Title of Invention: Transparent 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. 10-2020-0100368 dated August 11, 2020 and Korean Patent Application No. 10-2021-0091421 filed again on July 13, 2021 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 transparent thermoplastic resin, and more particularly, to a transparent thermoplastic resin that is excellent in transparency, impact strength, gloss and fluidity at the same time, and does not cause whitening during bending or hitting, and thus has excellent non-whitening properties, and a method for manufacturing the same. it's about
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 substrates 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 produce a final product. However, due to the characteristics of the thermoplastic ASA resin, when the above-described finishing treatment is applied at room temperature, there is a problem in that the original color is lost and the aesthetics is impaired.
[7]
[8]
[Prior art literature]
[9]
[Patent Literature]
[10]
Japanese registered patent JP 1995-033470 B2
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[11]
In order to solve the problems of the prior art as described above, the present invention is a transparent thermoplastic resin excellent in transparency, impact strength, gloss and fluidity at the same time, and excellent non-whitening properties by suppressing the occurrence of whitening even when bending or hitting, and a method for manufacturing the same aims to provide
[12]
Another object of the present invention is to provide a molded article made of the transparent thermoplastic resin.
[13]
The above and other objects of the present invention can all be achieved by the present invention described below.
means of solving the problem
[14]
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) an aromatic vinyl compound-vinyl cyan compound-alkyl methacrylate copolymer and a matrix resin comprising at least one selected from the group consisting of an alkyl methacrylate polymer; The transparency (haze value) measured according to 1003 is less than 5, 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, characterized in that A thermoplastic resin is provided.
[15]
[Equation 1]
[16]
X = {(GY)/Y} * 100
[17]
(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 of the thermoplastic resin.)
[18]
[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) an aromatic vinyl compound-vinyl cyan compound-alkyl methacrylate copolymer and a matrix resin comprising at least one selected from the group consisting of an alkyl methacrylate polymer; 1003 provides a thermoplastic resin, characterized in that the transparency (haze value) is less than 5, the total alkyl acrylate content is 20 to 50 wt%, and the elution amount of the alkyl acrylate in acetone is 0.1 wt% or more .
[20]
[21]
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) an aromatic vinyl compound-vinyl cyan compound-alkyl methacrylate copolymer and a matrix resin comprising at least one selected from the group consisting of an alkyl methacrylate polymer; The transparency (haze value) measured according to 1003 is less than 5, the total alkyl acrylate content is 20 to 50% by weight, and the (A) copolymer is based on 100% by weight of the (A) copolymer in total. , (a-1) 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 (a-2) 50 to 70 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer.
[22]
[23]
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-alkyl methacrylate The matrix resin including at least one selected from the group consisting of copolymers and alkyl methacrylate polymers may be preferably included in an amount of 0 to 50 wt%.
[24]
The thermoplastic resin may have an elution amount of the alkyl acrylate in acetone of 0.1 wt% or more.
[25]
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) 30 to 50% by weight; and (a-2) 50 to 70 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer.
[26]
The graft ratio of the copolymer (A) is preferably 60 to 150%, and the weight average molecular weight of the copolymer (a-2) may be preferably 40,000 to 120,000 g/mol.
[27]
The (a-1) rubber may further include an aromatic vinyl compound.
[28]
When the (a-1) rubber 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.
[29]
The (a-2) copolymer may further include preferably an alkyl acrylate, in this case, the (a-2) copolymer is preferably based on a total of 100 wt% of the (a-2) copolymer. As may be a copolymer comprising 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.
[30]
Preferably, the thermoplastic resin may have a difference between the refractive index of the sol and the refractive index of the gel under acetone (according to ASTM D542) of less than 0.025.
[31]
The thermoplastic resin is preferably extruded into a film having a thickness of 0.15 mm, and a weight of 1 kg is vertically placed on the film at a height of 100 mm using a Gardner impact tester under a temperature of 23° C. When dropped, 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.
[32]
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 compound-vinyl cyan compound-alkyl methacrylate copolymer and alkyl methacrylate polymer; The transparency measured according to ASTM D-1003 under the condition of a thickness of 3 mm of the thermoplastic resin is less than 5, the total alkyl acrylate content of the thermoplastic resin is 20 to 50 wt%, and the alkyl calculated by Equation 1 below of the thermoplastic resin The acrylate coverage value (X) may provide a method for producing a thermoplastic resin, characterized in that 65 or more.
[33]
[Equation 1]
[34]
X = {(GY)/Y} * 100
[35]
(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 of the thermoplastic resin.)
[36]
The graft copolymer (A) preferably contains 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 50 to 70% by weight of the aromatic vinyl compound and the vinyl cyan compound; may be prepared including the step of emulsion polymerization of 100 parts by weight of a total of 100 parts by weight of the monomer mixture.
[37]
In addition, the present invention may provide a molded article comprising the thermoplastic resin.
[38]
The molded article may preferably be a finishing material.
[39]
Effects of the Invention
[40]
According to the present invention, transparency, impact strength, gloss and fluidity are excellent at the same time by controlling the difference in refractive index between the sol and the gel of the resin, the particle size of the rubber, the rubber content, the graft rate and molecular weight, and the gel content of the resin, and even when bending or hitting There is an effect of providing a thermoplastic resin excellent in non-whitening properties by suppressing the occurrence of whitening and a method for manufacturing the same.
Brief description of the drawing
[41]
1 is a photograph taken after bending the films prepared in Examples (photo on the left) and Comparative Examples (photo on the right) in Md and Td directions, respectively, to check whether or not whitening occurs.
[42]
2 is a photograph taken after hitting each of the films prepared in Examples (left photo) and Comparative Example (right photo) with a Gardner impact tester to check whether or not whitening occurs.
Modes for carrying out the invention
[43]
Hereinafter, the thermoplastic resin of the present substrate will be described in detail.
[44]
While the present inventors were researching a transparent ASA resin that can provide a finishing material with a luxurious appearance, transparency is improved by controlling the difference in refractive index between the gel and the sol of the resin, the distance between rubber particles is narrowed, and the graft rate is reduced to a predetermined range In the case of height, it was confirmed that the non-whitening characteristics were greatly improved by minimizing the formation of voids due to cracks, and based on this, further research was completed to complete the present invention.
