WO2020050639A1 - Thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition which exhibits excellent transparency, impact resistance and fluidity and comprises: A-1) a first copolymer comprising a first conjugated diene polymer having an average particle diameter of 0.05 to 0.2 ㎛, an alkyl (meth)acrylate monomer unit and an aromatic vinyl monomer unit; A-2) a second copolymer comprising a second conjugated diene polymer having an average particle diameter of 0.23 to 0.5 ㎛, an alkyl (meth)acrylate monomer unit and an aromatic vinyl monomer unit; B) a third copolymer comprising an alkyl (meth)acrylate monomer unit and an aromatic vinyl monomer unit; and C) 0.3 to 5 wt% of a plasticizer having a viscosity of 700 to 10,000 cP.

Description

Thermoplastic resin composition

[Mutual citations with related applications]

The present invention claims the benefit of priority based on Korean Patent Application Nos. 10-2018-0106052 filed on September 5, 2018 and Korean Patent Application Nos. 10-2019-0108784 filed on September 3, 2019, and claims Korean patent applications All the contents disclosed in the literature of are included as a part of this specification.

[Technical field]

The present invention relates to a thermoplastic resin composition, and relates to a thermoplastic resin composition having improved transparency while maintaining basic properties.

Recently, as the industry is advanced and life is diversified, many studies have been conducted to give high functionality such as transparency to materials to differentiate product models. For example, research that gives more transparency to materials, such as a washing machine cover for viewing laundry contents, a vacuum cleaner for checking how much dust is collected, a toy, a game machine housing, a transparent window for home appliances, and a transparent window for office equipment, etc. Is being made.

However, the ABS graft copolymer used in these parts is excellent in quality such as impact resistance, chemical resistance, processability and surface gloss, but it is an opaque material and therefore cannot be used for materials requiring transparency.

Commonly used transparent materials include polycarbonate (PC), polymethyl methacrylate (PMMA), polystyrene (PS), and polyacrylonitrile-styrene (SAN). Polycarbonate resin has excellent impact strength and transparency, but 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, the impact resistance and chemical resistance of polystyrene (PS) and polyacrylonitrile-styrene (SAN) are very poor.

On the other hand, US Patent No. 4,767,833, Japanese Patent Publication No. Hei 11-147020, European Patent No. 703,252, and Japanese Patent Publication No. Hei 8-199008 have excellent impact resistance, chemical resistance, processability, etc. -A method of imparting transparency by introducing an alkyl (meth) acrylate monomer to a styrene-based graft copolymer is disclosed. However, since the haze of most products exceeds 2.0 due to the limitation of transparency, there are limitations in use for products using PMMA, PC, SAN, etc., products that require thick injection or high transparency.

Therefore, it is necessary to develop a product having excellent impact resistance and fluidity while maintaining transparency at a product level using PC, PMMA, SAN, etc. by further improving transparency.

It is an object of the present invention to provide a thermoplastic resin composition in which transparency is significantly improved while maintaining basic properties such as impact resistance and fluidity.

In order to solve the above-mentioned problems, the present invention comprises A-1) a first conjugated diene polymer, an alkyl (meth) acrylate monomer unit, and an aromatic vinyl monomer unit, and the first conjugated diene polymer is average A first copolymer having a particle size of 0.05 to 0.2 μm; A-2) 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 a second copolymer having an average particle diameter of 0.23 to 0.5 μm. ; B) a third copolymer comprising an alkyl (meth) acrylate monomer unit and an aromatic vinyl monomer unit; And C) a plasticizer having a viscosity of 700 to 10,000 cP, and a plasticizer containing 0.3 to 5% by weight of the plasticizer.

In addition, the present invention is made of the above-mentioned thermoplastic resin composition, including an impact reinforcement region and a matrix region, the impact reinforcement region being selected from the group consisting of the first conjugated diene-based polymer and the second conjugated diene-based polymer 1 It includes a species or more, and the matrix region includes the alkyl (meth) acrylate-based monomer unit and the aromatic vinyl-based monomer unit, and the impact reinforcement region and the matrix region provide a thermoplastic resin molded article having a refractive index difference of 0.01 or less.

The thermoplastic resin composition of the present invention is not only excellent in basic physical properties such as impact resistance and fluidity, but also transparency can be remarkably improved.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

The terms or words used in the present specification and claims should not be interpreted as being limited to ordinary or lexical meanings, and the inventor can appropriately define the concept of terms in order to best describe his or her invention. Based on the principle that it should be interpreted as meanings and concepts consistent with the technical spirit of the present invention.

