KR102494271B1 - Thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a graft copolymer comprising a unit derived from an alkyl (meth)acrylate-based monomer, a unit derived from an aromatic vinyl-based monomer, and a unit derived from a vinyl cyan-based monomer; a matrix copolymer comprising a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyan-based monomer; polyester-based elastomers; and a thermoplastic resin composition comprising a polymer having a syndiotactic structure and containing a unit derived from an aromatic vinyl-based monomer, wherein the thermoplastic resin composition can realize low gloss properties and excellent mechanical properties while maintaining basic physical properties.

Description

Thermoplastic resin composition {THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a thermoplastic resin composition, and relates to a thermoplastic resin composition that maintains basic physical properties, implements low gloss properties, and has excellent mechanical properties and colorability.

Graft copolymers containing alkyl (meth)acrylate monomer-derived units, aromatic vinyl-based monomer-derived units, and vinyl cyan-based monomer-derived units have excellent weatherability and aging resistance, so they can be used in automobiles, ships, leisure goods, building materials, and horticulture. It is used in various fields such as dragons.

Most of the products made of the graft copolymers described above are glossy and exhibit surface gloss within the range of high gloss (gloss at 75° to 90°) or medium gloss (gloss at 60° to 70°). .

However, in recent years, as the level of emotional quality demanded by users has increased, the demand for low-gloss or matte products has increased to create a more elegant atmosphere. There is a trend to directly use a thermoplastic resin composition that implements low gloss or matte properties.

In order to prepare a thermoplastic resin composition that implements low gloss or matte properties, a method of improving the low gloss properties by adding rubber particles or a matting agent has been disclosed. There is a problem with a sharp drop in strength.

Accordingly, research on a thermoplastic resin composition capable of implementing low gloss and excellent impact strength continues.

KR2016-0057601A

An object of the present invention is to provide a thermoplastic resin composition that implements low gloss properties and has excellent mechanical properties and colorability while maintaining basic physical properties.

In order to solve the above problems, the present invention is a graft copolymer comprising an alkyl (meth) acrylate-based monomer-derived unit, an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit; a matrix copolymer comprising a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyan-based monomer; polyester-based elastomers; and a polymer having a syndiotactic structure and including a unit derived from an aromatic vinyl-based monomer.

The thermoplastic resin composition according to the present invention maintains basic physical properties such as weather resistance and processability, implements low gloss properties, and has excellent mechanical properties and colorability.

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

Terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain his or her invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

In the present invention, the average particle diameter of the seed, core, and graft copolymer can be measured using a dynamic light scattering method, and in detail, it can be measured using Nicomp 380 HPL equipment (product name, manufacturer: Nicomp). can

In this specification, the average particle diameter may mean the arithmetic mean particle diameter in the particle size distribution measured by the dynamic light scattering method, and in detail, it may mean the scattering intensity average particle diameter.

In the present invention, the graft rate of the graft copolymer can be calculated by the following formula.

Graft rate (%): weight of grafted monomer (g)/rubber weight (g) Х 100

Weight (g) of grafted monomer: weight of insoluble matter (gel) after dissolving 1 g of graft copolymer in 30 g of acetone and centrifuging

Rubber weight (g): weight of C ₄ to C ₁₀ alkyl (meth)acrylate-based monomer theoretically added during the preparation of graft copolymer powder

In the present invention, the weight average molecular weight of the matrix copolymer, elastomer, and polymer can be measured as a relative value to a standard polystyrene (PS) sample through gel permeation chromatography using tetrahydrofuran as an eluent.

In the present invention, the stereoregularity of the polymer can be measured by nuclear magnetic resonance spectroscopy (Carbon-13 nuclear magnetic resonance: ¹³ C-NMR).

In the present invention, the rubber content in the thermoplastic resin composition can be measured by Agilent's 660-IR based on Fourier Transform Infrared Spectroscopy (FT-IR).

In the present invention, the polymer should be understood as a concept including both a homopolymer formed by polymerization of one type of monomer and a copolymer formed by polymerization of two or more types of monomers.

In the present invention, syndiotactic means a structure in which one repeating unit and the substituents (R) of the adjacent repeating unit are arranged on opposite sides of each other.

