Patent Grant
9365671
This application claims priority under 35 U.S.C. §119 to Korean Patent Application No. 10-2013-0149586, filed on Dec. 4, 2013, and No. 10-2014-0079092, filed on Jun. 26, 2014, in the Korean Intellectual Property Office, the disclosure of each of which is incorporated herein by reference in its entirety.
The present invention relates to a styrene-based copolymer and a thermoplastic resin composition including the same. More specifically, the present invention relates to a styrene-based copolymer capable of implementing a uniform and excellent low gloss property with minimal or no deterioration of physical properties such as impact resistance, heat resistance, and the like, by including a silicone-based compound having two or more unsaturated reactive groups, and a thermoplastic resin composition including the same.
Thermoplastic resins have a low specific gravity as compared to a glass or a metal, and excellent mechanical physical properties such as moldability, impact resistance, and the like. Accordingly, plastic products manufactured with thermoplastic resin are rapidly replacing existing glass or metal in electrical and electronic products, automobile components, and the like.
There has been an increased focus on low gloss resins for aesthetic and anti-glare reasons. In addition, there are environmental concerns associated with prior techniques for imparting a loss gloss effect, such as matt painting or covering a pad. Thus, low gloss resins are increasingly used.
A low gloss resin has been produced by adding or modifying a specific rubber-like component. However, the existing method has problems in that a low gloss effect is not sufficient, and impact strength and heat resistance are deteriorated.
As another method, a method of graft polymerizing a monomer such as an ethylene-unsaturated carboxylic acid with a resin was used. In this method, various physical properties are excellent, but heat resistance is rapidly deteriorated.
Korean Patent Laid-Open Publication No. 2009-0029539 discloses a styrene-based resin composition containing a syndiotactic polystyrene resin as a matting agent. The matting agent has a syndiotactic structure, that is, a three-dimensional structure in which a phenyl group or a substituted phenyl group which is a side chain is positioned in an opposite direction with respect to a main chain formed by a carbon-carbon bond. The matting agent has a property having crystallinity, unlike the existing amorphous polystyrene, such that a low gloss property may be implemented. However, there are still problems in that fluidity and molding workability may be deteriorated to bring poor appearance and deteriorate physical properties such as impact resistance, and the like.
U.S. Pat. No. 4,460,742 discloses a low gloss resin composition using a cross-linked copolymer. In this case, a low gloss effect is shown by introduction of rubber particles having a large diameter or a matting agent. However, the low gloss resin composition has problems in that impact strength, and the like, are deteriorated since an excessive amount of matting agent is needed, and a cost for process is increased since a corrosion molding should be used.
An embodiment of the present invention is directed to providing a styrene-based copolymer capable of having a uniform and excellent low gloss property with minimal or no deterioration of physical properties such as impact resistance, heat resistance, and the like.
Another embodiment of the present invention is directed to providing a thermoplastic resin composition including the styrene-based copolymer.
In exemplary embodiments, the present invention provides a styrene-based copolymer prepared from a mixture including: (A) an aromatic vinyl-based compound, (B) an unsaturated nitrile-based compound, and (C) a silicone-based compound having two or more unsaturated reactive groups.
The silicone-based compound having two or more unsaturated reactive groups (C) may be used in an amount of about 0.1 to about 10 parts by weight based on about 100 parts by weight of a monomer mixture including about 60 to about 80 wt % of the aromatic vinyl-based compound (A) and about 20 to about 40 wt % of the unsaturated nitrile-based compound (B).
The silicone-based compound having two or more unsaturated reactive groups (C) may be used in an amount of about 0.5 to about 5 parts by weight based on about 100 parts by weight of a monomer mixture including about 60 to about 80 wt % of the aromatic vinyl-based compound (A) and about 20 to about 40 wt % of the unsaturated nitrile-based compound (B).
The silicone-based compound having two or more unsaturated reactive groups may be a compound represented by the following Chemical Formula 1, wherein the compound may be used singly or as a mixture including two or more thereof:
wherein, in Chemical Formula 1, l, m and n are the same or different and are each independently an integer of 0 to 100 (provided that l, m and n are not 0 at the same time) and R1 to R8 are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C1 to C30 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, or a mercapto group, wherein at least two of R1 to R8 may include a polymerizable unsaturated reactive group, and the compound may have a linear or cyclic structure. When the compound has a cyclic structure, R1 to R8 are optionally linked with each other to thereby form a cyclic structure.
When the silicone-based compound having two or more unsaturated reactive groups has the cyclic structure, the silicone-based compound having two or more unsaturated reactive groups may be a compound represented by the following Chemical Formula 2, wherein the compound may be used singly or as a mixture including two or more thereof:
wherein, in Chemical Formula 2, R9 to R14 are the same or different and are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C20 aryl group, R15 to R17 are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C6 alkyl group, and is an integer of 1 to 6.
The silicone-based compound having two or more unsaturated reactive groups may be at least any one selected from the group consisting of 1,3,5-trimethyl-1,3,5-trivinyl-cyclotrisiloxane, 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-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 mixtures thereof.
The silicone-based compound having two or more unsaturated reactive groups may contain a vinyl silane compound represented by the following Chemical Formula 3:
(R18)2Si(CH═CH2)2 [Chemical Formula 3]
wherein, in Chemical Formula 3, R18 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a substituted or unsubstituted C6 to C20 aryl group.
The vinyl silane compound may be at least any one selected from the group consisting of divinyl silane, trivinyl silane, dimethyldivinylsilane, divinylmethylsilane, methyltrivinylsilane, diphenyldivinylsilane, divinylphenylsilane, trivinylphenylsilane, divinylmethylphenylsilane, tetravinylsilane, dimethylvinyldisiloxane, divinyldiphenylchlorosilane, and mixtures thereof.
The silicone-based compound having two or more unsaturated reactive groups may have a weight average molecular weight of about 150 to about 6,000 g/mol.
The styrene-based copolymer may include about 5 to about 100 wt % of an insoluble inclusion, which is measured by a Soxhlet extraction method.
The styrene-based copolymer may have about 0.1 to about 2.0 wt % of a silicone content, which is measured by an X-Ray Fluorescence Analyzer (X-ray Florescence Analysis: XRF).
The styrene-based copolymer may be prepared from a mixture further including a multi-functional vinyl-based compound. Examples of the multi-functional vinyl-based compound can include without limitation divinyl polydimethylsiloxane, vinyl-modified dimethylsiloxane, divinylbenzene, ethyleneglycol, di(meth)acrylate, allyl(meth)acrylate, diallylphthalate, diallylmaleate, triallylisocyanurate, and mixtures thereof.
