KR102382545B1 - Transparent thermoplastic resin composition for injection molding, method for preparing the composition and injection molding products comprising the composition - Google Patents

Abstract

The present invention relates to a transparent thermoplastic resin composition for injection molding, a method for manufacturing the same, and an injection-molded article comprising the same, and more particularly, two types of (meth)acrylic acid alkyl esters-aromatic vinyl compound- Conjugated diene rubber-vinyl cyan compound graft copolymer, (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer, and the compound of Formula 1 are included in a specific content range, and transparency equivalent to that of conventional transparent thermoplastic resins It relates to a transparent thermoplastic resin composition having an excellent flow index, which is significantly improved in impact strength while maintaining and provides advantageous advantages for injection molding, a method for manufacturing the same, and an injection molded article including the same.

Description

Transparent thermoplastic resin composition for injection molding, manufacturing method thereof, and injection-molded article comprising the same

The present invention relates to a transparent thermoplastic resin composition for injection molding, a method for manufacturing the same, and an injection molded article including the same, and more particularly, to include a specific sulfide-based compound, and maintains the same level of transparency as conventional transparent thermoplastic resins while maintaining the same level of impact strength is improved and relates to a transparent thermoplastic resin composition having a flow index suitable for injection molding, a method for manufacturing the same, and an injection molded article comprising the same.

Conventional transparent thermoplastic resins have excellent mechanical properties such as impact strength and excellent transparency, so they are widely used as various industrial resins such as parts of electric and electronic products. Recently, in order to use the transparent thermoplastic resin not only as a part of the product, but also as an exterior material by expanding the field of application, improvement of appearance quality is emerging as an important issue.

Therefore, it has excellent impact strength to withstand external impact while securing high transparency in terms of further improving aesthetics, and has a flow index suitable for injection molding so that it can be easily manufactured into products of various designs without limitation of shape. There is an increasing demand for the development of transparent thermoplastic resins.

In order to satisfy the above requirements, two types of methyl methacrylate-styrene-butadiene-acrylonitrile having different average particle diameters of butadiene were mixed and applied with methyl methacrylate-styrene-acrylonitrile (MSAN) to achieve a difference in refractive index There have been attempts such as maximizing transparency by minimizing

However, in the conventional method, it was difficult to simultaneously satisfy transparency, impact strength, and flow index, and there was a problem in that the manufacturing process was complicated by including a specific compound or controlling polymerization conditions during copolymer polymerization.

Development of a transparent thermoplastic resin that can withstand external shocks with improved impact strength while maintaining the same level of transparency as existing transparent thermoplastic resins without involving complicated process steps, and easy injection molding into various shapes without design restrictions this is required

Korean Patent Publication 10-2015-0026838 A

In order to solve the problems of the prior art as described above, the present invention maintains the same level of transparency as the conventional transparent thermoplastic resin composition without involving complicated process steps, provides the advantage of greatly improved impact strength, and limits the shape An object of the present invention is to provide a transparent thermoplastic resin composition that can be easily injection molded in various designs without requiring a variety of designs, and a method for manufacturing the same.

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

In order to achieve the above object, the present invention provides a first graft copolymer 10 to 20 in which an (meth)acrylic acid alkyl ester, an aromatic vinyl compound and a vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle diameter of 0.25 to 0.5 μm. weight%; 10 to 20 wt% of a second graft copolymer in which (meth)acrylic acid alkyl ester, aromatic vinyl compound and vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle diameter of 0.05 to 0.2 μm; And (meth) acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer 60 to 80% by weight; including 100 parts by weight of the base resin containing, 1 to 3 parts by weight of the compound represented by the following formula (1), the flow index (220 ° C., 10 kg) provides a transparent thermoplastic resin composition for injection molding, characterized in that 18 to 30 g / 10 min.

