KR101145834B1 - thermoplastic resin composition with low gloss - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, 20 to 70% by weight of polyester; 20 to 70% by weight aromatic polycarbonate; 1 to 15 weight percent acrylic rubber; And 0.1 to 10 weight percent quencher; By using a low gloss thermoplastic resin composition comprising an excellent matting effect, excellent impact resistance and mechanical strength, and excellent workability can produce products such as door handles, roof rack covers, etc. that require low gloss and impact resistance.

Thermoplastic, low gloss, polyester

Description

Thermoplastic resin composition with low gloss

The present invention relates to a low gloss thermoplastic resin composition. More specifically, the present invention relates to a low-gloss thermoplastic resin composition having mechanical strength and excellent processability.

In general, polyester resin compositions based on thermoplastic polyester resins and aromatic polycarbonates are resin compositions which improve weather resistance and chemical resistance while maintaining excellent impact resistance, heat resistance, and mechanical strength. Used extensively in However, the resin composition of the polyester copolymer exhibits high surface gloss, which may be an advantage of a plastic molded article, but in certain applications, it may also be a disadvantage such as easily causing fatigue or visual impairment due to excessive gloss.

For example, roof racks, door handles and the like require a low gloss surface for the purpose of eliminating visual impairment and a luxurious atmosphere. In addition, the coating process is performed to make the high gloss surface low gloss, which is a factor of the increase in cost, and there is also a problem of environmental pollution, which lowers the gloss of the resin itself and increases the demand for low gloss resin that does not need to be coated. Doing.

In order to meet the demand by reducing the surface gloss of the resin molded article, Korean Patent Publication No. 10-2007-0070686 discloses a method of adding a styrene-based rubbery copolymer, ethylene / alkyl (meth) acrylate, Fatigue resistance is reduced and weather resistance is deteriorated, indicating a fatal disadvantage that requires additional processing.

In order to solve the above problems, a method of adding an organic quencher has been proposed, but there is a problem of causing a decrease in impact strength and other important physical properties.

Accordingly, there is a need for a thermoplastic resin composition having low gloss, impact resistance, excellent mechanical strength, and excellent workability.

The present invention is to provide a thermoplastic resin composition excellent in matting properties.

In one aspect of the invention, 20 to 70% by weight of polyester; 20 to 70% by weight aromatic polycarbonate; 1 to 15 weight percent acrylic rubber; And 0.1 to 10 weight percent quencher; It provides a low gloss thermoplastic resin composition comprising a.

According to one embodiment, 1 to 10% by weight of the spherical polyalkyl methacrylate; may further include.

According to one embodiment, the matting agent may be ethylene-alkylacrylate-glycidyl methacrylate.

According to one embodiment, the ethylene-alkylacrylate-glycidyl methacrylate is 15 to 30% by weight alkylacrylate units, 5 to 12% by weight glycidyl methacrylate units and 58 to 80% by weight ethylene units It may be made of.

According to one embodiment, the polyester is at least one dica selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenylether dicarboxylic acid, diphenyl dicarboxylic acid and diphenylsulfone dicarboxylic acid Carboxylic acid and ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexane dimethylol, 2,2 bis (4-βhydroxy phenyl-phenyl) -propane, 4,4 It can be prepared by polymerizing; at least one diol selected from the group consisting of -bis- (β-hydroxy epoxy) -diphenyl sulfone and diethylene glycol.

According to one embodiment, the aromatic polycarbonate is bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxy Phenyl)-(4-isobutylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, 1-phenyl-1, 1-bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,10-bis (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, carbonyl chloride, carbonyl bromide, Bis halo formate, diphenyl carbonate, dimethyl carbonate, para-isopropylphenol, para-tert-butylphenol, para-cumylphenol, para-isoctylphenol, para-isononylphenol and para-tert-butylphenol (PTBP At least one compound selected from the group consisting of It can manufacture by sieve.

