Resin Composition

Abstract

According to one embodiment of the present invention, a resin composition may comprise: a graft copolymer composition comprising a first graft copolymer and a second graft copolymer, wherein the first graft copolymer comprises a rubber polymer having a glass transition temperature of -120°C or higher and -90°C or lower, and the second graft copolymer comprises a rubber polymer having a glass transition temperature of -70°C or higher and -40°C or lower; a matrix copolymer composition comprising any one selected from a first matrix copolymer comprising alkyl-substituted aromatic vinyl monomer units, a second matrix copolymer comprising maleimide monomer units, and a third matrix copolymer comprising alkyl-unsubstituted aromatic vinyl monomer units, or mixtures thereof; an elastomer comprising a polyolefin compound; and a third graft copolymer wherein aromatic vinyl monomer units and vinyl cyanide monomer units are grafted onto a polyalkylene backbone.

Description

Technical Field

[0001] [Cross-references to related applications]

[0002] This application claims the benefit of priority to Korean Patent Application No. 2023-0146520, filed on October 30, 2023, the disclosure of which is incorporated herein by reference in its entirety.

[0003] This invention relates to a resin composition. Background Technology

[0004] Acrylonitrile-butadiene-styrene (ABS) copolymers are prepared through graft copolymerization of styrene and acrylonitrile with butadiene rubber polymers. ABS copolymers offer advantages such as a balanced combination of rigidity, chemical resistance, impact resistance, and processability; excellent impact strength and mechanical properties; surface gloss; secondary processing characteristics including electroplating, printing, and coating; and the ability to produce products in various colors. Therefore, ABS resin is widely used in the manufacture of automotive interior parts.

[0005] However, when vibrations from driving cause ABS resin automotive interior parts to come into contact with each other, or when ABS resin automotive interior parts come into contact with and rub against other components such as polyvinyl chloride, neoprene, polyurethane, natural rubber, polyester or polyethylene lining sheets, foams, etc., a squeaking sound (friction noise) may be produced.

[0006] Because friction noise reduces the quietness inside a car, there is an increasing need to develop an ABS resin that produces less friction noise even when in contact with other components.

[0007] [Existing Technical Documents]

[0008] [Patent Literature]

[0009] (Patent Document 1) KR10-2015-0068313 A Summary of the Invention

[0010] Technical issues

[0011] One object of the present invention is to provide a resin composition that exhibits low frictional noise even at high temperatures and has excellent heat resistance and mechanical properties.

[0012] Technical solution

[0013] (1) The present invention provides a resin composition comprising: a graft copolymer composition comprising a first graft copolymer and a second graft copolymer, wherein the first graft copolymer comprises a rubber polymer having a glass transition temperature of -120°C or higher and -90°C or lower, and the second graft copolymer comprises a rubber polymer having a glass transition temperature of -70°C or higher and -40°C or lower; a matrix copolymer composition comprising any one selected from a first matrix copolymer comprising alkyl-substituted aromatic vinyl monomer units, a second matrix copolymer comprising maleimide monomer units, and a third matrix copolymer comprising alkyl-unsubstituted aromatic vinyl monomer units, or mixtures thereof; an elastomer comprising a polyolefin compound; and a third graft copolymer wherein the aromatic vinyl monomer units and vinyl cyanide monomer units are grafted onto the polyalkylene backbone.

[0014] (2) The present invention provides a resin composition according to (1) above, wherein the rubber polymer contained in the first graft copolymer comprises conjugated diene monomer units and the rubber polymer contained in the second graft copolymer comprises acrylic monomer units.

[0015] (3) The present invention provides a resin composition according to (1) or (2) above, wherein the first matrix copolymer comprises alkyl-substituted aromatic vinyl monomer units and vinyl cyanide monomer units.

[0016] (4) The present invention provides a resin composition according to any one of (1) to (3) above, wherein the second matrix copolymer comprises maleimide monomer units, aromatic vinyl monomer units and maleic anhydride monomer units.

[0017] (5) The present invention provides a resin composition according to any one of (1) to (4) above, wherein the third matrix copolymer comprises an alkyl-unsubstituted aromatic vinyl monomer unit and a vinyl cyanide monomer unit.

[0018] (6) The present invention provides a resin composition according to any one of (1) to (5) above, wherein, based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the content of the second graft copolymer is 4 parts by weight or more and 11 parts by weight or less.

[0019] (7) The present invention provides a resin composition according to any one of (1) to (6) above, wherein, based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the content of the first graft copolymer is 10 parts by weight or more and 30 parts by weight or less.

[0020] (8) The present invention provides a resin composition according to any one of (1) to (7) above, wherein, based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the content of the elastomer is 1 part by weight or more and 5 parts by weight or less.

[0021] (9) The present invention provides a resin composition according to any one of (1) to (8) above, wherein, based on the total amount of 100 parts by weight of the graft copolymer and the matrix copolymer, the content of the third graft copolymer is 1 part by weight or more and 5 parts by weight or less.

