CN115335454B - Thermoplastic resin composition, method for preparing the same, and molded article comprising the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, a method for preparing the thermoplastic resin composition, and a molded article comprising the thermoplastic resin composition. More specifically, the thermoplastic resin composition comprises a polycarbonate resin having a limited melt flow index, a polyorganosiloxane-polycarbonate resin, a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer, a polyester resin, and a resin containing an epoxy group in a predetermined weight ratio. The thermoplastic resin composition of the present invention has excellent mechanical properties, moldability, heat resistance and friction noise resistance.

Description

Thermoplastic resin composition, method for preparing the same, and molded article comprising the same

Technical Field

Cross reference to related applications

The present application claims priority from korean patent application No.10-2020-0173178 filed in the korean intellectual property office on 11 th 12 th 2020 and korean patent application No.10-2021-0175415 filed again on 09 th 2021 based on the priority of the above-mentioned patents, the respective disclosures of which are incorporated herein by reference.

The present invention relates to a thermoplastic resin composition, a method of preparing the same, and a molded article comprising the same, and more particularly, to a thermoplastic resin composition having significantly reduced friction noise at room temperature, at low temperature, at high temperature, and in a high humidity environment while maintaining excellent mechanical properties and heat resistance of a polycarbonate resin and a vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound copolymer, a method of preparing the same, and a molded article comprising the same.

Background

Vinyl cyanide compound-conjugated diene compound-aromatic vinyl compound copolymers (hereinafter referred to as "ABS-based resins") typified by acrylonitrile-butadiene-styrene resins have excellent processability, mechanical properties and appearance characteristics, and thus are widely used in parts of electric/electronic products, automobiles, toys, furniture, building materials, and the like. However, ABS resins lack heat resistance as compared with engineering plastics, and thus are limited in application to parts of electric/electronic products or interior materials of automobiles, which require heat resistance, high strength, and the like. Accordingly, ABS based resins are compounded with Polycarbonate (PC) having excellent mechanical properties, and thus used in the form of PC/ABS based alloy resin materials.

PC/ABS alloy resins are widely used in various applications such as automobiles and electric/electronic products due to their excellent mechanical properties and economical price. For automotive applications, PC/ABS alloy resins are mainly used for interior materials, particularly for center fascia (CENTER FASCIAS) and door trim, among others.

However, since the interior material of the automobile is manufactured by assembling, fastening, and fusing the respective components, vibration generated during the running of the vehicle causes friction between the components, thereby generating friction noise (squeak noise). Such noise is uncomfortable for the driver and passengers. In particular, since the demand for improvement of emotional quality including noise generation has been growing in recent years, it has been necessary to develop a material having low friction noise and high mechanical strength, moldability and heat resistance.

[ Related art literature ]

[ Patent literature ]

KR 10-0729873B1

Disclosure of Invention

Technical problem

Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a thermoplastic resin composition having excellent mechanical properties, moldability, heat resistance and friction noise resistance.

It is another object of the present invention to provide a method for preparing the thermoplastic resin composition and a molded article manufactured using the thermoplastic resin composition.

The above and other objects can be accomplished by the present invention as described below.

Technical proposal

In accordance with one aspect of the present invention, the above and other objects can be accomplished by the provision of a thermoplastic resin composition comprising: (A) 30 to 60 wt.% of a polycarbonate resin having a melt flow index (300 ℃, load: 1.2 kg) of 25g/10min to 35g/10min measured according to ISO 1133; (B) 25 to 50 weight percent of a polyorganosiloxane-polycarbonate resin; (C) 10 to 20% by weight of a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer; (D) 1 to 10% by weight of a polyester resin and (E) 2 to 5% by weight of a resin containing an epoxy group.

According to another aspect of the present invention, there is provided a thermoplastic resin composition comprising: (a) 30 to 60 wt% of a polycarbonate resin; (B) 25 to 50 weight percent of a polyorganosiloxane-polycarbonate resin; (C) 10 to 20% by weight of a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer; (D) 1 to 10% by weight of a polyester resin and (E) 2 to 5% by weight of a resin containing an epoxy group, wherein the weight ratio (B: D) of the resin (B) to the resin (D) is 3:1 to 15:1.

According to another aspect of the present invention, there is provided a thermoplastic resin composition comprising: (a) 30 to 60 wt% of a polycarbonate resin; (B) 25 to 50 weight percent of a polyorganosiloxane-polycarbonate resin; (C) 10 to 20% by weight of a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer; (D) 1 to 10% by weight of a polyester resin and (E) 2 to 5% by weight of a resin containing an epoxy group, wherein the weight average molecular weight of the polycarbonate resin (a) is 10,000 to 30,000g/mol.

According to another aspect of the present invention, there is provided a thermoplastic resin composition comprising: (a) 30 to 60 wt% of a polycarbonate resin; (B) 25 to 50 weight percent of a polyorganosiloxane-polycarbonate resin; (C) 10 to 20% by weight of a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer; (D) 1 to 10% by weight of a polyester resin and (E) 2 to 5% by weight of a resin containing an epoxy group, wherein the weight ratio (B: C) of the resin (B) to the copolymer (C) is 2:1 to 4:1.

According to another aspect of the present invention, there is provided a thermoplastic resin composition comprising: (a) 30 to 60 wt% of a polycarbonate resin; (B) 25 to 50 weight percent of a polyorganosiloxane-polycarbonate resin; (C) 10 to 20% by weight of a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer; (D) 1 to 10 wt.% of a polyester resin and (E) 2 to 5 wt.% of a resin containing an epoxy group, wherein the polycarbonate resin (a) has a melt flow index (300 ℃, load: 1.2 kg) of 25g/10min to 35g/10min, measured according to ISO1133, and the weight ratio (B: D) of the resin (B) to the resin (D) is 3:1 to 15:1.

According to another aspect of the present invention, there is provided a thermoplastic resin composition comprising: (a) 30 to 60 wt% of a polycarbonate resin; (B) 25 to 50 weight percent of a polyorganosiloxane-polycarbonate resin; (C) 10 to 20% by weight of a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer; (D) 1 to 10 wt.% of a polyester resin and (E) 2 to 5 wt.% of a resin containing an epoxy group, wherein the polycarbonate resin (a) has a melt flow index (300 ℃, load: 1.2 kg) of 25g/10min to 35g/10min, measured according to ISO1133, and the weight ratio (B: C) of the resin (B) to the copolymer (C) is 2:1 to 4:1.

Preferably, the thermoplastic resin composition may have a flexural strength of 78MPa or more, measured at 23℃under the conditions of a sample thickness of 4mm, a span of 64mm and a test rate of 2mm/min, according to ISO 178.

Preferably, the thermoplastic resin composition may have a flexural modulus of 2,110MPa or more, measured at 23℃under conditions of a sample thickness of 4mm, a span of 64mm and a test rate of 2mm/min, according to ISO 178.

Preferably, the thermoplastic resin composition may have a Heat Distortion Temperature (HDT) of 95 ℃ or more, measured under the condition of 1.8MPa according to ISO 75.

Preferably, the polycarbonate resin (a) may be at least one selected from the group consisting of a linear polycarbonate resin, a branched polycarbonate resin, and a polyester carbonate copolymer resin.

Preferably, the weight average molecular weight of the polycarbonate resin (a) may be 10,000 to 30,000g/mol.

Preferably, the resin (B) may contain 25 to 45 wt% of the polyorganosiloxane unit.