[45]
[46]
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.
[47]
In the present description, the composition ratio of the (co)polymer may mean the content of the units constituting the (co)polymer, or the content of the units input during polymerization of the (co)polymer.
[48]
[49]
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) an aromatic vinyl compound-vinyl cyan compound-alkyl methacrylate copolymer and a matrix resin comprising at least one selected from the group consisting of an alkyl methacrylate polymer; At 50 wt%, the transparency measured according to ASTM D-1003 under the condition of 3 mm in thickness is less than 5, and the alkyl acrylate coverage value (X) calculated by Equation 1 below is 65 or more, in this case Transparency, impact resistance, weather resistance and molding processability are excellent, and whitening does not occur due to bending or hitting, so it has an excellent effect of non-whitening properties.
[50]
[Equation 1]
[51]
X = {(GY)/Y} * 100
[52]
(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 of the thermoplastic resin.)
[53]
[54]
In addition, the thermoplastic resin of the present invention as another example (A) 50 to 100% by weight of a graft copolymer comprising an alkyl acrylate, an aromatic vinyl compound and a 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 compound-alkyl methacrylate copolymers and alkyl methacrylate polymers; It is characterized in that the X value calculated as 1 is 65% or more, and the transparency measured under 3 mm thickness is less than 5. It has the advantage of excellent non-whitening properties.
[55]
[Equation 1]
[56]
X(%) = {(GY)/Y} * 100
[57]
(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 of the thermoplastic resin.)
[58]
[59]
In another example, the thermoplastic resin of the present invention includes (A) 50 to 100 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; 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 compound-alkyl methacrylate copolymers and alkyl methacrylate polymers; The total alkyl acrylate content contained in the is 20 to 50% by weight, and the difference in refractive index (according to ASTM D542) of the sol and the gel under acetone is less than 0.025, and in this case, transparency and impact resistance , weather resistance and molding processability, while whitening does not occur on bending, there is an advantage of excellent non-whitening properties.
[60]
[61]
In another example, the thermoplastic resin of the present invention may include (A) 50 to 100 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; And (B) 0 to 50% by weight of a matrix resin comprising at least one selected from the group consisting of aromatic vinyl compounds-vinyl cyanide compounds-alkyl methacrylate copolymers and alkyl methacrylate polymers; including, a thickness of 3 mm Under the conditions, the transparency (haze value) measured according to ASTM D-1003 is less than 5, the total alkyl acrylate content is 20 to 50% by weight, and the elution amount of the alkyl acrylate in acetone is 0.1% by weight or more. , In this case, transparency, impact resistance, weather resistance, and molding processability are excellent, and whitening does not occur due to bending, so there is an advantage of excellent non-whitening properties.
[62]
[63]
In another example, the thermoplastic resin of the present invention may include (A) 50 to 100 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; And (B) 0 to 50% by weight of a matrix resin comprising at least one selected from the group consisting of aromatic vinyl compounds-vinyl cyanide compounds-alkyl methacrylate copolymers and alkyl methacrylate polymers; including, a thickness of 3 mm Under the condition, the transparency (haze value) measured according to ASTM D-1003 is less than 5, the total alkyl acrylate content is 20 to 50 wt%, and the (A) copolymer is 100 Based on the weight%, (a-1) 30 to 50% by weight 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 (a-2) 50 to 70 wt% of the aromatic vinyl compound-vinyl cyan compound copolymer; in this case, transparency, impact resistance, weather resistance and molding processability are excellent, and whitening against bending It has the advantage of excellent non-whitening properties because it does not occur.
[64]
[65]
In this description, the gel content is determined by adding 30 g of acetone to 0.5 g of dry thermoplastic resin powder, 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.
[66]
[Equation 2]
[67]
Gel content (%) = {weight of insoluble matter (gel) / weight of sample} * 100
[68]
[69]
In this description, the graft rate is obtained by adding 30 g of acetone to 0.5 g of the graft polymer 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 can be obtained by calculating by Equation 3 below.
[70]
[Equation 3]
[71]
Graft rate (%) = [weight of grafted monomer (g) / rubber weight (g)] * 100
[72]
In Equation 3, the weight (g) of the grafted monomer is the weight obtained by dissolving the graft copolymer in acetone and centrifuging it and subtracting the rubber weight (g) from the weight of the insoluble matter (gel), and the rubber weight ( g) is the weight of the theoretically added rubber component in the graft copolymer powder.
[73]
[74]
In the present 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) value can be measured. As a specific example, 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 Thus, it is measured with a flow cell, and the measurement mode can be obtained by dynamic light scattering method/Intensity 300KHz/Intensity-weight Gaussian Analysis.
[75]
[76]
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:
[77]
- Sample preparation: thermoplastic resin pellets made by extrusion kneader
[78]
- Sample pretreatment: Timing (23℃) → Hydrazine treatment (72℃, 5 days) → Sectioning (-120℃) → OsO 4 vapor staining (2 hours)
[79]
- Analysis instrument: TEM (JEM-1400, Jeol company)
[80]
- Analysis conditions: Acc. Volt 120 kV, SPOT Size 1 (X 10K, X 25K, X 50K)
[81]
- Size (average particle diameter) measurement: the average of the longest diameters of the particles with the top 10% in diameter size
[82]
Here, the average of the longest diameters of particles having a diameter size of the top 10% is, for example, randomly selecting 100 or more particles from a TEM image and measuring their longest diameter, and then the arithmetic mean value of the top 10% of the measured diameter it means.
[83]
[84]
Hereinafter, each component constituting the thermoplastic resin of the present disclosure will be described in detail as follows.
[85]
[86]
(A) copolymer
[87]
The copolymer (A) is a graft copolymer comprising an alkyl acrylate, an aromatic vinyl compound, and a vinyl cyan compound, and is included in an amount of 50 to 100% by weight in 100% by weight of the total thermoplastic resin.
