Title of Invention: Thermoplastic resin and manufacturing method thereof
technical field
[One]
[Cross Citation with Application(s)]
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0083267 dated July 7, 2020 and Korean Patent Application No. 10-2020-0172029, filed again on December 10, 2020 based thereon, All content disclosed in the literature of the application is incorporated as a part of this specification.
[3]
The present invention relates to a thermoplastic resin, and more particularly, to a thermoplastic resin excellent in impact strength, gloss, and fluidity at the same time, and excellent in non-whitening properties because whitening does not occur during bending, and a method for manufacturing the same.
background
[4]
Acrylonitrile-butadiene-styrene resin (hereinafter referred to as 'ABS resin') based on conjugated diene rubber has excellent processability, mechanical properties, and appearance characteristics, so parts of electrical and electronic products, automobiles, small toys, and furniture , building materials, etc. are widely used. However, since the ABS resin is based on butadiene rubber containing chemically unstable unsaturated bonds, the rubber polymer is easily aged by ultraviolet rays, and the weather resistance is very weak, so it is not suitable as an outdoor material.
[5]
In order to overcome the problems of the ABS resin as described above, an acrylic copolymer represented by an acrylate-styrene-acrylonitrile graft copolymer (hereinafter referred to as 'ASA resin') without an ethylenically unsaturated bond is used. . ASA resin has excellent properties such as processability, impact resistance, chemical resistance and weather resistance, so it is widely used in various fields such as construction materials, interior and exterior materials of vehicles such as automobiles and motorcycles, electrical and electronic products, as well as ships, leisure products, and gardening products. , its demand is rapidly increasing.
[6]
Meanwhile, as the demand for emotional quality in the market and its level are increasing, research is underway to realize a luxurious appearance, excellent colorability and weather resistance by finishing the outer surface of base materials such as ABS, PVC, and iron plate with ASA resin. is becoming These finishing materials are mainly manufactured in the form of a film and then go through a bending process such as bending or folding according to the shape of the substrate to be applied to manufacture a final product. However, due to the characteristics of the thermoplastic ASA resin, when the above-mentioned finishing treatment is applied at room temperature, there is a problem in that the original color is lost and the aesthetics is impaired.
[7]
[Prior art literature]
[8]
[Patent Literature]
[9]
Japanese registered patent JP 1995-033470 B2
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[10]
In order to solve the problems of the prior art as described above, the present invention is to provide a thermoplastic resin that is excellent in impact strength, gloss and fluidity at the same time, and is excellent in non-whitening properties because whitening does not occur even when bending or hitting, and a method for manufacturing the same The purpose.
[11]
Another object of the present invention is to provide a molded article made of the above thermoplastic resin.
[12]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[13]
In order to achieve the above object, the present invention comprises (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, or (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; and (B) a matrix resin comprising at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, alkyl methacrylates, and alkyl acrylates; and a total alkyl acrylate content of 20 to 50% by weight. , and the alkyl acrylate coverage value (X) calculated by Equation 1 below provides a thermoplastic resin, characterized in that it is 65 or more.
[14]
[Equation 1]
[15]
X = {(GY)/Y} * 100
[16]
(In Equation 1, G represents the total gel content (%) of the thermoplastic resin, and Y represents the weight% of the alkyl acrylate in the gel of the thermoplastic resin.)
[17]
[18]
In addition, the present invention comprises (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, or (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; and (B) a matrix resin comprising at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, alkyl methacrylates, and alkyl acrylates; and a total alkyl acrylate content of 20 to 50% by weight. It provides a thermoplastic resin, characterized in that the elution amount of the alkyl acrylate in acetone is 0.1% by weight or more.
[19]
In addition, the present invention comprises (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, or (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; and (B) a matrix resin comprising at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, alkyl methacrylates, and alkyl acrylates, wherein the total alkyl acrylate content is 20 to 50 wt% And, the (A) copolymer is, based on 100 wt% of the (A) copolymer, (a-1) DLS average particle diameter of 50 to 120 nm or TEM average particle diameter of 32.5 to 84 nm of alkyl acrylate rubber 25 to 50% by weight; and (b-1) 50 to 75 wt% of the aromatic vinyl compound-vinyl cyan compound copolymer.
[20]
The thermoplastic resin is preferably 50 to 100% by weight of the (A) alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, (B) aromatic vinyl compound, vinyl cyan compound, and alkyl methacrylate. And it may include preferably 0 to 50% by weight of the matrix resin comprising at least one selected from the group consisting of alkyl acrylates.
[21]
The thermoplastic resin may have an elution amount of the alkyl acrylate in acetone of 0.1 wt% or more.
[22]
The copolymer (A) is preferably (a-1) an alkyl acrylate rubber having a DLS average particle diameter of 50 to 120 nm or a TEM average particle diameter of 32.5 to 84 nm based on 100% by weight of the copolymer (A). 50% by weight; and (b-1) 50 to 70 wt% of the aromatic vinyl compound-vinyl cyan compound copolymer.
[23]
The graft ratio of the copolymer (A) is preferably 60 to 150%, and the weight average molecular weight of the copolymer (b-1) may be preferably 40,000 to 120,000 g/mol.
[24]
The (a-1) rubber may further include an aromatic vinyl compound.
[25]
When the (a-1) rubber preferably further includes an aromatic vinyl compound, the aromatic vinyl compound may be preferably included in an amount of 0.1 to 25 wt% in 100 wt% of the (a-1) rubber.
[26]
The (b-1) copolymer may further include an alkyl acrylate.
[27]
The copolymer (b-1) preferably contains 55 to 85% by weight of an aromatic vinyl compound, 10 to 30% by weight of a vinyl cyanide compound, and 0.1 to 0.1% by weight of an alkyl acrylate based on 100% by weight of the total of the copolymer (b-1). It may be a copolymer comprising 20% ​​by weight.
[28]
The thermoplastic resin is preferably extruded into a film having a thickness of 0.15 mm and a weight of 1 kg is dropped vertically onto the film from a height of 100 mm under a temperature of 23 ° C using a Gardner impact tester , The difference in haze values ​​measured according to ASTM D1003-95 before and after the impact of the impact part impacted by the weight (strike) may be 10 or less.
[29]
In addition, the present invention comprises the (A) alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, or (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; And (B) a matrix resin comprising at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, alkyl methacrylates and alkyl acrylates; The acrylate content is 20 to 50 wt%, and the alkyl acrylate coverage value (X) calculated by Equation 1 below of the thermoplastic resin may provide a method for producing a thermoplastic resin, characterized in that it is 65 or more.
[30]
[Equation 1]
[31]
X = {(GY)/Y} * 100
[32]
(In Equation 1, G represents the total gel content (%) of the thermoplastic resin, and Y represents the weight% of the alkyl acrylate in the gel of the thermoplastic resin.)
[33]
The (A) graft copolymer preferably comprises 30 to 50 wt% of an alkyl acrylate rubber having a DLS average particle diameter of 50 to 120 nm or a TEM average particle diameter of 32.5 to 84 nm; And it may be prepared including the step of emulsion-polymerizing a total of 100 parts by weight of a monomer mixture containing 50 to 70% by weight of an aromatic vinyl compound and a vinyl cyanide compound.
[34]
In addition, the present invention may provide a molded article comprising the thermoplastic resin.
[35]
The molded article may preferably be a finishing material.
Effects of the Invention
[36]
According to the present invention, by controlling the particle size, rubber content, graft rate and molecular weight of the rubber contained in the resin, the gel content of the resin, etc., the impact strength, gloss and fluidity are excellent at the same time, and the whitening does not occur even when bending or hitting, so no whitening It is effective to provide a thermoplastic resin having excellent properties and a method for manufacturing the same.
Brief description of the drawing
[37]
1 is a photograph taken after bending the films prepared in Examples (left photograph) and Comparative Example (right photograph) in Md and Td directions, respectively, to check whether or not whitening occurs.
[38]
2 is a photograph taken after hitting each of the films prepared in Examples (left photograph) and Comparative Example (right photograph) with a Gardner impact tester to check whether whitening occurs.
Modes for carrying out the invention
[39]
Hereinafter, the thermoplastic resin of the present substrate will be described in detail.
[40]
While researching ASA resin that can provide a finishing material with a luxurious appearance, the present inventors reduced the distance between rubber particles and increased the grafting rate to minimize the formation of voids due to cracks in the grafting particles, thereby greatly improving the non-whitening properties. The improvement was confirmed, and based on this, the present invention was completed by further concentrating on research.
[41]
In the present description, the resin does not mean only a single (co)polymer, and may include two or more (co)polymers as a main component.