[0022] (10) The present invention provides a resin composition according to any one of (1) to (9) above, wherein the matrix copolymer composition comprises the second matrix copolymer and the third matrix copolymer, wherein, based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the content of the second matrix copolymer is 5 parts by weight or more and 25 parts by weight or less, and based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the content of the third matrix copolymer is 50 parts by weight or more and 70 parts by weight or less.

[0023] (11) The present invention provides a resin composition according to any one of (1) to (10) above, wherein the RPN grade measured according to VDA230-206 at 75°C, relative humidity of 50%, speed of 1 mm / s and normal force of 10 N is 3 or less.

[0024] Beneficial effects

[0025] The resin composition according to the present invention exhibits low frictional noise even at high temperatures, and possesses excellent heat resistance and mechanical properties. Detailed Implementation

[0026] The invention will be described in more detail below to aid in understanding it.

[0027] The terms or words used in the specification and claims of this application should not be construed as limited to their ordinary or dictionary meanings, but rather based on the principle that the inventors may appropriately define the concepts of the terms to best describe their invention, and should be interpreted as having meanings and concepts consistent with the technical concept of the invention.

[0028] In this invention, the term "monomer unit" can refer to a component, structure, or substance derived from a monomer, and as a specific example, it can refer to a repeating unit in a polymer formed from a monomer introduced during polymer polymerization and participating in the polymerization reaction.

[0029] The term "composition" as used in this invention includes reaction products and decomposition products formed from the materials of the composition and mixtures of materials comprising the composition.

[0030] In this invention, the average particle size of the graft copolymer can be measured using a dynamic light scattering method. As a specific example, it can be measured using a Nicomp 380 HPL device (product name, manufactured by Nicomp). In this specification, the average particle size refers to the arithmetic mean particle size in the particle size distribution measured by the dynamic light scattering method, i.e., the average particle size based on scattering intensity.

[0031] In this invention, the weight-average molecular weight of each component forming the resin composition can be measured as a relative value to standard polystyrene, which is used as a standard sample, by gel permeation chromatography using tetrahydrofuran as the eluent.

[0032] <Resin Composition>

[0033] The present invention provides a resin composition.

[0034] According to one embodiment of the present invention, a resin composition comprises: a graft copolymer composition comprising a first graft copolymer and a second graft copolymer, wherein the first graft copolymer comprises a rubber polymer having a glass transition temperature of -120°C or higher and -90°C or lower, and the second graft copolymer comprises a rubber polymer having a glass transition temperature of -70°C or higher and -40°C or lower; a matrix copolymer composition comprising any one selected from a first matrix copolymer comprising alkyl-substituted aromatic vinyl monomer units, a second matrix copolymer comprising maleimide monomer units, and a third matrix copolymer comprising alkyl-unsubstituted aromatic vinyl monomer units, or mixtures thereof; an elastomer comprising a polyolefin compound; and a third graft copolymer wherein the aromatic vinyl monomer units and vinyl cyanide monomer units are grafted onto the polyalkylene backbone.

[0035] The inventors have discovered that when a resin composition comprises a first graft copolymer containing a rubber polymer with a glass transition temperature of -120°C or higher and -90°C or lower, and a second graft copolymer containing a rubber polymer with a glass transition temperature of -70°C or higher and -40°C or lower, the resin composition exhibits low frictional noise and excellent heat resistance and mechanical properties even at high temperatures, thus completing the present invention.

[0036] Specifically, the resin composition according to one embodiment of the invention has an RPN rating of less than 3, measured according to VDA 230-206 using a Ziegler stick-slip tester (SSP-04) under conditions of 75°C, 50% relative humidity, speed of 1 mm / s and normal force of 10 N, indicating a significantly lower likelihood of generating frictional noise at high temperatures.

[0037] In the following, each component of the resin composition according to one embodiment of the present invention will be described.

[0038] 1. Graft copolymer composition

[0039] According to one embodiment of the present invention, the graft copolymer composition may comprise a first graft copolymer and a second graft copolymer, wherein the first graft copolymer comprises a rubber polymer having a glass transition temperature of -120°C or higher and -90°C or lower, and the second graft copolymer comprises a rubber polymer having a glass transition temperature of -70°C or higher and -40°C or lower.

[0040] According to one embodiment of the present invention, the resin composition simultaneously comprises a first graft copolymer and a second graft copolymer, the first graft copolymer comprising a rubber polymer with a glass transition temperature of -120°C or higher and -90°C or lower, and the second graft copolymer comprising a rubber polymer with a glass transition temperature of -70°C or higher and -40°C or lower, thereby improving the stick-slip phenomenon and enabling the resin composition to generate less frictional noise even at high temperatures.

