KR101827063B1 - Thermoplastic resin composition for interior parts of vehicle and molded article for interior parts of vehicle using thereof - Google Patents
Thermoplastic resin composition for interior parts of vehicle and molded article for interior parts of vehicle using thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Abstract
The present invention relates to a thermoplastic resin composition for automobile interior parts and a molded article using the same, wherein the base resin comprises 55 to 90% by weight of a polycarbonate resin and 10 to 45% by weight of a vinyl cyanide-aromatic vinyl compound copolymer Wherein the impact modifier comprises 5 to 30 parts by weight of an impact modifier and 1 to 8 parts by weight of an extinction agent, wherein the impact modifier comprises a first impact modifier as a core-shell type acrylic rubber modified graft copolymer, - a second impact modifier which is a shell-type diene-acrylic rubber-modified graft copolymer.
According to the present invention, the addition of different impact modifiers in the core-shell type to the base resin at an optimum content ratio has the advantage of remarkably improving the deterioration of the impact resistance due to the quencher without problems such as generation of gas silver .
Description
The present invention relates to a thermoplastic resin composition for automobile interior parts and a molded article using the same. More specifically, by adding different impact modifiers and quenchers in the form of a core-shell to the polycarbonate resin in an optimum ratio, it is possible to dramatically reduce the impact resistance due to a quencher without problems such as generation of gas silver streaks To a thermoplastic resin composition for automotive interior parts having excellent low-light characteristics and impact resistance that can be improved and a molded article using the same.
Particularly for overhead consoles, parts that are directly exposed to ultraviolet rays (UV) are required to have UV stability and high shock resistance and heat resistance are required for the safety of the occupants .
For this reason, many automobile component manufacturers have applied post-processing such as painting to molded parts made of polycarbonate and acrylonitrile-butadiene-styrene copolymer (ABS), that is, PC / ABS resin, However, due to the manufacturing cost burden and environmental problems, there is a continuing demand for unpainted materials.
The PCA / ASA resin of polycarbonate and acrylonitrile-styrene-acrylate copolymer (hereinafter abbreviated ASA) is excellent in weather resistance and heat resistance and can be used for automobile exterior parts such as a radiator grill ), An outside mirror housing, and the like. However, due to the relatively low glass transition temperature (Tg) properties of acrylate-based rubbers, PC / ASA resins have a limited impact resistance relative to PC / ABS resins. In addition, some automotive interior parts such as the above-mentioned overhead console are required to have a low light property. However, if a quencher is added to the PC / ASA resin in order to exhibit low light properties, a further problem of a drop in impact resistance may occur.
As disclosed in Korean Patent Laid-Open Publication No. 2009-0038507, a variety of patents have been filed for ASA resin, but no description has been given on the impact resistance reinforcement of ASA resin.
Therefore, it is required to develop a technology for a thermoplastic resin composition for automobile interior parts, which can exhibit excellent impact resistance while realizing low light properties and does not cause problems such as gas silver.
The object of the present invention is to realize a low light property by adding a quencher to a base resin containing a polycarbonate resin and a vinyl cyanide-aromatic vinyl compound copolymer.
It is another object of the present invention to dramatically improve the deterioration of impact resistance due to a quencher without problems such as generation of gas silver by adding different impact modifiers in a core-shell type at an optimum content ratio.
It is another object of the present invention to provide an environmentally friendly thermoplastic resin composition for automobile interior parts, which can remarkably improve coloring property, heat resistance and light resistance by mixing each component at an optimum ratio, and is capable of unpainting.
In order to achieve the above object, the thermoplastic resin composition for automotive interior parts according to the present invention comprises 55 to 90% by weight of a polycarbonate resin and 10 to 45% by weight of a vinyl cyanide-aromatic vinyl compound copolymer 5 to 30 parts by weight of an impact modifier and 1 to 8 parts by weight of a light extinguishing agent may be added to 100 parts by weight of a base resin which is a core-shell type acrylic rubber modified graft copolymer 1 impact modifier and a second impact modifier as a core-shell type diene-acrylic rubber-modified graft copolymer.
The thermoplastic resin composition for automotive interior parts of the present invention may further comprise an alkyl (meth) acrylate compound-aromatic vinyl compound-vinyl cyanide copolymer.
