Resin composition

Abstract

A resin composition according to an embodiment of the present invention may comprise: a graft copolymer composition that contains a first graft copolymer including a rubber polymer with a glass transition temperature of -120°C to -90°C, and a second graft copolymer including a rubber polymer with a glass transition temperature of -70°C to -40°C; a matrix copolymer composition that contains any one selected from the group consisting of a first matrix copolymer including alkyl-substituted aromatic vinyl monomer units, a second matrix copolymer including maleimide-based monomer units, a third matrix copolymer including alkyl-unsubstituted aromatic vinyl monomer units, and a combination thereof; an elastomer including a polyolefin-based compound; and a third graft copolymer in which aromatic vinyl monomer units and vinyl cyanide monomer units are grafted onto a polyalkylene backbone.

Description

resin composition

[0001] [Cross-reference with related applications]

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

[0003]

[0004] [Technical Field]

[0005] The present invention relates to a resin composition.

[0006] Acrylonitrile-butadiene-styrene (ABS) copolymers are manufactured by grafting styrene and acrylonitrile onto a rubbery butadiene polymer. ABS copolymers offer a balanced combination of rigidity, chemical resistance, impact resistance, and processability. They also boast excellent impact strength, mechanical properties, surface gloss, and secondary processing characteristics such as plating, printing, and painting. Furthermore, they offer the advantage of being available in a variety of colors. Consequently, ABS resin is widely used in the manufacture of automotive interior components.

[0007] However, when the vibrations accompanying driving cause ABS resin automobile interior parts to come into contact with each other, or when ABS resin automobile interior parts and other materials such as polyvinyl chloride, chloroprene rubber, polyurethane, natural rubber, polyester or polyethylene lining sheets or foams come into contact and rub against each other, a squeaking sound (friction noise) may be generated.

[0008] As the above friction noise reduces the quietness inside the car, there is a growing need to develop ABS resin that produces less friction noise even when in contact with other materials.

[0009] [Prior Art Literature]

[0010] [Patent Document]

[0011] (Patent Document 0001) KR10-2015-0068313 A

[0012] The problem to be solved by the present invention is to provide a resin composition that has low friction noise even at high temperatures and excellent heat resistance and mechanical properties.

[0013] (1) The present invention provides a resin composition comprising a graft copolymer composition comprising a first graft copolymer comprising a rubber polymer having a glass transition temperature of -120°C or more and -90°C or less and a second graft copolymer comprising a rubber polymer having a glass transition temperature of -70°C or more and -40°C or less; a matrix copolymer composition comprising any one selected from the group consisting of a first matrix copolymer comprising an alkyl-substituted aromatic vinyl monomer unit, a second matrix copolymer comprising a maleimide-based monomer unit, and a third matrix copolymer comprising an alkyl-unsubstituted aromatic vinyl monomer unit, or a mixture thereof; an elastomer comprising a polyolefin-based compound; and a third graft copolymer in which an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit are grafted onto a polyalkylene main chain.

[0014] (2) The present invention provides a resin composition in which, in the above (1), the rubber polymer included in the first graft copolymer includes a conjugated diene monomer unit, and the rubber polymer included in the second graft copolymer includes an acrylic monomer unit.

[0015] (3) The present invention provides a resin composition in (1) or (2) above, wherein the first matrix copolymer includes an alkyl-substituted aromatic vinyl monomer unit and a vinyl cyan monomer unit.

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

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

[0018] (6) The present invention provides a resin composition comprising 4 to 11 parts by weight of the second graft copolymer, based on 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition, in any one of the above (1) to (5).

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

[0020] (8) The present invention provides a resin composition comprising, in any one of the above (1) to (7), 1 to 5 parts by weight of the elastomer relative to 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition.

[0021] (9) The present invention provides a resin composition comprising, in any one of the above (1) to (8), 1 to 5 parts by weight of the third graft copolymer relative to 100 parts by weight of the total of the graft copolymer and the matrix copolymer.

[0022] (10) The present invention provides a resin composition, wherein the matrix copolymer composition comprises the second matrix copolymer and the third matrix copolymer in any one of the above (1) to (9), and comprises 5 to 25 parts by weight of the second matrix copolymer relative to 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition, and comprises 50 to 70 parts by weight of the third matrix copolymer relative to 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition.

[0023] (11) The present invention provides a resin composition having an RPN grade of 3 or less, measured under the conditions of 75°C, relative humidity 50%, speed 1 mm / s, and vertical force 10 N according to VDA 230-206, in any one of the above (1) to (10).

[0024] The resin composition according to the present invention has low frictional noise even at high temperatures and excellent heat resistance and mechanical properties.

[0025] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0026] Terms or words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0027] In the present invention, the term 'monomer unit' may indicate a component, structure, or substance itself derived from a monomer, and as a specific example, may mean a repeating unit formed within a polymer by a monomer introduced during polymerization of the polymer and participating in the polymerization reaction.