If explained using the Fisher projection, when the polymer obtained from styrene has a syndiotactic structure, it may have the following structure.

(R: phenyl group)

1. Thermoplastic resin composition

A thermoplastic resin composition according to an embodiment of the present invention includes: 1) a graft copolymer including an alkyl (meth)acrylate-based monomer-derived unit, an aromatic vinyl-based monomer-derived unit, and a vinyl cyan-based monomer-derived unit; 2) a matrix copolymer comprising a unit derived from an aromatic vinyl monomer and a unit derived from a vinyl cyan monomer; 3) polyester-based elastomers; and 4) a thermoplastic resin composition including a polymer having a syndiotactic structure and including a unit derived from an aromatic vinyl-based monomer.

In addition, the thermoplastic resin composition according to an embodiment of the present invention may further include 5) a plasticizer.

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

One) graft copolymer

(One) graft copolymer

The graft copolymer includes a unit derived from an alkyl (meth)acrylate-based monomer, a unit derived from an aromatic vinyl-based monomer, and a unit derived from a vinyl cyan-based monomer.

The graft copolymer may impart excellent weatherability and mechanical properties to the thermoplastic resin composition.

The graft copolymer may include a core made of a crosslinked polymer including at least one member selected from the group consisting of an alkyl (meth)acrylate-based monomer-derived unit, an aromatic vinyl-based monomer-derived unit, and a vinyl cyanogen-derived unit-derived unit; and a shell including an aromatic vinyl-based monomer-derived unit and a vinyl cyan-based monomer-derived unit grafted onto the core-shell structure.

The graft copolymer may have an average particle diameter of 100 to 600 nm, 250 to 600 nm, or 350 to 500 nm of the core, preferably 350 to 500 nm.

If the above range is satisfied, the low gloss property and impact resistance of the thermoplastic resin composition can be further improved.

The core of the graft copolymer may be 15 to 45% by weight, 20 to 40% by weight, or 25 to 35% by weight based on the total weight of the thermoplastic resin composition, of which 25 to 35% by weight is preferable.

If the above conditions are satisfied, the weather resistance and mechanical properties of the thermoplastic resin composition can be further improved.

The alkyl (meth)acrylate-based monomer-derived unit may be a C ₁ to C ₁₅ alkyl (meth)acrylate-based monomer-derived unit.

The alkyl (meth) acrylate-based monomer-derived unit is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, )acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate and decyl (meth)acrylate It may be a unit derived from one or more monomers selected from the group consisting of, among them, a unit derived from butyl acrylate is preferred.

The alkyl (meth)acrylate-based monomer-derived unit may be included in 30 to 70% by weight, 40 to 60% by weight, or 45 to 55% by weight based on the total weight of the graft copolymer, of which 45 to 55 It is preferably included in weight percent.

When the above range is satisfied, weather resistance, low gloss properties, colorability and mechanical properties of the graft copolymer may be further improved.

The unit derived from the aromatic vinyl monomer is 1 selected from the group consisting of styrene, α-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, p-bromo styrene, o-bromo styrene and p-chloro styrene It may be a unit derived from more than one kind of monomer, among which a unit derived from styrene is preferable.

The unit derived from the aromatic vinyl-based monomer may be included in 20 to 60% by weight, 20 to 40% by weight, or 25 to 35% by weight, of which 25 to 35% by weight, based on the total weight of the graft copolymer it is desirable to be

When the above range is satisfied, not only the processability of the graft copolymer can be further improved, but also the compatibility between the graft copolymer and the matrix copolymer can be improved, so that the graft copolymer can be more uniformly dispersed in the thermoplastic resin composition.

The vinyl cyan-based monomer-derived unit may be a unit derived from at least one monomer selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, and among them, a unit derived from acrylonitrile is preferable. do.

The unit derived from the vinyl cyan-based monomer may be included in an amount of 5 to 40 wt% or 10 to 30 wt%, preferably 15 to 25 wt%, based on the total weight of the graft copolymer.

When the above range is satisfied, not only the chemical resistance and stiffness of the graft copolymer can be further improved, but also the compatibility between the graft copolymer and the matrix copolymer is improved, so that the graft copolymer can be more uniformly dispersed in the thermoplastic resin composition. there is.

