KR20160128534A - Thermoplastic resin composition and molded parts using the same - Google Patents
Thermoplastic resin composition and molded parts using the same Download PDFInfo
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- KR20160128534A KR20160128534A KR1020150059836A KR20150059836A KR20160128534A KR 20160128534 A KR20160128534 A KR 20160128534A KR 1020150059836 A KR1020150059836 A KR 1020150059836A KR 20150059836 A KR20150059836 A KR 20150059836A KR 20160128534 A KR20160128534 A KR 20160128534A
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/62—Mechanical aspects
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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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Abstract
Description
The present invention relates to a thermoplastic resin composition and a molded article produced therefrom, and more particularly, to a thermoplastic resin composition which is excellent in impact strength and high temperature tensile strength and can realize low light properties, and a molded article produced therefrom.
Acrylonitrile-butadiene-styrene (ABS) resin is excellent in impact resistance, excellent in electrical properties, chemical resistance, oil resistance, and excellent in workability, and can be formed into various forms such as injection molding, extrusion molding and vacuum molding It is widely used for household goods, housings of electric and electronic products, automobile parts, and interior and exterior materials.
In addition, the acrylonitrile-butadiene-styrene copolymer resin has excellent properties of glossiness. However, recently, as the demand for a resin having a soft texture of low gloss has been increased, the application range of a low-gloss resin has been expanded, and development of an acrylonitrile-butadiene-styrene copolymer resin having excellent low-light characteristics is required.
There is a method of removing the gloss through the injection molding or the low light painting process using the corrosion mold after the acrylonitrile-butadiene-styrene copolymer resin is manufactured. However, the manufacturing cost is increased due to the introduction of the additional process or equipment, And it is difficult to apply it in terms of environment.
As another method, there is a method of applying a gum polymer of large diameter or applying a light extinguishing agent so that the acrylonitrile-butadiene-styrene copolymer resin can attain a low light effect. However, in the case of a large amount of gum polymer, A large amount of the rubber polymer is required, and thus the rubber polymer thus increased can cause a decrease in ultraviolet stability and weatherability, and addition of a quencher also has a problem of lowering the impact strength.
Accordingly, in order to solve such a problem, it is required to develop a thermoplastic resin composition which does not deteriorate physical properties such as impact strength while realizing a low light effect by controlling the luster of the material itself.
Accordingly, it is an object of the present invention to provide a thermoplastic resin composition having excellent impact strength while realizing a low light effect by controlling the gloss of the resin composition itself, and a molded article produced therefrom.
It is also an object of the present invention to provide a thermoplastic resin composition which is excellent in high temperature tensile strength and excellent in vacuum moldability and a molded article produced therefrom.
In order to achieve the above object, the thermoplastic resin composition according to one embodiment of the present invention comprises (A) 20 to 40% by weight of an acrylonitrile-butadiene-styrene graft copolymer; (B) from 10 to 50% by weight of a styrene-acrylonitrile copolymer; And (C) a cross-linked copolymer 15 prepared from a mixture comprising an aromatic vinyl compound, (C-2) unsaturated nitrile compound and (C-3) a silicone compound having two or more unsaturated reactive groups, By weight to 50% by weight.
The weight ratio of the styrene-acrylonitrile copolymer (B) and the crosslinkable copolymer (C) may be 1: 0.3 to 1: 5.
The acrylonitrile-butadiene-styrene graft copolymer (A) may have an average particle diameter of the butadiene rubber-like polymer of 200 to 600 nm.
The acrylonitrile-butadiene-styrene graft copolymer (A) may contain 5 to 50% by weight of the butadiene rubber-like polymer.
The weight average molecular weight of the styrene-acrylonitrile copolymer (B) may be 100,000 to 350,000 g / mol.
The styrene-acrylonitrile copolymer (B) may contain 60 to 80% by weight of styrene as a repeating unit.
The crosslinkable copolymer (C) is obtained by reacting 100 parts by weight of a monomer mixture comprising 60 to 80% by weight of the aromatic vinyl compound (C-1) and 20 to 40% by weight of the unsaturated nitrile compound (C-2) , And 0.1 to 10 parts by weight of the silicone compound (C-3) having at least two unsaturated reactive groups.
