KR20210043307A - Thermoplastic resin composition, method for preparing the composition and molding products comprising the composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, a method for preparing the same and a molded article including the same. Particularly, the thermoplastic resin composition includes: 100 parts by weight of a base resin including (A) 5-70 wt% of a first graft copolymer including acrylate rubber having an average particle diameter of 50-200 nm as a core, (B) 10-70 wt% of a second graft copolymer including acrylate rubber having an average particle diameter of larger than 200 nm and equal to or smaller than 900 nm as a core, and (C) 20-80 wt% of an aromatic vinyl compound-vinyl cyanide compound copolymer; and (D) 0.5-4 parts by weight of a compound represented by Chemical Formula 1. The thermoplastic resin composition shows excellent impact strength and tensile strength and a suitable flow index, and thus allows easy injection molding into various shapes with no complicated processing steps. In Chemical Formula 1, S represents sulfur, each of R_1 and R_2 independently represents a C8-C20 alkyl group, and n is an integer of 2-5.

Description

Thermoplastic resin composition, its manufacturing method, and molded products including the same TECHNICAL FIELD [THERMOPLASTIC RESIN COMPOSITION, METHOD FOR PREPARING THE COMPOSITION AND MOLDING PRODUCTS COMPRISING THE COMPOSITION}

The present invention relates to a thermoplastic resin composition, a method of manufacturing the same, and a molded article including the same, and more particularly, a specific sulfide-based compound is included in a specific content to simultaneously satisfy impact strength and tensile strength, and in various shapes without complicated process steps. It relates to a thermoplastic resin composition for easy injection molding, a method for manufacturing the same, and a molded article including the same.

In general, ABS (acrylonitrile-butadiene-styrene) resin has excellent impact resistance and excellent processability, so it can be applied to various uses such as automobiles, electric and electronic devices, office equipment, home appliances, toys, and stationery, and is widely used.

However, the ABS resin is easily oxidized by oxygen, ultraviolet rays, light, and heat due to the double bond of the butadiene rubber in the resin, resulting in deterioration of weather resistance and chemical resistance, such as discoloration of the resin, and thus the appearance quality of the interior and exterior materials to which the resin is applied. This deteriorated, resulting in a problem of not satisfying the level of demands of consumers.

In order to solve this problem, in the art, instead of ABS resin, ASA (acrylonitrile-styrene-acrylate) resin was used to improve weather resistance and chemical resistance, which are the biggest drawbacks of ABS resin. As an example, the ASA resin has the advantage of being able to omit the painting process for improving weather resistance and chemical resistance because there is little change in the physical properties of the product and the appearance of the molded product even when it is used outdoors or exposed to chemicals for a long time.

With such advantages, ASA resin is used in a variety of fields such as automobiles, leisure goods, and construction materials, and especially in the field of building materials such as floors, siding, doors, and desks, and in the field of household goods, it is highly recommended by customers for luxurious finishes and eco-friendly materials. The usage is increasing rapidly.

However, conventional ASA resins are not satisfactory in fluidity that allows them to be manufactured into various products without limitation in shape, and it has been difficult to simultaneously satisfy impact strength and tensile strength. When the polymerization conditions are controlled, there has been a problem that the manufacturing process becomes complicated.

Accordingly, there is a need for a thermoplastic resin having improved impact strength and tensile strength without involving complicated process steps, and having easy flowability for injection molding into various shapes.

Korean Patent Registration No. 10-0815995

In order to solve the problems of the prior art as described above, the present invention is a thermoplastic resin composition having a flow index suitable for injection molding, easy injection molding in various shapes, and excellent in both impact strength and tensile strength, a method of manufacturing the same, and a molded article including the same. It aims to provide.

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 (A) 5 to 70% by weight of a first graft copolymer having an acrylate-based rubber as a core having an average particle diameter of 50 to 200 nm, (B) an average particle diameter of 200 nm 100 parts by weight of a base resin comprising 10 to 70% by weight of a second graft copolymer having an acrylate-based rubber having a core of greater than to 900 nm and 20 to 80% by weight of (C) an aromatic vinyl compound-vinyl cyan compound copolymer ; And (D) 0.5 to 4 parts by weight of the compound represented by the following formula (1); It provides a thermoplastic resin composition comprising a.

