[Citation with related applications]
[2]
The present invention claims the benefit of priority based on Korean Patent Application No. 10-2018-0106052 filed on September 5, 2018 and Korean Patent Application No. 10-2019-0108784 filed on September 3, 2019, and the corresponding Korean patent application All content disclosed in the literature is incorporated as a part of this specification.
[3]
[Technical field]
[4]
The present invention relates to a thermoplastic resin composition, and to a thermoplastic resin composition having significantly improved transparency while maintaining basic physical properties.
[5]
background
[6]
Recently, as the industry is advanced and life is diversified, many studies are being conducted to impart high functionality such as transparency to materials for differentiation of product models. For example, research focused on giving more transparency to materials, such as a washing machine cover that can see the contents of laundry, a vacuum cleaner that can check how much dust has accumulated, toys, game machine housings, transparent windows for home appliances, transparent windows for office equipment, etc. is being done
[7]
However, the ABS graft copolymer used in these parts has excellent quality such as impact resistance, chemical resistance, processability and surface gloss, but it is an opaque material, so it cannot be used for materials requiring transparency.
[8]
Commonly used transparent materials include polycarbonate (PC), polymethyl methacrylate (PMMA), polystyrene (PS), and polyacrylonitrile-styrene (SAN). Although polycarbonate resin has excellent impact strength and transparency, it is difficult to make complex products due to poor processability. Polymethyl methacrylate has excellent transparency, but has very poor impact resistance and chemical resistance. In addition, polystyrene (PS) and polyacrylonitrile-styrene (SAN) have very poor impact resistance and chemical resistance.
[9]
On the other hand, US Patent No. 4,767,833, Japanese Patent Application Laid-Open No. Hei 11-147020, European Patent No. 703,252, and Japanese Patent Application Laid-Open No. Hei 8-199008 are acrylonitrile-butadiene having excellent impact resistance, chemical resistance, processability, etc. - Disclosed is a method for imparting transparency by introducing an alkyl (meth)acrylate-based monomer to a styrene-based graft copolymer. However, there is a limit to transparency, and most products have haze exceeding 2.0, so there is a limit to use in products using PMMA, PC, SAN, etc., thick injection moldings, or products requiring high transparency.
[10]
Therefore, it is necessary to develop a product with excellent impact resistance and fluidity while maintaining transparency at the level of products using PC, PMMA, SAN, etc. by further improving transparency.
[11]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[12]
It is an object of the present invention to provide a thermoplastic resin composition with remarkably improved transparency while maintaining basic physical properties such as impact resistance and fluidity.
[13]
means of solving the problem
[14]
In order to solve the above problems, the present invention includes A-1) a first conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer unit, and an aromatic vinyl-based monomer unit, and the first conjugated diene-based polymer is an average a first copolymer having a particle diameter of 0.05 to 0.2 μm; A-2) A second copolymer comprising a second conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer unit, and an aromatic vinyl-based monomer unit, wherein the second conjugated diene-based polymer has an average particle diameter of 0.23 to 0.5 μm ; B) a third copolymer comprising an alkyl (meth)acrylate-based monomer unit and an aromatic vinyl-based monomer unit; and C) a plasticizer having a viscosity of 700 to 10,000 cP, and providing a thermoplastic resin composition comprising 0.3 to 5 wt% of the plasticizer.
[15]
In addition, the present invention is made of the above-described thermoplastic resin composition, and includes an impact reinforcing region and a matrix region, wherein the impact reinforcing region is 1 selected from the group consisting of the first conjugated diene-based polymer and the second conjugated diene-based polymer. It provides a thermoplastic resin molded article comprising at least one species, wherein the matrix region includes the alkyl (meth)acrylate monomer unit and the aromatic vinyl monomer unit, and the impact reinforcing region and the matrix region have a refractive index difference of 0.01 or less.
[16]
Effects of the Invention
[17]
The thermoplastic resin composition of the present invention may have excellent basic physical properties such as impact resistance and fluidity, as well as significantly improved transparency.
[18]
Modes for carrying out the invention
[19]
Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.
[20]
The terms or words used in the present specification and claims are not to be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[21]
[22]
In the present invention, refractive index refers to the absolute refractive index of a material, and the refractive index is recognized as the ratio of the speed of electromagnetic radiation in free space to the speed of radiation in a material, where the radiation is visible light with a wavelength of 450 to 680 nm. The refractive index can be measured using a known method, generally using an Abbe Refractometer.
[23]
In addition, the refractive index of the graft copolymer can be calculated according to the following formula using the refractive index and content ratio of each polymer of the graft copolymer composition:
[24]
[25]
Refractive index (RI) = {[content of alkyl (meth) acrylate monomer unit (weight %)] × [refractive index of alkyl (meth) acrylate homopolymer]} + {[content of aromatic vinyl monomer unit (weight) %)] × [refractive index of aromatic vinyl-based homopolymer]} + {[content of vinyl cyan-based monomer unit (weight %)] × [refractive index of vinyl-cyanic homopolymer]}
[26]
[27]
In the present invention, the average particle diameter of the first and second conjugated diene-based polymers can be measured using a dynamic light scattering method, and in detail, Nicomp 380 equipment (product name, manufacturer: PSS) to be measured using can
[28]
In the present specification, the average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, that is, an average particle diameter of scattering intensity.
[29]
[30]
In the present invention, the viscosity of the plasticizer may be measured using Brookfield under the following conditions.
[31]
Spindle type - Cone type (CPA-52Z), cone angle = 3°, cone radius = 1.2 cm, gap: 13 μm or less, measurement shear rate: 10-20/sec, measurement Temperature: 25 ℃
[32]
In the present invention, the graft rate is obtained by dissolving 1 g of the first copolymer powder, the second copolymer powder, or the thermoplastic resin composition in 50 g of acetone while stirring for 24 hours, and then a centrifugal separator (trade name: SUPRA 30 K, manufacturer: Hanil Science Industrial) The supernatant and the precipitate were separated by centrifugation for 4 hours under 16,000 rpm and -10 ℃ conditions, and the precipitate was dried with a hot air dryer at 50 ℃ for 12 hours, and then the weight of the obtained dried product was measured, according to the following formula can be measured by:
[33]
[34]
Graft rate (%) = {[(weight of dry matter) - (weight of conjugated diene-based polymer)]/(weight of conjugated diene-based polymer)}×100
[35]
[36]
Weight of the conjugated diene-based polymer = the weight of the solid content of the first and second conjugated diene-based polymers added during the preparation of the first copolymer, the second copolymer, or the thermoplastic resin composition; Alternatively, the solid content weight of the first and second conjugated diene-based polymers measured by analyzing the first copolymer, the second copolymer, or the thermoplastic resin composition by infrared spectroscopy.