[0028] The term 'composition' as used in the present invention includes a mixture of materials comprising the composition as well as reaction products and decomposition products formed from the materials of the composition.

[0029] In the present invention, the average particle diameter of the graft copolymer can be measured using the dynamic light scattering method, and as a specific example, can be measured using the Nicomp 380 HPL equipment (product name, manufacturer: Nicomp). In this specification, the average particle diameter means the arithmetic mean particle diameter in the particle size distribution measured by the dynamic light scattering method, i.e., the scattering intensity average particle diameter.

[0030] In the present invention, the weight average molecular weight of each component forming the resin composition can be measured as a relative value to a standard polystyrene, which is a standard sample, through gel permeation chromatography using tetrahydrofuran as an eluent.

[0031]

[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 including a rubber polymer having a glass transition temperature of -120°C or more and -90°C or less and a second graft copolymer including a rubber polymer having a glass transition temperature of -70°C or more and -40°C or less; a matrix copolymer composition comprising any one selected from the group consisting of a first matrix copolymer including an alkyl-substituted aromatic vinyl monomer unit, a second matrix copolymer including a maleimide-based monomer unit, and a third matrix copolymer including an alkyl-unsubstituted aromatic vinyl monomer unit, or a mixture thereof; an elastomer including a polyolefin-based compound; and a third graft copolymer in which an aromatic vinyl-based monomer unit and a vinylcyan-based monomer unit are grafted onto a polyalkylene main chain.

[0035]

[0036] The present inventors have found that when a resin composition includes a first graft copolymer including a rubber polymer having a glass transition temperature of -120°C or more and -90°C or less and a second graft copolymer including a rubber polymer having a glass transition temperature of -70°C or more and -40°C or less, frictional noise is reduced even at high temperatures and heat resistance and mechanical properties are excellent, thereby completing the present invention.

[0037]

[0038] Specifically, the resin composition according to one embodiment of the present invention has a RPN grade of 3 or less, measured using a stick-slip tester (SSP-04) of Ziegler according to VDA 230-206 under the conditions of 75°C, 50% relative humidity, 1 mm / s speed, and 10 N vertical force, indicating that the possibility of generating frictional noise at high temperatures is significantly low.

[0039]

[0040] Hereinafter, each component of a resin composition according to one embodiment of the present invention will be described.

[0041]

[0042] 1. Graft copolymer composition

[0043] According to one embodiment of the present invention, the graft copolymer composition may include a first graft copolymer including a rubber polymer having a glass transition temperature of -120°C or more and -90°C or less and a second graft copolymer including a rubber polymer having a glass transition temperature of -70°C or more and -40°C or less.

[0044]

[0045] According to one embodiment of the present invention, the resin composition simultaneously includes a first graft copolymer including a rubber polymer having a glass transition temperature of -120°C or more and -90°C or less and a second graft copolymer including a rubber polymer having a glass transition temperature of -70°C or more and -40°C or less, so that the stick-slip phenomenon is improved, and the resin composition can reduce frictional noise even at high temperatures.

[0046]

[0047] (1) First graft copolymer

[0048] According to one embodiment of the present invention, the first graft copolymer may be a component that improves the impact resistance of a resin composition, and may be a graft polymer that includes a conjugated diene polymer including a conjugated diene monomer unit as a rubber polymer and a shell including an aromatic vinyl monomer unit and a vinyl cyan monomer unit grafted onto the conjugated diene polymer. The shell may include an aromatic vinyl monomer unit and a vinyl cyan monomer unit that are not grafted onto the conjugated diene polymer.

[0049]

[0050] According to one embodiment of the present invention, the conjugated diene monomer for forming the conjugated diene monomer unit included in the first graft copolymer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and piperylene, and a specific example thereof may be 1,3-butadiene.

[0051] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit included in the first graft copolymer may be at least one selected from the group consisting of α-methyl styrene, α-ethyl styrene, p-methyl styrene, 2,4-dimethyl styrene, styrene, p-fluoro styrene, p-chloro styrene, and p-bromo styrene, and a specific example thereof may be styrene.

[0052] According to one embodiment of the present invention, the vinyl cyan monomer for forming the vinyl cyan monomer unit included in the first graft copolymer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, (Z)-3-phenyl acrylonitrile, and α-chloro acrylonitrile, and a specific example thereof may be acrylonitrile.

[0053]

[0054] According to one embodiment of the present invention, the content of the conjugated diene polymer included in the first graft copolymer may be 40 to 80 wt%, preferably 50 to 70 wt%, based on the total weight of the first graft copolymer. When the above conditions are satisfied, the impact resistance of the graft polymer composition can be further improved.

[0055] According to one embodiment of the present invention, the content of the aromatic vinyl monomer unit included in the first graft copolymer may be 10 to 50 wt%, preferably 20 to 40 wt%, based on the total weight of the first graft copolymer. When the above conditions are satisfied, the processability of the graft copolymer can be further improved.