In the present invention, the refractive index refers to the absolute refractive index of a material, which is recognized as the ratio of the rate of electromagnetic radiation in a free space to the rate of radiation in a material, where the radiation is visible light having a wavelength of 450 to 680 nm. The refractive index can be measured using a known method, generally using an Abbe Refractometer.

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:

Refractive index (RI) = {[content of alkyl (meth) acrylate-based monomer units (% by weight)] × [refractive index of alkyl (meth) acrylate-based homopolymers]} + {[content of aromatic vinyl-based monomer units (weight %)] × [Refractive index of aromatic vinyl-based homopolymer]} + {[Content of vinyl cyan-based monomer unit (% by weight)] × [Refractive index of vinyl cyan-based homopolymer]}

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 specifically, measured using Nicomp 380 equipment (product name, manufacturer: PSS). You can.

In the present specification, the average particle diameter may mean an arithmetic average particle size in the particle size distribution measured by the dynamic light scattering method, that is, the average particle size of the scattering intensity.

In the present invention, the viscosity of the plasticizer can be measured using Brookfield under the following conditions.

Spindle type-Cone type (CPA-52Z), cone angle = 3 °, cone radius = 1.2 cm, gap: 13 µm or less, measured shear rate: 10-20 / sec, measured Temperature: 25 ℃

In the present invention, the graft ratio is 1 g of the first copolymer powder, the 2nd copolymer powder or the thermoplastic resin composition dissolved in 50 g of acetone while stirring for 24 hours, and then centrifuged (trade name: SUPRA 30 K, manufacturer: Hanil Science Industrial) And supernatant and sediment were separated by centrifugation for 4 hours under conditions of 16,000 rpm and -10 ° C, and the precipitate was dried for 12 hours with a hot air dryer at 50 ° C, and then the weight of the dried product was measured. Can be measured by:

Graft ratio (%) = {[(Weight of dried product)-(Weight of conjugated diene polymer)] / (Weight of conjugated diene polymer)} × 100

Weight of the conjugated diene-based polymer = solid content weight of the first and second conjugated diene-based polymers introduced in 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 polymers measured by analyzing the first copolymer, the second copolymer, or the thermoplastic resin composition by infrared spectroscopy

In the present invention, the weight average molecular weight of the shells of the first and second copolymers is a copolymer comprising an alkyl (meth) acrylate-based monomer unit grafted to a conjugated diene-based polymer, an aromatic vinyl monomer unit, and a vinyl cyan monomer unit. It may mean the weight average molecular weight of the coalescence.

In the present invention, the weight average molecular weight of the shells of the first and second copolymers is dissolved in a tetrahydrofuran (THF) solution in a concentration of 1% by weight of the dried product described in the graft rate measurement method, filtered through a 1 μm filter, Gel permeation chromatography can be used to measure relative values to standard polystyrene (PS) samples.

In the present invention, the weight average molecular weight of the third copolymer is measured using tetrahydrofuran (THF) as the eluent, and measured relative to the standard PS (standard polystyrene) sample using gel permeation chromatography (GPC, waters breeze). can do.

Transparency in the present invention can be measured according to ASTM 1003.

In the present invention, the impact strength can be measured under 1/4 inch condition according to ASTM D256.

In the present invention, the flow index can be measured according to ASTM D1238, under 220 ° C and 10 kg conditions.

1. Thermoplastic resin composition

The thermoplastic resin composition according to an embodiment of the present invention includes A-1) a first conjugated diene polymer, an alkyl (meth) acrylate monomer unit, and an aromatic vinyl monomer unit, and the first conjugated diene polymer is A first copolymer having an average particle diameter of 0.05 to 0.2 μm; A-2) 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 a second copolymer having an average particle diameter of 0.23 to 0.5 μm. ; B) a third copolymer comprising an alkyl (meth) acrylate monomer unit and an aromatic vinyl monomer unit; And C) a plasticizer having a viscosity of 700 to 10,000 cP, and the plasticizer at 0.3 to 5% by weight.

Hereinafter, the components of the thermoplastic resin composition according to an embodiment of the present invention will be described in detail.

A-1) First copolymer

The first copolymer is a graft copolymer, and includes a first conjugated diene polymer, an alkyl (meth) acrylate monomer unit, and an aromatic vinyl monomer unit.

The first copolymer may provide excellent transparency and impact resistance to the thermoplastic resin composition in synergy with the second copolymer, and may particularly impart remarkably excellent transparency.