Examples of the aromatic vinyl-based compound can include without limitation styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and mixtures thereof.
Examples of the unsaturated nitrile-based compound can include without limitation acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and mixtures thereof.
The styrene-based copolymer may have a glass transition temperature (Tg) of about 95 to about 115° C.
In another exemplary embodiment, the present invention provides a thermoplastic resin composition including the styrene-based copolymer as described above.
Examples of the thermoplastic resin composition may include without limitation a styrene-acrylonitrile copolymer (SAN) resin composition, a methylmethacrylate-styrene-acrylonitrile copolymer (MSAN) resin composition, an acrylonitrile-butadiene-styrene copolymer (ABS) resin composition, a methylmethacrylate-acrylonitrile-butadiene-styrene copolymer (MABS) resin composition, an acrylonitrile-styrene-acrylate copolymer (ASA) resin composition, a polycarbonate (PC)/acrylonitrile-butadiene-styrene copolymer (ABS) alloy resin composition, a polycarbonate (PC) acrylonitrile-styrene-acrylate copolymer (ASA) alloy resin composition, a polymethylmethacrylate (PMMA)/acrylonitrile-butadiene-styrene copolymer (ABS) alloy resin composition, a polymethylmethacrylate (PMMA) methylmethacrylate-acrylonitrile-butadiene-styrene copolymer (MABS) alloy resin composition, a polymethylmethacrylate (PMMA)/acrylonitrile-styrene-acrylate copolymer (ASA) alloy resin composition, and mixtures thereof.
In another exemplary embodiment, the present invention provides a molded product including the thermoplastic resin composition including the styrene-based copolymer as described above.
The molded product may have a gloss of about 20 to about 90%, the gloss measured at an angle of about 60 degrees by an evaluation method defined by ASTM D523.
The molded product may have an absolute value of surface skewness (Rsk) of about 0.001 to about 1, the absolute value of surface skewness (Rsk) measured by an evaluation method defined by JIS B-0601.
The present invention now will be described more fully hereinafter in the following detailed description of the invention, in which some, but not all embodiments of the invention are described. Indeed, this invention may 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 satisfy applicable legal requirements.
Hereinafter, a styrene-based copolymer capable of implementing a low gloss property of the present invention is described in detail. The exemplary embodiments to be provided below are provided by way of example so that the idea according to the present invention can be sufficiently transferred to those skilled in the art to which the present invention pertains. As used here, unless technical and scientific terms used herein are defined otherwise, they have meanings understood by those skilled in the art to which the present invention pertains. Known functions and components which obscure the description and the accompanying drawings of the present invention with unnecessary detail will be omitted.
The present inventors studied to develop a styrene-based copolymer capable of implementing excellent low gloss property without deteriorating physical properties such as impact resistance, heat resistance, and the like, and surprisingly found that the styrene-based copolymer prepared from a mixture including an aromatic vinyl-based compound, an unsaturated nitrile-based compound, and a silicone-based compound having two or more unsaturated reactive groups may implement excellent low gloss property with minimal or no deterioration of various physical properties, thereby completing the present invention.
The styrene-based copolymer may be prepared from a mixture including (A) an aromatic vinyl-based compound, (B) an unsaturated nitrile-based compound, and (C) a silicone-based compound having two or more unsaturated reactive groups.
Hereinafter, each component is described in more detail.
(A) Aromatic Vinyl-Based Compound
Examples of the aromatic vinyl-based compound in the present invention may include without limitation styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like, and mixtures thereof.
In exemplary embodiments, the aromatic vinyl-based compound may include styrene, α-methyl styrene, or a mixture thereof.
The aromatic vinyl-based compound in the present invention may be used in an amount of about 60 to about 80 wt % based on the total weight (100 wt %) of a monomer mixture for preparing the styrene-based copolymer including the aromatic vinyl-based compound and the unsaturated nitrile-based compound. In some embodiments, the monomer mixture may include the aromatic vinyl-based compound in an amount of about 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, or 80 wt %. Further, according to some embodiments of the present invention, the amount of the aromatic vinyl-based compound can be in a range from about any of the foregoing amounts to about any other of the foregoing amounts.
In the above-described range, impact strength and heat resistance of the thermoplastic resin composition may be improved.
(B) Unsaturated Nitrile-Based Compound
Examples of the unsaturated nitrile-based compound may include without limitation acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like, and mixtures thereof.
In exemplary embodiments, the unsaturated nitrile-based compound may include acrylonitrile.
The unsaturated nitrile-based compound in the present invention may be used in an amount of about 20 to about 40 wt % based on the total weight (100 wt %) of the monomer mixture for preparing the styrene-based copolymer including the aromatic vinyl-based compound and the unsaturated nitrile-based compound. In some embodiments, the monomer mixture may include the unsaturated nitrile-based compound in an amount of about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 wt %. Further, according to some embodiments of the present invention, the amount of the unsaturated nitrile-based compound can be in a range from about any of the foregoing amounts to about any other of the foregoing amounts.
A weight mixing ratio (aromatic vinyl-based compound: unsaturated nitrile-based compound) between the aromatic vinyl-based compound and the unsaturated nitrile-based compound may be about 7:3 to about 9:1. When the amount of the unsaturated nitrile-based compound satisfies the above-described range, low gloss property may be improved with minimal or no deterioration of mechanical physical property and molding workability of the thermoplastic resin composition, in combination with other components.
(C) Silicone-Based Compound Having Two or More Unsaturated Reactive Groups
The silicone-based compound having two or more unsaturated reactive groups in the present invention may be used to maintain various physical properties such as impact resistance, heat resistance, and the like, and implement excellent low gloss property.
The silicone-based compound having two or more unsaturated reactive groups may be a compound represented by the following Chemical Formula 1, wherein the compound may be included singly or as a mixture including at least two or more thereof:
wherein in Chemical Formula 1, l, m and n are the same or different and are each independently an integer of 0 to 100 (provided that l, m and n are not 0 at the same time) and R1 to R8 are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 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, or a mercapto group, wherein at least two of R1 to R8 may include a polymerizable unsaturated reactive group, and the compound may have a linear or cyclic structure. When the compound, has a cyclic structure, R1 to R8 are optionally linked with each other to thereby form a cyclic structure
As used herein, unless otherwise defined, the term “substituted” means that one or more hydrogen atoms are substituted with a substituent group such as but not limited to halogen (—F, —Br, —Cl, —I), a hydroxy group, a nitro group, a cyano group, an amino group, a carboxyl group, C1 to C30 alkyl, C6 to C30 aryl, C2 to C30 heteroaryl, and/or C1 to C20 alkoxy.
