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. 10-2020-0100369 dated August 11, 2020 and Korean Patent Application No. 10-2021-0091422 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 excellent in transparency, impact strength, gloss, fluidity and weather resistance at the same time and excellent in non-whitening properties because whitening does not occur during bending or hitting, and manufacturing thereof it's about how
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. In order to solve this problem, a method of using the ABS resin after coating has been proposed, but environmental pollution during the coating process is problematic, and the painted product is difficult to recycle and has poor durability.
[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. However, ASA resin has inferior appearance characteristics such as colorability compared to ABS resin coating products, and the level of weather resistance required in the market is increasing, which is insufficient to satisfy this.
[6]
On the other hand, 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 a thermoplastic resin. . 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 deteriorated.
[7]
This whitening phenomenon is analyzed to be caused by voids due to cracks occurring inside the thermoplastic resin during bending. In order to solve this problem, a method for improving whitening properties by adjusting the rubber content in the thermoplastic resin or by mixing the thermoplastic resin and the elastomer to soften the thermoplastic resin has been proposed. However, through this, the occurrence of whitening can be improved, but there is a problem in that other mechanical properties, coloration, surface gloss, etc. are deteriorated, and development of a thermoplastic resin composition excellent in all of these physical properties is insufficient, and the whitening property is also It is not satisfactory.
[8]
[9]
[Prior art literature]
[10]
[Patent Literature]
[11]
Japanese registered patent JP 1995-033470 B2
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[12]
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, weather resistance and fluidity at the same time, and whitening is suppressed even when bending or hitting, and thus has excellent non-whitening properties, and manufacturing thereof The purpose is to provide a method. Another object of the present invention is to provide a molded article made of the 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-alkyl methacrylate graft copolymer, or (A) an alkyl acrylate-alkyl methacrylate graft copolymer; and (B) a matrix resin comprising at least one selected from the group consisting of alkyl methacrylate polymers and alkyl methacrylate-alkyl acrylate copolymers; and, according to ASTM D-1003 in a thickness of 0.15 mm condition The transparency (haze value) measured by The value (X) is 50 or greater.
[15]
[Equation 1]
[16]
X = {(G-Y)/Y} * 100
[17]
(In Equation 1, G represents the total gel content (%) of the thermoplastic resin, and Y represents the weight% of butyl acrylate in the gel of the thermoplastic resin.)
[18]
[19]
The present invention also relates to a composition comprising (A) an alkyl acrylate-alkyl methacrylate graft copolymer, or (A) an alkyl acrylate-alkyl methacrylate graft copolymer; and (B) a matrix resin comprising at least one selected from the group consisting of alkyl methacrylate polymers and alkyl methacrylate-alkyl acrylate copolymers; and, according to ASTM D-1003 in a thickness of 0.15 mm condition The transparency (haze value) measured by The difference in refractive index (according to ASTM D542) of is 0.02 or less.
[20]
[21]
The present invention also relates to a composition comprising (A) an alkyl acrylate-alkyl methacrylate graft copolymer, or (A) an alkyl acrylate-alkyl methacrylate graft copolymer; and (B) a matrix resin comprising at least one selected from the group consisting of alkyl methacrylate polymers and alkyl methacrylate-alkyl acrylate copolymers; and, according to ASTM D-1003 in a thickness of 0.15 mm condition The measured transparency (haze value) is 2 or less, the transparency measured under the condition of 3 mm thickness is 4 or less, the total alkyl acrylate content is 20 to 50 wt%, and the elution amount of butyl acrylate in acetone is 0.01 wt% It provides a thermoplastic resin characterized in that the above.
[22]
[23]
Preferably, the thermoplastic resin may have a difference in the refractive index of a sol (according to ASTM D542) and a refractive index of a gel under acetone of 0.02 or less.
[24]
The thermoplastic resin comprises preferably 50 to 100% by weight of the (A) alkyl acrylate-alkyl methacrylate graft copolymer, the (B) alkyl methacrylate polymer and the alkyl methacrylate-alkyl acrylate copolymer. The matrix resin including at least one selected from the group consisting of coalesces may be preferably included in an amount of 0 to 50% by weight.
[25]
The thermoplastic resin may have an elution amount of butyl acrylate in acetone of 0.01 wt% or more.
[26]
The copolymer (A) preferably contains (a-1) an alkyl acrylate rubber having a DLS average particle diameter of 40 to 120 nm or a TEM average particle diameter of 25 to 100 nm based on 100% by weight of the (A) copolymer. 50% by weight; and (a-2) 50 to 75 wt% of an alkyl acrylate-alkyl methacrylate copolymer.
[27]
The graft ratio of the copolymer (A) is preferably 60 to 200%, and the weight average molecular weight of the copolymer (a-2) may be 40,000 to 120,000 g/mol.
[28]
The glass transition temperature of the thermoplastic resin, the (a-1) rubber, or both may be preferably -50 to -20°C.
[29]
The (a-1) rubber may further preferably include an alkyl methacrylate, in which case the alkyl methacrylate is preferably 0.1 to 25 wt% based on 100 wt% of the (a-1) rubber. may be included as
[30]
The copolymer (a-2) preferably comprises 80 to 99.9% by weight of an alkyl methacrylate, and 0.1 to 20% by weight of an alkyl acrylate, based on 100% by weight of the copolymer (a-2) It may be a copolymer.
[31]
Preferably, the difference between the refractive index of the rubber (a-1) (according to ASTM D542) and the refractive index of the matrix (B) may be 0.02 or more.
[32]
The thermoplastic resin is preferably extruded into a film having a thickness of 0.15 mm, and a weight of 1 kg is applied vertically onto the film at a height of 100 mm using a Gardner impact tester at 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.
[33]
In addition, the present invention comprises (A) an alkyl acrylate-alkyl methacrylate graft copolymer, or (A) an alkyl acrylate-alkyl methacrylate graft copolymer; And (B) a matrix resin comprising at least one selected from the group consisting of alkyl methacrylate polymers and alkyl methacrylate-alkyl acrylate copolymers; The transparency (haze value) measured according to ASTM D-1003 under the condition of 0.15 mm thickness of the resin is 2 or less, and the transparency measured under the condition of 3 mm thickness is 4 or less, and the total alkyl acrylate contained in the thermoplastic resin is content is 20 to 50 wt%, and the butyl 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 50 or more.
[34]
[Equation 1]
[35]
X = {(G-Y)/Y} * 100
[36]
In Equation 1, G represents the total gel content (%) of the thermoplastic resin, and Y represents the weight% of butyl acrylate in the gel of the thermoplastic resin.
[37]
The graft copolymer (A) preferably contains 25 to 50 wt% of an alkyl acrylate rubber having a DLS average particle diameter of 40 to 120 nm or a TEM average particle diameter of 25 to 100 nm; and 50 to 75 wt% of an alkyl acrylate compound and an alkyl methacrylate compound; may be prepared by including a total of 100 parts by weight of a monomer mixture including emulsion polymerization.
[38]
In addition, the present invention may provide a molded article comprising the thermoplastic resin.
[39]
The molded article may preferably be a finishing material.
Effects of the Invention
[40]
According to the present invention, transparency, impact strength, weather resistance, gloss and fluidity are excellent at the same time 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, and the difference in refractive index between the sol and the gel of the resin. , there is an effect of providing a thermoplastic resin excellent in non-whitening properties and a manufacturing method thereof because whitening does not occur even when bending or hitting.