[42]
In the present description, the composition ratio of the (co)polymer may mean the content of the units constituting the (co)polymer, or may mean the content of the units input during polymerization of the (co)polymer.
[43]
The thermoplastic resin of the present invention comprises (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, or (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; and (B) a matrix resin comprising at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, alkyl methacrylates, and alkyl acrylates; and a total alkyl acrylate content of 20 to 50% by weight. and the alkyl acrylate coverage value (X) calculated by the following Equation 1 is 65% or more. It has an excellent effect of whitening properties.
[44]
[Equation 1]
[45]
X(%) = {(GY)/Y} * 100
[46]
(In Equation 1, G represents the total gel content (%) of the thermoplastic resin, and Y represents the weight% of the alkyl acrylate in the gel of the thermoplastic resin.)
[47]
In another example, the thermoplastic resin of the present invention may include: (A) 50 to 100% by weight of a copolymer comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound; and (B) 0 to 50 wt% of a matrix resin comprising at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, alkyl methacrylates and alkyl acrylates; It is characterized in that the value of X is 65% or more, and in this case, it has excellent impact resistance, weather resistance, and molding processability, and has an advantage in that whitening does not occur due to bending and excellent non-whitening properties.
[48]
[Equation 1]
[49]
X(%) = {(GY)/Y} * 100
[50]
(In Equation 1, G represents the total gel content (%) of the thermoplastic resin, and Y represents the weight% of the alkyl acrylate in the gel of the thermoplastic resin.)
[51]
In another example, the thermoplastic resin of the present invention includes (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, or (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer. copolymer; and (B) a matrix resin comprising at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, alkyl methacrylates, and alkyl acrylates, wherein the total alkyl acrylate content is 20 to 50 wt% It is characterized in that the elution amount of the alkyl acrylate under acetone is 0.1 wt% or more, and in this case, the impact resistance, weather resistance and molding processability are excellent, and whitening does not occur due to bending, and there is an advantage of excellent non-whitening properties.
[52]
In another example, the thermoplastic resin of the present invention includes (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, or (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer. copolymer; and (B) a matrix resin comprising at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, alkyl methacrylates, and alkyl acrylates, wherein the total alkyl acrylate content is 20 to 50 wt% And, the (A) copolymer is, based on 100 wt% of the (A) copolymer, (a-1) DLS average particle diameter of 50 to 120 nm or TEM average particle diameter of 32.5 to 84 nm of alkyl acrylate rubber 25 to 50% by weight; and (b-1) 50 to 75 wt% of the aromatic vinyl compound-vinyl cyan compound copolymer; It has the advantage of excellent non-whitening properties.
[53]
In this description, the gel content is determined by adding 30 g of acetone to 0.5 g of dry thermoplastic resin powder and stirring at 210 rpm at room temperature for 12 hours (SKC-6075, Lab companion) and centrifuging it (Supra R30, Hanil Science) After centrifugation at 0 ° C. at 18,000 rpm for 3 hours to collect insoluble fraction that did not dissolve in acetone, the weight was measured after drying (OF-12GW, Lab companion) at 85 ° C for 12 hours by forced circulation. It can be obtained by calculating by Equation 2 below.
[54]
[Equation 2]
[55]
Gel content (%) = {weight of insoluble matter (gel) / weight of sample} * 100
[56]
The graft rate of the present description was obtained by adding 30 g of acetone to 0.5 g of the graft polymer dry powder, stirring at 210 rpm at room temperature for 12 hours (SKC-6075, Lab companion), and using a centrifuge (Supra R30, Hanil Science) After centrifugation at 0 ° C. at 18,000 rpm for 3 hours to collect insoluble fraction that did not dissolve in acetone, the weight was measured after drying (OF-12GW, Lab companion) at 85 ° C. for 12 hours by forced circulation. It can be obtained by calculating with Equation (3).
[57]
[Equation 3]
[58]
Graft rate (%) = [weight of grafted monomer (g) / rubber weight (g)] * 100
[59]
In Equation 3, the weight (g) of the grafted monomer is the weight obtained by dissolving the graft copolymer in acetone and centrifuging the insoluble matter (gel) minus the rubber weight (g), and the rubber weight ( g) is a part by weight of the theoretically added rubber component in the graft copolymer powder.
[60]
In this description, the DLS average particle diameter can be measured using a dynamic light scattering method, and in detail, the intensity in the Gaussian mode using a particle size distribution analyzer (Nicomp CW380, PPS) in the latex state. (intensity) can be measured as a value. More specifically, after preparing a sample by diluting 0.1 g of latex having a solid content of 35 to 50% by weight with 100 g of deionized water, using a particle size distribution analyzer (Nicomp CW380, PPS) at 23° C., the measurement method is Auto -dilution is measured with a flow cell, and the measurement mode can be obtained by dynamic light scattering method/Intensity 300KHz/Intensity-weight Gaussian Analysis.
[61]
In the present description, the TEM average particle diameter may be measured using a transmission electron microscope (TEM) analysis, and as a specific example, it means a value obtained by numerically measuring the particle size on a high magnification image of a TEM and arithmetic average. In this case, specific measurement examples are as follows:
[62]
- Sample preparation: thermoplastic resin pellets manufactured by extrusion kneader
[63]
- Sample pretreatment: Timing (23℃) → Hydrazine treatment (72℃, 5 days) → Sectioning (-120℃) → OsO 4 vapor staining (2 hours)
[64]
- Analysis instrument: TEM (JEM-1400, Jeol company)
[65]
- Analysis conditions: Acc. Volt 120 kV, SPOT Size 1 (X 10K, X 25K, X 50K)
[66]
- Size (average particle diameter) measurement: the average of the longest diameters of particles with the top 10% diameter size
[67]
Here, the average of the longest diameters of particles having a diameter size of the top 10% means, for example, randomly selecting 100 or more particles from a TEM image, measuring their longest diameter, and then calculating the arithmetic mean value of the top 10% of the diameter. it means.
[68]
Hereinafter, each component constituting the thermoplastic resin of the present disclosure will be described in detail as follows.
[69]
(A) copolymer
[70]
The copolymer (A) comprises an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound, and is included in an amount of 50 to 100% by weight in 100% by weight of the total thermoplastic resin.
[71]
The (A) copolymer is, for example, (a-1) DLS average particle diameter of 50 to 120 nm or TEM average particle diameter of 32.5 to 84 nm, based on 100% by weight of the (A) copolymer, alkyl acrylate rubber 25 to 50 % by weight, preferably 30 to 50% by weight, more preferably 35 to 50% by weight, and (b-1) 50 to 75% by weight, preferably 50 to 70% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer %, more preferably 50 to 65% by weight, and has excellent impact resistance while having excellent gloss and non-whitening properties within this range.
[72]
The copolymer (A) has, for example, a graft rate of 60 to 150%, and the weight average molecular weight of the copolymer (b-1) may be 40,000 to 120,000 g/mol, and molding processability and non-whitening properties within this range All of these have great advantages. The graft ratio of the copolymer (A) may be preferably 62 to 140%, more preferably 65 to 130%, and within this range, there is an excellent effect of non-whitening properties without deterioration in impact resistance and molding processability. The weight average molecular weight of the copolymer (b-1) may be preferably 50,000 to 110,000 g/mol, more preferably 60,000 to 110,000 g/mol, and molding processability and non-whitening without deterioration in impact resistance within this range. Characteristics have an excellent effect.
[73]
In the present description, the weight average molecular weight may be measured using GPC (Gel Permeation Chromatography, waters breeze) unless otherwise defined, and as a specific example, standard polystyrene (PS) (standard polystyrene) through GPC using THF (tetrahydrofuran) as an eluent ) can be measured relative to the sample. At this time, as a specific example of measurement, solvent: THF, column temperature: 40°C, flow rate: 0.3ml/min, sample concentration: 20mg/ml, injection amount: 5 μl, 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): It can be measured under the conditions of OECD TG 118.
[74]
The (a-1) rubber may further include, for example, an aromatic vinyl compound, and in this case, chemical resistance and impact resistance are more excellent. The content of the aromatic vinyl compound contained in the (a-1) rubber is, for example, 0.1 to 25% by weight, preferably 2 to 23% by weight, more preferably based on 100% by weight of the (a-1) rubber. may be 5 to 20% by weight, and within this range, the desired effect can be sufficiently obtained without deterioration of physical properties.
[75]
The acrylate rubber can be prepared by emulsion polymerization of an acrylate-based compound, for example, and as a specific example, it can be prepared by emulsion polymerization by mixing an acrylate-based compound, an emulsifier, an initiator, a grafting agent, a crosslinking agent, an electrolyte, and a solvent. , in this case, the grafting efficiency is excellent and there is an effect of excellent physical properties such as impact resistance.