According to one embodiment, the acrylic rubber is methacrylonitrile-butadiene-styrene (MBS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene-propylene-diene terpolymer-styrene (AES) , Acrylonitrile-styrene-butylacrylate (ASA), ethylene-propylene-diene terpolymer (EPDM), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene (SB) Styrene-isoprene rubber, ethylene-vinylacetate (EVA), ethylene-ethyl acrylate (EEA), ethylene-vinyl alcohol (EVOH) copolymer, silicone-acrylic rubber core and methyl methacrylate shell, It may be at least one selected from the group consisting of a PBT-based elastomer, a PET-based elastomer and a Nylon-based elastomer.

According to one embodiment, the spherical polyalkyl methacrylate is one or more crosslinking agents selected from divinylbenzene, ethylene glycol dimethacrylate, diethyl glycol dimethacrylate and diethylene glycol dimethacrylate relative to the total weight It can be polymerized using 0.1 to 20% by weight.

According to one embodiment, the spherical polyalkyl methacrylate may be particles having an average particle diameter of 1 to 15μm.

According to one embodiment, the polyalkyl methacrylate may be polymethyl methacrylate.

In another aspect of the invention, the method for producing a low-gloss thermoplastic resin composition, 20 to 70% by weight of polyester; 20 to 70% by weight aromatic polycarbonate; 1 to 15 weight percent acrylic rubber; And 0.1 to 10% by weight of ethylene-alkylacrylate-glycidyl methacrylate; provides a method for producing a low gloss thermoplastic resin composition characterized in that the mixture is prepared.

The thermoplastic resin composition according to the present invention has excellent matting effect, excellent impact resistance and mechanical strength, and is excellent in workability, and is useful for producing products such as door handles and roof rack covers requiring low gloss and impact resistance.

As the invention allows for various changes and numerous embodiments, particular embodiments will be described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

Description of each component of the thermoplastic resin composition of this invention is as follows.

Polyester

Polyester according to an embodiment of the present invention can be prepared by polymerizing dicarboxylic acid (Dicarboxylic acid) and diol (Diol). For example, when a dicarboxylic acid such as Chemical Formula 1 and a diol such as Chemical Formula 2 are polymerized, a polyester such as Chemical Formula 3 may be produced.

[Formula 1]

[Formula 2]

(3)

In Formula 1, A may be a substituted or unsubstituted cyclic or chain hydrocarbon. More preferably, it may be a plurality of aromatic or heteroaromatic rings. Examples of dicarboxylic acids that can be used in the present invention are terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenylether dicarboxylic acid, diphenyl dicarboxylic acid or diphenylsulfone dicarboxylic acid.

In Formula 2, B may be a substituted or unsubstituted cyclic or chain hydrocarbon. Examples of diols that may be used in the present invention include ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexane dimethylol, 2,2 bis (4-βhydroxy phenyl-phenyl)- Propane, 4,4-bis- (β-hydroxy epoxy) -diphenyl sulfone or diethylene glycol. It is preferable to use α, ω-diol as in the above example.

The content of polyester is preferably 20 to 70% by weight, more preferably 30 to 60% by weight. When the content of the polyester is less than 20% by weight, the mechanical strength and fluidity is lowered, and when the content of the polyester is more than 70% by weight, it is difficult to obtain the desired physical properties as the impact properties are lowered.

Polycarbonate

Polycarbonate according to an embodiment of the present invention may be prepared from a dihydric phenol, a carbonate precursor or a molecular weight modifier to control the molecular weight.

The dihydric phenols can be any substance derived from the structure of the following formula (4).

[Formula 4]

In formula (4), C represents no alkyl group or functional group at all, or functional groups such as sulfide, ether, sulfoxide, sulfone and ketone or a straight, branched or cyclic alkyl group, preferably C is 1 to 10 carbons. A straight, branched or cyclic alkyl group containing is represented.

And R ¹ and R ² represent a hydrogen, a halogen atom, a straight, branched or cyclic alkyl group. On the other hand, n and m can independently select an integer of 0 to 4.

Specific examples of the dihydric phenols are as follows.

Bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl)-(4-isobutylphenyl) methane , 1,1-bis (4-hydroxyphenyl) ethane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane , 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,10-bis (4-hydroxyphenyl) decane, 2- Methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), and the like, of which 2,2-bis (4-hydroxy Phenyl) propane (bisphenol A).

As the carbonate precursor, phosgene (carbonyl chloride) is preferably applied as another monomer of polycarbonate, and carbonyl bromide, bis halo formate, diphenyl carbonate, dimethyl carbonate, and the like may be used.

Molecular weight modifiers can be used as monofunctional compounds which are similar to those already known, i.e., monomers used in the production of polycarbonates.

By way of example, derivatives (e.g., para-isopropylphenol, para-tert-butylphenol, para-cumylphenol, para-isooctylphenol or para-isononylphenol) based on phenol can be used and In addition, various kinds of substances such as aliphatic alcohols can be used, and among these, para-tert-butylphenol (PTBP) is preferably used.

On the other hand, it is preferable to apply what the aromatic average molecular weight (Mv) measured in the methylene chloride solution is 17,000-40,000, and, as for an aromatic polycarbonate, it is more preferable to use 20,000-30,000.

If the average molecular weight is less than 20,000, mechanical properties such as impact strength and tensile strength are significantly lowered. If the average molecular weight is more than 30,000, there is a problem in processing due to an increase in melt viscosity.

Polycarbonate used in one embodiment of the present invention may be used in the form of a homopolymer, a copolymer (polymer) or a blend thereof. In addition, the polycarbonate may be partially or entirely replaced by a copolycarbonate copolymerized with an aromatic polyester-carbonate resin or a silicone-based resin obtained by polymerizing in the presence of an ester precursor, such as a bifunctional carboxylic acid.

The content of the polycarbonate resin is 20 to 70% by weight is suitable, preferably 30 to 60% by weight. If the content is less than 20% by weight, the impact reinforcing effect is insignificant, and if it is more than 70% by weight, the fluidity may decrease.

Acrylic rubber

Acrylic rubber according to an embodiment of the present invention may serve as an impact modifier. Acrylic rubbers that may be used are methacrylonitrile-butadiene-styrene (MBS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene-propylene-diene terpolymer-styrene (AES), acrylonitrile -Styrene-butylacrylate (ASA), ethylene-propylene-diene terpolymer (EPDM), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene (SB), styrene-isoprene Rubber, ethylene-vinylacetate (EVA), ethylene-ethyl acrylate (EEA), ethylene-vinyl alcohol (EVOH) copolymer, silicone-acrylic rubber core, methyl methacrylate shell, elastomer, PBT elastomer, It may be any one selected from the group consisting of a PET-based elastomer and a Nylon-based elastomer.

In addition to the resins mentioned above, any resin that improves impact resistance may be used. Among the compounds, acrylic rubber of the core-shell type is preferable.

The core-shell type acrylic rubber has a two-layer structure composed of a core (core) and a shell (shell). This core portion is in a soft rubber state, the shell portion on the surface thereof is in a hard resin state, and a graft rubber elastic body in which the rubbery elastic body itself is powdery (particle state) can be suitably used.

The compounding quantity of an acrylic rubber is 1-15 weight%, Preferably it is 2-10 weight%. When the content of the acrylic rubber is less than 1% by weight, the impact resistance may be improved, and when the content is more than 15% by weight, other mechanical properties may be considerably degraded.

Matting agent

In one embodiment of the present invention, it is preferable to use a compound represented by the following formula (5) as a quencher.

[Chemical Formula 5]

R1 and R3 in Formula 5 may be a substituted or unsubstituted cyclic or chain hydrocarbon having 1 to 10 carbon atoms. In addition, R 2 is a substituted or unsubstituted cyclic or chain hydrocarbon having 1 to 10 carbon atoms, and may optionally include one or more non-carbon elements such as sulfur (S), oxygen (O), and nitrogen (N). .

