistance of the resin may be deteriorated.

On the other hand, the styrenic copolymer is not particularly limited and may be used in the manufacture or use of a commercially available substance.

When the styrenic copolymer is prepared and used, it is not particularly limited and it can be produced by a commonly known production method in the art. For example, the styrene-based monomer and the acrylonitrile-based monomer may be prepared by bulk polymerization or emulsion polymerization, preferably by bulk polymerization.

The bulk polymerization is not particularly limited and can be carried out by a conventional method known in the art. For example, the styrene-based monomer and the acrylonitrile-based monomer are mixed with the reaction medium and reacted with heating at a temperature of 80 to 160 ° C to prepare a polymerized product, and then the unreacted material and the reaction medium are removed can do.

The styrenic monomer may be one or more selected from the group consisting of styrene,? -Methylstyrene,? -Ethylstyrene, p-ethylstyrene, vinyltoluene and derivatives thereof, preferably styrene.

The acrylonitrile monomer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and their derivatives, And preferably acrylonitrile.

The reaction medium may be a conventional organic solvent, for example, an aromatic compound such as ethylbenzene, benzene, toluene, and xylene, and methyl ethyl ketone, acetone, n-hexane, chloroform, cyclohexane, It is not.

In addition to the above-described materials, the bulk polymerization may further include additives such as polymerization initiators and molecular weight regulators.

The polymerization initiator is not particularly limited. Examples of the polymerization initiator include water-soluble persulfate-based polymerization initiators such as potassium persulfate, sodium persulfate or ammonium persulfate, hydrogen peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, A redox-based polymerization initiator having a peroxide such as an oxide, a pyramentane hydroperoxide or the like as a single component, or the like can be added singly or in combination.

The molecular weight modifier may be a conventional material such as mercaptans, but may be n-butyl mercaptan, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan and the like, It may be a silmercap.

e) an acrylonitrile-butadiene-styrene (ABS) graft copolymer of core-shell structure

The acrylonitrile-butadiene-styrene (ABS) graft copolymer of the core-shell structure according to an embodiment of the present invention comprises a diene-based polymer core and a styrene-based monomer and an acrylonitrile-based monomer on the core The shell may be grafted.

Specifically, the acrylonitrile-butadiene-styrene (ABS) graft copolymer of the core-shell structure comprises 50 to 80% by weight of a diene-based polymer core, and a styrene-based monomer and an acrylonitrile-based monomer 20% to 50% by weight of the shell may be grafted. At this time, the styrene-based monomer and acrylonitrile-based monomer contained in the shell may have a weight ratio of 17: 3 to 11: 7.

The acrylonitrile-butadiene-styrene graft copolymer of the core-shell structure according to the present invention may be contained in the styrene resin composition in an amount of 20% by weight to 40% by weight. If the acrylonitrile-butadiene-styrene graft copolymer of the core-shell structure is included in the above range, the thermoplastic resin composition containing the acrylonitrile-butadiene-styrene graft copolymer is excellent in fluidity, And the impact strength of the produced resin can be improved.

On the other hand, the acrylonitrile-butadiene-styrene graft copolymer of the core-shell structure is not particularly limited, and may be prepared by using a conventionally known method in the art, or a commercially available material may be used.

For example, when the acrylonitrile-butadiene-styrene graft copolymer of the core-shell structure is prepared and used, the acrylonitrile-butadiene-styrene graft copolymer of the core- And then graft copolymerizing a styrene-based monomer and a shell containing an acrylonitrile-based monomer to the prepared diene-based polymer core.

The diene polymer core is not particularly limited and can be produced by a method commonly known in the art. For example, an additive such as ion-exchanged water, an emulsifier, a polymerization initiator, an electrolyte and a molecular weight adjuster is added to the conjugated diene monomer Or may be one prepared by emulsion polymerization.

The emulsion polymerization is not particularly limited and can be carried out by a conventional method known in the art. For example, additives such as ion-exchanged water, an emulsifier and a polymerization initiator are added to a conjugated diene monomer in a batch and reacted Or the reaction may be carried out by continuously feeding the components at the polymerization time.