Preferably, the melt flow index (300 ℃ C., load: 1.2 kg) of the resin (B) may be 0.5g/10min to 4g/10min, measured according to ISO 1133.

Preferably, the copolymer (C) may contain a conjugated diene rubber having an average particle diameter of 0.8 to 1.5. Mu.m.

Preferably, the content of the conjugated diene rubber may be 3 to 12% by weight based on the total weight of the copolymer (C).

Preferably, the copolymer (C) may contain 3 to 12% by weight of a conjugated diene rubber having an average particle diameter of 0.8 to 1.5 μm.

Preferably, the weight ratio (B: C) of the resin (B) to the copolymer (C) may be 2:1 to 4:1.

Preferably, the weight ratio (B: D) of the resin (B) to the resin (D) may be 3:1 to 15:1.

Preferably, the polyester resin (D) may be at least one selected from the group consisting of polyethylene adipate (PEA), polybutylene succinate (PBS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT) and polyethylene naphthalate (PEN).

Preferably, the intrinsic viscosity of the polyester resin (D) may be 1.0dl/g to 1.5dl/g, measured in the presence of a methylene chloride solvent at 25 ℃.

Preferably, the thermoplastic resin composition may include an impact modifier including 40 to 60 wt% of a conjugated diene rubber and 40 to 60 wt% of a (meth) acrylate compound.

According to another aspect of the present invention, there is provided a method for producing a thermoplastic resin composition, the method comprising: kneading and extruding (A) 30 to 60% by weight of a polycarbonate resin having a melt flow index (300 ℃ C., load: 1.2 kg) of 25 to 35g/10min measured according to ISO 1133, (B) 25 to 50% by weight of a polyorganosiloxane-polycarbonate resin, (C) 10 to 20% by weight of a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer, (D) 1 to 10% by weight of a polyester resin, and (E) 2 to 5% by weight of an epoxy group-containing resin at 200 to 280 ℃.

According to still another aspect of the present invention, there is provided a molded article comprising the thermoplastic resin composition.

Advantageous effects

As apparent from the above description, the present invention can provide a thermoplastic resin composition which exhibits significantly improved friction noise reduction effects at room temperature, at low temperature and in high humidity and high temperature environments, i.e., can provide excellent emotional quality over a wide temperature range and humidity range, while having excellent mechanical strength, moldability and heat resistance, a method for preparing the same, and a molded article manufactured by the method.

Drawings

Fig. 1 schematically illustrates a stick-slip noise measurement method of the present disclosure.

Fig. 2 illustrates a stick-slip noise measurement device for measuring stick-slip noise according to the present disclosure.

Detailed Description

Hereinafter, the thermoplastic resin composition of the present disclosure, the method of preparing the thermoplastic resin composition, and the molded article manufactured using the thermoplastic resin composition are described in detail.

The present inventors confirmed that by adjusting the melt flow index of the polycarbonate resin contained in the PC/ABS based alloy resin and containing the polyorganosiloxane-polycarbonate resin, the polyester resin, and the epoxy group-containing resin in a predetermined weight ratio, the friction noise resistance at room temperature, at low temperature, and in high humidity and high temperature environments, as well as the mechanical strength, the moldability, and the heat resistance are significantly improved. Based on these results, the present inventors have conducted further studies to complete the present invention.

The thermoplastic resin composition of the present invention comprises: (A) 30 to 60% by weight of a polycarbonate resin having a melt flow index (300 ℃, load: 1.2 kg) of 25g/10min to 35g/10min measured according to ISO 1133; (B) 25 to 50 weight percent of a polyorganosiloxane-polycarbonate resin; (C) 10 to 20% by weight of a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer; (D) 1 to 10% by weight of a polyester resin and (E) 2 to 5% by weight of a resin containing an epoxy group. In this case, mechanical properties, moldability and heat resistance are excellent, and particularly excellent friction noise resistance is exhibited over a wide temperature range and humidity range.

As another embodiment, the thermoplastic resin composition of the present invention comprises: (a) 30 to 60 wt% of a polycarbonate resin; (B) 25 to 50 weight percent of a polyorganosiloxane-polycarbonate resin; (C) 10 to 20% by weight of a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer; (D) 1 to 10% by weight of a polyester resin and (E) 2 to 5% by weight of a resin containing an epoxy group, wherein the weight ratio (B: D) of the resin (B) to the resin (D) is 3:1 to 15:1. In this case, mechanical properties, moldability and heat resistance are excellent, and particularly excellent friction noise resistance is exhibited over a wide temperature range and humidity range.

As another embodiment, the thermoplastic resin composition of the present invention comprises: (a) 30 to 60 wt% of a polycarbonate resin; (B) 25 to 50 weight percent of a polyorganosiloxane-polycarbonate resin; (C) 10 to 20% by weight of a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer; (D) 1 to 10% by weight of a polyester resin and (E) 2 to 5% by weight of a resin containing an epoxy group, wherein the weight ratio (B: C) of the resin (B) to the copolymer (C) is 2:1 to 4:1. In this case, mechanical properties, moldability and heat resistance are excellent, and particularly excellent friction noise resistance is exhibited over a wide temperature range and humidity range.

In the present disclosure, the composition ratio of the copolymer or the resin may refer to the content of units constituting the copolymer, or may refer to the content of units added during the polymerization of the copolymer.

In this disclosure, "content" refers to "weight percent" unless otherwise defined.

Hereinafter, each component constituting the thermoplastic resin composition of the present disclosure is described in detail.

(A) Polycarbonate resin

The content of the polycarbonate resin (a) may be 30 to 60 wt%, preferably 33 to 55 wt%, more preferably 35 to 50 wt%, based on 100 wt% total of the thermoplastic resin composition. In this case, excellent formability and mechanical hardness are exhibited without deteriorating other physical properties.

In the present disclosure, "100% by weight total of the thermoplastic resin composition" means: when the impact modifier (F) is not contained, the total weight of the sum of the polycarbonate resin (A) to the epoxy group-containing resin (E) is 100% by weight; and when the impact modifier (F) is contained, the total weight of the sum of the polycarbonate resin (A) to the impact modifier (F) is 100% by weight.

The melt flow index (300 ℃ C., 1.2 kg) of the polycarbonate resin (A) may be 25g/10min to 35g/10min, preferably 27g/10min to 35g/10min, more preferably 28g/10min to 34g/10min, measured according to ISO 1133. Within these ranges, moldability and friction noise resistance are excellent.

The type of the polycarbonate resin (a) is not particularly limited, and may be, for example, a resin prepared by polymerization of a bisphenol-based monomer and a carbonate precursor.

The bisphenol-based monomer may be, for example, a monomer selected from the group consisting of bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) propane (bisphenol a; BPA), 2-bis (4-hydroxyphenyl) butane, 1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2-bis (4-hydroxy-3-bromophenyl) propane, 2-bis (4-hydroxy-3-chlorophenyl) propane, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane and alpha, at least one of omega-bis [3- (ortho-hydroxyphenyl) propyl ] polydimethylsiloxane.

The carbonate precursor may be, for example, at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, xylene carbonate, di (chlorophenyl) carbonate, m-toluene carbonate (m-cresyl carbonate), dinaphthyl carbonate, bis (diphenyl) carbonate, phosgene (phosgene), triphosgene, diphosgene, carbonyl bromide, and dihaloformate.

