KR102177828B1 - Thermoplastic resin composition, method for preparing the resin composition and molding product comprising the resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, a method for producing the same, and an injection molded article including the same, and more particularly, A) 5 to 30% by weight of a graft copolymer having a small diameter core-shell structure, B) a core-shell structure Silicone-acrylate-based copolymer 10 to 40% by weight, C) (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer 1 to 25% by weight and D) (meth)acrylic acid alkyl ester compound polymer 30 to 100 parts by weight of the base resin containing 75% by weight; And E) 0.1 to 5 parts by weight of a siloxane polymer having a kinematic viscosity of 1,000,000 to 3,000,000 cSt; including, and having excellent physical properties such as mechanical strength, weather resistance, scratch resistance, etc., such as impact strength, and excellent processability and coloring property due to a high flow index, There is an effect of providing a high-quality thermoplastic resin composition and injection-molded article with improved releasability.

Description

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

The present invention relates to a thermoplastic resin composition, a method of manufacturing the same, and an injection molded article including the same, and more particularly, excellent mechanical strength such as impact strength, weather resistance, scratch resistance, etc., while excellent processability due to a high flow index It relates to a thermoplastic resin composition having improved colorability and releasability, a method of manufacturing the same, and an injection molded article including the same.

ABS resin is a graft resin produced by graft polymerization of an aromatic vinyl compound styrene monomer and a vinyl cyan compound acrylonitrile monomer in a conjugated diene rubber polymer. Mechanical strength such as impact strength, heat resistance, and processability are excellent. Therefore, it has been widely used in various fields such as electricity, electronics, and automobiles.

Recently, the demands of consumers for the trend of luxury appearance and non-painting of products including automobiles are continuously increasing, but ABS resins used as materials for these products are poor in scratch resistance, colorability, and weather resistance. There was a limit to meeting the needs.

In order to improve the scratch resistance, colorability, and weather resistance of the ABS-based resin, generally coating or coating treatment is performed, but there are disadvantages such as a complicated operation, an increase in defect rate, and a decrease in productivity due to the accompanying post-processing steps.

As another automobile exterior material, polymethyl methacrylate (PMMA), which has excellent weather resistance, colorability, and gloss, can be considered, but it is difficult to use as an exterior material due to poor impact resistance and injection moldability.

In addition, methyl methacrylate-acrylonitrile-butadiene-styrene resin, which can be used as an automobile exterior material, has good colorability, gloss and impact resistance, but has a problem of poor scratch resistance and heat resistance, and to compensate for this, butadiene rubber , Transparent acrylonitrile-styrene resin and siloxane-polyester copolymer were mixed and applied, but in this case, there was a limit to improving scratch resistance, and rather, there was a problem of lowering weather resistance and heat resistance.

In addition, when the acrylic rubber, polymethyl methacrylate, siloxane-polyester copolymer and the silicone acrylate copolymer having a core-shell structure are applied, mechanical strength and heat resistance are excellent, but flowability and glossiness are poor.

As another automobile exterior material, an acrylate-styrene-acrylonitrile-based copolymer with excellent weather resistance was proposed, but it does not require painting or coating, but does not undergo post-processing, so it lacks scratch resistance, colorability and gloss. There was a problem.

Recently, the standards of materials used for exterior materials such as automobiles are gradually strengthening, and accordingly, excellent physical properties such as weather resistance, scratch resistance, and impact resistance are excellent, while the appearance quality such as coloring and gloss is excellent, and processability and moldability are excellent. There is a need to develop technology for products.

Korean Patent Publication No. 2010-0022160

In order to solve the problems of the prior art as described above, the present invention maintains mechanical strength such as impact strength and heat resistance, while improving weather resistance, scratch resistance, complexion, gloss and processability, and a thermoplastic resin composition prepared including the same. It aims to provide an injection molded product.

It is another object of the present invention to provide a method for preparing the thermoplastic resin composition.

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) a small diameter core-shell structure of the graft copolymer 5 to 30% by weight; B) 10 to 40% by weight of a silicone-acrylate-based copolymer having a core-shell structure; C) (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer 1 to 25% by weight; And D) 30 to 75% by weight of a (meth)acrylic acid alkyl ester compound polymer; and 100 parts by weight of a base resin including E) 0.1 to 5 parts by weight of a siloxane polymer having a kinematic viscosity of 1,000,000 to 3,000,000 cSt; including, the D) ( The meth)acrylic acid alkyl ester compound polymer is D-1) a high heat-resistant (meth)acrylic acid alkyl ester compound polymer having a heat deflection temperature (HDT) of more than 91°C and a flow index (MI) of 1 to 5 g/10 min and D-2 ) Provides a thermoplastic resin composition comprising a high-flowing (meth)acrylic acid alkyl ester compound polymer having a heat deflection temperature (HDT) of 91°C or less and a flow index (MI) of more than 5 g/10 min.