The quencher may include an aromatic vinyl compound-cyanide vinyl compound copolymer having a weight average molecular weight of 1,000,000 g / mol to 10,000,000 g / mol, and the aromatic vinyl compound-cyanide vinyl compound copolymer may contain an aromatic vinyl compound in an amount of 65% To 85% by weight of a vinyl cyanide compound and 15% to 35% by weight of a vinyl cyanide compound.
Wherein the first impact modifier comprises an acrylic rubber polymer core comprising a polymer of an alkyl (meth) acrylate compound and an alkyl (meth) acrylate compound-aromatic vinyl compound copolymer; And a shell layer formed by grafting a copolymer of an aromatic vinyl compound and a vinyl cyanide compound on the acrylic rubber-like polymer core.
The first impact modifier may comprise 55% to 65% by weight of the acrylic rubber-like polymer core and 35% to 45% by weight of the shell layer. The content ratio of the aromatic vinyl compound and the vinyl cyanide component in the shell layer May be in a weight ratio of 4: 1 to 1.5: 1.
Wherein the second impact modifier comprises a diene-acrylic rubber-like polymer core comprising a polymer of a diene-based rubbery polymer and an alkyl (meth) acrylate compound; And a shell layer formed by grafting an alkyl (meth) acrylate polymer on the diene-based acrylic rubber-like polymer core.
The second impact modifier may comprise 55 wt% to 65 wt% of the diene-based acrylic rubber-like polymer core and 35 wt% to 45 wt% of the shell layer.
The weight ratio of the first impact modifier to the second impact modifier may be 3: 1 to 1: 1.
The alkyl (meth) acrylate compound-aromatic vinyl compound-cyanide vinyl compound copolymer may be included in an amount of 10 parts by weight to 20 parts by weight based on 100 parts by weight of the base resin.
The alkyl (meth) acrylate compound-aromatic vinyl compound-cyanide vinyl compound copolymer may be prepared by copolymerizing 2 to 10% by weight of a vinyl cyanide compound, 15 to 25% by weight of an aromatic vinyl compound, And from 65% to 80% by weight of the monomer mixture.
Next, the molded article for automotive interior parts according to the present invention may be a molded article using the thermoplastic resin composition for automobile interior parts.
The molded product may have an Izod impact strength (1/8 ", notched) measured at room temperature according to ASTM D256 of 55 kgf.cm/cm to 80 kgf.cm/cm and at an angle of 60 ° according to ASTM D523 The measured gloss may be from 15% to 50%.
Further, the molded article may have a color difference change (DELTA E) between 2.0 and 2.9 before and after the evaluation measured under weathering exposure conditions of 2,500 kJ / m 2 according to SAE J1960.
According to the thermoplastic resin composition for automobile interior parts of the present invention and the molded article using the same, it is possible to enhance the low light characteristic of automotive interior parts by adding a light extinguishing agent using a polycarbonate resin and a vinyl cyanide-aromatic vinyl compound copolymer as a base resin However, by adding different core-shell type impact modifiers in an optimal content ratio, it is possible to drastically improve the deterioration of impact resistance due to a quencher without problems such as generation of gas silver.
Further, by mixing the respective components at an optimum ratio, it is possible to remarkably improve the coloring property, the heat resistance and the light resistance, and the thermoplastic resin composition for an automobile interior part can be manufactured without pollution.
Hereinafter, the thermoplastic resin composition for automobile interior parts according to the present invention and molded articles using the same can be better understood by the following examples, and the following examples are for illustrative purposes of the present invention, It is not intended to limit the scope of protection defined by the scope.
Unless defined otherwise herein, "copolymerization" may mean block copolymerization, random copolymerization, graft copolymerization or alternating copolymerization, and "copolymer" is a block copolymer, random copolymer, graft copolymer or Quot; alternate copolymer ".
In the present specification, "(meth) acrylate" means "acrylate" and "methacrylate", and compounds including (meta) such as "(meth) acrylic acid" And a compound having no " meta ".
Thermoplastic resin composition for automotive interior parts
One aspect of the present invention relates to a thermoplastic resin composition for automobile interior parts. Specifically, the present invention relates to a thermoplastic resin composition optimized for an overhead console, a console box, a center facia, and the like of an automobile.