[0056] According to one embodiment of the present invention, the content of the vinyl cyan monomer unit included in the first graft copolymer may be 1 to 30 wt%, preferably 5 to 25 wt%, based on the total weight of the first graft copolymer. When the above conditions are satisfied, the chemical resistance of the graft polymer composition can be further improved.

[0057]

[0058] According to one embodiment of the present invention, the glass transition temperature of the rubber polymer included in the first graft copolymer may be -120°C or more and -90°C or less, and for specific examples, -118°C or more, -116°C or more, -114°C or more, -112°C or more, -110°C or more, -108°C or more, -106°C or more, or -104°C or more, -91°C or less, -92°C or less, -93°C or less, -94°C or less, -95°C or less, -96°C or less, -97°C or less, -98°C or less, or -99°C or less. The glass transition temperature of the rubber polymer included in the first graft copolymer may be measured using a differential scanning calorimeter with a solid content obtained by coagulating with a coagulant well known as a rubber polymer latex, such as sulfuric acid, MgSO4, CaCl2, Al2(SO4)3, etc.

[0059]

[0060] According to one embodiment of the present invention, the resin composition may contain the first graft copolymer in an amount of 10 parts by weight or more and 30 parts by weight or less, based on 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition, and for specific examples, 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 further, it may contain 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 range is satisfied, the impact strength and flow index of the resin composition may be improved.

[0061]

[0062] (2) Second graft copolymer

[0063] According to one embodiment of the present invention, the first graft copolymer may be a component that improves the impact resistance of a resin composition, and may be a graft polymer including an acrylic polymer including an acrylic monomer unit as a rubber polymer and a shell including an aromatic vinyl monomer unit and a vinyl cyan monomer unit grafted onto the acrylic polymer. The shell may include an aromatic vinyl monomer unit and a vinyl cyan monomer unit that are not grafted onto the acrylic polymer.

[0064]

[0065] According to one embodiment of the present invention, the acrylic monomer for forming the acrylic monomer unit included in the second graft copolymer is C4 to C 10It may be an alkyl (meth)acrylate monomer, and specific examples thereof may include at least one selected from the group consisting of butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, and decyl (meth)acrylate, and a more specific example thereof may be butyl acrylate.

[0066] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit included in the second graft copolymer may be at least one selected from the group consisting of α-methyl styrene, α-ethyl styrene, p-methyl styrene, 2,4-dimethyl styrene, styrene, p-fluoro styrene, p-chloro styrene, and p-bromo styrene, and a specific example thereof may be styrene.

[0067] According to one embodiment of the present invention, the vinyl cyan monomer for forming the vinyl cyan monomer unit included in the second graft copolymer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, (Z)-3-phenyl acrylonitrile, and α-chloro acrylonitrile, and a specific example thereof may be acrylonitrile.

[0068]

[0069] According to one embodiment of the present invention, the acrylic monomer may be introduced in an amount of 30 wt% or more and 70 wt% or less, or 35 wt% or more and 65 wt% or less, based on the total weight of monomers introduced during the production of the second graft copolymer, and more specifically, may be introduced in an amount of 40 wt% or more and 60 wt% or less. When the above range is satisfied, the weather resistance, impact resistance, surface gloss characteristics, elongation, and whitening characteristics of the second graft copolymer can be further improved.

[0070] According to one embodiment of the present invention, the aromatic vinyl monomer may be introduced in an amount of 20 wt% or more and 50 wt% or less, or 25 wt% or more and 45 wt% or less, based on the total weight of monomers introduced during the production of the second graft copolymer, and more specifically, may be introduced in an amount of 30 wt% or more and 40 wt% or less. When the above range is satisfied, not only can the processability of the second graft copolymer be further improved, but also the second graft copolymer can be more uniformly dispersed within the resin composition, and the colorability of the resin composition can be further improved.

[0071] According to one embodiment of the present invention, the vinyl cyan monomer may be introduced in an amount of 5 wt% or more and 25 wt% or less, or 7 wt% or more and 22 wt% or less, based on the total weight of monomers introduced during the production of the second graft copolymer, and more specifically, may be introduced in an amount of 10 wt% or more and 20 wt% or less. When the above range is satisfied, not only can the chemical resistance of the second graft copolymer be further improved, but the second graft copolymer can be more uniformly dispersed within the resin composition, and the colorability of the resin composition can be further improved.