[76]
The copolymer (b-1) may further include, for example, an alkyl acrylate, and in this case, the physical property balance of impact strength, weather resistance, molding processability, and whitening properties is excellent. The (b-1) copolymer is, for example, 55 to 85 wt% of an aromatic vinyl compound, 10 to 30 wt% of a vinyl cyanide compound, and 0.1 to 20 wt% of an alkyl acrylate based on 100 wt% of the (b-1) copolymer. It may be composed of a weight %, preferably 60 to 80% by weight of an aromatic vinyl compound, 13 to 26% by weight of a vinyl cyanide compound, 3 to 20% by weight of an alkyl acrylate, more preferably 65 to 78% by weight of an aromatic vinyl compound Weight %, may be made of a vinyl cyanide compound 15 to 22 weight %, alkyl acrylate 5 to 17 weight %, within this range, the impact strength and weather resistance are more excellent.
[77]
The (a-1) rubber may include, for example, a rubber seed.
[78]
The rubber seed is, for example, 1 to 20% by weight, preferably 2 to 15% by weight of one or more monomers selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl acrylate, based on 100% by weight of the copolymer (A) %, more preferably 3 to 10% by weight, can be prepared by polymerization, and within this range, there is an excellent effect in impact strength, weather resistance, balance of physical properties, and the like.
[79]
As a specific example, the rubber seed is added to a monomer comprising an aromatic vinyl compound and an alkyl acrylate, 0.01 to 3 parts by weight of a crosslinking agent, 0.01 to 3 parts by weight of an initiator, and 0.01 parts by weight of an emulsifier based on 100 parts by weight of the unit constituting the copolymer (A). It can be prepared by polymerization, including 5 parts by weight, within the above range, a polymer having an even size can be prepared within a short time, and physical properties such as weather resistance and impact strength can be further improved.
[80]
As another specific example, the rubber seed is added to a monomer comprising an aromatic vinyl compound and an alkyl acrylate, 0.1 to 1 part by weight of a crosslinking agent, 0.01 to 1 part by weight of an initiator, and 0.1 to 1 part by weight of a crosslinking agent based on 100 parts by weight of the unit constituting the copolymer (A); It can be prepared by polymerization including 0.1 to 3.0 parts by weight of an emulsifier, and a polymer having an even size can be prepared within a short time within the above range, and physical properties such as weather resistance and impact strength can be further improved.
[81]
The (A) copolymer is, for example, based on 100 parts by weight of the unit constituting the (A) copolymer, A-1) at least one compound 1 selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl acrylate preparing a seed by polymerizing a mixture comprising 0.001 to 1 part by weight of electrolyte, 0.01 to 3 parts by weight of a crosslinking agent, 0.01 to 3 parts by weight of an initiator, and 0.01 to 5 parts by weight of an emulsifier to 20 parts by weight; A-2) A mixture comprising an alkyl acrylate compound and optionally 25 to 55 parts by weight of an aromatic vinyl compound, 0.01 to 1 parts by weight of a crosslinking agent, 0.01 to 3 parts by weight of an initiator, and 0.01 to 5 parts by weight of an emulsifier in the presence of the seed polymerizing to prepare a rubber core; and A-3) 0.01 to 3 parts by weight of a crosslinking agent, 0.01 to 3 parts by weight of an initiator, 0.1 to 2 parts by weight of an emulsifier in 40 to 70 parts by weight of at least one compound from the group consisting of an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber core Preparing a graft shell by mixing 0.01 to 1 parts by weight of an activator; may be prepared including. In this case, there is an excellent effect in the balance of physical properties of impact resistance, weather resistance, molding processability and non-whitening characteristics.
[82]
In the present description, the alkyl acrylate compound may be, for example, an alkyl acrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylbutyl acrylic. It may be at least one selected from the group consisting of late, octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate and lauryl acrylate, preferably having 1 to 4 carbon atoms. It may be an alkyl acrylate containing a chain alkyl group, more preferably butyl acrylate.
[83]
In the present description, the aromatic vinyl compound is, for example, styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brobo styrene, ρ It may be at least one selected from the group consisting of -bromostyrene, m-bromostyrene, ο-chlorostyrene, ρ-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, preferably Preferably, it may be at least one selected from the group consisting of styrene and α-methyl styrene, and more preferably styrene. In this case, the fluidity is adequate and processability is excellent, and mechanical properties such as impact resistance are excellent.
[84]
In the present description, the vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methnitrolonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, and preferably acrylonitrile.
[85]
In the present description, the crosslinking agent is not particularly limited if it is a crosslinking agent generally used in the technical field to which the present invention belongs, unless otherwise defined. For example, a compound that includes two or more unsaturated vinyl groups and can serve as a crosslinking agent may be used. , specific examples of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, divinylbenzene, diethylene Glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butadiol dimethacrylate, hexanediol propoxylate diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxylate diacryl Late, neopentyl glycol propoxylate diacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, trimethylpropaneethoxylate triacrylate, trimethylpropanepropoxylate triacrylate, pentaerythritol ethoxy It may be at least one selected from the group consisting of late triacrylate, pentaerythritol propoxylate triacrylate and vinyl trimethoxysilane, allyl methacrylate, triallyl isocyanurate, triallyl amine and diallyl amine. Note that the present invention is not limited thereto.
[86]
In the present substrate, the electrolyte is, for example, KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , K 4 P 2 O 7 , Na 4 P 2 O 7 , K 3 PO 4 , Na 3 PO 4 , K 2 HPO 4 , Na 2 HPO 4, KOH, NaOH, and Na 2 S 2 O 7 One or two or more selected from the group consisting of may be used in combination, but is not limited thereto.
[87]
In the present description, as the initiator, if it is an initiator generally used in the technical field to which the present invention belongs, it may be used without particular limitation. For example, a radical initiator such as a water-soluble initiator and a fat-soluble initiator may be used, and these initiators are one or two More than one species can be mixed and used.
[88]
As the water-soluble initiator, at least one selected from the group consisting of inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide may be used, but not limited thereto.
[89]
As the fat-soluble initiator, at least one selected from the group consisting of dialkyl peroxide, diacyl peroxide, diperoxyketal, hydroperoxide, peroxyester, peroxydicarbonate, azo compound, and the like may be used. As a more specific example, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, di-t-amyl peroxide, di-t-butyl Peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane, 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, diisopropyl Benzene mono-hydroperoxide, t-amyl hydroperoxide, t-butyl hydroperoxide, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, di-(3,5,5-trimethylhexa noyl)-peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-amyl peroxy neodecanoate, t-amyl peroxy Oxy 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-ethylhexyl peroxydicarbonate, 3-hydroxy-1,1-dimethylbutylperoxy neodecanoate, acetyl per oxide, isobutyl peroxide, organic peroxides such as octanoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and t-butyl peroxy isobutylate; azobis isobutyronitrile, azobismethylbutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, At least one selected from the group consisting of azobis isobutyric acid (butyric acid) methyl may be used, but is not limited thereto.
[90]
In the manufacturing stage of the rubber seed, the manufacturing stage of the rubber core, and the manufacturing stage of the copolymer shell (graft shell), an oxidation-reduction catalyst may be optionally further used to further promote the initiation reaction together with the initiator, The oxidation-reduction catalyst may include, 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, but limited thereto it is not going to be
[91]
Preferably, an activator is used to promote the initiation reaction of the peroxide together with the polymerization initiator in at least one of the steps of producing the rubber seed, producing the rubber core, and producing the copolymer shell (graft shell). The activator may include sodium formaldehyde, sulfoxylate, sodium ethylenediamine, tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, sodium sulfite, sulfonatoacetic acid metal salt, and sulfinatoacetic acid metal salt. It is preferable to use one or two or more selected from
[92]
The activator may be added in an amount of 0.01 to 3 parts by weight, or 0.01 to 1 parts by weight, based on 100 parts by weight of the total monomers added during the preparation of the copolymer (A), and a high degree of polymerization can be achieved within this range. there is an advantage
[93]
In the step of preparing the seed and the core, batch input and continuous input may be used individually or a combination of the two methods may be used as the input method of the monomer.
[94]
In the present description, 'continuous input' means not 'batch input', for example, 10 minutes or more, 30 minutes or more, 1 hour or more, preferably 2 hours or more drop-by-drop within the polymerization reaction time range. by drop), little by little, step by step, or continuous flow.