[Formula 1]

(In Formula 1, R1 and R2 are the same as or different from each other, and each independently an alkyl group having 1 to 8 carbon atoms)

In addition, the present invention is a first graft copolymer (meth) acrylic acid alkyl ester, an aromatic vinyl compound and a vinyl cyan compound grafted on a conjugated diene rubber having an average particle diameter of 0.25 to 0.5 μm; 10 to 20 wt%; 10 to 20 wt% of a second graft copolymer in which (meth)acrylic acid alkyl ester, aromatic vinyl compound and vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle diameter of 0.05 to 0.2 μm; And (meth) acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer 60 to 80% by weight; to 100 parts by weight of the base resin containing; 1 to 3 parts by weight of the compound represented by Formula 1 is mixed and melted and kneaded It provides a method for producing a transparent thermoplastic resin composition for injection molding, characterized in that the flow index (220° C., 10 kg) of the composition obtained after melting and kneading is 18 to 30 g/10 min.

In addition, the present invention provides an injection molded article comprising the transparent thermoplastic resin composition.

According to the present invention, it is possible to provide a transparent thermoplastic resin composition with significantly improved impact strength while maintaining the same level of transparency as that of a conventional transparent thermoplastic resin composition without involving complicated process steps.

In addition, the present invention can provide a transparent thermoplastic resin composition that can be easily injection molded in various designs without limitation in shape.

That is, according to the present invention, it is possible to maintain the same level of transparency as the conventional transparent resin composition without significantly increasing the manufacturing cost, and at the same time improve the impact strength to improve the appearance characteristics and impact resistance of the product, and in addition to As it has a flow index within the range, it is possible to provide the advantage of easy injection molding with various designs without limitation of the shape.

Hereinafter, the transparent thermoplastic resin composition for injection molding of the present invention and a manufacturing method thereof will be described in detail.

The present inventors have found that when two types of graft copolymers having different average particle diameters of rubber, MSAN resin, and the compound of Formula 1 below are blended within a specific content range, while maintaining the same level of transparency as the conventional transparent thermoplastic resin composition, impact resistance It was confirmed that this greatly improved and excellent flow index can provide the advantage of easy injection molding with various designs, and based on this, the present invention was completed.

In the present invention, the term "transparent" means that the value measured according to ASTM D1003 of a 3 mm thick specimen prepared by injection molding the composition is 2% or less.

In the present invention, the excellent flow index means having a flow index within a specific range that can be injection molded in various designs.

The transparent thermoplastic resin composition for injection molding of the present invention is, for example, a first graft copolymer 10 in which an (meth)acrylic acid alkyl ester, an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber having an average particle diameter of 0.25 to 0.5 μm. to 20% by weight; 10 to 20 wt% of a second graft copolymer in which (meth)acrylic acid alkyl ester, aromatic vinyl compound and vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle diameter of 0.05 to 0.2 μm; And (meth) acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer 60 to 80% by weight; contains 1-3 parts by weight of the compound represented by the following formula (1) to 100 parts by weight of the base resin containing; (220 ° C, 10 kg) may be characterized as 18 to 30 g / 10 min, and while maintaining high transparency of the composition within this range, the impact strength is improved to provide high impact resistance, and in addition to various shapes There is an effect of easy injection molding.

[Formula 1]

In Formula 1, R1 and R2 are the same as or different from each other, and each independently represents an alkyl group having 1 to 8 carbon atoms.

Hereinafter, the transparent thermoplastic resin composition for injection molding of the present invention will be described in detail for each component.

A1) No. 1 graft copolymer

The composition of the present disclosure includes a copolymer in which an (meth)acrylic acid alkyl ester, an aromatic vinyl compound and a vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle diameter of 0.25 to 0.5 μm, for example, a first graft copolymer, 10 to 20% by weight, 12 to 18% by weight, 13 to 17% by weight or 15 to 20% by weight, based on a total of 100% by weight of the second graft copolymer and (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinylcyanide copolymer It may be included in an amount of 18% by weight, and while maintaining high transparency of the composition within this range, it provides the advantage of uniform physical property balance.

The average particle diameter of the conjugated diene rubber included in the first graft copolymer may be, for example, 0.25 to 0.5 μm, 0.25 to 0.4 μm, or 0.3 to 0.35 μm, and within this range, transparency is maintained high while impact resistance is improved It provides the advantage of easy injection molding due to an appropriate flow index.

In the present description, the average particle diameter of the conjugated diene rubber represents a value measured using an intensity Gaussian distribution in a dynamic light skating method using a particle size distribution analyzer (Nicomp 380) in a latex state, unless otherwise specified.

