KR101320326B1 - Thermoplastic resin composition revealing improved impact strength and melt flow property - Google Patents
Thermoplastic resin composition revealing improved impact strength and melt flow property Download PDFInfo
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Abstract
Styrene-based thermoplastic resin composition excellent in impact properties of the present invention is a thermoplastic resin 10 to 99 containing at least one selected from the group consisting of (A) styrene-based copolymer resin (a1) and rubber-modified vinyl-based graft copolymer (a2) It includes 1% by weight to 90% by weight, and branched styrene-based copolymer resin prepared by (B) a silicone compound. The thermoplastic resin composition of the present invention provides a resin composition having excellent physical properties such as improved flowability and moldability while showing improved impact strength by applying a branched styrene-based copolymer resin.
Description
The present invention relates to a styrene-based thermoplastic resin composition, and more particularly to a styrene-based thermoplastic resin composition having excellent impact resistance and fluidity.
The thermoplastic resin has a lower specific gravity than glass or metal, and has excellent physical properties such as moldability and impact resistance. In recent years, plastic products have been rapidly replacing the existing glass and metal areas in accordance with the trend of low cost, large size, and light weight of electric and electronic products, thereby widening the use range from electric / electronic products to automobile parts. Accordingly, the function of the exterior and the performance of the appearance become important, and the demand for external impact and workability is also increasing.
In particular, acrylonitrile-butadiene-styrene copolymer resin (hereinafter referred to as "ABS resin") is prepared by graft polymerization of an styrene monomer, an aromatic vinyl compound, and an acrylonitrile monomer, an unsaturated nitrile compound, in the presence of a butadiene rubbery polymer. It is prepared by blending a graft ABS resin (hereinafter "g-ABS resin") and styrene-acrylonitrile copolymer resin (hereinafter "SAN resin"). Such ABS resins are widely used in automobile parts and interior materials, electrical and electronic products, office equipment, toys, etc. because of their excellent impact resistance, weather resistance, chemical resistance, heat resistance, and mechanical strength, and easy molding processing.
However, in recent years, as the tendency of the housing of electronic component parts changes, various characteristics are increasingly required. In particular, as high impact strength, high colorability and high fluidity are important under the influence of thinning and appearance enhancement strategies, the demand for ABS resins having excellent impact resistance and fluidity is increasing.
Conventionally, in order to improve the impact resistance of the ABS resin, a method of increasing the molecular weight of the SAN resin or increasing the rubber content of the ABS resin was used, but this has the disadvantage of improving the impact resistance but lowering fluidity or heat resistance.
An object of the present invention is to provide a styrene-based thermoplastic resin composition excellent in impact resistance and fluidity.
It is another object of the present invention to add a branched styrene copolymer resin containing a silicone compound to a blend of styrene copolymer resin and rubber-modified vinyl graft copolymer resin, thereby improving impact resistance and fluidity simultaneously. It is for providing a resin composition.
Still another object of the present invention is to provide a molded article using the resin composition.
The above and other objects of the present invention can be achieved by the present invention described below.
The present invention is (A) (a1) 10 to 99% by weight of a thermoplastic resin comprising at least one selected from the group consisting of styrene copolymer resin and (a2) rubber-modified vinyl graft copolymer; And (B) provides a styrene-based thermoplastic resin composition comprising 1 to 90% by weight of the branched styrenic copolymer resin prepared by including a silicone compound.
In an embodiment of the present invention, the weight average molecular weight of the branched styrenic copolymer resin (B) prepared by containing the silicone compound is preferably 50,000 to 5,000,000.
The branched styrenic copolymer resin (B) prepared by including the silicone compound includes (b1) an aromatic vinyl monomer, (b2) an unsaturated nitrile monomer, (b3) a (meth) acrylic monomer, and (b4) two Copolymers of silicone-based compounds having the above unsaturated reactors or mixtures of these copolymers may be used. The content of the components of the branched styrenic copolymer resin (B) prepared by using the silicone compound is (b1) 10 to 85% by weight of an aromatic vinyl monomer, (b2) 10 to 85% by weight of an unsaturated nitrile monomer, (b3) 1 to 50% by weight of the (meth) acrylic monomer and (b4) 0.1 to 20% by weight of the silicone-based compound having two or more unsaturated reactors.