In one embodiment, the thermoplastic resin composition for automotive interior parts comprises 100 parts by weight of a base resin comprising 55% by weight to 90% by weight of a polycarbonate resin and 10% by weight to 45% by weight of a vinyl cyanide compound-aromatic vinyl compound copolymer 5 to 30 parts by weight of an impact modifier; And from 1 part by weight to 8 parts by weight of quenching.
Basic resin
The base resin of the present invention comprises 55 to 90% by weight of a polycarbonate resin and 10 to 45% by weight of a vinyl cyanide-aromatic vinyl compound copolymer.
Polycarbonate resin
As the polycarbonate resin in the present invention, a conventional one can be used. For example, an aromatic polycarbonate resin prepared by reacting a diphenol-based compound represented by the following formula (1) with phosgene, halogen formate or carbonic acid diester can be used:
[Chemical Formula 1]
In Formula 1, A represents a single bond, a substituted or unsubstituted C1 to C30 linear or branched alkylene group, a substituted or unsubstituted C2 to C5 alkenylene group, a substituted or unsubstituted C2 to C5 An alkylidene group, a substituted or unsubstituted C 1 to C 30 linear or branched haloalkylene group, a substituted or unsubstituted C 5 to C 6 cycloalkylene group, a substituted or unsubstituted C 5 to C 6 cycloalkenylene group, A substituted or unsubstituted C5 to C10 cycloalkylidene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C20 linear or branched alkoxysilyl group, a halogen acid ester group, CO, S and SO 2 , wherein R 1 and R 2 are each independently selected from a substituted or unsubstituted C1 to C30 alkyl group and a substituted or unsubstituted C6 to C30 aryl group , wherein n 1 n 2 are each independently an integer from 0 to 4.
In the present invention, the "substituted" means that the hydrogen atom is replaced by a halogen group, a C1 to C30 alkyl group, a C1 to C30 haloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, and a C1 to C20 alkoxy group ≪ / RTI > is substituted by one or more substituents.
The diphenols represented by the above formula (1) may be composed of two or more of them to form a repeating unit of a polycarbonate resin. Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (also referred to as bisphenol- (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis Propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis Bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfoxide, Bis (4-hydroxyphenyl) ketone, and bis (4-hydroxyphenyl) ether.
Among these diphenols, preferred are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl- Bis (3,5-dichloro-4-hydroxyphenyl) propane, or 1,1-bis (4-hydroxyphenyl) cyclohexane. For example, 2,2-bis (4-hydroxyphenyl) propane can be used.
The polycarbonate resin may have a weight average molecular weight of 5,000 g / mol to 200,000 g / mol. For example, from 10,000 g / mol to 30,000 g / mol. In another example, it is possible to use those having a molecular weight of 15,000 g / mol to 25,000 g / mol.
In the present invention, when considering the effect of mixing with the impact modifier and the quencher, excellent impact resistance can be obtained by using the polycarbonate resin in the weight-average molecular weight range, and appropriate fluidity can be obtained to realize excellent workability. In order to improve the flowability, two or more kinds of polycarbonate resins having different weight average molecular weights may be mixed and used.
The polycarbonate resin may be a mixture of copolymers prepared from two or more kinds of diphenols. The polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, or a polyester carbonate copolymer resin.
Examples of the linear polycarbonate resin include a bisphenol-A polycarbonate resin and the like. Examples of the branched polycarbonate resin include those prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride, trimellitic acid and the like with a diphenol and a carbonate. The polyfunctional aromatic compound may be contained in an amount of 0.05 mol% to 2 mol% based on the total amount of the branched polycarbonate resin. Examples of the polyester carbonate copolymer resin include those prepared by reacting a bifunctional carboxylic acid with a diphenol and a carbonate. As the carbonate, diaryl carbonate such as diphenyl carbonate, ethylene carbonate and the like can be used.
Vinyl cyanide Compound-aromatic vinyl compound copolymer
The cyanide vinyl compound-aromatic vinyl compound copolymer may include a copolymer of an aromatic vinyl monomer and a monomer mixture copolymerizable with the aromatic vinyl monomer. For example, by copolymerizing an aromatic vinyl monomer and a vinyl cyanide monomer.