[37]
[38]
In the present invention, the weight average molecular weight of the shells of the first and second copolymers is an alkyl (meth)acrylate-based monomer unit grafted to a conjugated diene-based polymer, an aromatic vinyl-based monomer unit, and a vinyl cyan-based monomer unit. It may mean the weight average molecular weight of the coal.
[39]
In the present invention, the weight average molecular weight of the shells of the first and second copolymers is obtained by dissolving the dry matter described in the graft rate measurement method in a tetrahydrofuran (THF) solution at a concentration of 1% by weight, then filtering it through a 1 μm filter, It can be measured relative to a standard PS (standard polystyrene) sample through gel permeation chromatography.
[40]
[41]
In the present invention, the weight average molecular weight of the third copolymer is measured as a relative value with respect to a standard PS (standard polystyrene) sample using tetrahydrofuran (THF) as an eluent, and gel permeation chromatography (GPC, waters breeze). can do.
[42]
[43]
In the present invention, transparency may be measured according to ASTM 1003.
[44]
[45]
In the present invention, the impact strength can be measured under 1/4 inch conditions according to ASTM D256.
[46]
[47]
According to ASTM D1238, the flow index in the present invention can be measured under conditions of 220 °C and 10 kg.
[48]
[49]
1. Thermoplastic resin composition
[50]
A thermoplastic resin composition according to an embodiment of the present invention includes A-1) a first conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer unit, and an aromatic vinyl-based monomer unit, wherein the first conjugated diene-based polymer is a first copolymer having an average particle diameter of 0.05 to 0.2 μm; A-2) A second copolymer comprising a second conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer unit, and an aromatic vinyl-based monomer unit, wherein the second conjugated diene-based polymer has an average particle diameter of 0.23 to 0.5 μm ; B) a third copolymer comprising an alkyl (meth)acrylate-based monomer unit and an aromatic vinyl-based monomer unit; and C) a plasticizer having a viscosity of 700 to 10,000 cP, and containing the plasticizer in an amount of 0.3 to 5% by weight.
[51]
[52]
Hereinafter, components of the thermoplastic resin composition according to an embodiment of the present invention will be described in detail.
[53]
[54]
A-1) first copolymer
[55]
The first copolymer is a graft copolymer and includes a first conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer unit, and an aromatic vinyl-based monomer unit.
[56]
The first copolymer may impart excellent transparency and impact resistance to the thermoplastic resin composition through a synergistic action with the second copolymer, and in particular may impart remarkably excellent transparency.
[57]
[58]
The first conjugated diene-based polymer may have an average particle diameter of 0.05 to 0.2 μm, preferably 0.07 to 0.18 μm. If it is less than the above range, excellent impact resistance cannot be implemented, and when it exceeds the above range, excellent transparency cannot be implemented.
[59]
[60]
The first conjugated diene-based polymer is prepared by polymerization of a conjugated diene-based monomer, or a conjugated diene-based monomer and a comonomer copolymerizable with the conjugated diene-based monomer, and may have a structure in which a double bond and a single bond are arranged across one another. have.
[61]
The first conjugated diene-based polymer may include a conjugated diene-based polymer modified by graft polymerization of an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer to the conjugated diene-based polymer.
[62]
The conjugated diene-based monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, piperylene, dicyclopentadiene, ethylidene norborene and vinyl norborene, of which 1,3-butadiene or ethylidene norborene may be preferred.
[63]
The comonomer copolymerizable with the conjugated diene-based monomer may be at least one selected from the group consisting of acrylonitrile, ethylene and propylene.
[64]
The first conjugated diene-based polymer is polybutadiene; a copolymer comprising 1,3-butadiene units and acrylonitrile units; and at least one selected from the group consisting of a copolymer including an ethylidene norborene unit, an ethylene unit, and a propylene unit, among which polybutadiene is preferable.
[65]
[66]
The first conjugated diene-based polymer may be included in 35 to 65% by weight or 40 to 60% by weight based on the total weight of the first copolymer, and preferably included in 40 to 60% by weight. When the above-described range is satisfied, the transparency and impact resistance of the first copolymer can be further improved.
[67]
[68]
The alkyl (meth)acrylate-based monomer unit may provide excellent transparency to the first copolymer.
[69]
The alkyl (meth) acrylate-based monomer unit is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate and It may be a unit derived from at least one selected from the group consisting of uryl (meth)acrylate, and among these, a unit derived from methyl methacrylate is preferable.
[70]
The alkyl (meth) acrylate-based monomer unit may be included in an amount of 20 to 50% by weight or 25 to 45% by weight, based on the total weight of the first copolymer, and preferably included in an amount of 25 to 45% by weight. do. When the above-described range is satisfied, the transparency of the first copolymer can be further improved.
[71]
[72]
The aromatic vinyl-based monomer unit may impart processability, rigidity, and mechanical properties of the first copolymer.
[73]
The aromatic vinyl-based monomer unit may be a unit derived from at least one selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, and among these, a unit derived from styrene is preferable. .
[74]
The aromatic vinyl-based monomer unit may be included in an amount of 7 to 30% by weight or 10 to 25% by weight based on the total weight of the first copolymer, of which 10 to 25% by weight is preferable. When the above-described range is satisfied, the processability, rigidity, and mechanical properties of the first copolymer may be further improved.
[75]
[76]
The first copolymer may further include a vinyl cyanide monomer unit to improve chemical resistance.