The first conjugated diene-based polymer may have an average particle size of 0.05 to 0.2 μm, and preferably 0.07 to 0.18 μm. If it is less than the above-mentioned range, excellent impact resistance cannot be achieved, and if it exceeds the above-described range, excellent transparency cannot be achieved.

The first conjugated diene-based polymer is prepared by polymerizing 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 double bonds and single bonds are arranged over one another. have.

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 on the conjugated diene-based polymer.

The conjugated diene-based monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, piperylene, dicyclopentadiene, ethylidene noborene, and vinyl noborene, of which 1,3-butadiene Or ethylidene novolene may be preferred.

The conjugated diene-based monomer and the comonomer copolymerizable may be at least one selected from the group consisting of acrylonitrile, ethylene and propylene.

The first conjugated diene-based polymer may include polybutadiene; A copolymer comprising 1,3-butadiene units and acrylonitrile units; And it may be at least one selected from the group consisting of a copolymer comprising an ethylidene novolene unit, an ethylene unit and a propylene unit, of which polybutadiene is preferred.

The first conjugated diene-based polymer may be included in 35 to 65% by weight or 40 to 60% by weight relative to the total weight of the first copolymer, and is preferably included in 40 to 60% by weight. If the above-mentioned range is satisfied, the transparency and impact resistance of the first copolymer can be further improved.

The alkyl (meth) acrylate-based monomer unit may impart excellent transparency to the first copolymer.

The alkyl (meth) acrylate monomer units are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, and la. It may be a unit derived from one or more selected from the group consisting of uryl (meth) acrylates, of which units derived from methyl methacrylate are preferred.

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 25 to 45% by weight. Do. If the above-described range is satisfied, the transparency of the first copolymer can be further improved.

The aromatic vinyl-based monomer unit may impart processability, rigidity, and mechanical properties of the first copolymer.

The aromatic vinyl monomer unit may be a unit derived from one or more selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, of which units derived from styrene are preferred. .

The aromatic vinyl-based monomer unit may be included in 7 to 30% by weight or 10 to 25% by weight relative to the total weight of the first copolymer, and it is preferably included in 10 to 25% by weight. If the above-described range is satisfied, the processability, rigidity and mechanical properties of the first copolymer can be further improved.

The first copolymer may further include a vinyl cyanide monomer unit in order to improve chemical resistance.

The vinyl cyan monomer unit may be a unit derived from one or more selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, from which acrylonitrile Derived units are preferred.

The vinyl cyan monomer unit may be included in 0.5 to 10% by weight or 1 to 7% by weight based on the total weight of the first copolymer, and is preferably included in 1 to 7% by weight. If the above-described range is satisfied, chemical resistance can be further improved without yellowing in the first copolymer. In addition, the polymerization stability of the first copolymer may be suppressed to suppress the formation of coagulum, thereby improving the polymerization stability.

The first copolymer may have a graft ratio of 40 to 80%, more preferably 45 to 70%, and most preferably 50 to 60%. When the above-described range is satisfied, transparency of the thermoplastic resin composition may be improved. If the graft ratio is less than the above-described range, even if the refractive indexes of the first to third copolymers coincide, the transparency of the thermoplastic resin composition may be lowered. If it exceeds the above-described range, the impact strength may be lowered.

Meanwhile, the transparency of the first copolymer may be determined by a difference between the refractive index of the first conjugated diene-based polymer and the refractive index of the shell including alkyl (meth) acrylate-based monomer units and aromatic vinyl-based monomer units. That is, in order for the first copolymer to have excellent transparency, a difference between the refractive index of the first conjugated diene polymer and the refractive index of the shell may be 0.01 or less, and it is preferable that there is no difference in refractive index.

In addition, in order to realize excellent transparency of the thermoplastic resin composition, the first copolymer to the third copolymer may have a difference in refractive index of 0.01 or less, respectively. Specifically, the difference between the refractive index of the first copolymer and the second copolymer is 0.01 or less, and the difference between the refractive index of the first copolymer and the third copolymer is 0.01 or less, and the second copolymer and the third copolymer The coalescence may have a difference in refractive index of 0.01 or less. And, it is preferable that there is no difference in refractive index between the first to third copolymers.

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 preferred. If the above-mentioned range is satisfied, the transparency of the thermoplastic resin composition can be further improved by synergy with the second and third copolymers, which will be described later.

The first copolymer may have a weight average molecular weight of shell 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 preferred. If the above-mentioned range is satisfied, fluidity and impact resistance can be further improved.

The first copolymer may be included in 5 to 40% by weight or 10 to 35% by weight based on the total weight of the thermoplastic resin composition, and is preferably included in 10 to 35% by weight. When the above-described range is satisfied, transparency of the thermoplastic resin composition may be improved.