The graft copolymer may have a graft ratio of 20 to 100%, 40 to 80%, or 45 to 60%, of which 45 to 60% is preferable.

When the above range is satisfied, the mechanical properties of the graft copolymer, that is, impact strength and mechanical properties, can be further improved.

(2) graft Copolymer manufacturing method

preparing a seed by adding at least one selected from the group consisting of an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, and a vinyl cyan-based monomer to the graft copolymer; In the presence of the seed, preparing a core by introducing an alkyl (meth) acrylate-based monomer and polymerizing; In the presence of the core, it may be prepared by a manufacturing method comprising the step of preparing a cell by adding and polymerizing an aromatic vinyl monomer and a vinyl cyan monomer.

In the seed preparation step, one or more selected from the group consisting of an initiator, an emulsifier, a crosslinking agent, a grafting agent, an electrolyte, and water may be further added.

The initiator may be a radical initiator, and the initiator may be an inorganic peroxide such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium superphosphate, or hydrogen peroxide; t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octa organic peroxides such as noyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide, and t-butyl peroxyisobutyrate; It may be at least one selected from the group consisting of azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and methyl azobisisobutyric acid (butyric acid), among which, Inorganic peroxides are preferred, and potassium persulfate is more preferred.

The emulsifier may contain at least one selected from the group consisting of metal salts of alkyl sulfosuccinic acid, metal salts of alkyl sulfates, metal salts of rosin acids, and metal salts of dimer acids, of which metal salts of alkyl sulfates are preferably added.

The alkyl sulfosuccinic acid metal salt is composed of sodium dicyclohexylsulfosuccinate, sodium dihexylsulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, di-2-ethylhexylsulfosuccinic acid potassium salt and di-2-ethylhexyl sulfosuccinic acid It may be one or more selected from the group.

The alkyl sulfate ester metal salt may be at least one selected from the group consisting of sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate and potassium octadecyl sulfate.

The metal salt of rosin acid may be at least one selected from the group consisting of potassium salt of rosin acid and sodium salt of rosin acid.

The crosslinking agent is ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, divinylbenzene, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, meth)acrylate, 1,3-butadiol dimethacrylate, hexanediol ethoxylate diacrylate, hexanediol propoxylate di(meth)acrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxy Rate di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, trimethylolmethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylpropane ethoxylate tri(meth)acrylate from the group consisting of acrylate, trimethylpropane propoxylate tri(meth)acrylate, pentaerythritol ethoxylate tri(meth)acrylate, pentaerythritol propoxylate tri(meth)acrylate, vinyltrimethoxysilane It may be one or more, of which ethylene glycol dimethacrylate is preferred.

The grafting agent may be at least one selected from the group consisting of allyl methacrylate, triallyl isocyanurate, diallylamine and triallylamine, of which allyl methacrylate is preferred.

The electrolyte is KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₄ , Na ₂ S ₂ O ₇ , K ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ It may be one or more selected from the group consisting of PO ₄ or Na ₂ HPO ₄ , KOH, and NaOH, and among these, KOH is preferred.

In the preparation step of the core, at least one selected from the group consisting of an initiator, an emulsifier, a crosslinking agent, a grafting agent, and water may be further added, and in order to easily control the core having heat removal and an appropriate average particle diameter during polymerization, alkyl It may be continuously introduced at a constant rate together with the (meth)acrylate-based monomer.

The type of the emulsifier is as described above, and it is preferable that an alkyl sulfate ester metal salt is added.

The type of the initiator is as described above, and among these, an inorganic peroxide is preferable and potassium persulfate is more preferable.

The type of the crosslinking agent is as described above.

The type of the grafting agent is as described above.

In the step of preparing the shell, at least one selected from the group consisting of an initiator, an emulsifier, a molecular weight modifier, and water may be further added, and the graft polymerization may be stably performed and the internal structure may be uniformly prepared. Aromatic It may be continuously introduced at a constant rate together with the vinyl-based monomer and the vinyl cyan-based monomer.

The type of the initiator is as described above, and among these, organic peroxides are preferred, and cumene hydroperoxide is more preferred.

The type of the emulsifier is as described above, and it is preferable that a metal salt of rosin acid is added.

The molecular weight regulator is a-methylstyrene dimer; mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and methylene bromide; sulfur-containing compounds such as tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylxantogen disulfide. Preferably, it may be t-dodecyl mercaptan.