As used herein, the term “hetero” refers to one or more of N, O, S, and/or P atoms, in place of a carbon atom.
In the styrene-based copolymer according to an exemplary embodiment of the present invention, when the silicone-based compound having two or more unsaturated reactive groups has a cyclic structure, the silicone-based compound having two or more unsaturated reactive groups may be represented by the following Chemical Formula 2:
wherein, in Chemical Formula 2, R9 to R14 are the same or different and are each independently substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C6 to C20 aryl group, R15 to R17 are the same or different and are each independently hydrogen, or a substituted or unsubstituted C1 to C6 alkyl group, and p is an integer of 1 to 6.
Examples of the silicone-based compound having two or more unsaturated reactive groups may include without limitation 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, 1,3,5-tri sec-butyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetra sec-butyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-penta sec-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-penta-isopropyl-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-cyclotetrasiloxane, 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-decaisopropyl-cyclopentasiloxane, 1,3,5-tri sec-butyl-1,3,5-trimethyl-cyclotrisiloxane, 1,3,5,7-tetra sec-butyl-1,3,5,7-tetramethyl-cyclotetrasiloxane, 1,3,5,7,9-penta sec-butyl-1,3,5,7,9-pentamethyl-cyclopentasiloxane, 1,3,5-tri sec-butyl-1,3,5-triethyl-cyclotrisiloxane, 1,3,5,7-tetra-sec-butyl-1,3,5,7-tetraethyl-cyclotetrasiloxane, 1,3,5,7,9-penta sec-butyl-1,3,5,7,9-pentaethyl-cyclopentasiloxane, 1,3,5-triisopropyl-cyclotrisiloxane, 1,3,5,7-tetraisopropyl-cyclotetrasiloxane, 1,3,5,7,9-pentaisopropyl-cyclopentasiloxane, 1,3,5-tri sec-butyl-cyclotrisiloxane, 1,3,5,7-tetra sec-butyl-cyclotetrasiloxane, 1,3,5,7,9-penta sec-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-1,3,5,7,9-pentavinyl-cyclopentasiloxane, 1,3,5-triethyl-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 the like, and mixtures thereof. In exemplary embodiments, at least any one selected from the group consisting of 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-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 mixtures thereof may be used. For example, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane may be used.
The silicone-based compound having two or more unsaturated reactive groups may contain a vinyl silane compound represented by the following Chemical Formula 3:
(R18)2Si(CH═CH2)2 [Chemical Formula 3]
wherein, in Chemical Formula 3, R18 is a substituted or unsubstituted C1 to 20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a substituted or unsubstituted. C6 to C20 aryl group.
The vinyl silane compound may be a silicone-based compound having at least two vinyl groups (—CH═CH2) on a silicon atom. Specific examples of the vinyl silane compound may include without limitation divinyl silane, trivinyl silane, dimethyldivinylsilane, divinylmethylsilane, methyltrivinylsilane, diphenyldivinylsilane, divinylphenylsilane, trivinylphenylsilane, divinylmethylphenylsilane, tetravinylsilane, dimethylvinyldisiloxane, divinyldiphenylchlorosilane, and the like, and mixtures thereof.
The silicone-based compound having two or more unsaturated reactive groups in the present invention may implement various excellent physical properties such as impact resistance, heat resistance, and the like, as well as the low gloss property which is difficult to be achieved with the existing cross-linking agent, singly or in combination with other components. In addition, as compared to the existing cross-linking agent, a degree of cross-linking and a polymerization reaction rate may be easily controlled in the silicone-based compound having two or more unsaturated reactive groups.
The silicone-based compound having two or more unsaturated reactive groups may have a molecular weight or a weight average molecular weight of about 150 to about 6,000 g/mol. When the above-described range is satisfied, the degree of cross-linking may be easily controlled and the cross-linking reaction may be smoothly performed, thereby implementing excellent low gloss property.
The silicone-based compound having two or more unsaturated reactive groups may be used in an amount of about 0.1 to about 10 parts by weight, for example, about 0.1 to about 8 parts by weight, and as another example, about 0.5 to about 5 parts by weight, based on about 100 parts by weight of a monomer mixture including the aromatic vinyl-based compound and the unsaturated nitrile-based compound. In some embodiments, the silicone-based compound having two or more unsaturated reactive groups may be used in an amount of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 parts by weight. Further, according to some embodiments of the present invention, the amount of the silicone-based compound having two or more unsaturated reactive groups can be in a range from about any of the foregoing amounts to about any other of the foregoing amounts.
When the above-described range is satisfied, the degree of cross-linking of the styrene-based copolymer may be easily controlled, the low gloss property may be improved with minimal or no deterioration of impact resistance and thermal resistance, and generally uniform low gloss property may be implemented.
The styrene-based copolymer according to the present invention may be prepared from the mixture further including one or more multi-functional vinyl-based compounds. Examples of the multi-functional vinyl-based compound can include without limitation divinyl polydimethylsiloxane, vinyl-modified dimethylsiloxane, divinylbenzene, ethyleneglycol, di(meth)acrylate, allyl(meth)acrylate, diallylphthalate, diallylmaleate, triallylisocyanurate, and the like, and mixtures thereof. In exemplary embodiments, at least any one selected from the group consisting divinyl polydimethylsiloxane, vinyl-modified dimethylsiloxane, and mixtures thereof, may be used.
The multi-functional vinyl-based compound may be used in an amount of about 0.001 to about 10.0 parts by weight, for example, about 0.01 to about 3.0 parts by weight, based on about 100 parts by weight of a monomer mixture including the aromatic vinyl-based compound and the unsaturated nitrile-based compound. In some embodiments, the multi-functional vinyl-based compound may be used in an amount of about 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 parts by weight. Further, according to some embodiments of the present invention, the amount of the multi-functional vinyl-based compound can be in a range from about any of the foregoing amounts to about any other of the foregoing amounts.
In the above-described range, the degree of cross-linking and the polymerization reaction rate of the styrene-based copolymer may be easily controlled, and the low gloss property may be implemented with minimal or no deterioration of impact resistance and thermal resistance in combination with other components.
The styrene-based copolymer according to the present invention may have a glass transition temperature (Tg) of about 95 to about 115° C. In the above-described range, a thermoplastic resin composition including the styrene-based copolymer may implement excellent low gloss property with minimal or no deterioration of impact resistance and heat resistance.