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 thermoplastic resin that can provide a finishing material having a luxurious appearance, transparency is improved by adjusting the difference in refractive index between the sol and the gel, the distance between rubber particles is narrowed, and the graft rate is increased to a predetermined range 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 devoted 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 may mean 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-alkyl methacrylate graft copolymer, or (A) an alkyl acrylate-alkyl methacrylate graft copolymer; And (B) a matrix resin comprising at least one selected from the group consisting of alkyl methacrylate polymers and alkyl methacrylate-alkyl acrylate copolymers; and, according to ASTM D-1003 at a thickness of 0.15 mm. The measured transparency is 2 or less, the transparency measured under the condition of 3 mm thickness is 4 or less, the total alkyl acrylate content is 20 to 50 wt%, and the butyl acrylate coverage value (X) calculated by the following Equation 1 It is characterized in that the silver is 50 or more, and in this case, transparency, impact resistance, weather resistance, and molding processability are excellent, and whitening does not occur due to bending or hitting, so there is an excellent effect of non-whitening properties.
[50]
[Equation 1]
[51]
X = {(G-Y)/Y} * 100
[52]
In Equation 1, G represents the total gel content (%) of the thermoplastic resin, and Y represents the weight% of butyl acrylate in the gel of the thermoplastic resin.
[53]
[54]
In another example, the thermoplastic resin of the present invention may include (A) 50 to 100% by weight of an alkyl acrylate-alkyl methacrylate graft copolymer; And (B) 0 to 50% by weight of a matrix resin comprising at least one selected from the group consisting of alkyl methacrylate polymers and alkyl methacrylate-alkyl acrylate copolymers, including; The transparency (haze value) measured according to D-1003 is 2 or less, the transparency measured under the condition of thickness 3 mm is 4 or less, and the X value calculated by the following Equation 1 is 50% or more, In the case of transparency, impact resistance, weather resistance and molding processability, while whitening does not occur for bending, there is an advantage of excellent non-whitening properties.
[55]
[Equation 1]
[56]
X(%) = {(G-Y)/Y} * 100
[57]
In Equation 1, G represents the total gel content (%) of the thermoplastic resin, and Y represents the weight% of butyl acrylate in the gel of the thermoplastic resin.
[58]
[59]
In another example, the thermoplastic resin of the present invention may include (A) 50 to 100% by weight of an alkyl acrylate-alkyl methacrylate graft copolymer; and (B) 0 to 50% by weight of a matrix resin comprising at least one selected from the group consisting of alkyl methacrylate polymers and alkyl methacrylate-alkyl acrylate copolymers, wherein the total alkyl acrylate content is 20 to 50% by weight, and the transparency (haze value) measured according to ASTM D-1003 under the condition of 0.15 mm in thickness is 2 or less, and the transparency measured in the condition of 3 mm in thickness is 4 or less, and sol under acetone And the difference in the refractive index (according to ASTM D542) of the gel is 0.02 or less, and in this case, transparency, impact resistance, weather resistance and molding processability are excellent, and whitening does not occur due to bending, so the whitening property is excellent There is an advantage.
[60]
[61]
In another example, the thermoplastic resin of the present invention may include (A) 50 to 100% by weight of an alkyl acrylate-alkyl methacrylate graft copolymer; and (B) 0 to 50% by weight of a matrix resin comprising at least one selected from the group consisting of alkyl methacrylate polymers and alkyl methacrylate-alkyl acrylate copolymers, wherein the total alkyl acrylate content is 20 to 50% by weight, and the transparency (haze value) measured according to ASTM D-1003 under a condition of 0.15 mm in thickness is 2 or less, and the transparency measured in a condition of 3 mm in thickness is 4 or less, and butyl acrylate in acetone It is characterized in that the dissolution amount is 0.01 wt % or more, and in this case, transparency, impact resistance, weather resistance and molding processability are excellent, and whitening does not occur due to bending, and thus there is an advantage of excellent whitening properties.
[62]
[63]
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 at 85 ° C. for 12 hours by forced circulation (OF-12GW, Lab companion). It can be obtained by calculating by Equation 2 below.
[64]
[Equation 2]
[65]
Gel content (%) = {weight of insoluble matter (gel) / weight of sample} * 100
[66]
[67]
In the present description, the graft rate is obtained by adding 30 g of acetone to 0.5 g of the graft polymer dry powder, followed by 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 at 85 ° C. for 12 hours by forced circulation (OF-12GW, Lab companion). It can be obtained by calculating by Equation 3 below.
[68]
[Equation 3]
[69]
Graft rate (%) = [weight of grafted monomer (g) / rubber weight (g)] * 100
[70]
In Equation 3, the weight (g) of the grafted monomer is the weight obtained by dissolving the graft copolymer in acetone and centrifuging the obtained by 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.
[71]
[72]
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 wt% with 100 g of deionized water, using a particle size distribution analyzer (Nicomp CW380, PPS Co.) 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.
[73]
[74]
In the present description, the TEM average particle size may be measured using a transmission electron microscope (TEM) analysis, and as a specific example, it refers to 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:
[75]
- Sample preparation: thermoplastic resin pellets made by extrusion kneader
[76]
- Sample pretreatment: Timing (23℃) → Hydrazine treatment (72℃, 5 days) → Sectioning (-120℃) → OsO 4 vapor staining (2 hours)
[77]
- Analysis instrument: TEM (JEM-1400, Jeol company)
[78]
- Analysis conditions: Acc. Vo lt 120 kV, SPOT Size 1 (X 10K, X 25K, X 50K)
[79]
- Size (average particle diameter) measurement: the average of the longest diameters of the particles with the top 10% in diameter size
[80]
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.
[81]
[82]
Hereinafter, each component constituting the thermoplastic resin of the present disclosure will be described in detail as follows.
[83]
[84]
(A) copolymer
[85]
The (A) copolymer is composed of an alkyl acrylate and an alkyl methacrylate, and is included in an amount of 50 to 100% by weight in 100% by weight of the total thermoplastic resin.
[86]
The (A) copolymer is, for example, (a-1) DLS average particle diameter of 40 to 120 nm or TEM average particle diameter of 25 to 100 nm, based on 100% by weight of the (A) copolymer, alkyl acrylate rubber 25 to 50 % by weight, preferably from 30 to 50% by weight, more preferably from 35 to 50% by weight, and (a-2) from 50 to 75% by weight of an alkyl acrylate-alkyl methacrylate copolymer, preferably from 50 to 70 % by weight, and more preferably 50 to 65% by weight. Within this range, transparency, gloss, and non-whitening properties are excellent, and impact resistance is excellent. The DLS average particle diameter of the (a-1) rubber is preferably 45 to 110 nm, more preferably 50 to 100 nm, and the TEM average particle diameter is preferably 27 to 95 nm, more preferably 30 to 100 nm. It may be 90 nm, and within this range, there is an excellent effect of transparency and weather resistance without deterioration of mechanical strength.
[87]
[88]
In the present description, the graft copolymer (A) comprising (a-1) an alkyl acrylate rubber, and (a-2) an alkyl acrylate-alkyl methacrylate copolymer is an alkyl acrylate rubber (a-1) ), and an alkyl acrylate-alkyl methacrylate copolymer (a-2) surrounding the alkyl acrylate rubber (a-1), which means a graft copolymer (A). Also, (a-1) may be expressed as a graft copolymer (A) in which an alkyl acrylate and an alkyl methacrylate are graft-polymerized on an alkyl acrylate rubber.
[89]
[90]
The copolymer (A) may have, for example, a graft rate of 60 to 200%, 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-forming properties within this range There is an advantage that all of the whitening properties are excellent. The grafting ratio of the copolymer (A) may be preferably 60 to 150%, more preferably 65 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 40,000 to 110,000 g/mol, more preferably 50,000 to 100,000 g/mol, and molding processability and non-whitening without deterioration in impact resistance within this range. Characteristics have an excellent effect.
[91]
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.
[92]
[93]
The (a-1) rubber may have, for example, a glass transition temperature of -50 to -20°C, preferably -48 to -21°C, and within this range, the impact strength is higher without deterioration of other physical properties. It has an excellent effect.
[94]
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.
[95]
[96]
The (a-1) rubber may further include, for example, alkyl methacrylate, and in this case, chemical resistance and impact resistance are more excellent. In this case, the content of the alkyl methacrylate contained in the (a-1) rubber is, for example, 0.1 to 25% by weight, preferably 1 to 20% by weight, based on 100% by weight of the (a-1) rubber. , more preferably 2 to 15% by weight, and within this range, the desired effect can be sufficiently obtained without lowering other physical properties.