The graft copolymer may be prepared in the form of latex by emulsion polymerization and then in the form of powder through aggregation, aging, washing and drying processes.

2) matrix copolymer

The matrix copolymer contains a unit derived from an aromatic vinyl monomer and a unit derived from a vinyl cyan monomer.

The matrix copolymer may impart excellent processability, mechanical properties and chemical resistance to the thermoplastic resin composition.

The matrix copolymer may include the aromatic vinyl monomer-derived unit and the vinyl cyan-based monomer-derived unit in a weight ratio of 60:40 to 90:10, 65:35 to 85:15, or 70:30 to 80:20, , Among them, it is preferable to include them in a weight ratio of 70:30 to 80:20.

When the above range is satisfied, the matrix copolymer may have better chemical resistance and processability.

Types of the aromatic vinyl-based monomer-derived unit and the vinyl cyan-based monomer-derived unit are as described above.

The matrix copolymer may have a weight average molecular weight of 50,000 to 250,000 g/mol, 80,000 to 220,000 g/mol, or 110,000 to 190,000 g/mol, of which 110,000 to 190,000 g/mol is preferable.

When the above range is satisfied, mechanical properties and chemical resistance of the thermoplastic resin composition may be further improved.

The matrix copolymer may be prepared by suspension polymerization or bulk polymerization.

The thermoplastic resin composition may include the graft copolymer and the matrix copolymer in a weight ratio of 85:15 to 50:50, 80:20 to 50:50, or 75:25 to 50:50, of which 75: It is preferably included in a weight ratio of 25 to 50:50.

When the above range is satisfied, excellent processability and mechanical properties can be imparted to the thermoplastic resin composition.

3) polyester elastomer

(One) polyester elastomer

The polyester-based elastomer may impart low whitening properties, excellent colorability, processability, aging resistance, and chemical resistance to the thermoplastic resin composition.

The polyester-based elastomer may include a hard part including a unit derived from an aromatic or aliphatic dicarboxylic acid or an ester thereof, and a unit derived from an aliphatic diol, and a soft part including a unit derived from polyalkylene oxide.

The aromatic or aliphatic dicarboxylic acid-derived units are terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid and 1,4-naphthalene dicarboxylic acid. It may be a unit derived from at least one selected from the group consisting of cyclohexane dicarboxylic acid, and among these, a unit derived from terephthalic acid is preferable.

The unit derived from the ester of the aromatic or aliphatic dicarboxylic acid is dimethyl terephthalate, dimethyl isophthalate, dimethyl 2,6-naphthalene dicarboxylate, dimethyl 1,5-naphthalene dicarboxylate, dimethyl 1,4-naphthalene dicarboxylate, It may be at least one derived unit selected from the group consisting of reboxylate and dimethyl 1,4-cyclohexane dicarboxylate, and among these, a unit derived from dimethyl terephthalate is preferable.

The unit derived from the aromatic or aliphatic dicarboxylic acid or its ester may be included in 25 to 65% by weight or 30 to 60% by weight based on the total weight of the polyester-based elastomer, of which 30 to 60% by weight is preferred. do.

The aliphatic diol-derived unit may be a unit derived from an aliphatic diol having a molecular weight of 300 g/mol or less.

The aliphatic diol-derived units include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentadiol, 1,6-hexanediol and 1,4-propanediol. It may be one or more derived units selected from the group consisting of cyclohexanedimethanol, and among them, a unit derived from 1,4-butanediol is preferable.

The aliphatic diol-derived unit may be included in 20 to 45% by weight or 25 to 40% by weight based on the total weight of the polyester-based elastomer, of which 25 to 40% by weight is preferable.

The polyalkylene oxide-derived unit may be an aliphatic polyether-derived unit.

The polyalkylene oxide-derived unit is polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, copolymers of ethylene oxide and propylene oxide, ethylene oxide addition polymers of polypropylene glycol, and ethylene oxide and tetrahydrofuran. It may be a unit derived from at least one selected from the group consisting of copolymers, and among these, a unit derived from an ethylene oxide addition polymer of polytetramethylene glycol or polypropylene glycol is preferable.