The first graft copolymer is, for example, 20 to 40 wt% of (meth)acrylic acid alkyl ester, 10 to 20 wt% of an aromatic vinyl compound, and 40 to 60 wt% of a conjugated diene rubber having an average particle diameter of 0.25 to 0.5 μm, and vinyl cyanide. 1 to 10% by weight of the compound may be a grafted copolymer, and in this case, the composition provides excellent balance and transparency.

In another example, the first graft copolymer is 29 to 40% by weight of (meth)acrylic acid alkyl ester, 10 to 15% by weight of an aromatic vinyl compound, and 1 to 8% by weight of a vinyl cyanide compound to 45 to 60% by weight of the conjugated diene rubber. may be a grafted copolymer, and within this range, the composition has excellent transparency while providing an excellent balance of other physical properties.

In another example, the first graft copolymer is 30 to 37% by weight of (meth)acrylic acid alkyl ester, 11 to 13% by weight of an aromatic vinyl compound, and 2 to 5% by weight of a vinyl cyanide compound to 50 to 57% by weight of the conjugated diene rubber % may be a grafted copolymer, and within this range, the composition has excellent transparency while providing an excellent balance of other physical properties.

For example, the first graft copolymer may have a weight average molecular weight of 80,000 to 150,000 g/mol or 80,000 to 130,000 g/mol, within this range, the composition has an excellent balance of properties and easy molding.

In the present description, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) after preparing by dissolving 1 g of a resin in a solvent capable of dissolving it, unless otherwise specified.

A2) 2nd graft copolymer

The composition of the present disclosure includes a copolymer in which (meth)acrylic acid alkyl ester, an aromatic vinyl compound and a vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle diameter of 0.05 to 0.2 μm, for example, a first graft copolymer, 10 to 20% by weight, 12 to 18% by weight, 13 to 17% by weight or 15 to 20% by weight, based on a total of 100% by weight of the second graft copolymer and (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinylcyanide copolymer It may be included in an amount of 18% by weight, and while maintaining high transparency of the composition within this range, there is an advantage in that the balance of physical properties is uniform.

The average particle diameter of the conjugated diene rubber included in the second graft copolymer may be, for example, 0.05 to 0.2 μm, 0.05 to 0.15 μm, or 0.08 to 0.12 μm, and the impact strength is improved while maintaining high transparency within this range. and easy injection molding.

The second graft copolymer is, for example, 20 to 40 wt% of (meth)acrylic acid alkyl ester, 10 to 20 wt% of an aromatic vinyl compound, and 40 to 60 wt% of a conjugated diene rubber having an average particle diameter of 0.05 to 0.2 μm, and vinyl cyanide. 1 to 10% by weight of the compound may be a grafted copolymer, and in this case, there is an advantage in that the composition has excellent transparency and a uniform balance of physical properties.

The second graft copolymer is, in another example, 29 to 40 wt% of (meth)acrylic acid alkyl ester, 10 to 15 wt% of an aromatic vinyl compound and 45 to 60 wt% of a conjugated diene rubber having an average particle diameter of 0.05 to 0.2 μm and a vinyl 1 to 8% by weight of the cyanide compound may be a grafted copolymer, and in this case, there is an advantage in that the composition has excellent transparency and a uniform balance of physical properties.

In another example, the second graft copolymer is 30 to 37% by weight of (meth)acrylic acid alkyl ester, 11 to 13% by weight of an aromatic vinyl compound, and 2 to 5% by weight of a vinyl cyanide compound to 50 to 57% by weight of the conjugated diene rubber. % may be a grafted copolymer, and within this range, the composition has excellent transparency and provides an effect of uniform physical property balance.

For example, the first graft copolymer may have a weight average molecular weight of 80,000 to 150,000 g/mol or 80,000 to 130,000 g/mol, within this range, the composition has an excellent balance of properties and easy molding.

Hereinafter, each component included in the first and second graft copolymers of the present disclosure will be described.

a1) conjugate diene rubber

The conjugated diene rubber included in each of the first and second graft copolymers of the present disclosure is, for example, 1,3-butadiene, isoprene, chloroprene, and piperylene containing at least one conjugated diene-based compound selected from It is a polymer, and if necessary, a polymer polymerized by further including styrene, acrylonitrile, and the like may be possible.