[0041] (1) First graft copolymer

[0042] According to one embodiment of the invention, the first graft copolymer is a component that improves the impact resistance of the resin composition, and may be a graft polymer comprising a conjugated diene monomer unit as a rubber polymer, and a shell grafted onto the conjugated diene polymer comprising aromatic vinyl monomer units and vinyl cyanide monomer units. The shell may comprise aromatic vinyl monomer units and vinyl cyanide monomer units not grafted onto the conjugated diene polymer.

[0043] According to one embodiment of the present invention, the conjugated diene monomer used to form the conjugated diene monomer unit contained in the first graft copolymer may be at least one selected from 1,3-butadiene, isoprene, chloroprene and isoprene, and as a specific example, it may be 1,3-butadiene.

[0044] According to one embodiment of the present invention, the aromatic vinyl monomer used to form the aromatic vinyl monomer unit contained in the first graft copolymer may be at least one selected from α-methylstyrene, α-ethylstyrene, p-methylstyrene, 2,4-dimethylstyrene, styrene, p-fluorostyrene, p-chlorostyrene, and p-bromostyrene, and as a specific example, it may be styrene.

[0045] According to one embodiment of the present invention, the vinyl cyanide monomer used to form the vinyl cyanide monomer unit contained in the first graft copolymer may be at least one selected from acrylonitrile, methacrylonitrile, (Z)-3-phenylacrylonitrile and α-chloroacrylonitrile, and as a specific example, may be acrylonitrile.

[0046] According to one embodiment of the present invention, the content of the conjugated diene polymer contained in the first graft copolymer can be from 40% to 80% by weight, preferably from 50% to 70% by weight, based on the total weight of the first graft copolymer. When the above conditions are met, the impact resistance of the graft polymer composition can be further improved.

[0047] According to one embodiment of the present invention, based on the total weight of the first graft copolymer, the content of aromatic vinyl monomer units contained in the first graft copolymer can be from 10% to 50% by weight, preferably from 20% to 40% by weight. When the above conditions are met, the processing performance of the graft copolymer can be further improved.

[0048] According to one embodiment of the invention, the content of vinyl cyanide monomer units contained in the first graft copolymer can be from 1% to 30% by weight, preferably from 5% to 25% by weight, based on the total weight of the first graft copolymer. When the above conditions are met, the chemical resistance of the graft polymer composition can be further improved.

[0049] According to one embodiment of the invention, the glass transition temperature of the rubber polymer contained in the first graft copolymer can be above -120°C and below -90°C. Specifically, it can be above -118°C, above -116°C, above -114°C, above -112°C, above -110°C, above -108°C, above -106°C, or above -104°C, and below -91°C, below -92°C, below -93°C, below -94°C, below -95°C, below -96°C, below -97°C, below -98°C, or below -99°C. The glass transition temperature of the rubber polymer contained in the first graft copolymer can be measured using a differential scanning calorimeter, using a solid obtained by coagulation with sulfuric acid, MgSO4, CaCl2, or Al2(SO4)3, etc., as well as well-known coagulants for rubber polymer latex.

[0050] According to one embodiment of the present invention, based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the resin composition may contain 10 parts by weight or more and 30 parts by weight of the first graft copolymer. Specifically, it may contain 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, 14 parts by weight or more, or 15 parts by weight or more, and 28 parts by weight or less, 26 parts by weight or less, 24 parts by weight or less, 22 parts by weight or less, or 20 parts by weight or less. When the above ranges are met, the impact strength and flow index of the resin composition can be improved.

[0051] (2) Second graft copolymer

[0052] According to one embodiment of the invention, the first graft copolymer is a component that improves the impact resistance of the resin composition, and may be a graft polymer comprising an acrylic monomer unit as a rubber polymer, and a shell grafted onto the acrylic polymer comprising aromatic vinyl monomer units and vinyl cyanide monomer units. The shell may comprise aromatic vinyl monomer units and vinyl cyanide monomer units not grafted onto the acrylic polymer.

[0053] According to one embodiment of the present invention, the acrylic monomer used to form the acrylic monomer unit contained in the second graft copolymer may be (meth)acrylic acid C4 to C4. 10 Alkyl ester monomers, as specific examples, may be at least one selected from (meth)acrylate, ... and (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate, (meth)acrylate,

[0054] According to one embodiment of the present invention, the aromatic vinyl monomer used to form the aromatic vinyl monomer unit contained in the second graft copolymer may be at least one selected from α-methylstyrene, α-ethylstyrene, p-methylstyrene, 2,4-dimethylstyrene, styrene, p-fluorostyrene, p-chlorostyrene, and p-bromostyrene, and as a specific example, it may be styrene.

[0055] According to one embodiment of the present invention, the vinyl cyanide monomer used to form the vinyl cyanide monomer unit contained in the second graft copolymer may be at least one selected from acrylonitrile, methacrylonitrile, (Z)-3-phenylacrylonitrile and α-chloroacrylonitrile, and as a specific example, may be acrylonitrile.