The aromatic vinyl compound (C-1) is at least one compound selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dibromostyrene , Vinyl naphthalene, and combinations thereof.
The unsaturated nitrile compound (C-2) may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof.
The silicone compound (C-3) having at least two unsaturated reactive groups may be represented by the following formula (1).
[Chemical Formula 1]
(1), l, m and n are each an integer of 0 to 100 (provided that they are not simultaneously 0), and R 1 to R 8 are each independently hydrogen, a substituted or unsubstituted C 1 to C 30 Alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 30 alkynyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 1 to C 30 heteroaryl group, a hydroxyl group, an alkoxy group, an amino group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group of the, or a mercapto group, the At least two of R < 1 > to R < 8 > include a polymerizable unsaturated reactive group, and the compound may have a linear or cyclic structure.
The silicone compound (C-3) having at least two unsaturated reactive groups may be represented by the following formula (2).
(2)
(Wherein R 9 to R 14 independently represent a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 2 to C 20 An alkenyl group and a substituted or unsubstituted C 6 to C 20 aryl group, R 15 to R 17 are each independently hydrogen or a substituted or unsubstituted C 1 to C 6 alkyl group, and p Is an integer of 1 to 6).
The silicone compound (C-3) having two or more unsaturated reactive groups may be 1,3,5-trimethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7- 3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, 1,3,5-tri Ethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetraethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9 -Pentaethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, and combinations thereof.
The molded article according to one embodiment of the present invention may include the thermoplastic resin composition described above.
The molded article may have a gloss of 0.5 to 15 GU measured at an angle of reflection of 20 degrees by the evaluation method defined in ASTM D523.
The molded product may have a tensile strength of 3 to 10 kgf / cm 2 measured after allowing the specimen for tensile strength measurement made of the thermoplastic resin composition to stand at 150 ° C for 2 hours.
The molded product is obtained by cutting the specimen prepared by injection molding the thermoplastic resin composition into a specimen for tensile strength measurement according to ASTM D638 in the machine direction (MD), measuring the tensile strength according to the evaluation method specified in ASTM D638 Is 403 to 420 kgf / cm 2 , and the injection-molded test piece is cut into a specimen for tensile strength measurement in the transverse direction (TD), and the tensile strength measured according to the evaluation method specified in ASTM D638 Can be 380 to 395 kgf / cm < 2 >.
The molded article can be produced by extruding the thermoplastic resin composition.
The molded article may be in the form of a sheet having a thickness of 5 mm or less.
The thermoplastic resin composition according to the present invention can realize low light properties without lowering the impact resistance by using a styrene-acrylonitrile copolymer and a crosslinking copolymer in combination in an acrylonitrile-butadiene-styrene graft copolymer.
Particularly, there is an effect of excellent impact resistance as compared with the case of producing a thermoplastic resin composition using a conventional quencher.
It is another object of the present invention to provide a thermoplastic resin composition having excellent high temperature tensile strength and excellent vacuum moldability by controlling the content of each component and the weight average molecular weight of the styrene-acrylonitrile copolymer.
Further, the thermoplastic resin composition according to the present invention can be extrusion-molded into a thin sheet to produce a vacuum molded product, which can be applied to automobile interior and exterior materials.
The effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned can be clearly understood by those skilled in the art from the description of the claims.
Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.
Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. Also, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.
Hereinafter, the thermoplastic resin composition according to one embodiment of the present invention will be described.
The thermoplastic resin composition according to the present invention comprises (A) an acrylonitrile-butadiene-styrene graft copolymer, (B) a styrene-acrylonitrile copolymer and (C) 2) an unsaturated nitrile-based compound and (C-3) a silicone-based compound having at least two unsaturated reactive groups.
Each component constituting the thermoplastic resin composition according to one embodiment of the present invention will be described in detail.
