KR102211145B1 - Low gloss polyester resin composition, method for preparing the composition and molding products comprising the composition - Google Patents

Abstract

The present invention relates to a low-gloss polyester-based resin composition, a method for producing the same, and a molded article including the same, and more particularly, to a polyester-based resin containing two kinds of bulk ABS resins having different physical properties in a specific ratio, additives, quenching It provides a low-light polyester resin composition, a method of manufacturing the same, and a molded article including the same, which can realize excellent appearance quality and moldability by adding an agent and an inorganic filler, while achieving low-light characteristics, and at the same time satisfying mechanical properties.

Description

Low-gloss polyester resin composition, its manufacturing method, and molded products including the same {LOW GLOSS POLYESTER RESIN COMPOSITION, METHOD FOR PREPARING THE COMPOSITION AND MOLDING PRODUCTS COMPRISING THE COMPOSITION}

The present invention relates to a low-light polyester-based resin composition, a method of manufacturing the same, and a molded article including the same, and more particularly, it has excellent appearance quality and can realize low-light characteristics, and at the same time satisfies mechanical properties suitable for use as an automobile exterior material. It relates to a low-light polyester resin composition, a method for producing the same, and a molded article including the same.

Polybutylene terephthalate (PBT) is a crystalline material that belongs to engineering plastics, and has a fast crystallization rate and an appropriate molding temperature range, so that it is easy to mold, and is thus used in various fields. For example, it is used for housing materials for home appliances closely related to daily life, connectors for signal transmission systems of automobiles, and exterior materials for automobiles such as door handles, garnishes, and bezels for headlamps and rear lamps.

Recently, as users' demands for the aesthetic characteristics of products increase, the exterior materials of products are designed not only in the existing glossy but also matte, so there have been attempts to develop materials that satisfy these requirements, but most of them are color matching. Was limited to.

In the case of color matching, as the material is extruded and then extruded while adding a colorant, the process is complicated and not preferable in terms of cost. Therefore, there is a need to secure a technology that can realize the low-light characteristics of the material itself, not color matching.

Korean Patent Registration 10-1367461 B1

In order to solve the problems of the prior art as described above, the present invention aims to provide a low-light polyester resin composition and a method for manufacturing the same, which can realize low-light characteristics while having excellent appearance quality, and at the same time satisfy mechanical properties. do.

In addition, it is an object of the present invention to provide a polyester-based resin molded article that can be used in a housing of a home appliance or an exterior material of an automobile by implementing low light characteristics while having excellent appearance characteristics and mechanical properties.

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

In order to achieve the above object, the present invention is a polyester-based resin 70 to 90% by weight; 5 to 20% by weight of bulk ABS resin; 0.01 to 5% by weight of additives; 0 to 15% by weight of matting agent; And 0 to 10% by weight of inorganic filler; wherein the bulk ABS resin includes a first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprising a conjugated diene rubber having an average particle diameter of 0.5 μm or more to less than 1.5 μm And a second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprising a conjugated diene rubber having an average particle diameter of 1.5 μm to 10 μm in a weight ratio of 1:1.5 to 1:2.5, and the matting agent or inorganic filler It provides a low-light polyester resin composition, characterized in that at least one of which is necessarily included.

In addition, the present invention 70 to 90% by weight of a polyester resin; 5 to 20% by weight of bulk ABS resin; 0.01 to 5% by weight of additives; Including the step of kneading and extruding, including a matting agent 0 to 15% by weight and inorganic fillers 0 to 10% by weight, wherein the bulk ABS resin comprises a conjugated diene rubber having an average particle diameter of 0.5㎛ or more to less than 1.5㎛ A first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer and a second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprising a conjugated diene rubber having an average particle diameter of 1.5 µm to 10 µm were 1:1.5 It provides a method for producing a low-light polyester resin composition comprising at least one of the matting agent and the inorganic filler in a weight ratio of 1:2.5.

In addition, the present invention provides a molded article comprising the low-light polyester resin composition.

According to the present invention, it is possible to provide an advantage in that the material itself has low light characteristics without a separate surface treatment process while having excellent moldability, appearance quality and mechanical properties.