The polytetramethylene glycol may have a number average molecular weight of 600 to 3,000 g/mol, 1,000 to 2,500 g/mol, or 1,800 to 2,200 g/mol, preferably 1,800 to 2,200 g/mol.

The ethylene oxide addition polymer of the polypropylene glycol may be polypropylene glycol end-capped with ethylene oxide, and may have a weight average molecular weight of 2,000 to 3,000 g/mol.

The polyalkylene oxide-derived unit may be included in an amount of 10 to 50% by weight or 15 to 45% by weight based on the total weight of the thermoplastic polyester elastomer. If the above range is satisfied, flexibility, heat resistance and usability of the polyester-based elastomer may be further improved.

The polyester-based elastomer may have a Shore D hardness of 35 to 55 or 40 to 50 according to ASTM D2240, of which 40 to 50 is preferable.

When the above range is satisfied, extrusion processing and molding of the thermoplastic resin composition may be facilitated and chemical resistance may be improved. In addition, the tensile strength, flexural strength, and impact strength of the thermoplastic resin composition can be remarkably improved, and whitening characteristics of the thermoplastic resin composition can be improved.

If it is less than the above-mentioned range, the tensile strength and flexural strength of the thermoplastic resin composition may be significantly reduced, and the whitening property may be significantly reduced.

If the above range is exceeded, the impact strength of the thermoplastic resin composition may be significantly reduced.

The polyester-based elastomer may have a flow index (230 ° C., 2.16 kg) of 1 to 15 g / 10 mins or 3 to 10 g / 10 mins according to ASTM D1238, of which 3 to 10 g / 10 mins desirable.

When the above range is satisfied, excellent extrusion processability and moldability can be imparted to the thermoplastic resin composition, and chemical resistance can be improved.

If the above range is not satisfied, workability may be deteriorated.

The polyester-based elastomer may be included in 1 to 20 parts by weight or 5 to 15 parts by weight based on 100 parts by weight of the graft copolymer and the matrix copolymer, preferably 5 to 15 parts by weight. .

If the above range is satisfied, the whitening property, colorability and aging resistance may be further improved.

The polyester-based elastomer may be directly prepared by the method described below, or KEYFLEX BT 2140D from LG Chem may be used among commercially available materials.

(2) A method for producing a polyester-based elastomer.

On the other hand, the polyester-based elastomer is produced by: ① preparing a polyester-based elastomer precursor by melt-polymerizing an aromatic or aliphatic dicarboxylic acid or an ester-forming derivative thereof, an aliphatic diol, and a polyalkylene oxide; and ② preparing a polyester-based elastomer by solid-state polymerization of the polyester-based elastomer precursor.

Hereinafter, each step of the manufacturing method of the polyester-based elastomer will be described in detail.

① Preparing a polyester-based elastomer precursor

First, aromatic or aliphatic dicarboxylic acids or their esters, aliphatic diols and polyalkylene oxides may be prepared as starting materials.

The aromatic or aliphatic dicarboxylic acid or its ester may be added in an amount of 25 to 65% by weight or 30 to 60% by weight, of which 30 to 60% by weight is preferred, based on the total weight of the starting material. If the above range is satisfied, the reaction balance is excellent and melt polymerization can be smoothly performed.

Specific examples of the aromatic or aliphatic dicarboxylic acid or its ester are as described above.

The aliphatic diol may be added in an amount of 20 to 45% by weight or 25 to 40% by weight based on the total weight of the starting material. If the above range is satisfied, the reaction balance is excellent and melt polymerization can be smoothly performed.

Specific examples of the aliphatic diol are as described above.

The polyalkylene oxide may be added in an amount of 10 to 50% by weight or 15 to 45% by weight, based on the total weight of the starting material, and preferably 15 to 45% by weight. If the above range is satisfied, flexibility, heat resistance and usability of the polyester-based elastomer may be further improved.

Specific examples of the polyalkylene oxide are as described above.

Subsequently, melt polymerization may be initiated after first adding a catalyst to the starting material and raising the temperature to 140 to 215 °C.

The catalyst may be titanium butoxide.

When the melt polymerization is initiated, a transesterification reaction may be performed between the starting materials, whereby oligomers, preferably bis(4-hydroxybutyl) terephthalate (BHBT) oligomers, may be prepared. The transesterification reaction may be performed for 1 to 3 hours or 1 hour 30 minutes to 2 hours 30 minutes.