The vinyl cyanide-aromatic vinyl compound copolymer according to one embodiment of the present invention is formed by copolymerizing a monomer mixture containing 55% by weight to 80% by weight of an aromatic vinyl compound and 20% by weight to 45% by weight of a vinyl cyanide compound .
As the vinyl cyanide compound for forming the copolymer, acrylonitrile, methacrylonitrile, and fumaronitrile may be used. These may be used alone or in combination of two or more. As the aromatic vinyl compound, it is preferable to use styrene,? -Methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, bromostyrene, chlorostyrene and vinyltoluene, or a mixture of two or more selected from these . However, the types of the vinyl cyanide compound and the aromatic vinyl compound usable for forming the copolymer are not limited to those listed above, and the vinyl cyanide compound and the aromatic vinyl compound may be used without limitation.
The weight average molecular weight of the vinyl cyanide-aromatic vinyl compound copolymer used in the present invention may be from 50,000 g / mol to 300,000 g / mol. For example, from 80,000 g / mol to 150,000 g / mol.
In one embodiment, the base resin may comprise from 55% to 90% by weight of a polycarbonate resin and from 10% to 45% by weight of a vinyl cyanide-aromatic vinyl compound copolymer. For example, from 68% by weight to 88% by weight of a polycarbonate resin and from 12% by weight to 32% by weight of a vinyl cyanide compound-aromatic vinyl compound copolymer. When the content is out of the above range, there is a problem that excellent impact resistance can not be realized due to a decrease in impact resistance due to a quencher.
For example, the polycarbonate resin may have a composition of 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72 , 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89 or 90 wt%.
For example, the vinylidene cyanide-aromatic vinyl compound copolymer may be used in an amount of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 , 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44 or 45 wt.
Impact modifier
The impact modifier includes a first impact modifier as a core-shell type acrylic rubber modified graft copolymer and a second impact modifier as a core-shell type diene-acrylic rubber modified graft copolymer.
1st Impact modifier
Wherein the first impact modifier comprises an acrylic rubber polymer core comprising a polymer of an alkyl (meth) acrylate compound and an alkyl (meth) acrylate compound-aromatic vinyl compound copolymer; And a shell layer formed by grafting a copolymer of an aromatic vinyl compound and a vinyl cyanide compound on the acrylic rubber-like polymer core. Through such a constitution, the compatibility with the aromatic vinyl compound-cyanide vinyl compound copolymer as the base resin can be improved and the impact resistance efficiency can be remarkably improved.
The polymer of the alkyl (meth) acrylate compound can be prepared by single polymerization or copolymerization of an alkyl (meth) acrylate monomer.
In the alkyl (meth) acrylate compound, alkyl refers to C1 to C10 alkyl, and specifically, the alkyl (meth) acrylate compound includes methyl (meth) acrylate, ethyl (meth) acrylate, Acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or a combination thereof.
The aromatic vinyl compound is preferably styrene,? -Methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, bromostyrene, chlorostyrene, vinyltoluene or a combination thereof. The vinyl cyanide compound is preferably acrylonitrile , Methacrylonitrile, fumaronitrile, or a combination thereof.
The first impact modifier may comprise 55% to 65% by weight of the acrylic rubber-like polymer core and 35% to 45% by weight of the shell layer. For example, it may comprise from 58% to 62% by weight of the acrylic rubber-like polymer core and from 38% to 42% by weight of the shell layer. When the content is within the above range, the impact resistance efficiency and dispersibility can be excellent.
In one embodiment, the content ratio of the aromatic vinyl compound and the vinyl cyanide compound component in the shell layer may be 4: 1 to 1.5: 1. For example, from 3: 1 to 2: 1. When included in the above range, the impact resistance efficiency and dispersibility are excellent.
Also, the first impact modifier has an acrylic rubber-like polymer core having a weight average molecular weight of 200,000 g / mol to 10,000,000 g / mol; And a shell layer having a weight average molecular weight of 50,000 g / mol to 500,000 g / mol.