In particular, the polyester-based resin composition according to the present invention satisfies the mechanical properties suitable for use as an automobile exterior material while being able to realize low light characteristics, and specifically, the molded article manufactured by molding the composition has a heat deflection temperature (4.6kgf) It is 140°C or higher, and the glossiness (60°) is 70 or lower, and has an advantage in that the material itself has low light characteristics without complicated processing while having excellent mechanical properties.

In addition, the polyester-based resin composition of the present invention provides an advantage of excellent mechanical properties while exhibiting low-light properties equivalent to or better than those of the conventional low-light polyester-based resin composition, even though it does not contain a matting agent.

Hereinafter, the low-light polyester resin composition of the present disclosure and a method for producing the same will be described in detail.

The present inventors mixed two types of bulk ABS resins having different average particle diameters of the conjugated diene rubber in a specific ratio in order to impart low light properties to the polybutylene terephthalate material used as a conventional automobile exterior material, and in addition to this, an antioxidant, a lubricant, A composition was prepared by adding additives such as a coupling agent, a matting agent, and an inorganic filler within a specific content range, and the specimen prepared with this composition satisfies the mechanical strength of a level suitable for use as an automobile exterior material, while providing low light properties. It was confirmed that the present invention was completed based on this. In the present invention, the term low light means that the glossiness of a 2mm-thick specimen prepared by injection molding the composition at an angle of 60° using a glossmeter is 70 or less.

Low-light polyester resin composition of the present invention, for example, 70 to 90% by weight of polyester resin; 5 to 20% by weight of bulk ABS resin; 0.01 to 5% by weight of additives; 0 to 15% by weight of matting agent; And 0 to 10% by weight of inorganic filler; wherein the bulk ABS resin includes a first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprising a conjugated diene rubber having an average particle diameter of 0.5 μm or more to less than 1.5 μm And a second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprising a conjugated diene rubber having an average particle diameter of 1.5 μm to 10 μm in a weight ratio of 1:1.5 to 1:2.5, and the matting agent or inorganic filler At least one of them is characterized by necessarily including, and in this case, it is possible to implement low-light characteristics while having excellent appearance quality, and at the same time, it is possible to provide mechanical properties suitable for use as an automobile exterior material.

In another example, the low-light polyester-based resin composition of the present invention is 70 to 90% by weight of a polyester-based resin; 5 to 20% by weight of bulk ABS resin; 0.01 to 5% by weight of additives; 0 to 15% by weight of matting agent; And inorganic filler 0 to 10% by weight; Including, wherein the bulk ABS resin, the first vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer and melt index having a melt index (220°C, 10kg) of 7g/10min or more (220° C., 10 kg) containing a second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer having a weight ratio of 1 :1.5 to 1 :2.5 in a weight ratio of 3 g/10 min to less than 7 g/10 min, and the matting agent or inorganic filler At least one of them is characterized in that it must be included, and in this case, it provides advantages of excellent appearance quality and mechanical properties while being able to implement low light characteristics.

In another example, the low-light polyester resin composition of the present invention comprises 70 to 90% by weight of a polyester resin; 5 to 20% by weight of bulk ABS resin; 0.01 to 5% by weight of additives; And 2 to 15% by weight of a matting agent, wherein the bulk ABS resin includes a first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprising a conjugated diene rubber having an average particle diameter of 0.5 μm or more to less than 1.5 μm, and It is characterized in that it comprises a second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprising a conjugated diene rubber having an average particle diameter of 1.5 μm to 10 μm in a weight ratio of 1:1.5 to 1:2.5, in this case It has excellent appearance quality and can realize low-light characteristics, and at the same time, it can provide mechanical properties suitable for use as an automobile exterior material.

In another example, the low-light polyester resin composition of the present invention comprises 70 to 90% by weight of a polyester resin; 5 to 20% by weight of bulk ABS resin; 0.01 to 5% by weight of additives; And 2 to 10% by weight of an inorganic filler, wherein the bulk ABS resin comprises a first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer and a conjugated diene rubber having an average particle diameter of 0.5 μm or more to less than 1.5 μm, and A second vinyl cyan compound containing a conjugated diene rubber having an average particle diameter of 1.5 μm to 10 μm-conjugated diene rubber-aromatic vinyl compound copolymer in a weight ratio of 1:1.5 to 1:2.5, and matting agent-free ), and in this case, despite not mixing a matting agent, the low-light properties are quite excellent, and both moldability and mechanical properties are excellent.