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 on a first conjugated diene-based polymer, 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.

A-2) Second copolymer

The second copolymer is a graft copolymer, and includes a second conjugated diene polymer, an alkyl (meth) acrylate monomer unit, and an aromatic vinyl monomer unit.

The second copolymer may impart excellent impact resistance and transparency to the thermoplastic resin composition, and may particularly impart remarkably excellent impact resistance.

The second conjugated diene-based polymer may have an average particle diameter of 0.23 to 0.5 μm, and preferably 0.25 to 0.48 μm. If it is less than the above-mentioned range, excellent impact resistance cannot be achieved, and if it exceeds the above-described range, excellent transparency cannot be achieved.

The second conjugated diene-based polymer may be included in an amount of 35 to 65% by weight or 40 to 60% by weight, and preferably 40 to 60% by weight, based on the total weight of the second copolymer. If the above-mentioned range is satisfied, the impact resistance and transparency of the second copolymer can be further improved.

In addition, the description of the second conjugated diene-based polymer is as described above in the description of the first conjugated diene-based polymer.

The alkyl (meth) acrylate-based monomer unit may impart excellent transparency to the second copolymer.

The type of the alkyl (meth) acrylate-based monomer unit is as described above.

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 second copolymer, and preferably 25 to 45% by weight. Do. If the above-mentioned range is satisfied, the transparency of the second copolymer can be further improved.

The aromatic vinyl-based monomer unit may impart processability, rigidity, and mechanical properties of the second copolymer.

The types of the aromatic vinyl monomer units are as described above.

The aromatic vinyl-based monomer unit may be included in 7 to 30% by weight or 10 to 25% by weight relative to the total weight of the second copolymer, and it is preferably included in 10 to 25% by weight. If the above-described range is satisfied, the processability, rigidity and mechanical properties of the second copolymer can be further improved.

The second copolymer may further include a vinyl cyanide monomer unit in order to improve chemical resistance.

The type of the vinyl cyan monomer unit is as described above.

The vinyl cyan monomer unit may be included in 0.5 to 10% by weight or 1 to 7% by weight based on the total weight of the second copolymer, and is preferably included in 1 to 7% by weight. If the above-mentioned range is satisfied, chemical resistance can be further improved without yellowing in the second copolymer. In addition, the polymerization stability of the second copolymer may be suppressed to suppress the formation of coagulum, thereby improving the polymerization stability.

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, transparency of the thermoplastic resin composition may be improved. If the graft ratio is less than the above-described range, even if the refractive indexes of the first to third copolymers coincide, the transparency of the thermoplastic resin composition may be lowered. If it exceeds the above-described range, the impact strength may be lowered.

Meanwhile, the transparency of the second copolymer includes the refractive index of the second conjugated diene-based polymer and the alkyl (meth) acrylate-based monomer unit and aromatic vinyl-based monomer unit, as described in the description of the first copolymer. 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, a difference between the refractive index of the second conjugated diene polymer and the refractive index of the shell may be 0.01 or less, and it is preferable that there is no difference in refractive index.

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 preferred. When the above-described range is satisfied, the transparency of the thermoplastic resin composition can be further improved by synergistically working with the first and third copolymers.

The second copolymer may have a weight average molecular weight of shell of 50,000 to 200,000 g / mol or 70,000 to 150,000 g / mol, of which 70,000 to 150,000 g / mol is preferred. If the above-mentioned range is satisfied, fluidity and impact resistance can be further improved.

The second copolymer, based on the total weight of the thermoplastic resin composition, may be included in 10 to 40% by weight or 13 to 35% by weight, preferably 13 to 35% by weight. If the above-mentioned range is satisfied, impact resistance of the thermoplastic resin composition may be further improved.

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 on a second conjugated diene-based polymer, of which the second copolymer has excellent impact resistance and transparency. It is preferable to prepare by emulsion polymerization so that it can be realized.

B) Third copolymer

The third copolymer is a matrix copolymer, and includes an alkyl (meth) acrylate monomer unit and a vinyl cyan monomer unit.

The third copolymer provides excellent transparency and processability to the thermoplastic resin composition.

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 preferred to include in a weight ratio of 60 to 75:25. If the above-described range is satisfied, transparency and processability of the thermoplastic resin composition can be further improved.

The types of the alkyl (meth) acrylate-based monomer units and the types of aromatic vinyl-based monomer units are as described above.

The third copolymer may further include a vinyl cyanide monomer unit in order to improve chemical resistance.