[88]
The (A) copolymer is, for example, (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 (A) copolymer. Weight%, preferably 35 to 50% by weight, and (a-2) an aromatic vinyl compound-vinyl cyan compound copolymer 50 to 70% by weight, preferably 50 to 65% by weight, It has excellent impact resistance while having excellent gloss and non-whitening properties within the range. The DLS average particle diameter of the (a-1) rubber may be preferably 50 to 110 nm, and the TEM average particle diameter may be preferably 35 to 80 nm, more preferably 40 to 78 nm, within this range. There is an excellent effect of colorability and weather resistance without lowering the mechanical strength.
[89]
[90]
In the present description, the graft copolymer (A) comprising (a-1) an alkyl acrylate rubber, and (a-2) an aromatic vinyl compound-vinyl cyan compound copolymer is an alkyl acrylate rubber (a-1) , and an aromatic vinyl compound surrounding the alkyl acrylate rubber (a-1)- means a graft copolymer (A) comprising a vinyl cyan compound copolymer (a-2). Also, (a-1) may be expressed as a graft copolymer (A) in which an aromatic vinyl compound and a vinyl cyan compound are graft-polymerized on an alkyl acrylate rubber.
[91]
[92]
The copolymer (A) has, for example, a graft rate of 60 to 150%, and the weight average molecular weight of the copolymer (a-2) 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 60 to 140%, more preferably 62 to 130%, and within this range, there is an excellent effect of non-whitening properties without deterioration of impact resistance and molding processability. The weight average molecular weight of the copolymer (a-2) may be preferably 50,000 to 110,000 g/mol, more preferably 60,000 to 110,000 g/mol, within this range, molding processability and non-whitening without lowering impact resistance. Characteristics have an excellent effect.
[93]
In this description, unless otherwise defined, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze), 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 OECD TG 118 conditions.
[94]
[95]
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. In this case, 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, based on 100% by weight of the total rubber (a-1), More preferably, it may be 5 to 20% by weight, and within this range, the desired effect can be sufficiently obtained without deterioration of other physical properties.
[96]
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.
[97]
[98]
The copolymer (a-2) 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 copolymer (a-2) is, for example, 55 to 85% by weight of an aromatic vinyl compound, 10 to 30% by weight of a vinyl cyanide compound, and 0.1 to 20% by weight of an alkyl acrylate based on 100% by weight of the (a-2) copolymer. It may be made by including 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, and more preferably 65 to 78% by weight of an aromatic vinyl compound. % by weight, may be made to include 15 to 22% by weight of the vinyl cyanide compound, and 5 to 17% by weight of an alkyl acrylate, within this range, the impact strength and weather resistance are more excellent.
[99]
[100]
The (a-1) rubber may include, for example, a rubber seed.
[101]
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.
[102]
As a specific example, the rubber seed is added to a monomer containing 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.
[103]
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.
[104]
[105]
The (A) copolymer is, for example, based on 100 parts by weight of the unit constituting the (A) copolymer, A-1) an alkyl acrylate compound and optionally 1 to 20 parts by weight of an aromatic vinyl compound 0.001 to 1 weight part of the electrolyte preparing a rubber seed by polymerizing a mixture containing parts, 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; A-2) comprising 25 to 55 parts by weight of an alkyl acrylate compound and optionally 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 rubber seed polymerizing the mixture 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. It may be prepared including; preparing a graft shell by mixing 0.01 to 1 parts by weight of an activator. In this case, there is an excellent effect in the physical property balance of impact resistance, weather resistance, molding processability and non-whitening characteristics.
[106]
[107]
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, 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, and preferably a chain alkyl group having 1 to 4 carbon atoms. It may be an alkyl acrylate containing, more preferably butyl acrylate.
[108]
[109]
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 -bromo styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyltoluene, vinylxylene, may be at least one selected from the group consisting of 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, so that the processability is excellent and mechanical properties such as impact resistance are excellent.
[110]
[111]
In the present description, the vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methyl acrylonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, and preferably acrylonitrile.
[112]
[113]
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 an unsaturated vinyl group and can serve as a crosslinking agent or two or more different reactivity At least one compound containing an unsaturated vinyl group having , ethylene glycol dimethacrylate, divinylbenzene, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butadiol dimethacrylate, hexanediol propoxylate diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxylate diacrylate, neopentyl glycol propoxylate diacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, trimethylpropaneethoxylate triacrylate, Trimethylpropanepropoxylate triacrylate, pentaerythritol ethoxylate triacrylate, pentaerythritol propoxylate triacrylate, vinyltrimethoxysilane, allyl methacrylate, triallyl isocyanurate, triallyl amine And it may be at least one selected from the group consisting of diallyl amine, but is not limited thereto.
[114]
In the present substrate, the electrolyte is, for example, KCl, NaCl, KHCO 3 , NaHCO 3 , K2CO 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 2S 2 O 7 One or more selected from the group consisting of may be used in combination, but is not limited thereto.
[115]
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.
[116]
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, but not limited thereto.
[117]
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.
[118]
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 organic peroxides such as oxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and t-butyl peroxy isobutylate; azobis isobutyronitrile, azobis methylbutyronitrile,
[119]
[120]
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 is, for example, from the group consisting of sodium pyrophosphate, dextrose, ferrous sulfide, sodium sulfite, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, sulfonatoacetic acid metal salt and sulfinatoacetic acid metal salt. One or more selected types may be used, but the present invention is not limited thereto.
[121]
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
[122]
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 of the 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
[123]
[124]
In the step of preparing the seed and the core, batch input and continuous input may be used individually as a method of inputting the monomer, or two methods may be used in combination.
[125]
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.
[126]
[127]
In the present description, the emulsifier is not particularly limited if it is an emulsifier generally used in the technical field to which the present invention belongs, and includes, for example, rosin acid salt, lauryl acid salt, oleic acid salt, stearic acid salt, etc. having 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 one or more phosphoric acid-based salts selected from the group consisting of mono alkyl ether phosphates or dialkyl ether phosphates.
[128]
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.
[129]
As another example, the emulsifier may be 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.
[130]
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.
[131]
[132]
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.
[133]
Examples of the molecular weight modifier include mercaptans such as α-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.
[134]
[135]
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 ℃.