Hereinafter, the composition of the present disclosure will be described in detail for each component.

A) Polyester resin

The polyester-based resin of the present disclosure provides basic mechanical properties and moldability suitable for use as a housing of home appliances or automobile exterior materials.

The polyester-based resin, for example, may be included in 70 to 90% by weight, 75 to 90% by weight, 75 to 85% by weight, or 78 to 84% by weight based on the total weight of the composition, and within this range, the mechanical properties of the final product, Formability, balance of physical properties, etc. provide excellent advantages.

The polyester-based resin may be characterized in that, for example, an intrinsic viscosity of 0.5 to 1.5 dl/g, 0.7 to 1.2 dl/g, 0.8 to 1.2 dl/g or 0.8 to 1.0 dl/g, preferably 0.8 To 0.9 dl/g. When the intrinsic viscosity of the polyester-based resin is within the above range, the melt index of the composition is appropriate, so that the molding is easy, and the heat deflection temperature is excellent.

In this description, the intrinsic viscosity is a value measured at 20°C using an Uberode viscometer after completely dissolving a sample to be measured in methylene chloride, and then filtering the filtrate using a filter unless otherwise noted.

The polyester resin is, for example, polyethylene adipate (PEA), polybutylene succinate (PBS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), and polyethylene. It is at least one selected from naphthalate (PEN), preferably PET or PBT, and most preferably PBT.

In this case, the overall mechanical properties of the composition are good, providing an advantage in that it is easy to mold while having an excellent balance of properties.

B) bulk ABS resin

The bulk ABS resin of this substrate is a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer prepared by bulk polymerization including rubber, which acts on the surface of the molded product and induces diffuse reflection, thereby lowering the glossiness of the product and has low light properties. Let it be implemented.

The bulk ABS resin, for example, may be included in 5 to 20% by weight, 10 to 20% by weight, or 12 to 18% by weight based on the total weight of the composition, and within this range, all of the mechanical properties, heat resistance and moldability of the composition There is an advantage of being good and excellent in low light characteristics.

The polyethylene resin composition of the present disclosure is based on the melt index, tensile properties, and flexural properties of the conventional polyester resin composition by mixing and applying two types of bulk ABS resins having different average particle diameters or physical properties of the conjugated diene rubber in a specific ratio. It provides the advantage of improving heat resistance and implementing low light characteristics while maintaining high physical properties.

For example, the two kinds of bulk ABS resins have a first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer containing a conjugated diene rubber having an average particle diameter of 0.5 μm or more to less than 1.5 μm and an average particle diameter of 1.5 μm to 10 μm It may be a second vinyl cyan compound containing phosphorus-conjugated diene rubber-conjugated diene rubber-aromatic vinyl compound copolymer, and in this case, it provides an advantage of improving heat resistance and implementing low light characteristics while maintaining high mechanical properties of the composition.

In another example, the two kinds of bulk ABS resins have a melt index (220° C., 10 kg) of 7 g/10 min or more and a first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer and a melt index (220° C., 10 kg). It may be a second vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer having 3 g/10min or more to less than 7 g/10min, and in this case, it is possible to provide low light properties while securing high mechanical properties and heat resistance of the composition. .

In another example, the two kinds of bulk ABS resins contain a conjugated diene rubber having an average particle diameter of 0.5 µm or more to less than 1.5 µm, and a melt index (220° C., 10 kg) of 7 g/10 min or more-conjugated diene A second vinyl cyanide compound-conjugated diene containing a rubber-aromatic vinyl compound copolymer and a conjugated diene rubber having an average particle diameter of 1.5 μm to 10 μm, and a melt index (220° C., 10 kg) of 3 g/10 min or more to less than 7 g/10 min. It may be a rubber-aromatic vinyl compound copolymer.

The conjugated diene rubber of the first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer may have an average particle diameter of 0.5 μm or more to less than 1.5 μm, 0.8 to 1.3 μm, or 1 to 1.3 μm, in this case, When blended with the second copolymer, it is possible to impart low light properties while maintaining high mechanical properties of the composition.

The conjugated diene rubber of the second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer has an average particle diameter of 1.5 to 10 μm, 1.5 to 9.5 μm, 1.5 to 5 μm, 2.5 to 9.5 μm, 2.5 to 4.5 μm, for example , 2.5 to 3.5 μm, 5 to 10 μm, or 8 to 10 μm, and in this case, when applied in combination with the first copolymer, mechanical properties, moldability, and heat resistance of the final product are maintained high. Yet, it can give the product low-light properties.