[Formula 1]

(In Formula 1, S is sulfur, R ₁ , R ₂ are independently an alkyl group having 8 to 20 carbon atoms, and n is an integer of 2 to 5)

In addition, the present invention is (A) 5 to 70% by weight of a first graft copolymer having an acrylate-based rubber having an average particle diameter of 50 to 200 nm as a core, (B) an acrylate having an average particle diameter of more than 200 nm to 900 nm or less 100 parts by weight of a base resin including 10 to 70% by weight of a second graft copolymer having a rubber as a core and 20 to 80% by weight of (C) an aromatic vinyl compound-vinyl cyan compound copolymer; And (D) 0.5 to 4 parts by weight of the compound represented by Chemical Formula 1; including kneading and extruding under conditions of 200 to 300 °C and 100 to 300 rpm. to provide.

In addition, the present invention provides a molded article comprising the thermoplastic resin composition.

According to the present invention, there is an effect of providing a thermoplastic resin composition having a flow index suitable for injection molding and excellent in both impact strength and tensile strength, a manufacturing method thereof, and a molded article including the same.

Hereinafter, the thermoplastic resin composition of the present disclosure, a method of manufacturing the same, and a molded article including the same will be described in detail.

When the present inventors contain two kinds of graft copolymers, aromatic vinyl compound-vinyl cyan compound copolymer resin, and a compound represented by the following formula (1) within a specific content range of different average particle diameters of rubber, the impact strength and tensile strength are It was confirmed that the improved and adequate flow index provided the advantage of easy injection molding in various shapes with only a simple process, and based on this, the present invention was completed.

The thermoplastic resin composition of the present invention comprises (A) 5 to 70% by weight of a first graft copolymer having an acrylate-based rubber having an average particle diameter of 50 to 200 nm as a core, (B) an average particle diameter of more than 200 nm to 900 nm 100 parts by weight of a base resin including 10 to 70% by weight of a second graft copolymer having the following acrylate-based rubber as a core and 20 to 80% by weight of (C) an aromatic vinyl compound-vinyl cyan compound copolymer; And (D) 0.5 to 4 parts by weight of the compound represented by the following formula (1), and in this case, the impact strength and tensile strength are improved and the fluidity is appropriate, so that injection molding into various shapes is easy. have.

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

(A) the first Graft Copolymer

The (A) first graft copolymer may include, for example, an acrylate-based rubber having an average particle diameter of 50 to 200 nm, preferably 60 to 200 nm, more preferably 100 to 180 nm, as a core, This range is smaller than the visible light wavelength range and has the advantage of providing a thermoplastic resin composition having excellent gloss and excellent both impact strength and tensile strength due to less light scattering.

In the present description, the average particle diameter represents a value measured using an intensity Gaussian distribution in a dynamic light scattering method using a particle size distribution analyzer (Nicomp 380) in a latex state.

The (A) first graft copolymer may include, for example, 10 to 70% by weight of an aromatic vinyl compound and 5 to 50% by weight of a vinyl cyan compound in 20 to 80% by weight of an acrylate-based rubber, and in this case It has excellent chemical properties, adequate fluidity, and excellent impact resistance.

In another example, the (A) first graft copolymer may include 20 to 50% by weight of an aromatic vinyl compound and 10 to 30% by weight of a vinyl cyan compound in 30 to 60% by weight of an acrylate-based rubber, Within the range, it has excellent impact resistance and weather resistance, and has an appropriate effect of fluidity.

The (A) first graft copolymer may include, for example, 20 to 80% by weight, 30 to 60% by weight, or 40 to 55% by weight of an acrylate-based rubber based on 100% by weight of the first graft copolymer. In this case, the impact strength and tensile strength are improved.

The acrylate rubber may be, for example, an alkyl acrylate rubber, and the alkyl acrylate rubber may be, for example, an acrylate rubber having 1 to 10 carbon atoms of the alkyl group, preferably methyl acrylate rubber, ethyl acrylate. It may be one or more selected from the group consisting of rubber, butyl acrylate rubber, and ethylhexyl acrylate rubber.

The (A) first graft copolymer may include, for example, 10 to 70% by weight, 20 to 70% by weight, or 20 to 50% by weight of an aromatic vinyl compound based on 100% by weight of the first graft copolymer. In this case, there is an effect of excellent impact resistance and easy injection molding into various shapes.

The aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, 2,4-dimethyl styrene, vinyltoluene, t-butylstyrene, and chlorostyrene, and preferably styrene.

The (A) first graft copolymer may include, for example, 5 to 50% by weight, 10 to 30% by weight, or 15 to 25% by weight of a vinyl cyan compound based on 100% by weight of the first graft copolymer. In this case, the fluidity is appropriate, so that the processability is excellent, and mechanical properties such as impact resistance are excellent.

The vinyl cyan compound may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, for example, and in this case, both impact resistance and processability are excellent.

The (A) first graft copolymer may be, for example, 5 to 70% by weight, 10 to 70% by weight, or 5 to 30% by weight, more preferably 7 to 25% by weight based on 100% by weight of the base resin. %, and more preferably 10 to 20% by weight, and within this range, both fluidity, tensile strength, and impact strength have excellent effects.

When the (A) first graft copolymer is less than the above range, the impact strength is greatly reduced, and when the first graft copolymer is less than the above range, the fluidity decreases, resulting in a problem of poor processability.

The (A) first graft copolymer may be prepared by emulsion polymerization as an example, and in this case, chemical resistance, weather resistance, fluidity, tensile strength and impact strength are excellent.

The emulsion polymerization is not particularly limited in the case of using the emulsion graft polymerization method commonly carried out in the technical field to which the present invention belongs.

(B) the second Graft Copolymer

The (B) second graft copolymer includes an acrylate-based rubber having an average particle diameter of more than 200 nm to 900 nm, preferably 300 to 800 nm, more preferably 400 to 600 nm, as a core. In this range, not only impact resistance but also flexural strength is excellent.

The (B) second graft copolymer may include 10 to 60% by weight of an aromatic vinyl compound and 5 to 40% by weight of a vinyl cyan compound in 10 to 80% by weight of an acrylate-based rubber, and within this range. It has excellent impact resistance and weather resistance, and has an appropriate effect of fluidity.

In another example, the (B) second graft copolymer may include 20 to 40% by weight of an aromatic vinyl compound and 10 to 30% by weight of a vinyl cyan compound in 40 to 60% by weight of an acrylate-based rubber, and Within the range, it has excellent weather resistance, improved mechanical properties such as tensile strength and impact strength, and has good processability due to proper fluidity.

The (B) second graft copolymer includes, for example, 10 to 80% by weight, 40 to 60% by weight, or 45 to 55% by weight of an acrylate-based rubber core based on 100% by weight of the second graft copolymer. In this range, impact strength and tensile strength are improved.

The (B) second graft copolymer may include, for example, 10 to 60% by weight, 20 to 40% by weight, or 25 to 35% by weight of an aromatic vinyl compound based on 100% by weight of the second graft copolymer. In addition, within this range, the fluidity is appropriate, so that injection molding into various shapes is easy.

The (B) second graft copolymer may include, for example, 5 to 40% by weight, 10 to 30% by weight, or 15 to 25% by weight of a vinyl cyan compound based on 100% by weight of the second graft copolymer. In this case, there are excellent effects in both impact resistance, tensile strength and workability.

The (B) second graft copolymer may be, for example, 10 to 70% by weight, 10 to 50% by weight, or 15 to 35% by weight, preferably 25 to 30% by weight based on 100% by weight of the base resin. If it is less than the content range, the impact strength is lowered, and when the content is more than the content range, the graft rate is lowered, thereby reducing hardness and scratch resistance.

The types of the acrylate rubber, aromatic vinyl compound, and vinyl cyan compound included in the (B) second graft copolymer are acrylate rubber and aromatic vinyl included in the (A) first graft copolymer of the present disclosure. It may be within the same range as the kind of the compound and the vinyl cyanide compound.

The (B) second graft copolymer may be prepared by emulsion polymerization as an example, and in this case, it has excellent effects in weather resistance, fluidity, tensile strength and impact strength.

The emulsion polymerization is not particularly limited in the case of using the emulsion graft polymerization method commonly carried out in the technical field to which the present invention belongs.

The (A) first graft copolymer may be included in an amount less than that of the (B) second graft copolymer, and as a specific example, (A) the first graft copolymer and (B) the second graft copolymer The weight ratio of the T copolymer may be 1:1.1 to 1:5, or 1:1.15 to 1:4, preferably 1:1.5 to 1:3, and within this range, flowability is appropriate and processability It has excellent tensile strength and impact strength at the same time and has excellent effects.