[136]
[137]
(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 the effect of improving mechanical strength and appearance characteristics.
[138]
In the present description, the coagulant content (%) can be calculated by measuring the weight of the coagulated material produced in the reaction tank, the total rubber weight, and the monomer weight, and using Equation 4 below.
[139]
[Equation 4]
[140]

[141]
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 , dehydration, washing, and drying processes may be performed to prepare a powder, but is not limited thereto.
[142]
[143]
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.
[144]
[145]
In the present description, % means % by weight unless otherwise defined.
[146]
[147]
(B) matrix resin
[148]
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-vinyl cyan compound-alkyl methacrylate copolymer and an alkyl methacrylate polymer, based on 100% by weight of the total thermoplastic resin. 0 to 50% by weight. 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.
[149]
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. 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 may be further improved within this range.
[150]
In the present substrate, the glass transition temperature can be measured using TA Instruments Q100 DSC (Differential Scanning Calorimetry) according to ASTM D 3418 at a temperature increase rate of 10° C./min.
[151]
[152]
In the present description, the alkyl methacrylate may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples thereof include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylbutyl methacrylate. , may be at least one selected from the group consisting of ethylhexyl methacrylate and lauryl methacrylate, and may preferably be an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms.
[153]
The alkyl methacrylate included in the matrix resin may preferably be methyl methacrylate, and in this case, the physical property balance between molding processability and other physical properties is more excellent.
[154]
The aromatic vinyl compound and the vinyl cyan compound contained in the matrix resin may be appropriately selected within the same range as those mentioned in the copolymer (A), respectively.
[155]
[156]
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 regulator, and may include suspension polymerization, emulsion polymerization, bulk polymerization, or solution. It can be prepared by a polymerization method.
[157]
Materials required 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, It can select suitably as needed.
[158]
As another example, the (B) matrix resin may use a commercially available product.
[159]
[160]
thermoplastic resin
[161]
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.
[162]
The total 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.
[163]
In the present description, the total content of the alkyl acrylate included in 100% by weight of the total weight of the thermoplastic resin may be calculated by adding parts by weight of the alkyl acrylate compound added during the preparation of the thermoplastic resin, for example. As another example, the thermoplastic resin may be quantitatively measured through NMR (Nuclear Magnetic Resonance) analysis or FT-IR (Fourier Transform Infrared Spectroscopy) analysis.
[164]
In the present description, NMR analysis refers to analysis by 1 H NMR unless otherwise specified .
[165]
In the present description, NMR analysis may be measured using a method commonly performed in the art, and specific examples of measurement are as follows.
[166]
- Equipment name: Bruker 600MHz NMR(AVANCE III HD) CPP BB(1H 19F tunable and broadband, with z-gradient) Prodigy Probe
[167]
- Measurement conditions: 1 H NMR (zg30): ns=32, d1=5s, TCE-d2, at room temp.
[168]
[169]
In the present description, FT-IR analysis may be measured using a method commonly performed in the art, and specific measurement examples are as follows.
[170]
- Equipment name: Agilent Cary 660
[171]
- Measurement condition: ATR mode
[172]
[173]
The thermoplastic resin is injected into a specimen having a thickness of 3 mm and has excellent transparency (haze value) measured according to ASTM D-1003 of less than 5, and the transparency is preferably 0.1 to 4.0, more preferably may be 0.1 to 3.5.
[174]
The haze of the thermoplastic resin may be measured using a method known in the related art for measuring transparency, and in detail, it may be measured according to ASTM D1003. As a specific example, using MURAKAMI's haze meter (model name: HM-150) equipment at a barrel temperature of 220°C (thickness 3 mm) for a specimen (thickness 3 mm) to measure the haze value (haze) at 23°C according to ASTM D1003. can
[175]
[176]
The thermoplastic resin may have an X value of 65% or more, preferably 65 to 150%, more preferably 68 to 140%, which is calculated by Equation 1 through the limited composition as described above, and has no whitening within this range. Characteristics are more effective.
[177]
[Equation 1]
[178]
X(%) = {(GY)/Y} * 100
[179]
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.
[180]
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 (gel) collected in the process of obtaining the above-described gel content (based on 100% by weight of the total injected thermoplastic resin) . Here, the gel content refers to the content of insolubles based on 100% by weight of the total thermoplastic resin.
[181]
[182]
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.
[183]
In the present description, the elution amount of the alkyl acrylate under acetone is after 30 g of acetone is 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 (SKC-6075, Lab companion) Supra R30, Hanil Science Co., Ltd.) was centrifuged at 0°C at 18,000 rpm for 3 hours, and the acetone solution from which the insoluble was separated was dried at 85°C for 12 hours by forced circulation (OF-12GW, Lab companion) to obtain a resin sol. (Sol) can be obtained, and it can be quantitatively measured by NMR analysis or FT-IR analysis.
[184]
[185]
For example, the thermoplastic resin may have a difference in refractive index (according to ASTM D542) of a sol and a gel under acetone of less than 0.025, preferably 0.001 or more to less than 0.020, more preferably 0.001 or more to 0.017 or more. It may be less than, and within this range, the haze of the thermoplastic resin is lower without deterioration of other physical properties, and thus the transparency is excellent.
[186]
In the present description, the difference in refractive index between the sol and the gel is obtained by adding 30 g of acetone to 0.5 g of the dry thermoplastic resin powder and stirring at 210 rpm for 12 hours at room temperature (SKC-6075, Lab companion) and centrifuging it (Supra) R30, Hanil Science Co., Ltd.), the dissolved portion in the acetone solution obtained 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 sol. The insoluble content can be obtained by drying (OF-12GW, Lab companion Co., Ltd.) in a forced circulation method at 85° C. for 12 hours to obtain a gel, and then measuring the refractive index of each of the sol and the gel according to ASTM D542. The present invention can provide a thermoplastic resin having better transparency by controlling the difference in refractive index between the sol and the gel within the above range.
[187]
In the present description, the refractive index may be measured at 25° C. using an Abbe refractometer in accordance with ASTM D542.