In the present description, the average particle diameter refers to a value measured using an intensity Gaussian distribution by a dynamic light scattering method using a particle size distribution analyzer (Nicomp 380) unless otherwise specified.

The first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer has a melt index of 7 g/10min or more, 7 to 20 g/10min, 7 to 15 /10min, or 7 to 12 g/10min as another example. It can be characterized, and within this range, the mechanical properties of the final product are excellent, while heat resistance is improved and low light characteristics are realized.

The second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer has a melt index (220° C., 10 kg) of 3 g/10 min or more to less than 7 g/10 min or 3 to 6 g/10 min as another example Within this range, the mechanical properties of the final product can be excellent, and low light properties can be given to the product.

As described above, the composition of the present disclosure comprises the first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer and the second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer in a specific ratio, and these The weight ratio of may be preferably 1:1.5 to 1:2.5, 1:1.8 to 1:2.5 or 1:1.8 to 1:2.2, for example, mechanical properties inherent in the polyester resin composition within this range, While maintaining high moldability, heat resistance is greatly improved, and at the same time, it is possible to impart low light characteristics to the material by lowering the glossiness of the product.

The first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer and the second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer may be prepared through a conventional bulk polymerization method, and are not particularly limited. Does not. It is distinguished from emulsified ABS resin because the polymerization environment is different and does not contain residues such as emulsifiers or electrolytes.

For example, the first and second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymers are mixed by dissolving and mixing an aromatic vinyl compound, a vinyl cyan compound, and a conjugated diene rubber in a reaction solvent, and a polymerization initiator, a molecular weight regulator, etc. It may be a bulk ABS resin prepared by adding and reacting, but it should be noted that the bulk polymerization method is not limited thereto.

Preferably, the first and second copolymers may be prepared through continuous block polymerization, which is more advantageous in terms of productivity.

The vinyl cyan compound of the present disclosure may be, for example, at least one selected from acrylonitrile, methacrylonitrile and ethacrylonitrile, and preferably acrylonitrile.

The conjugated diene rubber of the present disclosure is a polymer comprising at least one conjugated diene-based compound selected from 1,3-butadiene, isoprene, chloroprene, piperylene, for example, and a polymer polymerized by optionally further including styrene, etc. It is also possible.

The aromatic vinyl compound of the present disclosure may be, for example, at least one selected from styrene, α-methyl styrene, vinyl toluene, and chlorostyrene, and preferably includes styrene.

The first copolymer of the present disclosure may be, for example, 10 to 70% by weight, 10 to 50% by weight, or 10 to 30% by weight of a conjugated diene rubber; And 30 to 90% by weight, 50 to 90% by weight, or 70 to 90% by weight of an aromatic vinyl compound and a vinyl cyan compound, and within this range, the physical property balance of the composition provides an excellent advantage.

The second copolymer of the present disclosure may include, for example, 5 to 50% by weight, 5 to 30% by weight, or 8 to 20% by weight of a conjugated diene rubber; And 50 to 95% by weight, 70 to 95% by weight, or 80 to 92% by weight of the aromatic vinyl compound and the vinyl cyanide compound, and within this range, the physical property balance of the composition provides an excellent advantage.

C) additive

The composition of the present substrate is one or more additives selected from antioxidants, lubricants, coupling agents, dyes, pigments, colorants, release agents, antistatic agents, antibacterial agents, processing aids, metal deactivators, inhibitors, anti-drip agents, anti-friction agents and anti-wear agents Includes.

The additive may be included in an amount of 0.01 to 5% by weight, 0.05 to 3% by weight, 0.1 to 2% by weight, or 0.5 to 1% by weight based on the total weight of the composition, and within this range, a polyester-based resin-specific machine Without deteriorating the physical properties and heat resistance, while exhibiting low light properties, the effect of the additive formulation can be implemented.

Preferably, the additive may necessarily contain one or more of an antioxidant, a lubricant, and a coupling agent, and more preferably, all of them. In this case, there is an advantage in that the composition has excellent mechanical properties, heat resistance, and moldability, while low-light properties are realized.

