KR20230057940A - Thermoplastic resin composition, method for preparing the same and article prepared therefrom - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, a method for preparing the same, and a molded article manufactured therefrom, and more specifically, (A) including 70 to 85% by weight of an alkyl (meth)acrylate and 15 to 30% by weight of an aromatic vinyl compound, A polymer seed wrapped around the polymer seed and a rubber core comprising 78 to 90% by weight of an alkyl acrylate and 10 to 22% by weight of an aromatic vinyl compound, and 65 to 80% by weight of an aromatic vinyl compound and 65 to 80% by weight of vinyl cyanide wrapped around the rubber core An alkyl (meth)acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising a graft shell comprising 14 to 25% by weight of a compound and 3 to 15% by weight of an alkyl (meth)acrylate; and (B) a non-grafted copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound and a vinyl cyan compound; wherein the (A) average particle diameter and refractive index of each layer of the graft copolymer are appropriately It relates to a controlled thermoplastic resin composition, a method for preparing the same, and a molded article manufactured therefrom.
According to the present invention, there is an effect of providing a thermoplastic resin composition excellent in transparency, glossiness, weather resistance and impact resistance, a manufacturing method thereof, and a molded product manufactured therefrom.

Description

Thermoplastic resin composition, manufacturing method thereof, and molded article manufactured therefrom

The present invention relates to a thermoplastic resin composition, a method for preparing the same, and a molded product manufactured therefrom, and more particularly, to a graft copolymer having a structure of a polymer seed, a rubber core surrounding the seed, and a graft shell surrounding the core. A thermoplastic resin composition with excellent transparency, gloss, weather resistance and impact resistance by adjusting the composition and composition ratio of each layer and the morphology of the rubber core, and further adjusting the difference in refractive index with the matrix polymer, a method for manufacturing the same, and a molded product manufactured therefrom. it's about

Acrylate-styrene-acrylonitrile graft copolymer (hereinafter referred to as 'ASA resin') does not contain unstable double bonds in the polymer and has excellent weatherability, so it is used in electrical and electronic parts and building materials (eg, vinyl siding, etc.) ), extrusion profiles, and automobile parts, etc. Recently, in the field of outdoor products, market demand for high value-added products having properties such as uncoated, transparent, high chroma, and special colors is continuously increasing.

In order to realize transparency in the graft copolymer including the rubber core, the refractive index of the rubber core, the refractive index of the graft shell, and the refractive index of the matrix resin should be close to each other. Furthermore, in the resin composition including the graft copolymer and the matrix resin, the difference between the refractive index of the rubber core and the matrix resin should be small so that light is not refracted or reflected at the interface of the graft copolymer, so that the resin composition is transparent.

ASA resin composed of a butyl acrylate rubber core and a styrene-acrylonitrile copolymer shell has a refractive index of 1.46 for butyl acrylate rubber and a refractive index of 1.56 to 1.58 for styrene-acrylonitrile copolymer. The difference is large, making the resin opaque. In addition, when a styrene-acrylonitrile copolymer (hereinafter referred to as 'SAN resin') is used as a matrix resin in the ASA resin, the refractive index of the SAN resin is 1.56 to 1.58, so there is a difference in refractive index between the core of the ASA resin and the SAN resin. The cursor resin composition is opaque.

Therefore, it is necessary to develop a resin composition with excellent gloss and mechanical properties and improved weather resistance while realizing transparency by bringing the difference between the refractive index of each of the seeds, cores and shells constituting the ASA resin and the refractive index of the matrix resin into close proximity. The situation is.

Korean Patent Publication No. 2006-0118156

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a thermoplastic resin composition excellent in transparency, glossiness, weather resistance and impact resistance, a manufacturing method thereof, and a molded article manufactured therefrom.

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) a polymer seed comprising 70 to 85% by weight of an alkyl (meth)acrylate and 15 to 30% by weight of an aromatic vinyl compound, covering the polymer seed and containing 78% by weight of an alkyl acrylate to 90% by weight and 10 to 22% by weight of an aromatic vinyl compound, and covering the rubber core, 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyanide compound, and an alkyl (meth)acrylate 3 to 15% by weight of an alkyl (meth)acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising a graft shell; and (B) a non-grafted copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound, wherein the (A) graft copolymer simultaneously satisfies Equations 1 and 2 below: It provides a thermoplastic resin composition characterized in that.

[Equation 1]

200 ≤ 2*r2 ≤ 300

[Equation 2]

25 ≤ r2-r1 ≤ 45

(In Equations 1 and 2, r1 is the average radius (nm) from the center of the graft copolymer to the polymer seed, and r2 is the average radius (nm) from the center of the graft copolymer to the rubber core. )

In the (A) graft copolymer, the difference between the refractive index of the rubber core and the refractive index of the graft shell (μ _D ²⁵ ) may be 0.08 to 0.09.

The refractive index of the polymer seed of the (A) graft copolymer may have a difference between the refractive index of the polymer seed of the (A) graft copolymer and the refractive index of the (B) non-grafted copolymer (μ _D ²⁵ ) of 0.007 or less. there is.

The (A) graft copolymer may preferably include 5 to 35% by weight of the polymer seed, 25 to 55% by weight of the rubber core, and 25 to 55% by weight of the graft shell, based on 100% by weight of the total.

The (B) non-grafted copolymer may preferably include 55 to 85% by weight of an alkyl (meth)acrylate, 10 to 35% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyan compound.

The thermoplastic resin composition may preferably include (A) 10 to 90% by weight of the graft copolymer and (B) 10 to 90% by weight of the non-grafted copolymer.

The thermoplastic resin composition may preferably include (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an average rubber core diameter of 50 to 150 nm.

The thermoplastic resin composition is preferably separated into an insoluble sol and a soluble gel by stirring and centrifugation after adding acetone, and the refractive index of the sol and the refractive index of the gel (μ _D ²⁵ ) The difference of may be 0.01 or less.

The thermoplastic resin composition may preferably have a haze of 5% or less as measured by an injection specimen having a thickness of 3 mm according to ASTM D1003.

The thermoplastic resin composition may preferably have a glossiness of 120 or more as measured by an injection specimen having a thickness of 3 mm at 45° according to ASTM D2457.

The thermoplastic resin composition may preferably have an Izod impact strength of 13 kgf·cm/cm or more measured at room temperature using a specimen having a thickness of 1/4" according to ASTM D256.

In addition, the present invention (A) a polymer seed comprising 70 to 85% by weight of an alkyl (meth)acrylate and 15 to 30% by weight of an aromatic vinyl compound, surrounding the polymer seed and 78 to 90% by weight of an alkyl acrylate and an aromatic vinyl compound A rubber core comprising 10 to 22% by weight of a vinyl compound, and 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyan compound, and 3 to 15% by weight of an alkyl acrylate surrounding the rubber core an alkyl (meth)acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including a graft shell; And (B) a non-grafted copolymer comprising an alkyl (meth) acrylate, an aromatic vinyl compound and a vinyl cyan compound; including kneading and extruding under conditions of 180 to 300 ° C. and 80 to 400 rpm, The (A) graft copolymer provides a method for preparing a thermoplastic resin composition, characterized in that the following Equations 1 and 2 are simultaneously satisfied.

[Equation 1]

200 ≤ 2*r2 ≤ 300

[Equation 2]

25 ≤ r2-r1 ≤ 45

(In Equations 1 and 2, r1 is the average radius (nm) from the center of the graft copolymer to the seed, and r2 is the average radius (nm) from the center of the graft copolymer to the core.)

The kneading and extruding may preferably include (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an average rubber core diameter of 50 to 150 nm.

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 excellent impact resistance, transparency, gloss and weather resistance, a manufacturing method thereof, and a molded product manufactured therefrom.

In addition, the thermoplastic resin composition of the present invention is applied to automobile interior materials, automobile exterior materials, building materials, home appliances, or medical parts requiring high transparency, glossiness, and weather resistance, and has an advantage of imparting excellent impact resistance with a beautiful appearance.

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

In order to improve the transparency, gloss, weather resistance and impact resistance of the thermoplastic resin composition including the ASA resin and the matrix resin, the present inventors set the configuration, composition ratio, and refractive index difference of the seeds, cores and shells constituting the ASA resin within a predetermined range. When adjusting and further narrowing the difference in refractive index with the matrix resin, the effect of greatly improving transparency, gloss and weather resistance while having excellent impact resistance was confirmed, and based on this, further research was conducted to complete the present invention.

The thermoplastic resin composition of the present invention includes (A) a polymer seed comprising 70 to 85% by weight of an alkyl (meth)acrylate and 15 to 30% by weight of an aromatic vinyl compound, and 78 to 90% by weight of an alkyl acrylate surrounding the polymer seed. and 10 to 22% by weight of an aromatic vinyl compound, and 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyan compound, and 3 to 15% by weight of an alkyl (meth)acrylate surrounding the rubber core. An alkyl (meth)acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising a graft shell comprising %; and (B) a non-grafted copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound, wherein the (A) graft copolymer simultaneously satisfies Equations 1 and 2 below: Characterized in that, in this case, transparency, gloss, weather resistance and impact resistance are all excellent.