(A) acrylonitrile-butadiene-styrene graft copolymer (g-ABS) resin
The acrylonitrile-butadiene-styrene graft copolymer (A) is obtained by graft copolymerizing a core of a butadiene-based rubbery polymer component and a monomer mixture containing styrene and acrylonitrile around its core to form a shell And may have a formed core-shell structure.
Wherein the acrylonitrile-butadiene-styrene graft copolymer comprises 5 to 50% by weight of the butadiene rubber-like polymer, 20 to 80% by weight of the styrene, and 20 to 80% by weight of the butadiene-styrene graft copolymer, based on 100% by weight of the acrylonitrile- And 5 to 45% by weight of acrylonitrile.
The acrylonitrile-butadiene-styrene graft copolymer may have an average particle diameter of the butadiene-based rubbery polymer of 200 to 600 nm, preferably 250 to 550 nm.
With respect to the particle size of the rubbery polymer in the present invention, there is a method of expressing the average size of the population by quantification by the measurement method. However, the method is generally used, and the mode diameter indicating the maximum value of the distribution, (Average number, length average, area average, mass average, volume average, and the like). In the present invention, unless otherwise specified, the average particle diameter is a number average diameter, and D50 The particle size of the spot).
The content of the acrylonitrile-butadiene-styrene graft copolymer may be 20 to 35% by weight, preferably 25 to 33% by weight, based on 100% by weight of the thermoplastic resin composition. When the acrylonitrile-butadiene-styrene graft copolymer (A) is out of the above range, there is a problem that the impact resistance is lowered.
(B) styrene-acrylonitrile copolymer (SAN) resin
The styrene-acrylonitrile copolymer (B) may be formed by copolymerizing a mixture containing styrene and acrylonitrile.
The styrene-acrylonitrile copolymer (B) is formed by copolymerizing a mixture containing 60 to 80% by weight of styrene and 20 to 40% by weight of acrylonitrile, and preferably 70 to 80% by weight of styrene and acrylonitrile And 20 to 30% by weight of the composition.
When the content of the respective monomers constituting the styrene-acrylonitrile copolymer (B) is within the above range, the impact strength can be improved.
The weight average molecular weight of the styrene-acrylonitrile copolymer (B) may be 100,000 to 350,000 g / mol, and preferably 100,000 to 300,000 g / mol. When the weight average molecular weight of the styrene-acrylonitrile copolymer (B) is out of the above-mentioned range, extrusion molding in sheet form is difficult.
The content of the styrene-acrylonitrile copolymer (B) may be 30 to 60% by weight, preferably 30 to 55% by weight, based on 100% by weight of the thermoplastic resin composition. If the content of the styrene-acrylonitrile copolymer (B) is out of the above range, compatibility with the acrylonitrile-butadiene-styrene graft copolymer (A) may be poor or the impact strength may be lowered.
(C) a crosslinkable copolymer
The crosslinkable copolymer (C) of the present invention is obtained from a mixture comprising an aromatic vinyl compound (C-1), an unsaturated nitrile compound (C-2) and a silicone compound having at least two unsaturated reactive groups .
Hereinafter, each component will be described in more detail.
(C-1) aromatic vinyl compound
In the present invention, the aromatic vinyl compound (C-1) is preferably selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, Naphthalene, vinylnaphthalene, and combinations thereof, but the present invention is not limited thereto.
The aromatic vinyl compound (C-1) is preferably at least one selected from the group consisting of styrene,? -Methylstyrene, and combinations thereof.
In the present invention, the aromatic vinyl compound (C-1) may include 60 to 80% by weight based on the total weight of the monomer mixture for producing the crosslinkable copolymer. In the above range, the impact strength and heat resistance of the thermoplastic resin composition can be improved.
(C-2) Unsaturated nitrile compound
In the present invention, the unsaturated nitrile compound (C-2) may be any one or more selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof, but is not limited thereto.
The unsaturated nitrile compound (C-2) is preferably acrylonitrile.
In the present invention, the unsaturated nitrile compound (C-2) may include 20 to 40% by weight based on the total weight of the monomer mixture for producing the crosslinkable copolymer. In the above range, the impact strength and heat resistance of the thermoplastic resin composition can be improved.