The styrene-based thermoplastic resin composition may further improve performance by further including an impact modifier, a heat stabilizer, an antioxidant, a light stabilizer, a compatibilizer, a lubricant, a pigment, a dye, or an inorganic additive, depending on the use.
The present invention includes a pellet extruded from the styrene-based thermoplastic resin composition and a plastic molded article molded therefrom.
The styrene-based thermoplastic resin composition has a feature that can be alloyed with other resin (alloy), specifically, the styrene-based thermoplastic resin composition is polycarbonate (PC), polymethyl methacrylate (PMMA), polyolefin, polyphenyl May be alloyed with one or more resins selected from the group consisting of eneether (PPE), polyethylene terephthalate (PET), polyamide, polyimide, and mixtures thereof It is not limited to this. Furthermore, the present invention provides an alloy (alloy) styrene alloy thermoplastic resin composition as described above.
The present invention simultaneously improves impact strength and fluidity by adding a branched styrene copolymer resin containing a silicone compound to a blend of a styrene copolymer (SAN) and a rubber-modified vinyl graft copolymer (g-ABS). Has the effect of the invention to provide a styrenic thermoplastic resin composition and its molded article with improved properties.
Hereinafter, the present invention will be described in more detail.
Styrene-based thermoplastic resin composition of the present invention is 10 to 99% by weight of a thermoplastic resin comprising at least one selected from the group consisting of (A) (a1) styrene copolymer resin and (a2) rubber-modified vinyl graft copolymer, And (B) 1 to 90% by weight of a branched styrenic copolymer resin prepared by including a silicone compound.
The styrene-based thermoplastic resin composition of the present invention simultaneously improves impact resistance and fluidity by applying a branched styrene-based copolymer containing a silicone-based compound to a blend of a styrene-based copolymer resin and a rubber-modified vinyl-based graft copolymer resin. In particular, by applying a branched styrene-based copolymer containing a silicone-based compound, the impact resistance is improved to show excellent impact properties and at the same time the fluidity is improved by the branched structure to ensure excellent moldability.
Hereinafter, each component of the styrene-based thermoplastic resin composition of the present invention will be described in detail.
(a1) Styrene Copolymer Resin
The styrene-based copolymer resin of the present invention is 50 to 95% by weight of an aromatic vinyl compound or a mixture thereof and 5 to 50% by weight of an unsaturated nitrile compound, (meth) acrylic acid alkyl esters, maleic anhydride, maleimide compound or a mixture thereof. The% may be prepared by copolymerization in a conventional manner. The polymerization method is well known to those skilled in the art, and any of emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization may be used.
As the aromatic vinyl compound, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, halogen or alkyl substituted styrene may be used, but are not necessarily limited thereto. Among these, preferably styrene.
The unsaturated nitrile compound includes acrylonitrile, methacrylonitrile, and the like, but is not necessarily limited thereto.
The (meth) acrylic acid alkyl esters include C1-8 methacrylic acid alkyl esters and C1-8 acrylic acid alkyl esters. The C1-8 methacrylic acid alkyl esters or C1-8 acrylic acid alkyl esters are esters obtained from monohydryl alcohols containing 1 to 8 carbon atoms as alkyl esters of methacrylic acid or acrylic acid, respectively. Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester, acrylic acid methyl ester or methacrylic acid propyl ester, and the like, but are not necessarily limited thereto.
The maleimide compound includes C 1-4 alkyl or phenyl N-substituted maleimide, and the like, but is not necessarily limited thereto.
In one embodiment of the invention the styrenic copolymer (a1) is 50 to 95% by weight of styrene, α-methylstyrene, halogen or alkyl substituted styrene or mixtures thereof and acrylonitrile, methacrylonitrile, C1- Styrene-based copolymers obtained by copolymerizing 8 methacrylic acid alkyl esters, C1-8 acrylic acid alkyl esters, maleic anhydride, C1-4 alkyl or phenyl nucleosubstituted maleimides or mixtures thereof, or these copolymers Is a mixture of.
Preferred styrenic copolymers (a1) include monomer mixtures of styrene and acrylonitrile, optionally methacrylic acid methyl ester; monomer mixtures of α-methylstyrene with acrylonitrile, optionally, methacrylic acid methyl ester; Or those made from monomer mixtures of styrene, α-methylstyrene and acrylonitrile, optionally, methacrylic acid methyl ester.