[97]
The alkyl acrylate rubber can be prepared by emulsion polymerization of an alkyl 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.
[98]
[99]
The (a-2) copolymer may be, for example, comprising 80 to 99.9 wt% of an alkyl methacrylate and 0.1 to 20 wt% of an alkyl acrylate based on 100 wt% of the (a-2) copolymer and preferably comprising 85 to 99.5 wt% of an alkyl methacrylate and 0.5 to 15 wt% of an alkyl acrylate, more preferably 85 to 99 wt% of an alkyl methacrylate and 1 to 15 wt% of an alkyl acrylate It may be, and within this range, there is an effect that is more excellent in impact strength and weather resistance.
[100]
[101]
The (a-1) rubber may include, for example, a rubber seed.
[102]
The rubber seed may be prepared by, for example, polymerizing an alkyl acrylate and optionally an alkyl methacrylate, and in the case of including an alkyl methacrylate, 0.1 to 25% by weight, preferably 1 to 25% by weight, based on 100% by weight of the rubber seed 20% by weight, more preferably 2 to 15% 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.
[103]
As a specific example, the rubber seed is polymerized by including 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, based on 100 parts by weight of the unit constituting the copolymer (A) in an alkyl acrylate. It is possible to manufacture a polymer with an even size within a short time within the above range, and further improve physical properties such as weather resistance and impact strength.
[104]
As another specific example, the rubber seed is a monomer comprising an alkyl acrylate and an alkyl methacrylate, 0.1 to 1 part by weight of a crosslinking agent, 0.01 to 1 part by weight of an initiator, based on 100 parts by weight of the unit constituting the copolymer (A) And it can be prepared by polymerization including 0.1 to 3.0 parts by weight of an emulsifier, 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.
[105]
[106]
The (A) copolymer is, for example, based on 100 parts by weight of the unit constituting the (A) copolymer, A-1) alkyl acrylate and optionally alkyl methacrylate 1 to 15 parts by weight of electrolyte 0.001 to 1 weight parts, 0.01 to 5 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 prepare a rubber seed by polymerizing a mixture; A-2) A mixture comprising 20 to 50 parts by weight of an alkyl acrylate and optionally an alkyl methacrylate, 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 to prepare a rubber core; and A-3) 40 to 75 parts by weight of the sum of alkyl acrylate and alkyl methacrylate in the presence of the rubber core, 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 and an activator It can be prepared including; preparing a graft shell by mixing 0.01 to 1 part by weight. 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.
[107]
[108]
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.
[109]
[110]
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. , 2-ethylhexyl methacrylate It may be at least one selected from the group consisting of yt and lauryl methacrylate, preferably an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, and more preferably methyl methacrylate.
[111]
[112]
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.
[113]
In the present disclosure, the electrolyte is, for example, KCl, NaCl, KHCO 3, NaHCO 3, K 2CO 3, Na 2CO 3, KHSO 3, NaHSO 3, K 4P 2O 7, Na 4P 2O 7, K 3PO 4, Na 3PO 4, K 1 or 2 or more selected from the group consisting of 2HPO 4, Na 2HPO 4, KOH, NaOH, and Na 2S 2O 7 may be used, but not limited thereto.
[114]
As the initiator in the present description, 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.
[115]
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.
[116]
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.
[117]
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, 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, but not limited thereto, may be used.
[118]
[119]
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.
[120]
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
[121]
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
[122]
[123]
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.
[124]
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.
[125]
[126]
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.
[127]
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.
[128]
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. The derivatives 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.
[129]
In the present description, a derivative of a compound refers to one of hydrogen and a functional group of the compound.It refers to a substance substituted with another type of group such as an alkyl group or a halogen group.
[130]
[131]
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 part by weight, and a polymer having a desired molecular weight within this range can be easily prepared.
[132]
The molecular weight modifier may include, for example, 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.
[133]
[134]
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 ℃.
[135]
[136]
(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.
[137]
In the present description, the coagulant content (%) may 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.
[138]
[Equation 4]
[139]

[140]
[141]
The latex of the copolymer (A) may be in powder form through conventional processes such as agglomeration, washing, and drying, for example, and as a specific example, aggregation at a temperature of 60 to 100° C. by adding a metal salt or acid, and aging , dehydration, washing and drying processes, but may be prepared in a powder form, 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 alkyl methacrylate polymer and an alkyl methacrylate-alkyl acrylate copolymer, based on 100% by weight of the total thermoplastic resin, from 0 to 50. included in 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]
[151]
The (B) matrix resin includes at least one selected from the group consisting of an alkyl methacrylate polymer and an alkyl methacrylate-alkyl acrylate copolymer, and may preferably be an alkyl methacrylate polymer, in this case There is a more excellent effect of transparency without deterioration of other physical properties.
[152]
The alkyl methacrylate-alkyl acrylate copolymer that may be included in the (B) matrix resin is different from the (A) graft copolymer.
[153]
[154]
The alkyl methacrylate and the alkyl acrylate contained in the matrix resin may be appropriately selected within the same range as mentioned in the copolymer (A), respectively.
[155]
The alkyl methacrylate contained in the matrix resin may be preferably methyl methacrylate.
[156]
The alkyl acrylate included in the matrix resin may be preferably at least one selected from the group consisting of methyl acrylate and ethyl acrylate.
[157]
[158]
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.
[159]
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, It can select suitably as needed.
[160]
As another example, the (B) matrix resin may use a commercially available product.
[161]
[162]
thermoplastic resin
[163]
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.
[164]
The total content of the alkyl acrylate contained in the total 100% by weight of the thermoplastic resin is 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.
[165]
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 weight 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.
[166]
In the present description, NMR analysis means analysis by 1H NMR unless otherwise specified.
[167]
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.
[168]
- Equipment name: Bruker 600MHz NMR(AVANCE III HD) CPP BB(1H 19F tunable and broadband, with z-gradient) Prodigy Probe
[169]
- Measurement conditions: 1H NMR (zg30): ns=32, d1=5s, TCE-d2, at room temp.
[170]
[171]
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.
[172]
- Equipment name: Agilent Cary 660
[173]
- Measurement condition: ATR mode
[174]
[175]
The thermoplastic resin may have a butyl acrylate coverage value (X) of 50% or more, preferably 50 to 250%, more preferably 55 to 200%, calculated by Equation 1 through the limited composition as described above, Within this range, there is a more excellent effect of non-whitening properties.
[176]
[Equation 1]
[177]
X(%) = {(G-Y)/Y} * 100
[178]
In Equation 1, G represents the total gel content (%) of the thermoplastic resin, and Y represents the content (% by weight) of butyl acrylate in the gel of the thermoplastic resin.
[179]
In Equation 1, the content of butyl acrylate in the gel of the thermoplastic resin represents the content of butyl 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 represents the content (weight %) of the insoluble matter based on 100 weight % of the total thermoplastic resin.
[180]
The thermoplastic resin may include one or two or more alkyl acrylate compounds. Among them, the difference between the total gel content and the butyl acrylate content in the gel with respect to the butyl acrylate content in the gel of the thermoplastic resin is specified. By limiting the range, it is possible to provide a thermoplastic resin excellent in non-whitening properties as well as mechanical properties such as impact resistance, molding processability, and gloss.
[181]
[182]
In addition, the thermoplastic resin may have a transparency (haze value) of 2 or less, preferably 1.8 or less, more preferably 1.5 or less, measured according to ASTM D-1003 under a condition of 0.15 mm in thickness through the limited composition as described above, Transparency measured under the condition of 3 mm thickness may be 4 or less, preferably 3.8 or less, and more preferably 3.5 or less, and within this range, the transparency of the thermoplastic resin is excellent, thereby providing a finishing material having excellent appearance quality.