Subsequently, after the second addition of a catalyst to the oligomer, the temperature is raised to 215 to 245 ° C., and then a polycondensation reaction may be performed while reducing the pressure from 760 torr to 0.3 torr, and a polyester-based elastomer precursor is produced due to the polycondensation reaction. It can be.

The polycondensation reaction may be performed for 1 hour to 3 hours or 1 hour 30 minutes to 2 hours 30 minutes.

The polyester-based elastomer precursor may have a flow index (230 ° C., 2.16 kg) of 15 to 25 g / 10 min or 18 to 22 g / 10 min according to ASTM D1238.

Subsequently, the polyester-based elastomer precursor may be discharged in the form of a strand under nitrogen pressure and pelletized to produce a polyester-based elastomer precursor in the form of a pellet.

Meanwhile, during the melt polymerization, a branching agent may be further added to improve the melt viscosity and melt tension of the polyester-based elastomer.

The branching agent may be at least one selected from the group consisting of glycerol, pentaerythritol, trimellitic anhydride, trimellitic acid, trimethylol propane and neopentyl glycol, among which trimellitic anhydride is preferred. .

The branching agent may be included in an amount of 0.05 to 0.1% by weight based on 100 parts by weight of the starting material. When the above-mentioned range is satisfied, the melt viscosity and polymerization degree of the polyester-based elastomer are appropriate, so that the melt polymerization reaction can be easily controlled and the polyester-based elastomer precursor can be easily discharged to the outside of the reactor.

② Manufacturing step of polyester-based elastomer

Subsequently, a polyester-based elastomer may be prepared by solid state polymerization of the polyester-based elastomer precursor.

The solid-state polymerization may be carried out for 10 to 24 hours after the polyester-based elastomer precursor is introduced into a solid-state polymerization reactor at 140 to 200 ° C. under an inert atmosphere while gradually reducing the pressure to a high vacuum.

The solid-state polymerization reactor may be a vessel vacuum dryer connected to a rotatable high vacuum pump, and the inert atmosphere may be a nitrogen atmosphere.

4) polymers

The polymer contains units derived from aromatic vinyl monomers and has a syndiotactic structure.

The polymer has a crystalline structure due to the syndiotactic structure, and due to this structure, low gloss properties can be imparted to the thermoplastic resin composition.

If the polymer has an atactic structure or an isotatic structure, it has an amorphous structure rather than a crystalline structure, and thus cannot impart low gloss characteristics to the thermoplastic resin composition.

The aromatic vinyl-based monomer-derived unit may be a unit derived from at least one selected from the group consisting of styrene, halogen-substituted styrene, alkyl-substituted styrene, alkoxy-substituted styrene, aryl-substituted styrene, and benzoic acid ester styrene.

The halogenated styrene may be at least one selected from the group consisting of fluoro styrene, chloro styrene, and bromo styrene.

The alkyl-substituted styrene may be at least one selected from the group consisting of α-methyl styrene, p-methyl styrene, p-ethyl styrene, p-t-butyl styrene, 2,4-dimethyl styrene, and 4-cyclohexyl styrene.

The alkoxy-substituted styrene may be at least one selected from the group consisting of methoxy styrene, ethoxy styrene, and 4-t-butoxy styrene.

The aryl-substituted styrene may be at least one selected from the group consisting of 2-vinylbiphenyl, 3-phenylstyrene, and p-phenylstyrene.

The benzoate ester styrene may have a structure in which an olefin is attached to an end of a benzoate group.

Among them, the unit derived from the aromatic vinyl-based monomer is preferably a unit derived from styrene.

Meanwhile, the polymer may be syndiotactic polystyrene or a derivative thereof.

The polymer may further include at least one selected from the group consisting of a unit derived from a maleic acid monomer, a unit derived from a carboxylic acid monomer, and a unit derived from an ester monomer of (meth)acrylic acid, in addition to units derived from an aromatic vinyl monomer.

The maleic acid-based monomer-derived unit may be a unit derived from at least one selected from the group consisting of maleic anhydride, maleic acid, maleic acid monoester, and maleic diester. Among them, maleic anhydride and units derived from maleic acid are preferred.