[95]
In the present description, the emulsifier is not particularly limited if it is an emulsifier generally used in the art to which the present invention belongs, and for example, rosin acid salt, lauryl acid salt, oleic acid salt, stearic acid salt, etc. containing 20 carbon atoms or less or 10 to 20 low molecular weight carboxylates; an alkyl sulfosuccinic acid salt or derivative thereof having 20 or less or 10 to 20 carbon atoms; alkyl sulfates or sulfonates having up to 20 carbon atoms or from 10 to 20 carbon atoms; a polyfunctional carboxylic acid having 20 to 60, 20 to 55, or 30 to 55 carbon atoms and at least 2 or more, preferably 2 to 3 carboxyl groups in the structure, or a salt thereof; and at least one phosphoric acid-based salt selected from the group consisting of mono alkyl ether phosphate or dialkyl ether phosphate; it may be at least one selected from the group consisting of.
[96]
In another example, the emulsifier is sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, sodium styrene sulfonate, Sodium dodecyl allyl sulfosuccinate, styrene and sodium dodecyl allyl sulfosuccinate copolymer, polyoxyethylene alkylphenyl ether ammonium sulfates (polyoxyethylene alkylphenyl ether ammonium etc.), alkenyl C16 -18 Reactive emulsifier selected from succinic acid, di-potassium salt (alkenyl C16-18 succinic acid, di-potassium salt) and sodium methallyl sulfonate; and a non-reactive emulsifier selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, soaps of fatty acids, and alkali salts of rosin acids.
[97]
The emulsifier uses a derivative of a C12 to C18 alkyl sulfosuccinate metal salt, a C12 to C20 alkyl sulfate ester or a derivative of a sulfonic acid metal salt. Examples of the derivative of the C12 to C18 alkyl sulfosuccinate metal salt include sodium or potassium salts of dicyclohexyl sulfonate, dihexyl sulfosuccinate, and dioctyl sulfosuccinate, and C12 to C20 sulfuric acid esters. Alternatively, the sulfonic acid metal salt may be an alkyl sulfate metal salt such as sodium lauric sulfate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate, or potassium octadecyl sulfate. do. The emulsifier may be used alone or in combination of two or more.
[98]
In the present description, a derivative of a compound refers to a substance in which at least one of hydrogen and a functional group of the compound is substituted with another group such as an alkyl group or a halogen group.
[99]
In the present disclosure, when preparing the copolymer (A) in the present disclosure, it may optionally further include a molecular weight regulator for emulsion polymerization, and the molecular weight regulator may be 0.01 to 2 parts by weight based on 100 parts by weight of the unit constituting the copolymer (A). , 0.05 to 2 parts by weight or 0.05 to 1 parts by weight, and a polymer having a desired molecular weight within this range can be easily prepared.
[100]
Examples of the molecular weight modifier include mercaptans such as a-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and methylene bromide; and sulfur-containing compounds such as tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylxanthogen disulfide; may be at least one selected from the group consisting of, preferably tertiary dodecylmercaptan, etc. may be used, but is not limited thereto.
[101]
The polymerization temperature during the emulsion polymerization is not particularly limited, but in general, the polymerization may be carried out at 50 to 85 ℃, preferably 60 to 80 ℃.
[102]
The polymerization temperature during the emulsion polymerization is not particularly limited, but in general, the polymerization may be carried out at 50 to 85 ℃, preferably 60 to 80 ℃.
[103]
(A) copolymer latex prepared through the above step may be characterized in that, for example, the coagulant content is 1% or less, preferably 0.5% or less, and more preferably 0.1% or less. Within the above-described range, the resin has excellent productivity, and has an effect of improving mechanical strength and appearance characteristics.
[104]
In the present description, the coagulant content (%) can be calculated by measuring the weight of the coagulated material generated in the reaction tank, the total rubber weight, and the monomer weight, and using Equation 4 below.
[105]
[Equation 4]
[106]

[107]
The latex of the copolymer (A) may be in powder form through conventional processes such as agglomeration, washing, drying, etc., for example, by adding a metal salt or acid to agglomerate at a temperature of 60 to 100 ° C., and aging , may be prepared in a powder form through dehydration, washing and drying processes, but is not limited thereto.
[108]
Other conditions not specified in the method for preparing the copolymer (A) described above, that is, polymerization conversion, reaction pressure, reaction time, gel content, etc., are not particularly limited as long as they are within the range commonly used in the art to which the present invention belongs. , specify that it can be appropriately selected and implemented according to need.
[109]
(B) matrix resin
[110]
The thermoplastic resin of the present invention is a matrix resin comprising at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, an alkyl methacrylate, and an alkyl acrylate based on 100% by weight of the total weight of the thermoplastic resin. % included. When the (B) matrix resin is included in the thermoplastic resin, there is an advantage in that mechanical properties and molding processability are further improved.
[111]
The (B) matrix resin is a hard matrix melt-kneaded with the dry powder (DP) of the copolymer (A), and includes a hard polymer-forming monomer having a glass transition temperature of at least 60°C. Specifically, it is preferable to prepare a compound including an aromatic vinyl compound, a vinyl cyan compound, methyl methacrylate and an alkyl acrylate, or a unit derived therefrom, alone or by mixing two or more thereof. The glass transition temperature of the (B) matrix resin may be preferably 80 to 160° C., more preferably 90 to 150° C., and molding processability can be further improved within this range.
[112]
In the present substrate, the glass transition temperature may be measured at a temperature increase rate of 10° C./min using TA Instruments Q100 DSC (Differential Scanning Calorimetry) according to ASTM D 3418.
[113]
The (B) matrix resin is, for example, an aromatic vinyl compound-vinyl cyan compound copolymer, an aromatic vinyl compound-vinyl cyan compound-alkyl methacrylate copolymer, an alkyl methacrylate polymer, and an alkyl methacrylate-alkyl acrylate copolymer. It may include at least one selected from the group consisting of, and may further include an aromatic vinyl compound-vinyl cyan compound-alkyl acrylate copolymer, and in this case, the effect of better balance between molding processability and other physical properties is obtained. have.
[114]
The alkyl acrylate, aromatic vinyl compound and vinyl cyan compound contained in the matrix resin may be appropriately selected within the same range as those mentioned in the copolymer (A) above.
[115]
The alkyl methacrylate contained in the matrix resin may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl It may be at least one selected from the group consisting of methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate, preferably an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, and more Preferably it is methyl methacrylate.
[116]
The (B) matrix resin may be prepared by adopting a generally known method, and if necessary, may include one or more from an initiator, a crosslinking agent, and a molecular weight control agent, and may include suspension polymerization, emulsion polymerization, bulk polymerization, or solution. It can be prepared by a polymerization method.
[117]
Materials necessary for the reaction, such as solvents and emulsifiers, or conditions such as polymerization temperature and polymerization time, which must be added or changed according to the polymerization method, are generally applicable materials or conditions depending on the polymerization method selected when preparing each matrix resin. It does not restrict|limit especially, According to necessity, it can select suitably.
[118]
As another example, as the matrix resin (B), commercially available products may be used.
[119]
thermoplastic resin
[120]
The thermoplastic resin of the present invention may include (A) 50 to 100% by weight of the copolymer and (B) 0 to 50% by weight of the matrix resin, based on 100% by weight of the total of the thermoplastic resin, preferably (A) air 60 to 100% by weight of the copolymer and (B) 0 to 40% by weight of the matrix resin, more preferably (A) 60 to 90% by weight of the copolymer and (B) 10 to 40% by weight of the matrix resin, Within the range, it has excellent impact resistance, fluidity and non-whitening properties.
[121]
The content of the alkyl acrylate contained in the total 100% by weight of the thermoplastic resin may be, for example, 20 to 50% by weight, preferably 22 to 50% by weight, more preferably 25 to 50% by weight, within this range It has excellent impact strength and non-whitening properties without deterioration of weather resistance.
[122]
In the present description, the total content of the alkyl acrylate contained in the total 100% by weight of the thermoplastic resin means the total sum of the weights of the alkyl acrylate compound contained in each of the (A) copolymer and (B) the matrix resin, For example, it can be calculated by adding parts by weight of the alkyl acrylate compound added during the production of the thermoplastic resin. As another example, the thermoplastic resin may be quantitatively measured through NMR (Nuclear Magnetic Resonance) analysis or FT-IR (Fourier Transform Infrared Spectroscopy) analysis.
[123]
In the present description, NMR analysis means analysis by 1 H NMR unless otherwise specified .
[124]
In the present description, NMR analysis may be measured using a method commonly performed in the art, and specific measurement examples are as follows.