[183]
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, haze may be measured at a temperature of 23° C. according to ASTM D1003 using a haze meter (model name: HM-150) manufactured by MURAKAMI. At this time, thickness 0.1 A 5 mm specimen may be a film specimen extruded to a thickness of 0.15 mm at an extrusion temperature of 230°C, and a specimen having a thickness of 3 mm may be a specimen injected to a thickness of 3 mm at a barrel temperature of 220°C.
[184]
[185]
The thermoplastic resin preferably has an elution amount of butyl acrylate in acetone of 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 0.1 to 15% by weight, and more preferably 0.5 to 15% by weight. % by weight, and has an excellent effect of non-whitening properties within this range.
[186]
In the present description, the elution amount of the 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 centrifuged (Supra) R30, Hanil Science Co., Ltd.), the acetone solution from which the insolubles were separated by centrifugation at 0℃ at 18,000 rpm for 3 hours was dried (OF-12GW, Lab companion) by forced circulation at 85℃ for 12 hours to obtain a resin sol ( Sol), which can be quantitatively measured by NMR analysis or FT-IR analysis.
[187]
[188]
The difference in refractive index (according to ASTM D542) of the sol and the gel under acetone of the thermoplastic resin may be, for example, 0.02 or less, preferably 0.005 to 0.02, more preferably 0.009 to 0.019, Within this range, there is a more excellent effect of transparency without deterioration of other physical properties.
[189]
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 part 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.
[190]
In the present description, the refractive index may be measured at 25° C. using an Abbe refractometer in accordance with ASTM D542.
[191]
[192]
When the thermoplastic resin includes the (B) matrix, the difference in refractive index between the (a-1) rubber and the (B) matrix in the (A) copolymer included in the thermoplastic resin may be, for example, 0.02 or more, preferably may be 0.02 to 0.04, more preferably 0.02 to 0.03, and within this range, there is an effect of sufficiently exhibiting the desired effect without lowering other physical properties.
[193]
The present invention can provide the effect of further improving the transparency of the thermoplastic resin by adjusting the refractive index difference between the sol and the gel of the thermoplastic resin to 0.02 or less even when the refractive index difference between the rubber particles and the matrix is ​​0.02 or more as described above.
[194]
[195]
The glass transition temperature of the thermoplastic resin, the (a-1) rubber, or both of them may be, for example, -50 to -20°C, preferably -48 to -21°C, and other physical properties within this range There is a better effect of impact strength without lowering of the
[196]
[197]
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.
[198]
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 values ​​measured according to ASTM D1003-95 before and after the impact of the part hit 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.
[199]
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.
[200]
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.
[201]
[202]
The thermoplastic resin may have a gloss of 110 or more, preferably 110 to 150, more preferably 115 to 150, even more preferably 120 to 140, measured at an incident angle of 60° according to ASTM D528, for example, Within this range, it is possible to provide a molded article having excellent appearance quality due to excellent gloss without deterioration of other physical properties.
[203]
[204]
The thermoplastic resin has, for example, a melt flow index (MI) of 3 g/10 min or more, preferably 3-20 g/10 min, more preferably 5-20 g/ It may be 10 min, more preferably 7 to 15 g/10 min, and there is an excellent effect of molding processability without deterioration of other physical properties within this range.
[205]
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 more 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 resulting resin.
[206]
[207]
Method for producing thermoplastic resin
[208]
The method for producing the thermoplastic resin of the present invention comprises (A) 50 to 100 parts by weight of an alkyl acrylate-alkyl methacrylate graft copolymer and (B) an alkyl methacrylate polymer and an alkyl methacrylate-alkyl acrylate copolymer. Including 0 to 50 parts by weight of a matrix resin comprising at least one selected from the group consisting of, kneading and extruding, characterized in that the X value calculated by the following Equation 1 is 50% or more, in this case the conventional While maintaining the mechanical properties of the ASA-based resin, it has excellent molding processability, and at the same time, excellent transparency, gloss, and non-whitening properties, thereby providing excellent appearance quality.
[209]
[Equation 1]
[210]
X(%) = {(G-Y)/Y} * 100
[211]
In Equation 1, G represents the total gel content (%) of the thermoplastic resin, and Y represents the content (% by weight) of butyl acrylate in the gel of the thermoplastic resin.
[212]
[213]
The copolymer (A) used in the preparation of the thermoplastic resin may be prepared by the preparation method of the copolymer (A), and in this case, the graft rate and molecular weight are appropriately controlled, so that molding processability and whitening properties are excellent. have.
[214]
[215]
When manufacturing the thermoplastic resin of the present invention, optionally a lubricant, a heat stabilizer, a light stabilizer, an antioxidant, an ultraviolet stabilizer, a dye, a pigment, a colorant, a mold release agent, an antistatic agent, an antibacterial agent, a processing aid, a compatibilizer, if necessary during the kneading and extrusion process , metal deactivator, flame retardant, flame retardant, anti-drip agent, foaming agent, plasticizer, reinforcing agent, filler, matte agent, at least one selected from the group consisting of anti-friction agent and anti-wear agent (A) copolymer and (B) matrix resin It may further include 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, and within this range, the physical properties of the ASA-based resin are not reduced. There is an effect that the necessary physical properties are well realized without the need for it.
[216]
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.
[217]
The antioxidant may include, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, and the like, but is not limited thereto.
[218]
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.
[219]
The antistatic agent may include, for example, one or more anionic surfactants, non-ionic surfactants, and the like, but is not limited thereto.
[220]
The release agent may be used, for example, at least one selected from glycerin sterate, polyethylene tetra sterate, and the like.and is not limited thereto.
[221]
[222]
molded product
[223]
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.
[224]
The molded article may be, for example, a finishing material, and in this case, there is an advantage of excellent appearance quality due to excellent whitening properties.
[225]
[226]
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.
[227]
[228]
[Example]
[229]
[230]
Example 1
[231]

[232]
5 parts by weight of butyl acrylate, 1.0 parts by weight of sodium dodecyl sulfate, 0.1 parts by weight of ethylene glycol dimethacrylate, 0.1 parts by weight of allyl methacrylate, 0.1 parts by weight of sodium hydrogen carbonate and 60 parts by weight of distilled water in a nitrogen-substituted reactor After administration and heating to 70°C, 0.1 parts by weight of potassium persulfate was added to initiate the reaction. Then, polymerization was carried out for 1 hour.
[233]

[234]
35 parts by weight of butyl acrylate, 0.5 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of ethylene glycol dimethacrylate, 0.8 parts by weight of allyl methacrylate, 40 parts by weight of distilled water and 0.1 parts by weight of potassium persulfate mixed with the rubber seed The mixture was continuously added at 70° C. for 2.0 hours, and polymerization was further carried out for 1 hour after the addition was completed. The average size of the particles of the rubber polymer obtained after completion of the reaction was 80 nm.
[235]

[236]
Into the reactor in which the rubber core was obtained, 40 parts by weight of distilled water, 57 parts by weight of methyl methacrylate, 3 parts by weight of butyl acrylate, 1.0 parts by weight of sodium dodecylbenzene sulfonate and 0.05 parts by weight of tertiary dodecyl mercaptan and an initiator were used. A mixture of 0.1 parts by weight of t-butyl hydroperoxide, 0.015 parts by weight of the activator sodium ethylenediaminetetraacetate, 0.1 parts by weight of sodium formaldehyde sulfoxylate, and 0.002 parts by weight of ferrous sulfide were mixed at a temperature of 75° C. of 3.0 The polymerization reaction was carried out while continuously inputting for a period of time. 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.
[237]
The graft copolymer obtained after completion of the reaction had a graft rate of 85% and a weight average molecular weight of the shell of 71,000 (g/mol).
[238]

[239]
After applying 1.0 part by weight of calcium chloride aqueous solution to the prepared 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. t copolymer powder was prepared.