The total content of the acrylate rubber of the (A) first graft copolymer and the (B) second graft copolymer is, for example, (A) the first graft copolymer and (B) the second graft copolymer. It may be 10 to 30% by weight, 10 to 25% by weight, 15 to 20% by weight, or 18 to 25% by weight based on the total weight of the coalescence and (C) aromatic vinyl compound-vinyl cyan compound copolymer, and within this range It has excellent weather resistance and mechanical properties.

(C) Aromatic vinyl compound-vinyl cyan compound copolymer

The (C) aromatic vinyl compound-vinyl cyan compound copolymer may have, for example, a weight average molecular weight of 50,000 to 200,000 g/mol, or 70,000 to 190,000 g/mol, preferably 100,000 to 180,000 g/mol, and , In this range, the fluidity is appropriate, so that the processability is excellent and the impact resistance is excellent.

The weight average molecular weight of the (C) aromatic vinyl compound-vinyl cyan compound copolymer can be easily adjusted by adding a molecular weight control agent, for example, and the molecular weight control agent is, for example, tertiary dodecyl mercaptan (TDDM), n-dode It may be one or more selected from the group consisting of real mercaptan (NDDM), n-octyl mercaptan, and carbon tetrachloride, and in this case, the processability of the composition is improved by adjusting the weight average molecular weight of the aromatic vinyl compound-vinyl cyan compound copolymer. It works.

In the present description, the weight average molecular weight is prepared by dissolving 1 g of a copolymer in tetrahydrofuran (THF) at a temperature of 40° C., unless otherwise defined, and then measured using gel chromophorography (GPC) filled with porous silica. I can. At this time, the molecular weight is measured after calibration using polystyrene (PS) as a standard material.

The (C) aromatic vinyl compound-vinyl cyan compound copolymer may be made of, for example, two or more aromatic vinyl compound-vinyl cyan compound copolymers having different weight average molecular weights, and in this case, while having a flow index suitable for injection molding, impact Both strength and tensile strength have excellent effects.

In a specific example, the (C) aromatic vinyl compound-vinyl cyan compound copolymer contains two or more aromatic vinyl compound-vinyl cyan compound copolymers having different weight average molecular weights, respectively, from 10 to 50% by weight and 15% based on 100% by weight of the base resin. It may be included in to 40% by weight, 30 to 45% by weight, or 15 to 25% by weight, and within this range, there is an effect of excellent impact resistance and easy injection molding into various shapes.

The (C) aromatic vinyl compound-vinyl cyan compound copolymer may include, for example, 20 to 80% by weight, 30 to 70% by weight, or 50 to 65% by weight based on 100% by weight of the base resin, and within this range The impact strength and tensile strength are improved and the flow index is appropriate, so there is an effect of excellent workability.

The (C) aromatic vinyl compound-vinyl cyan compound copolymer may be prepared by solution polymerization or bulk polymerization, and in this case, heat resistance and fluidity are excellent.

The solution polymerization and block polymerization are not particularly limited when each of the solution polymerization and block polymerization methods commonly performed in the technical field to which the present invention pertains is used.

The base resin of the present substrate is preferably (A) 5 to 30% by weight of the first graft copolymer, (B) 10 to 50% by weight of the second graft copolymer, and (C) based on the total 100% by weight of the base resin. The aromatic vinyl compound-vinyl cyan compound copolymer may contain 20 to 80% by weight, and within this range, the impact strength and tensile strength are excellent.

In another example, the base resin is based on 100% by weight of the total base resin, (A) 30 to 80% by weight of the total of the first graft copolymer and (B) the second graft copolymer, and (C) an aromatic vinyl compound -It may contain 20 to 70% by weight of the vinyl cyan compound copolymer, and within this range, processing is easy, and impact strength and tensile strength are improved.

In a preferred example, the base resin is (A) 30 to 45% by weight of the sum of the first graft copolymer and (B) the second graft copolymer and (C) an aromatic vinyl compound based on 100% by weight of the total base resin- It may contain 55 to 70% by weight of the vinyl cyan compound copolymer, and within this range, the impact strength and tensile strength are improved, and the flow index is appropriate, so that the processability is excellent.