Specifically, when the reaction is carried out in a batch, 100 parts by weight of the conjugated diene monomer or conjugated diene monomer is reacted with 70 to 120 parts by weight of ion exchange water, 0.2 to 2.5 parts by weight of an emulsifier, 0.1 part by weight to 1.5 parts by weight of an electrolyte, 0.5 parts by weight to 2 parts by weight of an electrolyte and 0.1 parts by weight to 1 part by weight of a molecular weight modifier are fed into a polymerization reactor at a temperature ranging from 50 ° C to 90 ° C . ≪ / RTI > At this time, the conjugated diene-based monomer may be added in a batch with other constituent materials or additives and reacted, or the monomer may be added or continuously injected several times during the polymerization reaction.

The conjugated diene-based monomer may be one or more selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and pyrene. And preferably 1,3-butadiene.

The polymerization initiator and the molecular weight modifier may be the same or as mentioned above.

Examples of the emulsifier include, but are not limited to, a combination of one or more selected from the group consisting of alkylaryl sulfonates, alkaline methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and rosin acid alkali salts .

Examples of the electrolyte include, but are not limited to, potassium chloride, sodium chloride, potassium bicarbonate, potassium carbonate, potassium hydrogen sulfite, sodium hydrogen sulfite, sodium pyrophosphate, sodium pyrophosphate, tripotassium phosphate, trisodium phosphate, Potassium, and disodium hydrogenphosphate.

The shell containing the styrene-based monomer and the acrylonitrile-based monomer is obtained by adding an additive such as a styrene-based monomer and an acrylonitrile-based monomer, an emulsifier, a polymerization initiator, a molecular weight regulator and the like to the prepared diene-based polymer core and graft- Can be formed on the above-mentioned di-based polymer cores.

The additives such as the styrene-based monomer, the acrylonitrile-based monomer, and the emulsifier, the polymerization initiator, the molecular weight regulator, and the like may be the same as those mentioned above or may be included.

The present invention also provides a polyester resin produced from the thermoplastic resin composition.

In a basic resin composition comprising a waste polyester resin, a styrenic copolymer and an acrylonitrile-butadiene-styrene graft copolymer having a core-shell structure according to an embodiment of the present invention, The polyester resin prepared from the thermoplastic resin composition to which the nucleating agent is added can control the degree of crystallization of the waste polyester resin by controlling the molecular weight of the waste polyester resin and adding the organic nucleating agent by adding the compound represented by the formula (1) Not only the elongation and the melt index (moldability) are excellent but also a high gloss can be obtained.

Hereinafter, the present invention will be described in more detail with reference to the following examples and experimental examples. However, the following examples and experimental examples are provided for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example  One

A basic resin composition consisting of 27 wt% of a waste polyethylene terephthalate resin, 43 wt% of a styrenic copolymer (SAN) and 30 wt% of an acrylonitrile-butadiene-styrene graft copolymer (ABS) having a core-shell structure, 1 part by weight of a chain extender (ADR4368, BASF) and 0.5 part by weight of sodium benzoate were sufficiently mixed with 100 parts by weight of the resin composition, extruded at an extrusion temperature of 240 DEG C in a twin-screw extruder, cooled and solidified into pellets, And dried at a temperature of 240 캜 and a mold temperature of 65 캜 to prepare a polyethylene terephthalate resin specimen.

Example  2

A polyethylene terephthalate resin specimen was prepared in the same manner as in Example 1, except that 0.5 part by weight of sodium laurate was added instead of 0.5 part by weight of sodium benzoate.

Example  3

A base resin composition comprising 45% by weight of a waste polyethylene terephthalate resin (PET), 25% by weight of a styrenic copolymer (SAN) and 30% by weight of an acrylonitrile-butadiene-styrene graft copolymer (ABS) And 2 parts by weight of a chain extender (ADR4368, BASF) and 0.5 part by weight of sodium benzoate were thoroughly mixed with 100 parts by weight of the base resin composition, extruded at an extrusion temperature of 240 DEG C in a twin-screw extruder, After drying for 4 hours in a circulating hot air dryer maintained at 100 ° C, a polyethylene terephthalate resin specimen was prepared from a 160 ton injection machine at an injection temperature of 240 ° C and a mold temperature of 65 ° C.