The unit derived from the carboxylic acid-based monomer may be a unit derived from carboxylic acid and fumaric acid.

The unit derived from the ester-based monomer of (meth)acrylic acid may be a unit derived from glycidyl methacrylate.

The copolymers are syndiotactic polystyrene-maleic anhydride (sPS-MAH), carboxyl-terminated syndiotactic polystyrene, maleic acid-syndiotactic polystyrene, fumaric acid-syndiotactic polystyrene, and glycidylmethacrylate-synthetic polystyrene. It may be at least one selected from the group consisting of orthotic polystyrene.

The polymer or copolymer may have stereoregularity of 90% or more, 97% or more, or 99% or more, of which 99% or more is preferable.

When the above conditions are satisfied, low gloss characteristics of the thermoplastic resin composition may be further improved.

The polymer or copolymer may have a melting temperature of 240 to 300 °C or 260 to 280 °C, of which 260 to 280 °C is preferred.

When the above conditions are satisfied, low gloss characteristics of the thermoplastic resin composition may be further improved.

On the other hand, the melting temperature can be measured by differential scanning calorimetry (Differential Scanning Calorimeter).

The polymer may be included in an amount of 0.1 to 7 parts by weight or 1 to 5 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the graft copolymer and the matrix copolymer.

When the above range is satisfied, the low gloss property of the thermoplastic resin composition may be further improved.

The polymer may be prepared directly or use XAREX from Idemitsu Kosan among commercially available materials.

5) plasticizer

The plasticizer may impart low whitening properties and excellent processability to the thermoplastic resin composition.

The plasticizer may be a phthalate-based plasticizer, and may be at least one selected from the group consisting of diisopropyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, and butylbenzyl phthalate. Among them, diisopropyl phthalate is preferred.

The plasticizer may be included in 1 to 20 parts by weight, 2 to 15 parts by weight, or 3 to 10 parts by weight, based on 100 parts by weight of the sum of the graft copolymer and the matrix copolymer, of which 3 to 10 parts by weight it is desirable

When the above range is satisfied, processability of the thermoplastic resin composition may be further improved.

On the other hand, the thermoplastic resin composition according to an embodiment of the present invention is an anti-drip agent, a flame retardant, an antibacterial agent, an antistatic agent, a release agent, a heat stabilizer, a UV stabilizer, an inorganic additive, a lubricant, an antioxidant, a light stabilizer, a pigment, a dye, and an inorganic filler. It may further include one or more additives selected from the group consisting of.

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

Example and comparative example

The specifications of the components used in the following Examples and Comparative Examples are as follows.

(A): Graft copolymer: acrylic graft copolymer (butyl acrylate-derived unit: 50% by weight, styrene-derived unit: 30% by weight, acrylonitrile-derived unit 20% by weight, average particle diameter of core: 500 nm) was used.

(B) Matrix copolymer: LG Chem's 90HR (a copolymer of styrene and acrylonitrile, weight average molecular weight: 150,000 g/mol)

(C) Polyester-based elastomer: KEYFLEX BT2140D from LG Chem was used.

(D) Polymer: Idemitsu Kosan Co., Ltd.'s XAREC ^TM (syndiotactic polystyrene, stereoregularity: ≧99%) was used.

A thermoplastic resin composition was prepared by mixing and stirring the above components according to the amounts shown in [Table 1] below.

Experimental example One

In the thermoplastic resin compositions of Examples and Comparative Examples, 5 parts by weight of diisopropyl phthalate (trade name, manufacturer: LG Chem) as a plasticizer, 0.5 parts by weight of EBS resin (trade name, manufacturer: Suneon Chemical) as a lubricant, and Irgranox 1076 (trade name) as an antioxidant , Manufacturer: BASF) 0.4 parts by weight, Irgrafos 168 (trade name, manufacturer: BASF) 0.4 parts by weight, UV stabilizer Tinuvin 770 (trade name, manufacturer: BASF) 1 part by weight, Sunsorb 329 (trade name, manufacturer: Sunfine Global) 1 The mixture was mixed by weight, put into an extrusion kneader (cylinder temperature: 280 ° C.), and extruded to prepare pellets. The physical properties of the pellets were evaluated by the method described below, and the results are shown in [Table 1].