[Equation 1]

200 ≤ 2*r2 ≤ 300

[Equation 2]

25 ≤ r2-r1 ≤ 45

In Equations 1 and 2, r1 is the average polymer radius (nm) from the center of the graft copolymer, and r2 is the average radius (nm) from the center of the graft copolymer to the core.

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

(A) Alkyl (meth)acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer

The (A) graft copolymer is, for example, a polymer seed comprising 70 to 85% by weight of an alkyl (meth)acrylate and 15 to 30% by weight of an aromatic vinyl compound, surrounding the polymer seed and 78 to 90% by weight of an alkyl acrylate % and an aromatic vinyl compound 10 to 22% by weight, and the rubber core is wrapped around an aromatic vinyl compound 65 to 80% by weight, a vinyl cyan compound 14 to 25% by weight, and an alkyl (meth)acrylate 3 to 15 In this case, transparency, gloss, weather resistance and impact resistance are all excellent, and by introducing an alkyl acrylate into the graft shell, (B) the non-grafted copolymer and has the advantage of excellent compatibility.

seed

The polymer seed of the (A) graft copolymer is, for example, 70 to 85% by weight of an alkyl (meth)acrylate and 15 to 30% by weight of an aromatic vinyl compound, preferably 70 to 82% by weight of an alkyl (meth)acrylate and an aromatic It may be polymerized by including 18 to 30% by weight of a vinyl compound, more preferably 70 to 80% by weight of an alkyl (meth)acrylate and 20 to 30% by weight of an aromatic vinyl compound. In this case, the difference in refractive index with that of the (B) non-grafted copolymer is reduced, thereby providing excellent transparency, glossiness, and weather resistance.

The polymer seed of the (A) graft copolymer may have an average particle diameter of, for example, 120 to 220 nm, preferably 150 to 190 nm, and within this range, the thermoplastic resin composition finally prepared has excellent impact resistance, fluidity, and transparency , glossiness and weatherability can be imparted.

In the present description, the average particle diameter of the polymer seed, rubber core, and graft shell of the graft copolymer is measured by a measurement method commonly used in the art, including electron microscopy using SEM, TEM, etc. It is not limited, and for example, it can be measured using dynamic light scattering by sampling at the time when polymer seed preparation, rubber core preparation, and graft shell preparation are completed, respectively, and in detail, a particle meter (product name: Nicomp 380, manufacturer: PSS) is used to measure intensity values in Gaussian mode. At this time, as a specific measurement example, the sample is prepared by diluting 0.1 g of latex (TSC 35 ~ 50 wt%) 1,000 to 5,000 times with deionized water or distilled water, that is, appropriately diluted so as not to deviate greatly from the intensity setpoint of 300 kHz, put in a glass tube, and measure. The method is auto-dilution and measured with a flow cell, the measurement mode is dynamic light scattering method / Intensity 300KHz / Intensity-weight Gaussian Analysis, and the setting value is measured at a temperature of 23 ° C and a measurement wavelength of 632.8 nm can do.

The difference between the refractive index of the polymer seed of the (A) graft copolymer and the refractive index (μ _D ²⁵ ) of the (B) non-grafted copolymer is, for example, 0.007 or less, preferably 0.005 or less, and more preferably 0.003 or less. Within this range, there is an advantage in excellent weather resistance while transparency and gloss are implemented.

rubber core

The rubber core of the (A) graft copolymer encloses the polymer seed, for example, and contains 78 to 90% by weight of an alkyl acrylate and 10 to 22% by weight of an aromatic vinyl compound, preferably 80 to 90% by weight of an alkyl acrylate and an aromatic It can be polymerized by including 10 to 20% by weight of a vinyl compound, more preferably 82 to 88% by weight of an alkyl acrylate and 12 to 18% by weight of an aromatic vinyl compound. It has excellent gloss and weather resistance.

The rubber core may have, for example, an average particle diameter of 200 to 300 nm, preferably 220 to 280 nm, and more preferably 230 to 260 nm, and within this range, the physical property balance is excellent and the impact resistance is excellent. .

graft shell

The graft shell of the (A) graft copolymer encloses the rubber core and contains, for example, 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyan compound, and 3 to 15% by weight of an alkyl acrylate, preferably 67 to 77% by weight of an aromatic vinyl compound, 14 to 22% by weight of a vinyl cyan compound and 5 to 12% by weight of an alkyl acrylate, more preferably 70 to 75% by weight of an aromatic vinyl compound, 17 to 22% by weight of a vinyl cyan compound, and It may be polymerized by including 5 to 10% by weight of an alkyl acrylate. In this case, as the alkyl acrylate is introduced into the graft shell, (B) it has excellent compatibility with the non-grafted copolymer, excellent balance of physical properties, and excellent transparency, glossiness, and weather resistance.

The difference between the refractive index of the rubber core of the (A) graft copolymer and the refractive index of the graft shell (μ _D ²⁵ ) may be, for example, 0.08 to 0.09, preferably 0.081 to 0.089, more preferably 0.082 to 0.088 Within this range, transparency, gloss, weather resistance and impact resistance are all excellent.

In the present disclosure, aromatic vinyl compounds include, for example, styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brovo styrene, ρ - may be at least one selected from the group consisting of bromo styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene; Preferably it may be styrene.

In the present description, the vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethylacrylonitrile, and isopropylacrylonitrile, and is preferably acrylonitrile.

Alkyl (meth)acrylates herein may be defined to include both alkyl acrylates and alkyl methacrylates.

In the present description, the alkyl acrylate may be, for example, an alkyl acrylate having 1 to 15 carbon atoms in an alkyl group, preferably methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, It may be at least one selected from the group consisting of octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate and lauryl acrylate, preferably an alkyl group having 1 to 4 carbon atoms. It may be an alkyl acrylate containing, more preferably n-butyl acrylate, 2-ethylhexyl acrylate or a mixture thereof.

In the present description, the alkyl methacrylate may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in an alkyl group, preferably methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate rate, 2-ethylhexyl methacrylate, and may be at least one selected from the group consisting of lauryl methacrylate, more preferably an alkyl methacrylate containing an alkyl group having 1 to 4 carbon atoms, and more preferably Preferably it may be methyl methacrylate.

(A) graft copolymer

The (A) graft copolymer is, for example, the following Equations 1 and 2 are simultaneously satisfied, and in this case (B) the thickness of the rubber core of the graft copolymer (A) having a large refractive index difference with the non-grafted copolymer is reduced, resulting in excellent transparency, gloss and weather resistance, and impact resistance This has a great effect.

[Equation 1]

200 ≤ 2*r2 ≤ 300

[Equation 2]

25 ≤ r2-r1 ≤ 45

In Equations 1 and 2, r1 is the average radius (mm) from the center of the graft copolymer to the polymer seed, and r2 is the average radius (nm) from the center of the graft copolymer to the core.

The r1 may also be a value obtained by dividing the average particle diameter of the seed by half, and r2 may also be a value obtained by dividing the average particle diameter of the seed-containing core by half.

The r2-r1 denotes the thickness of the rubber core, and as the thickness of the rubber core becomes thinner, it is easier to transmit light, thereby improving transparency and gloss.

Equation 1 may be preferably 220 ≤ 2*r2 ≤ 280, more preferably 230 ≤ 2*r2 ≤ 260, and excellent impact resistance is effective within this range.

Equation 2 may be preferably 30 ≤ r2-r1 ≤ 40, more preferably 32 ≤ r2-r1 ≤ 37, and excellent transparency and glossiness are obtained within this range.

In the present description, the refractive index of each of the polymer seed, rubber core and graft shell of the graft copolymer and (B) the refractive index of the non-grafted copolymer can be calculated by Equation 3 below.

[Equation 3]

RI = Σ Wti * RIi

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

RIi = refractive index of the polymer of each component of the copolymer

In the present description, the refractive index of each component of the copolymer, that is, the polymer of the monomer, may use a value generally known in the art to which the present invention pertains, and for example, methyl methacrylate is 1.49, butyl acrylate is 1.46, and styrene is 1.592. , acrylonitrile may be 1.52.

The (A) graft copolymer may have, for example, a gel content of 70 to 98% by weight, preferably 80 to 95% by weight, more preferably 82 to 92% by weight, and within this range, impact resistance, etc. It has excellent mechanical properties.

The (A) graft copolymer may have, for example, a swelling index of 2.5 to 10, preferably 3 to 6, and more preferably 3.5 to 5, and within this range, it has excellent mechanical properties such as impact resistance and weather resistance. It has an excellent effect.

The (A) graft copolymer may have, for example, a graft rate of 30% or more, preferably 35 to 70%, more preferably 35 to 60%, and within this range, while having excellent mechanical properties such as impact resistance, It has excellent weather resistance.