The styrene-based copolymer in the present invention may be prepared by general polymerization methods such as a suspension polymerization, an emulsion polymerization, a solution polymerization, and the like. However, the present invention is not necessarily limited thereto. As an example of a method of preparing the copolymer, a suspension polymerization may be used. At the time of preparing the styrene-based copolymer by the suspension polymerization, dispersibility may be improved by using an inorganic dispersant and/or an organic dispersant. As the organic dispersant, a homopolymer and/or a copolymer of an acrylic acid and/or a methacrylic acid may be used. When used as the organic dispersant, the acrylic acid and/or the methacrylic acid homopolymer and/or copolymer may be present in an amount of about 50 parts by weight or more based on about 100 parts by weight of the copolymer. In addition, the acrylic acid and/or the methacrylic acid may be a sodium salt, a potassium salt, and/or an ammonium salt, in order to maintain an appropriate solubility.
As a polymerization initiator at the time of copolymerization of the styrene-based copolymer, azobisisobutyronitrile may be used. However, the present invention not necessarily limited thereto.
The styrene-based copolymer according to the present invention may have a linear or a cross-linked form. In exemplary embodiments, the styrene-based copolymer according to the present invention may have a cross-linked form.
Here, the cross-linking of the styrene-based copolymer may be confirmed by a content of an insoluble inclusion measured by a Soxhlet extraction method.
In the Soxhlet extraction method, an organic solvent selected from the group consisting of toluene, tetrahydrofuran, ethyl acetate, chloroform, and mixtures thereof, may be used. However, the present invention is not necessarily limited thereto. In exemplary embodiments, tetrahydrofuran (THF) may be used.
Specifically, the Soxhlet extraction method may be performed from a mixed solution in which the styrene-based copolymer according to the present invention is mixed with a solvent, by a Soxhlet extractor.
As an exemplary embodiment, the styrene-based copolymer according to the present invention may include about 5 to about 100 wt % of an insoluble inclusion, which is maintained after performing a Soxhlet extraction method for about 48 hours using tetrahydrofuran (THF).
In addition, the styrene-based copolymer according to the present invention may have about 0.1 to about 2.0 wt % of a silicone content, which is measured by an X-Ray Fluorescence Analyzer (X-ray Florescence Analysis: XRF).
Here, an XRF analysis, which is a method of analyzing a wavelength distribution of an x-ray which is conflicted onto a material and secondarily discharged therefrom and estimating the type and component ratio of the constituent elements of materials, is an X-ray florescence spectrometry. For the XRF analysis, general apparatuses may be used. In the present invention, an X-ray Fluorescence Spectrometer (Model: Axios advanced. Maker. PANalytical (Netherland)) was used.
For the analysis method of the silicone by XRF in the present invention, a sample is prepared by using the styrene-based copolymer according to the present invention. In addition, a standard sample for analysis is prepared. The silicone (Si) element contained in the standard sample is measured by X-ray fluorescent analysis (XRF) and a calibration thereof is prepared. Then, the silicone (Si) element in the sample is measured by X-ray fluorescent analysis (XRF), and then the measured values are introduced into the previously set calibration, such that a quantitative analysis is performed.
The styrene-based copolymer according to the present invention may be applied to implement a low gloss property of the thermoplastic resin composition.
Here, examples of the thermoplastic resin composition may include without limitation a styrene-acrylonitrile copolymer (SAN) resin composition, a methylmethacrylate-styrene-acrylonitrile copolymer (MSAN) resin composition, an acrylonitrile-butadiene-styrene copolymer (ABS) resin composition, a methylmethacrylate-acrylonitrile-butadiene-styrene copolymer (MABS) resin composition, an acrylonitrile-styrene-acrylate copolymer (ASA) resin composition, a polycarbonate (PC)/acrylonitrile-butadiene-styrene copolymer (ABS) alloy resin composition, a polycarbonate (PC)/acrylonitrile-styrene-acrylate copolymer (ASA) alloy resin composition, a polymethylmethacrylate (PMMA)/acrylonitrile-butadiene-styrene copolymer (ABS) alloy resin composition, a polymethylmethacrylate (PMMA)/methylmethacrylate-acrylonitrile-butadiene-styrene copolymer (MABS) alloy resin composition, a polymethylmethacrylate (PMMA)/acrylonitrile-styrene-acrylate copolymer (ASA) alloy resin composition, and the like, and mixtures thereof.
The thermoplastic resin composition containing the styrene-based copolymer may have excellent low gloss property with minimal or no deterioration of physical properties such as impact resistance, heat resistance, and the like.
The present invention provides a molded product including the thermoplastic resin composition including the styrene-based copolymer. For example, the molded product may be provided by using the thermoplastic resin composition including the styrene-based copolymer in the manufacture of products for use in various industrial fields such as various electrical and electronic products, automobile components, and the like. The molded products can be produced using conventional processes known in the art.
The molded product according to an exemplary embodiment of the present invention may have a gloss of about 20 to about 90%, the gloss measured at an angle of about 60 degrees by an evaluation method defined by ASTM D523.
The molded product according to an exemplary embodiment of the present invention may have an absolute value of surface skewness (Rsk) of about 0.001 to about 1, the absolute value of surface skewness (Rsk) measured by an evaluation method defined by JIS B-0601.
Hereinafter, the following Examples will be provided in order to describe the present invention in more detail. However, the present invention is not limited to these Examples.
Specifications of each component used in the following Examples and Comparative Examples are as follows.
Styrene is used as the aromatic vinyl-based compound (A).
Acrylonitrile is used as the unsaturated nitrile-based compound (B).
1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane (SKC Company, density: about 0.98 g/ml (20), Product Name: Vinyl D-4, molecular weight: about 344.7 g/mol) is used as the silicone-based compound having two or more unsaturated reactive groups (C).
Divinyl polydimethylsiloxane (KCC Corporation, Product Name SF3010PDX20, weight average molecular weight: about: 9,000 g/mol) is used as a multi-functional vinyl-based compound (D).
Divinylbenzene (Fluka Corporation, Product Name: DVB, molecular weight: about 130.2 g/mol) is used as a multi-functional vinyl-based compound (E).
Ethylene glycol dimethacrylate (Evonik Corporation, Product Name: EGDMA, molecular weight: about 198.2 g/ml) is used as a multi-functional vinyl-based compound (F).
Pentaerythritol tetraacrylate (Kyoeisha Inc., Product Name: PETTA, molecular weight: about 352.3 g/mol) is used as a multi-functional vinyl-based compound (G).