The type of the vinyl cyan monomer unit is as described above.

When the third copolymer further comprises a vinyl cyan-based monomer unit, the third copolymer is 60 to 80% by weight of the alkyl (meth) acrylate monomer unit relative to the total weight of the third copolymer; 15 to 35% by weight of the aromatic vinyl monomer unit; And 0.5 to 10% by weight of the vinyl cyan monomer unit, preferably 65 to 75% by weight of the alkyl (meth) acrylate monomer unit; 20 to 30% by weight of the aromatic vinyl monomer unit; And 1 to 10% by weight of the vinyl cyan monomer unit. If the above-described range is satisfied, chemical resistance can be further improved without causing yellowing in the third copolymer.

In the third copolymer, a difference in refractive index between each of the first copolymer and the second copolymer may be 0.01 or less, and it is preferable that there is no difference in refractive index between them.

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 preferred. If the above-mentioned range is satisfied, the transparency of the thermoplastic resin composition can be further improved by synergy with the first and second copolymers.

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 preferred. If the above-described range is satisfied, fluidity and impact resistance may be more excellent.

The third copolymer, based on the total weight of the thermoplastic resin composition, may be included in 20 to 75% by weight or 30 to 70% by weight, preferably 30 to 70% by weight. When the above-described range is satisfied, transparency and processability of the thermoplastic resin composition may be further improved.

The third copolymer may be prepared by suspension polymerization or bulk polymerization of an alkyl (meth) acrylate-based monomer and an aromatic vinyl-based monomer, and among them, a bulk polymerization capable of manufacturing a copolymer with high purity and cost reduction, In particular, it is preferable to manufacture by continuous bulk polymerization.

C) plasticizer

The plasticizer has a viscosity of 700 to 10,000 cP, and the plasticizer may impart excellent processability to the thermoplastic resin composition.

The plasticizer may have a viscosity of preferably 1,000 to 90,000 cP, more preferably 1,200 to 5,000 cP. If it is less than the above-mentioned range, the migration phenomenon of the plasticizer occurs in the thermoplastic resin composition. In addition, gas and mold deposits may occur during injection molding. When the above-mentioned range is exceeded, the workability of the thermoplastic resin composition decreases.

The plasticizer may be included in an amount of 0.3 to 5% by weight, preferably 0.5 to 4% by weight, and more preferably 1 to 4% by weight, based on the total weight of the thermoplastic resin composition. When the above-described range is satisfied, transparency and processability of the thermoplastic resin composition can be further improved, and the migration phenomenon of the plasticizer can be prevented. When included below the above-mentioned range, transparency and processability of the thermoplastic resin composition deteriorate. When included in excess of the above-described range, the transparency and impact strength of the thermoplastic resin composition is lowered. In addition, the phenomenon of plasticizer migration occurs.

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 preferred. When the above-described conditions are satisfied, the transparency of the manufactured thermoplastic resin molded article may be more excellent.

The plasticizer may include an aliphatic dicarboxylic acid-based monomer unit and an aliphatic dihydroxy-based monomer unit.

The aliphatic dicarboxylic acid-based monomer unit may be a unit derived from one or more selected from the group consisting of adipic acid, succinic acid and glutaric acid, and among these, a unit derived from adipic acid is preferred.

The aliphatic dihydroxy-based 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 one or more selected from the group consisting of 6-hexanediol, 1,4-hexanediol, 2-2-dimethyl-1,3-propanediol, of which 1,3-butanediol, 1 Preferred is a unit derived from one or more selected from the group consisting of, 2-propanediol, and 2-2-dimethyl-1,3-propanediol.

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.

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, 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 one or more 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 hexanedioic acid, polymer with 2,2-dimethyl-1,3-propanediol and 1,2-propanediol, and isononyl ester.

Among the commercially available substances, SONGCIZER ^TM P-2600 (trade name, manufacturer: Songwon Industry), SONGCIZER ^TM P-3600 (trade name, manufacturer: Songwon Industry), Palamoll ® 632 (trade name, manufacturer: BASF), Palamoll ® 638 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 Industries), Palamoll ® 638 (trade name, manufacturer: BASF), Palamoll ® 652 (trade name, manufacturer: BASF), and EDENOL ® 1225 (trade name, Manufacturer: EMERYOLECHEMICALS) is preferably one or more selected from the group consisting of.

On the other hand, it is preferable that the plasticizer is not a phthalate-based plasticizer that causes environmental problems.