[240]

[241]
70 parts by weight of the graft copolymer powder, 30 parts by weight of methyl methacrylate (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. When preparing the specimen for weather resistance evaluation, 1 part by weight of black colorant was added to 100 parts by weight of the total of the graft copolymer and the matrix resin and mixed. This was prepared into pellets using a 36-pi extrusion kneader at a cylinder temperature of 220 °C. 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.
[242]
The BA (butyl acrylate) content in the prepared thermoplastic resin is 30.1% (wt%), the glass transition temperature of the rubber is -47° C., the BA coverage value is 77.5%, and the BA elution amount in the resin sol is 1.89. % was.
[243]
The difference between the refractive index of Sol and Gel of the thermoplastic resin was 0.016, and the difference between the refractive index of the rubber (the rubber seed and the rubber core including the same) and the refractive index of the matrix resin was 0.03.
[244]

[245]
The thermoplastic resin pellets were prepared to a film thickness of 150 μm using a 20 pie single extrusion kneader equipped with a T-die at a cylinder temperature of 230° C.
[246]
[247]
Example 2
[248]
In Example 1, 25 parts by weight of butyl acrylate was used in the preparation of the rubber core, and 66.5 parts by weight of methyl methacrylate and 3.5 parts by weight of butyl acrylate were used in the preparation of the copolymer shell.
[249]
The graft copolymer obtained had a graft rate of 130% and a weight average molecular weight of the shell of 62,000.
[250]
The BA content in the prepared thermoplastic resin is 23.5%, the BA coverage value is 116%, and the BA elution amount in the resin Sol is 2.1%.
[251]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.013, and the difference in refractive index between the rubber and the matrix resin was 0.03.
[252]
[253]
Example 3
[254]
In Example 1, 45 parts by weight of butyl acrylate were used in the preparation of the rubber core, and 47.5 parts by weight of methyl methacrylate and 2.5 parts by weight of butyl acrylate were used in the preparation of the copolymer shell.
[255]
The graft copolymer obtained had a graft rate of 62% and a weight average molecular weight of the shell was 79,000.
[256]
The BA content in the prepared thermoplastic resin is 36.8%, the BA coverage value is 57.1%, and the BA elution amount in the resin Sol is 1.54%.
[257]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.019, and the difference in refractive index between the rubber and the matrix resin was 0.03.
[258]
[259]
Example 4
[260]
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 preparing the rubber seed.
[261]
The average size of the particles of the obtained rubber polymer (rubber core) was 50 nm, the graft ratio of the graft copolymer was 79%, and the weight average molecular weight of the shell was 50,000.
[262]
The BA content in the prepared thermoplastic resin is 30.1%, the BA coverage value is 72.2%, and the BA elution amount in the resin Sol is 1.99%.
[263]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.017, and the difference in refractive index between the rubber and the matrix resin was 0.03.
[264]
[265]
Example 5
[266]
It was prepared in the same manner as in Example 1, except that 0.4 parts by weight of sodium dodecyl sulfate was used in the preparation of the rubber seed.
[267]
The average size of the particles of the obtained rubber polymer was 100 nm, the graft ratio of the graft copolymer was 89%, and the weight average molecular weight of the shell was 80,000.
[268]
The BA content in the prepared thermoplastic resin is 30.1%, the BA coverage value is 80.9%, and the BA elution amount in the resin Sol is 1.81%.
[269]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.016, and the difference in refractive index between the rubber and the matrix resin was 0.03.
[270]
[271]
Example 6
[272]
It was prepared in the same manner as in Example 1, except that 0.3 parts by weight of sodium dodecyl sulfate was used in the preparation of the rubber seed.
[273]
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 100,000.
[274]
The BA content in the prepared thermoplastic resin is 30.1%, the BA coverage value is 83.6%, and the BA elution amount in the resin Sol is 1.76%.
[275]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.016, and the difference in refractive index between the rubber and the matrix resin was 0.03.
[276]
[277]
Example 7
[278]
In Example 1, 33.25 parts by weight of butyl acrylate and 1.75 parts by weight of methyl methacrylate were used in the preparation of the rubber core, and 0.95 parts by weight of sodium dodecyl sulfate, 4.75 parts by weight of butyl acrylate, and methyl methacrylate were used in the preparation of rubber seeds. It was prepared in the same manner except that 0.25 parts by weight of the rate was used.
[279]
The average size of the particles of the obtained rubber polymer was 80 nm, the graft ratio of the graft copolymer was 97%, and the weight average molecular weight of the shell was 68,000.
[280]
The BA content in the prepared thermoplastic resin is 28.7%, the rubber glass transition temperature is -41°C, the BA coverage value is 97.3%, and the BA elution amount in the resin Sol is 1.65%.
[281]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.015, and the difference in refractive index between the rubber and the matrix resin was 0.029.
[282]
[283]
Example 8
[284]
In Example 1, 29.75 parts by weight of butyl acrylate and 5.25 parts by weight of methyl methacrylate were used to prepare the rubber core, and 0.9 parts by weight of sodium dodecyl sulfate, 4.25 parts by weight of butyl acrylate, and methyl methacrylate were used to prepare the rubber seed. It was prepared in the same manner except that 0.75 parts by weight of the rate was used.
[285]
The average size of the particles of the obtained rubber polymer was 80 nm, the graft ratio of the graft copolymer was 103%, and the weight average molecular weight of the shell was 52,000.
[286]
The BA content in the prepared thermoplastic resin is 25.9%, the rubber glass transition temperature is -30°C, the BA coverage value is 125.2%, and the BA elution amount in the resin Sol is 1.52%.
[287]
The difference in refractive index between Sol and Gel of thermoplastic resin is 0.013, and between rubber and matrix resin The difference in refractive index of , was 0.026.
[288]
[289]
Example 9
[290]
In Example 1, 26.25 parts by weight of butyl acrylate and 8.75 parts by weight of methyl methacrylate were used in the preparation of the rubber core, and 0.8 parts by weight of sodium dodecyl sulfate, 3.75 parts by weight of butyl acrylate, and methyl methacrylate were used in the preparation of rubber seeds. It was prepared in the same manner except that 1.25 parts by weight of the rate was used, and 59.7 parts by weight of methyl methacrylate and 0.3 parts by weight of butyl acrylate were used when preparing the shell.
[291]
The average size of the particles of the obtained rubber polymer was 80 nm, the graft ratio of the graft copolymer was 140%, and the weight average molecular weight of the shell was 41,000.
[292]
The BA content in the prepared thermoplastic resin is 21.2%, the rubber glass transition temperature is -21°C, the BA coverage value is 217.0%, and the BA elution amount in the resin Sol is 0.04%.
[293]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.009, and the difference in refractive index between the rubber and the matrix resin was 0.023.
[294]
[295]
Example 10
[296]
It was prepared in the same manner as in Example 1, except that 54 parts by weight of methyl methacrylate and 6 parts by weight of butyl acrylate were used in preparing the copolymer shell.
[297]
The graft copolymer obtained had a graft rate of 81% and a weight average molecular weight of the shell of 76,000.
[298]
The BA content in the resin is 32.2%, the BA coverage value is 67.4%, and the BA elution amount in the resin Sol is 3.92%.
[299]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.017, and the difference in refractive index between the rubber and the matrix resin was 0.03.
[300]
[301]
Example 11
[302]
It was prepared in the same manner as in Example 1, except that 48 parts by weight of methyl methacrylate and 12 parts by weight of butyl acrylate were used in preparing the copolymer shell.
[303]
The graft copolymer obtained had a graft rate of 76% and a weight average molecular weight of the shell of 95,000.
[304]
The BA content in the resin is 36.4%, the glass transition temperature of the rubber is -35°C, the BA coverage value is 52.8%, and the BA elution amount in the resin Sol is 8.17%.
[305]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.017, and the difference in refractive index between the rubber and the matrix resin was 0.03.
[306]
[307]
Example 12
[308]
In Example 2, the same preparation was made except that 100 parts by weight of the graft copolymer was used without using a matrix resin when preparing the thermoplastic resin.