In addition, the present invention is A) 5 to 30% by weight of a graft copolymer having a small diameter core-shell structure, B) 10 to 40% by weight of a silicone-acrylate-based copolymer having a core-shell structure, C) (meth)acrylic acid 100 parts by weight of a base resin containing 1 to 25% by weight of an alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer and 30 to 75% by weight of a D-1) (meth)acrylic acid alkyl ester compound polymer; And E) 0.1 to 5 parts by weight of a siloxane polymer having a kinematic viscosity of 1,000,000 to 3,000,000 cSt; and then kneading and extruding the same. It provides a method for producing a thermoplastic resin composition.

In addition, the present invention provides an injection molded article, characterized in that produced by injecting the thermoplastic resin composition.

According to the present invention, a high-quality thermoplastic resin composition with improved weather resistance, scratch resistance, complexion, gloss, processability, moldability, etc., while maintaining high mechanical strength and heat resistance such as impact strength, and injection molded articles manufactured including the same Has the effect it provides.

Specifically, the molded article manufactured by injecting the thermoplastic resin composition of the present invention has a high heat resistance with a heat deflection temperature of 85°C or higher, and has a high mechanical strength with an impact strength of 10kgfcm/cm or more, while the ΔL value by the Ericsson test The colorability is excellent below 1, and the gray scale according to the discoloration standard gray color table is grade 4 or higher, which has excellent weather resistance, excellent processability and moldability.

The inventors of the present invention are a graft copolymer having a small-diameter core-shell structure having an average particle diameter of 2,000 Å or less, a silicone-acrylate-based copolymer having a core-shell structure, a (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer In the case of a thermoplastic resin composition prepared by blending two kinds of (meth)acrylic acid alkyl ester compound polymers having different coalescence, fluidity and heat resistance and a siloxane polymer having a kinematic viscosity of 1,000,000 to 3,000,000 cSt in a specific content, scratch resistance, colorability, and gloss , Impact strength, weather resistance, heat resistance, etc., while excellent properties such as processing properties such as releasability was confirmed to be improved, and based on this, the present invention was completed by further striving.

The thermoplastic resin composition of the present invention comprises A) 5 to 30% by weight of a graft copolymer having a small diameter core-shell structure, B) 10 to 40% by weight of a silicone-acrylate copolymer having a core-shell structure, C) (meth ) 100 parts by weight of a base resin including 1 to 25% by weight of an acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer and D) 30 to 75% by weight of a (meth)acrylic acid alkyl ester compound polymer; And E) 0.1 to 5 parts by weight of a siloxane polymer having a kinematic viscosity of 1,000,000 to 3,000,000 cSt; it may be characterized as containing.

In another example, the thermoplastic resin composition comprises A) 10 to 30% by weight of a graft copolymer having a small diameter core-shell structure, B) 15 to 40% by weight of a silicone-acrylate-based copolymer having a core-shell structure, C) ( 100 parts by weight of a base resin comprising 5 to 25% by weight of a meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer and 40 to 70% by weight of D) a (meth)acrylic acid alkyl ester compound polymer; And E) 0.1 to 5 parts by weight of a siloxane polymer having a kinematic viscosity of 1,000,000 to 3,000,000 cSt; in this case, there is an excellent balance of physical properties such as impact resistance, weather resistance, scratch resistance, and colorability.

As another example, A) 15 to 25% by weight of a graft copolymer having a small-diameter core-shell structure, B) 15 to 30% by weight of a silicone-acrylate-based copolymer having a core-shell structure, C) an alkyl (meth)acrylate 100 parts by weight of a base resin comprising 5 to 15% by weight of an ester compound-aromatic vinyl compound-vinyl cyan compound copolymer and 50 to 65% by weight of a D) (meth)acrylic acid alkyl ester compound polymer; And E) 0.1 to 5 parts by weight of a siloxane polymer having a kinematic viscosity of 1,000,000 to 3,000,000 cSt; and within this range, there is an effect excellent in physical properties such as impact resistance, weather resistance, scratch resistance, colorability, processability, and moldability. .