[0072]

[0073] According to one embodiment of the present invention, the glass transition temperature of the rubber polymer included in the second graft copolymer may be -70°C or more and -40°C or less, and for specific examples, -68°C or more, -66°C or more, -64°C or more, -62°C or more, -60°C or more, -58°C or more, -56°C or more, -54°C or more, or -52°C or more, and -41°C or less, -42°C or less, -43°C or less, -44°C or less, -45°C or less, -46°C or less, -47°C or less, -48°C or less, or -49°C or less. The glass transition temperature of the rubber polymer included in the second graft copolymer may be measured using a differential scanning calorimeter with a solid content obtained by coagulating with a coagulant well known as a rubber polymer latex, such as sulfuric acid, MgSO4, CaCl2, Al2(SO4)3, etc.

[0074]

[0075] According to one embodiment of the present invention, the resin composition may contain the second graft copolymer in an amount of 4 parts by weight or more and 11 parts by weight or less, based on 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition, and for specific examples, it may contain 4.2 parts by weight or more, 4.4 parts by weight or more, 4.6 parts by weight or more, 4.8 parts by weight or more, or 5 parts by weight or more, and further, it may contain 10.8 parts by weight or less, 10.6 parts by weight or less, 10.4 parts by weight or less, 10.2 parts by weight or less, or 10 parts by weight or less. When the above range is satisfied, the impact strength and weather resistance of the resin composition may be improved.

[0076]

[0077] 2. Matrix copolymer composition

[0078] According to one embodiment of the present invention, the matrix copolymer composition may include one or a mixture thereof selected from the group consisting of a first matrix copolymer including an alkyl-substituted aromatic vinyl monomer unit, a second matrix copolymer including a maleimide monomer unit, and a third matrix copolymer including an alkyl unsubstituted aromatic vinyl monomer unit.

[0079] As a specific example, the matrix copolymer composition according to one embodiment of the present invention may include any one of the first matrix copolymer, the second matrix copolymer, or the third matrix copolymer, or may include a mixture of two selected from the group consisting of the first matrix copolymer, the second matrix copolymer, or the third matrix copolymer, or may include the first matrix copolymer, the second matrix copolymer, and the third matrix copolymer.

[0080] When the matrix copolymer composition according to one embodiment of the present invention includes the second matrix copolymer and the third matrix copolymer, the frictional noise properties of the resin composition can be further improved.

[0081]

[0082] Hereinafter, each of the first matrix copolymer, the second matrix copolymer, and the third matrix copolymer forming the matrix copolymer composition will be described.

[0083]

[0084] (1) First matrix copolymer

[0085] 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 include an alkyl-substituted aromatic vinyl monomer unit and a vinyl cyan monomer unit.

[0086]

[0087] According to one embodiment of the present invention, the alkyl-substituted aromatic vinyl monomer for forming the alkyl-substituted aromatic vinyl monomer unit included in the first matrix copolymer may be at least one selected from the group consisting of α-methyl styrene, p-methyl styrene, and 2,4-dimethyl styrene, and a specific example thereof may be α-methyl styrene.

[0088] According to one embodiment of the present invention, the vinyl cyan monomer unit for forming the vinyl cyan monomer unit included in the first matrix copolymer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, (Z)-3-phenyl acrylonitrile, and α-chloro acrylonitrile, and a specific example thereof may be acrylonitrile.

[0089]

[0090] According to one embodiment of the present invention, the content of the alkyl-substituted aromatic vinyl monomer unit included in the first matrix copolymer may be 60 to 90 wt%, preferably 65 to 85 wt%, based on the total weight of the first matrix copolymer.

[0091] In addition, according to one embodiment of the present invention, the content of the vinyl cyan monomer unit included in the first matrix copolymer may be 10 to 40 wt%, preferably 15 to 35 wt%, based on the total weight of the first matrix copolymer.

[0092] If the above-described conditions are satisfied, the first matrix copolymer can be prevented from being phase separated from the resin composition.

[0093]

[0094] According to one embodiment of the present invention, the first matrix copolymer may further include an alkyl unsubstituted aromatic vinyl monomer unit to realize excellent formability. The alkyl unsubstituted aromatic vinyl monomer for forming the alkyl unsubstituted aromatic vinyl monomer unit may be at least one selected from the group consisting of styrene, 4-fluorostyrene, 4-chlorostyrene, 2-chlorostyrene, 4-bromostyrene, and 2-bromostyrene, and a specific example thereof may be styrene.

[0095] At this time, the content of the alkyl unsubstituted aromatic vinyl monomer unit included in the first matrix copolymer may be 15 wt% or less, preferably 10 wt% or less, based on the total weight of the first matrix copolymer.

[0096]

[0097] According to one embodiment of the present invention, when the resin composition includes the first matrix copolymer, the first matrix copolymer may be included in an amount of 15 parts by weight or more and 85 parts by weight or less, based on 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition, and for specific examples, the first matrix copolymer may be included in an amount of 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 further, 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 range is satisfied, the heat resistance of the resin composition can be improved.

[0098]

[0099] (2) Second matrix copolymer

[0100] According to one embodiment of the present invention, the second matrix copolymer is a component that improves the heat resistance and processability of the resin composition, is a non-grafted copolymer, and may include a maleimide monomer unit, an aromatic vinyl monomer unit, and a maleic acid monomer unit.