[0056] According to one embodiment of the present invention, based on the total weight of monomers introduced during the production of the second graft copolymer, the amount of acrylic monomers introduced can be 30% by weight or more and 70% by weight, or 35% by weight or more and 65% by weight, more specifically, 40% by weight or more and 60% by weight. When the above ranges are met, the weather resistance, impact resistance, surface gloss properties, elongation, and whitening properties of the second graft copolymer can be further improved.

[0057] According to one embodiment of the present invention, based on the total weight of monomers introduced during the production of the second graft copolymer, the amount of aromatic vinyl monomers introduced can be 20% by weight or more and 50% by weight, or 25% by weight or more and 45% by weight, more specifically, 30% by weight or more and 40% by weight. When the above ranges are met, not only can the processing properties of the second graft copolymer be further improved, but the second graft copolymer can also be more uniformly dispersed in the resin composition, and the colorability of the resin composition can be further improved.

[0058] According to one embodiment of the present invention, based on the total weight of monomers introduced during the production of the second graft copolymer, the amount of vinyl cyanide monomers introduced may be 5% by weight or more and 25% by weight or less, or 7% by weight or more and 22% by weight or less, more specifically, 10% by weight or more and 20% by weight or less. When the above ranges are met, not only can the chemical resistance of the second graft copolymer be further improved, but the second graft copolymer can also be more uniformly dispersed in the resin composition, and the colorability of the resin composition can be further improved.

[0059] According to one embodiment of the invention, the glass transition temperature of the rubber polymer contained in the second graft copolymer can be above -70°C and below -40°C. Specifically, it is above -68°C, above -66°C, above -64°C, above -62°C, above -60°C, above -58°C, above -56°C, above -54°C, or above -52°C, and below -41°C, below -42°C, below -43°C, below -44°C, below -45°C, below -46°C, below -47°C, below -48°C, or below -49°C. The glass transition temperature of the rubber polymer contained in the second graft copolymer can be measured using a differential scanning calorimeter, using a solid obtained by coagulation with sulfuric acid, MgSO4, CaCl2, or Al2(SO4)3, etc., as well as well-known coagulants for rubber polymer latex.

[0060] According to one embodiment of the present invention, based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the resin composition may contain 4 or more and 11 or less of a second graft copolymer. Specifically, it may contain 4.2 or more, 4.4 or more, 4.6 or more, 4.8 or more, or 5 or more, and 10.8 or less, 10.6 or less, 10.4 or less, 10.2 or less, or 10 or less of the second graft copolymer. When the above ranges are met, the impact strength and weather resistance of the resin composition can be improved.

[0061] 2. Matrix copolymer composition

[0062] According to one embodiment of the invention, the matrix copolymer composition may comprise any one of a first matrix copolymer comprising alkyl-substituted aromatic vinyl monomer units, a second matrix copolymer comprising maleimide monomer units, and a third matrix copolymer comprising alkyl-unsubstituted aromatic vinyl monomer units, or a mixture thereof.

[0063] As a specific example, the matrix copolymer composition according to one embodiment of the present invention may contain any one of a first matrix copolymer, a second matrix copolymer, or a third matrix copolymer, or may contain a mixture of two selected from the first matrix copolymer, the second matrix copolymer, or the third matrix copolymer, or may contain the first matrix copolymer, the second matrix copolymer, and the third matrix copolymer.

[0064] When the matrix copolymer composition according to one embodiment of the present invention comprises a second matrix copolymer and a third matrix copolymer, the frictional noise performance of the resin composition can be further improved.

[0065] In the following text, each of the first matrix copolymer, the second matrix copolymer, and the third matrix copolymer that form the matrix copolymer composition will be described.

[0066] (1) First matrix copolymer

[0067] According to one embodiment of the present invention, the first matrix copolymer is a component that improves the heat resistance of the resin composition, is a non-grafted copolymer, and may contain alkyl-substituted aromatic vinyl monomer units and vinyl cyanide monomer units.

[0068] According to one embodiment of the present invention, the alkyl-substituted aromatic vinyl monomer used to form the alkyl-substituted aromatic vinyl monomer unit contained in the first matrix copolymer may be at least one selected from α-methylstyrene, p-methylstyrene and 2,4-dimethylstyrene, and as a specific example, it may be α-methylstyrene.

[0069] According to one embodiment of the present invention, the vinyl cyanide monomer used to form the vinyl cyanide monomer unit contained in the first matrix copolymer may be at least one selected from acrylonitrile, methacrylonitrile, (Z)-3-phenylacrylonitrile and α-chloroacrylonitrile, and as a specific example, may be acrylonitrile.

[0070] According to one embodiment of the invention, based on the total weight of the first matrix copolymer, the content of alkyl-substituted aromatic vinyl monomer units contained in the first matrix copolymer can be from 60% to 90% by weight, preferably from 65% to 85% by weight.