When an antioxidant is included as an additive, the content thereof may be 0.1 to 0.5% by weight, 0.1 to 0.4% by weight, or 0.2 to 0.3% by weight based on the total weight of the composition. Within this range, the composition has excellent physical property balance and heat And light-stable characteristics.

When a lubricant is included as an additive, the content thereof may be 0.1 to 1% by weight, 0.2 to 0.8% by weight, or 0.3 to 0.5% by weight based on the total weight of the composition, and within this range, the composition has excellent physical property balance and is easy to process. It provides an easy advantage.

When a coupling agent is included as an additive, the content thereof may be 0.01 to 0.2% by weight, 0.03 to 0.1% by weight or 0.05 to 0.07% by weight, based on the total weight of the composition, and in this case, by inhibiting hydrolysis between the polyester resins Overall physical properties such as mechanical properties, heat resistance, and moldability can be maintained high.

The coupling agent may be, for example, a carbodiimide-based compound, and specifically, may be at least one selected from aromatic carbodiimide, aliphatic carbodiimide, or polycarbodiimide, which promotes hydrolysis of polyester resin. It contributes to improvement and maintenance of physical properties by suppressing the reaction of the carboxyl group at the end of the polyester resin.

In addition, it may optionally include a colorant as needed, in this case, the content thereof may be 0.01 to 3% by weight or 0.5 to 2% by weight or 0.8 to 1.5% by weight based on the total weight of the composition, within this range It provides the advantage of easy coloring without deteriorating the mechanical properties of the composition.

It may be preferable to use a master batch using a polyester-based resin as a carrier resin in terms of easily dispersing the colorant in the composition.

D) Quencher

In order to realize the low-light properties of the composition of the present substrate, two types of bulk ABS resins having different physical properties are mixed in a specific ratio, and if necessary, a matting agent may be mixed together.

The matting agent acts on the surface of the final product to roughen the surface to induce diffuse reflection, thereby lowering the product surface gloss, thereby making the material have matte properties.

The matting agent may be included in an example of 2 to 15% by weight, 3 to 10% by weight, 3 to 8% by weight, or 5 to 8% by weight based on the total weight of the composition, and within this range, the heat resistance or moldability of the composition There is an advantage that the light does not deteriorate and low light characteristics are implemented.

The matting agent may be, for example, an organic polymer matting agent, and in this case, the final product may have excellent mechanical strength such as heat resistance and low light characteristics may be effectively implemented.

The organic polymer matting agent may be, for example, a spherical polymer bead, and in this case, the matting effect is excellent.

The form of the matting agent can be confirmed through microscopic analysis as an example.

For example, the organic polymer matting agent may be a polymer or a copolymer of an aromatic vinyl compound, and specifically, a graft copolymer of polystyrene, polystyrene and an acrylonitrile-styrene copolymer, and a crosslinked styrene-acrylonitrile copolymer And the like may be possible, and in this case, the heat resistance or moldability of the final product may be excellent, and low light characteristics may be effectively implemented.

The organic polymer matting agent may have an average particle diameter of 1 to 20 μm, for example, and excellent moldability within this range, while inducing diffuse reflection on the product surface, may effectively implement low light characteristics.

The average particle diameter of the quencher is, for example, a value measured by a dynamic scattering method using a particle size analyzer or through an electron microscope analysis.

The organic polymer matting agent may have a weight average molecular weight of 1 million to 10 million g/mol or 2 million to 8 million g/mol, for example, and induce diffuse reflection on the product surface within this range to effectively implement low light characteristics. I can.

In the present description, the weight average molecular weight is a value measured using gel permeation chromatography unless otherwise specified.

E) Inorganic filler

The composition of the present disclosure may be formulated with an inorganic filler to prevent mechanical strength from being lowered while implementing the low-light properties of the material, and to improve heat resistance and processability.

The inorganic filler may be included in an amount of 2 to 10% by weight, 3 to 8% by weight, or 4 to 6% by weight based on the total weight of the composition, and within this range, while maintaining high molding processability, heat resistance is improved and low light properties There is this excellent advantage.

In particular, when the resin composition of the present disclosure contains an inorganic filler within the above range, even if a matting agent is not mixed, that is, a matting agent-free (fee) composition provides a considerably excellent advantage of low light properties, and in addition to mechanical strength , Heat resistance, and workability can provide excellent effects.