It is preferable to use the styrene-type copolymer (a1) whose weight average molecular weights are 15,000-250,000.
Another preferred styrene copolymer is a copolymer of styrene and maleic anhydride, which can be prepared using a continuous block polymerization method or a solution polymerization method. The composition ratio of the two monomer components can be varied in a wide range, it is preferable that the content of maleic anhydride is 5 to 50% by weight. The molecular weight of the styrene / maleic anhydride copolymer may also be used in a wide range, but it is preferable to use a weight average molecular weight of 15,000 to 250,000.
In another embodiment, the styrene-based copolymer (a1) may be produced as a by-product in the preparation of the rubber-modified vinyl-based graft copolymer (a2) described below. This is especially the case when grafting an excess monomer mixture to a small amount of rubbery polymer or when an excessive amount of a chain transfer agent used as a molecular weight control agent is used. The content of the styrene-based copolymer used in the preparation of the resin composition of the present invention is not shown including the by-product of the graft copolymer.
(a2) Rubber modified vinyl graft copolymer
The rubber-modified vinyl graft copolymer (a2) is prepared by ordinary graft polymerization of 5 to 95% by weight of a rubbery polymer and 5 to 95% by weight of a vinyl monomer mixture. The method for preparing the rubber-modified vinyl graft copolymer (a2) is well known to those skilled in the art, and any of emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization may be used. Can be used. Preferably it is emulsion polymerization or block polymerization.
The vinyl monomer mixture is an aromatic vinyl compound, (meth) acrylic acid alkyl esters or 50 to 95% by weight of the mixtures thereof, and an unsaturated nitrile compound, (meth) acrylic acid alkyl esters, maleimide compounds or a mixture thereof 5 to 50 Contains weight percent.
Preferably, the vinyl monomer mixture is 60 to 90% by weight of an aromatic vinyl compound, (meth) acrylic acid alkyl esters or mixtures thereof, and an unsaturated nitrile compound, (meth) acrylic acid alkyl esters, maleimide compound or mixtures thereof. 10 to 40% by weight.
As the aromatic vinyl compound, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, halogen or alkyl substituted styrene may be used, but are not necessarily limited thereto.
The (meth) acrylic acid alkyl esters include C1-8 methacrylic acid alkyl esters and C1-8 acrylic acid alkyl esters. The C1-8 methacrylic acid alkyl esters or C1-8 acrylic acid alkyl esters are esters obtained from monohydryl alcohols containing 1 to 8 carbon atoms as alkyl esters of methacrylic acid or acrylic acid, respectively. Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester, acrylic acid methyl ester or methacrylic acid propyl ester, and the like, but are not necessarily limited thereto.
The unsaturated nitrile compound includes acrylonitrile, methacrylonitrile, and the like, but is not necessarily limited thereto.
The maleimide compound includes C 1-4 alkyl or phenyl N-substituted maleimide, and the like, but is not limited thereto.
The rubbery polymers include butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, terpolymer (EPDM) of ethylene-propylene-diene and polyorganosiloxane / polyalkyl (Meth) acrylate rubber composites, and the like, but is not necessarily limited thereto. The average particle diameter of the rubber particles is preferably 0.05 to 4 µm in order to improve impact resistance and surface properties of the molded product.
In one embodiment of the invention the rubber modified vinyl graft copolymer (a2) is styrene, α-methylstyrene, halogen or alkyl substituted styrene, C1-8 methacrylic acid alkyl esters, C1-8 acrylic acid alkyl ester 50 to 95% by weight or mixtures thereof and acrylonitrile, methacrylonitrile, C1-8 methacrylic acid alkyl esters, C1-8 acrylic acid alkyl esters, maleic anhydride, C1-4 alkyl or phenyl N-substituted 5 to 95% by weight of the monomer mixture, including 5 to 50% by weight of maleimide or mixtures thereof, is obtained from butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene- Propylene-diene terpolymer (EPDM) and polyorganosiloxane / polyalkyl (meth) acrylate rubber composites selected from the group consisting of one or a mixture thereof 5 to 95 may be used is manufactured by graft-polymerization to the weight%.