[0071] Furthermore, according to one embodiment of the invention, based on the total weight of the first matrix copolymer, the content of vinyl cyanide monomer units contained in the first matrix copolymer can be from 10% to 40% by weight, preferably from 15% to 35% by weight.

[0072] When the above conditions are met, phase separation of the first matrix copolymer from the resin composition can be prevented.

[0073] According to one embodiment of the invention, the first matrix copolymer may further comprise alkyl-unsubstituted aromatic vinyl monomer units to achieve excellent molding properties. The alkyl-unsubstituted aromatic vinyl monomer used to form the alkyl-unsubstituted aromatic vinyl monomer units may be at least one selected from styrene, 4-fluorostyrene, 4-chlorostyrene, 2-chlorostyrene, 4-bromostyrene, and 2-bromostyrene; as a specific example, it may be styrene.

[0074] In this case, based on the total weight of the first matrix copolymer, the content of alkyl unsubstituted aromatic vinyl monomer units contained in the first matrix copolymer can be less than 15% by weight, preferably less than 10% by weight.

[0075] According to one embodiment of the present invention, when the resin composition contains a first matrix copolymer, the content of the first matrix copolymer can be 15 parts by weight or more and 85 parts by weight or less, based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition. Specifically, it is 17 parts by weight or more, 19 parts by weight or more, 21 parts by weight or more, 23 parts by weight or more, or 25 parts by weight or more, and 83 parts by weight or less, 81 parts by weight or less, 79 parts by weight or less, 77 parts by weight or less, or 75 parts by weight or less. When the above ranges are met, the heat resistance of the resin composition can be improved.

[0076] (2) Second matrix copolymer

[0077] According to one embodiment of the present invention, the second matrix copolymer is a component that improves the heat resistance and processing properties of the resin composition, is a non-grafted copolymer, and may contain maleimide monomer units, aromatic vinyl monomer units, and maleic acid monomer units.

[0078] According to one embodiment of the present invention, the maleimide monomer used to form the maleimide monomer unit contained in the second matrix copolymer may be selected from maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N... At least one of phenylmaleimide, N-(4-chlorophenyl)maleimide, 2-methyl-N-phenylmaleimide, N-(4-bromophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, N-(4-methoxyphenyl)maleimide, N-(4-carboxyphenyl)maleimide, and N-benzylmaleimide, may be used as a specific example, N-phenylmaleimide.

[0079] According to one embodiment of the present invention, the aromatic vinyl monomer used to form the aromatic vinyl monomer unit contained in the second matrix copolymer may be at least one selected from α-methylstyrene, α-ethylstyrene, p-methylstyrene, 2,4-dimethylstyrene, styrene, p-fluorostyrene, p-chlorostyrene and p-bromostyrene, and as a specific example, it may be styrene.

[0080] According to one embodiment of the present invention, the maleic acid monomer used to form the maleic acid monomer unit contained in the second matrix copolymer may be at least one selected from maleic anhydride, maleic acid, maleic acid monoester and maleic acid diester, and as a specific example, it may be maleic anhydride.

[0081] According to one embodiment of the invention, based on the total weight of the second matrix copolymer, the content of units derived from maleimide monomers in the second matrix copolymer can be 35% to 65% by weight, 40% to 60% by weight, or 45% to 55% by weight, preferably 45% to 55% by weight. When the above ranges are met, the heat resistance of the resin composition can be further improved.

[0082] According to one embodiment of the invention, based on the total weight of the second matrix copolymer, the content of units from aromatic vinyl monomers can be 30% to 60% by weight, 35% to 55% by weight, or 40% to 50% by weight, preferably 40% to 50% by weight. When the above ranges are met, the resin composition has the advantages of excellent mechanical properties and a good balance of properties.

[0083] According to one embodiment of the invention, based on the total weight of the second matrix copolymer, the content of units from maleic acid monomers can be from 0.1% to 10% by weight, 0.5% to 7% by weight, or 1% to 5% by weight, preferably 1% to 5% by weight. When the above ranges are met, the resin composition has the advantages of excellent mechanical properties and a good balance of properties.

[0084] According to one embodiment of the present invention, when the resin composition contains a second matrix copolymer, the content of the second matrix copolymer can be 5 parts by weight or more and 50 parts by weight, based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition. Specifically, it can be 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, or 10 parts by weight or more, and 48 parts by weight or less, 46 parts by weight or less, 44 parts by weight or less, 42 parts by weight or less, 40 parts by weight or less, 38 parts by weight or less, 36 parts by weight or less, 34 parts by weight or less, 32 parts by weight or less, 30 parts by weight or less, 28 parts by weight or less, 26 parts by weight or less, 25 parts by weight or less, 22 parts by weight or less, or 20 parts by weight or less. When the above ranges are met, the impact strength, heat resistance, and flow index of the resin composition can be improved, and the friction noise performance of the resin composition can be improved.