The inorganic filler may be one or more selected from talc, mica, glass fiber, glass beads, glass flakes, calcium carbonate, calcium sulfate, magnesium oxide, calcium stearate, silica, calcium silicate, and clay, and preferably talc. It includes.

The inorganic filler may have an average particle diameter of 1 to 10 μm and 2 to 4 μm, for example, and may be preferably 1 to 3 μm in terms of improving physical properties.

The average particle diameter of the inorganic filler is, for example, a value measured by a dynamic light scattering method using a particle size analyzer.

The composition of the present disclosure including the constituents within a specific content range has a heat deflection temperature (4.6kgf) of 140°C or higher, 140 to 200°C, 150 to 200°C, 160 to 200°C, 170 to 200°C, 175 To 200°C, 180 to 200°C, while excellent in heat resistance, a glossiness (60°) of 70 or less, 69 or less, or 64 or less, for example, may provide an advantage of excellent low light characteristics.

The composition of the present disclosure provides an advantage in that mechanical strength, heat resistance, and moldability are excellent in a specific composition, and an excellent low-light effect is realized even without mixing a matting agent. In the following matting agent-free composition, technical features are common to parts excluding the composition of the present disclosure and the matting agent described above, and descriptions overlapping with the above are omitted.

The composition of the present substrate may include 70 to 90% by weight of a polyester resin; 5 to 20% by weight of bulk ABS resin; 2 to 10% by weight of inorganic filler; 0.1 to 0.5% by weight of antioxidant; 0.1 to 1% by weight of lubricant; 0.01 to 0.2% by weight of a coupling agent; And 0.01 to 3% by weight of a colorant, wherein the bulk ABS resin includes a first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer and an average particle diameter of 0.5 μm or more to less than 1.5 μm. A second vinyl cyan compound containing a conjugated diene rubber having a particle diameter of 1.5 μm to 10 μm-conjugated diene rubber-aromatic vinyl compound copolymer in a weight ratio of 1:1.5 to 1:2.5, and matting agent-free It can be characterized by being.

In this case, the composition has excellent moldability and mechanical strength, but has a melt index (250°C, load 2.16 kg) of 30 to 45 g/10min, 35 to 45 g/10min, or 38 to 42 g/10min. And, the heat deflection temperature (4.6kgf) is 165 ℃ or more, 165 to 200 ℃, 175 to 200 ℃ or 180 to 200 ℃, for example, shows significantly improved heat resistance, gloss (60°) is 65 or less, for example, Low light properties of 64.5 or less or 60 or less also provide superior advantages.

Hereinafter, a method of preparing the low-light polyester resin composition of the present disclosure will be described. The manufacturing method described below includes all the technical features of the above-described composition, and therefore, descriptions of the overlapping portions will be omitted.

The method for preparing the composition according to the present disclosure includes, for example, 70 to 90% by weight of a polyester resin; 5 to 20% by weight of bulk ABS resin; 0.01 to 5% by weight of additives; Including the step of kneading and extruding, including 0 to 15% by weight of a matting agent and 0 to 10% by weight of an inorganic filler, wherein the bulk ABS resin is a first vinyl containing a conjugated diene rubber of 0.5㎛ or more to less than 1.5㎛ A cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer and a second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer comprising a conjugated diene rubber having an average particle diameter of 1.5 μm to 10 μm are prepared from 1:1.5 to 1: It is included in a weight ratio of 2.5, and at least one of the matting agent and the inorganic filler is necessarily included.

The kneading and extrusion may be performed at 200 to 280°C or 220 to 280°C using a twin screw extruder as an example, and within this range there is no side reaction such as decomposition of the resin component, and the composition may be uniformly kneaded.

Furthermore, the composition prepared as described above may be molded by a method suitable for use, such as injection molding, and provided as a molded article.

The injection may be performed at 200 to 280°C or 220 to 280°C, for example, but is not limited thereto.

The molded article of the present disclosure can be used for various purposes, such as a housing of a home appliance, an automotive exterior material, and in particular, has excellent heat resistance and mechanical strength, and thus provides suitable properties as an automotive exterior material.

As a more specific example, the molded article may be used as a bezel among lamp components of automobiles whose appearance is important as they have excellent mechanical properties and heat resistance and have low light characteristics.