[77]
The vinyl cyan-based monomer unit may be a unit derived from at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, of which, from acrylonitrile Derived units are preferred.
[78]
The vinyl cyan-based monomer unit may be included in an amount of 0.5 to 10% by weight or 1 to 7% by weight, preferably 1 to 7% by weight, based on the total weight of the first copolymer. If the above-described range is satisfied, the first copolymer may have more improved chemical resistance without yellowing. In addition, the polymerization stability may be improved by suppressing the formation of a coagulum during polymerization of the first copolymer.
[79]
[80]
The first copolymer may have a graft rate of 40 to 80%, more preferably 45 to 70%, and most preferably 50 to 60%. When the above-described range is satisfied, the transparency of the thermoplastic resin composition may be further improved. If the graft ratio is less than the above range, even if the refractive indices of the first to third copolymers match, the transparency of the thermoplastic resin composition may be reduced. If it exceeds the above range, the impact strength may be lowered.
[81]
[82]
Meanwhile, the transparency of the first copolymer may be determined by the difference between the refractive index of the first conjugated diene-based polymer and the refractive index of the shell including the alkyl (meth)acrylate-based monomer unit and the aromatic vinyl-based monomer unit. That is, in order for the first copolymer to have excellent transparency, the difference between the refractive index of the first conjugated diene-based polymer and the refractive index of the shell may be 0.01 or less, and it is preferable that there is no difference in the refractive index.
[83]
In addition, in order to realize excellent transparency of the thermoplastic resin composition, the first to third copolymers may each have a difference in refractive index of 0.01 or less. Specifically, the first copolymer and the second copolymer have a refractive index difference of 0.01 or less, the first copolymer and the third copolymer have a refractive index difference of 0.01 or less, and the second copolymer and the third copolymer The coalescence may have a refractive index difference of 0.01 or less. And, it is preferable that there is no difference in refractive index between the first to third copolymers.
[84]
[85]
The first copolymer may have a refractive index of 1.5 to 1.525 or 1.51 to 1.52, of which 1.51 to 1.52 is preferable. When the above-described range is satisfied, the transparency of the thermoplastic resin composition may be further improved by a synergistic action with the second and third copolymers to be described later.
[86]
[87]
The first copolymer may have a weight average molecular weight of 50,000 to 200,000 g/mol or 60,000 to 150,000 g/mol of the shell, of which 60,000 to 150,000 g/mol is preferable. If the above-described range is satisfied, fluidity and impact resistance may be further improved.
[88]
[89]
The first copolymer may be included in an amount of 5 to 40% by weight or 10 to 35% by weight based on the total weight of the thermoplastic resin composition, and it is preferably included in an amount of 10 to 35% by weight. When the above-described range is satisfied, the transparency of the thermoplastic resin composition may be further improved.
[90]
[91]
The first copolymer may be prepared by emulsion polymerization or bulk polymerization of an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer to a first conjugated diene-based polymer, and of which the first copolymer has excellent transparency and impact resistance It is preferable to prepare by emulsion polymerization so that it can be implemented.
[92]
[93]
A-2) Second copolymer
[94]
The second copolymer is a graft copolymer and includes a second conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer unit, and an aromatic vinyl-based monomer unit.
[95]
[96]
The second copolymer may impart excellent impact resistance and transparency to the thermoplastic resin composition, and in particular may impart remarkably excellent impact resistance.
[97]
[98]
The second conjugated diene-based polymer may have an average particle diameter of 0.23 to 0.5 μm, preferably 0.25 to 0.48 μm. If it is less than the above range, excellent impact resistance cannot be implemented, and when it exceeds the above range, excellent transparency cannot be implemented.
[99]
[100]
The second conjugated diene-based polymer may be included in an amount of 35 to 65% by weight or 40 to 60% by weight, preferably 40 to 60% by weight, based on the total weight of the second copolymer. When the above-described range is satisfied, the impact resistance and transparency of the second copolymer can be further improved.
[101]
[102]
In addition, the description of the second conjugated diene-based polymer is the same as described above in the description of the first conjugated diene-based polymer.
[103]
[104]
The alkyl (meth)acrylate-based monomer unit may provide excellent transparency to the second copolymer.
[105]
The type of the alkyl (meth)acrylate-based monomer unit is the same as described above.
[106]
The alkyl (meth) acrylate-based monomer unit may be included in an amount of 20 to 50% by weight or 25 to 45% by weight, preferably 25 to 45% by weight, based on the total weight of the second copolymer. do. When the above-described range is satisfied, the transparency of the second copolymer can be further improved.
[107]
[108]
The aromatic vinyl-based monomer unit may impart processability, rigidity, and mechanical properties of the second copolymer.
[109]
The type of the aromatic vinyl-based monomer unit is the same as described above.
[110]
The aromatic vinyl-based monomer unit may be included in an amount of 7 to 30% by weight or 10 to 25% by weight based on the total weight of the second copolymer, of which 10 to 25% by weight is preferable. When the above-described range is satisfied, the processability, rigidity, and mechanical properties of the second copolymer may be further improved.
[111]
[112]
The second copolymer may further include a vinyl cyanide-based monomer unit to improve chemical resistance.
[113]
The type of the vinyl cyan-based monomer unit is the same as described above.
[114]
The vinyl cyan-based monomer unit may be included in an amount of 0.5 to 10% by weight or 1 to 7% by weight, preferably 1 to 7% by weight, based on the total weight of the second copolymer. If the above-described range is satisfied, the second copolymer may have more improved chemical resistance without yellowing. In addition, the polymerization stability may be improved by suppressing the formation of a coagulum during polymerization of the second copolymer.
[115]
[116]
The amount of the second copolymer may be 35 to 70%, more preferably 38 to 60%, and most preferably 40 to 50%. When the above-described range is satisfied, the transparency of the thermoplastic resin composition may be further improved. If the graft ratio is less than the above range, even if the refractive indices of the first to third copolymers match, the transparency of the thermoplastic resin composition may be reduced. If it exceeds the above range, the impact strength may be lowered.