[0101]

[0102] According to one embodiment of the present invention, the maleimide monomer for forming the maleimide monomer unit included in the second matrix copolymer is maleimide, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-isobutyl maleimide, Nt-butyl maleimide, N-lauryl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N-(4-chlorophenyl) maleimide, 2-methyl-N-phenyl maleimide, N-(4-bromophenyl) maleimide, N-(4-nitrophenyl) maleimide, N-(4-hydroxyphenyl) maleimide, N-(4-methoxyphenyl) maleimide, N-(4-carboxyphenyl) maleimide, and N-benzyl maleimide. It may be one or more selected from the group consisting of, and a specific example may be N-phenyl maleimide.

[0103] According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit included in the second matrix copolymer may be at least one selected from the group consisting of α-methyl styrene, α-ethyl styrene, p-methyl styrene, 2,4-dimethyl styrene, styrene, p-fluoro styrene, p-chloro styrene, and p-bromo styrene, and a specific example thereof may be styrene.

[0104] According to one embodiment of the present invention, the maleic acid monomer for forming the maleic acid monomer unit included in the second matrix copolymer may be at least one selected from the group consisting of maleic anhydride, maleic acid, maleic monoester, and maleic diester, and a specific example thereof may be maleic anhydride.

[0105]

[0106] According to one embodiment of the present invention, the content of the maleimide-based monomer-derived unit included in the second matrix copolymer may be included in an amount of 35 to 65 wt%, 40 to 60 wt%, or 45 to 55 wt% based on the total weight of the second matrix copolymer, and among these, it is preferable that it is included in an amount of 45 to 55 wt%. When the above range is satisfied, the heat resistance of the resin composition can be further improved.

[0107] According to one embodiment of the present invention, the aromatic vinyl monomer-derived unit may be included in an amount of 30 to 60 wt%, 35 to 55 wt%, or 40 to 50 wt% based on the total weight of the second matrix copolymer, and preferably 40 to 50 wt%. When the above range is satisfied, the resin composition has the advantage of excellent mechanical properties and property balance.

[0108] According to one embodiment of the present invention, the maleic acid-based monomer-derived unit may be included in an amount of 0.1 to 10 wt%, 0.5 to 7 wt%, or 1 to 5 wt% based on the total weight of the second matrix copolymer, and among these, it is preferably included in an amount of 1 to 5 wt%. When the above range is satisfied, the resin composition has the advantage of excellent mechanical properties and property balance.

[0109]

[0110] According to one embodiment of the present invention, when the resin composition includes the second matrix copolymer, the second matrix copolymer may be included in an amount of 5 parts by weight or more and 50 parts by weight or less, based on 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition, and for specific examples, the second matrix copolymer may be included in an amount of 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 further, the second matrix copolymer may be included in an amount of 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 range is satisfied, the impact strength, heat resistance and fluidity index of the resin composition can be improved, and the frictional noise properties of the resin composition can be improved.

[0111]

[0112] (3) Third matrix copolymer

[0113] According to one embodiment of the present invention, the third matrix copolymer is a component that improves the tensile strength and processability of the resin composition, is a non-grafted copolymer, and may include an alkyl unsubstituted aromatic vinyl monomer unit and a vinyl cyan monomer unit.

[0114]

[0115] According to one embodiment of the present invention, the alkyl unsubstituted aromatic vinyl monomer for forming the alkyl unsubstituted aromatic vinyl monomer unit included in the third matrix copolymer may be at least one selected from the group consisting of styrene, 4-fluorostyrene, 4-chlorostyrene, 2-chlorostyrene, 4-bromostyrene, and 2-bromostyrene, and a specific example thereof may be styrene.

[0116] According to one embodiment of the present invention, the vinyl cyan monomer for forming the vinyl cyan monomer unit included in the third matrix copolymer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, (Z)-3-phenyl acrylonitrile, and α-chloro acrylonitrile, and a specific example thereof may be acrylonitrile.

[0117]

[0118] According to one embodiment of the present invention, the content of the alkyl unsubstituted aromatic vinyl monomer unit included in the third matrix copolymer may be 60 to 90 wt%, preferably 65 to 85 wt%, based on the total weight of the third matrix copolymer. When the above-described conditions are satisfied, the processability of the resin composition can be further improved.

[0119] According to one embodiment of the present invention, the content of the vinyl cyan monomer unit included in the third matrix copolymer may be 10 to 40 wt%, preferably 15 to 35 wt%, based on the total weight of the third matrix copolymer. When the above-described conditions are satisfied, the chemical resistance of the resin composition can be further improved.