In describing the composition, manufacturing method, and molded article of the present disclosure, other conditions or equipment that are not explicitly described may be appropriately selected within the range commonly practiced in the art, and are not particularly limited.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It is natural that such modifications and modifications fall within the appended claims.

Materials used in the following Examples and Comparative Examples are as follows.

A) Polyester resin

a1) Polybutylene terephthalate resin having an intrinsic viscosity of 1.00 dl/g was used.

a2) Polybutylene terephthalate resin having an intrinsic viscosity of 0.83 dl/g was used.

B) bulk ABS resin

b1) An acrylonitrile-butadiene-styrene copolymer prepared by bulk polymerization including 14% by weight of butadiene rubber having an average particle diameter of 1.2 µm and having a melt index (220°C, 10kg) of 7.0 g/10min was used.

b2) An acrylonitrile-butadiene-styrene copolymer prepared by bulk polymerization including 9% by weight of butadiene rubber having an average particle diameter of 10 μm and having a melt index (220° C., 10 kg) of 5 g/10 min was used.

b3) An acrylonitrile-butadiene-styrene copolymer prepared by bulk polymerization including 18% by weight of butadiene rubber having an average particle diameter of 2.5 to 3.5 μm and having a melt index (220° C., 10 kg) of 5 g/10 min was used. .

B') MBS resin

As a methacrylate-butadiene-styrene copolymer, an EM520 product manufactured by LG Chem was used.

C) additive

c1) Antioxidant: pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate] was used.

c2) Lubricant: A pentaerythritol ester-based or montanic acid-based lubricant was used.

c3) Coupling agent: A polycarbodiimide compound having a weight average molecular weight of about 3000 g/mol was used.

c4) Colorant: A carbon black master batch in which carbon black was dispersed in a polybutylene terephthalate carrier resin at a concentration of 20% by weight was used.

D) matting agent

As a polystyrene bead, Xphere NGR product of Posera Co., Ltd. was used.

E) Inorganic filler

e1) Talc having an average particle diameter of about 4.0 μm was used.

e2) Talc having an average particle diameter of about 2.0 μm was used.

[Example]

Example 1 to 3 and Comparative example 1 to 12

After mixing each component as shown in Tables 1, 2, and 3 using a supermixer, melting and kneading at a temperature range of 200 to 280°C using a twin screw extruder, and extrusion processing the polyester resin composition Was obtained in the form of a pellet. After drying the pellets at 120° C. for 8 hours or more, an injection molded article was manufactured by molding at an injection temperature of 200 to 280° C. and a mold temperature of 60 to 100° C. using an 80MT ENGEL injection machine.

[Test Example]

The physical properties of the injection molded articles manufactured in Examples and Comparative Examples were measured by the following method, and the results are shown in Tables 1, 2, and 3 below.

* Heat Deflection Temperature (HDT): Measured under conditions of 4.6kgf load by the method specified in ASTM D648. At this time, a specimen having a thickness of 6.4 mm was used.

* Specific gravity: It was measured according to the method specified in ASTM D792.

* Melt Index (MI): Measured under conditions of 250°C and a load of 2.16kg according to the method specified in ASTM D1238.

* Tensile strength: measured under the condition of tensile speed = 5mm/min according to the method specified in ASTM D638 At this time, a specimen having a thickness of 6.4 mm was used.

* Flexural modulus: It was measured under the conditions of span = 100mm and test speed = 5mm/min according to the method specified in ASTM D790. At this time, a specimen having a thickness of 6.4 mm was used.

* Glossiness: Using a glossmeter, the glossiness was measured at an angle of 60° for a 2mm-thick specimen.

As shown in Table 1, in the case of Examples 1 to 3, which are blended in the composition ratio according to the present invention, the melt index and specific gravity are appropriate, providing the advantage of easy molding and processing, and excellent tensile strength and flexural modulus. I can confirm. Above all, it was confirmed that Examples 1 to 3 exhibited low light characteristics while exhibiting physical properties equivalent to or better than those of the conventional composition (Comparative Example 1) due to excellent heat distortion temperature and low gloss.