[117]
[118]
On the other hand, as described in the description of the first copolymer, the transparency of the second copolymer includes the refractive index of the second conjugated diene-based polymer and an alkyl (meth)acrylate-based monomer unit and an aromatic vinyl-based monomer unit. It can be determined by the difference in the refractive index of the shell. That is, in order for the second copolymer to have excellent transparency, the difference between the refractive index of the second conjugated diene-based polymer and the refractive index of the shell may be 0.01 or less, and it is preferable that there is no difference in the refractive index.
[119]
[120]
The second copolymer may have a refractive index of 1.5 to 1.525 or 1.51 to 1.52, of which 1.51 to 1.52 is preferable. When the above-described range is satisfied, the transparency of the thermoplastic resin composition may be further improved by a synergistic action with the first and third copolymers.
[121]
[122]
The second copolymer may have a weight average molecular weight of 50,000 to 200,000 g/mol or 70,000 to 150,000 g/mol of the shell, of which 70,000 to 150,000 g/mol is preferable. If the above-described range is satisfied, fluidity and impact resistance may be further improved.
[123]
[124]
The second copolymer may be included in an amount of 10 to 40 wt% or 13 to 35 wt%, based on the total weight of the thermoplastic resin composition, of which 13 to 35 wt% is preferably included. When the above-described range is satisfied, the impact resistance of the thermoplastic resin composition may be further improved.
[125]
[126]
The second copolymer may be prepared by emulsion polymerization or bulk polymerization of an alkyl (meth)acrylate-based monomer and an aromatic vinyl-based monomer to a second conjugated diene-based polymer, and the second copolymer has excellent impact resistance and transparency. It is preferable to prepare by emulsion polymerization so that it can be implemented.
[127]
[128]
B) third copolymer
[129]
The third copolymer is a matrix copolymer and includes an alkyl (meth)acrylate-based monomer unit and a vinyl cyan-based monomer unit.
[130]
The third copolymer imparts excellent transparency and processability to the thermoplastic resin composition.
[131]
[132]
The third copolymer may include the alkyl (meth)acrylate-based monomer unit and the aromatic vinyl-based monomer unit in a weight ratio of 30:70 to 80:20 or 40:60 to 75:25, of which 40: It is preferable to include it in a weight ratio of 60 to 75:25. When the above-described range is satisfied, the transparency and processability of the thermoplastic resin composition can be further improved.
[133]
[134]
The type of the alkyl (meth)acrylate-based monomer unit and the type of the aromatic vinyl-based monomer unit are the same as described above.
[135]
[136]
The third copolymer may further include a vinyl cyanide-based monomer unit to improve chemical resistance.
[137]
The type of the vinyl cyan-based monomer unit is the same as described above.
[138]
When the third copolymer further includes a vinyl cyan-based monomer unit, the third copolymer may include 60 to 80 wt% of the alkyl (meth)acrylate-based monomer unit, based on the total weight of the third copolymer; 15 to 35% by weight of the aromatic vinyl-based monomer unit; and 0.5 to 10 wt% of the vinyl cyan-based monomer unit, preferably 65 to 75 wt% of the alkyl (meth)acrylate-based monomer unit; 20 to 30% by weight of the aromatic vinyl-based monomer unit; and 1 to 10 wt% of the vinyl cyan-based monomer unit. If the above-described range is satisfied, the third copolymer may have more improved chemical resistance without yellowing.
[139]
[140]
The third copolymer may have a refractive index difference of 0.01 or less from each of the first copolymer and the second copolymer, and it is preferable that there is no difference in refractive index with them.
[141]
[142]
The third copolymer may have a refractive index of 1.5 to 1.525 or 1.51 to 1.52, of which 1.5 to 1.52 is preferable. When the above-described range is satisfied, the transparency of the thermoplastic resin composition may be further improved by a synergistic action with the first and second copolymers.
[143]
[144]
The third copolymer may have a weight average molecular weight of 50,000 to 200,000 g/mol or 60,000 to 150,000 g/mol, of which 60,000 to 150,000 g/mol is preferable. If the above-mentioned range is satisfied, fluidity and impact resistance may be more excellent.
[145]
[146]
The third copolymer may be included in an amount of 20 to 75 wt% or 30 to 70 wt%, based on the total weight of the thermoplastic resin composition, and preferably included in an amount of 30 to 70 wt%. When the above-described range is satisfied, transparency and processability of the thermoplastic resin composition may be further improved.
[147]
[148]
The third copolymer can be prepared by suspension polymerization or bulk polymerization of an alkyl (meth) acrylate-based monomer and an aromatic vinyl-based monomer, and among them, bulk polymerization capable of reducing costs while producing a copolymer with high purity; It is especially preferable to manufacture by continuous bulk polymerization.
[149]
[150]
C) plasticizer
[151]
The plasticizer has a viscosity of 700 to 10,000 cP, and the plasticizer may impart excellent processability to the thermoplastic resin composition.
[152]
The plasticizer may have a viscosity of preferably 1,000 to 90,000 cP, more preferably 1,200 to 5,000 cP. When it is less than the above-mentioned range, the plasticizer migration phenomenon occurs in the thermoplastic resin composition. In addition, gas and mold deposits may occur during injection molding. When it exceeds the above-mentioned range, the processability of a thermoplastic resin composition will fall.
[153]
[154]
The plasticizer may be included in an amount of 0.3 to 5% by weight, preferably in an amount of 0.5 to 4% by weight, and more preferably in an amount of 1 to 4% by weight, based on the total weight of the thermoplastic resin composition. When the above-described range is satisfied, the transparency and processability of the thermoplastic resin composition can be further improved, and migration of the plasticizer can be prevented. When included below the above-mentioned range, transparency and processability of the thermoplastic resin composition are reduced. When included in excess of the above range, the transparency and impact strength of the thermoplastic resin composition is reduced. In addition, the plasticizer migration phenomenon also occurs.
[155]
[156]
The plasticizer may have a refractive index of 1.45 or more, 1.45 to 1.6, or 1.45 to 1.52, of which 1.45 to 1.52 is preferable. When the above-described conditions are satisfied, the transparency of the manufactured thermoplastic resin molded article may be improved.