As described in the composition (unit: part by weight) shown in the following Table 1 with the above-mentioned components, about 0.2 parts by weight of t-dodecyl mercaptan (TDM), about 0.2 parts by weight of azobisisobutyronitrile (AIBN), and about 0.5 parts by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane (C), based on 100 parts by weight of the monomer mixture containing 71 wt % of styrene (A) and 29 wt % of acrylonitrile (B) are put into a reactor, followed by a suspension polymerization, thereby preparing a copolymer. The copolymer is washed, dehydrated, dried at about 80° C. for about 48 hours, and extruded at a barrel temperature of about 250° C. by a twin screw extruder having T-die mounted therein, thereby preparing a sample for evaluating physical properties, having a sheet form with a thickness of about 1 mm. Glass transition temperature, gloss, and surface roughness property are evaluated by the prepared sheet, and results thereof were shown in the following Table 2.
Example 2 is conducted by the same method as Example 1 except for using about 1 part by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane (C).
Example 3 is conducted by the same method as Example 1 except for using about 2 parts by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane (C).
Example 4 is conducted by the same method as Example 1 except for using about 2 parts by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane (C) and further containing about 0.5 parts by weight of divinyl polydimethylsiloxane (D) based on 100 parts by weight of the monomer mixture.
Comparative Example 1 is conducted by the same method as Example 1 except for not using 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane (C).
Comparative Example 2 is conducted by the same method as Example 1 except for using about 0.5 parts by weight of divinyl polydimethylsiloxane (D) instead of using about 0.5 part by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane (C).
Comparative Example 3 is conducted by the same method as Example 1 except for using about 0.5 parts by weight of divinylbenzene (E) instead of using about 0.5 part by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane (C).
Comparative Example 4 is conducted by the same method as Example 1 except for using about 0.5 parts by weight of ethylene glycol dimethacrylate instead of using about 0.5 part by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane (C).
Comparative Example 5 is conducted by the same method as Example 1 except for using about 0.5 parts by weight of pentaerythritol tetraacrylate (G) instead of using about 0.5 part by weight of 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane (C).
(Analysis by Soxhlet Extraction)
The copolymer prepared by Example 1 is extracted with toluene by a Soxhlet extractor for about 48 hours, and components contained in the extracted copolymer are analyzed by gas chromatography (hereinafter, GPC) and a nuclear magnetic resonance spectrometer (NMR), and as a result, it is confirmed that an inclusion soluble in toluene has a content of about 15.4 wt %, and an insoluble inclusion has a content of about 84.6 wt %. The insoluble inclusion is extracted with tetrahydrofuran (THF) again for about 48 hours, and components contained in the extracted copolymer are analyzed by GPC and NMR, and as a result, it is confirmed that about 84.6 wt % of the insoluble inclusion in THF has a content of about 41.5 wt %, and an insoluble inclusion has a content of about 43.1 wt %. Accordingly, it could be confirmed that the copolymer prepared by Example 1 is a partially cross-linked component.
About 0.1 parts by weight of a hindered phenol-based heat stabilizer (BASF Corporation, Product Name: IRGANOX 1010) is added to 100 parts by weight of a base resin containing: about 20 parts by weight of the styrene-based copolymer according to Example 1; about 55 parts by weight of a styrene-acrylonitrile copolymer (SAN) resin (Cheil Industries Inc.) containing about 28.5 wt % of acrylonitrile and having a weight average molecular weight of about 125,000 g/mol; about 25 parts by weight of an acrylonitrile-butadiene-styrene graft copolymer (g-ABS) resin (Cheil Industries, Inc.) containing about 58 wt % of a rubber-like copolymer and having an average particle diameter of about 260 nm, followed by melting, mixing, and extruding processes, thereby preparing a pellet.
Here, the extruding process is performed at a barrel temperature of about 250° C. by a twin screw extruder satisfying L/D of about 29, diameter of about 45 mm, and the prepared pellet is dried at about 80° C. for about 2 hours and injection-molded at a cylinder temperature of about 230° C. in a 6 oz injection molding machine, thereby preparing a sample for evaluating physical properties. Izod impact strength, a Vicat softening point, gloss, and surface skewness of the prepared sample are measured. The measuring method thereof is as follows, and results thereof are shown in the following Table 3.
Example 6 is conducted by the same method as Example 5 except for using the styrene-based copolymer according to Example 2 instead of using the styrene-based copolymer according to Example 1.
Example 7 is conducted by the same method as Example 5 except for using the styrene-based copolymer according to Example 3 instead of using the styrene-based copolymer according to Example 1.
Example 8 is conducted by the same method as Example 5 except for using the styrene-based copolymer according to Example 4 instead of using the styrene-based copolymer according to Example 1.
Comparative Example 6 is conducted by the same method as Example 5 except for using the styrene-based copolymer according to Comparative Example 1 instead of using the styrene-based copolymer according to Example 1.
Comparative Example 7 is conducted by the same method as Example 5 except for using the styrene-based copolymer according to Comparative Example 2 instead of using the styrene-based copolymer according to Example 1.
Comparative Example 8 is conducted by the same method as Example 5 except for using the styrene-based copolymer according to Comparative Example 3 instead of using the styrene-based copolymer according to Example 1.
Comparative Example 9 is conducted by the same method as Example 5 except for using the styrene-based copolymer according to Comparative Example 4 instead of using the styrene-based copolymer according to Example 1.
Comparative Example 10 is conducted by the same method as Example 5 except for using the styrene-based copolymer according to Comparative Example 5 instead of using the styrene-based copolymer according to Example 1.
Comparative Example 11 is conducted by the same method as Example 5 except for using 5 parts by weight of a matting agent (Galata Chemicals, Product Name: BLENDEX BMAT) based on 100 parts by weight of a base resin further containing the styrene-acrylonitrile copolymer (SAN) resin (Cheil Industries Inc.) containing about 28.5 wt % of acrylonitrile and having a weight average molecular weight of about 125,000 g/mol instead of about 20 parts by weight of the styrene-based copolymer according to Example 1.
Comparative Example 12 is conducted by the same method as Example 5 except that an average particle diameter of a dispersed phase as a base resin is about 10 μm, and based on 100 parts by weight of the total base resin, a content of the rubber-like polymer contained in the dispersed phase is about 14 wt %, a content of the acrylonitrile of the SAN resin having a continuous phase is about 5 wt %, and the ABS resin (Cheil Industries Inc.) having an weight average molecular weight of about 150,000 g/mol and prepared by a bulk polymerization method is used.
(Evaluation)
(1) Glass Transition Temperature (Tg)
A temperature is increased up to 160° C. at a rate of 20° C./mins by a Q2910 manufactured by TA Instrument, then slowly decreased and maintained an equivalent state at 50° C., and the temperature is increased again up to 160° C. at a rate of 10° C./mins. An inflection point of the endothermic transition curve is determined as a glass transition temperature.