Preferred examples of the rubber-modified vinyl graft copolymer (a2) include butadiene rubber, acrylic rubber, or styrene / butadiene rubber in the form of a mixture of styrene and acrylonitrile and optionally (meth) acrylic acid alkyl ester monomers. The copolymerized thing is mentioned.
Another preferred example of the rubber-modified vinyl graft copolymer (a2) includes graft copolymerization of a monomer of (meth) acrylic acid methyl ester to butadiene rubber, acrylic rubber, or styrene / butadiene rubber.
The most preferable example of the rubber modified vinyl graft copolymer (a2) is an ABS graft copolymer.
(B) Branched Styrene Copolymer Resin Containing Silicone Compound
The branched styrenic copolymer resin (B) prepared by using the silicone compound used in the present invention includes (b1) an aromatic vinyl monomer, (b2) an unsaturated nitrile monomer, (b3) a (meth) acrylic monomer, and ( b4) Copolymers of silicone-based compounds having two or more unsaturated reactors or mixtures of these copolymers may be used. The content of the components of the branched styrenic copolymer resin (B) prepared by using the silicone compound is (b1) 10 to 85% by weight of an aromatic vinyl monomer, (b2) 10 to 85% by weight of an unsaturated nitrile monomer, (b3) 1 to 50% by weight of the (meth) acrylic monomer and (b4) 0.1 to 20% by weight of the silicone-based compound having two or more unsaturated reactors.
It is preferable that the weight average molecular weight of the branch structure styrene-type copolymer resin (B) manufactured containing the said silicone type compound is 5,000-5,000,000.
Specific examples of the aromatic vinyl monomer (b1) include styrene, p-methylstyrene, α-methylstyrene, halogen or alkyl substituted styrene, acrylonitrile, methacrylonitrile, maleic anhydride, C1-4 alkyl or phenyl Nuclear-substituted maleimide etc. can be mentioned, These can be used individually or in mixture of 2 or more types.
Specific examples of the unsaturated nitrile monomer (b2) include acrylonitrile, methacrylonitrile, and the like, and one or more thereof may be mixed and used, but is not necessarily limited thereto.
As the (meth) acrylic monomer (b3), preferably, a mixture of an aromatic or aliphatic methacrylate having a structure represented by the following Formula 1 or Formula 2 and a (meth) acrylic monomer copolymerizable therewith may be used.
[Formula 1]
In Formula 1, m is an integer of 0 to 20, X is hydrogen or methyl, Y is methyl, cyclohexyl, phenyl, benzyl, methylphenyl, methylethylphenyl, methoxyphenyl, cyclohexylphenyl, chlorophenyl, It may be selected from the group consisting of bromophenyl group, phenylphenyl group, benzylphenyl group.
(2)
In Formula 2, m is an integer of 0 to 20, X is hydrogen or methyl group, Z is oxygen (O) or sulfur (S), Ar is a methyl group, cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, me It may be selected from the group consisting of oxyphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group, phenylphenyl group, benzylphenyl group.
As the (meth) acrylic monomer (b3), for example, methacrylic acid esters, acrylic acid esters, unsaturated carboxylic acids, acid anhydrides, esters containing hydroxy groups, etc. may be used, and these may be used alone or in combination. It can be used by mixing the above. Specific examples include methacrylic acid esters including methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate and benzyl methacrylate; Acrylic esters including methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate; Unsaturated carboxylic acids including acrylic acid and methacrylic acid; Acid anhydrides including maleic anhydride; It may be selected from the group consisting of esters containing hydroxy groups including 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and monoglycerol acrylate and mixtures thereof.
As the silicone compound (b4) having two or more unsaturated reactors, preferably, a silicone compound having two or more unsaturated reactors in a terminal or side chain having a structure represented by the following general formula (3) or a mixture of two or more thereof is used. Can lose.
(3)
In Formula 3, l, m and n are integers of 0 to 100, l + m + n is not 0, and R 1 to R 8 are each independently or simultaneously hydrocarbon group, vinyl group, hydroxyl group, amino group, Ureido group, isocyanate group, episulfide group, epoxy group or mercapto group. At least two or more of the R 1 ~ R 8 includes a polymerizable unsaturated reactor and has a linear or cyclic structure (bonding of R 1 and R 8 ).