The polycarbonate resin (a) may be, for example, at least one selected from the group consisting of a linear polycarbonate resin, a branched polycarbonate resin, and a polyester carbonate copolymer resin, preferably a linear polycarbonate resin. In this case, fluidity is improved, and thus excellent formability and appearance characteristics are provided.

As a preferred example, the linear polycarbonate resin may be a bisphenol a type polycarbonate resin.

The weight average molecular weight of the polycarbonate resin (A) may be, for example, 10,000 to 30,000g/mol, preferably 10,000 to 20,000g/mol, more preferably 12,000 to 19,000g/mol. Within these ranges, the balance of physical properties is excellent.

In the present disclosure, the weight average molecular weight may be measured using Tetrahydrofuran (THF) as an eluent and using a Gel Permeation Chromatograph (GPC) filled with porous silica as a column packing, unless otherwise defined. In this case, the weight average molecular weight can be obtained as a relative value of a Polystyrene (PS) standard sample. The specific measurement conditions are as follows: solvent: THF, column temperature: 40 ℃, flow rate: 0.3ml/min, sample concentration: 20mg/ml, sample injection amount: 5 μl, column number ：1×PLgel 10μm MiniMix-B(250×4.6mm)+1×PLgel 10μm MiniMix-B(250x 4.6mm)+1×PLgel 10μmMiniMix-B Guard(50×4.6mm), instrument name: agilent 1200 series system, refractive index detector: agilent G1362 RID, RI temperature: 35 ℃, data processing: agilent ChemStation S/W, test methods (Mn, mw and PDI): OECD TG 118.

The polycarbonate resin (A) may have an Izod impact strength of, for example, 60 kg-cm/cm or more, preferably 60 to 80 kg-cm/cm, measured at 23℃under a thickness condition of 1/8″ according to ASTM D256. Within these ranges, excellent mechanical properties are exhibited without deteriorating other physical properties.

The production method of the polycarbonate resin (a) is not particularly limited as long as it is a production method commonly used in the art, and a commercially available product can be used within the scope of the present invention.

(B) Polyorganosiloxane-polycarbonate resin

The content of the polyorganosiloxane-polycarbonate resin (B) (hereinafter referred to as "resin (B)") may be 25 to 50 wt%, preferably 25 to 45 wt%, more preferably 25 to 40 wt%, based on 100 wt% of the total thermoplastic resin composition. In this case, mechanical properties, moldability and heat resistance are excellent, and excellent friction noise resistance is exhibited in a wide temperature range and humidity range.

In the present disclosure, a polyorganosiloxane-polycarbonate copolymer is different from the polycarbonate resin (a) in that the polyorganosiloxane-polycarbonate copolymer contains a polyorganosiloxane incorporated into a polycarbonate main chain. That is, the polycarbonate resin (a) may be represented as "polycarbonate resin (a) (containing no polyorganosiloxane)", as needed.

The resin (B) may comprise, for example, 25 to 45 wt%, preferably 25 to 40 wt%, more preferably 28 to 40 wt%, even more preferably 28 to 35 wt%, even more preferably 30 to 35 wt% of polyorganosiloxane units. Within these ranges, the balance of anti-friction noise properties and physical properties is excellent.

The polyorganosiloxane unit may be derived from, for example, one or more selected from polydimethylsiloxane, polydiethylsiloxane, polydipropylsiloxane, polydibutylsiloxane and polydipentylsiloxane, and preferably may be derived from polydimethylsiloxane. In this case, the balance of mechanical strength and physical properties is excellent.

The polycarbonate unit contained in the resin (B) may be appropriately selected within the same ranges as those mentioned for the polycarbonate (a).

The melt flow index (300 ℃ C., load: 1.2 kg) of the resin (B) may be, for example, 0.5g/10min to 4g/10min, preferably 0.7g/10min to 3g/10min, more preferably 0.7g/10min to 1.5g/10min, measured according to ISO 1133. Within these ranges, the balance of anti-friction noise properties and physical properties is excellent.

The weight average molecular weight of the resin (B) may be, for example, 40,000 to 160,000g/mol, preferably 45,000 to 150,000g/mol, more preferably 50,000 to 100,000g/mol. Within these ranges, the balance of anti-friction noise properties and physical properties is excellent.

The production method of the resin (B) is not particularly limited as long as it is a production method commonly used in the art, and a commercially available product can be used within the scope of the present invention.

(C) Vinyl cyanide-conjugated diene rubber-aromatic vinyl compound copolymer

The content of the vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer (C) (hereinafter referred to as "copolymer (C)") may be 10 to 20 wt%, preferably 12 to 20 wt%, more preferably 15 to 20 wt%, based on the total 100 wt% of the thermoplastic resin composition. Within these ranges, the balance of mechanical properties, formability, and physical properties is excellent. As a preferred example, the content of the copolymer (C) may be 13 to 18% by weight, more preferably 15 to 17% by weight. Within these ranges, moldability and bending characteristics are excellent.

The average particle diameter of the conjugated diene rubber contained in the copolymer (C) may be, for example, 0.8 to 1.5. Mu.m, preferably 1.0 to 1.3. Mu.m. In this case, the balance of mechanical properties, moldability and physical properties is excellent.

In the present disclosure, the average particle diameter of the conjugated diene rubber may be measured by dynamic light scattering, in particular, a sample in the form of latex may be used and measured as an intensity value in gaussian mode using a particle size analyzer (Nicomp CW380, PSS co.). More specifically, samples were prepared by diluting 0.1g of latex having a solid content of 35 to 50 wt% with 100g of deionized water, and DLS average particle diameter of the samples was measured at 23 ℃ using a particle size analyzer (Nicomp CW380, PPS co.) in a measurement mode using an automatic dilution and flow cell and dynamic light scattering/intensity 300 kHz/intensity-weighted gaussian analysis.

The content of the conjugated diene rubber of the copolymer (C) may be, for example, 3 to 12% by weight, preferably 5 to 12% by weight, more preferably 5 to 10% by weight, based on the total weight of the copolymer (C). In this case, the balance between mechanical properties and moldability is excellent.

The copolymer (C) may preferably be a graft copolymer prepared by graft polymerizing 3 to 12% by weight of a conjugated diene rubber, 15 to 40% by weight of a vinyl cyanide compound and 50 to 75% by weight of an aromatic vinyl compound, more preferably a graft copolymer prepared by graft polymerizing 5 to 12% by weight of a conjugated diene rubber, 15 to 35% by weight of a vinyl cyanide compound and 55 to 75% by weight of an aromatic vinyl compound, even more preferably a graft copolymer prepared by graft polymerizing 5 to 10% by weight of a conjugated diene rubber, 20 to 35% by weight of a vinyl cyanide compound and 55 to 70% by weight of an aromatic vinyl compound, based on the total weight of the copolymer (C). In this case, mechanical properties and moldability are excellent.

The degree of grafting of the copolymer (C) may be, for example, 20% to 50%, preferably 20% to 45%, more preferably 25% to 45%. Within these ranges, compatibility and formability can be appropriately ensured, and the balance between these properties and other mechanical properties is excellent.

In the present disclosure, when the degree OF grafting is measured, 30g OF acetone is added to 0.5g OF the powdered graft polymer, stirred at 210rpm and room temperature for 12 hours using a shaker (SKC-6075,Lab Companion Co.), centrifuged at 18,000rpm and at 0 ℃ for 3 hours using a centrifuge (Supra R30, HANIL SCIENCE co.) to separate only insoluble matters insoluble in acetone, and the separated insoluble matters are dried at 85 ℃ for 12 hours by forced circulation using a forced convection oven (OF-12GW,Lab Companion Co). Then, the weight of the dried insoluble matter was measured, and the degree of grafting was calculated by the following equation 1.