For example, the conjugated diene rubber may have a gel content of 60 to 98% by weight, 60 to 90% by weight, or 70 to 90% by weight, and within this range, both transparency and impact strength of the final product are excellent.

In the present substrate, the gel content of rubber is determined by coagulating rubber latex with acid or metal salt, washing and drying in a vacuum oven at 60° C. for 24 hours, and then chopping the obtained rubber mass with scissors, It is put in 100 g and stored in a dark room at room temperature for 48 hours, separated into a sol and a gel, and is a value calculated according to Equation 1 below.

[Equation 1]

Gel content (wt%) = [weight of insoluble matter (gel) / weight of sample] X 100

a2) ( met ) acrylic acid alkyl ester

The (meth)acrylic acid alkyl ester contained in each of the first graft copolymer and the second graft copolymer of the present disclosure is, for example, an alkyl methacrylic acid alkyl ester or acrylic acid having 1 to 20 or 1 to 10 carbon atoms in the alkyl group. It may be at least one selected from among alkyl esters.

As a more specific example, (meth)acrylic acid alkyl ester is (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid 2-ethylhexyl ester, ( It may be at least one selected from meth)acrylic acid decyl ester, (meth)acrylic acid lauryl ester, and the like, and preferably includes (meth)acrylic acid methyl ester or (meth)acrylic acid ethyl ester, more preferably methacrylic acid methyl esters. In this case, the transparency of the composition provides a further advantage.

a3) aromatic vinyl compounds

The aromatic vinyl compound included in the first and second graft copolymers of the present disclosure may be, for example, at least one selected from styrene, alpha-methylstyrene, para-methylstyrene or vinyltoluene, and preferably includes styrene. will do

a4) vinyl cyanide compound

The vinyl cyan compound included in the first and second graft copolymers of the present disclosure may be, for example, at least one selected from acrylonitrile, methacrylonitrile, and ethacrylonitrile, preferably including acrylonitrile will do

In each of the first and second graft copolymers of the present disclosure, the difference between the refractive index of the conjugated diene rubber and the total refractive index of the (meth)acrylic acid alkyl ester, aromatic vinyl compound and vinyl cyan compound grafted thereto is 0.01 or less, 0.007 or less, Preferably, it may be characterized as 0.005 or less, and in this case, it provides an advantage of excellent transparency of the composition.

The total refractive index of the grafted (meth)acrylic acid alkyl ester, the aromatic vinyl compound, and the vinyl cyan compound means the refractive index of a mixture of compounds grafted to rubber or a copolymer thereof.

In the present description, the refractive index may be calculated by the following [Equation 1] unless otherwise specified.

[Equation 1]

Refractive Index (RI) = Σ Wti * RIi

- Wti = weight fraction (%) of each component in the copolymer

- RIi = refractive index of each component in the copolymer

For reference, specific examples of the refractive index of some monomer components are the same as butadiene 1.518, methyl methacrylate 1.49, styrene 1.592, and acrylonitrile 1.52.

In the present substrate, the difference between the refractive index of the first graft copolymer and the refractive index of the second graft copolymer may be 0.01 or less, 0.007 or less, preferably 0.005 or less, in which case the transparency of the composition is maximized. can provide an advantage.

B) ( met ) acrylic acid alkyl Ester-aromatic vinyl compound-vinyl cyan compound copolymer

The composition of the present disclosure comprises a (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer, a first graft copolymer, a second graft copolymer, and (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound. It contains 60 to 80% by weight, 64 to 76% by weight, 66 to 74% by weight, or 64 to 70% by weight based on 100% by weight of the total copolymer, and in this case, the transparency of the composition and the balance of physical properties are excellent. .

The (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer is, for example, 40 to 75 wt% of (meth)acrylic acid alkyl ester, 15 to 45 wt% of an aromatic vinyl compound, and 1 to 20 wt% of a vinyl cyan monomer It may be characterized as including, and within this range, the composition has excellent transparency and provides the advantage of even physical properties.