[188]
[189]
The thermoplastic resin of the present invention is excellent in whitening resistance against bending such as bending or folding, for example, the thermoplastic resin is extruded into a film having a width and length of 100 mm x 100 mm and a thickness of 0.15 mm to 180 ° under a temperature of 23 ° C. Whitening does not occur when bent, and it is characterized by excellent non-whitening properties.
[190]
In addition, the thermoplastic resin of the present invention has excellent whitening resistance against external impact (strike). For example, the thermoplastic resin is extruded into a film having a thickness of 0.15 mm, and the weight 1 using a Gardner impact tester under a temperature of 23 ° C. When a weight of kg is vertically dropped on 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 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 preventing the problem of poor quality due to uneven appearance quality, which has excellent appearance quality. It has the effect of providing a molded article.
[191]
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 center of the film before and after impact is measured and obtained from the difference.
[192]
The haze before and after the impact may be measured using a method known in the related art for measuring transparency, and in detail, it may be measured according to ASTM D1003. As a specific example, according to ASTM D1003 for a film specimen extruded at an extrusion temperature of 230 ° C using a haze meter (model name: HM-150) equipment of MURAKAMI, haze can be measured at a temperature of 23 ° C.
[193]
[194]
The thermoplastic resin may have, for example, a gloss of 120 or more, preferably 125 to 160, more preferably 130 to 160, still more preferably 135 to 160, measured at an incident angle of 60° according to ASTM D528. Within the range, it is possible to provide a molded article having excellent appearance quality due to excellent gloss without deterioration of other physical properties.
[195]
The thermoplastic resin may have, for example, a melt flow index (MI) measured according to ASTM D1238 of 5 or more, preferably 6 to 20, more preferably 7 to 20, and other physical properties within this range There is an effect of excellent molding processability without deterioration of the.
[196]
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. As a specific example, 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 resin.
[197]
[198]
Method for producing thermoplastic resin
[199]
The method for producing the thermoplastic resin of the present invention comprises (A) 50 to 100 wt% of an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer and (B) an aromatic vinyl compound-vinyl cyan compound-alkyl methacrylate copolymer. Including 0 to 50% by weight of a matrix resin comprising at least one selected from the group consisting of coalescing and alkyl methacrylate polymer, kneading and extruding, wherein the thickness of the prepared thermoplastic resin is 3 mm ASTM D- Transparency (haze value) measured according to 1003 is less than 5, and the X value calculated by Equation 1 below is 65% or more, and in this case, the mechanical properties of the conventional ASA-based resin are maintained while excellent molding processability At the same time, it is excellent in transparency, glossiness and whitening properties to provide excellent appearance quality.
[200]
[Equation 1]
[201]
X(%) = {(GY)/Y} * 100
[202]
(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.)
[203]
The copolymer (A) used in manufacturing 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. .
[204]
[205]
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 at least one selected from the group consisting of the (A) copolymer and (B) ) may be further included in an amount of 0.01 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, based on 100 parts by weight of the total of the matrix resin, and within this range, the ASA-based resin composition There is an effect that the necessary physical properties are well realized without degrading the physical properties.
[206]
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.
[207]
The antioxidant may include, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, and the like, but is not limited thereto.
[208]
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.
[209]
The antistatic agent may include, for example, one or more anionic surfactants, nonionic surfactants, and the like, but is not limited thereto.
[210]
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.
[211]
[212]
molded product
[213]
The molded article of the present invention is characterized in that it contains a thermoplastic resin having excellent whitening properties of the present invention. 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.
[214]
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 non-whitening properties.
[215]
[216]
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.
[217]
[218]
[Example]
[219]
In the following examples, the X value calculated by Equation 1 is described as "alkyl acrylate coverage" for convenience.
[220]
[221]
Example 1
[222]

[223]
In a nitrogen-substituted reactor, 30 parts by weight of distilled water, 4.25 parts by weight of butyl acrylate, 0.75 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 0.1 parts by weight of sodium and 80 parts by weight of distilled water were administered at once, and 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.
[224]

[225]
43 parts by weight of distilled water, 34 parts by weight of butyl acrylate, 6 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.
[226]
The average size of the particles of the rubber polymer (the rubber seed and the rubber core including the same) obtained after the completion of the reaction was 90 nm.
[227]

[228]
Into the reactor in which the core was obtained, 27 parts by weight of distilled water, 40 parts by weight of styrene, 11.2 parts by weight of acrylonitrile, 3.8 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 A mixture of cumene hydroperoxide and 0.1 parts by weight of cumene hydroperoxide as an initiator and 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 were continuously added at 75° C. for 3.0 hours. 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.
[229]
The graft copolymer obtained after completion of the reaction had a graft rate of 85%, and a weight average molecular weight of the shell was 83,000 (g/mol).
[230]

[231]
After applying 1.0 parts by weight of an aqueous calcium chloride solution to the prepared acrylate graft copolymer latex, atmospheric agglomeration at 60 to 85° C., aging at 70 to 95° C., dehydration and washing, and drying at 85° C. hot air for 2 hours. After the graft copolymer powder was prepared.
[232]

[233]
70 parts by weight of the graft copolymer powder, 30 parts by weight of a methyl methacrylate polymer (BA611, manufactured by LGMMA) as a matrix resin, 1.5 parts by weight of a lubricant, 1.0 parts by weight of an antioxidant, and 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. The produced pellets were injected and used at a barrel temperature of 220° C. to prepare a specimen with physical properties such as impact strength.
[234]
The BA (butyl acrylate) content in the prepared thermoplastic resin was 29.5% (wt%), the alkyl acrylate coverage value was 103.4%, and the BA elution amount in the resin sol was 1.97%.
[235]

[236]
The thermoplastic resin pellets were extruded to a film thickness of 0.15 μm using a 20 pie single extrusion kneader equipped with a T-die at a cylinder temperature of 230° C.
[237]
[238]
Example 2
[239]
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.
[240]
The BA content in the prepared thermoplastic resin is 29.5%, the alkyl acrylate coverage value is 103.4%, and the BA elution amount in the resin Sol is 1.97%.