Specific examples of the silicone compound (b4) include dimethoxymethylvinylsilane, diethoxymethylvinylsilane, diacetoxy methylvinylsilane, 1,1,1,3,5,5,5, -heptamethyl-3-vinyl Trisiloxane, 2,4,6,8-tetramethyl tetravinyl cyclotetrasiloxane, α, ω-divinyl polydimethylsiloxane, vinyl-modified dimethylsiloxane, and the like can be used, and can be used alone or in combination of two or more thereof. .
The silicone compound (b4) has a viscosity of 5,000 cps or less, preferably (1 to 500) cps. Also preferably, the silicon compound (b4) has a vinyl content of 0.05 to 10 mmol / g. If the vinyl content of (b4) is less than 0.05 mmol / g, the above range does not form a critically branched structure, and when the vinyl content is more than 10 mmol / g, a high crosslinked structure does not occur and impact and fluidity cannot be improved at the same time.
The silicone compound (b4) is used in the range of 0.1 to 10% by weight, preferably 0.1 to 8% by weight of the total monomer mixture. If more than 10% by weight can reduce the fluidity and processability due to the rapid increase in molecular weight, less than 0.1% will reduce the impact improvement effect.
It is preferable that the weight average molecular weights of the branch structure styrene-type copolymer resin (B) containing the said silicone type compound are 5,000-5000,000. Branched structure styrene copolymer resin (B) comprising a silicone-based compound having the above molecular weight range can improve the processability and impact resistance of the thermoplastic resin while maintaining the existing excellent physical properties.
Branched structure styrene-based copolymer resin containing a silicone-based compound according to another embodiment of the present invention is a branched structure that can improve the fluidity at the same time as the silicone-based compound having a high molecular weight during copolymerization can improve the impact of the resin Is done.
The content of the branched styrenic copolymer resin (B) containing the silicone compound is 1 to 80% by weight, preferably 5 to 50% by weight, and even more preferably 10 to 50% by weight of the total resin composition. Do. If the content of the branched styrene-based copolymer resin (B) containing the silicon-based monomer is less than 1% by weight, sufficient impact resistance and fluidity improvement cannot be obtained.
The branched styrenic copolymer resin (B) containing the silicone compound may be polymerized by conventional bulk polymerization, emulsion polymerization or suspension polymerization.
Styrene-based thermoplastic resin composition according to an embodiment of the present invention may further include an additive optionally depending on its use. The additives include surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, thermal stabilizers, antioxidants, light stabilizers, compatibilizers, inorganic additives, colorants, stabilizers, lubricants, antistatic agents, pigments , Dyes, flame retardants, and the like, but are not necessarily limited thereto. These may be used alone or in combination of two or more.
The styrenic thermoplastic resin composition of the present invention can be produced by a known method for producing a resin composition. For example, the components of the present invention and other additives may be mixed simultaneously and then melt extruded in an extruder to produce pellet form. Such pellets can be used to produce plastic injection or compression molded articles.
Styrene-based thermoplastic resin composition of the present invention has excellent impact strength, moldability, etc. due to the improved compatibility, and can be used in the molding of various products because it can be colored. In particular, it is widely applicable to exterior materials, components or automobile parts, lenses, glass windows of various electrical and electronic products.
In one embodiment, the styrenic thermoplastic resin composition is molded to manufacture a housing of an electric and electronic product such as a television, a washing machine, a cassette player, an MP3, a DMB, a navigation, a mobile phone, a phone, a game machine, an audio player, a computer, a printer, a copy machine, and the like. can do.
The molding method is not particularly limited, and for example, extrusion molding, injection molding, calender molding, vacuum molding, etc. may all be applied, and these may be easily carried out by those skilled in the art. have.
The styrene-based thermoplastic resin composition of the present invention has a feature that can be alloyed with other resin compositions. Specifically, examples of the resin composition which may be alloyed with the present invention include polycarbonate (PC), polymethyl methacrylate (PMMA), polyolefin, polyphenylene ether (PPE), and polyethylene terephthalate (PET). ), Polyamide, polyimide, and mixtures thereof, but are not necessarily limited thereto. Accordingly, the present invention provides a styrene-based thermoplastic resin composition of the present invention, polycarbonate (PC), polymethyl methacrylate (PMMA), polyolefin, polyphenylene ether (PPE), polyethylene terephthalate (PET), polyamide (polyamide) The present invention provides a styrenic alloy thermoplastic resin composition alloyed with one or more resins of polyimide, and a mixture thereof.