In another example, the (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer comprises 55 to 75 wt% of (meth)acrylic acid alkyl ester, 20 to 40 wt% of an aromatic vinyl compound, and 1 to 15 wt% of a vinyl cyanide compound may include, and within this range, the composition has excellent transparency while providing excellent advantages in impact resistance, moldability, and the like.

In another example, the (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer comprises 65 to 75 wt% of (meth)acrylic acid alkyl ester, 20 to 30 wt% of an aromatic vinyl compound, and 1 to 5 wt% of a vinyl cyanide compound %, and within this range, the composition is excellent in transparency and has an excellent balance of physical properties such as impact strength and moldability.

The (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer includes, for example, (meth)acrylic acid alkyl ester having 1 to 20 or 1 to 10 carbon atoms in the alkyl group, methacrylic acid alkyl ester or acrylic acid. It may be at least one selected from among alkyl esters.

As a more specific example, (meth)acrylic acid alkyl ester is (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid 2-ethylhexyl ester, ( It may be at least one selected from meth)acrylic acid decyl ester, (meth)acrylic acid lauryl ester, and the like, and preferably includes (meth)acrylic acid methyl ester or (meth)acrylic acid ethyl ester, more preferably methacrylic acid methyl esters. In this case, the transparency of the composition provides a further advantage.

The aromatic vinyl compound included in the (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer may be, for example, at least one selected from styrene, alpha-methylstyrene, para-methylstyrene, and vinyltoluene, preferably Preferably, it contains styrene.

The (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound included in the copolymer may be, for example, at least one selected from acrylonitrile, methacrylonitrile, and ethacrylonitrile, preferably It contains acrylonitrile.

In addition, in terms of maximizing transparency, the difference between the refractive index of the (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer and the refractive index of the first graft copolymer and the second graft copolymer is 0.01 Hereinafter, it may be desirable to be 0.007 or less, preferably 0.005 or less.

The (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer may be prepared by, for example, bulk polymerization and suspension polymerization, but is not limited thereto.

C) polysulfide compound

The composition of the present disclosure includes a polysulfide-based compound represented by the following Chemical Formula 1, for example, the first graft copolymer, the second graft copolymer, and (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound It may be included in an amount of 1 to 3 parts by weight based on 100 parts by weight of the total copolymer. In the present invention, when the compound of Formula 1 is included in an amount of less than 1 part by weight, the impact strength and the flow index are not improved at the same time, and in particular, the flow index is not appropriate, and thus injection moldability is poor. In addition, when the compound of Formula 1 is included in excess of 3 parts by weight, the transparency of the composition is significantly reduced, which is not preferable.

In another example, the compound of Formula 1 may be included in 1 to 2.5 parts by weight or 1 to 2 parts by weight. Within this range, the transparency of the composition is maintained high while the impact strength is improved, so that the impact resistance of the product can be improved, and the flow index is appropriate to provide the advantage of easy injection molding.

[Formula 1]

For example, in Formula 1, R1 and R2 are the same as or different from each other, and each independently may be an alkyl group having 1 to 8 carbon atoms. In this case, while maintaining high transparency of the composition, impact strength is improved and injection molding is performed without limitation of shape. This provides an easy-to-use advantage.

In another example, in Formula 1, R1 and R2 are the same as or different from each other, and each independently may be an alkyl group having 2 to 6, 3 to 6, 4 to 8, or 4 to 6 carbon atoms, in which case the transparency of the composition It provides the advantage of further improved impact strength and easy injection molding while maintaining the

As another specific example, the compound represented by Chemical Formula 1 may be di-tert-butyl trisulfide, and when it is included, the transparency is significantly improved, the impact strength of the composition is greatly improved, and injection molding is performed. This provides an easy-to-use advantage.

The composition of the present disclosure may optionally further include additives as needed, and the additives include, for example, antioxidants, heat stabilizers, lubricants, dyes, pigments, colorants, mold release agents, antistatic agents, antibacterial agents, processing aids, metal deactivators, It may be at least one selected from a flame retardant, a flame retardant, an anti-drip agent, an anti-friction agent, an anti-wear agent, and the like, but is not limited thereto.

The additive may be included, for example, 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, within this range, the base inherent in the transparent thermoplastic resin composition The effect according to the additive formulation can be realized without reducing the physical properties.