(2) Gloss (Surface Gloss)
Surface gloss is measured at an angle of about 60 degrees by an evaluation method defined by ASTM D523, using a BYK-Gardner Gloss Meter manufactured by BYK Company.
(3) Surface Roughness (Ra)
Surface roughness is measured by an evaluation method defined by JIS B-0601, using a laser microscope for measuring a shape, VK-X200, manufactured by KEYENCE Company.
(4) Surface Skewness (Rsk)
Surface skewness is measured by an evaluation method defined by JIS B-0601, using a laser microscope for measuring a shape, VK-X200, manufactured by KEYENCE Company. As an absolute value of the surface skewness (Rsk) is close to 0, it means that a surface is smooth.
(5) Izod Impact Strength
Izod impact strength is measured on a sample having a thickness of ⅛″ by an evaluation method defined by ASTM D256, under a notched condition.
(6) Vicat Softening Point
Vicat softening point is measured on a sample having a thickness of ¼″ by an evaluation method defined by ISO 306 B50.
It can be seen from Table 2 that the styrene-based copolymer according to Examples 1 to 4 of the present invention have high surface roughness after the molding process to implement excellent low gloss property. Meanwhile, it can be seen that Comparative Example 1 not using the silicone-based compound having two or more unsaturated reactive groups (C) according to the present invention and Comparative Example 2 using the divinyl polydimethylsiloxane (D) alone did not implement sufficient low gloss property. In addition, it can be seen that Comparative Examples 3 to 5 using the divinylbenzene (E), the ethylene glycol dimethacrylate (F), and the pentaerythritol tetraacrylate (G), all of which are existing multi-functional vinyl-based compounds, respectively, exhibit excellent low gloss property.
Meanwhile, it can be seen from Table 3 and
The styrene-based copolymer according to the present invention may implement uniform and excellent low gloss property with minimal or no deterioration of physical properties such as impact resistance, heat resistance, and the like.
In addition, a thermoplastic resin composition that can have excellent impact resistance, heat resistance, and a uniform low gloss property by including the styrene-based copolymer may be provided.
Hereinabove, although the present invention is described by specific matters such as concrete components, and the like, exemplary embodiments, and drawings, they are provided only for assisting in the entire understanding of the present invention. Therefore, the present invention is not limited to the exemplary embodiments. Various modifications and changes may be made by those skilled in the art to which the present invention pertains from this description.
Therefore, the spirit of the present invention should not be limited to the above-described exemplary embodiments, and the following claims as well as all modified equally or equivalently to the claims are intended to fall within the scopes and spirit of the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2013-0149586 | Dec 2013 | KR | national |
| 10-2014-0079092 | Jun 2014 | KR | national |
| Number | Name | Date | Kind |
|---|---|---|---|
| 3322853 | Trementozzi et al. | May 1967 | A |
| 3742092 | Duke et al. | Jun 1973 | A |
| 3839513 | Patel | Oct 1974 | A |
| 3898300 | Hilliard | Aug 1975 | A |
| 4027073 | Clark | May 1977 | A |
| 4045514 | Iwahashi et al. | Aug 1977 | A |
| 4062909 | Morgan et al. | Dec 1977 | A |
| 4102853 | Kawamura et al. | Jul 1978 | A |
| 4117041 | Guschl | Sep 1978 | A |
| 4287315 | Meyer et al. | Sep 1981 | A |
| 4303772 | Novicky | Dec 1981 | A |
| 4391935 | Bialous et al. | Jul 1983 | A |
| 4400333 | Neefe | Aug 1983 | A |
| 4460742 | Kishida et al. | Jul 1984 | A |
| 4632946 | Muench et al. | Dec 1986 | A |
| 4634734 | Hambrecht et al. | Jan 1987 | A |
| 4652614 | Eichenauer et al. | Mar 1987 | A |
| 4659790 | Shimozato et al. | Apr 1987 | A |
| 4668737 | Eichenauer et al. | May 1987 | A |
| 4692488 | Kress et al. | Sep 1987 | A |
| 4745029 | Kambour | May 1988 | A |
| 4757109 | Kishida et al. | Jul 1988 | A |
| 4883835 | Buysch et al. | Nov 1989 | A |
| 4906696 | Fischer et al. | Mar 1990 | A |
| 4914144 | Muehlbach et al. | Apr 1990 | A |
| 4918159 | Nakamura et al. | Apr 1990 | A |
| 4983658 | Kress et al. | Jan 1991 | A |
| 4988748 | Fuhr et al. | Jan 1991 | A |
| 4997883 | Fischer et al. | Mar 1991 | A |
| 5025066 | DeRudder | Jun 1991 | A |
| 5061558 | Fischer et al. | Oct 1991 | A |
| 5061745 | Wittmann et al. | Oct 1991 | A |
| 5091470 | Wolsink et al. | Feb 1992 | A |
| 5200492 | Ohnaga et al. | Apr 1993 | A |
| 5204394 | Gosens et al. | Apr 1993 | A |
| 5206404 | Gunkel et al. | Apr 1993 | A |
| 5218030 | Katayose et al. | Jun 1993 | A |
| 5219907 | Niessner et al. | Jun 1993 | A |