The average particle diameter (d50) of the acrylic rubber-like polymer core may be 210 nm to 400 nm. For example, from 210 nm to 350 nm. When the above range is satisfied, there is an advantage in that the impact resistance and the coloring property are excellent.
Here, the average particle size of the acrylic rubber-like polymer core is expressed by a measurement method to represent the average size of the population. However, the average particle size of the acrylic rubber-like polymer core is generally used so that the mode diameter representing the maximum value of the distribution is equivalent to the median value of the integral distribution curve (Number average, length average, area average, mass average, volume average, etc.), and the like. In the present invention, unless otherwise stated, the "average particle diameter" means "number average particle diameter", and means d50 (particle diameter at the point where the distribution ratio is 50%).
In one embodiment, the refractive index of the first impact modifier may be 1.51 to 1.54. The thermoplastic resin composition can be imparted with excellent coloring property within the above range.
Second Impact modifier
The second impact modifier is a core-shell type diene-acrylic rubber-modified graft copolymer comprising a diene-based rubbery polymer and a polymer of an alkyl (meth) acrylate; And a shell layer formed by grafting a polymer of alkyl (meth) acrylate on the diene-based acrylic rubber-like polymer core. This serves to increase the impact resistance efficiency at the interface between the polycarbonate resin and the vinyl cyanide-aromatic vinyl compound copolymer.
In one embodiment, the second impact modifier may be a mixture of a diene rubber polymer polymerized with a diene monomer and an acrylic rubber polymer polymerized with an alkyl (meth) acrylate monomer, and the diene monomer, Acrylate monomer mixture may be used.
In one embodiment, butadiene and isoprene can be used as the diene monomer. For example, butadiene can be used. In one embodiment, the alkyl (meth) acrylate monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, (Meth) acrylate such as hexyl methacrylate can be used. Wherein said alkyl means C1 to C10 alkyl.
In one embodiment, the diene-based rubbery polymer polymerized with the diene-based monomer may be polybutadiene or the like.
In addition, the second impact modifier may comprise 55 wt% to 65 wt% of the diene-based acrylic rubber-like polymer core and 35 wt% to 45 wt% of the shell layer. For example, it may comprise 58 wt% to 62 wt% of the diene-based acrylic rubber-like polymer core and 38 wt% to 42 wt% of the shell layer. In this case, the appearance characteristics, impact resistance and coloring property of the final molded article can be improved.
The average particle diameter (d50) of the diene-based acrylic rubber-like polymer core may be 100 nm to 200 nm. For example, from 150 nm to 200 nm. When this range is satisfied, the impact resistance reinforcing effect can be maximized, and at the same time, coloring property and glossiness can be improved.
The weight ratio of the first impact modifier to the second impact modifier may be 3: 1 to 1: 1. For example, from 2.5: 1 to 1.5: 1. Within this content ratio, the first impact modifier acting on the aromatic vinyl compound-cyanide vinyl compound copolymer continuous phase and the improvement of the impact resistance on the interface between the polycarbonate resin and the aromatic vinyl compound-cyanide vinyl compound copolymer, The synergistic effect of the reinforcing agent is maximized.
The total amount of the first impact modifier and the second impact modifier may be 5 to 30 parts by weight based on 100 parts by weight of the base resin containing the polycarbonate resin and the aromatic vinyl compound-vinyl cyanide compound. For example, 15 parts by weight to 25 parts by weight. When the impact modifier is contained in an amount of less than 5 parts by weight, the effect of improving impact resistance is insignificant. When the impact modifier is contained in an amount exceeding 30 parts by weight, other properties such as heat resistance and rigidity are deteriorated. For example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 28, 29, 30 parts by weight.
In one embodiment, the refractive index of the second impact modifier may be 1.52 to 1.55. Within the above range, the thermoplastic resin composition can have excellent coloring properties.
Quencher
In the present invention, the quencher may include an ultrahigh molecular weight aromatic vinyl compound-cyanide vinyl compound copolymer having a weight average molecular weight of 1,000,000 g / mol to 10,000,000 g / mol. The aromatic vinyl compound-cyanide vinyl compound copolymer may be a copolymer of a monomer mixture comprising 65 wt% to 85 wt% of an aromatic vinyl compound and 15 wt% to 35 wt% of a vinyl cyanide compound. This is effective for imparting low light properties.