(D) compound represented by formula (1)

The thermoplastic resin composition of the present disclosure may preferably include a compound represented by the following formula (1), and in this case, the impact strength and tensile strength are improved and the flow index is appropriate, making it easy to injection molding into various shapes without complicated process steps. It works.

[Formula 1]

(In Formula 1, S is sulfur, R ₁ , R ₂ are independently an alkyl group having 8 to 20 carbon atoms, and n is an integer of 2 to 5)

For example, in Formula 1, R ₁ , R ₂ are independently an alkyl group having 9 to 15 carbon atoms, and n may be 2, 3 or 4, and in this case, while providing an advantage of easy injection molding, impact strength and tensile strength There is an effect that is further improved.

In another preferred example, the compound represented by Formula 1 is di-n-nonyl trisulfide, di-t-nonyl trisulfide, di-n-decyl Di-n-decyl trisulfide, di-n-undecyl trisulfide, di-n-dodecyl trisulfide and di-tert-dode It may be one or more selected from the group consisting of di-tert-dodecyl trisulfide, and in this case, the impact strength and tensile strength are quite excellent, and the fluidity is adequate, making it easy to injection molding into various shapes without complicated process steps. There is.

(D) The compound represented by Formula 1 may preferably be 0.5 to 4 parts by weight based on 100 parts by weight of the base resin, and if it is less than the above range, the impact strength and flow index are not simultaneously improved, and in particular, the flow index is not appropriate. There is a disadvantage in that the injection moldability is poor, and if it exceeds the above range, there is a problem that the tensile strength is greatly reduced.

In a more preferred example, (D) the compound represented by Formula 1 may be 1 to 3 parts by weight, or 1 to 2 parts by weight based on 100 parts by weight of the base resin, and the flow index within this range is appropriate, so injection molding is easy. The impact strength is improved, so the impact resistance of the molded product is improved, and the tensile strength is excellent.

The thermoplastic resin composition of the present disclosure is, for example, a UV stabilizer, an antioxidant, an optical brightener, a chain extender, a release agent, a pigment, a dye, an antibacterial agent, a processing aid, a metal deactivator, an inorganic filler, a glass fiber, an anti-friction agent, and an anti-wear agent. It may further include one or more additives selected from the group consisting of, for example, the additive may be 0.1 to 5 parts by weight, or 0.1 to 3 parts by weight based on 100 parts by weight of the base resin, in this case, excellent physical properties improvement and manufacturing Low cost has excellent economical effects.

The antioxidant may be, for example, 0.01 to 2 parts by weight based on 100 parts by weight of the total content of (A) the first graft, (B) the second graft, and (C) the aromatic vinyl compound-vinyl cyan compound copolymer, preferably It may be 0.5 to 1.5 parts by weight, more preferably, it may be one containing 0.3 to 0.7 parts by weight of each of the two antioxidants, within this range, without impairing the impact strength and fluidity, the antioxidant effect is completely There is an advantage to be expressed.

The UV stabilizer may be 0.01 to 2 parts by weight based on 100 parts by weight of the total content of (A) the first graft, (B) the second graft and (C) an aromatic vinyl compound-vinyl cyan compound copolymer, and is preferably Preferably, it may be 0.5 to 1.5 parts by weight, and more preferably, it may include 0.3 to 0.7 parts by weight of each of the two UV stabilizers, and within this range, there is an effect of maintaining adequate fluidity without deteriorating mechanical properties. have.

The thermoplastic resin composition of the present disclosure may have, for example, a flow index (220° C., 10 kg) of 8 to 30 g/10min, 10 to 25 g/10min, or 12 to 25 g/10min, and has a flowability within this range. Excellent, can provide the advantage of easy injection molding into a variety of shapes.

The thermoplastic resin composition of the present disclosure has an Izod impact strength (1/4 inch, 23° C.) measured according to ASTM D256, for example, of 22 kgf·cm/cm or more, 23 to 40 kgf·cm/cm, or 23 to 30 kgf It may be cm/cm, and there is an effect excellent in impact resistance within this range.

The thermoplastic resin composition of the present disclosure may have a tensile strength of 400 kgf/cm ² or more, 400 to 500 kgf/cm ² , or 410 to 480 kgf/cm ² , as measured according to ASTM D638, for example, and within this range Excellent mechanical properties.