The gel content, swelling index and graft rate of the present substrate were measured by adding 30 g of acetone to 0.5 g of the graft copolymer powder, stirring at 210 rpm for 12 hours at room temperature (SKC-6075, Lab companion), and centrifuging (Supra R30) , Hanil Science Co., Ltd.) after centrifugation at 0 ℃ at 18,000 rpm for 3 hours to collect only the insoluble matter that was not dissolved in acetone, and then dried by forced circulation at 85 ℃ for 12 hours (OF-12GW, Lab companion Co.) By measuring the weight, it can be obtained by calculating with Equations 4, 5 and 6 below.

[Equation 4]

Gel content (% by weight) = [weight of insoluble content (gel) (g) / sample weight (g)] * 100

[Equation 5]

Swelling index = weight of insoluble matter after centrifugation before drying (g) / weight of insoluble matter after centrifugation and drying (g)

[Equation 6]

Graft rate (%) = [weight of grafted monomer (g) / rubbery weight (g)] * 100

The weight (g) of the grafted monomer in Equation 6 is the weight obtained by subtracting the weight (g) of rubber from the weight (g) of the insoluble material (gel) after dissolving the graft copolymer in acetone and centrifuging, and rubber The weight (g) is the weight (g) of the theoretically added rubbery component in the graft copolymer powder.

The graft copolymer (A) may include, for example, 5 to 35% by weight, preferably 10 to 30% by weight, more preferably 15 to 25% by weight of the polymer seed, based on 100% by weight of the total, Within this range, there is an effect of excellent impact resistance and physical property balance. When the content of the polymer seed is less than the above range, transparency decreases, and when the content exceeds the above range, impact resistance decreases.

The (A) graft copolymer may include, for example, 25 to 55% by weight of the rubber core, preferably 30 to 50% by weight, and more preferably 35 to 45% by weight, based on 100% by weight of the total, Within this range, there is an effect of excellent impact resistance and physical property balance. If the content of the rubber core is less than the above range, the rubber content is reduced, and the impact reinforcing effect as a graft copolymer may be reduced. Compatibility with the raft copolymer is remarkably lowered, and thus, a desired refractive index may not be obtained with a decrease in the impact modifier effect.

The (A) graft copolymer may include, for example, 25 to 55% by weight, preferably 30 to 50% by weight, more preferably 35 to 45% by weight of the graft shell, based on 100% by weight of the total, , There is an effect of excellent impact resistance and physical property balance within this range. When the content of the graft shell is less than the above range, the graft efficiency is reduced and the rubber is agglomerated, thereby reducing the compatibility with the non-grafted copolymer and reducing the impact reinforcing effect, and when the content of the graft shell is excessive, the relative There is a problem that the impact efficiency is lowered due to the decrease in the rubber content.

The core of the rubber component may be, for example, an acrylic rubber polymerized by including an alkyl acrylate, an aromatic vinyl compound, and a crosslinking agent, and when the crosslinking agent is included, the gel content can be controlled and impact resistance is excellent.

The polymer seed, rubber core, or both may be divinylbenzene, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol diacrylate, and the like. Butanediol Dimethacrylate, Aryl Acrylate, Aryl Methacrylate, Trimethylolpropane Triacrylate, Tetraethylene Glycol Diacrylate, Ethylene Glycol Dimethacrylate, Diethylene Glycol Dimethacrylate, Triethylene Glycol Dimethacrylate rate, neopentyl glycol dimethacrylate, triallyl isocyanurate, triarylamine, diallylamine, and at least one selected from the group consisting of a compound represented by Formula 1 below.

[Formula 1]

In Formula 1, A is independently a substituent having a vinyl group or a (meth)acrylate group, and A′ is a hydrogen group, a substituent having a vinyl group, an alkyl group having 1 to 30 carbon atoms, an allylalkyl group having 5 to 24 carbon atoms, and a carbon number. An arylamine group having 5 to 24 carbon atoms or an allyl group having 6 to 30 carbon atoms, R is independently a divalent ethyl group or propyl group, n is 0 to 15, preferably 0 to 5, more preferably 0 to 4 is an integer of

For example, the crosslinking agent is used in an amount of 0.001 to 3 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the total monomers used in the preparation of each of the polymer seed, rubber core and graft shell of the (A) graft copolymer. Use 1 part by weight.

In the present description, the content of the monomer in the polymer may mean the weight % of the monomer added during the preparation of the polymer or the weight % of the unit in the polymer in terms of monomer.

The (A) method for preparing the graft copolymer includes, for example, i) preparing a polymer seed by including 70 to 85 wt% of an alkyl (meth)acrylate and 15 to 30 wt% of an aromatic vinyl compound; ii) preparing a rubber core comprising 78 to 90% by weight of an alkyl acrylate and 10 to 22% by weight of an aromatic vinyl compound in the presence of the polymer seed; and iii) preparing a graft copolymer by graft polymerization including 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyan compound, and 3 to 15% by weight of an alkyl acrylate in the presence of the rubber core. It may contain, and in this case, transparency, gloss, weather resistance and impact resistance are excellent.

The method for preparing the (A) graft copolymer is preferably i) a polymer seed including 70 to 85% by weight of an alkyl (meth)acrylate and 15 to 30% by weight of an aromatic vinyl compound, an electrolyte, a crosslinking agent, an initiator and an emulsifier Preparing a; ii) preparing a rubber core including 78 to 90% by weight of an alkyl acrylate, 10 to 22% by weight of an aromatic vinyl compound, a crosslinking agent, an initiator and an emulsifier in the presence of the polymer seed; and iii) graft polymerization including 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyan compound, 3 to 15% by weight of an alkyl acrylate, a crosslinking agent, an initiator and an emulsifier in the presence of the rubber core. It may include a step of preparing a copolymer, and in this case, there is an effect of excellent transparency and gloss.

In steps i), ii) and iii), the emulsifier is not particularly limited as long as it is an emulsifier commonly used in the technical field to which the present invention pertains, and for example, an alkyl sulfosuccinate metal salt having 12 to 18 carbon atoms or a derivative thereof , C 12 to C 20 alkyl sulfuric acid esters or derivatives thereof, C 12 to C 20 alkyl sulfonic acid metal salts or derivatives thereof, fatty acid soaps, and rosin acid soaps.

The C12-C18 alkyl sulfosuccinate metal salt or its derivative is preferably dicyclohexyl sulfosuccinate, dihexyl sulfosuccinate, di-2-ethylhexyl sulfosuccinate sodium salt, di-2 - It may be at least one selected from the group consisting of ethyl hexyl sulfosuccinate potassium salt, dioctyl sulfosuccinate sodium salt, and dioctyl sulfosuccinate potassium salt.

The alkyl sulfuric ester having 12 to 20 carbon atoms or a derivative thereof, the metal salt of an alkyl sulfonic acid having 12 to 20 carbon atoms or a derivative thereof, preferably contains sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, It may be at least one selected from the group consisting of sodium oleic sulfate, potassium dodecyl sulfate, and potassium octadecyl sulfate.

The fatty acid soap may be preferably one or more selected from the group consisting of oleic acid, stearic acid, lauric acid, and sodium or potassium salts of mixed fatty acids.

The rosin acid soap may preferably be an abietic acid salt.

For example, the emulsifier is 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the total monomers used in the preparation of each of the polymer seed, rubber core and graft shell of the (A) graft copolymer. parts, more preferably 1 to 3 parts by weight.

In the steps i), ii) and iii), the initiator is not particularly limited, but a radical initiator may be preferably used.

The radical initiator may be, for example, at least one selected from the group consisting of inorganic peroxides, organic peroxides, peroxyketal peroxides, peroxycarbonate peroxides, and azo compounds.

The inorganic peroxide may be preferably one or more selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, potassium persulfate, and hydrogen peroxide.

The organic peroxides include t-butyl peroxide, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2, 5di(t-butyl peroxy)-hexane, di-t-amyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di( t-butylperoxy)-cyclohexane, 1,1-di(t-amylperoxy)-cyclohexane, ethyl 3,3-di(t-amylperoxy)-butyrate, diisopropylbenzene mono-hydroper oxide, t-amyl hydroperoxide, t-butyl hydroperoxide, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, di-(3,3,5-trimethylhexanoyl)-peroxide , t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3,3,5-trimethylhexanoyl, t-amyl peroxy neodecanoate, t-amyl peroxy pivalate, t- Amyl peroxy-2-ethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-amyl peroxy 2-ethylhexyl carbonate, t-butyl peroxy 2-ethylhexyl carbonate, t- Butyl peroxy isopropyl monocarbonate, t-butyl peroxy maleic acid, cumyl peroxyneodecanoate, 1,1,3,3,-tetramethylbutyl peroxy neodecanoate, 1,1,3,3 ,-tetramethylbutyl peroxy 2-ethylhexanoate, di-2-2ethylhexyl peroxydicarbonate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, acetyl peroxide, isobutyl per oxide, octanoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, 3,5,5-trimethylhexanol peroxide, and t-butyl peroxy isobutyrate. .