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% by weight of the alkyl (meth) acrylate monomer unit; 10 to 30% by weight of the aromatic vinyl 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% by weight of the alkyl (meth) acrylate monomer unit; 15 to 25% by weight of the aromatic vinyl monomer unit; And 0.5 to 4% by weight of the plasticizer. When the above-described range is satisfied, transparency, processability, and impact resistance of the thermoplastic resin composition may be further improved.

When the thermoplastic resin composition according to an embodiment of the present invention further comprises a vinyl cyanide monomer unit, it may include 0.5 to 10% by weight or 1 to 7% by weight relative to the total weight of the thermoplastic resin composition, It is preferable to include 1 to 7% by weight. When the above-described range is satisfied, the chemical resistance of the thermoplastic resin composition is improved, and yellowing does not occur.

The thermoplastic resin composition according to an embodiment of the present invention has a graft ratio of 35 to 65% or 40 to 60%, and preferably 40 to 60%. When the above-described range is satisfied, transparency of the thermoplastic resin composition may be improved.

Thermoplastic resin composition according to an embodiment of the present invention, the flow index at 220 ℃, 15 to 45 g / 10mins or 18 to 30 g / 10mins, it is preferred that the 18 to 30 g / 10mins. If the above-described range is satisfied, the processability of the thermoplastic resin composition can be further improved.

2. Thermoplastic molded products

The thermoplastic resin molded article according to another embodiment of the present invention is made of a thermoplastic resin composition according to an embodiment of the present invention, and the impact-reinforced 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-based monomer unit and the aromatic vinyl-based monomer unit is 0.01 or less.

If the above conditions are satisfied, the transparency of the thermoplastic resin molded article can be further improved.

The thermoplastic resin molded article may have a haze of 1.3 or less, an impact strength of 7 kg.cm/cm or more, a transparency of 1.2 or less, and an impact strength of 9 kg.cm/cm or more. When the above conditions are satisfied, the transparency and impact resistance of the thermoplastic resin molded article may be further improved.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily practice. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein.

Manufacturing example  1: Preparation of A-1-1

Polybutadiene latex (polymerization method: emulsion polymerization, gel content: 90%, average particle diameter: 0.12 μm) 50 parts by weight, 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, 0.5 parts by weight of sodium alkylarylsulfonate (sodium dodecylbenzene sulfonate) 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, and sodium formaldehyde 0.1 part by weight of oxylate, 0.001 part by weight of ferrous sulfate and 0.1 part by weight of cumene hydroperoxide as an initiator were polymerized while continuously being charged at a constant rate for 5 hours at 70 ° C. After the continuous input was completed, the temperature was raised to 80 ° C, aged for 1 hour, and polymerization was terminated to obtain a graft copolymer latex. Then, 2 parts by weight of magnesium sulfate was added to the graft copolymer latex as a coagulant to agglomerate, 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 ratio of 55%.

Manufacturing example  2: Preparation of A-2-1

Polybutadiene latex (polymerization method: emulsion polymerization, gel content: 70%, average particle size: 0.3 µm) 50 parts by weight, 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, 0.5 parts by weight of sodium alkylarylsulfonate (sodium dodecylbenzene sulfonate) 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 oxidation-reduction catalyst ethylenediaminetetraacetic acid, sodium formaldehyde 0.1 parts by weight of oxylate, 0.001 parts by weight of ferrous sulfate, and 0.1 parts by weight of cumene hydroperoxide as an initiator were polymerized while continuously being charged at a constant rate for 5 hours at 70 ° C. After the continuous input was completed, the temperature was raised to 80 ° C, aged for 1 hour, and polymerization was terminated to obtain a graft copolymer latex. Then, 2 parts by weight of magnesium sulfate was added to the graft copolymer latex as a coagulant to agglomerate, 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 ratio of 45%.

Manufacturing example  3: Preparation of A-2-2

Polybutadiene latex (polymerization method: emulsion polymerization, gel content: 70%, average particle diameter: 0.3 μm) 50 parts by weight, 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, 0.5 parts by weight of sodium alkylarylsulfonate (sodium dodecylbenzene sulfonate) 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 0.1 parts by weight of sulfoxylate, 0.001 part by weight of ferrous sulfate, and 0.1 part by weight of cumene hydroperoxide were polymerized at 70 ° C. for 5 hours while being continuously charged. After the continuous input was completed, the temperature was raised to 80 ° C, aged for 1 hour, and polymerization was terminated to obtain a graft copolymer latex. Then, 2 parts by weight of magnesium sulfate was added to the graft copolymer latex as a coagulant to agglomerate, 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 ratio of 47%.