(C-3) a silicone compound having two or more unsaturated reactive groups
In the present invention, the silicone compound (C-3) having two or more unsaturated reactive groups can be used for realizing excellent low light properties while maintaining various physical properties such as impact resistance and heat resistance.
The silicone compound (C-3) having two or more unsaturated reactive groups may include one or more compounds represented by the following formula (1).
[Chemical Formula 1]
In Formula 1, l , m and n are each an integer of 0 to 100 (but not simultaneously 0), and R 1 to R 8 are each independently hydrogen, a substituted or unsubstituted C 1 to C 30 alkyl group , A substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 30 alkynyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 1 to C 30 heteroaryl group, a hydroxyl group, an alkoxy group, an amino group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group of the, or a mercapto group, the R At least two of R 1 to R 8 include a polymerizable unsaturated reactive group, and the compound may have a linear or cyclic structure.
In the crosslinkable copolymer according to one embodiment of the present invention, the silicone compound (C-3) having two or more unsaturated reactive groups may be represented by the following formula (2).
(2)
In the formula (2), R 9 to R 14 independently represent a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 2 to C 20 An alkenyl group and a substituted or unsubstituted C 6 to C 20 And R 15 to R 17 are each independently hydrogen or a substituted or unsubstituted C 1 to C 6 alkyl group, and p is an integer of 1 to 6.
The silicone compound (C-3) having two or more unsaturated reactive groups is, for example, 1,3,5-triisopropyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7 - tetraisopropyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentaisopropyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane Butyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetra-sec-butyl-1,3,5,7-tetravinyl-cyclo Tetrasiloxane, 1,3,5,7,9-pentac-butyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, 1,3,5-triisopropyl-1,3,5 -Trimethyl-cyclotrisiloxane, 1,3,5,7-tetraisopropyl-1,3,5,7-tetramethyl-cyclotetrasiloxane, 1,3,5,7,9-pentaisopropyl-1, 3,5,7,9-pentamethyl-cyclopentasiloxane, 1,3,5-triisopropyl-1,3,5-triethyl-cyclotrisiloxane, 1,3,5,7-tetraisopropyl- 1,3,5,7-tetraethyl-cyclotetra 1,3,5,7,9-pentaisopropyl-1,3,5,7,9-pentaethyl-cyclopentasiloxane, 1,1,3,3,5,5-hexaisopropyl- Cyclotrisiloxane, 1,1,3,3,5,5,7,7-octaisopropyl-cyclotetrasiloxane, 1,1,3,3,5,5,7,7,9,9-decaiso Propyl-cyclopentasiloxane, 1,3,5-tri-sec-butyl-1,3,5-trimethyl-cyclotrisiloxane, 1,3,5,7-tetra- Tetramethyl-cyclotetrasiloxane, 1,3,5,7,9-pentac-butyl-1,3,5,7,9-pentamethyl-cyclopentasiloxane, 1,3,5-tri- 1,3,5-triethyl-cyclotrisiloxane, 1,3,5,7-tetra-sec-butyl-1,3,5,7-tetraethyl-cyclotetrasiloxane, 1,3,5,7,9 Butyl-1,3,5,7,9-pentaethyl-cyclopentasiloxane, 1,3,5-triisopropyl-cyclotrisiloxane, 1,3,5,7-tetraisopropyl-cyclo Tetrasiloxane, 1,3,5,7,9-pentaisopropyl-cyclopentasiloxane, 1,3,5-tri-sec-butyl-cyclo 1,3,5,7-tetra-sec-butyl-cyclotetrasiloxane, 1,3,5,7,9-pentac-butyl-cyclopentasiloxane, 1,3,5-trimethyl-1,3 , 5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentamethyl- , 3,5,7,9-pentavinyl-cyclopentasiloxane, 1,3,5-triethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetraethyl- , 3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentaethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, and combinations thereof. And is not necessarily limited thereto. Preferred are 1,3,5-trimethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, 1,3,5-triethyl-1,3,5-trivinyl- Siloxane, 1,3,5,7-tetraethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentaethyl-1,3,5,7,9 - pentabinyl-cyclopentasiloxane, and combinations thereof. More preferably, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane can be used.