The quencher may be added in an amount of 1 part by weight to 8 parts by weight based on 100 parts by weight of the base resin containing the polycarbonate resin and the aromatic vinyl compound-vinyl cyanide compound. For example, 3 parts by weight to 6 parts by weight. When the light extinguishing agent is contained in an amount of less than 1 part by weight, the light-reducing effect is insignificant. When the light extinguishing agent is contained in an amount exceeding 8 parts by weight, general properties such as impact resistance and fluidity are deteriorated.
Alkyl (meth) acrylate Compound-aromatic Vinyl-based Monomer-cyanide Vinyl-based Monomer copolymer
The thermoplastic resin composition for automobile interior parts of the present invention may further comprise an alkyl (meth) acrylate compound-aromatic vinyl compound-cyanide vinyl compound copolymer, and plays a role in improving the coloring property of the thermoplastic resin composition.
In the alkyl (meth) acrylate compound, alkyl refers to C1 to C10 alkyl, and specifically, the alkyl (meth) acrylate compound includes methyl (meth) acrylate, ethyl (meth) acrylate, Acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.
The aromatic vinyl compound may include at least one of styrene,? -Methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, bromostyrene, chlorostyrene and vinyltoluene. The vinyl cyanide compound may include at least one of acrylonitrile, methacrylonitrile, and fumaronitrile.
The weight average molecular weight of the alkyl (meth) acrylate compound-aromatic vinyl compound-cyanide vinyl compound copolymer may be from 50,000 g / mol to 200,000 g / mol. For example from 80,000 g / mol to 120,000 g / mol.
In one embodiment, the refractive index of the alkyl (meth) acrylate compound-aromatic vinyl compound-cyanide vinyl compound copolymer may be 1.51 to 1.54. The thermoplastic resin composition can be imparted with excellent coloring property within the above range.
The difference between the refractive index of the alkyl (meth) acrylate compound-aromatic vinyl compound-cyanide vinyl compound copolymer and the refractive index of the impact modifier (the average refractive index of the first impact modifier and the second impact modifier) may be from 0.001 to 0.02 . Within this range, the thermoplastic resin composition can achieve more excellent coloring property.
The alkyl (meth) acrylate compound-aromatic vinyl compound-cyanide vinyl compound copolymer may be included in an amount of 10 to 20 parts by weight based on 100 parts by weight of the base resin. For example, 12 parts by weight to 15 parts by weight. Excellent colorability can be achieved while maintaining excellent impact resistance within this range. For example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 parts by weight.
The alkyl (meth) acrylate compound-aromatic vinyl compound-cyanide vinyl compound copolymer may be prepared by copolymerizing 2 to 10% by weight of a vinyl cyanide compound, 15 to 25% by weight of an aromatic vinyl compound, And from 65% to 80% by weight of the monomer mixture. Within the above-mentioned range, the thermoplastic resin composition can realize more excellent coloring property.
In addition to the above components, the thermoplastic resin composition for automotive interior parts of the present invention may further contain additives necessary for improving the injection moldability of the thermoplastic resin composition for automobile interior parts, balancing the physical properties, or depending on the end use of the thermoplastic resin composition. Specific examples of the additives include flame retardants, surfactants, nucleating agents, coupling agents, fillers, plasticizers, lubricants, antibacterial agents, mold release agents, heat stabilizers, antioxidants, light stabilizers, inorganic additives, stabilizers, antistatic agents, pigments, These can be used alone or in combination of two or more.
These additives may be suitably included within a range that does not impair the physical properties of the thermoplastic resin composition. Specifically, 20 parts by weight or less based on 100 parts by weight of the base resin including the polycarbonate resin and the aromatic vinyl compound-vinyl cyanide compound, but is not limited thereto.