The peroxyketal peroxide is preferably 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 1, The group consisting of 1-di(t-amylperoxy)cyclohexane, ethyl-3,3-di(t-butylperoxy)butylate, and ethyl-3,3-di(t-amylperoxy)butylate It may be one or more selected from.

The peroxycarbonate peroxide is preferably dicumylperoxide, di(t-butylperoxy)-m/p-diisopropylbenzene, 2,5-dimethyl-2,5-(t-butylperoxy) ) dialkyl peroxides such as hexane, t-butylcumyl peroxide, 2,5-methyl-2,5-(t-butylperoxy)hexyne-3, t-butyl peroxy 2-ethylhexyl monocarbonate, and It may be at least one selected from the group consisting of t-butyl peroxybenzoate.

The azo compound is preferably one selected from the group consisting of azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyrate (butyrate)methyl. may be ideal

In at least one of the steps i), ii) and iii), an activator may be used to accelerate the peroxide initiation reaction together with the polymerization initiator.

The activator is not particularly limited if it is an activator commonly used in the art to which the present invention pertains.

The activator may be added in an amount of 0.01 to 3 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the graft copolymer, and a high degree of polymerization can be achieved within this range.

Steps i), ii) and iii) may use, for example, an oxidation-reduction system catalyst in order to further accelerate the initiation reaction together with the initiator.

The oxidation-reduction catalyst may be, for example, at least one selected from the group consisting of sodium pyrophosphate, dextrose, ferrous sulfide, sodium sulfite, sodium formaldehyde sulfoxylate and sodium ethylenediamine tetraacetate, preferably may be a mixture of sodium pyrophosphate, dextrose and ferrous sulfide, but is not limited thereto.

In step i), the electrolyte is, for example, KCl, NaCl, KHCO ₃ , NaHCO ₃ , K _{2 CO 3 , Na 2 CO 3} , KHSO _{3 ,} NaHSO ₄ , Na ₂ S ₂ O ₇ , K ₃ P ₂ O ₇ , K At least one selected from the group consisting of ₃ PO ₄ , Na ₃ PO ₄ , and Na ₂ HPO ₄ may be used, but is not limited thereto.

Step iii) may include, for example, a molecular weight modifier.

The molecular weight modifier may be, for example, 0.01 to 2 parts by weight, preferably 0.05 to 2 parts by weight, more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the total graft copolymer, within this range the desired molecular weight A polymer having a can be easily prepared.

Examples of the molecular weight modifier include α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethyl thiuram disulfide, and dipentamethylene thioate. At least one selected from the group consisting of uram disulfide and diisopropylxantogen disulfide may be used, but is not limited thereto.

In this description, 100 parts by weight of the graft copolymer means 100 parts by weight of the total weight of the finally obtained graft copolymer, or since almost all of the input monomers participate in the polymer, it is convenient to use the monomers used in the polymer seed, rubber core, and graft shell. It may mean based on 100 parts by weight of the total weight of all or the combined weight of the monomers added during the manufacture of the polymer seed and the rubber core and the monomers added during the manufacture of the graft shell.

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

The emulsion polymerization is not particularly limited when the emulsion polymerization method is commonly performed in the art.

The polymerization temperature during the emulsion polymerization is not particularly limited, but may be carried out at, for example, 50 to 85°C, preferably 60 to 80°C.

The (A) latex of the graft copolymer may be in powder form through conventional processes such as coagulation, washing, and drying, and specifically, coagulation at a temperature of 60 to 100 ° C. by adding a metal salt or acid, It may be prepared in powder form through aging, dehydration, washing and drying processes, but is not limited thereto.

The (A) graft copolymer is, for example, 10 to 90% by weight, preferably 30 to 70% by weight, more preferably 30 to 70% by weight, for example, based on the total weight of (A) graft copolymer and (B) non-grafted copolymer Preferably, it is 40 to 60% by weight, and within this range, transparency, gloss, weather resistance and impact resistance are all excellent.

(B) a non-grafted copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound and a vinyl cyan compound

The (B) non-grafted copolymer is a matrix resin, and includes, for example, an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound, preferably 55 to 85% by weight of an alkyl (meth)acrylate, It is composed of 10 to 35% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyan compound, and within this range, compatibility with the (A) graft copolymer is excellent, and transparency, glossiness, weather resistance and resistance All impact properties have excellent effects.

The (B) non-grafted copolymer preferably comprises 60 to 80% by weight of an alkyl (meth)acrylate, 15 to 30% by weight of an aromatic vinyl compound, and 1 to 15% by weight of a vinyl cyan compound, and within this range has excellent compatibility with the graft copolymer (A) and excellent transparency, glossiness and impact resistance.

The (B) non-grafted copolymer more preferably comprises 65 to 75% by weight of an alkyl (meth)acrylate, 20 to 25% by weight of an aromatic vinyl compound, and 5 to 10% by weight of a vinyl cyan compound, within this range. It has excellent compatibility with the (A) graft copolymer and excellent transparency, glossiness, weather resistance and impact resistance.

In the present description, 'non-grafted' means not grafted, and more specifically means not grafted under rubber.

The types of the alkyl (meth)acrylate, aromatic vinyl compound and vinyl cyan compound included in the (B) non-grafted copolymer are the alkyl (meth)acrylate and aromatic vinyl contained in the (A) graft copolymer of the present description It may be within the same category as the type of compound and vinyl cyan compound.

The (B) non-grafted copolymer may preferably be a methyl methacrylate-styrene-acrylonitrile copolymer, and in this case, the difference in refractive index of the (A) graft copolymer with the polymer seed is reduced, thereby improving transparency and It has an excellent gloss effect.

The (B) non-grafted copolymer may have, for example, a weight average molecular weight of 50,000 to 150,000 g/mol, preferably 60,000 to 130,000 g/mol, and more preferably 70,000 g/mol to 100,000 g/mol. There is an effect of excellent impact resistance and moldability within this range.

In the present description, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze) unless otherwise defined, and as a specific example, GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent. ), it can be measured as a relative value for a standard PS (standard polystyrene) sample. At this time, as a specific measurement example, solvent: THF, column temperature: 40 ℃, flow rate: 0.3ml / min, sample concentration: 20mg / ml, injection amount: 5μl, column model: 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI temperature: 35℃, data processing: Agilent ChemStation S/W, test method (Mn, Mw and PDI): can be measured under OECD TG 118 conditions.

The (B) non-grafted copolymer is, for example, i) 55 to 85 parts by weight of an alkyl (meth)acrylate, 10 to 35 parts by weight of an aromatic vinyl compound, and 1 to 20 parts by weight of a vinyl cyan compound for a total of 100 parts by weight of the reaction medium Preparing a reaction mixture by mixing 25 to 35 parts by weight; ii) adding 0.005 to 0.05 parts by weight of an organic peroxide initiator having a bifunctional group to the reaction mixture of step i) based on 100 parts by weight of the reaction mixture; and iii) polymerizing the mixture to which the initiator of step ii) is added.

Polymerization in step iii) may be preferably carried out at 110 to 140°C for 2 to 4 hours, followed by further polymerization at 120 to 160°C for 2 to 4 hours.

In step i), the reaction medium may be, for example, at least one selected from the group consisting of ethylbenzene, toluene, and xylene, and is preferably toluene.

The organic peroxide initiator having a bifunctional group in step ii) is, for example, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 1, 1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and 1,1-bis(t-butylperoxy)2 - At least one selected from the group consisting of methylcyclohexane, and in this case, there is an advantage in that productivity is excellent and thermal discoloration is reduced.

Step iii) may include, for example, an antioxidant, preferably 0.05 to 1 part by weight, more preferably 0.05 to 1 part by weight based on 100 parts by weight of the aromatic vinyl compound, alkyl (meth)acrylate, and vinyl cyan compound in total. It may be 0.05 to 0.5 parts by weight.

The (B) non-grafted copolymer may be prepared by, for example, solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, preferably bulk polymerization. The solution polymerization, block polymerization, emulsion polymerization, and suspension polymerization are not particularly limited when each of the polymerization, block polymerization, emulsion polymerization, or suspension polymerization commonly performed in the art to which the present invention pertains.

The (B) non-grafted polymer is, for example, 10 to 90% by weight, preferably 30 to 70% by weight, more preferably 30 to 70% by weight, for example, based on the total weight of (A) graft copolymer and (B) non-grafted copolymer is 40 to 60% by weight, and within this range, transparency, gloss, weather resistance and impact resistance are all excellent.

In the present description, a polymer comprising a certain compound means a polymer polymerized including the compound, and a unit in the polymer is derived from the compound.

(C) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an average rubber core diameter of 50 to 150 nm

The thermoplastic resin composition may include, for example, (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an average particle diameter of 50 to 150 nm of the rubber core, and in this case, (B) non-grafted It has excellent compatibility with the copolymer and has the advantage of further improving transparency and glossiness.