In the present invention, the silicone compound (C-3) having two or more unsaturated reactive groups can be used alone or in combination with other components to realize various physical properties such as excellent impact resistance and heat resistance as well as low light properties which are difficult to achieve with conventional crosslinking agents And it is easier to control the degree of crosslinking and the polymerization reaction rate as compared with the conventional crosslinking agent.
The silicone compound (C-3) having two or more unsaturated reactive groups may have a molecular weight or a weight average molecular weight of 150 to 6,000 g / mol. When the above-mentioned range is satisfied, the degree of crosslinking is easily controlled and the crosslinking reaction progresses smoothly, so that excellent low light characteristics can be realized.
In the present invention, the silicone compound (C-3) having two or more unsaturated reactive groups is added in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 8 parts by weight, per 100 parts by weight of the monomer mixture containing an aromatic vinyl compound and an unsaturated nitrile compound. By weight, more preferably 0.5 to 5 parts by weight.
When the above range is satisfied, it is easy to control the degree of crosslinking of the crosslinkable copolymer (C), the appearance characteristics can be improved without lowering impact strength and heat resistance, and uniform low light characteristics can be realized.
The crosslinkable copolymer (C) according to the present invention is a crosslinkable copolymer obtained by copolymerizing at least one monomer selected from the group consisting of divinylpolydimethylsiloxane, vinyl modified dimethylsiloxane, divinylbenzene, ethylene glycol di (meth) acrylate, allyl (meth) acrylate, diallyl phthalate, And a polyfunctional vinyl compound selected from the group consisting of triallyl isocyanurate, triallyl isocyanurate, and combinations thereof. Preferably, at least one selected from the group consisting of divinylpolydimethylsiloxane, vinyl-modified dimethylsiloxane, and combinations thereof can be used.
The polyfunctional vinyl compound may be used in an amount of 0.001 to 10 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the monomer mixture containing an aromatic vinyl compound and an unsaturated nitrile compound. Within the above range, the crosslinking degree and the polymerization reaction rate of the crosslinkable copolymer (C) can be easily controlled, and the combination of the crosslinking copolymer (C) with other components can realize low light properties without deteriorating impact resistance and heat resistance.
The crosslinkable copolymer (C) according to the present invention may have a glass transition temperature (Tg) of 95 to 115 캜. Within the above range, the thermoplastic resin composition containing the crosslinkable copolymer (C) can exhibit excellent low light properties without lowering the impact resistance and heat resistance.
In the present invention, the crosslinkable copolymer (C) can be produced by a conventional polymerization method such as suspension polymerization, emulsion polymerization, solution polymerization and the like, but is not necessarily limited thereto. As an example of the method for producing the copolymer, suspension polymerization may be used.
When the crosslinked copolymer (C) is prepared by the suspension polymerization method, the dispersibility can be improved by using an inorganic dispersant or an organic dispersant. As the organic dispersing agent, a homopolymer or copolymer of acrylic acid or methacrylic acid can be used. When a copolymer is used as the organic dispersant, the content of acrylic acid or methacrylic acid used may be 50 parts by weight or more based on 100 parts by weight of the copolymer. In addition, the acrylic acid or methacrylic acid may preferably be in the form of a salt of sodium, potassium or ammonium to maintain adequate solubility.
As the polymerization initiator in the copolymerization of the crosslinkable copolymer (C), azobisisobutyronitrile can be preferably used, but not always limited thereto.
The content of the crosslinkable copolymer (C) may be 20 to 50% by weight, preferably 20 to 45% by weight, based on 100% by weight of the thermoplastic resin composition.
The weight ratio of the styrene-acrylonitrile copolymer (B) and the crosslinkable copolymer (C) may be 1: 0.3 to 1: 5, preferably 1: 0.4 to 1: 3.