[0120]

[0121] According to one embodiment of the present invention, when the resin composition includes the second matrix copolymer, the third matrix copolymer may be included in an amount of 15 parts by weight or more and 75 parts by weight or less, based on 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition, and for specific examples, the third matrix copolymer may be included in an amount of 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 further, 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 range is satisfied, the impact strength and flow index of the resin composition are improved, and the frictional noise properties of the resin composition may be improved.

[0122]

[0123] According to one embodiment of the present invention, the matrix copolymer composition may include the second matrix copolymer and the third matrix copolymer, and in this case, the second matrix copolymer and the third matrix copolymer may be included within the above-described range, based on 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition. As a specific example, when the matrix copolymer composition includes the second matrix copolymer and the third matrix copolymer, the second matrix copolymer may be included in an amount of 5 parts by weight or more and 25 parts by weight or less, and the third matrix copolymer may be included in an amount of 50 parts by weight or more and 70 parts by weight or less, based on 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition. In this case, the frictional noise properties of the resin composition may be further improved.

[0124]

[0125] 3. Elastomer

[0126] According to one embodiment of the present invention, the elastomer may include a polyolefin compound as a component for imparting frictional noise resistance to the resin composition.

[0127] According to one embodiment of the present invention, the polyolefin compound included in the elastomer may be a copolymer of ethylene and an alpha-olefin having 3 to 8 carbon atoms, and a more specific example may be a copolymer of ethylene and 1-butene.

[0128] According to one embodiment of the present invention, the resin composition may contain the elastomer in an amount of 1 part by weight or more and 5 parts by weight or less, based on 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition, and for specific examples, 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 may contain 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, there is an effect of improving the frictional noise properties of the resin composition while preventing peeling of the resin composition.

[0129]

[0130] 4. Third graft copolymer

[0131] According to one embodiment of the present invention, the third graft copolymer may be a copolymer in which an aromatic vinyl monomer unit and a vinyl cyan monomer unit are grafted onto a polyalkylene main chain, as a component that serves to improve compatibility with all components of the resin composition. Meanwhile, the third graft copolymer may also be referred to as a compatibilizer in the present specification.

[0132]

[0133] According to one embodiment of the present invention, the third graft copolymer may be a polyolefin in which a vinyl cyan monomer unit and an aromatic vinyl monomer unit are graft polymerized, and as a more specific example, it may be a polyethylene-based acrylonitrile-styrene copolymer in which an acrylonitrile unit and a styrene unit are graft polymerized onto polyethylene. In this case, the polyethylene-based acrylonitrile-styrene copolymer may include 30 wt% to 70 wt% of polyethylene and 30 wt% to 70 wt% of acrylonitrile units and styrene units.

[0134]

[0135] According to one embodiment of the present invention, the resin composition may contain the third graft copolymer in an amount of 1 part by weight or more and 5 parts by weight or less, based on 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition, and for specific examples, 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 may contain 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, there is an effect of improving compatibility for all components of the resin composition, thereby preventing peeling of the resin composition.

[0136]

[0137] 5. Other additives

[0138] According to one embodiment of the present invention, the resin composition may further include other additives. The additives may be at least one selected from the group consisting of a lubricant, an antioxidant, a pigment, a light stabilizer, a hydrolysis stabilizer, a release agent, an antistatic agent, a conductive agent, an electromagnetic shielding agent, a magnetizing agent, a mineral filler, a crosslinking agent, an antibacterial agent, a processing aid, a metal deactivator, a flame retardant, an antifriction and wear-resistant agent, and a coupling agent.

[0139] The above additives can be used without limitation as long as they are used in the technical field of the present invention, and a person skilled in the art can select the additives included in the present invention according to the purpose.

[0140]

[0141] <Molded product>

[0142] The present invention provides a molded product molded from the resin composition.

[0143] According to one embodiment of the present invention, the molded product may be extruded and injection molded from the resin composition, and may be applied to a product group that requires mechanical properties, heat resistance, and friction noise resistance at the same time, and a specific example thereof may be an automobile interior material.

[0144]

[0145] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0146]

[0147] Examples and Comparative Examples

[0148] The materials used in the examples and comparative examples are as follows.

[0149]

[0150] (1) Graft copolymer (A1): An emulsion polymerized ABS graft copolymer (manufactured by LG Chemical; product name DP270E) containing 60 wt% of a butadiene polymer having a Tg of -104°C and an average particle size of 300 nm, 10 wt% of acrylonitrile, and 30 wt% of styrene was used.

[0151]

[0152] (2) Graft copolymer (A2): An ASA graft copolymer (manufactured by LG Chemical; product name SA927) containing 50 wt% of butyl acrylate polymer having a Tg of -53°C and an average particle size of 450 nm, 14 wt% of acrylonitrile, and 36 wt% of styrene was used.

[0153]

[0154] (3) Graft copolymer (A3): A graft copolymer containing 60 wt% of a styrene-butadiene (styrene 25 wt%, butadiene 75 wt%) rubber polymer having a Tg of -29°C, 10 wt% of acrylonitrile, and 30 wt% of styrene was used.