[157]
[158]
The plasticizer may include an aliphatic dicarboxylic acid-based monomer unit and an aliphatic dihydroxy-based monomer unit.
[159]
The aliphatic dicarboxylic acid-based monomer unit may be a unit derived from at least one selected from the group consisting of adipic acid, succinic acid, and glutaric acid, and among these, a unit derived from adipic acid is preferable.
[160]
The aliphatic dihydroxy monomer unit is 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1, It may be a unit derived from at least one selected from the group consisting of 6-hexanediol, 1,4-hexanediol, and 2-2-dimethyl-1,3-propanediol, of which 1,3-butanediol, 1 A unit derived from at least one selected from the group consisting of ,2-propanediol and 2-2-dimethyl-1,3-propanediol is preferable.
[161]
[162]
The plasticizer may further include an aliphatic ester-based monomer unit and an acetate-based monomer unit, and the aliphatic ester-based monomer unit is derived from at least one selected from the group consisting of 2-ethylhexyl ester, octyl ester and isononyl ester. may be a unit. The acetate-based monomer unit may be a unit derived from acetate.
[163]
[164]
The plasticizer is polydi (2-ethylhexyl) glycol adipate (CAS NO. 73018-26-5); 2,2'-methylenebis[6-(2H-benzotrizol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (CAS NO. 103597-45-1); Hexanedioic acid, polymer with 2,2-dimethyl-1,3-propanediol and 1,2-propanediol, isononyl ester (Hexanedioic acid, polymer with 2,2-dimethyl-1,3-propanediol and 1,2 -propanediol, isononyl ester, CAS NO. 208945-13-5); Hexanedioic acid, polymer with 1,2-propanediol, n-octyl ester (Hexanedioic acid, polymer with 1,2-propanediol, n-octyl ester, CAS NO. 82904-80-1); And hexanedioic acid, polymer with 1,2-propanediol, acetate (Hexanedioic acid, polymer with 1,2-propanediol, acetate, CAS NO. 55799-38-7) may be at least one selected from the group consisting of, Among them, polydi(2-ethylhexyl)glycol adipate; 2,2'-methylenebis[6-(2H-benzotrizol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol]; And at least one selected from the group consisting of hexanedioic acid, polymer with 2,2-dimethyl-1,3-propanediol and 1,2-propanediol, and isononyl ester is preferable.
[165]
[166]
The plasticizer is SONGCIZER TM P-2600 (trade name, manufacturer: Songwon Industrial), SONGCIZER TM P-3600 (trade name, manufacturer: Songwon Industrial), Palamoll ® 632 (trade name, manufacturer: BASF), Palamoll ® 638 ( At least one selected from the group consisting of trade name, manufacturer: BASF), Palamoll ® 652 (trade name, manufacturer: BASF), Admex TM 760 Polymeric Plasticizer (trade name, manufacturer: EASTMAN), and EDENOL ® 1225 (trade name, manufacturer: EMERYOLECHEMICALS) SONGCIZER TM P-2600 (trade name, manufacturer: Songwon Industrial), Palamoll ® 638 (trade name, manufacturer: BASF), Palamoll ® 652 (trade name, manufacturer: BASF), and EDENOL ® 1225 (trade name, Manufacturer: at least one selected from the group consisting of EMERYOLECHEMICALS) is preferable.
[167]
[168]
On the other hand, it is preferable that the plasticizer is not a phthalate-based plasticizer that causes environmental problems.
[169]
[170]
On the other hand, the thermoplastic resin composition according to an embodiment of the present invention, in the total weight of the thermoplastic resin composition, the first conjugated diene-based polymer 3 to 20% by weight; 3 to 20% by weight of the second conjugated diene-based polymer; 45 to 65 wt% of the alkyl (meth)acrylate-based monomer unit; 10 to 30% by weight of the aromatic vinyl-based monomer unit; and 0.3 to 5% by weight of the plasticizer, preferably 5 to 15% by weight of the first conjugated diene-based polymer; 5 to 15% by weight of the second conjugated diene-based polymer; 50 to 65 wt% of the alkyl (meth)acrylate-based monomer unit; 15 to 25% by weight of the aromatic vinyl-based monomer unit; and 0.5 to 4% by weight of the plasticizer. When the above-mentioned range is satisfied, transparency, processability and impact resistance of the thermoplastic resin composition may be further improved.
[171]
[172]
When the thermoplastic resin composition according to an embodiment of the present invention further includes a vinyl cyanide-based monomer unit, it may be included in an amount of 0.5 to 10% by weight or 1 to 7% by weight, based on the total weight of the thermoplastic resin composition, It is preferable to include 1 to 7% by weight of this. When the above-described range is satisfied, the chemical resistance of the thermoplastic resin composition is further improved, and yellowing does not occur.
[173]
[174]
The thermoplastic resin composition according to an embodiment of the present invention has a graft ratio of 35 to 65% or 40 to 60%, of which 40 to 60% is preferable. When the above-described range is satisfied, the transparency of the thermoplastic resin composition may be further improved.
[175]
[176]
The thermoplastic resin composition according to an embodiment of the present invention has a flow index of 15 to 45 g/10mins or 18 to 30 g/10mins at 220° C., of which 18 to 30 g/10mins is preferable. When the above-described range is satisfied, the processability of the thermoplastic resin composition may be further improved.
[177]
[178]
2. Thermoplastic resin molded products
[179]
A thermoplastic resin molded article according to another embodiment of the present invention is made of the thermoplastic resin composition according to an embodiment of the present invention, and includes an impact reinforcing region comprising the first conjugated diene-based polymer and the second conjugated diene-based polymer; The difference in refractive index between the matrix region including the alkyl (meth)acrylate monomer unit and the aromatic vinyl monomer unit is 0.01 or less.
[180]
When the above conditions are satisfied, the transparency of the thermoplastic resin molded article may be further improved.
[181]
[182]
The thermoplastic resin molded article may have a haze of 1.3 or less, an impact strength of 7 kg.cm/cm or more, and a transparency of 1.2 or less and an impact strength of 9 kg.cm/cm or more. When the above conditions are satisfied, transparency and impact resistance of the thermoplastic resin molded article may be further improved.