The (C) graft copolymer may have, for example, an average particle diameter of 50 to 150 nm, preferably 70 to 130 nm, and more preferably 80 to 110 nm, and has excellent physical property balance and impact resistance within this range. It has an excellent effect.

The (C) graft copolymer is, for example, a rubber core comprising 78 to 90% by weight of an alkyl acrylate and 10 to 22% by weight of an aromatic vinyl compound, and 65 to 80% by weight of an aromatic vinyl compound surrounding the rubber core, It may be a graft copolymer including a graft shell comprising 14 to 25% by weight of a vinyl cyan compound and 3 to 15% by weight of an alkyl acrylate, in which case (B) compatibility with the non-grafted copolymer is It has the advantage of being superior in transparency, gloss and weather resistance while being excellent in impact resistance.

The (C) graft copolymer is preferably a rubber core comprising 80 to 90% by weight of an alkyl acrylate and 10 to 20% by weight of an aromatic vinyl compound, and 67 to 77% by weight of an aromatic vinyl compound surrounding the rubber core , 14 to 22% by weight of a vinyl cyan compound, and 5 to 12% by weight of an alkyl acrylate, and in this case, (B) has excellent compatibility with the non-grafted copolymer and has excellent impact resistance While this is excellent, there is an advantage in that transparency, glossiness, and weather resistance are further improved.

The (C) graft copolymer is more preferably a rubber core comprising 82 to 88% by weight of an alkyl acrylate and 12 to 18% by weight of an aromatic vinyl compound, and 70 to 75% by weight of an aromatic vinyl compound surrounding the rubber core %, 17 to 22% by weight of a vinyl cyan compound, and 5 to 10% by weight of an alkyl acrylate, and in this case, (B) has excellent compatibility with the non-grafted copolymer and There is an advantage in that transparency, glossiness, and weather resistance are further improved while impact resistance is excellent.

The (C) graft copolymer comprises, for example, 30 to 60% by weight of a rubber core and 40 to 70% by weight of a graft shell, preferably 35 to 55% by weight of a rubber core and 45 to 65% by weight of a graft shell, more preferably Preferably, 40 to 50% by weight of the rubber core and 50 to 60% by weight of the graft shell may be used, and within this range, there is an advantage in that the mechanical properties are excellent.

The types of the alkyl acrylate, aromatic vinyl compound, and vinyl cyan compound included in the (C) graft copolymer are the alkyl acrylate, aromatic vinyl compound, and vinyl cyan compound included in the graft copolymer (A) of the present description. It may be within the same category as the type.

The (C) method for preparing the graft copolymer includes, for example, i) preparing a rubber core by including 78 to 90% by weight of an alkyl acrylate and 10 to 22% by weight of an aromatic vinyl compound; and ii) preparing a graft copolymer by graft polymerization including 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyan compound, and 3 to 15% by weight of an alkyl acrylate in the presence of the rubber core. It may contain, and in this case, there is an effect of excellent transparency and gloss.

The (C) method for preparing the graft copolymer preferably includes i) preparing a rubber core including 78 to 90% by weight of an alkyl acrylate, 10 to 22% by weight of an aromatic vinyl compound, a crosslinking agent, an initiator and an emulsifier; and iii) graft polymerization including 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyan compound, 3 to 15% by weight of an alkyl acrylate, a crosslinking agent, an initiator and an emulsifier in the presence of the rubber core. It may include a step of preparing a copolymer, and in this case, there is an effect of excellent transparency and gloss.

The types of crosslinking agent, initiator, and emulsifier used in steps i) and/or ii) may be within the same range as the types of crosslinking agent, initiator, and emulsifier used in the emulsion polymerization step of (A) graft copolymer of the present description. there is.

The total sum of the weights of the (A) graft copolymer and (C) graft copolymer is (A) graft copolymer, (B) non-grafted copolymer and (C) graft copolymer total 100% by weight For example, 10 to 90% by weight, preferably 30 to 70% by weight, more preferably 40 to 60% by weight based on, and within this range, transparency, glossiness, weather resistance and impact resistance are all excellent. there is

The weight ratio (A:C) of the graft copolymer (A) and the graft copolymer (C) is, for example, 5:5 to 7:3, preferably 5.5:4.5 to 6.5:3.5, more preferably 5.7 : 4.3 to 6.2 : 3.8, and within this range, transparency, glossiness, weather resistance and impact resistance are more excellent.

thermoplastic resin composition

The thermoplastic resin composition is preferably separated into an insoluble sol and a soluble gel by stirring and centrifugation after adding acetone, and the refractive index of the sol and the refractive index of the gel (μ _D ²⁵ ) The difference of is 0.01 or less, more preferably 0.007 or less, still more preferably 0.005 or less, and even more preferably 0.003 or less, and within this range, there is an advantage that transparency, glossiness and weather resistance are further improved.

Specifically, the difference in refractive index between the sol and the gel of the thermoplastic resin composition in the present substrate was measured by adding 0.5 g of the thermoplastic resin composition pellet to 30 g of acetone and then stirring at 210 rpm for 12 hours at room temperature (SKC-6075, Lab companion). , It is centrifuged for 3 hours at 0 ° C. and 18,000 rpm with a centrifuge (Supra R30, Hanil Scientific Co.) to separate gel, an insoluble material that is not dissolved in acetone, and sol, a soluble material. After drying at 85 ° C. for 12 hours in a forced circulation method (OF-12GW, Lab companion Co.), the refractive index of each gel and sol is measured according to ASTM D542.

In the present description, the refractive index is specifically measured at room temperature using an Abbe refractometer according to ASTM D542.

In the present description, room temperature may be a point in the range of 20 ± 5 ° C.

The present invention has an effect of providing a resin composition having better transparency and gloss by controlling the difference between the refractive index of the sol and the refractive index of the gel within the above range.

The thermoplastic resin composition preferably has a haze of 5% or less, more preferably 4.5% or less, still more preferably 4% or less, even more preferably, as measured by an injection specimen having a thickness of 3 mm in accordance with ASTM D1003 Preferably, it is 3.8% or less, particularly preferably 0.1 to 3.8%, and within this range, all of the physical property balances have excellent effects.

The thermoplastic resin composition preferably has a haze of 2.5% or less, more preferably 2% or less, still more preferably 1.8% or less, even more preferably 0.1 to 1.8%, and within this range, all of the physical property balances have excellent effects.

In this description, the haze is specifically measured according to ASTM D1003 for each of the injection specimen having a thickness of 3 mm and the extrusion specimen having a thickness of 0.15 mm using a haze meter (MURAKAMI, model name: HM-150), and the haze value is small. The better the transparency.

The thermoplastic resin composition preferably has a gloss of 120 or more, more preferably 130 or more, still more preferably 135 or more, even more preferably, measured at 45 ° with an injection specimen having a thickness of 3 mm according to ASTM D2457 135 to 145, and within this range, there is an effect of excellent physical property balance.

The thermoplastic resin composition preferably has a gloss of 120 or more, more preferably 125 or more, and still more preferably 125 to 135, as measured at 60 ° with an extruded specimen having a thickness of 0.15 mm according to ASTM D2457, within this range has an excellent effect on all of the physical property balance.

The thermoplastic resin composition preferably has an Izod impact strength of 13 kgf cm / cm or more, more preferably 15 kgf cm / cm or more, more preferably, measured at room temperature with a specimen having a thickness of 1/4 "in accordance with ASTM D256 It may be 15 to 20 kgf cm / cm, and within this range, all of the physical property balance has an excellent effect.

The thermoplastic resin composition is preferably tested using an accelerated weathering tester (Weather-o-meter, ATLAS, Ci4000, xenon arc lamp, Quartz (inner)/S.Boro (outer) filter, irradiance 0.55 W/m2 at 340 nm). After being allowed to stand for 3,000 hours under SAE J1960 conditions, the degree of discoloration is measured with a color difference meter and the weatherability (ΔE) calculated by Equation 7 below is 2.8 or less, more preferably 2.6 or less, still more preferably 2.5 or less, More preferably, it may be 0.1 to 2.5, and within this range, all of the physical property balances have excellent effects.

[Equation 7]

The β is the arithmetic average value of L, a, and b values obtained by measuring the specimens before and after the accelerated weathering test using the CIE LAB color coordinate system, and the closer the ΔE value is to 0, the better the weatherability.

The thermoplastic resin composition may include, for example, at least one selected from the group consisting of a lubricant, an antioxidant, and an ultraviolet absorber.

The lubricant may be, for example, at least one selected from the group consisting of ethylene bis steramide, polyethylene oxide wax, magnesium stearate, calcium steramide, and stearic acid, and in this case, heat resistance and fluidity are improved. .

The lubricant may be 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the total of (A) the graft copolymer and (B) the non-grafted copolymer.

The antioxidant may include, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, or a mixture thereof, and may preferably be a phenol-based antioxidant. In this case, oxidation by heat is prevented during the extrusion process, and mechanical properties and heat resistance are improved. This has an excellent effect.