| 5229443 | Wroczynski | Jul 1993 | A |
| 5237004 | Wu et al. | Aug 1993 | A |
| 5239001 | Fischer et al. | Aug 1993 | A |
| 5274031 | Eichenauer et al. | Dec 1993 | A |
| 5280070 | Drzewinski et al. | Jan 1994 | A |
| 5284916 | Drzewinski | Feb 1994 | A |
| 5292809 | Drzewinski et al. | Mar 1994 | A |
| 5306778 | Ishida et al. | Apr 1994 | A |
| 5354796 | Creecy et al. | Oct 1994 | A |
| 5412036 | Traugott et al. | May 1995 | A |
| 5446103 | Traugott et al. | Aug 1995 | A |
| 5449557 | Liebler et al. | Sep 1995 | A |
| 5451650 | Siol et al. | Sep 1995 | A |
| 5473019 | Siol et al. | Dec 1995 | A |
| 5475053 | Niessner et al. | Dec 1995 | A |
| 5574099 | Noro et al. | Nov 1996 | A |
| 5605962 | Suzuki et al. | Feb 1997 | A |
| 5627228 | Kobayashi | May 1997 | A |
| 5635565 | Miyajima et al. | Jun 1997 | A |
| 5643981 | Yang et al. | Jul 1997 | A |
| 5672645 | Eckel et al. | Sep 1997 | A |
| 5731390 | van Helmond et al. | Mar 1998 | A |
| 5750602 | Kohler et al. | May 1998 | A |
| 5833886 | Dashevsky et al. | Nov 1998 | A |
| 5905122 | Ohtsuka et al. | May 1999 | A |
| 5955184 | Honda et al. | Sep 1999 | A |
| 6022917 | Kobayashi | Feb 2000 | A |
| 6063889 | Friebe et al. | May 2000 | A |
| 6083428 | Ueda et al. | Jul 2000 | A |
| 6111024 | McKee et al. | Aug 2000 | A |
| 6127465 | Nodera | Oct 2000 | A |
| 6174945 | Kim et al. | Jan 2001 | B1 |
| 6252002 | Yamada et al. | Jun 2001 | B1 |
| 6337371 | Kurata et al. | Jan 2002 | B2 |
| 6369141 | Ishii et al. | Apr 2002 | B1 |
| 6380304 | Vanspeybroeck et al. | Apr 2002 | B1 |
| 6437029 | Lim et al. | Aug 2002 | B1 |
| 6528559 | Nakacho et al. | Mar 2003 | B1 |
| 6528561 | Zobel et al. | Mar 2003 | B1 |
| 6566428 | Ecket et al. | May 2003 | B1 |
| 6576161 | Lim et al. | Jun 2003 | B2 |
| 6596794 | Ecket et al. | Jul 2003 | B1 |
| 6596893 | Nakacho et al. | Jul 2003 | B2 |
| 6613822 | Eckel et al. | Sep 2003 | B1 |
| 6613824 | Campbell et al. | Sep 2003 | B2 |
| 6630524 | Lim et al. | Oct 2003 | B1 |
| 6646068 | Chisholm et al. | Nov 2003 | B2 |
| 6686404 | Eckel et al. | Feb 2004 | B1 |
| 6716900 | Jang et al. | Apr 2004 | B2 |
| 6762228 | Seidel et al. | Jul 2004 | B2 |
| 6849689 | Yamada et al. | Feb 2005 | B2 |
| 6890979 | Eichenauer et al. | May 2005 | B2 |
| 6914089 | Eckel et al. | Jul 2005 | B2 |
| 6956072 | Kanaka et al. | Oct 2005 | B1 |
| 7001944 | Vathauer et al. | Feb 2006 | B2 |
| 7067188 | Yang et al. | Jun 2006 | B1 |
| 7094818 | Lim et al. | Aug 2006 | B2 |
| 7294659 | Yatake | Nov 2007 | B2 |
| 7511088 | Lim et al. | Mar 2009 | B2 |
| 7550523 | Lim et al. | Jun 2009 | B2 |
| 7659332 | Kang et al. | Feb 2010 | B2 |
| 7732515 | Jang et al. | Jun 2010 | B2 |
| 7767738 | Gaggar et al. | Aug 2010 | B2 |
| 7956127 | Lee et al. | Jun 2011 | B2 |
| 8119726 | Lim et al. | Feb 2012 | B2 |
| 8304494 | Park et al. | Nov 2012 | B2 |
| 20010009946 | Catsman et al. | Jul 2001 | A1 |
| 20020042483 | Vanderbilt | Apr 2002 | A1 |
| 20020115759 | Eckel et al. | Aug 2002 | A1 |
| 20020115794 | Singh et al. | Aug 2002 | A1 |
| 20020151624 | Kobayashi | Oct 2002 | A1 |
| 20030139504 | Miebach et al. | Jul 2003 | A1 |
| 20040013882 | Gorny et al. | Jan 2004 | A1 |
| 20040097648 | Nakai et al. | May 2004 | A1 |
| 20040122139 | Yang et al. | Jun 2004 | A1 |
| 20040192814 | Yang et al. | Sep 2004 | A1 |
| 20040198877 | Yang et al. | Oct 2004 | A1 |
| 20040249027 | Lim et al. | Dec 2004 | A1 |
| 20040249070 | Lim et al. | Dec 2004 | A1 |
| 20050159533 | Nabeshima et al. | Jul 2005 | A1 |
| 20050245648 | Lim et al. | Nov 2005 | A1 |
| 20050253277 | Yamanaka et al. | Nov 2005 | A1 |
| 20060004154 | DeRudder et al. | Jan 2006 | A1 |
| 20060014863 | Lim et al. | Jan 2006 | A1 |
| 20060030647 | Ebeling et al. | Feb 2006 | A1 |
| 20060074148 | Ahn et al. | Apr 2006 | A1 |
| 20060100307 | Uerz et al. | May 2006 | A1 |
| 20070100073 | Lee et al. | May 2007 | A1 |
| 20070155873 | Kang et al. | Jul 2007 | A1 |
| 20070249767 | Kang et al. | Oct 2007 | A1 |
| 20070249768 | Hong et al. | Oct 2007 | A1 |
| 20070287799 | Ha et al. | Dec 2007 | A1 |
| 20070295946 | Lim et al. | Dec 2007 | A1 |
| 20080182926 | Lim et al. | Jul 2008 | A1 |
| 20090054568 | Uejima et al. | Feb 2009 | A1 |
| 20090080079 | Kogure et al. | Mar 2009 | A1 |
| 20090093583 | Kawato et al. | Apr 2009 | A1 |
| 20090118402 | Jang et al. | May 2009 | A1 |
| 20100029855 | Matsuoka et al. | Feb 2010 | A1 |
| 20100152357 | Kwon et al. | Jun 2010 | A1 |
| 20100168272 | Park et al. | Jul 2010 | A1 |
| 20100168354 | Hong et al. | Jul 2010 | A1 |
| 20100240831 | Kim et al. | Sep 2010 | A1 |
| 20100256288 | Kim et al. | Oct 2010 | A1 |
| 20110009524 | Kwon et al. | Jan 2011 | A1 |
| 20110021677 | Kwon et al. | Jan 2011 | A1 |
| 20110040019 | Kwon et al. | Feb 2011 | A1 |
| 20110160377 | Chung et al. | Jun 2011 | A1 |