Hereinafter, a method for preparing the thermoplastic resin composition of the present invention and a molded article including the composition will be described. In describing the method of manufacturing the thermoplastic resin composition of the present invention and a molded article including the composition, all the contents of the above-described thermoplastic resin composition are included.

The manufacturing method of the thermoplastic resin composition of the present disclosure includes, for example, (A) 5 to 70% by weight of a first graft copolymer having an acrylate-based rubber having an average particle diameter of 50 to 200 nm as a core, and (B) an average particle diameter of 200 100% by weight of a base resin comprising 10 to 70% by weight of a second graft copolymer having an acrylate-based rubber having a core of greater than nm to 900 nm and 20 to 80% by weight of (C) an aromatic vinyl compound-vinyl cyan compound copolymer part; And (D) 0.5 to 4 parts by weight of a compound represented by the following Formula 1; Including a step of kneading and extruding under conditions of 200 to 300 °C and 100 to 300 rpm, in this case, the impact strength and tensile strength The improved and adequate flow index provides the advantage of easy injection molding into various shapes without complicated process steps.

[Formula 1]

(In Formula 1, S is sulfur, R ₁ , R ₂ are independently an alkyl group having 8 to 20 carbon atoms, and n is an integer of 2 to 5)

The kneading may be, for example, mixing the first graft copolymer, the second graft copolymer, and the aromatic vinyl compound-vinyl cyan compound copolymer first, and then mixing the compound represented by the formula (1). As another example, the first graft copolymer, the second graft copolymer, the aromatic vinyl compound-vinyl cyan compound copolymer, and the compound represented by Formula 1 may be kneaded at once.

The kneading and extrusion may be performed through, for example, a single screw extruder, a twin screw extruder, or a Benbury mixer, and in this case, the composition is uniformly dispersed and thus has excellent compatibility.

The kneading and extrusion may be performed within a range of 200 to 300° C., or 200 to 250° C., for example, in a barrel temperature, and in this case, a sufficient amount of processing per unit time may be performed and sufficient melt-kneading may be possible, and thermal decomposition of the resin component, etc. There is an advantage that does not cause any problems.

The kneading and extrusion may be performed under conditions in which, for example, the number of screw rotations is 100 to 300 rpm, or 100 to 200 rpm, and in this case, the throughput per unit time is appropriate, so the process efficiency is excellent, and there is an effect of suppressing excessive cutting. .

The molded article of the present substrate may include, for example, the thermoplastic resin composition of the present substrate, and the molded article has the advantage of excellent impact resistance due to external impact due to excellent impact strength and tensile strength. There is an advantage that injection molding is possible.

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

[Example]

Example One

A first graft copolymer obtained by graft polymerization of 50% by weight of a butyl acrylate rubber having an average particle diameter of 130 nm as a core and 30% by weight of styrene and 20% by weight of acrylonitrile and a butyl having an average particle diameter of 500 nm An acrylate rubber 50% by weight as a core and 26% by weight of a second graft copolymer in which 30% by weight of styrene and 20% by weight of acrylonitrile were graft-polymerized were used as the ASA graft resin. In addition, a SAN resin having a weight average molecular weight of 150,000 g/mol (90HR resin, manufactured by LG Chem) (hereinafter referred to as'first matrix copolymer') 40% by weight and a SAN resin having a weight average molecular weight of 170,000 g/mol (97HC resin) , Manufactured by LG Chem) (hereinafter referred to as'second matrix copolymer') 22% by weight was used as a matrix SAN resin. Di-tert-dodecyl trisulfide 1 part by weight per 100 parts by weight of the base resin including the ASA graft resin and the matrix SAN resin, Irgranox 1076 and Irgrafos 168 (made by BASF) as antioxidants, 0.5 parts by weight, respectively, and UV stabilizer Tinuvin 770 0.6 parts by weight of (BASF product) and 0.4 parts by weight of Sunsorb329 (manufactured by Sunfine Global) were added, and the pellets were made into pellets under the condition of a cylinder temperature of 230° C. using a compression kneader, and a thermoplastic resin composition specimen was prepared by injection.

Example 2

It was carried out in the same manner as in Example 1, except that 2 parts by weight of Di-tert-dodecyl trisulfide was added in Example 1.