In particular, in the case of Examples 2 and 3 of the present application, even though it does not contain a matting agent, it shows the same or much lower level of gloss as Comparative Examples 2 to 6 including the same, and it is confirmed that a low-gloss material can be implemented without the addition of a matting agent. Could

In addition, as in Comparative Examples 2 to 5, when the mixing ratio of the two bulk ABS resins is out of the scope of the present invention, the heat deflection temperature is not satisfactory, or the gloss is high, so that the low-light characteristics of the present application cannot be expressed. It can be seen that, in the case of Comparative Example 2, it was confirmed that the melt index was too low and the moldability and processability were poor.

In addition, when two types of bulk ABS resins are not mixed, and only one type of bulk ABS resin is mixed as in Comparative Examples 6 to 10, it can be confirmed that low light properties are not implemented, and the physical property balance is poor compared to the examples. I could confirm that.

In addition, in the case of Comparative Examples 11 and 12 in which MBS resin was applied instead of bulk ABS resin, it was confirmed that low-light characteristics were not realized due to high gloss, and mechanical properties such as tensile strength and flexural modulus were uneven.

In summary, when the above experimental results are mixed and applied in a specific ratio of two specific bulk ABS resins, while maintaining high mechanical strength, it is possible to simultaneously secure moldability, heat resistance and low light characteristics, and in particular, no matting agent is added. Even excellent low-light characteristics can be implemented.

Claims (15)

75 to 85% by weight of a polyester resin; 10 to 20% by weight of bulk ABS resin; 0.1 to 2% by weight of additives; And 3 to 8% by weight of inorganic filler; including,
The bulk ABS resin contains a conjugated diene rubber having an average particle diameter of 0.8 to 1.3 µm and a melt index (220° C., 10 kg) of 7 to 12 g/10 min. The first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer A second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer containing a conjugated diene rubber having a coalescence and an average particle diameter of 2.5 μm to 10 μm and having a melt index (220° C., 10 kg) of 3 to 6 g/10 min. Included in a weight ratio of :1.8 to 1:2.5,
The polyester-based resin is polybutylene terephthalate having an intrinsic viscosity of 0.5 to 1.5 dl/g,
Quencher-free, characterized in that
Low-light polyester resin composition. delete The method of claim 1,
The additive comprises at least one selected from antioxidants, lubricants, coupling agents, dyes, pigments, colorants, release agents, antistatic agents, antibacterial agents, processing aids, metal deactivators, inhibitors, anti-drip agents, anti-friction agents, and anti-wear agents. Characterized by
Low-light polyester resin composition. The method of claim 3,
The antioxidant, characterized in that contained in 0.1 to 0.5% by weight based on the total weight of the composition
Low-light polyester resin composition. The method of claim 3,
The lubricant, characterized in that contained in 0.1 to 1% by weight based on the total weight of the composition
Low-light polyester resin composition. The method of claim 3,
The coupling agent, characterized in that contained in 0.01 to 0.2% by weight based on the total weight of the composition
Low-light polyester resin composition. The method of claim 6,
The coupling agent is characterized in that the carbodiimide-based compound
Low-light polyester resin composition. The method of claim 3,
The colorant, characterized in that it is contained in an amount of 0.01 to 3% by weight based on the total weight of the composition
Low-light polyester resin composition. delete delete The method of claim 1,
The composition has a melt index (250°C, load 2.16kg) of 30 to 45 g/10min, a heat deflection temperature (4.6kgf) of 140°C or higher, and a glossiness (60°) of 70 or less.
Low-light polyester resin composition. delete delete 75 to 85% by weight of a polyester resin; 10 to 20% by weight of bulk ABS resin; 0.1 to 2% by weight of additives; And Inorganic filler 0.1 to 2% by weight; Including the step of kneading and extruding,
The bulk ABS resin contains a conjugated diene rubber having an average particle diameter of 0.8 to 1.3 µm and a melt index (220° C., 10 kg) of 7 to 12 g/10 min. The first vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer A second vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound copolymer containing a conjugated diene rubber having a coalescence and an average particle diameter of 2.5 μm to 10 μm and having a melt index (220° C., 10 kg) of 3 to 6 g/10 min. Included in a weight ratio of :1.8 to 1:2.5,
The polyester-based resin is polybutylene terephthalate having an intrinsic viscosity of 0.5 to 1.5 dl/g,
Quencher-free, characterized in that
A method for producing a low-light polyester resin composition. A molded article comprising the low-light polyester resin composition of any one of claims 1, 3 to 8, and 11.