[ Formula 1]

Grafting degree (%) = [ weight of grafting monomer (g)/weight of rubber (g) ]. 100

In formula 1, the weight of the graft monomer is a value obtained by subtracting the weight (g) of the rubber, which is the weight of the rubber component theoretically contained in the graft copolymer powder, from the weight of the insoluble matter (gel) obtained by dissolving the graft copolymer in acetone and centrifuging.

The weight average molecular weight of the copolymer (C) may be, for example, 100,000 to 1,000,000g/mol, preferably 200,000 to 900,000g/mol, more preferably 230,000 to 500,000g/mol. Within these ranges, fluidity is appropriate, and thus processability and impact resistance are excellent.

The conjugated diene rubber may include, for example, a conjugated diene compound.

The conjugated diene compound may be, for example, one or more selected from 1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, 2-ethyl-1, 3-butadiene, 1, 3-pentadiene, isoprene and chloroprene, preferably 1, 3-butadiene.

The vinyl cyanide compound may be, for example, one or more selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, and isopropyl acrylonitrile, preferably acrylonitrile.

The aromatic vinyl compound may be, for example, at least one selected from styrene, α -methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, isobutylstyrene, t-butylstyrene, o-bromostyrene, p-bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene and vinylnaphthalene, preferably at least one selected from styrene and α -methylstyrene, even more preferably styrene. In this case, fluidity is appropriate, so that processability is excellent and mechanical properties such as impact resistance are excellent.

The copolymer (C) can be prepared by, for example, known preparation methods including emulsion polymerization, suspension polymerization and bulk polymerization, preferably emulsion polymerization. As the copolymer (C), commercially available products can be used within the scope of the present invention.

(D) Polyester resin

The content of the polyester resin (D) may be 1 to 10wt%, preferably 2 to 8wt%, more preferably 3 to 7wt%, based on 100 wt% total of the thermoplastic resin composition. In this case, the moldability is excellent without deterioration of other physical properties, and the friction noise resistance is excellent in a wide temperature range and humidity range.

The intrinsic viscosity of the polyester resin (D) may be, for example, 1.0dl/g to 1.5dl/g, preferably 1.0dl/g to 1.3dl/g, more preferably 1.0dl/g to 1.2dl/g, measured at 25℃in the presence of a methylene chloride solvent. Within these ranges, mechanical properties and processability are further improved.

In the present disclosure, when measuring intrinsic viscosity, unless otherwise noted, a sample to be measured is completely dissolved in a dichloromethane solvent at a concentration of 0.05g/ml, and then filtered using a filter to obtain a filtrate. Then, using the obtained filtrate, the intrinsic viscosity was measured at 25℃using an Ubbelohde viscometer.

The polyester resin (D) may be, for example, one or more selected from polyethylene adipate (PEA), polybutylene succinate (PBS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT) and polyethylene naphthalate (PEN), preferably one or more selected from polyethylene terephthalate and polybutylene terephthalate, more preferably polybutylene terephthalate. In this case, the composition exhibits satisfactory mechanical properties and moldability, excellent balance of physical properties, and excellent friction noise resistance over a wide temperature range and humidity range.

The polyester resin (D) may be prepared using, for example, a polymer copolymer including at least one selected from polytetramethylene glycol (PTMG), polyethylene glycol (PEG), polypropylene glycol (PPG), and low molecular weight aliphatic polyamide. In this case, the mechanical properties are further improved.

The production method of the polyester resin (D) is not particularly limited as long as it is a production method commonly used in the art, and a commercially available product can be used within the scope of the present invention.

(E) Epoxy group-containing resin

The content of the epoxy group-containing resin (E) may be 2 to 5% by weight based on 100% by weight of the total thermoplastic resin composition. Within these ranges, excellent moldability and friction noise resistance are exhibited without deteriorating other physical properties.

The content of the epoxy group-containing resin (E) may be preferably 2 to 3.8 wt%, more preferably 2 to 3.5 wt%, based on 100 wt% of the total thermoplastic resin composition. In this case, the formability and mechanical hardness are further improved.

The epoxy group-containing resin (E) may contain, for example, a glycidyl compound, and preferably may contain at least one selected from the group consisting of an olefin compound, vinyl acetate, and an alkyl acrylate compound together with the glycidyl compound. In this case, the physical property balance and the friction noise resistance are further improved.

The epoxy group-containing resin (E) may more preferably contain 5 to 25% by weight of a glycidyl compound, 1 to 10% by weight of an unsaturated acetate compound and 70 to 90% by weight of an olefin compound, and even more preferably contain 10 to 20% by weight of a glycidyl compound, 1 to 7% by weight of an unsaturated acetate compound and 75 to 85% by weight of an olefin compound. In this case, the physical property balance and the friction noise resistance are further improved.

The glycidyl compound may preferably be glycidyl (meth) acrylate.

The unsaturated acetate compound may be, for example, an acetate compound containing an alkenyl group having 2 to 5 carbon atoms, preferably vinyl acetate.

The olefinic compound may be, for example, an olefin having 2 to 5 carbon atoms, preferably at least one selected from ethylene and propylene.

The alkyl acrylate compound may be, for example, one or more selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate and dodecyl acrylate, preferably n-butyl acrylate or 2-ethylhexyl acrylate.

In the present disclosure, alkyl (meth) acrylates may be defined to include both alkyl acrylates and alkyl methacrylates.

As a preferred example, the epoxy group-containing resin (E) may be an ethylene-glycidyl methacrylate copolymer grafted with vinyl acetate. In this case, the physical property balance is further improved.

The epoxy group-containing resin (E) may further contain, for example, maleic acid or maleic anhydride. In this case, heat resistance and physical property balance are further improved.

The production method of the epoxy group-containing resin (E) is not particularly limited as long as it is a production method commonly used in the art, and a commercially available product can be used within the scope of the present invention.

(F) Impact modifier

The thermoplastic resin composition may optionally contain an impact modifier (F). In this case, excellent mechanical properties are exhibited without deteriorating other physical properties.

The impact modifier (F) may be contained in an amount of, for example, 1 to 3.3 wt%, preferably 2 to 3 wt%, more preferably 2.5 to 3 wt%, based on 100 wt% of the total thermoplastic resin composition (from the polycarbonate resin (a) to the impact modifier (F)). Within these ranges, excellent mechanical properties are exhibited without deteriorating other physical properties.

The impact modifier (F) may contain, for example, a conjugated diene rubber and a (meth) acrylic compound. Based on 100% by weight of the total of the conjugated diene rubber and the (meth) acrylic compound contained in the impact modifier (F), 30 to 70% by weight of the conjugated diene rubber and 30 to 70% by weight of the (meth) acrylic compound may be preferably contained, and 50 to 70% by weight of the conjugated diene rubber and 30 to 50% by weight of the (meth) acrylic compound are more preferably contained. In this case, the balance of mechanical properties and physical properties is further improved.

The conjugated diene rubber may be appropriately selected within the same ranges as those mentioned for the copolymer (C).

The (meth) acrylic acid ester compound may be, for example, at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, and decyl (meth) acrylate, preferably methyl methacrylate.

In the present disclosure, (meth) acrylate refers to a range that includes both methacrylate and acrylate.