The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
Specifications of each component used in the following Examples and Comparative Examples are as follows.
(a1) Styrene Copolymer Resin
A styrene-acrylonitrile (SAN) copolymer resin having a weight average molecular weight of 150,000 prepared by suspension polymerization of 75 parts by weight of styrene and 25 parts by weight of acrylonitrile at 75 ° C. for 5 hours was used.
(a2) Modified Rubber Styrene Graft Copolymer
Polybutadiene rubber latex was added so that the butadiene content was 45 parts by weight based on the total amount of the monomers, 1.0 parts by weight of potassium oleate, 1.0 part by weight of cumene hydroperoxide 0.4 parts by weight of the seed and 0.3 parts by weight of the t-dodecyl mercaptan chain transfer agent were added and then reacted while maintaining at 75 ° C. for 5 hours to prepare an ABS graft latex. A 1% sulfuric acid solution was added to the resulting polymer latex, solidified and dried to prepare a graft copolymer resin in a powder state.
(B) branched styrenic copolymer prepared by containing a silicone compound
(B1) Branched Copolymer Resin-1 Containing Silicone Compound
70.5 parts by weight of styrene, 23.5 parts by weight of acrylonitrile, 5 parts by weight of butyl acrylate and prepared by conventional suspension polymerization using 1 part by weight of a vinyl-modified dimethylsiloxane compound having a viscosity of 100 cPs and a vinyl content of 0.5 mmol / g. A styrenic copolymer having an average molecular weight of 120,000 was used.
(B2) Branched Copolymer Resin 2 Containing Silicone Compound
67.5 parts by weight of styrene, 22.5 parts by weight of acrylonitrile, 5 parts by weight of butyl acrylate and prepared by conventional suspension polymerization using 5 parts by weight of a vinyl-modified dimethylsiloxane compound having a viscosity of 100 cPs and a vinyl content of 0.5 mmol / g. A styrenic copolymer having an average molecular weight of 600,000 was used.
(B3) Branched Copolymer Resin-3 Containing Silicone Compound
Weight prepared by conventional suspension polymerization using 64 parts by weight of styrene, 19 parts by weight of acrylonitrile, and 5 parts by weight of butyl acrylate using 10 parts by weight of a vinyl-modified dimethylsiloxane compound having a viscosity of 100 cPs and a vinyl content of 0.5 mmol / g. A styrenic copolymer having an average molecular weight of 1,000,000 was used.
(B4) Branched Copolymer Resin-4 Containing Silicone Compound
66.7 parts by weight of styrene, 22.3 parts by weight of acrylonitrile, 10 parts by weight of butyl acrylate, and a weight prepared by conventional suspension polymerization using 1 part by weight of a vinyl-modified dimethylsiloxane compound having a viscosity of 100 cPs and a vinyl content of 0.5 mmol / g. A styrenic copolymer having an average molecular weight of 120,000 was used.
(B5) Branched Copolymer Resin-5 Containing Silicone Compound
Weight prepared by conventional suspension polymerization using 63 parts by weight of styrene, 21 parts by weight of acrylonitrile and 15 parts by weight of butyl acrylate using 1 part by weight of a vinyl-modified dimethylsiloxane compound having a viscosity of 100 cPs and a vinyl content of 0.5 mmol / g. A styrenic copolymer having an average molecular weight of 120,000 was used.
(B6) Branched Copolymer Resin 6 Containing Silicone Compound
Styrene air having a weight average molecular weight of 120,000 prepared by conventional suspension polymerization using 74 parts by weight of styrene, 25 parts by weight of acrylonitrile, and 1 part by weight of a vinyl-modified dimethylsiloxane compound having a viscosity of 100 cPs and a vinyl content of 0.5 mmol / g. Coalescing was used.
(B7) Linear Copolymer Resin-7
A styrenic copolymer having a weight average molecular weight of 120,000 prepared by conventional suspension polymerization using 75 parts by weight of styrene monomer and 25 parts by weight of acrylonitrile monomer using 5 parts by weight of butyl acrylate was used.