The content ranges and ratios are optimum ranges for improving the low light properties by controlling the gloss of the thermoplastic resin composition without deteriorating physical properties such as impact resistance and heat resistance. When the range is out of the above range, the impact resistance of the thermoplastic resin composition is remarkably deteriorated There is a problem that low-light characteristics can not be realized.
The thermoplastic resin composition may further include additives in accordance with the use thereof. The additive may further include a flame retardant, a lubricant, a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer or a colorant, and may be used in a mixture of two or more kinds depending on the properties of the final molded product.
The flame retardant is a material that reduces combustibility and may be a phosphate compound, a phosphite compound, a phosphonate compound, a polysiloxane, a phosphazene compound, a phosphinate compound or a melamine compound But it is not limited thereto.
The lubricant is a material which lubricates the surface of the metal contacting with the thermoplastic resin composition during processing, molding or extrusion to help flow or move the resin composition, and a commonly used material can be used.
The plasticizer is a material which increases the flexibility, workability or extensibility of the thermoplastic resin composition, and a commonly used material can be used.
The heat stabilizer is a substance which inhibits thermal decomposition of the thermoplastic resin composition when kneaded or molded at a high temperature, and a commonly used material can be used.
The antioxidant is a substance that prevents the resin composition from being decomposed and lost its inherent property by inhibiting or blocking the chemical reaction between the thermoplastic resin composition and oxygen. The antioxidant may be a phenol type, phosphite type, thioether type or amine type antioxidant But it is not limited thereto.
The light stabilizer may contain at least one of hindered phenol-type, benzophenone-type, or benzotriazole-type light stabilizer, which inhibits or blocks the loss of color or mechanical properties of the thermoplastic resin composition from ultraviolet rays. However, the present invention is not limited thereto.
Conventional pigments or dyes may be used as the colorant.
The additive may be included in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the thermoplastic resin composition.
The molded article according to one embodiment of the present invention can be produced from the above-mentioned thermoplastic resin composition. The thermoplastic resin composition can be applied to various industrial fields such as various electric and electronic products and automobile parts which require a low light-emitting material because it can realize low light properties while maintaining excellent impact strength, tensile strength and extrusion stability, And can be easily applied to exterior materials.
The molded article may have a gloss of 0.5 to 15 GU measured at an angle of reflection of 20 degrees by the evaluation method defined in ASTM D523.
The molded product may have a tensile strength of 3 to 10 kgf / cm 2 measured after allowing the tensile strength side applied specimen made of the thermoplastic resin composition to stand at 150 ° C for 2 hours. The higher the tensile strength at the high temperature (150 ° C), the better the vacuum formability.
The molded product is obtained by cutting the specimen prepared by injection molding the thermoplastic resin composition into a specimen for tensile strength measurement according to ASTM D638 in the machine direction (MD), measuring the tensile strength according to the evaluation method specified in ASTM D638 Is 403 to 420 kgf / cm 2 , and the injection-molded test piece is cut into a specimen for tensile strength measurement in the transverse direction (TD), and the tensile strength measured according to the evaluation method specified in ASTM D638 Can be 380 to 395 kgf / cm < 2 >. As the MD tensile strength and the TD tensile strength are both excellent, the tensile strength is excellent regardless of the processing direction and the extrusion stability is excellent.
The molded article according to the present invention can be provided with a thin sheet-shaped molded article with excellent high-temperature tensile strength and extrusion stability, and the sheet can be produced with a thickness of 5 mm or less, preferably 0.5 to 4.5 mm .
Further, the molded article can be produced by vacuum-molding the extruded sheet in various forms.
[Example]
Hereinafter, the results of experiments conducted to demonstrate the excellent effects of the thermoplastic resin composition of the present invention are shown.
The components used in the thermoplastic resin compositions of the following examples and comparative examples are as follows.
(a) an acrylonitrile-butadiene-styrene graft copolymer
An acrylonitrile-butadiene-styrene graft copolymer (g-ABS) having an average particle diameter of 260 nm of a polybutadiene rubber polymer of Samsung SDI was used.