Hereinafter, the composition will be described in a manner described above for each component.

A) Graft copolymer of small diameter core-shell structure

The average particle diameter (greater than the average particle diameter of the core) of the graft copolymer having a small diameter core-shell structure of the present disclosure is, for example, 2,000 Å or less, 1,500 Å or less, 500 to 2,000 Å, 500 to 1,500 Å, or 500 to 1,000 Å Phosphorus can be used, and within this range, there is an advantage of excellent mechanical strength such as impact strength of the resin composition and excellent balance of properties.

In the present description, the average particle diameter can be measured using Nicomp 380 by the dynamic ride scattering method.

The A) copolymer may be, for example, 10 to 20% by weight or 15 to 20% by weight with respect to the base resin, and within this range, mechanical strength such as impact strength or appearance properties such as glossiness are excellent. .

The core-shell structured graft copolymer may be, for example, a copolymer including an alkyl acrylate rubber polymer as a core component and a copolymer obtained by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound as a shell component. , In this case, there are excellent effects such as weather resistance and impact resistance.

The alkyl acrylate-based rubber polymer (core) may preferably have an average particle diameter of 300 to 1,500 Å, more preferably 300 to 1,200 Å, and most preferably 500 to 900 Å (however, in the present description, The average particle diameter is smaller than the average particle diameter of the core-shell structured graft copolymer).

Within the above range, there is an advantage of excellent mechanical strength such as impact strength of the final molded product, good physical properties such as moldability and flow index, and excellent glossiness.

The core-shell structured graft copolymer may include 20 to 70% by weight of an alkyl acrylate rubber polymer, 10 to 50% by weight of an aromatic vinyl compound, and 5 to 40% by weight of a vinyl cyan compound, as a specific example. In this case, the balance of physical properties and properties such as weather resistance and impact strength is excellent.

In another example, the core-shell structured graft copolymer may include 20 to 50% by weight of an alkyl acrylate rubber polymer, 20 to 40% by weight of an aromatic vinyl compound, and 10 to 40% by weight of a vinyl cyan compound, Within the above-described range, there is an advantage of excellent balance of physical properties and properties such as weather resistance and impact strength.

In another example, the core-shell structured graft copolymer may include 30 to 50% by weight of an alkyl acrylate rubber polymer, 25 to 40% by weight of an aromatic vinyl compound, and 10 to 30% by weight of a vinyl cyan compound, , Within this range, there is an effect of excellent physical property balance.

In addition, the core-shell structured graft copolymer may preferably have a core-shell weight ratio of 10:90 to 70:30 or 30:70 to 90:10, and if it is within the above range, the ratio of the core to the shell As this is appropriate, the final product has excellent impact strength, excellent scratch resistance, weather resistance, etc., and has excellent workability.

In the present description, the alkyl acrylate-based rubber polymer may be, for example, one or more selected from the group consisting of acrylate rubber, butyl acrylate rubber, ethyl acrylate rubber, and ethylhexyl acrylate rubber, and polymers derived therefrom.

The term "polymer derived" in the present description means that other monomers or polymers not originally included in the copolymer are copolymerized together, or copolymerized as a derivative of the monomer.

In the present description, a derivative is a compound in which a hydrogen atom or an atomic group of the original compound is substituted with another atom or an atomic group, and, for example, refers to a compound substituted with a halogen or alkyl group.

In the present description, the aromatic vinyl compound may be one or more selected from the group consisting of styrene, alpha-methylstyrene, para-methylstyrene, and vinyltoluene, unless otherwise specified, and in this case, it has excellent processability and heat resistance.

In the present description, the vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, unless otherwise specified, and in this case, there is an advantage of excellent physical properties such as processability and heat resistance. .

As a more specific example, the core-shell structured graft copolymer may be a copolymer having an average particle diameter of 800 to 1,200Å in which styrene and acrylonitrile are grafted onto an acrylate rubber polymer, but is not limited thereto.

B) Core-shell structured silicone-alkyl acrylate copolymer

In the present description, the core-shell structured silicone-alkyl acrylate-based copolymer may be used in, for example, 10 to 40% by weight, 15 to 35% by weight, or 15 to 30% by weight, in this case, the impact resistance of the thermoplastic resin composition, While excellent in physical properties such as weather resistance, there is an effect of improving scratch resistance.