[183]
[184]
Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.
[185]
[186]
Preparation Example 1: Preparation of A-1-1
[187]
50 parts by weight of polybutadiene latex (polymerization method: emulsion polymerization, gel content: 90%, average particle diameter: 0.12 μm), 50 parts by weight of ion-exchanged water, 8.8 parts by weight of methyl methacrylate, 3 parts by weight of styrene, acrylonitrile 0.8 parts by weight of divinylbenzene as a crosslinking agent, 0.1 parts by weight of divinylbenzene as an initiator, 0.2 parts by weight of cumene hydroperoxide as an initiator, and 0.5 parts by weight of sodium alkylarylsulfonate (sodium dodecylbenzenesulfonate) as an emulsifier, mixed for 5 hours, and then methyl 26.2 parts by weight of methacrylate, 9 parts by weight of styrene, 2.2 parts by weight of acrylonitrile, 0.5 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.05 parts by weight of ethylenediaminetetraacetic acid as an oxidation-reduction catalyst, sodium formaldehyde sulfonate Polymerization was carried out while continuously adding 0.1 parts by weight of foxylate, 0.001 parts by weight of ferrous sulfate, and 0.1 parts by weight of cumene hydroperoxide as an initiator at 70° C. for 5 hours at a constant rate. After the continuous input was completed, the temperature was raised to 80° C., and after aging for 1 hour, polymerization was terminated to obtain a graft copolymer latex. Then, 2 parts by weight of magnesium sulfate as a coagulant was added to the graft copolymer latex for coagulation, followed by dehydration and drying to obtain a graft copolymer powder. The refractive index of the obtained graft copolymer powder was 1.516, and the graft ratio was 55%.
[188]
[189]
Preparation Example 2: Preparation of A-2-1
[190]
50 parts by weight of polybutadiene latex (polymerization method: emulsion polymerization, gel content: 70%, average particle diameter: 0.3 μm), 50 parts by weight of ion-exchanged water, 8.8 parts by weight of methyl methacrylate, 3 parts by weight of styrene, acrylonitrile 0.8 parts by weight, 0.1 parts by weight of divinylbenzene as a crosslinking agent, 0.2 parts by weight of cumene hydroperoxide as an initiator, and 0.5 parts by weight of sodium alkylarylsulfonate (sodium dodecylbenzenesulfonate) as an emulsifier, and mixed for 3 hours, 26.2 parts by weight of methyl methacrylate, 9 parts by weight of styrene, 2.2 parts by weight of acrylonitrile, 0.5 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.05 parts by weight of ethylenediaminetetraacetic acid as an oxidation-reduction catalyst, sodium formaldehyde sulfide Polymerization was carried out while continuously introducing 0.1 parts by weight of foxylate, 0.001 parts by weight of ferrous sulfate, and 0.1 parts by weight of cumene hydroperoxide as an initiator at 70° C. for 5 hours at a constant rate. After the continuous input was completed, the temperature was raised to 80° C., and the polymerization was terminated after aging for 1 hour to obtain a graft copolymer latex. Then, 2 parts by weight of magnesium sulfate as a coagulant was added to the graft copolymer latex for agglomeration, followed by dehydration and drying to obtain a graft copolymer powder. The obtained graft copolymer powder had a refractive index of 1.516 and a graft rate of 45%.
[191]
[192]
Preparation Example 3: Preparation of A-2-2
[193]
50 parts by weight of polybutadiene latex (polymerization method: emulsion polymerization, gel content: 70%, average particle diameter: 0.3 μm), 50 parts by weight of ion-exchanged water, 7.5 parts by weight of methyl methacrylate, 4.8 parts by weight of styrene, acrylonitrile 0.8 parts by weight, 0.1 parts by weight of divinylbenzene as a crosslinking agent, 0.2 parts by weight of cumene hydroperoxide as an initiator, and 0.5 parts by weight of sodium alkylarylsulfonate (sodium dodecylbenzenesulfonate) as an emulsifier, and mixed for 3 hours, 22.3 parts by weight of methyl methacrylate, 14.4 parts by weight of styrene, 2.2 parts by weight of acrylonitrile, 0.5 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.05 parts by weight of ethylenediaminetetraacetic acid as an oxidation-reduction catalyst, sodium formaldehyde Polymerization was carried out while continuously introducing 0.1 parts by weight of sulfoxylate, 0.001 parts by weight of ferrous sulfate, and 0.1 parts by weight of cumene hydroperoxide at 70° C. at a constant rate for 5 hours. After the continuous input was completed, the temperature was raised to 80° C., and the polymerization was terminated after aging for 1 hour to obtain a graft copolymer latex. Then, 2 parts by weight of magnesium sulfate as a coagulant was added to the graft copolymer latex for agglomeration, followed by dehydration and drying to obtain a graft copolymer powder. The obtained graft copolymer powder had a refractive index of 1.53 and a graft rate of 47%.
[194]
[195]
Preparation Example 4: Preparation of B-1
[196]
70.4 parts by weight of methyl methacrylate, 24.6 parts by weight of styrene, and 5 parts by weight of acrylonitrile were mixed with 30 parts by weight of toluene as a solvent and 0.15 parts by weight of t-dodecyl mercaptan as a molecular weight regulator so that the average reaction time was 3 hours. The reaction temperature was maintained at 148 °C by continuously introducing into the reactor. The polymerization solution discharged from the reaction tank was heated in a preheating tank, unreacted monomers were volatilized in the volatilization tank, and the temperature of the polymer was maintained at 210 ° C. Using a polymer transfer pump extrusion machine, MSAN copolymer in pellet form was obtained. The prepared MSAN copolymer had a refractive index of 1.516.
[197]
[198]
Examples and Comparative Examples
[199]
A thermoplastic resin composition was prepared by mixing the graft copolymer, the matrix copolymer and the plasticizer in the amounts shown in the table below.