The antioxidant may be, for example, 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, based on the total 100 parts by weight of (A) the graft copolymer and (B) the non-grafted copolymer, and within this range, the physical properties It has an effect of improving heat resistance while being excellent in balance.

The UV absorber may be, for example, at least one selected from the group consisting of a triazine-based UV absorber, a benzophenone-based UV absorber, a benzotriazole-based UV absorber, a benzoate-based UV absorber, and a cyanoacrylate-based UV absorber, but is limited thereto It is not.

The UV absorber may be, for example, 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the total of (A) the graft copolymer and (B) the non-grafted copolymer, and has excellent physical property balance. There is an effect of improving light fastness.

The thermoplastic resin composition is, for example, a fluorescent whitening agent, an antistatic agent, a chain extender, a release agent, a pigment, a dye, an antibacterial agent, a processing aid, a metal deactivator, a smoke suppressant, an inorganic filler, a glass fiber, a friction agent, and a wear resistance group consisting of It may further include one or more additives selected from.

The additive is, for example, 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total of (A) graft copolymer and (B) non-grafted copolymer. In this case, the improvement in physical properties is excellent and the manufacturing cost is low, so there is an effect of excellent economic feasibility.

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

Manufacturing method of thermoplastic resin composition

A method for producing the thermoplastic resin composition of the present disclosure includes (A) a polymer seed comprising 70 to 85% by weight of an alkyl (meth)acrylate and 15 to 30% by weight of an aromatic vinyl compound; A rubber core comprising 90% by weight and 10 to 22% by weight of an aromatic vinyl compound, and 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyan compound, and 3 to 15% by weight of an alkyl acrylate surrounding the rubber core An alkyl (meth)acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising a graft shell comprising %; And (B) a non-grafted copolymer comprising an alkyl (meth) acrylate, an aromatic vinyl compound and a vinyl cyan compound; including kneading and extruding under conditions of 180 to 300 ° C. and 80 to 400 rpm, The (A) graft copolymer is characterized in that it simultaneously satisfies Equations 1 and 2 below, and in this case, it has excellent transparency, glossiness, weather resistance and impact resistance.

[Equation 1]

200 ≤ 2*r2 ≤ 300

[Equation 2]

25 ≤ r2-r1 ≤ 45

In Equations 1 and 2, r1 is the average radius (nm) from the center of the graft copolymer to the seed, and r2 is the average radius (nm) from the center of the graft copolymer to the core.

The kneading and extruding step may preferably include (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an average particle diameter of 50 to 150 nm of the rubber core, more preferably (C ) A rubber core having an average particle diameter of 50 to 150 nm and containing 78 to 90% by weight of an alkyl acrylate and 10 to 22% by weight of an aromatic vinyl compound, and 65 to 80% by weight of an aromatic vinyl compound and a vinyl cyan compound surrounding the rubber core It may include an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including a graft shell comprising 14 to 25% by weight and 3 to 15% by weight of an alkyl acrylate, and in this case, the impact resistance is While excellent, there is an effect of greatly improving transparency and glossiness.

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

The kneading and extrusion may be carried out, for example, at a barrel temperature of 180 to 300 ° C, preferably 190 to 280 ° C, more preferably 200 to 260 ° C, in which case the throughput per unit time is appropriate and sufficient melting Kneading may be possible, and there is an effect of not causing problems such as thermal decomposition of the resin component.

The kneading and extruding may be performed, for example, under the condition that the number of rotations of the screw is 80 to 400 rpm, preferably 100 to 300 rpm, and more preferably 150 to 250 rpm. It has an excellent effect.

The thermoplastic resin composition obtained through the extrusion may be made into pellets using, for example, a pelletizer.

Furthermore, the resin composition may be manufactured into molded articles in various industrial fields through molding processes such as a blow process and an injection process.

molding

The molded article of the present substrate may include, for example, the thermoplastic resin composition of the present substrate, and has excellent transparency, gloss, weather resistance and impact resistance, so that it can be applied with high quality to fields requiring transparency.

The molded product may be, for example, an injection molded product, a film or a sheet, and in this case, the thermoplastic resin composition of the present substrate has the advantage of being able to provide higher quality than the impact resistance, transparency, weather resistance and gloss required by the market.

The molded article may be, for example, an automobile interior material, an automobile exterior material, a building material, a home appliance, or a medical part. there is.

The manufacturing method of the molded article is preferably (A) a polymer seed comprising 70 to 85% by weight of an alkyl (meth)acrylate and 15 to 30% by weight of an aromatic vinyl compound, and wrapping the polymer seed with 78 to 90% by weight of an alkyl acrylate A rubber core comprising 10 to 22% by weight and an aromatic vinyl compound, and 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyan compound, and 3 to 15% by weight of an alkyl acrylate surrounding the rubber core An alkyl (meth)acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising a graft shell comprising; And (B) a non-grafted copolymer comprising alkyl (meth) acrylate, an aromatic vinyl compound and a vinyl cyan compound; including, kneading and extruding under conditions of 180 to 300 ° C. and 80 to 400 rpm to produce pellets. doing; and injecting or extruding the prepared pellets using an extruder or an extruder, wherein the (A) graft copolymer simultaneously satisfies Equations 1 and 2 below, and in this case, transparency and gloss It has excellent properties in terms of durability, weather resistance and impact resistance, so it can be applied with high quality to areas where transparency is required.

[Equation 1]

200 ≤ 2*r2 ≤ 300

[Equation 2]

25 ≤ r2-r1 ≤ 45

In Equations 1 and 2, r1 is the average radius (nm) from the center of the graft copolymer to the polymer seed, and r2 is the average radius (nm) from the center of the graft copolymer to the rubber core.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention, but the following examples are merely illustrative of the present invention, and various changes and modifications are possible within the scope and spirit of the present invention. It is obvious to those skilled in the art, It goes without saying that these variations and modifications fall within the scope of the appended claims.

[Example]

Materials used in Examples and Comparative Examples are as follows.

* (A) Graft Copolymer: Prepared in Examples 1 to 10 and Comparative Examples 1 to 11 below

* (B-1) SAMMA copolymer: methyl methacrylate-styrene-acrylonitrile non-grafted copolymer comprising 71% by weight of methyl methacrylate, 22% by weight of styrene and 7% by weight of acrylonitrile

* (B-2) SAN copolymer: styrene-acrylonitrile non-grafted copolymer (LG Chemical Co., Ltd., 90HR) comprising 73% by weight of styrene and 27% by weight of acrylonitrile

* (C) Graft Copolymer: A rubber core comprising 85% by weight of butyl acrylate and 15% by weight of styrene and having an average particle diameter of 90 mm, and 72% by weight of styrene, 20% by weight of acrylonitrile and Graft copolymer comprising a graft shell consisting of 8% by weight of butyl acrylate (45% by weight rubber core and 55% by weight graft shell)

* Lubricant: SUNLUBE EBS (Seonpione)

* Antioxidants: Songnox 1076 (Songwon) and Irgafos 168 (BASF)

* UV absorber: Tinuvin 770 (BASF Company), Tinuvin P (BASF Company)

Example 1

As a polymer seed, methyl methacrylate (hereinafter referred to as 'MMA') and styrene (hereinafter referred to as 'SM') were included in a weight ratio of 72/28, and butyl acrylate (hereinafter referred to as 'BA') was used as a rubber core. ) and SM in a weight ratio of 85/15, and (A) acrylate- A styrene-acrylonitrile graft copolymer was prepared. In this case, (A) the graft copolymer was composed of 20% by weight of the polymer seed, 40% by weight of the rubber core, and 40% by weight of the graft shell.

50 parts by weight of the prepared (A) graft copolymer and 50 parts by weight of the non-grafted copolymer (B) were mixed with 1 part by weight of a lubricant, 1 part by weight of an antioxidant, and 0.6 part by weight of a UV absorber and kneaded at 220 ° C. and 200 rpm and extruded to produce pellets. The prepared pellets were injected at a molding temperature of 220 ° C to produce an injection specimen for measuring physical properties, and also extruded with a single-screw film extruder under the conditions of 220 ° C and 200 rpm with the prepared pellets to produce an extruded specimen for measuring physical properties.

Examples 2 to 8

In Example 1, the (A) graft copolymer was polymerized with the components and contents listed in Tables 1 and 2, and the same procedure as in Example 1 was performed except for changing .

Example 9

Example 7, except that 50 parts by weight of (A) graft copolymer prepared in Example 7 was changed to 30 parts by weight of (A) graft copolymer and (C) 20 parts by weight of graft copolymer. It was carried out in the same way as in 7.

Example 10

Example 7, except that 50 parts by weight of (A) graft copolymer prepared in Example 7 was changed to 35 parts by weight of (A) graft copolymer and 15 parts by weight of (C) graft copolymer. It was carried out in the same way as in 7.

Comparative Examples 1 to 10

In Example 1, (A) ASA graft copolymer, the same as in Example 1 except for changing to (A) ASA graft copolymer polymerized with the components and contents shown in Tables 3 to 4 below. conducted.