[0085] (3) Third matrix copolymer

[0086] According to one embodiment of the present invention, the third matrix copolymer is a component that improves the tensile strength and processing properties of the resin composition. It is a non-grafted copolymer and may contain alkyl-unsubstituted aromatic vinyl monomer units and vinyl cyanide monomer units.

[0087] According to one embodiment of the present invention, the alkyl-unsubstituted aromatic vinyl monomer used to form the alkyl-unsubstituted aromatic vinyl monomer unit contained in the third matrix copolymer may be at least one selected from styrene, 4-fluorostyrene, 4-chlorostyrene, 2-chlorostyrene, 4-bromostyrene and 2-bromostyrene, and as a specific example, may be styrene.

[0088] According to one embodiment of the present invention, the vinyl cyanide monomer used to form the vinyl cyanide monomer unit contained in the third matrix copolymer may be at least one selected from acrylonitrile, methacrylonitrile, (Z)-3-phenylacrylonitrile and α-chloroacrylonitrile, and as a specific example, may be acrylonitrile.

[0089] According to one embodiment of the invention, based on the total weight of the third matrix copolymer, the content of alkyl-unsubstituted aromatic vinyl monomer units contained in the third matrix copolymer can be from 60% to 90% by weight, preferably from 65% to 85% by weight. When the above conditions are met, the processing properties of the resin composition can be further improved.

[0090] According to one embodiment of the invention, the content of vinyl cyanide monomer units contained in the third matrix copolymer can be from 10% to 40% by weight, preferably from 15% to 35% by weight, based on the total weight of the third matrix copolymer. When the above conditions are met, the chemical resistance of the resin composition can be further improved.

[0091] According to one embodiment of the present invention, when the resin composition contains a second matrix copolymer, the content of the third matrix copolymer can be 15 parts by weight or more and 75 parts by weight or less, based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition. Specifically, it can be 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more, 45 parts by weight or more, or 50 parts by weight or more, and 73 parts by weight or less, 70 parts by weight or less, 69 parts by weight or less, 67 parts by weight or less, or 65 parts by weight or less. When the above ranges are met, the impact strength and flow index of the resin composition can be improved, and the frictional noise performance of the resin composition can be improved.

[0092] According to one embodiment of the present invention, the matrix copolymer composition may comprise a second matrix copolymer and a third matrix copolymer. In this case, based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the second matrix copolymer and the third matrix copolymer may each be included within the aforementioned range. As a specific example, when the matrix copolymer composition comprises a second matrix copolymer and a third matrix copolymer, based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the content of the second matrix copolymer may be 5 parts by weight or more and 25 parts by weight or less, and the content of the third matrix copolymer may be 50 parts by weight or more and 70 parts by weight or less. In this case, the frictional noise performance of the resin composition can be further improved.

[0093] 3. Elastomers

[0094] According to one embodiment of the invention, the elastomer is a component used to impart frictional noise resistance to the resin composition, and may contain polyolefin compounds.

[0095] According to one embodiment of the present invention, the polyolefin compound contained in the elastomer may be a copolymer of ethylene and an α-olefin with 3 to 8 carbon atoms, more specifically, it may be a copolymer of ethylene and 1-butene.

[0096] According to one embodiment of the present invention, based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the resin composition may contain 1 part by weight and 5 parts by weight of elastomer. Specifically, it may contain 1.1 parts by weight or more, 1.2 parts by weight or more, 1.3 parts by weight or more, 1.4 parts by weight or more, or 1.5 parts by weight or more, and 4.8 parts by weight or less, 4.6 parts by weight or less, 4.4 parts by weight or less, 4.2 parts by weight or less, or 4 parts by weight or less of elastomer. Within the above range, it has the effect of preventing the resin composition from peeling while improving the frictional noise performance of the resin composition.

[0097] 4. Third graft copolymer

[0098] According to one embodiment of the present invention, the third graft copolymer is a component used to improve the compatibility of all components of the resin composition, and may be a copolymer in which aromatic vinyl monomer units and vinyl cyanide monomer units are grafted onto the polyalkylene backbone. The third graft copolymer may also be referred to as a compatibilizer in this specification.

[0099] According to one embodiment of the invention, the third graft copolymer may be a copolymer in which vinyl cyanide monomer units and aromatic vinyl monomer units are grafted to a polyolefin, and as a more specific example, a polyethylene-acrylonitrile-styrene copolymer in which acrylonitrile units and styrene units are grafted to polyethylene. In this case, the polyethylene-acrylonitrile-styrene copolymer may contain 30% to 70% by weight of polyethylene; 30% to 70% by weight of acrylonitrile units and styrene units.