Preferably, Formula 5 may be an ethylene-alkylacrylate-glycidyl methacrylate copolymer wherein R 1 is alkyl and R 2 is glycidyl and R 3 is methyl. More preferred examples may be ethylene-normal butyl acrylate-glycidyl methacrylate.

x, y and z may each be 2 to 30,000 as the average degree of polymerization. For example, the ethylene-normal butyl acrylate-glycidyl methacrylate copolymer has 15 to 30 wt% of normal butyl acrylate units, 5 to 12 wt% of glycidyl methacrylate units and 58 to ethylene units. It is preferably made up of 80% by weight.

The copolymer represented by Chemical Formula 5 performs an impact modifier and a quencher function, thereby improving the hydrolysis resistance by reducing the carboxyl end group reaction and carboxyl end group concentration of the PBT resin due to the structure of the repeating unit z. It also functions. When the content of the copolymer represented by Formula 5 is less than 0.1% by weight, the impact resistance may be improved. If the content is more than 10% by weight, other mechanical properties may be considerably lowered.

Spherical Polyalkylmethacrylates

Spherical polyalkyl methacrylate of one embodiment of the present invention is the total weight of at least one crosslinking agent selected from divinylbenzene, ethylene glycol dimethacrylate, diethyl glycol dimethacrylate, diethylene glycol dimethacrylate It is a spherical particle having a size of 1 to 15μm average particle size polymerized using 0.1 to 20% by weight.

The alkyl group of the aforementioned polyalkyl methacrylate may be a substituted or unsubstituted cyclic or chain hydrocarbon having 1 to 10 carbon atoms.

In a preferred embodiment, polymethylmethacrylate may be used.

When the content of the spherical polyalkyl methacrylate is less than 1% by weight, the matting effect may be insignificant, and when the content is more than 10% by weight, other mechanical properties may be considerably degraded.

Other additives

The resin composition of the present invention may further include an antioxidant or a lubricant generally used in polycarbonate and polyester-based resin. For example, phosphite-based, thioester-based antioxidants and stearates or fatty acids may be used, and 0.05 to 1 parts by weight may be added based on 100 parts by weight of the resin composition.

It will be described in more detail through the following examples.

Hereinafter, the present invention will be described with reference to preferred embodiments, but those skilled in the art can variously change the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. It will be appreciated that modifications and variations can be made.

Many embodiments other than the above-described embodiments are within the scope of the claims of the present invention.

Example

The raw materials were mixed in the compositions and contents shown in Table 1 below, and kneaded and extruded by a twin screw melt kneading extruder at a temperature of 230 to 260 ° C. to prepare a molding pallet. Then, after hot-drying at 100 ℃ for 6 hours, the specimen was prepared by injection molding at a temperature of 250 ~ 270 ℃.

division Example One 2 3 Polyester 46 47.5 57 Polycarbonate 46 47.5 38 Acrylic rubber 4 4 4 Ethylene-Normalbutylacrylate-Glycidylmethacrylate One One One Spherical Polyalkylmethacrylates 3

Polyester used TRIBIT 1700S manufactured by Samyang Corporation. The polycarbonate used TRIREX 3022PJ manufactured by Samyang Corporation. Acrylic rubber was W450A manufactured by Mitsubishi Rayon. It is an impact modifier of the structure in which the acrylic rubber is the core and the polymethyl methacrylate is the shell.

The ethylene-normal butyl acrylate-glycidyl methacrylate copolymer used Elvaloy PTW manufactured by Dupont. This is a normal butyl acrylate / methacrylate copolymer having 5% by weight of glycidyl methacrylate as a functional group relative to 100% by weight of the total copolymer.

As the spherical polymethyl methacrylate, Ganzpearl GM-0600 manufactured by Ganz Chemical was used.