11 in comparison

Example 5 was carried out in the same manner as in Example 1, except that (B-1) SAMMA copolymer was changed to (B-2) SAN copolymer.

12 in comparison

A transparent acrylonitrile-butadiene-styrene resin (LG Chemical Co., TR557) was injected to prepare an injection specimen for measuring physical properties.

[Test Example]

The properties of the pellets and specimens prepared in Examples 1 to 10 and Comparative Examples 1 to 12 were measured by the following method, and the results are shown in Tables 1 to 4 below.

* The refractive index of the seed, core, and shell of the graft copolymer and the refractive index of the non-grafted copolymer: calculated by Equation 3 below.

[Equation 3]

RI = Σ Wti * RIi

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

RIi = refractive index of the polymer of each component of the copolymer

* Average particle diameter (nm) of polymer seed, rubber core, and graft shell: Sampled at the time when polymer seed preparation, rubber core preparation, and graft shell preparation were completed, respectively, and measured using dynamic light scattering. In detail, it was measured as an intensity value in Gaussian mode using a particle meter (product name: Nicomp 380, manufacturer: PSS). At this time, as a specific measurement example, 0.1 g of latex having a total solid content of 35 to 50% by weight is prepared by diluting 1,000 to 5,000 times with distilled water as a sample, the measurement method is auto-dilution and measurement is performed with a flow cell, and the measurement mode is dynamic light scattering Method (Dynamic light scattering) method / Intensity 300KHz / Intensity-weight Gaussian Analysis was used, and the setting value was measured at a temperature of 23 ° C. and a measurement wavelength of 632.8 nm.

For reference, r1 is a value obtained by dividing the average particle diameter of the seed by half, and r2 is a value obtained by dividing the average particle diameter of the seed-containing core by half.

* Izod impact strength (IMP; kgf cm/cm): Measured at room temperature with an injection specimen having a thickness of 1/4" according to ASTM D256.

* Haze (%): Haze was measured according to ASTM D1003 for each of the 3 mm thick injection specimen and the 0.15 mm thick extruded specimen. The lower the haze, the better the transparency.

* Gloss of injection specimen: Gloss was measured at 45 ° with an injection specimen having a thickness of 3 mm in accordance with ASTM D2457.

* Glossiness of the extruded specimen: The glossiness was measured at 60 ° with an extruded specimen having a thickness of 0.15 mm in accordance with ASTM D2457.

* Difference in refractive index between sol and gel in thermoplastic resin composition: After adding 30 g of acetone to 0.5 g of pellets of thermoplastic resin composition, stirring at 210 rpm for 12 hours at room temperature (SKC-6075, Lab companion Co.) Then, it was centrifuged for 3 hours at 0 ° C. and 18,000 rpm using a centrifuge (Supra R30, Hanil Scientific Co.) to separate a gel, which is an insoluble material that is not dissolved in acetone, and a sol, which is a soluble material. After drying at 85℃ for 12 hours by forced circulation method (OF-12GW, Lab companion), each refractive index is measured at room temperature using an Abbe refractometer according to ASTM D542, and the difference between them is calculated did

* Weatherability (ΔE): Accelerated weatherability tester (Weather-o-meter, ATLAS, Ci4000, xenon arc lamp, Quartz (inner)/S.Boro (outer) filter, irradiance 0.55 W/m ² at 340 nm) After leaving it for 3,000 hours under SAE J1960 conditions using a color difference meter, the degree of discoloration was measured and ΔE was calculated by Equation 7 below. The following ΔE is the arithmetic average value of L, a, and b values measured using the CIE LAB color coordinate system for specimens before and after the accelerated weathering test, and the closer the ΔE value is to 0, the better the weatherability.

[Equation 7]

In Equation 7, L', a', and b' are L, a, and b values respectively measured by the CIE LAB color coordinate system after leaving the specimen for 3,000 hours under SAE J1960 conditions, and L ₀ , a ₀ , b ₀ is the L, a, and b values respectively measured in the CIE LAB color coordinate system before leaving.

division Example 1 Example 2 Example 3 Example 4 (A)
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sifter seed MMA/SM
(weight%) 72/28 72/28 72/28 72/28 core BA/SM
(weight%) 85/15 85/15 85/15 85/15 shell SM/AN/BA (% by weight) 76/16/8 71/18/11 71/24/5 68/22/10 2*r2 (nm) 240 240 240 240 r2-r1 (nm) 35 35 35 35 The difference between the refractive index of the core and the refractive index of the shell 0.089 0.083 0.087 0.082 Thermoplastic resin composition (A) Graft
Copolymer (% by weight) 50 50 50 50 (B-1) SAMMA copolymer
(weight%) 50 50 50 50 (C) Graft
Copolymer (% by weight) - - - - (A) of the graft copolymer
Seed's refractive index and
(B) of the non-grafted copolymer
Difference from refractive index 0.004 0.004 0.004 0.004 ejaculation
Psalter Haze (%) 4.7 4.5 4.3 4.8 Impact strength (kgf cm/cm) 14 15 13 15 Glossiness 135 132 134 131 Weather resistance (ΔE) 2.6 2.2 2.4 2.2 extrusion
Psalter Haze (%) 2.2 2.1 2.3 2.1 Glossiness 127 123 123 124 In the thermoplastic resin composition
Difference in refractive index between sol and gel 0.0034 0.0020 0.0031 0.0024

division Example
5 Example
6 Example
7 Example
8 Example
9 Example
10 (A)
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sifter seed MMA/SM
(weight%) 72/28 76/24 78/22 82/18 78/22 78/22 core BA/SM
(weight%) 85/15 87/13 85/15 85/15 85/15 85/15 shell SM/AN/BA (% by weight) 72/20/8 72/20/8 72/20/8 72/20/8 72/20/8 72/20/8 2*r2 (nm) 240 240 240 240 240 240 r2-r1 (nm) 35 35 35 35 35 35 The difference between the refractive index of the core and the refractive index of the shell 0.086 0.088 0.086 0.086 0.086 0.086 Thermoplastic resin composition (A) Graft
Copolymer (% by weight) 50 50 50 50 30 35 (B-1) SAMMA copolymer
(weight%) 50 50 50 50 50 50 (C) Graft
Copolymer (% by weight) - - - - 20 15 (A) of the graft copolymer
Seed's refractive index and
(B) of the non-grafted copolymer
Difference from refractive index 0.004 0.000 0.002 0.006 0.002 0.002 ejaculation
Psalter Haze (%) 4.1 3.7 3.5 3.6 2.2 2.6 Impact strength (kgf cm/cm) 14 16 16 15 16 15 Glossiness 131 135 137 138 137 138 Weather resistance (ΔE) 2.4 2.5 2.3 2.6 2 2 extrusion
Psalter Haze (%) 2 1.8 1.6 1.6 1.5 1.5 Glossiness 126 123 125 126 123 122 In the thermoplastic resin composition
Difference in refractive index between sol and gel 0.0016 0.0025 0.0030 0.0034 0.0025 0.0027

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 (A)
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sifter seed MMA/SM
(weight%) 92/8 68/32 72/28 72/28 72/28 72/28 core BA/SM
(weight%) 85/15 85/15 95/5 70/30 85/15 85/15 shell SM/AN/BA (% by weight) 72/20/8 72/20/8 72/20/8 72/20/8 8/20/72 75/25/0 2*r2 (nm) 240 240 240 240 240 240 r2-r1 (nm) 35 35 35 35 35 35 The difference between the refractive index of the core and the refractive index of the shell 0.086 0.086 0.099 0.066 0.079 0.093 Thermoplastic resin composition (A) Graft
Copolymer (% by weight) 50 50 50 50 50 50 (B-1) SAMMA copolymer
(weight%) 50 50 50 50 50 50 (C) Graft
Copolymer (% by weight) - - - - - - (A) the refractive index of the seed of the graft copolymer and
(B) of the non-grafted copolymer
Difference from refractive index 0.016 0.008 0.004 0.004 0.004 0.004 ejaculation
Psalter Haze (%) 43 15 50 32 41 18 impact strength
(kgf cm/cm) 8 9 16 6 7 12 Glossiness 94 98 91 95 86 99 Weather resistance (ΔE) 2.6 2.2 2.2 2.2 2.4 2.8 extrusion
Psalter Haze (%) 5.1 4.2 6.5 4.3 5.6 4.8 Glossiness 98 102 95 90 79 95 In the thermoplastic resin composition
Difference in refractive index between sol and gel 0.0071 0.0085 0.0093 0.0080 0.0131 0.0137

division comparative example
7 comparative example
8 comparative example
9 comparative example
10 comparative example
11 comparative example
12 (A)
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sifter seed MMA/SM
(weight%) 72/28 72/28 0/100 100/0 72/28 - core BA/SM
(weight%) 85/15 85/15 100/0 81/19 85/15 - shell SM/AN/BA
(weight%) 72/20/8 72/20/8 75/25/0 100
(MMA) 72/20/8 - 2*r2 (nm) 360 160 230 240 240 - r2-r1 (nm) 52 23 40 35 35 - The refractive index of the core and the shell
Difference from refractive index 0.086 0.086 0.112 0.005 0.086 - Thermoplastic resin composition (A) Graft
Copolymer (% by weight) 50 50 50 50 50 - (B-1) SAMMA copolymer
(weight%) 50 50 50 50 - - (B-2) SAN copolymer
(weight%) - - - - 50 - (C) Graft
Copolymer (% by weight) - - - - - - (A) of the graft copolymer
Seed's refractive index and
(B) of the non-grafted copolymer
Difference from refractive index 0.004 0.004 0.076 0.024 0.052 - injection specimen Haze (%) 22 2 65 42 85 2 impact strength
(kgf cm/cm) 18 4.2 18 6.5 13 17 Glossiness 101 141 91 95 89 150 Weather resistance (ΔE) 3 2.2 2.9 2.2 3.1 8.5 extrusion specimen Haze (%) 5.2 1.4 5.2 3.9 15 - Glossiness 95 126 92 95 92 - In the thermoplastic resin composition
Difference in refractive index between sol and gel 0.0039 0.0012 0.0105 0.0248 0.0460 -