[125]
- Equipment name: Bruker 600MHz NMR(AVANCE III HD) CPP BB(1H 19F tunable and broadband, with z-gradient) Prodigy Probe
[126]
- Measurement conditions: 1 H NMR (zg30): ns=32, d1=5s, TCE-d2, at room temp.
[127]
In the present description, the FT-IR analysis may be measured using a method commonly performed in the art, and specific measurement examples are as follows.
[128]
- Equipment name: Agilent Cary 660
[129]
- Measurement condition: ATR mode
[130]
The thermoplastic resin may have an X value of 65% or more, preferably 65 to 150%, more preferably 68 to 140%, calculated by Equation 1 through the limited composition as described above, and non-whitening within this range Characteristics are more effective.
[131]
[Equation 1]
[132]
X(%) = {(GY)/Y} * 100
[133]
(In Equation 1, G represents the total gel content (%) of the thermoplastic resin, and Y represents the content (weight %) of the alkyl acrylate in the gel of the thermoplastic resin.)
[134]
In Equation 1, the content of the alkyl acrylate in the gel of the thermoplastic resin represents the content of the alkyl acrylate in the insoluble matter collected in the process of obtaining the above-described gel content (based on 100% by weight of the total added thermoplastic resin). Here, the gel content refers to the content of insolubles based on 100% by weight of the total thermoplastic resin.
[135]
The thermoplastic resin preferably has an elution amount of the alkyl acrylate in acetone of 0.1 wt% or more, more preferably 0.5 wt% or more, preferably 0.1 to 15 wt%, and more preferably 0.5 to 15 wt% % by weight, and has an excellent effect of non-whitening properties within this range.
[136]
In the present description, the elution amount of alkyl acrylate under acetone is measured by adding 30 g of acetone to 0.5 g of dry thermoplastic resin powder, followed by stirring at 210 rpm at room temperature for 12 hours (SKC-6075, Lab companion), and then centrifuging (Supra) R30, Hanil Science Co., Ltd.), the acetone solution from which the insoluble content was separated by centrifugation at 0°C at 18,000 rpm for 3 hours was dried (OF-12GW, Lab companion) by forced circulation at 85°C for 12 hours to obtain a resin sol ( Sol), which can be quantitatively measured by NMR analysis or FT-IR analysis.
[137]
The thermoplastic resin of the present invention has excellent whitening resistance against bending such as bending or folding. It is characterized by excellent non-whitening properties.
[138]
In addition, the thermoplastic resin of the present invention is excellent in whitening resistance against external impact (strike), for example, the thermoplastic resin is extruded into a film having a thickness of 0.15 mm and a weight of 1 kg using a Gardner impact tester under a temperature of 23 ° C. When the weight of the weight is dropped vertically onto the film from a height of 100 mm, the difference in haze value measured according to ASTM D1003-95 before and after the impact of the part impacted by the weight is 10 or less, preferably 5 or less, More preferably, it may be 3 or less. In this case, the occurrence of whitening due to bending or external impact is greatly reduced, and the inherent color due to whitening is inhibited, making it difficult to express the desired color, and it prevents the problem of poor quality due to uneven appearance and excellent appearance quality. It has the effect of providing a molded article.
[139]
In this description, the difference in haze before and after impact is specifically measured by using BYK Gardner's Impact Tester 5545 as a Gardner impact tester for a film specimen having a width and length of 100 mm x 100 mm and a thickness of 0.15 mm, and Cat No. The middle of the film is impacted using 1249 (falling weight 1 kg), and the haze of the middle portion of the film before and after impact is measured and obtained from the difference.
[140]
In the present description, haze may be measured using a method known in the related art for measuring transparency, and in detail, may be measured according to ASTM D1003. More specifically, the haze value (haze) can be measured at 23 °C according to ASTM D1003 for a film specimen extruded at an extrusion temperature of 230 °C using a haze meter (model name: HM-150) of MURAKAMI. .
[141]
The thermoplastic resin may have a glossiness of 117 or more, preferably 120 or more, more preferably 121 or more, measured under an incident angle of 60° in accordance with ASTM D528, in accordance with ASTM D528. It is possible to provide a molded article having excellent appearance quality.
[142]
The thermoplastic resin may have, for example, a melt flow index (MI) measured according to ASTM D1238 of 5 g/10 min or more, preferably 8 g/10 min or more, and lowering of other physical properties within this range. There is an effect of excellent molding processability without
[143]
In the present description, the flow index can be measured at 220° C. with a weight of 10 kg and a reference time of 10 minutes, and the melt index can be measured according to ASTM D1238. More specifically, using GOETTFERT 's melting index measuring equipment, the specimen is heated to a temperature of 220 °C, placed in a cylinder of a melt indexer, a load of 10 kg is applied with a piston, and melted for 10 minutes. It can be obtained by measuring the weight (g) of the resulting resin.
[144]
Method for producing thermoplastic resin
[145]
The method for producing the thermoplastic resin of the present invention comprises (A) 50 to 100 parts by weight of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) an aromatic vinyl compound, a vinyl cyan compound, an alkyl methacrylate and Including 0 to 50 parts by weight of a matrix resin including at least one selected from the group consisting of alkyl acrylates, kneading and extruding. At this time, the thermoplastic resin is characterized in that the X value calculated by the following Equation 1 is 65% or more. It can provide excellent appearance quality.
[146]
[Equation 1]
[147]
X(%) = {(GY)/Y} * 100
[148]
(In Equation 1, G represents the total gel content (%) of the thermoplastic resin, and Y represents the content (weight %) of the alkyl acrylate in the gel of the thermoplastic resin.)
[149]
The copolymer (A) used in the preparation of the thermoplastic resin may be prepared by the method for preparing the copolymer (A), and in this case, the graft rate and molecular weight are appropriately controlled, so that molding processability and non-whitening properties are excellent. have.
[150]
When manufacturing the thermoplastic resin of the present invention, optionally a lubricant, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet stabilizer, a light stabilizer, a dye, a pigment, a colorant, a mold release agent, an antistatic agent, an antibacterial agent, and a processing aid as needed during the kneading and extrusion process , compatibilizers, metal deactivators, flame retardants, flame retardants, anti-drip agents, foaming agents, plasticizers, reinforcing agents, fillers, matting agents, anti-friction agents, and anti-wear agents 0.01 to 100 parts by weight of the base resin at least one selected from the group consisting of to 5 parts by weight, 0.05 to 3 parts by weight, 0.05 to 2 parts by weight, or 0.05 to 1 parts by weight, within this range, the required physical properties are well implemented without reducing the original physical properties of the ASA-based resin composition It works.
[151]
The lubricant may be, for example, at least one selected from ethylene bis steramide, polyethylene oxide wax, magnesium stearate, calcium steramide, and stearic acid, but is not limited thereto.
[152]
The antioxidant may include, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, and the like, but is not limited thereto.
[153]
The light stabilizer may include, for example, a Hals light stabilizer, a benzophenone light stabilizer, a benzotriazole light stabilizer, and the like, but is not limited thereto.
[154]
The antistatic agent may include, for example, one or more anionic surfactants, non-ionic surfactants, and the like, but is not limited thereto.
[155]
The release agent may be used, for example, at least one selected from glycerin sterate, polyethylene tetra sterate, and the like, but is not limited thereto.
[156]
molded product
[157]
The molded article of the present invention is characterized in that it contains a thermoplastic resin excellent in the non-whitening properties of the base material. In this case, it can be applied to film or sheet products because it can provide excellent appearance quality due to excellent weather resistance and impact resistance, excellent molding processability, and excellent gloss and whitening resistance at the same time.
[158]
The molded article may be, for example, a finishing material, and in this case, there is an advantage in that the appearance quality is excellent due to excellent whitening properties.
[159]
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 changes and modifications fall within the scope of the appended claims.
[160]
[Example]
[161]
In the following examples, the X value calculated by Equation 1 is described as "alkyl acrylate coverage" for convenience.
[162]
Example 1
[163]

[164]
In a nitrogen-substituted reactor, 30 parts by weight of distilled water, 4.75 parts by weight of butyl acrylate, 0.25 parts by weight of styrene, 0.4 parts by weight of sodium dodecyl sulfate, 0.1 parts by weight of ethylene glycol dimethacrylate, 0.05 parts by weight of allyl methacrylate, hydrogen carbonate After administering 0.1 parts by weight of sodium and 80 parts by weight of distilled water in a batch, the temperature was raised to 70° C., and then 0.1 parts by weight of potassium persulfate was added to initiate the reaction. Then, polymerization was carried out for 1 hour.