Manufacturing example  4: Preparation of B-1

70.4 parts by weight of methyl methacrylate, 24.6 parts by weight of styrene, 5 parts by weight of acrylonitrile, and a mixture of 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 is 3 hours. The reaction temperature was continuously added to the reaction tank to maintain the reaction temperature at 148 ° C. The polymerization solution discharged from the reaction tank was heated in a preliminary heating tank, unreacted monomer was volatilized in a volatilization tank, and the polymer temperature was maintained at 210 ° C to obtain a pelletized MSAN copolymer using a polymer transfer pump extrusion processor. The prepared MSAN copolymer had a refractive index of 1.516.

Example  And Comparative example

A graft copolymer, a matrix copolymer and a plasticizer were mixed at the contents shown in the table below to prepare a thermoplastic resin composition.

Experimental example  One

100 parts by weight of the thermoplastic resin composition of Examples and Comparative Examples, antioxidant (trade name: Irganox 1010, manufacturer: BASF) was 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 manner, and are listed in the following table.

① Flow index (g / 10mins): According to ASTM1238, it was performed at 220 ℃ and 10 kg.

Experimental example  2

The pellets prepared in Experimental Example 1 were injected to prepare specimens, and the physical properties of the specimens were measured in the following manner, and the results are shown in the following table.

② Haze (Haze Value,%): Transparency was measured according to ASTM1003.

③ Notched Izod Impact Strength (1/4 INCH, kg · cm / cm): Notched Izod impact strength was measured at 23 ° C. according to ASTM245 D256.

④ Migration: The specimen was placed on an oil paper in an oven at 70 ° C., and after loading 10 kg of weight, it was stored for one week, and then the change of the oil paper was examined to evaluate the performance. When the plasticizer is implemented, the color of the oil paper is changed by moistening the oil paper, so that the color change occurs because the plasticizer is deposited on the oil paper. Therefore, those without changes were indicated as OK, and those without changes were indicated as NG.

division		Comparative example	Example					Comparative example
		One	One	2	3	4	5	2	3
Graft copolymer (% by weight)	A-1-1	15	15	15	15	15	15	15	15
	A-2-1	20	20	20	20	20	20	20	20
Matrix copolymer (% by weight)	B-1	65	64.7	64.5	63	62	61	59	55
Plasticizer (% by weight)	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
Performance		-	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 rate: 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 Industry, viscosity: 2,200 cP, refractive index: 1.466, material name: polydi (2-ethylhexyl) glycol adipate)

division		Example
		6	7	8	9	10
Graft copolymer (% by weight)	A-1-1	18	15	15	27	20
	A-2-1	22	20	20	15	15
Matrix copolymer (% by weight)	B-1	57	63	63	55	62
Plasticizer (% by weight)	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
Performance		OK	OK	OK	OK	OK
A-1-1 : Graft copolymer (average particle diameter of polybutadiene: 0.12 μm, refractive index: 1.516, graft rate: 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 Industry, viscosity: 2,200 cP, refractive index: 1.466, material name: polydi (2-ethylhexyl) glycol adipate) C-2 : Palamoll® 652 (brand name, manufacturer: BASF, viscosity: 2,000 cP, refractive index: 1.465, material 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 (brand 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)

division		Comparative example
		4	5	6	7	8
Graft copolymer (% by weight)	A-1-1	18	15	18	35	18
	A-2-1	22	20	20	-	-
	A-2-2	-	-	-	-	22
Matrix copolymer (% by weight)	B-1	56	63	62	63	60
Plasticizer (% by weight)	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
Performance		OK	NG	-	OK	-
A-1-1 : Graft copolymer (average particle diameter of polybutadiene: 0.12 μm, refractive index: 1.516, graft rate: 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 Industry, viscosity: 2,200 cP, refractive index: 1.466, material name: polydi (2-ethylhexyl) glycol adipate) C-5 : GL-500 (brand name, manufacturer : LG Chemical, Refractive Index: 1.41, Viscosity 60 cP, Material 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)

It was confirmed that Examples 1 to 5 containing a plasticizer having a viscosity of 2,200 cP at 0.3 to 4 wt% had a high flow index and low haze, so that processability and transparency were improved. In addition, it was confirmed that as the content of the plasticizer increases, the flow index increases to improve processability. Meanwhile, Comparative Example 1 without plasticizer has a low flow index and high haze compared to Examples 1 to 5, so that the processability and You can see that the transparency decreases. It can be seen that Comparative Examples 2 and 3 containing 6, 10 and 10% by weight of plasticizers having a viscosity of 2,200 cP, respectively, exhibited too high a flow index and haze, low impact strength, and reduced transferability. From these results, it was confirmed that even when a plasticizer having a viscosity of 2,200 cP was used in an excessive amount, processability, transparency, impact resistance, and transferability were rather reduced.