The impact modifier (F) may further comprise, for example, an aromatic vinyl compound. The aromatic vinyl compound may be appropriately selected within the same ranges as those mentioned for the copolymer (C).

The method for preparing the impact modifier (F) is not particularly limited as long as it is a method commonly used in the art, and a commercially available product can be used within the scope of the present invention.

Thermoplastic resin composition

The thermoplastic resin composition of the present invention may comprise: (A) 30 to 60% by weight of a polycarbonate resin having a melt flow index (300 ℃, load: 1.2 kg) of 25g/10min to 35g/10min measured according to ISO 1133; (B) 25 to 50 weight percent of a polyorganosiloxane-polycarbonate resin; (C) 10 to 20% by weight of a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer; (D) 1 to 10% by weight of a polyester resin and (E) 2 to 5% by weight of a resin containing an epoxy group. In this case, mechanical strength, moldability and heat resistance are excellent. In particular, the friction noise resistance is excellent in a wide temperature range and humidity range.

The weight ratio (B: D) of the resin (B) to the resin (D) contained in the thermoplastic resin composition may be, for example, 3:1 to 15:1, preferably 3:1 to 14:1, more preferably 3:l to 13.5:1. In this case, the friction noise resistance is further improved in a wide temperature range and humidity range without deteriorating other physical properties.

The weight ratio (B: C) of the resin (B) to the copolymer (C) contained in the thermoplastic resin composition may be, for example, 2:1 to 4:1, preferably 2:1 to 3:1, more preferably 2:l to 2.5:1. In this case, the friction noise resistance is further improved in a wide temperature range and humidity range without deteriorating other physical properties.

The flexural strength of the thermoplastic resin composition may be, for example, 71MPa or more, or 78MPa or more, preferably 78 to 90MPa, more preferably 78 to 85MPa, measured at 23℃under conditions of a sample thickness of 4mm, a span of 64mm and a test rate of 2mm/min, according to ISO 178. Within these ranges, the balance of mechanical and physical properties is excellent.

The flexural modulus of the thermoplastic resin composition may be, for example, 1,900MPa or more, or 2,110MPa or more, preferably 2,110 to 2,300MPa, more preferably 2,110 to 2,200MPa, measured at 23℃with a sample thickness of 4mm, a span of 64mm and a test rate of 2mm/min, according to ISO 178. Within these ranges, the balance of mechanical and physical properties is excellent.

The stick-slip noise of the thermoplastic resin composition may be, for example, grade 3 or less, preferably grade 1 to 3, more preferably grade 1 to 2, measured at 23 ℃ and 50% relative humidity according to Verband Der Automobilindustrie e.v. (VDA) 230-206. Within these ranges, the room temperature friction noise resistance and physical property balance are excellent.

The stick-slip noise of the thermoplastic resin composition may be, for example, grade 3 or less, preferably grade 1 to 3, more preferably grade 1 to 2, as measured at-25 ℃ and 50% relative humidity according to VDA 230-206. Within these ranges, the low temperature friction noise resistance and physical property balance are excellent.

According to VDA 230-206, the stick-slip noise of the thermoplastic resin composition may be, for example, grade 3 or less, preferably grade 1 to 3, more preferably grade 1 to 2, measured at 75℃and 50% relative humidity. Within these ranges, a high Wen Kangma noise-wiping property and a physical property balance are excellent.

According to VDA 230-206, the stick-slip noise of the thermoplastic resin composition may be, for example, grade 3 or less, preferably grade 1 to 3, more preferably grade 1 to 2, measured at 50℃and 90% relative humidity. Within these ranges, the balance of friction noise resistance and physical properties at medium and high humidity is excellent.

In the present disclosure, relative humidity means a ratio (%) of water vapor pressure to saturated water vapor pressure at a given temperature, and can be measured using a method of measuring relative humidity known in the related art. For example, a commercially available hygrometer may be used.

Fig. 1 and 2 show a measurement method and apparatus for measuring stick-slip noise in the examples and comparative examples of the present invention, respectively.

As a specific example of measuring stick-slip noise according to VDA 230-206, a flat plate sample having a width, length, and thickness 100mm x 100mm x 30mm was fixed on a movable fixed plate that reciprocates left and right, and a flat plate sample having a width, length, and thickness 25mm x50mm x 30mm was fixed on an upper fixed plate equipped with springs using Ziegler SSP-04 apparatus. Next, the centers of the two samples were adjusted to coincide with each other, and acceleration, pulse, frequency, friction, and fluctuation were measured under the conditions of four loads (i.e., contact force applied to the two samples) of (10 n,1 mm/s), (10 n,4 mm/s), (40 n,1 mm/s), and (40 n,4 mm/s) and moving speed in a state where the two samples were in contact with each other. Dynamic and static friction coefficients are derived from these measurements and can be calculated as RPN (risk priority) values according to the following equation 2.

[ Formula 2]

In formula 2, grad _{energie_rate} represents kinetic energy, grad _{impulse_rate} represents pulse number within 1mm displacement, and grad _acceleration represents maximum vibration value

< Friction noise Performance evaluation >

RPN 1 to 3: good (very low possibility of friction noise)

RPN 4 to 5: part is good

RPN 6 to 10: is bad

In the present disclosure, stick-slip noise is related to buzz, squeak, and rattle (BSR) generated in the vehicle, which is an aesthetically related performance. Stick-slip noise occurs at the assembly joints, or friction areas of the system, also known as noise. Here, the buzzing is a drum noise caused by structural vibration and generated by the part panels alone, the creaking is a noise generated by friction between the parts in the shearing direction, and the creaking is a noise generated by vertical collision between the parts.

As a preferred example, all stick-slip noise values of the thermoplastic resin composition of the present invention satisfy grade 3 or less as measured according to VDA 230-206 in a temperature range of-25 ℃ to 75 ℃ and a relative humidity range of 50% to 90%, and thus can provide molded articles having excellent friction noise resistance in a wide temperature range and humidity range. For example, when used as automotive interior materials, high emotional quality can be achieved regardless of temperature and rainfall environment.

The melt flow index (260 ℃ C., load: 5 kg) of the thermoplastic resin composition may be, for example, 10g/10min or more, preferably 10g/10min to 30g/10min, more preferably 13g/10min to 25g/10min, as measured according to ISO 1133. Within these ranges, the moldability is further improved without deteriorating other physical properties.

The Heat Distortion Temperature (HDT) of the thermoplastic resin composition may be, for example, 95 ℃ or higher, preferably 95 ℃ to 120 ℃, more preferably 96 ℃ to 110 ℃ measured under the condition of 1.8MPa according to ISO 75. Within these ranges, heat resistance is further improved without deteriorating other physical properties. In particular, the thermoplastic resin composition is suitable for use as an automobile material.

Process for producing thermoplastic resin composition

The preparation method of the thermoplastic resin composition comprises the following steps: 30 to 60 wt.% of (A) a polycarbonate resin having a melt flow index (300 ℃, load: 1.2 kg) of 25g/10min to 35g/10min measured according to ISO 1133; (B) 25 to 50 weight percent of a polyorganosiloxane-polycarbonate resin; (C) 10 to 20% by weight of a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer; (D) 1 to 10% by weight of a polyester resin and (E) 2 to 5% by weight of a resin containing an epoxy group are kneaded and extruded at 200 to 300 ℃. In this case, all of the mechanical properties, moldability, heat resistance and friction noise resistance are excellent.