[309]
The BA content in the resin is 33.5%, the BA coverage value is 116.0%, and the BA elution amount in the resin Sol is 5.00%.
[310]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.012.
[311]
[312]
Comparative Example 1
[313]
The same preparation was performed in Example 1, except that 55 parts by weight of butyl acrylate was used in the preparation of the rubber core and 40 parts by weight of methyl methacrylate was used in the preparation of the body copolymerized shell.
[314]
The average size of the particles of the obtained rubber polymer was 85 nm, the graft ratio of the graft copolymer was 38%, and the weight average molecular weight of the shell was 82,000.
[315]
The BA content in the resin is 42.0%, the rubber glass transition temperature is -47°C, the BA coverage value is 38.0%, and the BA elution amount in the resin Sol is 0%.
[316]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.022, and the difference in refractive index between the rubber and the matrix resin was 0.03.
[317]
[318]
Comparative Example 2
[319]
It was prepared in the same manner as in Example 2, except that 20 parts by weight of butyl acrylate was used to prepare the rubber core and 75 parts by weight of methyl methacrylate was used to prepare the body copolymerized shell.
[320]
The average size of the particles of the obtained rubber polymer was 75 nm, the grafting rate of the graft copolymer was 100%, and the weight average molecular weight of the shell was 71,000.
[321]
The BA content in the resin is 17.5%, the rubber glass transition temperature is -47°C, the BA coverage value is 100.0%, and the BA elution amount in the resin Sol is 0%.
[322]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.015, and the difference in refractive index between the rubber and the matrix resin was 0.029.
[323]
[324]
Comparative Example 3
[325]
In Example 3, 0.11 parts by weight of sodium dodecyl sulfate was used to prepare the rubber seed, and 50 parts by weight of methyl methacrylate was used to prepare the shell.
[326]
The average size of the particles of the obtained rubber polymer was 150 nm, the graft ratio of the graft copolymer was 98%, and the weight average molecular weight of the shell was 126,000.
[327]
The BA content in the resin is 35.0%, the BA coverage value is 98.0%, and the BA elution amount in the resin Sol is 0%.
[328]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.015, and the difference in refractive index between the rubber and the matrix resin was 0.030.
[329]
[330]
Comparative Example 4
[331]
In Example 1, 0.75 parts by weight of sodium dodecyl sulfate, 3.5 parts by weight of butyl acrylate, and 1.5 parts by weight of methyl methacrylate were used in the preparation of the rubber seed, and 24.5 parts by weight of butyl acrylate and methyl methacrylate were used in the preparation of the rubber core. It was prepared in the same manner except that 10.5 parts by weight of the rate was used, and 60 parts by weight of methyl methacrylate was used in preparing the shell.
[332]
The graft copolymer obtained had a graft rate of 120% and a weight average molecular weight of the shell of 32,000.
[333]
The BA content in the resin is 19.6%, the rubber glass transition temperature is -14°C, the BA coverage value is 214.3%, and the BA elution amount in the resin Sol is 0%.
[334]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.01, and the difference in refractive index between the rubber and the matrix resin was 0.021.
[335]
[336]
Comparative Example 5
[337]
In Example 1, the shell was prepared in the same manner except that 45 parts by weight of methyl methacrylate and 15 parts by weight of butyl acrylate were used.
[338]
The graft copolymer obtained had a graft rate of 59% and a weight average molecular weight of the shell of 121,000.
[339]
The BA content in the resin is 38.5%, the BA coverage value is 38.6%, and the BA elution amount in the resin Sol is 11.48%.
[340]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.018, and the difference in refractive index between the rubber and the matrix resin was 0.030.
[341]
[342]
Comparative Example 6
[343]
It was prepared in the same manner as in Example 1, except that 40 parts by weight of the graft copolymer powder and 60 parts by weight of the matrix resin were used when preparing the thermoplastic resin.
[344]
The BA content in the resin is 17.2%, the BA coverage value is 77.5%, and the BA elution amount in the resin Sol is 0.74%.
[345]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.017, and the difference in refractive index between the rubber and the matrix resin was 0.030.
[346]
[347]
Comparative Example 7
[348]
It was prepared in the same manner as in Comparative Example 1, except that 85 parts by weight of the graft copolymer powder and 15 parts by weight of the matrix resin were used in the preparation of the thermoplastic resin.
[349]
The BA content in the resin is 51.0%, the BA coverage value is 38.0%, and the BA elution amount in the resin Sol is 0%.
[350]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.022, and the difference in refractive index between the rubber and the matrix resin was 0.030.
[351]
[352]
Comparative Example 8
[353]
In Comparative Example 1, 38 parts by weight of methyl methacrylate and 2 parts by weight of butyl acrylate were used in the preparation of the shell, and 85 parts by weight of the graft copolymer powder and 15 parts by weight of the matrix resin were used in the preparation of the thermoplastic resin. It was prepared in the same way.
[354]
The grafting ratio of the obtained graft copolymer was 35.0%, and the weight average molecular weight of the shell was 98,000.
[355]
The BA content in the resin is 52.7%, the BA coverage value is 32.7%, and the BA elution amount in the resin Sol is 2.59%.
[356]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.022, and the difference in refractive index between the rubber and the matrix resin was 0.030.
[357]
[358]
Comparative Example 9
[359]
In Example 1, when preparing the rubber seed, 0.7 parts by weight of sodium dodecyl sulfate, 3.75 parts by weight of butyl acrylate, and 1.25 parts by weight of styrene were used, and 26.25 parts by weight of butyl acrylate and 8.75 parts by weight of styrene were used in preparing the rubber core. And, the shell was prepared in the same manner except that 47 parts by weight of styrene and 13 parts by weight of acrylonitrile were used.
[360]
The average size of the particles of the obtained rubber polymer was 80 nm, the graft ratio of the graft copolymer was 107.0%, and the weight average molecular weight of the shell was 98,000.
[361]
The BA content in the resin is 21.0%, the rubber glass transition temperature is -21°C, the BA coverage value is 176.0%, and the BA elution amount in the resin Sol is 0%.
[362]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.021, and the difference in refractive index between the rubber and the matrix resin was 0.002.
[363]
[364]
Comparative Example 10
[365]
In Example 1, a styrene-acrylonitrile resin (S85RF, manufactured by LG Chem) was used in the same manner as in Example 1, except that 30 parts by weight was used as the matrix resin.
[366]
The BA coverage value is 77.5%, and the BA elution amount in the resin Sol is 1.89%.
[367]
The difference in refractive index between Sol and Gel of the thermoplastic resin is 0.064,The difference in refractive index between the rubber and the matrix resin was 0.107.
[368]
[369]
Comparative Example 11
[370]
In Example 1, a styrene-acrylonitrile-methyl methacrylate copolymer (XT500, manufactured by LG Chem) was used in the same manner as in Example 1, except that 30 parts by weight was used as the matrix resin.
[371]
The BA coverage value is 77.5%, and the BA elution amount in the resin Sol is 1.89%.
[372]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.031, and the difference in refractive index between the rubber and the matrix resin was 0.054.
[373]
[374]
Comparative Example 12
[375]
In Example 1, when washing the rubber seed, 4.25 parts by weight of butyl acrylate and 0.75 parts by weight of methyl methacrylate were used, and 34 parts by weight of butyl acrylate and 6 parts by weight of methyl methacrylate were used in preparing the rubber core, A graft copolymer was prepared in the same manner except that 52.25 parts by weight of methyl methacrylate and 2.75 parts by weight of butyl acrylate were used in preparing the body copolymer shell.
[376]
The graft copolymer obtained had a graft ratio of 103%, and a weight average molecular weight of the shell was 61,000.
[377]
When preparing the thermoplastic resin, 50 parts by weight of the prepared graft copolymer and 50 parts by weight of an alphamethylstyrene-styrene-acrylonitrile copolymer (S99UH, manufactured by LG Chem) as the matrix resin were used in the same manner except that 50 parts by weight was used.