Example 3

It was carried out in the same manner as in Example 1, except that 3 parts by weight of Di-tert-dodecyl trisulfide was added in Example 1.

Example 4

Example 1 except that 62% by weight of the first matrix copolymer was added instead of 40% by weight of the first matrix copolymer, the second matrix copolymer was not added, and 3 parts by weight of Di-tert-dodecyl trisulfide was added. It was carried out in the same way as.

Comparative example One

It was carried out in the same manner as in Example 1, except that Di-tert-dodecyl trisulfide was not used in Example 1.

Comparative example 2

It was carried out in the same manner as in Example 1, except that 5 parts by weight of Di-tert-dodecyl trisulfide was added in Example 1.

Comparative example 3

It was carried out in the same manner as in Example 4, except that Di-tert-dodecyl trisulfide was not used in Example 4.

Comparative example 4

In Example 1, 30% by weight of ABS (acrylonitrile-butadiene-styrene) resin was used instead of the first graft copolymer and the second graft copolymer, and the weight of the first matrix copolymer and the second matrix copolymer A SAN resin having an average molecular weight of 80,000 g/mol (hereinafter referred to as'third matrix copolymer') was 70% by weight and carried out in the same manner as in Example 1, except that Di-tert-dodecyl trisulfide was not used. I did.

Comparative example 5

In Comparative Example 4, except that 1 part by weight of Di-tert-dodecyl trisulfide was added, it was carried out in the same manner as in Comparative Example 4.

Comparative example 6

In Comparative Example 4, it was carried out in the same manner as in Comparative Example 4, except that 3 parts by weight of Di-tert-dodecyl trisulfide was added.

[Test Example]

The properties of the specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 6 were measured by the following method, and the results are shown in Table 1 below.

* Flow index (Melt Index; MI): According to ASTM D1238, the flow index of the extruded pellet was measured under the condition of 220°C and a load of 10 kg.

* Notched Izod Impact Strength: Izod impact strength was measured by giving a notch to the specimen according to ASTM D256. The thickness of the measurement specimen was 6.4 mm (1/4 inch).

* Tensile strength: According to ASTM D638, U.T.M (manufacturer; Zwick, model name; Z010) was used to pull the cross head speed at 50 mm/min, and then the point at which the 3.2T specimen was cut was measured. Tensile strength was calculated as follows.

Tensile strength (kgf/cm ² ) = load (kgf) / thickness (cm) x width (cm)

division Example Comparative example One 2 3 4 One 2 3 4 5 6 First graft copolymer
(weight%) 12 12 12 12 12 12 12 - - - Second Graft Copolymer (% by weight) 26 26 26 26 26 26 26 - - - ABS resin (% by weight) - - - - - - - 30 30 30 First matrix copolymer ( % by weight) 40 40 40 62 40 40 62 - - - Second matrix copolymer ( % by weight) 22 22 22 - 22 22 - - - - Third matrix copolymer (% by weight) - - - - - - - 70 70 70 Di-tert-dodecyl trisulfide (parts by weight) One 2 3 3 0 5 0 0 One 3 Fluidity (g/10min) 12.2 13.9 16.2 19.5 10.7 23.6 14.5 18 19.1 23.4 Impact strength (kgf·cm/cm) 23.4 24.0 25.4 23.6 21.9 26.2 20.6 9 10.7 10.3 Tensile strength (kgf/cm ² ) 446 437 427 405 454 401 425 530 525 517

As shown in Table 1, it was confirmed that the thermoplastic resin compositions prepared according to Examples 1 to 4 of the present invention had excellent fluidity, impact strength, and tensile strength. In particular, in the case of Examples 1 to 3 including two kinds of aromatic vinyl compound-vinyl cyan compound copolymer having different weight average molecular weight, it was confirmed that the tensile strength was further improved.

On the other hand, in the case of Comparative Examples 1 and 3 that do not contain the compound represented by Chemical Formula 1 of the present invention, it was confirmed that the flowability and impact strength were reduced, so that the impact resistance to external impact was lowered, and injection molding was not easy.

In addition, in the case of Comparative Example 2 containing an excessive amount of the compound represented by Formula 1 of the present invention, the tensile strength was greatly reduced, resulting in a problem of reducing the efficiency during injection.