In the kneading and extrusion steps, the temperature of the extruder and the screw rotation speed may be, for example, 200℃to 300℃and 200 to 350rpm, preferably 220℃to 280℃and 240 to 300rpm, respectively. In this case, mechanical properties, chemical resistance, heat resistance, and appearance quality are excellent.

The kneading and extruding steps may be performed, for example, using one or more selected from the group consisting of a single screw extruder, a twin screw extruder, and a Banbury mixer. Preferably, the kneading and extruding steps may be performed by uniformly mixing the components using an extruder and then extruding to obtain the thermoplastic resin composition in the form of pellets. In this case, deterioration of mechanical properties and deterioration of heat resistance can be prevented, and excellent appearance quality can be provided.

The thermoplastic resin composition may further comprise, for example, one or more selected from the group consisting of a lubricant, a heat stabilizer, and a UV absorber. In this case, workability, thermal stability, and light stability during high temperature molding can be ensured.

The lubricant may be, for example, one or more selected from fatty acid amide-based compounds, montan-based waxes, and olefin-based waxes, preferably olefin-based waxes, more preferably polyethylene waxes. In this case, the moldability and the mold release property are excellent, and the friction noise resistance can be further improved.

The fatty acid amide-based compound may be, for example, at least one selected from the group consisting of stearamide, behenamide, ethylenebis (stearamide), N "-ethylenebis (12-hydroxystearamide), erucamide, oleamide, and ethylenebis (oleamide).

The montan wax may be, for example, a montan wax, a montan ester wax, or a mixture thereof.

The olefinic wax may be, for example, polyethylene wax, polypropylene wax, or a mixture thereof.

The content of the lubricant may be, for example, 0.05 to 1.0 parts by weight, preferably 0.1 to 0.7 parts by weight, more preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the total of the polycarbonate resin (a), the resin (B), the copolymer (C), the polyester resin (D) and the epoxy group-containing resin (E). Within these ranges, the physical property balance is excellent, and the friction noise resistance is further improved.

The heat stabilizer may include, for example, a phenolic heat stabilizer, a phosphorous heat stabilizer, or a mixture thereof, and preferably may be a phenolic heat stabilizer. In this case, oxidation due to heat during extrusion can be prevented, and mechanical properties and heat resistance are excellent.

For example, the phenolic heat stabilizer may include one or more selected from the group consisting of N, N '-hexane-1, 6-diyl-bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl propionamide) ], pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], N' -hexamethylene-bis (3, 5-di-t-butyl-4-hydroxy-hydrocinnamamide), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate ], diethyl 3, 5-di-t-butyl-4-hydroxybenzylphosphonate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, and 1,3, 5-tris (4-t-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate. In this case, heat resistance can be greatly improved while maintaining a high level of balance of physical properties.

For example, the phosphorus-based heat stabilizer may include one or more selected from the group consisting of triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (2, 6-di-t-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl-monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2-methylenebis (4, 6-di-t-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, octadecyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, and trimethyl phosphate.

The content of the heat stabilizer may be, for example, 0.05 to 1.0 parts by weight, preferably 0.1 to 0.7 parts by weight, more preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight in total of the polycarbonate resin (a), the resin (B), the copolymer (C), the polyester resin (D) and the epoxy group-containing resin (E). Within these ranges, the balance of physical properties is excellent, and heat resistance is improved.

For example, the UV absorber may include one or more selected from triazine-based UV absorbers, benzophenone-based UV absorbers, benzotriazole-based UV absorbers, quinolinone-based UV absorbers, benzoate-based UV absorbers, cyanoacrylate-based UV absorbers, and benzoxazole-based UV absorbers, preferably benzotriazole-based UV absorbers. In this case, the physical property balance may be excellent, and the light resistance may be further improved.

For example, the number of the cells to be processed, the triazine-based UV absorbers may be selected from the group consisting of 2, 4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3, 5-triazine, 2, 4-diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -1,3, 5-triazine, 2, 4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3, 5-triazine, 2, 4-diphenyl- (2-hydroxy-4-butoxyphenyl) -1,3, 5-triazine, 2, 4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3, 5-triazine, 2, 6-diphenyl-4- (2-hydroxy-4-hexyloxyphenyl) -1,3, 5-triazine, 2, 4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3, 5-triazine, 2, 4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3, 5-triazine, 2, 4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3, 5-triazine, 2, 6-diphenyl-4- (2-hydroxy-4-butoxyphenyl) -1,3, 5-triazine, 2, 4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3, 5-triazine, 2, 4-diphenyl-6-octyloxyphenyl-triazine, 2,4, 6-tris (2-hydroxy-4-butoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4-hexyloxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4-octyloxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4-dodecyloxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4-benzyloxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4-ethoxyethoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4-butoxyoxyphenyl) -1,3, 5-triazine 2,4, 6-tris (2-hydroxy-4-propoxyethoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4-methoxycarbonylpropoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4-ethoxycarbonylethoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4- (1- (2-ethoxyhexyloxy) -1-oxopropan-2-yloxy) phenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-3-methyl-4-ethoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-3-methyl-4-propoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-3-methyl-4-butoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-3-methyl-4-octyloxyphenyl) -1,3, 5-triazine 2,4, 6-three (2-hydroxy-3-methyl-4-twelve alkyl oxygen phenyl) -1,3, 5-three, 2,4, 6-three (2-hydroxy-3-methyl-4 benzyl oxygen phenyl) -1,3, 5-three, 2,4, 6-three (2-hydroxy-3-methyl-4-ethoxy phenyl) -1,3, 5-three, 2,4, 6-three (2-hydroxy-3-methyl-4-butoxy ethoxy phenyl) -1,3, 5-three, 2,4, 6-three (2-hydroxy-3-methyl-4-propoxy ethoxy phenyl) -1,3, 5-three, three, at least one of 2,4, 6-tris (2-hydroxy-3-methyl-4-methoxycarbonylpropoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-3-methyl-4-ethoxycarbonylethoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-3-methyl-4- (1- (2-ethoxyhexyloxy) -1-oxopropan-2-yloxy) phenyl) -1,3, 5-triazine, 2, 4-bis (2, 4-dimethylphenyl) -6- (2-hydroxy-4-N-octyloxyphenyl) -1,3, 5-triazine and 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- (2- (2-ethylhexanoyloxy) ethoxy) phenol.

For example, the benzophenone-based UV absorbers may be selected from the group consisting of 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxy-benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone (2-hydroxy-4-methoxy-5-sulfoxybenzophenone), 2-hydroxy-4-methoxy-5-sulfoxy-trihydrate-benzophenone (2-hydroxy-4-methoxy-5-sulfoxytrihydratebenzophenone), 2-hydroxy-4-dodecoxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2 "-dihydroxy-4-methoxybenzophenone, 2", 4' -tetrahydroxybenzophenone, 2"-dihydroxy-4,4" -dimethoxy-benzophenone, 2"-dihydroxy-4,4" -dimethoxy-5-benzophenone sodium sulfonate (2, 2"-dihydroxy-4,4" -dimethoxy-5-sodiumsulfoxybenzophenone), bis (5-benzoyl-4-hydroxy-phenyl-2-hydroxy-4-methoxybenzophenone, n-hydroxy-4-methoxybenzophenone), at least one of 2-hydroxy-4-methoxy-2 "-carboxybenzophenone and 4,4" -bis (diethylamino) benzophenone.