[378]
The BA content in the resin is 20.5%, the rubber glass transition temperature is -30°C, the BA coverage value is 125.2%, and the BA elution amount in the resin Sol is 0.4%.
[379]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.087, and the difference in refractive index between the rubber and the matrix resin was 0.106.
[380]
[381]
Comparative Example 13
[382]
It was prepared in the same manner as in Example 1, except that 45.6 parts by weight of methyl methacrylate and 14.4 parts by weight of butyl acrylate were used in preparing the shell.
[383]
The graft copolymer obtained had a graft rate of 62%, and a weight average molecular weight of the shell was 118,000.
[384]
The BA content in the resin is 38.1%, the BA coverage value is 41.0%, and the BA elution amount in the resin Sol is 10.82%.
[385]
The difference in refractive index between Sol and Gel of the thermoplastic resin was 0.018, and the difference in refractive index between the rubber and the matrix resin was 0.030.
[386]
[387]
[Test Example]
[388]
Each physical property was measured by the following method using the physical property specimens and films prepared in Examples 1 to 12 and Comparative Examples 1 to 13, and the results are shown in Tables 1 and 2 below.
[389]
[390]
* 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.
[391]
* Graft rate (%): After adding 30 g of acetone to 0.5 g of the dry graft polymer powder, stirring at 210 rpm for 12 hours at room temperature (23°C) (SKC-6075, Lab companion) and centrifuging it (Supra R30, After centrifugation at 0°C at 18,000 rpm for 3 hours with Hanil Science Co., Ltd.) to collect insoluble fraction that did not dissolve in acetone, the weight after drying (OF-12GW, Lab companion) at 85°C for 12 hours by forced circulation It can be obtained by measuring by Equation 3 below.
[392]
[Equation 3]
[393]
Graft rate (%) = [weight of grafted monomer (g) / rubber weight (g)] * 100
[394]
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 component in the graft copolymer powder. Here, the parts by weight of the rubber refer to the total sum of parts by weight of the unit component added during the manufacture of the rubber seed and the core.
[395]
* Weight average molecular weight of the shell (g/mol): The portion (sol) dissolved in acetone obtained at the time of measuring the graft rate was dissolved in a THF solution, 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.
[396]
- Solvent: THF (tetrahydrofuran)
[397]
- Column temperature: 40℃
[398]
- Flow rate: 0.3 mL/min
[399]
- Sample concentration: 20 mg/mL
[400]
- Injection volume: 5 μl
[401]
- Column model: 1xPLgel 10um MiniMix-B (250x4.6mm) + 1xPLgel 10um MiniMix-B (250x4.6mm) + 1xPLgel 10um MiniMix-B Guard (50x4.6mm)
[402]
- Equipment name: Agilent 1200 series system
[403]
- Refractive index detector: Agilent G1362 RID
[404]
- RI temperature: 35℃
[405]
- Data processing: Agilent ChemStation S/W
[406]
- Test method: measured according to OECD TG 118
[407]
* BA content (wt%): quantitatively measured through 1H NMR analysis or FT-IR analysis. Specific measurement conditions are as follows.
[408]
1H NMR
[409]
- Equipment name: Bruker 600MHz NMR(AVANCE III HD) CPP BB(1H 19F tunable and broadband, with z-gradient) Prodigy Probe
[410]
- Measurement conditions: 1H NMR (zg30): ns=32, d1=5s, TCE-d2, at room temp.
[411]
FT-IR
[412]
- Equipment name: Agilent Cary 660
[413]
- Measurement condition: ATR mode
[414]
* Gel content: After adding 30 g of acetone to 0.5 g of the prepared thermoplastic resin dry 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 was calculated by Equation 2.
[415]
[Equation 2]
[416]
Gel content (%) = [weight of insoluble matter (gel) / weight of sample] * 100
[417]
* Butyl acrylate (BA) coverage (%): It was calculated by Equation 1 below.
[418]
[Equation 1]
[419]
X(%) = {(G-Y)/Y} * 100
[420]
In Equation 1, G represents the total gel content (%) of the thermoplastic resin, and Y represents the weight% of butyl acrylate in the gel. Here, the butyl acrylate content (wt%) in the gel was quantitatively measured using 1NMR analyzer or FT-IR.
[421]
* Butyl acrylate elution amount (wt%): 30 g of acetone was added to 0.5 g of dry thermoplastic resin powder, stirred at 210 rpm at room temperature for 12 hours (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 1NMR analyzer or FT-IR analysis.
[422]
* Rubber refractive index: After drying the manufactured rubber core in a forced circulation method at 90°C for 24 hr (OF-12GW, Lab companion), it was measured at 25°C using an Abbe refractometer in accordance with ASTM D542.
[423]
* Refractive index of matrix resin: After the matrix resin was press-processed at 190°C, it was measured at 25°C using an Abbe refractometer in accordance with ASTM D542.
[424]
* Refractive index of Sol and Gel: Using the gel obtained by the above 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) was obtained.
[425]
* Glass transition temperature: It was measured under a temperature increase rate of 10 °C / min. using TA Instruments Q100 DSC in accordance with ASTM D 3418.
[426]
* Impact strength (1/4"; kgf·cm/cm): Measured at 23°C according to ASTM D256.
[427]
* Melt flow index (MI): Measured at 220°C under 10 kg in accordance with ASTM D-1238. Specifically, the specimen was measured at a temperature of 220°C using GOETTFERT's melting index measuring equipment. 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.
[428]
* Weather resistance (ΔE): A specimen prepared by adding 1 part by weight of black colorant to 100 parts by weight of the thermoplastic resin, accelerated weather resistance test apparatus (weather-o-meter, ATLAS Ci4000, xenon arc lamp, Quartz (inner)) /S.Boro(outer) filter, irradiance 0.55W/m 2 at 340nm) 6,000 hours under SAE J2527 condition After the measurement, it was evaluated as ΔE calculated by Equation 5 below. The following ΔE is an arithmetic mean value of Hunter Lab (L, a, b) values ​​measured before and after the accelerated weather resistance test, and the closer the ΔE value is to 0, the better the weather resistance is.
[429]
[Equation 5]
[430]
ΔE= √{(L-L') 2 + (a-a') 2 + (b-b') 2} (√ : radical sign)
[431]
* 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°.
[432]
* Transparency (Haze): Prepare an extruded film with a thickness of 0.15 mm and an injection specimen with a thickness of 3 mm, and use MURAKAMI’s haze meter (model name: HM-150) equipment at 23°C according to ASTM D-1003. Each haze value was measured.
[433]
* 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).
[434]
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 6 (Nakgu Baekhwa).
[435]
[Equation 6]
[436]
Haze difference = haze value after falling ball - haze value before falling ball
[437]
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 6 above.
[438]
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.