Comparative example

In order to compare the effects of the matting agent of the above-described embodiment, the raw materials were mixed in the composition and content as shown in Table 2, except for the matting agent, and kneaded and extruded by a twin screw melt kneading extruder at a temperature of 230 to 260 ° C to form a pallet. Was prepared. Then, after hot-drying at 100 ℃ for 6 hours, the specimen was prepared by injection molding at a temperature of 250 ~ 270 ℃.

division Comparative example One 2 Polyester 48 57.6 Polycarbonate 48 38.4 Acrylic rubber 4 4

Polyester used TRIBIT 1700S manufactured by Samyang Corporation. The polycarbonate used TRIREX 3022PJ manufactured by Samyang Corporation. Acrylic rubber was W450A manufactured by Mitsubishi Rayon. It is an impact modifier of the structure in which the acrylic rubber is the core and the polymethyl methacrylate is the shell.

Experimental Example

Measurement of the surface glossiness of the Examples and Comparative Examples prepared by the above-described method was measured at an angle of 60 ° according to ASTM D-523, the flowability of the melt index at 250 ℃, 5kg load conditions (ASTM D-1238) Melt Index) was measured, and the Izod impact strength was measured with a 1/8 inch specimen notched according to ASTM-D256. Tensile strength was measured under a condition of 50 mm / min based on ASTM-D638. The physical property evaluation results thus measured are shown in Table 3 below.

division Example Comparative example One 2 3 One 2 Tensile Strength (kg _f / cm ² ) 585 586 586 628 634 Izod impact strength (kg _f cm / cm) 70 72 73 14 55 Glossiness (%) 48 65 74 91 96 Flowability (g / 10min) 20 21 21 25 22

As shown in Table 3, the compositions of Examples 1 to 3 according to the present invention have a similar quenching effect and impact compared to the compositions of Comparative Examples 1 to 2, while having a tensile strength and flowability similar to those of Comparative Examples 1 or 2 The strength was found to increase. The small gloss means that the matting effect of the present invention is excellent.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (9)

20 to 70 wt% polyester, 20 to 70 wt% aromatic polycarbonate, 1 to 15 wt% acrylic rubber and 0.1 to 10 wt% ethylene-alkylacrylate-glycidyl methacrylate; Low gloss thermoplastic resin composition. The method of claim 1, A low gloss thermoplastic resin composition further comprising 1 to 10% by weight of a spherical polyalkyl methacrylate. delete The method of claim 1, The ethylene-alkylacrylate-glycidyl methacrylate is composed of 15 to 30% by weight of alkyl acrylate units, 5 to 12% by weight of glycidyl methacrylate units and 58 to 80% by weight of ethylene units. Low gloss thermoplastic resin composition. The method according to claim 1 or 2, The polyester is at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl dicarboxylic acid and diphenylsulfone dicarboxylic acid; and Ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexane dimethylol, 2,2 bis (4-βhydroxy phenyl-phenyl) -propane, 4,4-bis- (β At least one diol selected from the group consisting of -hydroxy epoxy) -diphenyl sulfone and diethylene glycol; and a low gloss thermoplastic resin composition prepared by polymerizing. The method according to claim 1 or 2, The acrylic rubber is methacrylonitrile-butadiene-styrene (MBS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene-propylene-diene terpolymer-styrene (AES), acrylonitrile-styrene -Butyl acrylate (ASA), ethylene-propylene-diene terpolymer (EPDM), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene (SB), styrene-isoprene rubber , Ethylene-vinylacetate (EVA), ethylene-ethyl acrylate (EEA), ethylene-vinyl alcohol (EVOH) copolymer, silicone-acrylic rubber core, methyl methacrylate shell, polybutylene terephthalate A low gloss thermoplastic resin composition, characterized in that at least one selected from the group consisting of an elastomer, a polyethylene terephthalate elastomer and a nylon elastomer. The method of claim 2, The spherical polyalkyl methacrylate is 0.1 to 20% by weight of one or more crosslinking agents selected from divinylbenzene, ethylene glycol dimethacrylate, diethyl glycol dimethacrylate and diethylene glycol dimethacrylate. Low-polymer thermoplastic resin composition, characterized in that the polymerization. The method of claim 2, The spherical polyalkyl methacrylate is a low gloss thermoplastic resin composition, characterized in that the particles having an average particle diameter of 1 to 15μm. The method according to claim 1 or 2, A low gloss thermoplastic resin composition further comprising an antioxidant or a lubricant.