[241]
[242]
Example 3
[243]
In Example 1, 3.75 parts by weight of butyl acrylate and 1.25 parts by weight of styrene were used to prepare the rubber seed, 18.75 parts by weight of butyl acrylate and 6.25 parts by weight were used to prepare the rubber core, and 46.5 parts by weight of styrene was used to prepare the shell. It was prepared in the same manner except that parts by weight, 13 parts by weight of acrylonitrile, and 10.5 parts by weight of butyl acrylate were used.
[244]
The average size of the particles of the obtained rubber polymer was 90 nm, the graft ratio of the graft copolymer was 99%, and the weight average molecular weight of the shell was 80,000.
[245]
The BA content in the resin is 23.1%, the value of the alkyl acrylate coverage is 99.3%, and the BA elution in the resin Sol is 7.27%.
[246]
[247]
Example 4
[248]
In Example 1, 29.75 parts by weight of butyl acrylate and 5.25 parts by weight of styrene were used in the preparation of the rubber core, and 43.6 parts by weight of styrene, 12.2 parts by weight of acrylonitrile, and 4.2 parts by weight of butyl acrylate were used in the preparation of the copolymer shell. Except that, a graft copolymer was prepared in the same manner.
[249]
The thermoplastic resin 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.
[250]
The average size of the particles of the obtained rubber polymer was 90 nm, the graft ratio of the graft copolymer was 105%, and the weight average molecular weight of the shell was 81,000. The BA content in the resin is 30.6%, the alkyl acrylate coverage value is 122%, and the BA elution amount in the resin Sol is 2.93%.
[251]
[252]
Example 5
[253]
In Example 1, 38.25 parts by weight of butyl acrylate and 6.75 parts by weight of styrene were used in preparing the rubber core, and 36.3 parts by weight of styrene, 10.2 parts by weight of acrylonitrile, and 3.5 parts by weight of butyl acrylate were used in the preparation of the copolymer shell. Except for, a graft copolymer was prepared in the same manner.
[254]
When the thermoplastic resin was prepared, it was prepared in the same manner except that 50 parts by weight of the graft copolymer and 50 parts by weight of the matrix resin were used.
[255]
The average size of the particles of the obtained rubber polymer was 90 nm, the graft ratio of the graft copolymer was 66%, and the weight average molecular weight of the shell was 78,000.
[256]
The BA content in the resin is 23.0%, the value of the alkyl acrylate coverage is 85.2%, and the BA elution amount in the resin Sol is 1.02%.
[257]
[258]
Example 6
[259]
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.
[260]
The average size of the particles of the obtained rubber polymer was 90 nm, the graft ratio of the graft copolymer was 82%, and the weight average molecular weight of the shell was 89,000.
[261]
The BA content in the resin is 31.0%, the value of the alkyl acrylate coverage is 90.1%, and the BA elution amount in the resin Sol is 2.08%.
[262]
[263]
Example 7
[264]
In Example 1, 4.0 parts by weight of butyl acrylate and 1.0 parts by weight of styrene were used in preparing 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.
[265]
The average size of the particles of the obtained rubber polymer was 90 nm, the graft ratio of the graft copolymer was 78%, and the weight average molecular weight of the shell was 95,000.
[266]
The BA content in the resin is 27.9%, the value of the alkyl acrylate coverage is 108.3%, and the BA elution amount in the resin Sol is 2.22%.
[267]
[268]
Example 8
[269]
It was prepared in the same manner as in Example 1, except that 2.0 parts by weight of sodium dodecyl sulfate was used when preparing the rubber seed.
[270]
The average size of the particles of the obtained rubber polymer was 50 nm, the graft ratio of the graft copolymer was 74%, and the weight average molecular weight of the shell was 72,000.
[271]
The BA content in the resin is 29.4%, the value of the alkyl acrylate coverage is 93.0%, and the BA elution amount in the resin Sol is 2.35%.
[272]
[273]
Example 9
[274]
It was prepared in the same manner as in Example 1, except that 0.25 parts by weight of sodium dodecyl sulfate was used in the preparation of the rubber seed.
[275]
The average size of the particles of the obtained rubber polymer was 110 nm, the graft ratio of the graft copolymer was 93%, and the weight average molecular weight of the shell was 101,000.
[276]
The BA content in the resin is 29.5%, the value of the alkyl acrylate coverage is 110.9%, and the BA elution amount in the resin Sol is 1.64%.
[277]
[278]
Example 10
[279]
In Example 1, 3.75 parts by weight of butyl acrylate and 1.25 parts by weight of styrene were used in preparing the rubber seed, 18.75 parts by weight of butyl acrylate and 6.25 parts by weight of styrene were used in preparing the rubber core, and styrene was used in the preparation of the copolymer shell. A graft copolymer was prepared in the same manner except that 45.04 parts by weight, 12.57 parts by weight of acrylonitrile, and 12.39 parts by weight of butyl acrylate were used.
[280]
When the thermoplastic resin was prepared, 100 parts by weight of the graft copolymer was used and the matrix resin was not used.
[281]
The average size of the particles of the obtained rubber polymer was 90 nm, the graft ratio of the graft copolymer was 150%, and the weight average molecular weight of the shell was 83,000.
[282]
The BA content in the resin is 34.9%, the value of the alkyl acrylate coverage is 146.18%, and the BA elution amount in the resin Sol is 17.7%.
[283]
[284]
Comparative Example 1
[285]
In Example 1, the thermoplastic resin was prepared in the same manner except that 30 parts by weight of a styrene-acrylonitrile resin (S95RF, manufactured by LG Chem) was used as the matrix resin.
[286]
The BA content in the resin is 29.5%, the value of the alkyl acrylate coverage is 103.4%, and the BA elution amount in the resin Sol is 1.97%.
[287]
[288]
Comparative Example 2
[289]
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, 49.5 parts by weight of butyl acrylate and 5.5 parts by weight of styrene were used to prepare the rubber core, and styrene was used to prepare the copolymer shell. 29.1 parts by weight, 8.1 parts by weight of acrylonitrile, and 2.8 parts by weight of butyl acrylate were prepared in the same manner.
[290]
The average size of the particles of the obtained rubber polymer was 90 nm, the graft ratio of the graft copolymer was 50%, and the weight average molecular weight of the shell was 75,000.