The core of the core-shell structured silicone-alkyl acrylate-based copolymer may be, for example, at least one selected from the group consisting of a silicone rubber polymer, a silicone-alkyl acrylate-based rubber polymer, or a mixture thereof.

The shell of the core-shell structured silicone-alkyl acrylate copolymer may include, for example, at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylic acid alkyl ester compound. (However, if the core contains a silicone rubber polymer, the (meth)acrylic acid alkyl ester compound must be included)

As a specific example, the core-shell structured silicone-alkyl acrylate-based copolymer may use a silicone-acrylic rubber polymer as a core component and an aromatic vinyl compound and a vinyl cyan compound as a shell component, but limited thereto. It is not possible.

C) (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer

In the present description, the (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer is a copolymerized non-grafted copolymer comprising a (meth)acrylic acid alkyl ester compound, an aromatic vinyl compound, and a vinyl cyan compound. Not the same as coalescence

In the present description, the copolymer C) may include, for example, 55 to 85% by weight of a (meth)acrylic acid alkyl ester compound, 10 to 30% by weight of an aromatic vinyl compound, and 5 to 15% by weight of a vinyl cyan compound, within this range Heat resistance properties such as heat deflection temperature and flow index are excellent.

In another example, the copolymer C) may include 65 to 85% by weight of a (meth)acrylic acid alkyl ester compound, 10 to 25% by weight of an aromatic vinyl compound, and 5 to 12% by weight of a vinyl cyan compound, within this range It has excellent advantages in heat resistance such as heat deflection temperature, processability, and moldability.

In another example, the copolymer C) may include 70 to 80% by weight of a (meth)acrylic acid alkyl ester compound, 15 to 22% by weight of an aromatic vinyl compound, and 5 to 10% by weight of a vinyl cyan compound, within this range It has excellent advantages in heat resistance such as heat deflection temperature, workability, and moldability.

More preferably, in the copolymer C), the sum of the aromatic vinyl compound and the vinyl cyan compound may be 30% by weight or less or 20 to 30% by weight based on 100% by weight of the copolymer, and in this case, excellent fluidity may be implemented.

The C) copolymer may be, for example, 1 to 25% by weight, 5 to 25% by weight, 5 to 15% by weight, or 5 to 10% by weight based on the base resin, and within this range, scratch resistance, weather resistance, etc. This has an excellent effect.

In the present description, the (meth)acrylic acid alkyl ester compound is one selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl acrylate unless otherwise specified. It can be more than that.

In a more specific example, the copolymer C) may be a methyl methacrylate-styrene-acrylonitrile copolymer, but is not limited thereto.

D) (meth)acrylic acid alkyl ester compound polymer

In the present description, the (meth)acrylic acid alkyl ester compound polymer may be a polymerized polymer including at least one monomer selected from a methacrylic acid alkyl ester compound and an acrylic acid alkyl ester compound.

In a specific example, the D) polymer is prepared by including at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl ethacrylate and ethyl acrylate. It may be a polymer, preferably one containing polymethyl methacrylate (PMMA).

The (meth)acrylic acid alkyl ester compound polymer may be included in an amount of 30 to 75% by weight, 45 to 70% by weight, or 50 to 65% by weight based on the base resin, in this case, the impact resistance and scratch resistance of the final product It has the effect of improving heat resistance and fluidity while having excellent physical properties such as property and weather resistance.

In the present invention, in order to improve heat resistance and fluidity at the same time without deteriorating physical properties such as impact resistance, scratch resistance and weather resistance of the final product, it is proposed to mix and use two types of (meth)acrylic acid alkyl ester compound polymers having different heat resistance and fluidity. Suggest.

As an example, the (meth)acrylic acid alkyl ester compound polymer has a heat distortion temperature (HDT) of greater than 91°C or 92 to 120°C, and a flow index (MI) of 1 to 5 g/10 min. High fluidity (meth)acrylic acid alkyl ester with a compound polymer and a heat deflection temperature (HDT) of 91°C or less or 80 to 91°C, and a flow index (MI) of more than 5g/10min, 7g/10min or more, or 7 to 20g/10min Compound polymers can be mixed and used.

In a specific example, the (meth)acrylic acid alkyl ester compound polymer may include 45 to 70% by weight of the high heat-resistant (meth)acrylic acid alkyl ester compound polymer and 30 to 55% by weight of the high fluidity (meth)acrylic acid alkyl ester compound polymer Within this range, there is an effect of simultaneously improving heat resistance and fluidity without deteriorating physical properties such as impact resistance, scratch resistance and weather resistance.