① Rubber content (% by weight): Measured with Agilent's 660-IR based on Fourier Transform Infrared Spectroscopy (FT-IR).

② Flow index (g / 10 mins): measured according to ASTM D1238.

Experimental example 2

A specimen was prepared by injecting the pellet prepared in Experimental Example 1. The physical properties of the specimen were evaluated by the method described below, and the results are shown in [Table 1].

③ Hardness: measured according to ASTM D785.

④ Surface gloss (%): measured according to ASTM D528 at 45 °.

⑤ Impact strength (1/4 In, kg cm/cm): Measured according to ASTM D256.

⑥ Flexural strength (kg/cm2): Measured according to ASTM D790.

⑦ Tensile strength (kg/cm2): Measured according to ASTM D638.

division Example comparative example One 2 3 4 5 6 One 2 3 4 (A) graft copolymer (parts by weight) 50 70 50 50 50 50 50 50 70 70 (B) matrix copolymer (parts by weight) 50 30 50 50 50 50 50 50 30 30 (C) polyester elastomer (parts by weight) 5 5 10 15 20 5 - 5 - 5 (D) polymer (parts by weight) 3 3 3 3 3 5 3 - 3 - rubber content 25 35 25 25 25 25 25 25 35 35 liquidity index 12 12 21 20 24 12 8 13 One 11 Hardness 70 45 53 30 16 72 80 71 42 46 surface gloss 35 35 35 35 34 25 35 96 34 72 impact strength 20 34 20 32 34 12 10 46 20 40 tensile strength 300 162 210 175 160 304 330 300 200 190 flexural strength 485 250 290 257 230 487 500 480 300 290

Referring to Table 1, it was confirmed that Examples 1 to 6 had adequate flow index, hardness, surface gloss, impact strength, tensile strength and flexural strength.

Referring to Example 1 and Example 3 to Example 5, it was confirmed that as the content of the polyester-based elastomer increased, the hardness decreased and the impact strength improved.

Referring to Examples 1 and 6, it was confirmed that as the content of the polymer increased, the low gloss property improved and the impact strength decreased.

Referring to Example 1, Example 2, Comparative Example 1 and Comparative Example 3, it was confirmed that the flow index and impact strength were lowered when the polyester-based elastomer was not included.

Referring to Example 1, Example 2, Comparative Example 2, and Comparative Example 4, it was confirmed that the low gloss property could not be implemented unless the polymer was included.

Claims (10)

graft copolymers containing units derived from alkyl (meth)acrylate-based monomers, units derived from aromatic vinyl-based monomers, and units derived from vinyl cyan-based monomers;
a matrix copolymer comprising a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyan-based monomer;
polyester-based elastomers; and
A polymer containing a unit derived from an aromatic vinyl-based monomer and having a syndiotactic structure;
Based on 100 parts by weight of the graft copolymer and the matrix copolymer,
A thermoplastic resin composition comprising 1 to 3 parts by weight of the polymer.
The method of claim 1,
The graft copolymer is a thermoplastic resin composition having an average particle diameter of 100 to 600 nm of the core.
The method of claim 1,
The graft copolymer is
With respect to the total weight of the graft copolymer,
30 to 70% by weight of units derived from the alkyl (meth)acrylate-based monomer;
20 to 60% by weight of units derived from the aromatic vinyl-based monomer; and
The thermoplastic resin composition comprising 5 to 40% by weight of the unit derived from the vinyl cyan-based monomer.
The method of claim 1,
The thermoplastic resin composition of claim 1, wherein the matrix copolymer has a weight average molecular weight of 50,000 to 250,000 g/mol.
The method of claim 1,
The thermoplastic resin composition of which the polymer has a stereoregularity of 90% or more.
The method of claim 1,
The thermoplastic resin composition of which the polymer has a stereoregularity of 97% or more.
The method of claim 1,
The thermoplastic resin composition is
Based on 100 parts by weight of the graft copolymer and the matrix copolymer,
A thermoplastic resin composition comprising 1 to 20 parts by weight of the elastomer.
The method of claim 1,
The thermoplastic resin composition is
Based on 100 parts by weight of the graft copolymer and the matrix copolymer,
A thermoplastic resin composition comprising 5 to 15 parts by weight of the elastomer.
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