[291]
The BA content in the resin is 39.8%, the value of the alkyl acrylate coverage is 60.4%, and the BA elution amount in the resin Sol is 1.32%.
[292]
[293]
Comparative Example 3
[294]
In Example 1, 3.5 parts by weight of butyl acrylate and 1.5 parts by weight of styrene were used to prepare the rubber seed, 14 parts by weight of butyl acrylate and 6 parts by weight of styrene were used to prepare the rubber core, and styrene was used to prepare the copolymer shell. A graft copolymer was prepared in the same manner except that 54.5 parts by weight, 15.2 parts by weight of acrylonitrile, and 5.3 parts by weight of butyl acrylate were used.
[295]
When preparing the thermoplastic resin, the graft copolymer was prepared in the same manner except that 50 parts by weight and 50 parts by weight of the matrix resin were used.
[296]
The average size of the particles of the obtained rubber polymer was 90 nm, the graft ratio of the graft copolymer was 143%, and the weight average molecular weight of the shell was 78,000.
[297]
The BA content in the resin is 11.4%, the value of the alkyl acrylate coverage is 203.7%, and the BA elution amount in the resin Sol is 1.97%.
[298]
[299]
Comparative Example 4
[300]
In Example 1, 4.75 parts by weight of butyl acrylate and 0.25 parts by weight of styrene were used to prepare the rubber seed, 52.25 parts by weight of butyl acrylate and 2.75 parts by weight were used to prepare the rubber core, and styrene was used to prepare the copolymer shell. 29.1 parts by weight, 8.1 parts by weight of acrylonitrile, and 2.8 parts by weight of butyl acrylate were used, and 85 parts by weight of the graft copolymer and 15 parts by weight of the matrix resin were used in the preparation of the thermoplastic resin.
[301]
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.
[302]
The BA content in the resin is 50.8%, the value of the alkyl acrylate coverage is 43.2%, and the BA elution amount in the resin Sol is 3.33%.
[303]
[304]
[Test Example]
[305]
Each physical property was measured by the following method using the physical property specimens and films prepared in Examples 1 to 10 and Comparative Examples 1 to 4, and the results are shown in Tables 1 and 2 below.
[306]
[307]
* DLS average particle size: After preparing a sample by diluting 0.1 g of the prepared rubber latex (solid content 35 to 50 wt%) with 100 g of deionized water, at 23° C. using a particle size distribution analyzer (Nicomp CW380, PPS) , the particle diameter was measured under an intensity value of 300 kHz in Intensity-weighted Gaussian Analysis mode by a dynamic light scattering method, and the average value of the hydrodynamic diameter obtained from the scattering intensity distribution was obtained as the DLS average particle diameter.
[308]
* Graft ratio (%): 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℃ for 3 hours at 18,000 rpm 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 can be calculated by Equation 3 below.
[309]
[Equation 3]
[310]
Graft rate (%) = [weight of grafted monomer (g) / rubber weight (g)] * 100
[311]
In Equation 3, the weight (g) of the grafted monomer is the weight obtained by dissolving the graft copolymer in acetone and centrifuging it to the weight of the insoluble matter (gel) obtained by subtracting 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. 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.
[312]
* Weight average molecular weight of the shell (g/mol): The portion (sol) dissolved in acetone obtained when measuring the graft rate was dissolved in a THF solvent, and then using GPC to obtain a relative value with respect to a standard PS (standard polystyrene) sample. Specific measurement conditions are as follows.
[313]
- Solvent: THF (tetrahydrofuran)
[314]
- Column temperature: 40℃
[315]
- Flow rate: 0.3 mL/min
[316]
- Sample concentration: 20 mg/mL
[317]
- Injection volume: 5 μl
[318]
- Column model: 1xPLgel 10um MiniMix-B (250x4.6mm) + 1xPLgel 10um MiniMix-B (250x4.6mm) + 1xPLgel 10um MiniMix-B Guard (50x4.6mm)
[319]
- Equipment name: Agilent 1200 series system
[320]
- Refractive index detector: Agilent G1362 RID
[321]
- RI temperature: 35℃
[322]
- Data processing: Agilent ChemStation S/W
[323]
- Test method: measured according to OECD TG 118
[324]
* BA content (wt%): quantitatively measured through 1 H NMR analysis or FT-IR analysis. Specific measurement conditions are as follows.
[325]
1 H NMR
[326]
- Equipment name: Bruker 600MHz NMR(AVANCE III HD) CPP BB(1H 19F tunable and broadband, with z-gradient) Prodigy Probe
[327]
- Measurement conditions: 1 H NMR (zg30): ns=32, d1=5s, TCE-d2, at room temp.
[328]
FT-IR
[329]
- Equipment name: Agilent Cary 660
[330]
- Measurement condition: ATR mode
[331]
* 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 gel was dried at 85 ° C for 12 hours by forced circulation (OF-12GW, Lab companion) by measuring the weight of the resulting gel. , was calculated by Equation 2 below.
[332]
[Equation 2]
[333]
Gel content (%) = [weight of insoluble matter (gel) / weight of sample] * 100
[334]
* Alkyl acrylate coverage (%): It was calculated by Equation 1 below.
[335]
[Equation 1]
[336]
X(%) = {(GY)/Y} * 100
[337]
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. Here, the content of alkyl acrylate in the gel (wt%) was quantitatively measured using 1 NMR analyzer or FT-IR.
[338]
* 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.) by centrifugation at 0° C. at 18,000 rpm for 3 hours, and drying the acetone solution from which insoluble components are separated 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 NMR analyzer or FT-IR analysis.
[339]
* Refractive index: Using the gel obtained by the gel content measurement method and the sol obtained by the alkyl acrylate elution amount measurement method, each refractive index was measured at 25 ° C using an Abbe refractometer according to ASTM D542, and the difference (ΔRI) saved
[340]
* Impact strength (1/4"; kgf·cm/cm): Measured at 23°C according to ASTM D256.
[341]
* Melt flow index (MI): Measured at 220 °C and 10 kg in accordance with ASTM D-1238 It was heated with a furnace, put into a cylinder of a melt indexer, and 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.