Molded parts for automotive interior parts
Another aspect of the present invention relates to a molded article for an automotive interior part formed using the thermoplastic resin composition for automobile interior parts. The molded article for automobile interior parts includes an aromatic vinyl compound-cyanide vinyl compound copolymer having a weight average molecular weight of 1,000,000 g / mol to 10,000,000 g / mol, which is a quencher, and has Izod impact strength (1/8 ", Notched) may be 55 kgf · cm / cm to 80 kgf · cm / cm. The molded product for automobile interior parts may have a gloss of 15% to 50% measured at an angle of 60 ° according to ASTM D523. The molded article for automobile interior parts may have a color difference change (DELTA E) between 2.0 and 2.9 before and after the evaluation measured under weathering exposure conditions of 2,500 kJ / m 2 according to SAE J1960. This is the result of several experiments, confirming the critical significance of achieving excellent impact resistance and weatherability when used in automotive interior parts in thermoplastics within the range.
The value of DELTA E is an index indicating a color difference in the CIE Lab color indicator. The equation for calculating DELTA E is as follows:
[Equation 1]
In the CIE Lab color indicator, the lightness is indicated by L, and the chromaticity representing the color and saturation is indicated by a and b. The larger the value of a, the closer to red, and the smaller the value of a, the closer to green. The larger the b value, the closer to yellow, and the smaller the b value, the closer to blue.
The smaller the change in color difference (? E) measured before and after the evaluation measured under weathering conditions of 2,500 kJ / m 2 according to SAE J1960, the better the weatherability.
Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.
Examples and Comparative Examples
Specific specifications of the components used in Examples and Comparative Examples of the present invention are as follows.
(A) the first impact modifier
60 wt% of an acrylic rubber-like polymer core comprising a butyl acrylate polymer and a butyl acrylate-styrene copolymer was emulsion graft-polymerized with 40 wt% of a monomer mixture composed of 33 wt% of acrylonitrile and 67 wt% of styrene, Shell type graft copolymer was used. The average particle diameter (d50) of the acrylic rubber-like polymer core was 320 nm, and the refractive index of the first impact modifier was 1.511.
(B) Second impact modifier
A graft copolymer in the form of a core-shell in which 40 wt% of methyl methacrylate was emulsion graft-polymerized to 60 wt% of a diene-acrylic rubber-like polymer core containing polybutadiene and butyl acrylate polymer was used. The average particle size (d50) of the diene-based acrylic rubber-like polymer core was 170 nm, and the refractive index of the second impact modifier was 1.528.
(C) Alkyl (meth) acrylate compound-aromatic vinyl compound-cyanide vinyl compound copolymer
Styrene-acrylonitrile copolymer having a weight average molecular weight of 120,000 g / mol and a refractive index of 1.511, a copolymer consisting of 5% by weight of acrylonitrile, 20% by weight of styrene and 75% by weight of methyl methacrylate MSAN) resin.
(D) a vinyl cyanide compound-aromatic vinyl compound copolymer
A styrene-acrylonitrile copolymer (SAN) resin having a weight average molecular weight of 100,000 g / mol was used as a copolymer consisting of 24% by weight of acrylonitrile and 76% by weight of styrene.
(E) Polycarbonate resin
A linear bisphenol A polycarbonate resin having a weight average molecular weight of 20,000 g / mol was used.
(F) Extinguishing agent
A high molecular weight styrene-acrylonitrile copolymer (SAN) resin having a weight average molecular weight of 1,000,000 g / mol was used as a copolymer consisting of 24% by weight of acrylonitrile and 76% by weight of styrene.
The above components were mixed in the amounts shown in Table 1 below and extruded and processed to prepare a thermoplastic resin composition in the form of a pellet. Extrusion was performed using a twin-screw extruder with L / D = 29 and a diameter of 45 mm, and the barrel temperature was set at 260 ° C. The prepared pellets were dried at 80 ° C for 2 hours and then set to a cylinder temperature of 250 ° C and a mold temperature of 60 ° C using a 6 oz injection molding machine to prepare specimens for measurement of physical properties and specimens for weatherability measurement.
(Unit: parts by weight)
The physical properties of the thermoplastic resin composition prepared according to Table 1 were measured according to the following physical properties evaluation methods, and the results are shown in Table 2 below.
Property evaluation method
(1) Impact resistance (unit: kgf · cm / cm): Izod impact strength was measured for a 1/8 "thick notched specimen according to ASTM D256.
(2) Gloss (unit:%): The gloss was measured at an angle of 60 ° in accordance with ASTM D523.