[165]

[166]
43 parts by weight of distilled water, 38 parts by weight of butyl acrylate, 2 parts by weight of styrene, 1.0 parts by weight of sodium dodecyl sulfate, 0.4 parts by weight of ethylene glycol dimethacrylate, 0.5 parts by weight of allyl methacrylate, 30 parts by weight of distilled water to the rubber seed A mixture of parts and 0.1 parts by weight of potassium persulfate was continuously added at 70° C. for 2.0 hours, and polymerization was further carried out for 1 hour after the addition was completed.
[167]
The average size of the particles of the rubber polymer obtained after completion of the reaction was 90 nm.
[168]

[169]
Into the reactor in which the core was obtained, 27 parts by weight of distilled water, 37 parts by weight of styrene, 14 parts by weight of acrylonitrile, 4 parts by weight of butyl acrylate, 1.5 parts by weight of potassium rosinate as an emulsifier and 0.05 parts by weight of tertiary dodecyl mercaptan Polymerization while continuously introducing a mixture of cumene hydroperoxide and 0.1 parts by weight of cumene as an initiator, 0.09 parts by weight of sodium pyrophosphate, 0.12 parts by weight of dextrose, and 0.002 parts by weight of ferrous sulfide as an activator at 75° C. for 3.0 hours, respectively. The reaction was carried out. After the continuous input was completed, polymerization was further carried out at 75° C. for 1 hour, and then the polymerization reaction was terminated by cooling to 60° C. to prepare a graft copolymer latex.
[170]
After completion of the reaction, the graft copolymer obtained had a graft ratio of 85%, and the weight average molecular weight of the shell was 83,000.
[171]

[172]
The acrylate graft copolymer latex prepared above was subjected to atmospheric coagulation at 60 to 85°C by applying 1.0 parts by weight of an aqueous calcium chloride solution, then aged at 70 to 95°C, dehydrated and washed, and dried with 85°C hot air for 2 hours. After the graft copolymer powder was prepared.
[173]

[174]
70 parts by weight of the graft copolymer powder, 30 parts by weight of a styrene-acrylonitrile resin (S95RF, manufactured by LG Chem) as a matrix resin, 1.5 parts by weight of a lubricant, 1.0 parts by weight of an antioxidant, 1.5 parts by weight of a UV stabilizer were added and mixed. . This was prepared into pellets using a 36-pi extrusion kneader at a cylinder temperature of 220 °C.
[175]
The prepared pellets were injected using an injection machine at a barrel temperature of 220° C. to prepare a specimen with physical properties such as impact strength.
[176]
The BA (butyl acrylate) content in the prepared thermoplastic resin was 33% (wt%), the alkyl acrylate coverage value was 83%, and the BA elution amount in the resin sol was 1.97%.
[177]

[178]
The thermoplastic resin pellets were prepared to a film thickness of 0.15 mm using a 20-pi single extrusion kneader equipped with a T-die at a cylinder temperature of 230°C.
[179]
Example 2
[180]
In Example 1 , the thermoplastic resin was prepared in the same manner except that 30 parts by weight of a styrene-acrylonitrile-methyl methacrylate copolymer (XT500, manufactured by LG Chem) was used as the matrix resin.
[181]
The BA content in the prepared thermoplastic resin is 33%, the alkyl acrylate coverage value is 83%, and the BA elution amount in the resin Sol is 1.97%.
[182]
Example 3
[183]
In Example 1, the thermoplastic resin was prepared in the same manner except that 30 parts by weight of a methyl methacrylate copolymer (BA611, manufactured by LGMMA) was used as the matrix resin.
[184]
The BA content in the resin is 33%, the value of the alkyl acrylate coverage is 83%, and the BA elution amount in the resin Sol is 1.97%.
[185]
Example 4
[186]
In Example 1, 42.75 parts by weight of butyl acrylate and 2.25 parts by weight of styrene were used to prepare the rubber core, and 33.7 parts by weight of styrene, 12.7 parts by weight of acrylonitrile, and 3.6 parts by weight of butyl acrylate were used to prepare the copolymer shell. When the thermoplastic resin was prepared, 50 parts by weight of the prepared graft copolymer and 50 parts by weight of the alphamethylstyrene-styrene-acrylonitrile copolymer (S99UH, manufactured by LG Chem) were used as the matrix resin. .
[187]
The average size of the particles of the obtained rubber polymer was 93 nm, the graft ratio of the graft copolymer was 68%, and the weight average molecular weight of the shell was 81,000. The BA content in the resin is 26%, the alkyl acrylate coverage value is 68%, and the BA elution amount in the resin Sol is 0.97%.
[188]
Example 5
[189]
In Example 1, 28.5 parts by weight of butyl acrylate and 1.5 parts by weight of styrene were used in preparing the rubber core, and 43.8 parts by weight of styrene, 16.5 parts by weight of acrylonitrile, and 4.7 parts by weight of butyl acrylate were used in the preparation of the copolymer shell. , It was prepared in the same manner except that 100 parts by weight of the graft copolymer was used without using a matrix resin when preparing the thermoplastic resin.
[190]
The average size of the particles of the obtained rubber polymer was 84 nm, the graft ratio of the graft copolymer was 68%, and the weight average molecular weight of the shell was 80,000. The BA content in the resin is 38%, the value of the alkyl acrylate coverage is 117%, and the BA elution in the resin Sol is 7%.
[191]
Example 6
[192]
In Example 1, 33.25 parts by weight of butyl acrylate and 1.75 parts by weight of styrene were used to prepare the rubber core, and 40.3 parts by weight of styrene, 15.3 parts by weight of acrylonitrile, and 4.4 parts by weight of butyl acrylate were used in the preparation of the copolymer shell. , was prepared in the same manner except that 80 parts by weight of the graft copolymer and 20 parts by weight of the matrix resin were used during the production of the thermoplastic resin.
[193]
The average size of the particles of the obtained rubber polymer was 88 nm, the graft ratio of the graft copolymer was 103%, and the weight average molecular weight of the shell was 81,000. The BA content in the resin is 34%, the value of the alkyl acrylate coverage is 99%, and the BA elution amount in the resin Sol is 2.78%.
[194]
Example 7
[195]
It was prepared in the same manner as in Example 1, except that 39.1 parts by weight of styrene, 13.1 parts by weight of acrylonitrile, and 2.8 parts by weight of butyl acrylate were used in preparing the copolymer shell.
[196]
The average size of the particles of the obtained rubber polymer was 90 nm, the graft ratio of the graft copolymer was 83%, and the weight average molecular weight of the shell was 83,000. The BA content in the resin is 32%, the value of the alkyl acrylate coverage is 85%, and the BA elution amount in the resin Sol is 1.46%.
[197]
Example 8
[198]
It was prepared in the same manner as in Example 1, except that 35 parts by weight of styrene, 11.7 parts by weight of acrylonitrile, and 8.3 parts by weight of butyl acrylate were used in the preparation of the copolymer shell.
[199]
The average size of the particles of the obtained rubber polymer was 90 nm, the graft ratio of the graft copolymer was 81%, and the weight average molecular weight of the shell was 81,000. The BA content in the resin is 36%, the value of the alkyl acrylate coverage is 94%, and the BA elution in the resin Sol is 4.53%.
[200]
Example 9
[201]
In Example 1, 4.5 parts by weight of butyl acrylate and 0.5 parts by weight of styrene were used to prepare the rubber seed, and 36 parts by weight of butyl acrylate and 4 parts by weight of styrene were used to prepare the rubber core.
[202]
The average size of the particles of the obtained rubber polymer was 90 nm, the graft ratio of the graft copolymer was 86%, and the weight average molecular weight of the shell was 80,000. The BA content in the resin is 31%, the value of the alkyl acrylate coverage is 94%, and the BA elution amount in the resin Sol is 1.93%.
[203]
Example 10
[204]
In Example 1, 4.25 parts by weight of butyl acrylate and 0.75 parts by weight of styrene were used to prepare the rubber seed, and 34 parts by weight of butyl acrylate and 6 parts by weight of styrene were used in the preparation of the rubber core.
[205]
The average size of the particles of the obtained rubber polymer was 90 nm, the graft ratio of the graft copolymer was 88%, and the weight average molecular weight of the shell was 78,000. The BA content in the resin is 29%, the value of the alkyl acrylate coverage is 106%, and the BA elution amount in the resin Sol is 1.85%.
[206]
Example 11
[207]
In Example 1, 4 parts by weight of butyl acrylate and 1 part by weight of styrene were used to prepare the rubber seed, and 32 parts by weight of butyl acrylate and 8 parts by weight of styrene were used in the preparation of the rubber core.