Example  4

A polyethylene terephthalate resin specimen was prepared in the same manner as in Example 3 except that 1 part by weight of dibenzylidene sorbitol was added instead of 0.5 part by weight of sodium benzoate.

Comparative Example  One

A polyethylene terephthalate resin specimen was prepared in the same manner as in Example 1 except that no chain extender and sodium benzoate were added.

Comparative Example  2

A polyethylene terephthalate resin specimen was prepared in the same manner as in Example 1 except that no chain extender was added.

Comparative Example  3

A polyethylene terephthalate resin specimen was prepared in the same manner as in Example 3 except that 2 parts by weight of a chain extender (ADR4368, BASF) was added and sodium benzoate was not added.

Comparative Example  4

A polyethylene terephthalate resin specimen was prepared in the same manner as in Example 3 except that 1 part by weight of glass fiber was added instead of 0.5 part by weight of sodium benzoate.

Comparative Example  5

A polyethylene terephthalate resin specimen was prepared in the same manner as in Example 3 except that 1 part by weight of talc was added instead of 0.5 part by weight of sodium benzoate.

Comparative Example  6

A polyethylene terephthalate resin specimen was prepared in the same manner as in Example 3 except that 1 part by weight of silica was added instead of 0.5 part by weight of sodium benzoate.

The materials and contents used in the preparation of each of the polyethylene terephthalate resin specimens are shown in Table 1 below.

division Base resin (% by weight) Chain extender (parts by weight) Organic nucleating agent (parts by weight) Waste PET SAN ABS Sodium benzoate Sodium laurate Dibenzylidene sorbitol Glass fiber Talc Silica Example 1 27 43 30 One 0.5 - - - - - Example 2 27 43 30 One - 0.5 - - - - Example 3 45 25 30 2 0.5 - - - - - Example 4 45 25 30 2 - - One - - - Comparative Example 1 27 43 30 - - - - - - - Comparative Example 2 27 43 30 - 0.5 - - - - - Comparative Example 3 45 25 30 2 - - - - - - Comparative Example 4 45 25 30 2 - - - One - - Comparative Example 5 45 25 30 2 - - - - One - Comparative Example 6 45 25 30 2 - - - - - One

Experimental Example

The impact strength, tensile elongation, melt index (flowability) and gloss of each of the specimens were measured in order to comparatively analyze the characteristics of the respective polyethylene terephthalate resin specimens prepared in Examples and Comparative Examples. The results are shown in Table 2 below.

(1) Impact strength (1/4 ")

The impact strength of each of the polyethylene terephthalate resin specimens prepared in the above Examples and Comparative Examples was measured according to ASTM D256.

(2) Tensile elongation (%)

Each of the polyethylene terephthalate resin specimens prepared in the above Examples and Comparative Examples was measured for tensile elongation at a rate of 5 cm / min according to ASTM D638.

(3) Melt index

Each of the polyethylene terephthalate resin specimens prepared in the above-mentioned Examples and Comparative Examples was tested for the weight (g) of the molten resin at a temperature of 250 DEG C and under a load of 10 kg and the weight of the resin melted for 10 minutes (g ) Were measured.

(4) Glossiness

The gloss of each of the polyethylene terephthalate resin specimens prepared in Examples and Comparative Examples was measured with a gloss meter at an angle of 45 degrees. The larger the gloss value, the better the gloss of the surface.

division Impact strength (J / m) Tensile elongation (%) Glossiness Melt Index (MI) 0 minutes 10-minute stay Example 1 18 42 92 23 28 Example 2 16 42 92 23 29 Example 3 13 36 91 19 24 Example 4 13 38 92 19 23 Comparative Example 1 5.1 15 78 43 62 Comparative Example 2 8.6 18 88 33 44 Comparative Example 3 11 26 90 28 38 Comparative Example 4 8.5 23 62 30 42 Comparative Example 5 7.3 19 60 28 36 Comparative Example 6 8.6 22 82 33 41

As shown in Table 2, the polyethylene terephthalate resins of Examples 1 to 4 according to one embodiment of the present invention are superior in impact strength, tensile elongation, gloss, and melt index .