The weight ratio of the conjugated diene rubber having an average particle diameter of 0.25 to 0.5 μm and the conjugated diene rubber having an average particle diameter of 0.05 to 0.2 μm included in the composition of the present disclosure is, for example, 1:0.8 or more to less than 1:2, 1:0.9 or more to It may be less than 1:2, preferably 1:0.8 to 1:1.5, 1:0.9 to 1:1.5, 1:0.85 to 1:1.2 or 1:0.85 to 1:1.15, within this range the composition It can provide an excellent flow index that is easy for injection molding while having excellent impact strength and transparency.

The composition of the present disclosure contains the first graft copolymer, the second graft copolymer, the (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer, and the specific polysulfide-based compound represented by Formula 1 in a specific ratio. As an example, the flow index (20° C., 10 kg) is excellent, for example, 18 to 30 g/10 min or 18 to 25, while excellent in transparency, thereby providing the advantage of easy injection molding without limitation of the shape.

Hereinafter, a method of manufacturing the transparent thermoplastic resin composition for injection molding of the present invention will be described. The manufacturing method described below shares all the technical characteristics of the above-described transparent thermoplastic resin for injection molding, and therefore, a description of the overlapping part will be omitted.

The method for producing the transparent thermoplastic resin composition for injection molding of the present invention is, for example, a first graft grafted (meth)acrylic acid alkyl ester, an aromatic vinyl compound and a vinyl cyan compound to a conjugated diene rubber having an average particle diameter of 0.25 to 0.5 μm. 10 to 20% by weight of the phosphorus copolymer; 10 to 20 wt% of a second graft copolymer in which (meth)acrylic acid alkyl ester, aromatic vinyl compound and vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle diameter of 0.05 to 0.2 μm; And (meth) acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer 60 to 80% by weight; to 100 parts by weight of the base resin containing; 1 to 3 parts by weight of the compound represented by Formula 1 is mixed and melted and kneaded The composition may be characterized in that the flow index (220° C., 10 kg) of the composition obtained after melting and kneading is 18 to 30 g/10 min.

The melting and kneading may be performed, for example, under a cylinder temperature of 200 to 280 °C or 210 to 230 °C, but is not limited thereto.

After the melting and kneading, the composition may be provided in the form of pellets through extrusion, and the extrusion is not particularly limited when using an extruder commonly used in the art, and is preferably performed using a twin-screw extrusion kneader. can be

Furthermore, the composition of the present invention prepared as described above may be provided as a molded article through injection molding.

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

The molded article of this base material has excellent transparency and excellent impact strength, which provides a strong advantage against external impact, and has excellent flow index and can be used as an exterior material for home appliances or electronic products as it can be injected into various shapes.

As a specific example, the molded article of the present substrate provides an excellent advantage of transparency (ASTM D1003, thickness 3mm) of 2.0% or less or 1.5% or less.

As a specific example, the molded article of the present disclosure has an impact strength of 10 kgf·cm/cm or more, 10 to 15 kgf·cm/cm, 10.3 kgf·cm/cm or more, 10.5 kgf·cm/cm or more, 10.3 to 15 kgf·cm/cm , or 10.5 to 15 kgf·cm/cm, which provides the advantage of excellent impact resistance.

In describing the composition, manufacturing method, and molded article of the present disclosure, other conditions or equipment not explicitly described may be appropriately selected within the range commonly practiced in the art, and it is specified that there is no particular limitation.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that such variations and modifications fall within the scope of the appended claims.

Materials used in the following Examples and Comparative Examples were prepared as follows.

A1) first graft copolymer

To 50 parts by weight (based on solid content) of polybutadiene rubber latex having an average particle diameter of 0.3 μm and a refractive index of 1.516, 100 parts by weight of ion-exchanged water, 0.7 parts by weight of sodium dodecylbenzenesulfonate as an emulsifier, and 35.2 parts by weight of methyl methacrylate as a monomer 12.3 parts by weight of styrene, 2.5 parts by weight of acrylonitrile, 0.45 parts by weight of tert-dodecyl mercaptan as a molecular weight regulator, 0.048 parts by weight of sodium formaldehyde sulfoxylate as a redox agent, 0.012 parts by weight of sodium ethylenediaminetetraester , 0.001 parts by weight of ferrous sulfide and 0.04 parts by weight of cumene hydroperoxide as an initiator were continuously added at 75° C. for 5 hours to react, then the temperature was raised to 80° C., and aged for 1 hour, and the reaction was terminated. Next, an aqueous solution of calcium chloride was added to coagulate the latex, washed and dried to obtain a powdery first graft copolymer.