[0100] According to one embodiment of the present invention, based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the resin composition may contain 1 part by weight and 5 parts by weight of a third graft copolymer. Specifically, it may contain 1.1 parts by weight or more, 1.2 parts by weight or more, 1.3 parts by weight or more, 1.4 parts by weight or more, or 1.5 parts by weight or more, and 4.8 parts by weight or less, 4.6 parts by weight or less, 4.4 parts by weight or less, 4.2 parts by weight or less, or 4 parts by weight or less. Within the above range, it has the effect of improving the compatibility of all components of the resin composition, thereby preventing peeling of the resin composition.

[0101] 5. Other additives

[0102] According to one embodiment of the invention, the resin composition may further comprise other additives. The additives may be selected from at least one of the following: lubricants, antioxidants, pigments, light stabilizers, hydrolytic stabilizers, release agents, antistatic agents, conductive agents, electromagnetic shielding agents, magnetic agents, mineral fillers, crosslinking agents, antibacterial agents, processing aids, metal passivators, inhibitors, anti-friction and anti-wear agents, and coupling agents.

[0103] Any additive may be used without restriction, as long as it is applicable to the technical field of this invention. Those skilled in the art may select the additives included in this invention according to their purpose.

[0104] <Molded Products>

[0105] The present invention provides a molded article formed from the resin composition.

[0106] According to one embodiment of the present invention, the molded article can be extruded and injection molded from a resin composition, and can be applied to product groups that simultaneously require mechanical properties, heat resistance and friction noise resistance, as a specific example being automotive interior materials.

[0107] Embodiments of the present invention will be described in detail below to enable those skilled in the art to readily implement the invention. However, the invention may be embodied in various forms and is not limited to the embodiments described in this specification.

[0108] Examples and Comparative Examples

[0109] The materials used in the embodiments and comparative examples are as follows: (1) Graft copolymer (A1): ABS graft copolymer (manufactured by LGC Chemical; product name: DP270E) using emulsion polymerization of butadiene polymer containing 60% by weight of butadiene polymer with Tg of -104°C and average particle size of 300 nm, 10% by weight of acrylonitrile and 30% by weight of styrene.

[0110] (2) Graft copolymer (A2): ASA graft copolymer (manufactured by LG Chemical; product name: SA927) containing 50% by weight of butyl acrylate polymer with a Tg of -53°C and an average particle size of 450 nm, 14% by weight of acrylonitrile and 36% by weight of styrene.

[0111] (3) Graft copolymer (A3): using a graft copolymer containing 60% by weight of styrene-butadiene (25% by weight of styrene and 75% by weight of butadiene) rubber polymer with a Tg of -29°C, 10% by weight of acrylonitrile and 30% by weight of styrene.

[0112] (4) Graft copolymer (A4): ABS graft copolymer (manufactured by LGC Chemical; product name: ER400) made by bulk polymerization of butadiene polymer containing 11% by weight of butadiene polymer with a Tg of -104°C and an average particle size of 1000 nm, 18% by weight of acrylonitrile and 71% by weight of styrene.

[0113] (5) Matrix copolymer (B1): A heat-resistant resin containing 65% by weight of α-methylstyrene, 28% by weight of acrylonitrile and 7% by weight of styrene (manufactured by LG Chemical; product name: 99UH).

[0114] (6) Matrix copolymer (B2): PMI-type heat-resistant resin (manufactured by DENKA; product name: MSNB) containing 52% by weight of N-phenylmaleimide (PMI), 46% by weight of styrene and 2% by weight of maleic anhydride (MAH).

[0115] (7) Matrix copolymer (B3): SAN resin containing 27% by weight acrylonitrile and 76% by weight styrene (manufactured by LG Chemical; product name: 80HF).

[0116] (8) Elastomer (C): Use an elastomer containing polyolefin compounds (manufactured by LG Chemical; product name: LC565).

[0117] (9) Compatibilizer (D): A graft copolymer in which aromatic vinyl monomer units and vinyl cyanide monomer units are grafted to the polyalkylene backbone (manufactured by NOF; product name: MODIPER A1401).

[0118] Resin compositions were prepared by mixing graft copolymers, matrix copolymers, elastomers, and compatibilizers in the amounts described in Tables 1 to 3 below. Granular resin compositions were prepared using a twin-screw extruder kneader along with lubricants and stabilizers at a barrel temperature of 220°C.

[0119] Experimental Example

[0120] The resin compositions prepared in the above examples and comparative examples were extruded together with lubricants and stabilizers using a twin-screw extruder at a barrel temperature of 240°C to produce granules, which were then injected into samples at 240°C. Impact strength, tensile strength, heat distortion temperature, friction noise resistance at room temperature, and friction noise resistance at high temperature were measured using the methods described below and are shown in Tables 1 to 3.

[0121] Notched cantilever beam impact strength (J / m): The impact strength of a notched cantilever beam with a thickness of 1 / 4 inch is measured at 23°C according to ASTM D256.

[0122] Tensile strength (MPa): Tensile strength is measured according to ASTM D638 at a tensile speed of 50 mm / min.

[0123] Heat distortion temperature (°C): Measured according to ASTM D648 under a load of 18.6 kgf and a temperature of 120°C / hour.