For example, the benzotriazole UV absorber may be selected from the group consisting of 2- (2 "-hydroxy-5" -methylphenyl) benzotriazole, 2-2 "-hydroxy-3", 2- (2 "-hydroxy-3" -tert-butyl-5 "-methylphenyl) benzotriazole, 2- (2" -hydroxy-5 "-methylphenyl) benzotriazole, 5" -bis (. Alpha.,. Alpha. -dimethylbenzyl) phenyl ] -benzotriazole, 2- (2 "-hydroxy-3", 5 "-di-tert-butylphenyl) -benzotriazole, 2- (2" -hydroxy-3 "-tert-butyl-5" -methylphenyl) -5-chlorobenzotriazole, 2- (2 "-hydroxy-3", 5 "-di-tert-butyl-phenyl) -5-chlorobenzotriazole, 2- (2" -hydroxy-3 ",5" -di-tert-amyl) -benzotriazole, 2- (2 hydroxy-3 ",5" -di-tert-amyl) -benzotriazole, 5' -di-tert-pentylphenyl) -5-chlorobenzotriazole, 2- (2 "-hydroxy-3" - (4 ",5",6 "-tetrahydrophthalimidomethyl) -5" -benzotriazol, 2- (2 "-hydroxy-3", 5-di-tert-amyl) benzotriazole, at least one of 2- (2 "-hydroxy-5" -tert-octylphenyl) benzotriazole and 2,2 "-methylenebis [4- (1, 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol.

For example, the indole UV absorber may be 2- [ (1-methyl-2-phenyl-1H-indol-3-yl) methylene ] malononitrile.

For example, the quinolinone UV absorber may be 4-hydroxy-3- [ (phenylimino) methyl ] -2 (1H) -quinolinone.

For example, the benzoate UV absorber may be selected from 2, 4-di-tert-butylphenyl-3 ', 5' -di-tert-butyl-4 '-hydroxybenzoate, 2, 6-di-tert-butylphenyl-3', at least one of 5 '-di-tert-butyl-4' -hydroxybenzoate, n-hexadecyl-3, 5-di-tert-butyl-4-hydroxybenzoate and n-octadecyl-3, 5-di-tert-butyl-4-hydroxybenzoate.

For example, the cyanoacrylate UV absorber may be 2 "-ethylhexyl-2-cyano-3, 3-diphenylacrylate, ethyl-2-cyano-3- (3", 4 "-methylenedioxyphenyl) -acrylate, or mixtures thereof.

The content of the UV absorber may be, for example, 0.05 to 1.0 parts by weight, preferably 0.1 to 0.7 parts by weight, more preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight in total of the polycarbonate resin (a), the resin (B), the copolymer (C), the polyester resin (D) and the epoxy group-containing resin (E). Within these ranges, the balance of properties is excellent, and the light resistance is further improved.

In addition to the above components, the thermoplastic resin composition may optionally further contain one or more additives selected from the group consisting of antioxidants, dyes, pigments, colorants, mold release agents, antistatic agents, antibacterial agents, processing aids, compatibilizers, metal deactivators, flame retardants, smoke suppressants, anti-dripping agents, foaming agents, plasticizers, reinforcing agents, fillers, matte agents, friction reducing agents, and antiwear agents, as required during kneading and extrusion. The content of the additive may be, for example, 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, 0.05 to 2 parts by weight, or 0.05 to 1 part by weight, based on 100 parts by weight of the total of the polycarbonate resin (a), the resin (B), the copolymer (C), the polyester resin (D), and the epoxy group-containing resin (E). Within this range, the desired physical properties are well achieved without degrading the initial physical properties of the thermoplastic resin composition.

For example, as the antistatic agent, one or more selected from anionic surfactants and nonionic surfactants may be used, without being limited thereto.

For example, as the mold release agent, one or more selected from the group consisting of glyceryl stearate and polyethylene glycol tetrastearate may be used without limitation thereto.

Molded article

The molded article of the present invention comprises the thermoplastic resin composition according to the present disclosure. In this case, mechanical properties, moldability and heat resistance are excellent, and friction noise resistance is excellent in a wide temperature range and humidity range.

The molded article may be manufactured by a method commonly used in the art. For example, using the melt-kneaded material or pellet of the thermoplastic resin composition according to the present invention as a raw material, an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a compression molding method, a pressure molding method, a heat bending method, a compression molding method, a calender molding method, a rotational molding method, or the like can be applied. Here, the size and thickness of the molded article may be appropriately adjusted according to the purpose of use, and a flat plate or curved shape may be used according to the purpose of use.

As a specific example, the method of manufacturing a molded article may include a step of injecting a melt-kneaded material or pellets of the thermoplastic resin composition according to the present invention using an injection machine.

The molded article has excellent mechanical strength, heat resistance and friction noise resistance, and is therefore suitable for application to automobile interior materials. As a specific example, the automotive interior material may be a vehicle console, center fascia, door trim, or trim.

The thermoplastic resin composition of the present invention exhibits excellent mechanical strength, heat resistance and friction noise resistance, and thus is suitable for application to fields requiring a high level of emotional quality, particularly for molded articles of electric automobile parts.

In describing the thermoplastic resin composition, the method of producing the thermoplastic resin composition, and the molded article produced therefrom, other conditions or equipment not explicitly described may be appropriately selected within the scope of common practice in the art without particular limitation.

Hereinafter, the present invention will be described in more detail with reference to the following preferred examples. However, these examples are provided for illustrative purposes only and should not be construed as limiting the scope and spirit of the invention. Further, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and that such changes and modifications are also within the scope of the appended claims.

Examples (example)

The materials used in the following examples and comparative examples are as follows.

(A-1) polycarbonate resin: bisphenol A type PC resin having a melt flow index (300 ℃ C., load: 1.2 kg) of 30g/10min (weight average molecular weight: 15,000g/mol, intrinsic viscosity (25 ℃ C.): 1.0dl/g measured according to ISO 1133)

(A-2) polycarbonate resin: bisphenol A type PC resin having a melt flow index (300 ℃ C., load: 1.2 kg) of 22g/10min (weight average molecular weight: 10,000g/mol, intrinsic viscosity (25 ℃ C.): 0.9dl/g measured according to ISO 1133)

(B) Polyorganosiloxane-polycarbonate resin: polyorganosiloxane-polycarbonate resin having a melt flow index (300 ℃ C., load: 1.2 kg) of 0.8g/10min, measured according to ISO 1133, and comprising 30% by weight of polydimethylsiloxane units (weight-average molecular weight: 100,000 g/mol)

(C) Vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer: ABS resin (weight average molecular weight: 300,000 g/mol) comprising 10% by weight of butadiene rubber having an average particle diameter of 1. Mu.m, 28% by weight of acrylonitrile and 62% by weight of styrene

(D) Polyester resin: polybutylene terephthalate with an intrinsic viscosity (25 ℃) of 1.2dl/g (weight-average molecular weight: 15,000 g/mol)

(E) Epoxy group-containing resin: ethylene copolymer comprising 12% by weight of glycidyl methacrylate units and 5% by weight of vinyl acetate units (weight average molecular weight: 50,000 g/mol)

(F) Impact modifier: MMA-BD-based impact modifier (EM 520 manufactured by LG Chem) comprising butadiene rubber and methacrylate and having a core-shell structure

Examples 1 to 5 and comparative examples 1 to 12

The polycarbonate resin (a-1) or the polycarbonate resin (a-2), the polyorganosiloxane-polycarbonate resin (B), the copolymer (C), the polyester resin (D), the epoxy group-containing resin (E) and the impact modifier (F) were mixed in the amounts summarized in the following tables 1 and2 using a super mixer, and then extruded using a twin screw extruder (screw diameter: 26mm, l/d=40) under extrusion conditions of an extrusion temperature of 260 ℃ and a screw rotation speed of 250rpm, thereby producing pellets.