A2) second graft copolymer

A second graft copolymer was prepared under the same conditions and methods as those of the first graft copolymer, except that polybutadiene rubber latex having an average particle diameter of 0.1 μm and a refractive index of 1.516 was used.

B) methyl methacrylate-styrene-acrylonitrile copolymer

After mixing 73 parts by weight of methyl methacrylate, 25 parts by weight of styrene, and 2 parts by weight of acrylonitrile to 30 parts by weight of toluene as a solvent and 0.15 parts by weight of tert-dodecyl mercaptan as a molecular weight regulator, the average reaction time was 3 hours. It was continuously introduced into the reaction tank as much as possible, and the reaction temperature was maintained at 150°C. The polymerization solution discharged from the reaction tank was heated in a preheating tank, and unreacted monomers and the like were volatilized in the volatilization tank. Next, while maintaining the temperature of 210 ℃, using a polymer transfer pump extrusion processor to obtain a Pelhet type methyl methacrylate-styrene-acrylonitrile copolymer (MSAN resin).

C1) Di-tert-butyl trisulfide was used.

C2) Di-tert-dodecyl pentasulfide was used.

[Examples and Comparative Examples]

After mixing each component as shown in Table 1 below, using a twin-screw extrusion kneader, melt-kneading and extrusion were performed under the condition of a cylinder temperature of 220° C. to obtain a transparent thermoplastic resin composition in the form of pellets. After drying the pellets, physical properties were measured under the following conditions and methods.

division A1 [wt%] A2 [wt%] B [wt%] C [parts by weight] C1 C2 Example 1 15 15 70 One - Example 2 3 - Comparative Example 1 - - Comparative Example 2 0.5 - Comparative Example 3 4 - Comparative Example 4 - One Comparative Example 5 - 3 Reference Example 1 20 15 65 One - Reference Example 2 15 30 55 One -

(In Table 1, the content of each of A1, A2 and B is A1 + A2 + B = weight% based on 100% by weight in total, and the content of each of C1 and C2 is A1 + A2 + B = 100 parts by weight based on do.)

[Test Example]

The physical properties of the injection-molded articles manufactured according to Examples, Comparative Examples and Reference Examples were measured by the following method, and the results are shown in Table 2 below.

* Melt Index (MI): Measured under the conditions of 220 ℃, load 10kg according to ASTM D1238.

* 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).

* Transparency: The haze value of the 3mm thick specimen was measured according to ASTM D1003.

division impact strength
[kgf cm/cm] flow index
[g/10min] transparency
[Haze, %] Example 1 10.75 19.17 1.5 Example 2 10.36 23.49 2.0 Comparative Example 1 9.0 14.48 1.4 Comparative Example 2 10.77 17.64 1.4 Comparative Example 3 10.84 25.32 3.5 Comparative Example 4 10.84 17.64 2.2 Comparative Example 5 11.35 18.62 10.4 Reference Example 1 12.2 17.20 1.4 Reference Example 2 8.3 17.29 1.4

As shown in Table 1, in the case of Examples 1 to 3 containing di-tert-butyl trisulfide within a specific range according to the present invention, the impact strength was improved while maintaining the same level of transparency as Comparative Example 1 which did not include it. It was confirmed that the improvement was confirmed, and it was confirmed that the flow index could provide the advantage of easy injection molding within an appropriate range.

In addition, when a small amount of 0.5 parts by weight of di-tert-butyl trisulfide was applied (Comparative Example 2), it was confirmed that injection molding was not easy due to a low flow index, and 4 parts by weight of di-tert-butyl trisulfide was applied in excess. In the case of (Comparative Example 3), it was confirmed that the transparency was greatly reduced and did not meet the purpose of the present invention.