(b) styrene-acrylonitrile copolymer resin
(b-1) A styrene-acrylonitrile copolymer resin product having a weight average molecular weight of 112,000 g / mol by Samsung SDI was used.
(b-2) A styrene-acrylonitrile copolymer resin product having a weight average molecular weight of 259,000 g / mol by Samsung SDI was used.
(c) a crosslinkable copolymer
2 parts by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane was added to 100 parts by weight of a monomer mixture comprising 76% by weight of styrene and 24% by weight of acrylonitrile And a crosslinked styrene-acrylonitrile copolymer of Samsung SDI having a weight average molecular weight of 170,000 g / mol was used.
(d) quenching agent
Blendex BMAT, a quencher product from Chemtura, was used.
The thermoplastic resin compositions of Examples and Comparative Examples were prepared in accordance with the component content ratios described in Table 1 below. Acrylonitrile copolymer (a), the styrene-acrylonitrile copolymer (b) and the crosslinkable copolymer (c) in an amount of 100% by weight and the content of each component in terms of% by weight , And the quencher (d) is expressed in parts by weight based on 100 parts by weight of the total of (a), (b) and (c).
The components listed in Table 1 were homogeneously mixed in a tumbler mixer, and the mixture was put into a feed part of a biaxial extruder (L / D = 29, f = 45 mm), melted and kneaded to prepare a thermoplastic resin composition in the form of pellets . The pellets were dried at 80 ° C for 4 hours, injection molded into a 6oz injection molding machine with a cylinder temperature of about 260 ° C and a mold temperature of about 60 ° C, aged for 4 hours after injection molding, The measurement was carried out.
The tensile strength, gloss, high temperature tensile strength, MD (injection molding direction) / TD (direction perpendicular to injection molding) tensile strength of the specimens obtained by the composition of the components as shown in Table 1 were evaluated in the following manner, Are shown in Table 2 below.
Property evaluation method
(1) Izod Impact Strength (kgf? Cm / cm): A specimen for 1/8 "notch Izod impact strength measurement was measured at room temperature according to the evaluation method specified in ASTM D256.
(2) Glossiness (GU): Glossiness was measured at a reflection angle of 20 ° by the BYK-Gardner gloss meter of BYK by the evaluation method defined in ASTM D523.
(3) High Tensile Strength (kgf / cm 2 ): A specimen for measuring a tensile strength of 64 mm × 3.02 mm × 3.00 mm was left at 150 ° C. for 2 hours and then the tensile strength was measured (measuring speed: 254 mm / min, 25.4 mm).
(4) MD / TD Tensile Strength (kgf / cm 2 ): Injection molding specimen (Specimen Specification: 254 mm × 254 mm × 3.2 mm) was subjected to ASTM D638 Specimen Specification for Tensile Strength Measurement (170 mm × 12.7 mm × 3.2 mm) MD, and TD, respectively, and measured according to the evaluation method specified in ASTM D638 (measurement speed: 5 mm / min, span distance: 50 mm).
(kgf · cm / cm)
(kgf / cm 2 )
(kgf / cm 2 )
From Tables 1 and 2, it was found that the thermoplastic resin compositions according to the Examples were excellent in impact strength, low light property, high temperature tensile strength, and extrusion stability.
On the other hand, in the case of Comparative Example 1 in which the component (c) was not added, the gloss was measured to be high, and the low light characteristic could not be realized.
Further, even when the component (c) was added, the glossiness was relatively high (Comparative Example 2) when the content of the present invention was deviated as in Comparative Examples 2 and 3, and the impact strength and the high temperature tensile strength were low, I could not.
In addition, in Comparative Examples 4 and 5 using a quencher, it was found that the low light properties were significantly lower than those of the thermoplastic resin compositions according to Examples.
The scope of the present invention is not limited to the above-described embodiments, but may be embodied in various forms of embodiments within the scope of the appended claims. 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 present invention as defined by the appended claims.
Claims (18)
(B) from 10 to 50% by weight of a styrene-acrylonitrile copolymer; And
(C) a cross-linked copolymer produced from a mixture comprising an aromatic vinyl compound, (C-2) an unsaturated nitrile compound and (C-3) a silicone compound having two or more unsaturated reactive groups, By weight of the thermoplastic resin composition.