Specifically, the polyester resin prepared from the thermoplastic resin composition containing the compound represented by the formula (1) and the organic nucleating agent according to the present invention is a polyester resin of the comparative example 1 which does not contain the compound represented by the formula (1) and the organic nucleating agent, Compared with the polyester resin of Comparative Example 3 containing only the organic nucleating agent and the polyester resin of Comparative Example 2 and the compound represented by the formula (1), not only the impact strength and tensile elongation characteristics are remarkably improved, but also the gloss and melt index characteristics .

Further, it was confirmed that the polyester resins of Comparative Examples 4 to 6 containing an inorganic nucleating agent which is not an organic nucleating agent according to the present invention were significantly superior in impact strength, tensile elongation, gloss and melt index.

Accordingly, the thermoplastic resin composition of the present invention is a resin composition comprising a base resin composition comprising a waste polyester resin, a styrene-based copolymer and an acrylonitrile-butadiene-styrene graft copolymer having a core-shell structure, By incorporating an organic nucleating agent, a polyester resin having excellent impact strength, tensile elongation, gloss and melt index characteristics can be produced.

Claims (11)

0.1 to 5 parts by weight of a compound represented by the following formula (1) and 0.1 to 1 part by weight of an organic nucleating agent based on 100 parts by weight of the base resin composition;
The base resin composition
a) from 25% to 50% by weight of waste polyester resin;
b) 20% to 45% by weight of a styrenic copolymer; And
c) 20% to 40% by weight of an acrylonitrile-butadiene-styrene graft copolymer.
[Chemical Formula 1]

Wherein R, R _1, R _2, R _3, R ₄ and R ₅ are each other at the same time or independently H, CH _3, higher alkyl, and R ₆ is an alkyl group, x, y, z is an integer from 1 to 20, respectively to be.
The method according to claim 1,
Wherein the compound represented by the formula (1) has a number average molecular weight (Mn) of 3,000 or less.
The method according to claim 1,
The thermoplastic resin composition according to claim 1, wherein the compound represented by the formula (1) has at least four epoxy groups per chain.
The method according to claim 1,
Wherein the compound represented by Formula 1 has an epoxy equivalent weight (EEW) of 270 g / mol to 300 g / mol.
The method according to claim 1,
Wherein the organic nucleating agent is sodium benzoate, sodium laurate, dibenzylidene sorbitol (DBS) or a mixture thereof.
The method according to claim 1,
Wherein said a) polyester resin is at least one selected from the group consisting of waste polyethylene terephthalate, waste polybutylene terephthalate, waste polyethylene naphthalate, waste polybutylene terephthalate and waste polypropylene terephthalate. Resin composition.
The method according to claim 1,
The styrene-based copolymer (b) is a styrene-acrylonitrile copolymer (SAN) comprising 60% by weight to 80% by weight of a styrene monomer and 20% by weight to 40% by weight of an acrylonitrile monomer. Composition.
The method according to claim 1,
(C) an acrylonitrile-butadiene-styrene (ABS) graft copolymer having a core-shell structure comprises 50 to 80% by weight of a diene-based polymer core, and a styrene-based monomer grafted on the core and acrylonitrile From 20% to 50% by weight of the shell comprising the monomers;
Wherein the shell comprises a styrene-based monomer and an acrylonitrile-based monomer in a weight ratio of 17: 3 to 11: 7.
9. The method according to claim 7 or 8,
Wherein the styrene-based monomer is at least one selected from the group consisting of styrene,? -Methylstyrene,? -Ethylstyrene, and p-methylstyrene.
9. The method according to claim 7 or 8,
Wherein the acrylonitrile-based monomer is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile.
A thermoplastic resin produced from the thermoplastic resin composition according to any one of claims 1 to 10.