In addition, referring to Comparative Examples 4 and 5, which were tested under the same conditions as Examples 1 and 2, except that di-tert-dodecyl pentasulfide was used, the flow index was low or the transparency was low to achieve the purpose of the present application I was able to see what I couldn't do.

In addition, comparing the result values of Reference Examples 1 and 2 and Example 1 in Table 2, Reference Example 1 including an excessive amount of the rubber polymer having a relatively large average particle diameter has a lower flow index compared to Example 1, and on the contrary, the average It was confirmed that the impact strength of Reference Example 2 containing an excessive amount of the rubber polymer having a small particle size was lower than that of Example 1.

Claims (11)

10 to 20% by weight of a first graft copolymer in which an (meth)acrylic acid alkyl ester, an aromatic vinyl compound and a vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle diameter of 0.25 to 0.5 μm;
10 to 20 wt% of a second graft copolymer in which (meth)acrylic acid alkyl ester, aromatic vinyl compound and vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle diameter of 0.05 to 0.2 μm; and
(Meth) acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer 60 to 80% by weight; in 100 parts by weight of the base resin containing,
Formula 1
[Formula 1]

(In Formula 1, R1, R2 are the same as or different from each other, and each independently contains 1 to 3 parts by weight of a compound represented by an alkyl group having 2 to 6 carbon atoms),
Flow index (220 ℃, 10kg) characterized in that 18 to 30g / 10min
A transparent thermoplastic resin composition for injection molding. The method of claim 1,
Each of the first graft copolymer and the second graft copolymer is 20 to 40 wt% of (meth)acrylic acid alkyl ester, 10 to 20 wt% of an aromatic vinyl compound, and a vinyl cyan compound in 40 to 60 wt% of a conjugated diene rubber 1 to 10% by weight of the grafted copolymer
A transparent thermoplastic resin composition for injection molding. The method of claim 1,
The (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer comprises 40 to 75 wt% of (meth)acrylic acid alkyl ester, 15 to 45 wt% of an aromatic vinyl compound, and 1 to 20 wt% of a vinyl cyan monomer characterized by
A transparent thermoplastic resin composition for injection molding. delete The method of claim 1,
The compound represented by the formula (1), characterized in that di-tert-butyl trisulfide (di-tert-butyl trisulfide)
A transparent thermoplastic resin composition for injection molding. The method of claim 1,
In each of the first graft copolymer and the second graft copolymer, the difference between the refractive index of the conjugated diene rubber and the total refractive index of the (meth)acrylic acid alkyl ester, aromatic vinyl compound and vinyl cyan compound grafted thereto is 0.01 or less characterized
A transparent thermoplastic resin composition for injection molding. The method of claim 1,
The difference between the refractive indices of the first graft copolymer and the second graft copolymer and the refractive index of the (meth)acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer is 0.01 or less, characterized in that
A transparent thermoplastic resin composition for injection molding. 10 to 20% by weight of a first graft copolymer in which an (meth)acrylic acid alkyl ester, an aromatic vinyl compound and a vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle diameter of 0.25 to 0.5 μm; 10 to 20 wt% of a second graft copolymer in which (meth)acrylic acid alkyl ester, aromatic vinyl compound and vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle diameter of 0.05 to 0.2 μm; And (meth) acrylic acid alkyl ester-aromatic vinyl compound-vinyl cyan compound copolymer 60 to 80% by weight; in 100 parts by weight of a base resin containing,
Formula 1
[Formula 1]

(in Formula 1, R1 and R2 are the same as or different from each other, and each independently represents an alkyl group having 2 to 6 carbon atoms) by mixing 1 to 3 parts by weight of the compound represented by the melting and kneading step,
The composition obtained after melting and kneading has a flow index (220° C., 10 kg) of 18 to 30 g/10 min.
A method for producing a transparent thermoplastic resin composition for injection molding. Claims 1 to 3 and Claims 5 to 7, characterized in that it comprises the thermoplastic resin composition of any one of claims
injection molded products. 10. The method of claim 9,
Transparency (ASTM D1003, thickness 3mm) characterized in that less than 2.0%
injection molded products. 10. The method of claim 9,
Characterized in that the impact strength is 10 kgf cm/cm or more
injection molded products.