[208]
The average size of the particles of the obtained rubber polymer was 90 nm, the graft ratio of the graft copolymer was 91%, and the weight average molecular weight of the shell was 75,000. The BA content in the resin is 28%, the value of the alkyl acrylate coverage is 121%, and the BA elution in the resin Sol is 1.73%.
[209]
Example 12
[210]
It was prepared in the same manner as in Example 1, except that 2.0 parts by weight of sodium dodecyl sulfate was used in the preparation of the rubber seed.
[211]
The average size of the particles of the obtained rubber polymer was 50 nm, the graft ratio of the graft copolymer was 75%, and the weight average molecular weight of the shell was 65,000. The BA content in the resin is 33%, the value of the alkyl acrylate coverage is 75%, and the BA elution in the resin Sol is 2.32%.
[212]
Example 13
[213]
It was prepared in the same manner as in Example 1, except that 0.25 parts by weight of sodium dodecyl sulfate was used when preparing the rubber seeds.
[214]
The average size of the particles of the obtained rubber polymer was 110 nm, the graft ratio of the graft copolymer was 92%, and the weight average molecular weight of the shell was 106,000. The BA content in the resin is 33%, the value of the alkyl acrylate coverage is 89%, and the BA elution amount in the resin Sol is 1.69%.
[215]
Comparative Example 1
[216]
In Example 1, 52.25 parts by weight of butyl acrylate and 2.75 parts by weight of styrene were used in preparing the rubber core, and 27 parts by weight of styrene, 10 parts by weight of acrylonitrile, and 3 parts by weight of butyl acrylate were used in preparing the copolymer shell. Except that, it was prepared in the same manner.
[217]
The average size of the particles of the obtained rubber polymer was 96 nm, the graft ratio of the graft copolymer was 40%, and the weight average molecular weight of the shell was 83,000. The BA content in the resin is 42%, the value of the alkyl acrylate coverage is 43%, and the BA elution in the resin Sol is 1.9%.
[218]
Comparative Example 2
[219]
In Example 1, 14.25 parts by weight of butyl acrylate and 0.75 parts by weight of styrene were used in preparing the rubber core, and 53.8 parts by weight of styrene, 20.4 parts by weight of acrylonitrile, and 5.8 parts by weight of butyl acrylate were used in the preparation of the copolymer shell. Except that, it was prepared in the same manner.
[220]
The average size of the particles of the obtained rubber polymer was 77 nm, the graft ratio of the graft copolymer was 143%, and the weight average molecular weight of the shell was 78,000. The BA content in the resin is 17%, the value of the alkyl acrylate coverage is 131%, and the BA elution amount in the resin Sol is 3.82%.
[221]
Comparative Example 3
[222]
It was prepared in the same manner as in Example 1, except that 40 parts by weight of the graft copolymer and 60 parts by weight of the matrix resin were used in the preparation of the thermoplastic resin.
[223]
The BA content in the resin is 19%, the value of the alkyl acrylate coverage is 83%, and the BA elution in the resin Sol is 0.7%.
[224]
Comparative Example 4
[225]
In Example 1, 52.25 parts by weight of butyl acrylate and 2.75 parts by weight of styrene were used to prepare the rubber core, and 27 parts by weight of styrene, 10 parts by weight of acrylonitrile, and 3 parts by weight of butyl acrylate were used in the preparation of the copolymer shell. , was prepared in the same manner except that 85 parts by weight of the prepared graft copolymer and 15 parts by weight of the SAN resin were used as the matrix resin when preparing the thermoplastic resin.
[226]
The obtained rubber polymer had an average particle diameter of 96 nm, the graft copolymer had a graft rate of 40%, and the shell had a weight average molecular weight of 83,000. The BA content in the resin is 51%, the value of the alkyl acrylate coverage is 43%, and the BA elution in the resin Sol is 3.33%.
[227]
[Test Example]
[228]
Physical properties of the specimens and films prepared in Examples 1 to 13 and Comparative Examples 1 to 4 were measured in the following manner, and the results are shown in Tables 1 and 2 below.
[229]
* Average particle diameter (DLS average particle diameter): After preparing a sample by diluting 0.1 g of the prepared rubber latex (solid content 35 to 50% by weight) with 100 g of deionized water, a particle size distribution analyzer (Nicomp CW380, PPS company) at 23 ° C. Using a dynamic light scattering method, the particle diameter was measured under an intensity value of 300 kHz in the intensity-weighted Gaussian analysis mode, and the average value of the hydrodynamic diameter obtained from the scattering intensity distribution was obtained as the DLS average particle diameter.
[230]
* Graft rate (%): After adding 30 g of acetone to 0.5 g of the prepared graft polymer dry powder, stirring at 210 rpm for 12 hours at room temperature (23°C) (SKC-6075, Lab companion) and centrifuging it (Supra) R30, Hanil Science Co.), centrifuged at 0℃ at 18,000 rpm for 3 hours to collect insoluble fraction that was not dissolved in acetone, and then dried at 85℃ for 12 hours by forced circulation (OF-12GW, Lab companion). After measuring the weight, it was calculated by Equation 3 below.
[231]
[Equation 3]
[232]
Graft rate (%) = [weight of grafted monomer (g) / rubber weight (g)] * 100
[233]
In Equation 3, the weight (g) of the grafted monomer is the weight obtained by dissolving the graft copolymer in acetone and centrifuging to subtract the rubber weight (g) from the weight of the insoluble matter (gel), and the rubber weight ( g) is a part by weight of the theoretically added rubber in the graft copolymer powder. Here, the part by weight of the rubber means the total sum of parts by weight of the unit component added during the manufacture of the rubber seed and the core.
[234]
* Weight average molecular weight of the shell (g/mol): When the graft rate was measured, the portion (sol) dissolved in acetone was dissolved in a THF solvent, and then it was obtained as a relative value with respect to a standard PS (standard polystyrene) sample using GPC. Specific measurement conditions are as follows.
[235]
- Solvent: THF (tetrahydrofuran)
[236]
- Column temperature: 40℃
[237]
- Flow rate: 0.3 mL/min
[238]
- Sample concentration: 20 mg/mL
[239]
- Injection volume: 5 μl
[240]
- Column model: 1xPLgel 10um MiniMix-B (250x4.6mm) + 1xPLgel 10um MiniMix-B (250x4.6mm) + 1xPLgel 10um MiniMix-B Guard (50x4.6mm)
[241]
- Equipment name: Agilent 1200 series system
[242]
- Refractive index detector: Agilent G1362 RID
[243]
- RI temperature: 35℃
[244]
- Data processing: Agilent ChemStation S/W
[245]
- Test method: measured according to OECD TG 118
[246]
* BA content (wt%): quantitatively measured through 1 H NMR analysis or FT-IR analysis. Specific measurement conditions are as follows.
[247]
NMR
[248]
- Equipment name: Bruker 600MHz NMR(AVANCE III HD) CPP BB(1H 19F tunable and broadband, with z-gradient) Prodigy Probe
[249]
- Measurement conditions: 1 H NMR (zg30): ns=32, d1=5s, TCE-d2, at room temp.
[250]
FT-IR
[251]
- Equipment name: Agilent Cary 660
[252]
- Measurement condition: ATR mode
[253]
* Gel content: After adding 30 g of acetone to 0.5 g of the prepared thermoplastic resin dry powder, stirring at 210 rpm for 12 hours at room temperature (SKC-6075, Lab companion) and centrifuging it (Supra R30, Hanil Science) After centrifugation at 0 ° C. at 18,000 rpm for 3 hours to collect insoluble fraction that did not dissolve in acetone, the weight was measured after drying (OF-12GW, Lab companion) at 85 ° C. for 12 hours by forced circulation. It was calculated by Equation 2.
[254]
[Equation 2]
[255]
Gel content (%) = {weight of insoluble matter (gel) / weight of sample} * 100
[256]
* Alkyl acrylate coverage (%): It was calculated by Equation 1 below.
[257]
[Equation 1]
[258]
X(%) = {(GY)/Y} * 100
[259]
(In Equation 1, G is the total gel content (%) of the thermoplastic resin, and Y is the weight% of the alkyl acrylate in the gel.) Here, the alkyl acrylate content (wt%) in the gel is 1 H Quantitatively measured using NMR analyzer or FT-IR.