[200]
[201]
Experimental Example 1
[202]
100 parts by weight of the thermoplastic resin composition of Examples and Comparative Examples and 0.3 parts by weight of an antioxidant (trade name: Irganox 1010, manufacturer: BASF) were uniformly mixed, and then injected into a twin-screw extrusion kneader at a cylinder temperature of 220 ° C. to prepare pellets . The physical properties of the pellets were measured in the following way, and are described in the table below.
[203]
[204]
① Flow index (g/10mins): It was carried out at 220 °C and 10 kg according to ASTM1238.
[205]
[206]
Experimental Example 2
[207]
A specimen was prepared by injecting the pellets prepared in Experimental Example 1, and the physical properties of the specimen were measured in the following manner, and are described in the table below.
[208]
[209]
② Haze (Haze Value, %): Transparency was measured according to ASTM1003.
[210]
③ Impact strength (Notched Izod Impact Strength, 1/4 INCH, kg·cm/cm): The notched Izod impact strength was measured at 23 ℃ according to ASTM245 D256.
[211]
④ Migration: After placing the specimen on oiled paper in an oven at 70 ℃, placing a weight of 10 kg, and storing it for 1 week, the migration was evaluated by examining the change of the oiled paper. When the plasticizer is transferred, the oiled paper is wetted and the color of the oiled paper is changed, so the change in color means that the transfer occurs and the plasticizer is stained on the oiled paper. Therefore, no change was marked as OK, and a change with no change was marked as NG.
[212]
[213]
[Table 1]
division comparative example Example comparative example
One One 2 3 4 5 2 3
Graft copolymer (wt%) A-1-1 15 15 15 15 15 15 15 15
A-2-1 20 20 20 20 20 20 20 20
Matrix copolymer (wt%) B-1 65 64.7 64.5 63 62 61 59 55
plasticizer (wt%) C-1 - 0.3 0.5 2 3 4 6 10
flow index 14.3 18.1 18.9 22.0 23.1 24.2 27.8 43.7
haze 1.6 1.1 1.1 0.9 1.0 1.0 2.2 2.9
impact strength 10.1 9.8 10.1 9.8 10.2 10.1 8.7 7.8
transitivity - OK OK OK OK OK NG NG
A-1-1 : graft copolymer (average particle diameter of polybutadiene: 0.12 μm, refractive index: 1.516, graft ratio: 55%) A-2-1 : graft copolymer (average particle diameter of polybutadiene: 0.3 μm, refractive index : 1.516, Graft rate: 45 %) B-1 : Matrix copolymer (refractive index: 1.516) C-1 : SONGCIZER TM P-2600 (brand name, manufacturer: Songwon, Viscosity: 2,200 cP, refractive index: 1.466, material name: Polydi (2-ethylhexyl) glycol adipate)
[214]
[Table 2]
division Example
6 7 8 9 10
Graft copolymer (wt%) A-1-1 18 15 15 27 20
A-2-1 22 20 20 15 15
Matrix copolymer (wt%) B-1 57 63 63 55 62
plasticizer (wt%) C-1 3 - - - -
C-2 - 2 - - -
C-3 - - 2 3 -
C-4 - - - - 3
flow index 19.8 20.5 21.4 18.2 19.2
haze 1.0 1.1 1.0 1.0 1.1
impact strength 12.2 10.3 9.7 10.5 8.5
transitivity OK OK OK OK OK
A-1-1 : graft copolymer (average particle diameter of polybutadiene: 0.12 μm, refractive index: 1.516, graft ratio: 55%) A-2-1 : graft copolymer (average particle diameter of polybutadiene: 0.3 μm, refractive index : 1.516, Graft rate: 45 %) B-1 : Matrix copolymer (refractive index: 1.516) C-1 : SONGCIZER TM P-2600 (brand name, manufacturer: Songwon, Viscosity: 2,200 cP, refractive index: 1.466, material name: Polydi (2-ethylhexyl) glycol adipate) C-2 : Palamoll ® 652 (trade name, manufacturer: BASF, viscosity: 2,000 cP, refractive index: 1.465, substance name: hexanedioic acid, polymer with 2,2-dimethyl-1,3 -Propanediol and 1,2-propanediol, isononyl ester, CAS NO. 208945-13-5) C-3 : EDENOL ® 1225 (trade name, manufacturer: EMERYOLECHEMICALS, viscosity: 1,200 cP, refractive index: 1.463) C-4 : Palamoll ® 638 (trade name, manufacturer: BASF, viscosity: 8,000 cP, refractive index: 1.468, substance name: hexanedioic acid, polymer with 1,2-propanediol, n-octyl ester, CAS NO. 82904-80-1)
[215]
[Table 3]
division comparative example
4 5 6 7 8
Graft copolymer (wt%) A-1-1 18 15 18 35 18
A-2-1 22 20 20 - -
A-2-2 - - - - 22
Matrix copolymer (wt%) B-1 56 63 62 63 60
plasticizer (wt%) C-1 - - - 2 -
C-5 4 - - - -
C-6 - 2 - - -
flow index 25.9 31.2 13.8 22.1 11.3
haze 1.6 1.7 1.0 0.6 1.4
impact strength 9.4 8.5 12.9 2.8 11.2
transitivity OK NG - OK -
A-1-1 : graft copolymer (average particle diameter of polybutadiene: 0.12 μm, refractive index: 1.516, graft ratio: 55%) A-2-1 : graft copolymer (average particle diameter of polybutadiene: 0.3 μm, refractive index : 1.516, graft rate: 45%) A-2-2 : graft copolymer (average particle diameter of polybutadiene: 0.3 μm, refractive index: 1.53, graft rate: 47%) B-1 : matrix copolymer (refractive index: 1.516) C -1 : SONGCIZER TM P-2600 (brand name, manufacturer: Songwon Industrial Co., Ltd., viscosity: 2,200 cP, refractive index: 1.466, material name: polydi(2-ethylhexyl)glycol adipate) C-5 : GL-500 (brand name, manufacturer) : LG Chem, refractive index: 1.41, viscosity 60 cP, substance name: Reaction product of disubstitutedcarbomonocycle, alkyl(C=1~3)alkanol(C=4~6) and alkanol(C=3~5)) C-6 : SONGCIZER TM P-1500 (trade name, manufacturer: Songwon Industries, viscosity: 150 cP, refractive index: 1.456, material name: polydi(2-ethylhexyl)glycol adipate)
[216]
Examples 1 to 5 containing a plasticizer having a viscosity of 2,200 cP in an amount of 0.3 to 4 wt % had a high flow index and a low haze, so it was confirmed that processability and transparency were improved. In addition, it was confirmed that the flow index increased as the content of the plasticizer increased, thereby improving processability. On the other hand, Comparative Example 1 not including a plasticizer had a lower flow index and higher haze compared to Examples 1 to 5, so that processability and It can be seen that the transparency is reduced. In Comparative Examples 2 and 3 containing a plasticizer having a viscosity of 2,200 cP in an amount of 6 wt% and 10 wt%, respectively, it was confirmed that the flow index and haze were excessively high, the impact strength was low, and the transferability was lowered. From these results, it was confirmed that even if a plasticizer having a viscosity of 2,200 cP is used in excess, processability, transparency, impact resistance, and transferability are rather deteriorated.