Referring to Examples 4 and 6, it can be seen that when the content of the graft copolymer is increased, the impact strength is improved and the content of the matrix copolymer is relatively decreased, so that the processability is somewhat lowered.

It can be seen that Examples 6 to 10 including plasticizers having a viscosity of 2,200 cP, 2,000 cP, 1,200 cP, and 8,000 cP, respectively, implement excellent flow index, haze, impact strength, and performance.

On the other hand, it can be seen that Comparative Example 4 including a plasticizer having a viscosity of 60 cP and Comparative Example 5 containing a plasticizer having a viscosity of 150 cP have high haze and deteriorate transparency.

In Comparative Example 6, by containing the graft copolymer having an average particle diameter of polybutadiene of 0.12 µm in an excessive amount compared to Comparative Example 1, 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 workability is significantly lowered.

Comparative Example 7 containing 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, can be confirmed that impact strength is significantly reduced.

In Comparative Example 8, which does not contain a plasticizer and has an average particle diameter of polybutadiene of 0.3 µm and a refractive index of 1.53, Comparative Example 8 is an excess of a graft copolymer having an average particle diameter of polybutadiene of 0.12 µm. By including, it was possible to lower haze, but it was difficult to realize excellent transparency. In addition, since it does not contain a plasticizer, it was confirmed that the flow index was lowered and the workability was significantly reduced.

Claims (14)

1. 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 has a first copolymer having an average particle size of 0.05 to 0.2 μm. ; A-2) 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 a second copolymer having an average particle diameter of 0.23 to 0.5 μm. ; B) a third copolymer comprising an alkyl (meth) acrylate monomer unit and an aromatic vinyl monomer unit; And

   C) a plasticizer having a viscosity of 700 to 10,000 cP,

   Thermoplastic resin composition comprising the plasticizer in an amount of 0.3 to 5% by weight.
2. The method according to claim 1,

   C) The plasticizer is a thermoplastic resin composition having a refractive index of 1.45 or more.
3. The method according to claim 1,

   C) The plasticizer is a thermoplastic resin composition comprising an aliphatic dicarboxylic acid-based monomer unit and an aliphatic dihydroxy-based monomer unit.
4. The method according to claim 3,

   C) The plasticizer further comprises at least one member selected from the group consisting of aliphatic ester monomer units and acetate monomer units.
5. The method according to claim 1,

   The A-1) the first copolymer is a thermoplastic resin composition having a graft ratio of 40 to 80%.
6. The method according to claim 1,

   The A-2) the second copolymer is a thermoplastic resin composition having a graft rate of 35 to 70%.
7. The method according to claim 1,

   Each of the first to third copolymers is a thermoplastic resin composition having a difference in refractive index of 0.01 or less.
8. The method according to claim 1,

   The first to third copolymers are thermoplastic resin compositions each further comprising a vinyl cyanide monomer unit.
9. The method according to claim 1,

   The thermoplastic resin composition

   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

   The C) thermoplastic resin composition comprising 0.3 to 5% by weight of a plasticizer.
10. The method according to claim 1,

    The thermoplastic resin composition

    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% by weight of the alkyl (meth) acrylate monomer unit;

    10 to 30% by weight of the aromatic vinyl monomer unit; And

    A thermoplastic resin composition comprising 0.3 to 5% by weight of the plasticizer.
11. The method according to claim 1,

    The thermoplastic resin composition is a thermoplastic resin composition having a graft rate of 35 to 65%.
12. The method according to claim 1,

    The thermoplastic resin composition is a thermoplastic resin composition having a flow index of 220 to 15 to 45 g / 10mins.
13. It is made of a thermoplastic resin composition according to any one of claims 1 to 12,

    Including an impact reinforcement area and a matrix area,

    The impact reinforcement region includes at least one member selected from the group consisting of the first conjugated diene-based polymer and the second conjugated diene-based polymer,

    The matrix region includes the alkyl (meth) acrylate monomer unit and the aromatic vinyl monomer unit,

    The impact-reinforcement region and the matrix region are thermoplastic resin molded products having a refractive index difference of 0.01 or less.
14. The method according to claim 13,

    The thermoplastic resin molded article is a thermoplastic resin molded article having a haze of 1.3 or less and an impact strength of 7 kg · cm / cm or more.