As shown in Tables 1 to 4, the thermoplastic resin compositions (Examples 1 to 10) according to the present invention showed excellent effects in impact strength, haze, gloss and weather resistance compared to Comparative Examples 1 to 12. Here, Examples 9 and 10 including (A) the graft copolymer and (C) the graft copolymer had better haze and weather resistance.

On the other hand, Comparative Examples 1 and 2 in which the composition ratio of the polymer seed of the (A) graft copolymer is outside the scope of the present invention are (A) the refractive index of the polymer seed of the graft copolymer and (B) the refractive index of the non-grafted copolymer As the difference between them increased, haze, glossiness, and impact strength decreased in both the injected and extruded specimens.

In addition, (A) Comparative Examples 3 and 4, in which the configuration of the rubber core of the graft copolymer is outside the scope of the present invention, (A) the difference in refractive index between the rubber core and the graft shell of the graft copolymer is outside the range of 0.08 to 0.09 The haze and glossiness of both the injected specimen and the extruded specimen were lowered, and Comparative Example 4 had low impact strength.

In addition, (A) Comparative Examples 5 and 6, in which the configuration of the graft shell of the graft copolymer is outside the scope of the present invention, the difference in refractive index between the rubber core and the graft shell of (A) the graft copolymer is in the range of 0.08 to 0.09 The haze and glossiness of both the injection and extrusion specimens were lowered and the impact strength was also low.

In addition, (A) Comparative Example 7 in which 2*r2 and r2-r1 of the rubber core of the graft copolymer exceeded the range of the present invention had low haze, gloss and weather resistance, and (A) graft copolymer Comparative Example 8, in which 2*r2 and r2-r1 of the rubber core was less than the range of the present invention, had very poor impact strength.

In addition, Comparative Example 9 including only styrene in the seed and only butyl acrylate in the core, as in the prior art, (A) outside the range of the refractive index difference between the core and the seed of the graft copolymer of 0.08 to 0.09 and (A) graft air The difference in refractive index between the seed of the composite and (B) the non-grafted copolymer and the difference in refractive index between the sol and the gel in the thermoplastic resin composition increased, resulting in poor haze and gloss, and poor weather resistance and impact resistance for both the injected and extruded specimens.

In addition, Comparative Example 10 containing only methyl methacrylate in each of the seed and shell of (A) the graft copolymer has a difference between the refractive index of the seed of (A) the graft copolymer and (B) the refractive index of the non-grafted copolymer The difference in refractive index between the sol and the gel in the thermoplastic resin composition was also large, and haze, gloss, and impact strength were all poor.

In addition, Comparative Example 12, which was tested with a transparent acrylonitrile-butadiene-styrene resin, had very poor weather resistance.

In conclusion, according to the present invention, (A) the composition and composition ratio of the polymer seed, core, and shell constituting the alkyl (meth)acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer are adjusted within a predetermined range, and the core When narrowing the difference between the refractive index of the cell and the refractive index of the cell, and (A) the refractive index of the polymer seed of the graft copolymer and (B) the refractive index of the non-grafted copolymer, transparency, gloss and It was confirmed that the effect of excellent weather resistance was confirmed.

Claims (14)

(A) a polymer seed comprising 70 to 85% by weight of an alkyl (meth)acrylate and 15 to 30% by weight of an aromatic vinyl compound, covering the polymer seed and containing 78 to 90% by weight of an alkyl acrylate and 10 to 22% by weight of an aromatic vinyl compound; Including a rubber core comprising a weight %, and a graft shell surrounding the rubber core and containing 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyan compound, and 3 to 15% by weight of an alkyl acrylate an alkyl (meth)acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; and
(B) a non-grafted copolymer comprising an alkyl (meth)acrylate, an aromatic vinyl compound and a vinyl cyan compound;
The (A) graft copolymer is characterized in that it simultaneously satisfies the following Equations 1 and 2
Thermoplastic resin composition.
[Equation 1]
200 ≤ 2*r2 ≤ 300
[Equation 2]
25 ≤ r2-r1 ≤ 45
(In Equations 1 and 2, r1 is the average radius (nm) from the center of the graft copolymer to the seed, and r2 is the average radius (nm) from the center of the graft copolymer to the core.)
According to claim 1,
The (A) graft copolymer is characterized in that the difference between the refractive index of the rubber core and the refractive index of the graft shell (μ _D ²⁵ ) is 0.08 to 0.09
Thermoplastic resin composition.
According to claim 1,
The refractive index of the polymer seed of the (A) graft copolymer is characterized in that the difference from the refractive index (μ _D ²⁵ ) of the (B) non-grafted copolymer is 0.007 or less
Thermoplastic resin composition.
According to claim 1,
The (A) graft copolymer comprises 5 to 35% by weight of a polymer seed, 25 to 55% by weight of a rubber core and 25 to 55% by weight of a graft shell, based on a total of 100% by weight thereof
Thermoplastic resin composition.
According to claim 1,
The (B) non-grafted copolymer comprises 55 to 85% by weight of an alkyl (meth)acrylate, 10 to 35% by weight of an aromatic vinyl compound, and 1 to 20% by weight of a vinyl cyan compound.
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition is characterized in that it comprises (A) 10 to 90% by weight of the graft copolymer and (B) 10 to 90% by weight of the non-grafted copolymer
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition (C) characterized in that it comprises an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an average particle diameter of 50 to 150 nm of the rubber core
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition was separated into insoluble sol and soluble gel by stirring and centrifugation after adding acetone, and the difference between the refractive index of the sol and the refractive index of the gel (μ _D ²⁵ ) was measured. characterized in that it is less than 0.01
Thermoplastic resin composition.
According to claim 1,
Characterized in that the thermoplastic resin composition has a haze of 5% or less as measured by an injection specimen having a thickness of 3 mm in accordance with ASTM D1003
Thermoplastic resin composition.
According to claim 1,
Characterized in that the thermoplastic resin composition has a glossiness of 120 or more as measured by an injection specimen having a thickness of 3 mm at 45 ° in accordance with ASTM D2457
Thermoplastic resin composition.
According to claim 1,
The thermoplastic resin composition is characterized in that the Izod impact strength measured at room temperature with a specimen having a thickness of 1/4 "is 13 kgf cm / cm or more in accordance with ASTM D256
Thermoplastic resin composition.
(A) a polymer seed comprising 70 to 85% by weight of an alkyl (meth)acrylate and 15 to 30% by weight of an aromatic vinyl compound, covering the polymer seed and containing 78 to 90% by weight of an alkyl acrylate and 10 to 22% by weight of an aromatic vinyl compound; Including a rubber core comprising a weight %, and a graft shell surrounding the rubber core and containing 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyan compound, and 3 to 15% by weight of an alkyl acrylate an alkyl (meth)acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; And (B) a non-grafted copolymer comprising an alkyl (meth) acrylate, an aromatic vinyl compound and a vinyl cyan compound; including kneading and extruding under conditions of 180 to 300 ° C. and 80 to 400 rpm,
The (A) graft copolymer is characterized in that it simultaneously satisfies the following Equations 1 and 2
A method for producing a thermoplastic resin composition.
[Equation 1]
200 ≤ 2*r2 ≤ 300
[Equation 2]
25 ≤ r2-r1 ≤ 45
(In Equations 1 and 2, r1 is the average radius (nm) from the center of the graft copolymer to the seed, and r2 is the average radius (nm) from the center of the graft copolymer to the core.)
According to claim 12
The kneading and extruding step comprises (C) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an average particle diameter of 50 to 150 nm of the rubber core.
A method for producing a thermoplastic resin composition.
Characterized in that it comprises the thermoplastic resin composition of any one of claims 1 to 11
molding.