The prepared pellet-shaped thermoplastic resin composition was dried at 100℃for 2 hours or more, and then injection molded using an injection machine under the conditions of an injection temperature of 260℃and a mold temperature of 60℃and an injection rate of 30mm/sec, thereby producing a sample. The fabricated test pieces were left at room temperature (20 ℃ C. To 26 ℃ C.) for more than 48 hours, and then the properties were measured.

Test example

The properties of the samples produced by examples and comparative examples were measured according to the following methods, and the results are summarized in tables 3 and 4 below.

* Stick-slip noise: the flat panel samples of width, length and thickness 100mm x 100mm x 30mm were fixed on a movable fixed plate and the flat panel samples of width, length and thickness 25mm x 50mm x 30mm were fixed on a spring-equipped upper fixed plate using Ziegler SSP-04 equipment (Ziegler instrument GmbH) according to VDA 230-206. Next, centers of two samples are adjusted to coincide with each other, and acceleration, pulse, frequency, friction, and fluctuation are measured, respectively, in a state where the two samples are in contact. The RPN (risk priority number) is calculated according to the following formula 2, and then the frictional noise performance is evaluated according to the following criteria. The load and the moving speed applied to the test specimen are four conditions in total: (10N, 1 mm/s); (10N, 4 mm/s); (40N, 1 mm/s); and (40N, 4 mm/s).

[ Formula 2]

< Friction noise Performance evaluation >

RPN 1 to 3: good (very low possibility of friction noise)

RPN 4 to 5: good local area

RPN 6 to 10: is bad

Frictional noise performance was measured under a total of four environmental conditions: the relative humidity was 50% and room temperature (23 ℃); the relative humidity is 50% and at low temperature (-25 ℃); the relative humidity is 50% and at high temperature (75 ℃); and a relative humidity of 90% and a medium temperature (50 ℃). These are denoted as stick-slip noise at room temperature, stick-slip noise at low temperature, stick-slip noise at high temperature, and stick-slip noise at medium temperature and high humidity, respectively. For reference, tables 3 and 4 show the highest RPN level of the frictional noise values measured under these four motion conditions.

* Melt flow index (g/10 min): measured according to ISO 1133 at 260℃under a load of 5kg for 10 minutes.

* Heat distortion temperature (c): measured according to ISO75 at a pressure of 1.8 MPa.

* Flexural strength and flexural modulus (MPa): the flexural strength and flexural modulus were measured according to ISO 178 at a sample thickness of 4mm, a span of 64mm and a test rate of 2mm/min, respectively.

TABLE 1

TABLE 2

TABLE 3 Table 3

TABLE 4 Table 4

Referring to tables 1 and 2, it was confirmed that: in the case of examples 1 to 5 prepared according to the present invention, the friction noise performance was 3 or less under all conditions of room temperature, low temperature, high temperature, and medium temperature and high humidity, indicating excellent friction noise resistance; the heat distortion temperature is 95 ℃ or higher, indicating excellent heat resistance; a melt flow index of 11 or more, indicating proper molding processability; the flexural strength was 78MPa or more and the flexural modulus was 2,110MPa or more, indicating excellent flexural properties.

On the other hand, it was confirmed that: in the case of comparative examples 1 to 12 different from the present invention, the anti-friction noise property, heat resistance, fluidity, flexural strength and flexural modulus were out of the range of the examples of the present invention.

Claims (15)

1. A thermoplastic resin composition comprising:

(A) 30 to 60 weight percent of a polycarbonate resin having a melt flow index of 25g/10min to 35g/10min at 300 ℃ under a load of 1.2kg, measured according to ISO 1133;

(B) 25 to 50 weight percent of a polyorganosiloxane-polycarbonate resin;

(C) 10 to 20% by weight of a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer;

(D) 1 to 10% by weight of a polyester resin; and

(E) 2 to 5% by weight of a resin containing an epoxy group,

Wherein the weight ratio of the resin (B) to the resin (D), namely the weight ratio of B to D, is 3:1 to 15:1.

2. The thermoplastic resin composition of claim 1, wherein the flexural strength of the thermoplastic resin composition is 78MPa or more, measured according to ISO 178 at 23 ℃, a sample thickness of 4mm, a span of 64mm, and a test rate of 2 mm/min.

3. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a flexural modulus of 2,110mpa or greater, measured according to ISO 178 at 23 ℃, a sample thickness of 4mm, a span of 64mm, and a test rate of 2 mm/min.

4. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a heat distortion temperature of 95 ℃ or greater, measured according to ISO 75 under 1.8 MPa.

5. The thermoplastic resin composition according to claim 1, wherein the polycarbonate resin (a) is at least one selected from the group consisting of a linear polycarbonate resin, a branched polycarbonate resin and a polyester carbonate copolymer resin.

6. The thermoplastic resin composition according to claim 1, wherein the weight average molecular weight of the polycarbonate resin (a) is 10,000 to 30,000g/mol.

7. The thermoplastic resin composition according to claim 1, wherein the resin (B) comprises 25 to 45 wt% of the polyorganosiloxane unit.

8. The thermoplastic resin composition according to claim 1, wherein the melt flow index of the resin (B) is 0.5g/10min to 4g/10min at 300 ℃ under a load of 1.2kg, measured according to ISO 1133.

9. The thermoplastic resin composition according to claim 1, wherein the content of the conjugated diene rubber having an average particle diameter of 0.8 to 1.5 μm is 3 to 12% by weight based on the total weight of the copolymer (C).

10. The thermoplastic resin composition according to claim 1, wherein the weight ratio of the resin (B) to the copolymer (C), namely B: C weight ratio, is 2:1 to 4:1.

11. The thermoplastic resin composition according to claim 1, wherein the polyester resin (D) is at least one selected from the group consisting of polyethylene adipate, polybutylene succinate, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate and polyethylene naphthalate.

12. The thermoplastic resin composition according to claim 1, wherein the intrinsic viscosity of the polyester resin (D) is 1.0dl/g to 1.5dl/g, measured in the presence of a methylene chloride solvent at 25 ℃.

13. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition comprises an impact modifier comprising 40 to 60 weight percent conjugated diene rubber and 40 to 60 weight percent (meth) acrylate compound.

14. A method for producing a thermoplastic resin composition, the method comprising: 30 to 60 wt.% of a polycarbonate resin having a melt flow index of 25g/10min to 35g/10min at 300 ℃ under a load of 1.2kg measured according to ISO 1133; (B) 25 to 50 weight percent of a polyorganosiloxane-polycarbonate resin; (C) 10 to 20% by weight of a vinyl cyanide compound-conjugated diene rubber-aromatic vinyl compound copolymer; (D) A step of kneading and extruding 1 to 10% by weight of a polyester resin and (E) 2 to 5% by weight of an epoxy group-containing resin at 200 to 300 ℃,

Wherein the weight ratio of the resin (B) to the resin (D), namely the weight ratio of B to D, is 3:1 to 15:1.

15. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 13.