Further, in the case of Comparative Examples 4 to 6 containing ABS resins other than two types of ASA resins, even if the compound represented by Formula 1 of the present invention was added, the impact strength was not improved at all, thus satisfying all of the fluidity, impact strength and tensile strength. It was confirmed that the present invention could not be reached.

Claims (13)

(A) 5 to 70% by weight of a first graft copolymer comprising an acrylate-based rubber having an average particle diameter of 50 to 200 nm as a core,
(B) 10 to 70% by weight of a second graft copolymer containing an acrylate-based rubber having an average particle diameter of more than 200 nm to 900 nm or less as a core, and
(C) 100 parts by weight of a base resin containing 20 to 80% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer; And
(D) 0.5 to 4 parts by weight of a compound represented by the following Formula 1;
Thermoplastic resin composition.
[Formula 1]

(In Formula 1, S is sulfur, R ₁ , R ₂ are independently an alkyl group having 8 to 20 carbon atoms, and n is an integer of 2 to 5)
The method of claim 1,
The (A) first graft copolymer is characterized in that comprising 10 to 70% by weight of an aromatic vinyl compound and 5 to 50% by weight of a vinyl cyan compound in 20 to 80% by weight of an acrylate-based rubber.
Thermoplastic resin composition.
The method of claim 1,
The (B) second graft copolymer is characterized in that comprising 10 to 60% by weight of an aromatic vinyl compound and 5 to 40% by weight of a vinyl cyan compound in 10 to 80% by weight of an acrylate-based rubber.
Thermoplastic resin composition.
The method of claim 1,
The weight ratio of the (A) first graft copolymer and the (B) second graft copolymer is 1:1.1 to 1:5.
Thermoplastic resin composition.
The method of claim 1,
The (C) aromatic vinyl compound-vinyl cyan compound copolymer has a weight average molecular weight of 50,000 to 200,000 g/mol.
Thermoplastic resin composition.
The method of claim 1,
The (C) aromatic vinyl compound-vinyl cyan compound copolymer is characterized by consisting of two or more aromatic vinyl compound-vinyl cyan compound copolymers having different weight average molecular weights.
Thermoplastic resin composition.
The method of claim 1,
In Formula 1, R ₁ , R ₂ are independently an alkyl group having 9 to 15 carbon atoms, and n is 2, 3 or 4
Thermoplastic resin composition.
The method of claim 1,
(D) The compound represented by Formula 1 is di-n-nonyl trisulfide, di-t-nonyl trisulfide, di-n-decyl trisulfide (di-n-decyl trisulfide), di-n-undecyl trisulfide, di-n-dodecyl trisulfide and di-tert-dodecyl tree Sulfide (di-tert-dodecyl trisulfide), characterized in that at least one selected from the group consisting of
Thermoplastic resin composition.
The method of claim 1,
The thermoplastic resin composition is characterized in that the flow index (220 ℃, 10 kg) is 8 to 30 g / 10min
Thermoplastic resin composition.
The method of claim 1,
The thermoplastic resin composition is characterized in that the Izod impact strength (1/4 inch, ASTM D256) is 22 kgf · cm / cm or more.
Thermoplastic resin composition.
The method of claim 1,
The thermoplastic resin composition is characterized in that the tensile strength (ASTM D638) is 400 kgf / cm ² or more
Thermoplastic resin composition.
(A) 5 to 70% by weight of a first graft copolymer having an acrylate-based rubber having an average particle diameter of 50 to 200 nm as a core, (B) an acrylate rubber having an average particle diameter of more than 200 nm to 900 nm or less as a core 100 parts by weight of a base resin comprising 10 to 70% by weight of the second graft copolymer and 20 to 80% by weight of (C) an aromatic vinyl compound-vinyl cyan compound copolymer; And (D) 0.5 to 4 parts by weight of a compound represented by the following formula (1); characterized in that it comprises the step of kneading and extruding under conditions of 200 to 300 ℃ and 100 to 300 rpm, including
Method for producing a thermoplastic resin composition.
[Formula 1]

(In Formula 1, R ₁ and R ₂ are independently an alkyl group having 8 to 20 carbon atoms, and n is an integer of 2 to 5)
It comprises the thermoplastic resin composition of any one of claims 1 to 11, characterized in that
Molded products.