[439]
[440]
[Table 1]
Classification Thermoplastic resin
BA content (wt%) BA coverage (%) Between Sol and Gel
refractive index difference
Example 1 30.1 77.5 0.016
Example 2 23.5 116.0 0.013
Example 3 36.8 57.1 0.019
Example 4 30.1 72.2 0.017
Example 5 30.1 80.9 0.016
Example 6 30.1 83.6 0.016
Example 7 28.7 97.3 0.015
Example 8 25.9 125.2 0.013
Example 9 21.2 217.0 0.009
Example 10 32.2 67.4 0.017
Example 11 36.4 52.8 0.017
Example 12 33.5 116.0 0.012
Comparative Example 1 42.0 38.0 0.022
Comparative Example 2 17.5 100.0 0.015
Comparative Example 3 35.0 98.0 0.015
Comparative Example 4 19.6 214.3 0.010
Comparative Example 5 38.5 38.6 0.018
Comparative Example 6 17.2 77.5 0.017
Comparative Example 7 51.0 38.0 0.022
Comparative Example 8 52.7 32.7 0.022
Comparative Example 9 21.0 176.0 0.021
Comparative Example 10 30.1 77.5 0.064
Comparative Example 11 30.1 77.5 0.031
Comparative Example 12 20.5 125.2 0.087
Comparative Example 13 38.1 41.0 0.018
[441]
[Table 2]
Category 　 Current Index
[g/10min] Impact strength
[kg·cm/cm] Film Gloss Weatherability
ΔE Transparency Whitening
0.15 mm 3 mm TD MD Falling Ball
Example 1 7.6 5.3 130 0.8 0.8 2.1 X X 2.5
Example 2 9.3 4.9 134 1.5 0.6 1.7 X X 1.9
Example 3 5.8 5.8 127 0.7 1.0 2.5 X X 3.5
Example 4 9.5 4.0 131 0.5 0.7 2.0 X X 1.6
Example 5 7.2 5.7 125 2.0 0.8 2.2 X X 2.7
Example 6 6.5 6.4 123 2.6 0.9 2.5 X X 2.9
Example 7 8.5 4.9 132 0.7 0.6 1.7 X X 2.3
Example 8 12.0 4.5 133 0.5 0.4 1.2 X X 2.0
Example 9 14.9 4.2 138 0.4 0.3 0.9 X X 1.9
Example 10 7.3 5.3 128 1.5 0.8 1.9 X X 2.1
Example 11 6.6 5.8 123 1.8 0.7 1.7 X X 1.3
Example 12 7.3 7.0 126 1.8 0.8 1.9 X X 1.5
Comparative Example 1 2.4 6.8 90 2.4 4.8 5.7 O O 76.3
Comparative Example 2 8.3 2.0 122 1.2 0.7 1.9 O O 43.9
Comparative Example 3 4.6 6.9 96 3.9 2.6 6.1 O O 38.0
Comparative Example 4 16.2 1.5 140 1.7 0.6 1.7 X X 28.3
Comparative Example 5 4.1 6.2 98 1.9 1.0 2.1 O O 22.5
Comparative Example 6 10.3 2.1 123 2.2 0.9 2.4 O O 39.8
Comparative Example 7 1.7 8.3 90 3.8 4.1 5.5 O O 70.7
Comparative Example 8 1.3 8.7 86 4.0 3.2 4.9 O O 50.5
Comparative Example 9 11.2 4.3 128 3.8 2.3 4.5 X X 2.1
Comparative Example 10 10.5 5.1 123 2.1 20.4 81.7 X X 2.6
Comparative Example 11 6.6 5.3 125 1.5 2.3 6.3 X X 2.8
Comparative Example 12 6.1 4.9 107 1.7 29.2 98.1 X X 3.9
Comparative Example 13 4.8 6.4 102 1.8 1.0 2.2 O O 19.7
[442]
Referring to Tables 1 and 2, the thermoplastic resins (Examples 1 to 12) according to the present invention have excellent transparency, gloss, and weather resistance while maintaining a proper balance of flow index and impact strength, and in particular, bending whitening does not occur. The difference in haze before and after the falling ball impact was 10 or less, confirming that the whitening property was very excellent. On the other hand, in the case of the thermoplastic resin (Comparative Examples 1 to 13) outside the scope of the present invention, the balance between the flow index and impact strength is lowered, transparency, gloss and weather resistance are generally reduced, or whitening occurs during bending and falling The difference in haze before and after impact was found to exceed 10, confirming that the property balance of transparency, glossiness, weather resistance, and non-whitening properties was very poor.
[443]
[444]
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.
[445]
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-alkyl methacrylate graft copolymer, or (A) an alkyl acrylate-alkyl methacrylate graft copolymer; And (B) a matrix resin comprising at least one selected from the group consisting of alkyl methacrylate polymers and alkyl methacrylate-alkyl acrylate copolymers; and, according to ASTM D-1003 in a thickness of 0.15 mm condition The transparency (haze value) measured by A thermoplastic resin, characterized in that the value (X) is 50 or more. [Equation 1] X = {(G-Y)/Y} * 100 (in Equation 1, G is the total gel content (%) of the thermoplastic resin, Y is the weight % of butyl acrylate in the gel of the thermoplastic resin indicates.)
[Claim 2]
The thermoplastic resin according to claim 1, wherein the difference in refractive indices (according to ASTM D542) of the sol and the gel under acetone in the thermoplastic resin is 0.02 or less.
[Claim 3]
The thermoplastic resin according to claim 1, wherein the (A) copolymer is 50 to 100 wt%, and the (B) matrix resin is 0 to 50 wt%.
[Claim 4]
The thermoplastic resin according to claim 1, wherein the amount of butyl acrylate elution in acetone is 0.01 wt% or more.
[Claim 5]
The alkyl acryl according to claim 1, wherein the (A) copolymer is (a-1) DLS average particle diameter of 40 to 120 nm or TEM average particle diameter of 25 to 100 nm based on 100 wt% of the (A) copolymer. 25 to 50% by weight of late rubber; and (a-2) 50 to 75 wt% of an alkyl acrylate-alkyl methacrylate copolymer.
[Claim 6]
The thermoplastic resin according to claim 5, wherein the copolymer (A) has a graft ratio of 60 to 200%, and the copolymer (a-2) has a weight average molecular weight of 40,000 to 120,000 g/mol.
[Claim 7]
The thermoplastic resin according to claim 5, wherein the glass transition temperature of the thermoplastic resin, the (a-1) rubber, or both of them is -50 to -20°C.
[Claim 8]
[6] The thermoplastic resin according to claim 5, wherein the (a-1) rubber further comprises an alkyl methacrylate.
[Claim 9]
The thermoplastic resin according to claim 8, wherein the alkyl methacrylate is included in an amount of 0.1 to 25 wt% based on 100 wt% of the (a-1) rubber.
[Claim 10]
The method according to claim 5, wherein the (a-2) copolymer is 80 to 99.9 of alkyl methacrylate based on 100 wt% of the (a-2) copolymer in total.Thermoplastic resin, characterized in that it comprises 0.1 to 20% by weight of an alkyl acrylate.
[Claim 11]
The thermoplastic resin according to claim 5, wherein a difference in refractive index (according to ASTM D542) between the (a-1) rubber and the (B) matrix is ​​0.02 or more.
[Claim 12]
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 temperature of 1 kg weight is dropped vertically onto the film at a height of 100 mm. The thermoplastic resin, characterized in that 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 when dropped.
[Claim 13]
(A) an alkyl acrylate-alkyl methacrylate graft copolymer, or (A) an alkyl acrylate-alkyl methacrylate graft copolymer; And (B) a matrix resin comprising at least one selected from the group consisting of alkyl methacrylate polymers and alkyl methacrylate-alkyl acrylate copolymers; The transparency (haze value) measured according to ASTM D-1003 under the condition of 0.15 mm thickness is 2 or less, the transparency measured under the condition of 3 mm thickness is 4 or less, and the total alkyl acrylate content of the thermoplastic resin is 20 to 50 weight %, and the butyl acrylate coverage value (X) calculated by the following Equation 1 of the thermoplastic resin is 50 or more. [Equation 1] X = {(G-Y)/Y} * 100 (in Equation 1, G is the total gel content (%) of the thermoplastic resin, Y is the weight % of butyl acrylate in the gel of the thermoplastic resin indicates.)
[Claim 14]
14. The method of claim 13, wherein the (A) graft copolymer comprises: 25 to 50 parts by weight of an alkyl acrylate rubber having a DLS average particle diameter of 40 to 120 nm or a TEM average particle diameter of 25 to 100 nm; and 50 to 75 parts by weight of an alkyl acrylate compound and an alkyl methacrylate compound; emulsion-polymerizing a total of 100 parts by weight of a monomer mixture comprising a method for producing a thermoplastic resin.
[Claim 15]
A molded article comprising the thermoplastic resin of any one of claims 1 to 12.
[Claim 16]
The molded article according to claim 15, wherein the molded article is a finishing material.