In another specific example, the (meth)acrylic acid alkyl ester compound polymer includes 50 to 65% by weight of the high heat-resistant (meth)acrylic acid alkyl ester compound polymer and 35 to 50% by weight of the high fluidity (meth)acrylic acid alkyl ester compound polymer In this range, heat resistance and fluidity are simultaneously improved without deteriorating physical properties such as impact resistance, scratch resistance, and weather resistance.

In addition, the (meth) acrylic acid alkyl ester compound polymer has a weight ratio of the high heat-resistant (meth) acrylic acid alkyl ester compound polymer and the high fluidity (meth) acrylic acid alkyl ester compound polymer in a weight ratio of 1:9 to 9:1, 3:7 to It may be preferable that it is 7:3, 4:6 to 8:2, 5:5 to 8:2, or 4:6 to 6:4, and in this case, there is an effect of excellent heat resistance and fluidity and excellent physical property balance.

In a more specific example, the (meth)acrylic acid alkyl ester compound polymer has a heat deflection temperature (HDT) of more than 91°C, a melt index (MI) of 1 to 5 g/10 min, and a heat deflection temperature of polymethyl methacrylate. (HDT) may be a mixture of 91° C. or less and high-flow polymethyl methacrylate having a melt index (MI) of more than 5 g/10 min.

E) siloxane polymer

In the present description, a siloxane polymer having a kinematic viscosity of 1,000,000 to 3,000,000 cSt may be used, and in this case, the final product has excellent scratch resistance and weather resistance, and improved releasability, thereby facilitating processing and molding.

In this description, the kinematic viscosity can be measured according to ASTM D-445.

The siloxane polymer may be preferably used in an amount of 0.1 to 5 parts by weight, 0.5 to 3 parts by weight, or 0.5 to 1 parts by weight based on 100 parts by weight of the base resin, and in this case, the mechanical strength, heat resistance, etc. This is improved and there is an effect that processing and molding are easy.

The siloxane polymer may be, for example, a siloxane polymer masterbatch in which 25 to 50% by weight of a siloxane compound having a kinematic viscosity of 1,000,000 to 3,000,000 cSt is dispersed, and in this case, the compatibility between the resin compositions is improved, so that processing and molding are easy. have.

The siloxane compound may be, for example, one or more selected from the group consisting of polydimethylsiloxane, polydiphenylsiloxane, polymethylphenylsiloxane, and polymethylhydrogensiloxane, but is not limited thereto.

In addition, the siloxane polymer masterbatch is a carrier resin, for example, polymethyl methacrylate (PMMA), epoxy-modified methyl methacrylate copolymer (Epoxy-modified MMA copolymer), and at least one of styrene-acrylonitrile copolymer It may include, and in this case, there is an advantage of excellent processability while having excellent physical properties such as scratch resistance, weather resistance, and impact resistance.

Furthermore, the thermoplastic resin composition of the present invention may contain at least one additive selected from the group consisting of a lubricant, a heat stabilizer, a plasticizer, a light stabilizer, an antistatic agent, a nucleating agent, a flame retardant, an impact modifier, a pigment, an optical brightener, and an inorganic compound. Optionally, it may further include. The additive may be included in an amount of 0.1 to 1.5 parts by weight or 0.5 to 1.2 parts by weight based on 100 parts by weight of the base resin, and within this range, the properties of the thermoplastic resin composition of the present disclosure may not be deteriorated, and the effect of the additive may be expressed.

Hereinafter, a method for manufacturing a thermoplastic resin composition and an injection molded article of the present disclosure will be described.

The thermoplastic resin composition of the present disclosure comprises A) 5 to 30% by weight of a graft copolymer having a small-diameter core-shell structure, B) 10 to 40% by weight of a silicone-acrylate-based copolymer having a core-shell structure, C) (meth ) 100 parts by weight of a base resin including 1 to 25% by weight of an acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyanide compound copolymer and D) 30 to 75% by weight of a (meth)acrylic acid alkyl ester compound polymer; And E) 0.1 to 5 parts by weight of a siloxane polymer having a kinematic viscosity of 1,000,000 to 3,000,000 cSt; and then kneading and extruding the same.