[217]
Referring to Examples 4 and 6, when the content of the graft copolymer is increased, the impact strength is improved, and since the content of the matrix copolymer is relatively decreased, it can be seen that the processability is somewhat reduced.
[218]
It can be seen that Examples 6 to 10 containing plasticizers having viscosities of 2,200 cP, 2,000 cP, 1,200 cP, and 8,000 cP, respectively, implement excellent flow index, haze, impact strength and transferability.
[219]
On the other hand, in Comparative Example 4 including a plasticizer having a viscosity of 60 cP and Comparative Example 5 including a plasticizer having a viscosity of 150 cP, it was confirmed that haze was increased and transparency was lowered.
[220]
Comparative Example 6 contained an excess of the graft copolymer having an average particle diameter of 0.12 μm of polybutadiene compared to Comparative Example 1, so that haze was lowered and excellent transparency could be realized. However, since it does not contain a plasticizer, it can be confirmed that the flow index is lowered and the workability is remarkably reduced.
[221]
Comparative Example 7 including a plasticizer having a viscosity of 2,200 cP, but not including a graft copolymer having an average particle diameter of polybutadiene of 0.3 μm, showed a remarkably lowered impact strength.
[222]
Comparative Example 8, which does not contain a plasticizer, and includes a graft copolymer having an average particle diameter of polybutadiene of 0.3 μm and a refractive index of 1.53, contains an excess of the graft copolymer having an average particle diameter of polybutadiene of 0.12 μm compared to Comparative Example 1. By including, it was possible to lower the haze, but it was difficult to implement excellent transparency. In addition, since the plasticizer was not included, it was confirmed that the flow index was lowered and the workability was remarkably deteriorated.
Claims
[Claim 1]
A-1) A first copolymer comprising a first conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer unit and an aromatic vinyl-based monomer unit, wherein the first conjugated diene-based polymer has an average particle diameter of 0.05 to 0.2 μm ; A-2) A second copolymer comprising a second conjugated diene-based polymer, an alkyl (meth)acrylate-based monomer unit, and an aromatic vinyl-based monomer unit, wherein the second conjugated diene-based polymer has an average particle diameter of 0.23 to 0.5 μm ; B) a third copolymer comprising an alkyl (meth)acrylate-based monomer unit and an aromatic vinyl-based monomer unit; and C) a plasticizer having a viscosity of 700 to 10,000 cP, wherein the thermoplastic resin composition comprises 0.3 to 5% by weight of the plasticizer.
[Claim 2]
The thermoplastic resin composition of claim 1, wherein C) the plasticizer has a refractive index of 1.45 or more.
[Claim 3]
The thermoplastic resin composition of claim 1, wherein C) the plasticizer comprises an aliphatic dicarboxylic acid-based monomer unit and an aliphatic dihydroxy-based monomer unit.
[Claim 4]
The thermoplastic resin composition of claim 3, wherein C) the plasticizer further comprises at least one selected from the group consisting of an aliphatic ester-based monomer unit and an acetate-based monomer unit.
[Claim 5]
The thermoplastic resin composition of claim 1, wherein the A-1) first copolymer has a graft ratio of 40 to 80%.
[Claim 6]
The thermoplastic resin composition of claim 1, wherein the A-2) second copolymer has a graft ratio of 35 to 70%.
[Claim 7]
The thermoplastic resin composition of claim 1, wherein the first to third copolymers each have a difference in refractive index of 0.01 or less.
[Claim 8]
The thermoplastic resin composition of claim 1, wherein each of the first to third copolymers further comprises a vinyl cyan-based monomer unit.
[Claim 9]
The method according to claim 1, wherein the thermoplastic resin composition is A-1) 5 to 40% by weight of the first copolymer; A-2) 10 to 40% by weight of the second copolymer; B) 20 to 75% by weight of the third copolymer; And C) a thermoplastic resin composition comprising 0.3 to 5% by weight of a plasticizer.
[Claim 10]
The method according to claim 1, wherein the thermoplastic resin composition is 3 to 20% by weight of the first conjugated diene-based polymer; 3 to 20% by weight of the second conjugated diene-based polymer; 45 to 65 wt% of the alkyl (meth)acrylate-based monomer unit; 10 to 30% by weight of the aromatic vinyl-based monomer unit; and 0.3 to 5% by weight of the plasticizer.
[Claim 11]
The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a graft ratio of 35 to 65%.
[Claim 12]
The method according to claim 1, wherein the thermoplastic resin composition has a flow index of 15 to 45 g/10mins at 220 °C.
[Claim 13]
It is made of the thermoplastic resin composition according to any one of claims 1 to 12, and includes an impact reinforcing region and a matrix region, wherein the impact reinforcing region is from the group consisting of the first conjugated diene-based polymer and the second conjugated diene-based polymer. a thermoplastic resin molded article comprising at least one selected
[Claim 14]
The thermoplastic resin molded article according to claim 13, wherein the thermoplastic resin molded article has a haze of 1.3 or less and an impact strength of 7 kg·cm/cm or more.