Wherein the weight ratio of the styrene-acrylonitrile copolymer (B) and the crosslinkable copolymer (C) is 1: 0.3 to 1: 5.
Wherein the acrylonitrile-butadiene-styrene graft copolymer (A) has an average particle size of the butadiene rubber-like polymer of 200 to 600 nm.
The acrylonitrile-butadiene-styrene graft copolymer (A) is obtained by copolymerizing a thermoplastic resin (A) containing 5 to 50% by weight of a butadiene rubber polymer with respect to 100% by weight of the acrylonitrile-butadiene-styrene graft copolymer (A) Composition.
The styrene-acrylonitrile copolymer (B) has a weight average molecular weight of 100,000 to 350,000 g / mol.
The styrene-acrylonitrile copolymer (B) contains 60 to 80% by weight of styrene as a repeating unit.
The crosslinkable copolymer (C) is obtained by reacting 100 parts by weight of a monomer mixture comprising 60 to 80% by weight of the aromatic vinyl compound (C-1) and 20 to 40% by weight of the unsaturated nitrile compound (C-2) , And 0.1 to 10 parts by weight of a silicone compound (C-3) having at least two unsaturated reactive groups.
The aromatic vinyl compound (C-1) is at least one compound selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dibromostyrene , Vinyl naphthalene, and combinations thereof.
The unsaturated nitrile compound (C-2) is selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof.
The silicone compound (C-3) having two or more unsaturated reactive groups is represented by the following formula (1).
[Chemical Formula 1]
(1), l, m and n are each an integer of 0 to 100 (provided that they are not simultaneously 0), and R 1 to R 8 are each independently hydrogen, a substituted or unsubstituted C 1 to C 30 Alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 30 alkynyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 1 to C 30 heteroaryl group, a hydroxyl group, an alkoxy group, an amino group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group of the, or a mercapto group, the At least two of R < 1 > to R < 8 > include a polymerizable unsaturated reactive group, and the compound may have a linear or cyclic structure.
The silicone compound (C-3) having two or more unsaturated reactive groups is represented by the following formula (2).
(2)
(Wherein R 9 to R 14 independently represent a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 2 to C 20 An alkenyl group and a substituted or unsubstituted C 6 to C 20 aryl group, R 15 to R 17 are each independently hydrogen or a substituted or unsubstituted C 1 to C 6 alkyl group, and p Is an integer of 1 to 6).
The silicone compound (C-3) having two or more unsaturated reactive groups may be 1,3,5-trimethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7- 3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, 1,3,5-tri Ethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetraethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9 - penta- ethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, and combinations thereof.
Wherein the molded article has a gloss of 0.5 to 15 GP as measured at an angle of reflection of 20 degrees by the evaluation method defined in ASTM D523.
Wherein the molded article has a tensile strength of 3 to 10 kgf / cm 2 measured after the specimen for tensile strength measurement made of the thermoplastic resin composition is left at 150 ° C for 2 hours.
The molded product is obtained by cutting the specimen prepared by injection molding the thermoplastic resin composition into a specimen for tensile strength measurement according to ASTM D638 in the machine direction (MD), measuring the tensile strength according to the evaluation method specified in ASTM D638 Is 403 to 420 kgf / cm 2 , and the injection-molded test piece is cut into a specimen for tensile strength measurement in the transverse direction (TD), and the tensile strength measured according to the evaluation method specified in ASTM D638 Is 380 to 395 kgf / cm 2 .
Wherein the molded article is produced by extruding the thermoplastic resin composition.
The molded article is in the form of a sheet having a thickness of 5 mm or less.
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| WO2024090993A1 (en) * | 2022-10-25 | 2024-05-02 | 주식회사 엘지화학 | Thermoplastic resin composition |
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| WO2024090993A1 (en) * | 2022-10-25 | 2024-05-02 | 주식회사 엘지화학 | Thermoplastic resin composition |
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