(B8) Branched Copolymer Resin 8 Containing Silicone Compound
70.5 parts by weight of styrene, 23.5 parts by weight of acrylonitrile, 5 parts by weight of butyl acrylate, and a weight average prepared by conventional suspension polymerization using 1 part by weight of a vinyl-modified dimethylsiloxane compound having a viscosity of 10 cPs and a vinyl content of 15 mmol / g. A styrene copolymer having a molecular weight of 250,000 was used.
Examples 1-6 and Comparative Examples 1-4
Each of the components was added to the content as shown in Table 1, and then melted, kneaded and extruded to prepare pellets. At this time, the extrusion was used a twin screw extruder L / D = 29, 45 mm in diameter, the prepared pellet was dried at 70 ℃ for 6 hours and then injected into a 6 Oz injection machine to prepare a specimen.
Impact strength was evaluated by making a notch in the 1/8 "Izod specimen by the evaluation method specified in ASTM D256, and the results are shown in Table 1 below.
Flow index was measured at 220 ℃, 10kg conditions by the evaluation method specified in ASTM D1238 and the results are shown in Table 1 below.
Flexural modulus was measured on a 1/4 "thick specimen by the method specified in ASTM D790 and the results are shown in Table 1 below.
The heat resistance was measured at 5 kg conditions by the method specified in ASTM D1525 Vicot softening temperature (VST) and the results are shown in Table 1 below.
Table 1
When high impact is required for a resin in which a rubber-modified vinyl graft copolymer (g-ABS) is blended in the same styrene copolymer resin (SAN) as in Comparative Example 1, g-ABS is improved as in Comparative Example 2 to improve impact properties. The content is increased, but impact properties are improved, but fluidity and mechanical properties decrease rapidly.
Therefore, in order to simultaneously improve impact and fluidity, the branched styrene-based copolymer including the silicone-based compound is replaced with the existing styrene-based copolymer (SAN) and the rubber-modified vinyl-based graft copolymer (g-ABS) as in Examples 1 to 4. When applied at the blending of), the impact property is improved by the increased molecular weight and the silicone-based compound, and the flowability is simultaneously improved by the branched structure, and thus the moldability is improved.
As shown in Examples 1 and 2, when having an appropriate silicon compound content, the impact resistance and fluidity are excellent, and the heat resistance and the mechanical property decrease are not large. In addition, in the content of the branched copolymer resin itself compared with Examples 2 and 3, the higher the applied content is greater the impact and fluidity improvement effect.
Comparing Examples 1, 2, and 4, the higher the content of the silicone-based compound, the higher the flow rate and impact resistance of the entire resin, but at the same time, the flow increases but the impact strength decreases. It can be seen that. As in Example 4, when the silicon compound content is increased, the impact improvement effect is reduced compared to Example 2, but the flowability is further increased.
When the content of the (meth) acrylic monomer is increased during the polymerization of the branched copolymer including the silicon compound as in Examples 5 and 6, the effect of improving the fluidity is improved along with the impact improvement, and thus it is applicable to an ultra high flow material.
When copolymerizing aromatic vinyl monomer (b1) and unsaturated nitrile monomer (b2) as in Comparative Examples 3 and 4, when only silicone compound is applied without (meth) acrylic monomer (Comparative Example 3) or when only (meth) acrylic monomer is applied In case of (Comparative 4), the fluidity is increased slightly, but there is almost no impact improvement effect. In addition, when the (meth) acrylic monomer and a vinyl compound having a high vinyl content (10 mmol / g or more) as in Comparative Example 5 can be seen that the fluidity and impact improvement effect does not appear.
Claims (19)
(B) copolymers prepared by copolymerizing (b1) aromatic vinyl monomers, (b2) unsaturated nitrile monomers, (b3) (meth) acrylic monomers, and (b4) silicone-based compounds having two or more unsaturated reactors or these 1 to 90% by weight of a branched styrenic copolymer resin prepared by including a silicone compound which is a mixture of copolymers;
In the styrene-based thermoplastic resin composition comprising:
The (meth) acrylic monomer (b3) is a styrene-based thermoplastic resin composition, characterized in that a mixture of an aromatic or aliphatic methacrylate having a structure represented by the following formula (1) or (2) and a (meth) acrylic monomer copolymerizable therewith:
[Formula 1]
(In Formula 1, m is an integer of 0 to 20, X is hydrogen or methyl group, Y is methyl group, cyclohexyl group, phenyl group, benzyl group, methylphenyl group, methylethylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group , Bromophenyl group, phenylphenyl group, benzylphenyl group)
(2)
(In Chemical Formula 2, m is an integer of 0 to 20, X is hydrogen or methyl group, Z is oxygen (O) or sulfur (S), Ar is methyl group, cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, Methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group, phenylphenyl group, benzylphenyl group).