[342]
* 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°.
[343]
* Transparency (Haze): The haze value was measured according to ASTM D-1003 under a temperature of 23° C. using a haze meter (model name: HM-150) of MURAKAMI with an injection specimen having a thickness of 3 mm .
[344]
* Whitening: When the prepared film was bent 180˚ in the longitudinal direction (MD) and transverse direction (TD), it was visually determined whether whitening occurred (bending whitening).
[345]
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, Falling Weight 1 kg) is dropped vertically onto the film from a height of 100 mm, and the haze before and after the impact of the impact part (center of the film) impacted by the weight is measured according to ASTM D1003-95, and then the following math It was calculated by Equation 5 (Nakgu Baekhwa).
[346]
[Equation 5]
[347]
Haze difference = haze value after falling ball - haze value before falling ball
[348]
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.
[349]
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.
[350]
[351]
[Table 1]
division BA content in resin % BA coverage% Flow index
[g/10min] Impact strength
[kg cm/cm] Film gloss all sorts of flowers transparency
TD MD falling ball Haze ΔRI
Example 1 29.5 103.4 9.9 4.8 141.4 X X 2.5 3.23 0.0103
Example 2 29.5 103.4 10.1 5.1 129.1 X X 2.7 2.82 0.0068
Example 3 23.1 99.3 6.5 7.9 140.7 X X 2.1 2.34 0.0029
Example 4 30.6 122.0 8.1 6.2 143.1 X X 3.0 2.46 0.0038
Example 5 23.0 85.2 12.2 4.2 141.0 X X 2.2 3.88 0.0157
Example 6 31.0 90.1 9.5 5.9 140.8 X X 3.0 2.56 0.0046
Example 7 27.9 108.3 10.1 4.2 142.9 X X 2.3 3.10 0.0092
Example 8 29.5 93.0 10.7 4.2 141.4 X X 2.2 2.34 0.0029
Example 9 29.5 110.9 8.3 6.9 143.2 X X 3.1 3.91 0.0159
Example 10 34.9 146.18 5.5 8.5 130.1 X X 2.9 4.63 0.0236
[352]
[Table 2]
division BA content in resin % BA coverage% Flow index
[g/10min] Impact strength
[kg cm/cm] Film gloss all sorts of flowers transparency
TD MD falling ball Haze ΔRI
Comparative Example 1 29.5 103.4 11.2 5.9 126.9 X X 3.2 63.07 0.0506
Comparative Example 2 39.8 60.4 10.5 4.0 140.2 O O 20.4 2.27 0.0023
Comparative Example 3 11.4 203.7 6.2 5.2 144.4 O O 69.2 10.54 0.0295
Comparative Example 4 50.8 43.2 8.0 9.1 137.2 O O 18.9 12.58 0.0299
[353]
As shown in Table 1, the thermoplastic resin according to the present invention (see Examples 1 to 10) has impact strength, gloss and fluidity (molding processability) compared to the thermoplastic resin (see Comparative Examples 1 to 4) outside the scope of the present invention. At the same time, it is excellent, and the difference in refractive index between the sol and the gel is less than 0.025, so the transparency is excellent, bending whitening does not occur at all, and the difference in the haze value before and after hitting is 4 or less even at the time of hitting, showing excellent non-whitening properties could check
[354]
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, in order 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 in the comparative example outside the scope of the present invention, severe whitening occurred in the bent area.
[355]
In addition, the following Figure 2 is a photograph taken after each hit with a Gardner impact tester to check whether the films prepared in Examples (left photo) and Comparative Example (right photo) are whitened. In the example, whitening did not occur in the impact part, so the non-whitening characteristics were 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) an aromatic vinyl compound-vinyl cyan compound-alkyl methacrylate copolymer and a matrix resin comprising at least one selected from the group consisting of an alkyl methacrylate polymer; The transparency (haze) measured according to 1003 is less than 5, 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, characterized in that Thermoplastics. [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 copolymer The matrix resin comprising at least one selected from the group consisting of coalescing and alkyl methacrylate polymers is a thermoplastic resin, characterized in that it is contained 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. 30 to 50% by weight of late rubber; and (a-2) 50 to 70 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer.
[Claim 5]
[5] The thermoplastic resin according to claim 4, wherein the copolymer (A) has a graft ratio of 60 to 150%, and the copolymer (a-2) 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 (a-2) copolymer further comprises an alkyl acrylate.
[Claim 9]
The method according to claim 8, wherein the (a-2) 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 (a-2) copolymer. A thermoplastic resin, characterized in that it comprises a rate of 0.1 to 20% by weight.
[Claim 10]
The thermoplastic resin according to claim 1, wherein the difference in refractive index (according to ASTM D542) of the sol and the gel under acetone is less than 0.025.
[Claim 11]
The method according to claim 1, wherein the thermoplastic resin is extruded into a film having a thickness of 0.15 mm and a 1 kg weight is vertically dropped onto the film from a height of 100 mm under a temperature of 23° C. using a Gardner impact tester. When, 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 12]
(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) an aromatic vinyl compound-vinyl cyan compound-alkyl methacrylate copolymer and a matrix resin comprising at least one selected from the group consisting of an alkyl methacrylate polymer; The transparency (haze) measured according to ASTM D-1003 under the condition of a thickness of 3 mm of the thermoplastic resin is less than 5, and the total alkyl acrylate content of the thermoplastic resin is 20 to 50 wt%, and the thermoplastic resin is expressed by Equation 1 below. A method for producing a thermoplastic resin, characterized in that the calculated alkyl acrylate coverage value (X) 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 13]
13. The method of claim 12, wherein the (A) graft copolymer comprises: 30 to 50 parts by weight 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 50 to 70 parts by weight of an aromatic vinyl compound and a vinyl cyan compound; emulsion polymerization of 100 parts by weight of a monomer mixture comprising a method for producing a thermoplastic resin, characterized in that it is prepared.
[Claim 14]
A molded article comprising the thermoplastic resin of any one of claims 1 to 11.
[Claim 15]
15. The molded article according to claim 14, wherein the molded article is a finishing material.