[260]
* Alkyl acrylate elution amount (wt%): 30 g of acetone was added to 0.5 g of dry thermoplastic resin powder and stirred at 210 rpm for 12 hours at room temperature (SKC-6075, Lab companion), and then centrifuged (Supra R30) , Hanil Science Co., Ltd.), the acetone solution from which the insoluble content was separated by centrifugation at 0° C. at 18,000 rpm for 3 hours was dried at 85° C. for 12 hours by forced circulation (OF-12GW, Lab companion) to obtain a resin sol (Sol). ), which was quantitatively measured by 1 H NMR analyzer or FT-IR analysis.
[261]
* Impact strength (1/4"; kgf·cm/cm): Measured at 23°C according to ASTM D256.
[262]
* Melt flow index (MI): Measured at 220°C under 10 kg according to ASTM D-1238 It was heated with a furnace and put into a cylinder of a melt indexer, a load of 10 kg was applied with a piston, and the weight (g) of the resin melted for 10 minutes was measured and obtained.
[263]
* Surface gloss (%): Using a Gloss meter (VG7000, NIPPON DENSHOKU Co., Ltd.), it was measured according to ASTM D528 at a temperature of 23°C and an incident angle of 60°.
[264]
* Whitening: When the prepared film was bent 180˚ in the longitudinal direction (MD) and transverse direction (TD) at 23° C., it was visually determined whether whitening occurred (bending whitening).
[265]
In addition, a film specimen having a width and length of 100 mm x 100 mm and a thickness of 0.15 mm was prepared and a weight of 1 kg (Cat No. 1249, When the Falling Weight 1 kg) was dropped vertically onto the film from a height of 100 mm, the haze before and after the impact of the impact part (center of the film) impacted by the weight was measured according to ASTM D1003-95, and then the following formula It was counted as 5 (fallen ball efflorescence).
[266]
[Equation 5]
[267]
Haze difference = Haze value after falling ball - Haze value before falling ball
[268]
In Tables 1 and 2 below, bending whitening was expressed as O when whitening occurred, and X when whitening did not occur (no whitening), and falling whitening was expressed as the haze difference obtained by Equation 5 above.
[269]
At this time, haze was measured at 23° C. in accordance with ASTM D1003-95 using a haze meter (model name: HM-150) of MURAKAMI.
[270]
[Table 1]
division BA content in resin % BA coverage% Flow index
[g/10min] Impact strength
[kg cm/cm] Film gloss all sorts of flowers
TD MD falling ball
Example 1 33 83 12.5 6.1 125.3 X X 3.3
Example 2 33 83 13.5 4.4 127.5 X X 2.9
Example 3 33 83 13.6 4.2 139.5 X X 2.7
Example 4 26 68 8.5 6.8 124.2 X X 3.5
Example 5 38 117 10 6.6 129.1 X X 1.8
Example 6 34 99 11.2 5.3 126.1 X X 2.3
Example 7 32 85 12.1 5.3 124.8 X X 3.7
Example 8 36 69 12.5 6.2 124.8 X X 2.6
Example 9 31 94 12.5 5.8 121.3 X X 3.0
Example 10 29 106 13.2 5.6 121.9 X X 2.8
Example 11 28 121 13.4 4.6 122.4 X X 2.5
Example 12 33 75 14.3 4 125.5 X X 2.6
Example 13 33 89 9.5 6.4 134.5 X X 3.6
[271]
[Table 2]
division BA content in resin % BA coverage% Flow index
[g/10min] Impact strength
[kg cm/cm] Film gloss all sorts of flowers
TD MD falling ball
Comparative Example 1 42 43 4.6 10.5 99.8 O O 15.3
Comparative Example 2 17 131 14.6 2.6 118.2 O O 43.5
Comparative Example 3 19 83 16.1 3.5 102.5 O O 39.4
Comparative Example 4 51 43 2.1 16.8 98.3 O O 13.3
[272]
As shown in Table 1 above, the thermoplastic resin according to the present invention (see Examples 1 to 13) has impact strength, gloss and fluidity (molding processability) compared to the thermoplastic resin (refer to Comparative Examples 1 to 4) outside the scope of the present invention. At the same time, while excellent, bending whitening did not occur at all, and the difference in haze values ​​before and after hitting was 4 or less even when hitting, confirming that the whitening property was excellent.
[273]
1 is a photograph taken after bending the films prepared in Examples (left photograph) and Comparative Example (right photograph) in Md and Td directions, respectively, to check whether or not whitening occurs. Although whitening did not occur in the site, the non-whitening characteristic was confirmed, but it was confirmed that the comparative example outside the scope of the present invention had severe whitening in the bent area.
[274]
In addition, the following Figure 2 is a photograph taken after each hit with a Gardner impact tester in order to check whether the films prepared in Examples (left photo) and Comparative Example (right photo) are whitened, here as well according to the present invention In the example, whitening did not occur in the impact part, and thus the non-whitening characteristic was confirmed, but in the comparative example outside the scope of the present invention, it was confirmed that the whitening occurred severely in the impact part.
Claims
[Claim 1]
(A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, or (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; and (B) a matrix resin comprising at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, alkyl methacrylates, and alkyl acrylates, wherein the total alkyl acrylate content is 20 to 50 wt% and the alkyl acrylate coverage value (X) calculated by the following Equation 1 is 65 or more. [Equation 1] X = {(GY) / Y} * 100 (in Equation 1, G is the total gel content (%) of the thermoplastic resin, Y is the weight% of the alkyl acrylate in the gel of the thermoplastic resin indicates.)
[Claim 2]
The method according to claim 1, wherein the (A) alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer is 50 to 100 wt%, and the (B) aromatic vinyl compound, vinyl cyan compound, alkyl methacrylate and The matrix resin comprising at least one selected from the group consisting of alkyl acrylates is a thermoplastic resin, characterized in that it is included in an amount of 0 to 50% by weight.
[Claim 3]
The thermoplastic resin according to claim 1, wherein the amount of eluted alkyl acrylate in acetone is 0.1 wt% or more.
[Claim 4]
The alkyl acryl according to claim 1, wherein the (A) copolymer is (a-1) DLS average particle diameter of 50 to 120 nm or TEM average particle diameter of 32.5 to 84 nm based on 100% by weight of the (A) copolymer in total. 25 to 50% by weight of late rubber; and (b-1) 50 to 75 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer.
[Claim 5]
The thermoplastic resin according to claim 4, wherein the copolymer (A) has a graft ratio of 60 to 150%, and the copolymer (b-1) has a weight average molecular weight of 40,000 to 120,000 g/mol.
[Claim 6]
The thermoplastic resin according to claim 4, wherein the (a-1) rubber further comprises an aromatic vinyl compound.
[Claim 7]
The thermoplastic resin according to claim 6, wherein the aromatic vinyl compound is included in an amount of 0.1 to 25 wt% based on 100 wt% of the rubber (a-1).
[Claim 8]
The thermoplastic resin according to claim 4, wherein the copolymer (b-1) further comprises an alkyl acrylate.
[Claim 9]
The method according to claim 8, wherein the (b-1) copolymer comprises 55 to 85 wt% of an aromatic vinyl compound, 10 to 30 wt% of a vinyl cyanide compound, and an alkyl acryl compound based on 100 wt% of the (b-1) copolymer. A thermoplastic resin, characterized in that it comprises a rate of 0.1 to 20% by weight.
[Claim 10]
According to claim 1, wherein the thermoplastic resin is extruded into a film having a thickness of 0.15 mm using a Gardner impact tester (gardner impact tester) under a temperature of 23 ℃ under a weight of 1 kg from a height of 100 mm vertically dropped onto the film At this time, the difference between the haze value measured according to ASTM D1003-95 before and after the impact of the impact part impacted by the weight is 10 or less.
[Claim 11]
(A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, or (A) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; And (B) a matrix resin comprising at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, alkyl methacrylates and alkyl acrylates; The acrylate content is 20 to 50% by weight, and the alkyl acrylate coverage value (X) calculated by the following Equation 1 of the thermoplastic resin is 65 or more. [Equation 1] X = {(GY) / Y} * 100 (in Equation 1, G is the total gel content (%) of the thermoplastic resin, Y is the weight% of the alkyl acrylate in the gel of the thermoplastic resin indicates.)
[Claim 12]
The method according to claim 11, wherein (A) the graft copolymer comprises: 30 to 50 wt% of an alkyl acrylate rubber having a DLS average particle diameter of 50 to 120 nm or a TEM average particle diameter of 32.5 to 84 nm; and emulsion polymerization of 100 parts by weight of a monomer mixture containing 50 to 70% by weight of an aromatic vinyl compound and a vinyl cyanide compound.
[Claim 13]
A molded article comprising the thermoplastic resin of any one of claims 1 to 10.
[Claim 14]
The molded article according to claim 13, wherein the molded article is a finishing material.