(3) Weatherability: According to SAE J1960, the chromaticity change (ΔE) before and after the evaluation of the specimen was measured under a weathering exposure condition of 2,500 kJ / m 2 .
As shown in Table 2, Examples 1 to 8 belonging to the scope of the present invention exhibited an Izod impact strength of at least 55 kgf · cm / ㎝, even though they contained a quencher, It was found that the impact resistance was excellent in comparison with the comparative example, except for Comparative Examples 1 and 7. The low light properties were also superior to the comparative examples in the examples of the present invention.
Also, in Examples 1 to 8 of the present invention, ΔE value was 2.0 to 2.9, while in the comparative example, ΔE value was as high as 4.5.
That is, Examples 1 to 8 belonging to the scope of the present invention are excellent in impact resistance, gloss and weatherability, and thus are suitable for use in automobile interior parts. Therefore, through the above experiments, the critical significance of the content ratio between the constituent components of the thermoplastic resin composition of the present invention and the superiority of the thermoplastic resin composition of the present invention have been proved.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (14)
5 to 30 parts by weight of an impact modifier; And
From 1 part by weight to 8 parts by weight of quenching;
/ RTI >
Wherein the impact modifier comprises a first impact modifier as a core-shell type acrylic rubber modified graft copolymer and a second impact modifier as a core-shell type diene-acrylic rubber modified graft copolymer,
Wherein the color difference change (DELTA E) before and after the evaluation measured in the weathering exposure condition of 2,500 kJ / m 2 according to SAE J1960 of the molded article is 2.0 to 2.9.
Wherein the weight ratio of the aromatic vinyl compound to the cyanide vinyl compound in the shell layer is from 4: 1 to 1.5: 1.
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| DE102015122922.6A DE102015122922B4 (en) | 2014-12-31 | 2015-12-29 | Thermoplastic resin composition for automobile interior components and molding for automobile interior components using the same |
| US14/982,165 US10000635B2 (en) | 2014-12-31 | 2015-12-29 | Thermoplastic resin composition for automotive interior components and molded article for automotive interior components using the same |
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| KR102119031B1 (en) | 2017-12-05 | 2020-06-04 | 롯데첨단소재(주) | Thermoplastic resin composition and molded article using the same |
| KR101958884B1 (en) | 2017-12-29 | 2019-03-15 | 롯데첨단소재(주) | Thermoplastic resin composition and molded article using the same |
| KR102194062B1 (en) * | 2018-04-27 | 2020-12-22 | 롯데첨단소재(주) | Thermoplastic resin composition and article including same |
| KR102221622B1 (en) * | 2018-06-29 | 2021-02-26 | 롯데첨단소재(주) | Thermoplastic resin composition and article including same |
| KR102400080B1 (en) * | 2019-08-30 | 2022-05-18 | 롯데첨단소재(주) | Thermoplastic resin composition and article including same |
| KR20240003152A (en) | 2022-06-30 | 2024-01-08 | 현대모비스 주식회사 | Polyphenylene sulfide resin composition and molded articles for automobiles manufactured using the same |
| KR20240025343A (en) | 2022-08-18 | 2024-02-27 | 현대모비스 주식회사 | Polyphenylene sulfide resin composition and molded articles for automobiles manufactured using the same |
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| KR100680338B1 (en) * | 2005-12-07 | 2007-02-08 | 기아자동차주식회사 | Thermoplastic polycarbonate alloy with low gloss |
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| KR101267271B1 (en) | 2009-12-30 | 2013-05-27 | 제일모직주식회사 | Thermoplastic Resin Having Excellent Low Gloss Characteristic and Good Weatherability |
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| KR100680338B1 (en) * | 2005-12-07 | 2007-02-08 | 기아자동차주식회사 | Thermoplastic polycarbonate alloy with low gloss |
| KR100876844B1 (en) | 2007-12-31 | 2008-12-31 | 제일모직주식회사 | Scratch-resistant flameproof thermoplastic resin composition with improved transparency |
| KR101267271B1 (en) | 2009-12-30 | 2013-05-27 | 제일모직주식회사 | Thermoplastic Resin Having Excellent Low Gloss Characteristic and Good Weatherability |
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