As described above, the thermoplastic resin composition may further include one or more additives such as a lubricant, a heat stabilizer, a plasticizer, a light stabilizer, an antistatic agent, a nucleating agent, and a flame retardant during kneading.

The extrusion may be performed under conditions of 200 to 270°C or 220 to 250°C, and there is an advantage of excellent processability and moldability within the range.

Further, the thermoplastic resin composition of the present invention may be manufactured into an injection molded article through an injection process, and the injection may be performed under conditions of 200 to 270°C or 220 to 250°C, for example.

The injection-molded product of the present description can be characterized by having excellent colorability with a ΔL value of 1 or less by an elimination test, and excellent weather resistance with a gray scale of grade 4 or higher according to the standard gray color table of discoloration. .

In addition, the injection-molded article of the present disclosure has excellent heat resistance properties at a heat deflection temperature of 85°C or higher or 85 to 90°C, for example, but has a high mechanical strength such as 10 kgfcm/cm or 10 to 15 kgfcm/cm. It can be characterized.

In addition, the injection-molded article of the present disclosure may be characterized by excellent processability with a flow index of 10 g/10min or more or 10 to 15 g/10min, for example.

In the description of the thermoplastic resin composition of the present disclosure, its manufacturing method, and injection-molded products, conditions not specifically specified are not particularly limited if they are within the range commonly practiced in the technical field to which the present invention belongs, and can be appropriately selected and performed. State.

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) Graft copolymer having a small diameter core-shell structure: ASA having an average particle diameter of 1,000 Å or less in which 20 to 40% by weight of styrene and 10 to 40% by weight of acrylonitrile are copolymerized with 20 to 70% by weight of an acrylate rubber polymer System copolymer was used.

(A') Graft copolymer having a large-diameter core-shell structure: An average particle diameter of 4,000 to 5,000 Å in which 20 to 40% by weight of styrene and 10 to 40% by weight of acrylonitrile are copolymerized with 20 to 70% by weight of an acrylate rubber polymer Phosphorus ASA-based copolymer was used.

B) Core-shell structured silicone-acrylate-based copolymer:

A silicone-acrylate-based copolymer of a core-shell structure in which a silicone and acrylic rubber polymer forms a core, and an aromatic vinyl compound and a vinyl cyan compound form a shell, and the content of the silicone-acrylate impact modifier is 10% by weight or more. The company's SX-006 was used.

C) (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer:

A copolymer comprising 74% by weight of methyl methacrylate, 19% by weight of styrene and 7% by weight of acrylonitrile was used.

D) (meth)acrylic acid alkyl ester compound polymer:

(D-1) Using LG MMA's IH830C as a highly heat-resistant polymethyl methacrylate having a heat deflection temperature (HDT) of more than 91°C and a flow index (MI) of 1 to 5 g/10min, (D-2) LG MMA's HP210 was used as a high-flow polymethyl methacrylate having an HDT of 91° C. or less and an MI exceeding 5 g/10 min.

E) siloxane polymer:

A siloxane polymer masterbatch (manufactured by Dow Corning Korea, CF-1501) in which a siloxane compound having a kinematic viscosity of 1,000,000 to 3,000,000 cSt was dispersed in an amount of 25 to 50% by weight was used.

F) additives:

Calcium stearate, a metallic external lubricant, was used.

[Example]

Example 1

(A) 20 parts by weight of the core-shell structured alkyl acrylate-styrene-acrylonitrile graft copolymer prepared above, (B) 15 parts by weight of the core-shell structured silicone-acrylate-based copolymer, (C ) (Meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer 10 parts by weight, (D-1) 35 parts by weight of high heat-resistant polymethyl methacrylate, (D-2) high fluidity polymethyl methacrylate 20 parts by weight, (E) 2 parts by weight of a siloxane polymer, and (F) 0.5 parts by weight of an additive were kneaded and extruded (240°C) using a twin screw extruder to prepare a resin composition in the form of pellets, dried and then dried using an injection machine. By injection under conditions of to 250 ℃ to prepare a specimen for measuring physical properties.

Examples 2 to 5 and Comparative Examples 1 to 6

A specimen for measuring physical properties was prepared in the same manner as in Example 1, except for using the components and contents of Table 1 below.

The specimen for the colorability test was prepared by further including 1 to 5 parts by weight of carbon black when kneading the composition.