(b1) 10 to 85% by weight of an aromatic vinyl monomer;
(b2) 10 to 85 wt% of an unsaturated nitrile monomer;
(b3) 1 to 50% by weight of (meth) acrylic monomers; And
(b4) 0.1 to 20% by weight of a silicone-based compound having two or more unsaturated reactors;
Styrene-based thermoplastic resin composition, characterized in that the copolymer prepared by copolymerizing or a mixture of these copolymers.
(3)
(In Formula 3, l, m, n are integers of 0 to 100, l + m + n is not 0, and R 1 to R 8 are each independently or simultaneously hydrocarbon, vinyl, hydroxyl, and amino groups. It may be a ureido group, an isocyanate group, an episulfide group, an epoxy group, or a mercapto group, wherein at least two or more of R1 to R8 include a polymerizable unsaturated reactor and are linear or cyclic (combination of R1 and R8). Has a structure of).
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| US12/971,333 US8735490B2 (en) | 2009-12-30 | 2010-12-17 | Thermoplastic resin composition having improved impact strength and melt flow properties |
| EP10196531.7A EP2341102B1 (en) | 2009-12-30 | 2010-12-22 | Thermoplastic resin composition revealing improved impact strength and melt flow property |
| CN201010613292.8A CN102115564B (en) | 2009-12-30 | 2010-12-29 | Thermoplastic resin composition having improved impact strength and melt flow property, products and alloying compound prepared thereby |
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| KR20220049706A (en) | 2020-10-15 | 2022-04-22 | 주식회사 엘지화학 | Thermoplastic transparent resin composition and molded product therefrom |
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| KR20140092485A (en) | 2012-12-28 | 2014-07-24 | 제일모직주식회사 | Thermoplastic resin composition and molded article using the same |
| KR101664844B1 (en) * | 2013-01-29 | 2016-10-11 | 롯데첨단소재(주) | Polycarbonate Thermoplastic Resin Composition and Molded Articles thereof |
| WO2014119827A1 (en) * | 2013-01-29 | 2014-08-07 | 제일모직주식회사 | Polycarbonate-based thermoplastic resin composition and molded article |
| KR101702710B1 (en) * | 2013-12-04 | 2017-02-03 | 롯데첨단소재(주) | Styrenic copolymers and thermoplastic resin composition comprising thereof |
| US9902850B2 (en) | 2014-06-26 | 2018-02-27 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition |
| KR101717821B1 (en) * | 2014-06-27 | 2017-03-17 | 롯데첨단소재(주) | Styrenic copolymers and thermoplastic resin composition comprising thereof |
| US9850333B2 (en) | 2014-06-27 | 2017-12-26 | Lotte Advanced Materials Co., Ltd. | Copolymers and thermoplastic resin composition including the same |
| US9856371B2 (en) | 2014-06-27 | 2018-01-02 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and low-gloss molded article made therefrom |
| US10435495B2 (en) * | 2014-06-27 | 2019-10-08 | Lotte Advanced Materials Co., Ltd. | Copolymers and thermoplastic resin composition comprising the same |
| KR101717819B1 (en) * | 2014-06-27 | 2017-03-17 | 롯데첨단소재(주) | Styrenic copolymers and thermoplastic resin composition comprising thereof |
| US9790362B2 (en) | 2014-06-27 | 2017-10-17 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and molded article made using the same |
| KR101752527B1 (en) | 2014-06-27 | 2017-06-30 | 롯데첨단소재(주) | Thermoplastic resin composition and impact resistance and molded article using thereof |
| KR101822697B1 (en) | 2014-11-18 | 2018-01-30 | 롯데첨단소재(주) | Thermoplastic resin composition with excellent appearance and molded article using thereof |
| KR101810294B1 (en) | 2015-08-31 | 2018-01-25 | 롯데첨단소재(주) | Thermoplastic resin composition having paper texture and molded article produced therefrom |
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