[0124] Room temperature friction noise resistance (risk priority number): According to VDA 230-206, the friction noise resistance of a pair of identically prepared specimens was measured using a Ziegler stick-slip tester (SSP-04) at 23°C, 50% relative humidity, a speed of 1 mm / s, and a normal force of 10 N, and expressed as room temperature RPN level.

[0125] High-temperature friction noise resistance (risk priority number): According to VDA 230-206, the friction noise resistance of a pair of identically prepared specimens was measured using a Ziegler stick-slip tester (SSP-04) at 75°C, 50% relative humidity, a speed of 1 mm / s, and a normal force of 10 N, and expressed as the high-temperature RPN level.

[0126] [Table 1]

[0127] [Table 2]

[0128] [Table 3]

[0129] Referring to Tables 1 to 3 above, it can be confirmed that in Examples 1 to 7, the use of a first graft copolymer containing a rubber polymer with a glass transition temperature of -120°C or higher and -90°C or lower, and a second graft copolymer containing a rubber polymer with a glass transition temperature of -70°C or higher and -40°C or lower, results in low frictional noise even at high temperatures, and excellent heat resistance and mechanical properties.

[0130] It can be confirmed that in Comparative Examples 1 to 4 and Comparative Examples 7 to 9, which only use the first graft copolymer containing a rubber polymer with a glass transition temperature of -120°C or higher and -90°C or lower, the high-temperature RPN grade is significantly lower than that of Examples 1 to 7.

[0131] It can be confirmed that in Comparative Examples 5 and 6, which use a first graft copolymer containing a rubber polymer with a glass transition temperature of -120°C or higher and -90°C or lower, and a graft copolymer containing a rubber polymer with a glass transition temperature of -70°C or higher and -40°C or lower, the high-temperature RPN grade is significantly lower than that of Examples 1 to 7.

[0132] It can be confirmed that in Comparative Example 10, which uses different graft copolymers of rubber polymers with glass transition temperatures above -120°C and below -90°C, the high-temperature RPN grade is significantly lower than that of Examples 1 to 7.

Claims

1. A resin composition comprising: A graft copolymer composition comprising a first graft copolymer and a second graft copolymer, wherein the first graft copolymer comprises a rubber polymer having a glass transition temperature of -120°C or higher and -90°C or lower, and the second graft copolymer comprises a rubber polymer having a glass transition temperature of -70°C or higher and -40°C or lower. A matrix copolymer composition comprising any one selected from a first matrix copolymer comprising alkyl-substituted aromatic vinyl monomer units, a second matrix copolymer comprising maleimide monomer units, and a third matrix copolymer comprising alkyl-unsubstituted aromatic vinyl monomer units, or a mixture thereof; Elastomers that contain polyolefin compounds; and The third graft copolymer, wherein aromatic vinyl monomer units and vinyl cyanide monomer units are grafted onto the polyalkylene backbone.

2. The resin composition according to claim 1, wherein, The rubber polymer contained in the first graft copolymer comprises conjugated diene monomer units. The rubber polymer contained in the second graft copolymer comprises acrylic monomer units.

3. The resin composition according to claim 1, wherein, The first matrix copolymer comprises alkyl-substituted aromatic vinyl monomer units and vinyl cyanide monomer units.

4. The resin composition according to claim 1, wherein, The second matrix copolymer comprises maleimide monomer units, aromatic vinyl monomer units, and maleic anhydride monomer units.

5. The resin composition according to claim 1, wherein, The third matrix copolymer comprises alkyl-unsubstituted aromatic vinyl monomer units and vinyl cyanide monomer units.

6. The resin composition according to claim 1, wherein, Based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the content of the second graft copolymer is 4 parts by weight or more and 11 parts by weight or less.

7. The resin composition according to claim 1, wherein, Based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the content of the first graft copolymer is 10 parts by weight or more and 30 parts by weight or less.

8. The resin composition according to claim 1, wherein, Based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the content of the elastomer is more than 1 part by weight and less than 5 parts by weight.

9. The resin composition according to claim 1, wherein, Based on the total amount of 100 parts by weight of the graft copolymer and the matrix copolymer, the content of the third graft copolymer is more than 1 part by weight and less than 5 parts by weight.

10. The resin composition according to claim 1, wherein, The matrix copolymer composition comprises the second matrix copolymer and the third matrix copolymer. Wherein, based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the content of the second matrix copolymer is 5 parts by weight or more and 25 parts by weight or less. Based on the total amount of 100 parts by weight of the graft copolymer composition and the matrix copolymer composition, the content of the third matrix copolymer is 50 parts by weight or more and 70 parts by weight or less.

11. The resin composition according to claim 1, wherein, According to VDA 230-206, the RPN rating measured under the conditions of 75°C, 50% relative humidity, 1 mm / s velocity and 10 N normal force is 3 or lower.

Images