A A' B C D-1 D-2 E F Example 1 20 - 15 10 35 20 2 0.5 Example 2 10 - 30 10 30 20 3 1.0 Example 3 15 - 15 5 35 30 2 0.5 Example 4 20 - 15 10 30 25 3 0.5 Example 5 10 - 25 10 30 25 3 0.5 Comparative Example 1 35 - - 10 35 20 3 0.5 Comparative Example 2 - 20 15 10 30 25 2 1.0 Comparative Example 3 20 - 15 10 30 25 - - Comparative Example 4 5 - 10 15 30 30 3 0.5 Comparative Example 5 20 - 15 - 65 - 3 1.0 Comparative Example 6 20 - 15 30 - 35 2 1.0

(In Table 1, the content of each component is A or A'+ B + C + D in parts by weight based on a total of 100 parts by weight.)

[Test Example]

The properties of the specimens prepared in the Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2 below.

1) Izod impact strength (IMP, kgfcm/cm): According to ASTM D256, a notch was made in a specimen having a thickness of 3.2 mm and measured.

2) Flow index (MI, g/10min): According to ASTM D1238, it was measured under conditions of 220°C and a load of 10 kg.

3) Heat deflection temperature (HDT, ℃): According to ASTM D648, a 1/4" specimen was used and measured under conditions of a load of 18.6kgf/cm ² .

4) Colorability test: Based on the CIE1976 L*a*b colorimeter, the color L value was measured using a color difference meter (model name: Color-Eye7000A, manufacturer: GRETAGMACBETH). At this time, if L=100, it means pure white, and if L=0, it means pure black. The lower the L value, the better the black feeling.

5) Scratch resistance test: A value of ΔL (brightness by CIE1976 L*a*b colorimeter) was measured according to the Erichsen test.

6) Gray scale: Weatherability was evaluated based on the Gray scale for evaluating change in color. The larger this value, the better the weather resistance.

7) Ejection force (N): For quantitative evaluation of the releasability, comparison between materials was conducted by comparing the pressure delivered to the mold during injection. During injection, a pressure sensor was attached to the ejection plate located on the moving side, and the pressure (ejection force, N) applied during injection molding was processed as numerical data. For precise comparison, the releasability measurement was performed at least 10 times.

8) Gloss measurement: was measured using a gloss meter at 45° according to ASTM D2457.

IMP MI HDT Coloring Scratch resistance Grayscale Dysplasia Gloss Example 1 11 11 88 24.6 ΔL <1 Level 4 970 91 Example 2 13 12 86 24.2 ΔL <1 Level 4 700 89 Example 3 10 10 86 24.5 ΔL <1 Level 4 980 90 Example 4 11 11 85 24.7 ΔL <1 Level 4 850 91 Example 5 12 11 85 24.1 ΔL <1 Level 4 840 90 Comparative Example 1 7 12 88 25.3 ΔL <1.5 Level 4 960 91 Comparative Example 2 17 8 85 25.7 ΔL <1 Level 3 980 83 Comparative Example 3 11 11 85 24.8 ΔL =5 Level 4 1,700 90 Comparative Example 4 6 15 83 24.2 ΔL <1 Level 2 820 92 Comparative Example 5 11 4 89 24.8 ΔL <1 Level 4 870 90 Comparative Example 6 11 20 79 24.7 ΔL <1 Level 4 920 91

As shown in Table 2, the specimens of Examples 1 to 5 according to the present description have good impact strength, flow index, heat deflection temperature, colorability, and gloss when compared to Comparative Examples 1 to 6 that do not conform to the present description. While it was confirmed that scratch resistance, gloss, gray scale and releasability were very excellent.

Specifically, (A') Comparative Example 2 prepared including a graft copolymer having a large-diameter core-shell structure, compared to Examples including a graft copolymer having a small-diameter core-shell structure (A) It was confirmed that the index and gray scale were poor.

In addition, D) (meth)acrylic acid alkyl ester compound polymer Comparative Example 5 prepared using only high heat-resistant polymethyl methacrylate was found to have a significantly lower flow index compared to the examples, and Comparative Example 6 prepared using only high-flow polymethyl methacrylate had a remarkably heat deflection temperature. It could be confirmed that it was low.

In addition, in the case of Comparative Example 3 that did not contain the siloxane polymer, it was confirmed that the scratch resistance and releasability were significantly inferior to the Example.