[0155]

[0156] (4) Graft copolymer (A4): A bulk polymerized ABS graft copolymer (manufactured by LG Chemical; product name ER400) containing 11 wt% of butadiene polymer having a Tg of -104°C and an average particle size of 1000 nm, 18 wt% of acrylonitrile, and 71 wt% of styrene was used.

[0157]

[0158] (5) Matrix copolymer (B1): A heat-resistant resin (manufactured by LG Chemical; product name 99UH) containing 65 wt% alpha-methylstyrene, 28 wt% acrylonitrile, and 7 wt% styrene was used.

[0159]

[0160] (6) Matrix copolymer (B2): A PMI-based heat-resistant resin (manufactured by DENKA; product name: MSNB) containing 52 wt% of N-phenylmaleimide (PMI), 46 wt% of styrene, and 2 wt% of maleic anhydride (MAH) was used.

[0161]

[0162] (7) Matrix copolymer (B3): SAN resin (manufactured by LG Chemical; product name 80HF) containing 27 wt% acrylonitrile and 76 wt% styrene was used.

[0163]

[0164] (8) Elastomer (C): An elastomer containing a polyolefin compound (manufactured by LG Chemical; product name LC565) was used.

[0165]

[0166] (9) Commercializing agent (D): A graft copolymer (manufactured by NOF; product name MODIPER A1401) in which an aromatic vinyl monomer unit and a vinyl cyan monomer unit are grafted onto a polyalkylene main chain was used.

[0167]

[0168] A resin composition was prepared by mixing the graft copolymer, matrix copolymer, elastomer, and compatibilizer in the contents described in Tables 1 to 3 below. A resin composition in pellet form was prepared using a twin-screw extrusion mixer together with a lubricant and stabilizer at a cylinder temperature of 220°C.

[0169]

[0170] Experimental example

[0171] The resin compositions manufactured in the above examples and comparative examples were extruded with a twin-screw extruder at a cylinder temperature of 240°C together with a lubricant and a stabilizer to manufacture pellets, and then a specimen was injected at 240°C, and the impact strength, tensile strength, heat distortion temperature, room temperature friction noise, and high temperature friction noise were measured using the following methods, and the results are shown in Tables 1 to 3 below.

[0172]

[0173] * Notched Izod Impact Strength (J / m): Notched Izod impact strength was measured on 1 / 4 inch thick specimens at 23°C according to ASTM D256.

[0174]

[0175] * Tensile strength (MPa): Tensile strength was measured at a tensile speed of 50 mm / min according to ASTM D638.

[0176]

[0177] * Heat Deflection Temperature (℃): Heat deflection temperature was measured under the conditions of 18.6 kgf load and 120℃ / hour according to ASTM D648.

[0178]

[0179] * Room temperature friction noise (Risk Priority Number): According to VDA 230-206, the friction noise was measured using a Ziegler stick-slip tester (SSP-04) under the conditions of 23℃, 50% relative humidity, 1 mm / s speed, and 10 N normal force using a pair of identically manufactured specimens, and expressed as the room temperature RPN grade.

[0180]

[0181] * High temperature friction noise (Risk Priority Number): According to VDA 230-206, friction noise was measured using a stick-slip tester (SSP-04) from Ziegler under the conditions of 75℃, 50% relative humidity, 1 mm / s speed, and 10 N normal force using a pair of identically manufactured specimens, and expressed as a high temperature RPN grade.

[0182]

[0183] Example 1234567 Graft copolymer composition (A1) (parts by weight) 15152015151515 (A2) (parts by weight) 1010510101010 Matrix copolymer composition (B1) (parts by weight) 50-7575-30- (B2) (parts by weight) -10--202030 (B3) (parts by weight) 2565--552545 (C) Elastomer (parts by weight) 2.52.52.52.52.52.52.5 (D) Compatibilizer (parts by weight) 2222222 Impact strength (J / m) 160140140100909080 Tensile strength (MPa) 49485051514645 Heat distortion temperature (℃)9797102102102106106RPN, room temperature (@ 23℃)3333333RPN, high temperature (@ 75℃)3233233

[0184] Comparative Example 12345 Graft copolymer composition (A1) (parts by weight) 2525252520 (A3) (parts by weight)----5 Matrix copolymer composition (B1) (parts by weight) 50-757575 (B2) (parts by weight) -10---(B3) (parts by weight) 2565---(C) Elastomer (parts by weight) 2.52.5-2.52.5 (D) Compatibilizer (parts by weight) 22-22 Impact strength (J / m) 220200170180110 Tensile strength (MPa) 4746514950 Heat deflection temperature (℃) 9797102102102 RPN, room temperature (@ 23℃) 33533 RPN, high temperature (@ 75℃) 55756