Claims (17)

A) 5 to 30% by weight of a graft copolymer having a small diameter core-shell structure; B) 10 to 40% by weight of a silicone-acrylate-based copolymer having a core-shell structure; C) 5 to 10% by weight of (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer; And D) 50 to 65% by weight of a (meth)acrylic acid alkyl ester compound polymer; and 100 parts by weight of a base resin including E) 0.1 to 5 parts by weight of a siloxane polymer having a kinematic viscosity of 1,000,000 to 3,000,000 cSt;
The D) (meth)acrylic acid alkyl ester compound polymer is a high heat-resistant (meth)acrylic acid alkyl ester compound polymer having a D-1) heat deflection temperature (HDT) of more than 91°C and a flow index (MI) of 1 to 5 g/10 min. 50 to 65% by weight and D-2) 35 to 50% by weight of a high-flowing (meth)acrylic acid alkyl ester compound polymer having a heat deflection temperature (HDT) of 91°C or less and a flow index (MI) of more than 5 g/10min. Characterized in that it comprises
Thermoplastic resin composition. The method of claim 1,
The A) small-diameter core-shell structure graft copolymer is a copolymer obtained by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound to an alkyl acrylate rubber polymer.
Thermoplastic resin composition. The method of claim 2,
The A) small-diameter core-shell structured graft copolymer is 20 to 70% by weight of an alkyl acrylate rubber polymer having an average particle diameter of 300 to 1,500Å, 10 to 50% by weight of an aromatic vinyl compound, and 5 to 40% by weight of a vinyl cyan compound Characterized in that it contains%
Thermoplastic resin composition. The method of claim 1,
The A) small-diameter core-shell structured graft copolymer has an average particle diameter of 2,000 Å or less (greater than the average particle diameter of the core).
Thermoplastic resin composition. The method of claim 1,
The core of the B) core-shell structured silicone-acrylate copolymer is at least one selected from the group consisting of a silicone rubber polymer, a silicone-alkyl acrylate compound rubber polymer, or a mixture thereof.
Thermoplastic resin composition. The method of claim 1,
The shell of the B) core-shell structured silicone-acrylate copolymer comprises at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and a (meth)acrylic acid alkyl ester compound.
Thermoplastic resin composition. The method of claim 1,
The C) (meth)acrylic acid alkyl ester compound-aromatic vinyl compound-vinyl cyan compound copolymer is 55 to 85% by weight of the (meth)acrylic acid alkyl ester compound, 10 to 30% by weight of aromatic vinyl compound and 5 to 15% by weight of vinyl cyanide compound Characterized in that it contains%
Thermoplastic resin composition. delete delete The method of claim 1,
The E) siloxane polymer is characterized in that it contains 25 to 50% by weight of the siloxane compound.
Thermoplastic resin composition. A) 5 to 30% by weight of a graft copolymer having a small diameter core-shell structure, B) 10 to 40% by weight of a silicone-acrylate-based copolymer having a core-shell structure, C) (meth)acrylic acid alkyl ester compound-aromatic 100 parts by weight of a base resin comprising 5 to 10% by weight of a vinyl compound-vinyl cyan compound copolymer and 50 to 65% by weight of a D) (meth)acrylic acid alkyl ester compound polymer; And E) 0.1 to 5 parts by weight of a siloxane polymer having a kinematic viscosity of 1,000,000 to 3,000,000 cSt; and then kneading and extruding the same,
The D) (meth)acrylic acid alkyl ester compound polymer is a high heat-resistant (meth)acrylic acid alkyl ester compound polymer having a D-1) heat deflection temperature (HDT) of more than 91°C and a flow index (MI) of 1 to 5 g/10 min. 50 to 65% by weight; And D-2) 35 to 50% by weight of a high fluidity (meth)acrylic acid alkyl ester compound polymer having a heat deflection temperature (HDT) of 91° C. or less and a flow index (MI) of more than 5 g/10 min. With
Method for producing a thermoplastic resin composition. delete It is characterized in that produced by injection of the thermoplastic resin composition according to any one of claims 1 to 7 or 10
Injection molded products. The method of claim 13,
The molded article is characterized in that the ΔL value by the Ericsen test is 1 or less.
Injection molded products. The method of claim 13,
The molded article is characterized in that the gray scale (Grey scale) according to the faded standard gray color table is 4 or higher
Injection molded products. The method of claim 13,
The molded article is characterized in that the thermal deformation temperature is 85 ℃ or more, the impact strength is 10kgfcm / cm or more
Injection molded products. The method of claim 13,
The molded article is characterized in that the flow index is 10g/10min or more
Injection molded products.