[0185] Comparative Example 678910 Graft copolymer composition (A1) (parts by weight) 15 25 25 25 10 (A3) (parts by weight) 10 ---- (A4) (parts by weight) ---- 60 Matrix copolymer composition (B1) (parts by weight) 75-30 -- (B2) (parts by weight) -20 20 30 20 (B3) (parts by weight) -55 25 45 10 (C) Elastomer (parts by weight) 2.5 2.5 2.5 2.5 2.5 (D) Compatibilizer (parts by weight) 22 22 2 Impact strength (J / m) 70 15 0 16 0 15 0 12 0 Tensile strength (MPa) 5 14 9 48 47 46 Heat distortion temperature (℃) 10 2 10 2 10 6 10 6 10 2 RPN, room temperature (@ 23℃) 33 33 RPN, high temperature (@ 75℃)65557

[0186] Referring to Tables 1 to 3 above, it was confirmed that Examples 1 to 7 using a first graft copolymer including a rubber polymer having a glass transition temperature of -120°C or more and -90°C or less and a second graft copolymer including a rubber polymer having a glass transition temperature of -70°C or more and -40°C or less had low frictional noise and excellent heat resistance and mechanical properties even at high temperatures.

[0187]

[0188] Comparative Examples 1 to 4 and Comparative Examples 7 to 9, which used only the first graft copolymer including a rubber polymer having a glass transition temperature of -120°C or higher and -90°C or lower, showed significantly lower high-temperature RPN ratings compared to Examples 1 to 7.

[0189]

[0190] Comparative Examples 5 and 6, which used a first graft copolymer including a rubber polymer having a glass transition temperature of -120°C or more and -90°C or less, and a graft copolymer including a rubber polymer having a glass transition temperature exceeding a range of -70°C or more and -40°C or less, showed a significantly lower high-temperature RPN rating compared to Examples 1 to 7.

[0191]

[0192] Comparative Example 10, which uses different graft copolymers including rubber polymers having a glass transition temperature of -120°C or higher and -90°C or lower, showed a significantly lower high-temperature RPN rating compared to Examples 1 to 7.

Claims

1. A graft copolymer composition comprising a first graft copolymer comprising a rubber polymer having a glass transition temperature of -120°C or more and -90°C or less and a second graft copolymer comprising a rubber polymer having a glass transition temperature of -70°C or more and -40°C or less; A matrix copolymer composition comprising one or a mixture thereof selected from the group consisting of a first matrix copolymer comprising an alkyl-substituted aromatic vinyl monomer unit, a second matrix copolymer comprising a maleimide-based monomer unit, and a third matrix copolymer comprising an alkyl unsubstituted aromatic vinyl monomer unit; An elastomer comprising a polyolefin compound; and A resin composition comprising a third graft copolymer in which an aromatic vinyl monomer unit and a vinyl cyan monomer unit are grafted onto a polyalkylene main chain.

2. In paragraph 1, The rubber polymer included in the first graft copolymer includes a conjugated diene monomer unit, A resin composition wherein the rubber polymer included in the second graft copolymer comprises an acrylic monomer unit.

3. In paragraph 1, A resin composition wherein the first matrix copolymer comprises an alkyl-substituted aromatic vinyl monomer unit and a vinyl cyan monomer unit.

4. In paragraph 1, A resin composition wherein the second matrix copolymer comprises a maleimide monomer unit, an aromatic vinyl monomer unit, and a maleic anhydride monomer unit.

5. In paragraph 1, A resin composition wherein the third matrix copolymer comprises an alkyl unsubstituted aromatic vinyl monomer unit and a vinyl cyan monomer unit.

6. In paragraph 1, A resin composition comprising the second graft copolymer in an amount of 4 parts by weight or more and 11 parts by weight or less, based on 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition.

7. In paragraph 1, For 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition, A resin composition comprising the first graft copolymer in an amount of 10 parts by weight or more and 30 parts by weight or less.

8. In paragraph 1, For 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition, A resin composition comprising the above elastomer in an amount of 1 part by weight or more and 5 parts by weight or less.

9. In paragraph 1, For 100 parts by weight of the total of the graft copolymer and the matrix copolymer, A resin composition comprising the third graft copolymer in an amount of 1 part by weight or more and 5 parts by weight or less.

10. In paragraph 1, The above matrix copolymer composition comprises the second matrix copolymer and the third matrix copolymer, The second matrix copolymer is included in an amount of 5 to 25 parts by weight, based on 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition. A resin composition comprising the third matrix copolymer in an amount of 50 parts by weight or more and 70 parts by weight or less, based on 100 parts by weight of the total of the graft copolymer composition and the matrix copolymer composition.

11. In paragraph 1, A resin composition having an RPN grade of 3 or less measured under the conditions of 75°C, 50% relative humidity, 1 mm / s speed, and 10 N normal force according to VDA 230-206.