| 20110160380 | Kwon et al. | Jun 2011 | A1 |
| 20150152205 | Kim et al. | Jun 2015 | A1 |
| Number | Date | Country |
|---|---|---|
| 1 121 535 | Apr 1982 | CA |
| 1377913 | Nov 2002 | CN |
| 101061179 | Oct 2007 | CN |
| 19614845 | Oct 1997 | DE |
| 196 32 675 | Feb 1998 | DE |
| 19801198 | Jul 1999 | DE |
| 10061081 | Jun 2002 | DE |
| 0149813 | Jul 1985 | EP |
| 0370344 | May 1990 | EP |
| 0 449 689 | Oct 1991 | EP |
| 0483717 | May 1992 | EP |
| 0 612 806 | Aug 1994 | EP |
| 0640655 | Mar 1995 | EP |
| 0 661 342 | Jul 1995 | EP |
| 0 700 968 | Mar 1996 | EP |
| 0721962 | Jul 1996 | EP |
| 0 728 811 | Aug 1996 | EP |
| 0 767 204 | Apr 1997 | EP |
| 0771852 | May 1997 | EP |
| 0 795 570 | Sep 1997 | EP |
| 0909790 | Apr 1999 | EP |
| 0 970 997 | Jan 2000 | EP |
| 1010725 | Jun 2000 | EP |
| 1 069 156 | Jan 2001 | EP |
| 1069154 | Jan 2001 | EP |
| 1209163 | May 2002 | EP |
| 2204412 | Jul 2010 | EP |
| 1042783 | Sep 1966 | GB |
| 59-149912 | Aug 1984 | JP |
| 59-202240 | Nov 1984 | JP |
| 04-023856 | Jan 1992 | JP |
| 04-359954 | Dec 1992 | JP |
| 61 00785 | Jan 1994 | JP |
| 06-100785 | Apr 1994 | JP |
| 06-313089 | Nov 1994 | JP |
| 7-76649 | Mar 1995 | JP |
| 08-012868 | Jan 1996 | JP |
| 8-208884 | Aug 1996 | JP |
| 08-239544 | Sep 1996 | JP |
| 09-053009 | Feb 1997 | JP |
| 10-017762 | Jan 1998 | JP |
| 2000-154277 | Jun 2000 | JP |
| 2001-049072 | Feb 2001 | JP |
| 2001-316580 | Nov 2001 | JP |
| 2002-080676 | Mar 2002 | JP |
| 2002-348457 | Dec 2002 | JP |
| 2005-247999 | Sep 2005 | JP |
| 2006-131833 | May 2006 | JP |
| 2006-249288 | Sep 2006 | JP |
| 2006-249292 | Sep 2006 | JP |
| 2006-257126 | Sep 2006 | JP |
| 2006-257284 | Sep 2006 | JP |
| 2006-342246 | Dec 2006 | JP |
| 2007-023227 | Feb 2007 | JP |
| 2008-292853 | Dec 2008 | JP |
| 1994-0014647 | Jul 1994 | KR |
| 1996-14253 | May 1996 | KR |
| 1999-33150 | May 1999 | KR |
| 1999-47019 | Jul 1999 | KR |
| 2000 41992 | Jan 2000 | KR |
| 1020000009218 | Feb 2000 | KR |
| 10-2000-0048033 | Jul 2000 | KR |
| 1020000041993 | Jul 2000 | KR |
| 10-2000-0055347 | Sep 2000 | KR |
| 2001 109044 | Dec 2001 | KR |
| 2002 6350 | Jan 2002 | KR |
| 100360710 | Oct 2002 | KR |
| 2002 83711 | Nov 2002 | KR |
| 2001 107423 | Dec 2002 | KR |
| 1020020094345 | Dec 2002 | KR |
| 10-2003-0020584 | Mar 2003 | KR |
| 10-2003-0055443 | Jul 2003 | KR |
| 2003-0095537 | Dec 2003 | KR |
| 10-2004-0007788 | Jan 2004 | KR |
| 1020040058809 | Jul 2004 | KR |
| 2004-079118 | Sep 2004 | KR |
| 648114 | Nov 2006 | KR |
| 10-0767428 | Oct 2007 | KR |
| 885819 | Dec 2007 | KR |
| 2009-0029539 | Mar 2009 | KR |
| 10-902352 | Jun 2009 | KR |
| 99 19383 | Apr 1999 | WO |
| 9957198 | Nov 1999 | WO |
| 00 00544 | Jan 2000 | WO |
| 00 09518 | Feb 2000 | WO |
| 0018844 | Apr 2000 | WO |
| 0166634 | Sep 2001 | WO |
| 02 46287 | Jun 2002 | WO |
| 03020827 | Mar 2003 | WO |
| 03022928 | Mar 2003 | WO |
| 03042303 | May 2003 | WO |
| 03042305 | May 2003 | WO |
| 2004007611 | Jan 2004 | WO |
| 2006 041237 | Apr 2006 | WO |
| 2007004434 | Jan 2007 | WO |
| 2007119920 | Oct 2007 | WO |
| 2007140101 | Dec 2007 | WO |
| 2008081791 | Jul 2008 | WO |
| 2009078593 | Jun 2009 | WO |
| 2009078602 | Jun 2009 | WO |
| 2009113762 | Sep 2009 | WO |
| 2009116722 | Sep 2009 | WO |
| 2009128601 | Oct 2009 | WO |
| Entry |
|---|
| “Silicones: An Introduction to Their Chemistry and Application” © The Plastics Institute 1962, p. 27. |
| European Search Report for commonly owned European Application No. EP 04808586, completed on Sep. 25, 2007. |
| Chinese Office Action in commonly owned Chinese Application No. 200880128614.0 dated Mar. 7, 2012, pp. 1-5. |
| English-translation of Chinese Office Action in commonly owned Chinese Application No. 200880128614.0 dated Mar. 7, 2012, pp. 1-2. |
| Advisory Action in commonly owned U.S. Appl. No. 12/631,018 mailed Nov. 7, 2012, pp. 1-3. |
| Final Office Action in commonly owned U.S. Appl. No. 12/817,302 mailed Feb. 7, 2013, pp. 1-6. |
| Final Office Action in commonly owned U.S. Appl. No. 12/884,549 mailed Dec. 18, 2012, pp. 1-7. |
| Notice of Allowance in commonly owned U.S. Appl. No. 12/884,549 mailed Apr. 11, 2013, pp. 1-8. |
| European Search Report in commonly owned European Application No. 07024808, dated Mar. 18, 2008, pp. 1-2. |
| Machine Translation of JP 10-017762. |
| Derwent Abstract of JP 2002348457 (A) (2003). |
| Full English Translation of JP-10-017762 (2011). |
| Advisory Action in commonly owned U.S. Appl. No. 12/817,302 mailed May 16, 2013, pp. 1-5. |
| Office Action in commonly owned U.S. Appl. No. 12/898,012 mailed Dec. 21, 2012, pp. 1-6. |
| Notice of Allowance in commonly owned U.S. Appl. No. 12/972,795 mailed May 24, 2013, pp. 1-8. |
| Chinese Office Action in commonly owned Chinese Application No. 201010597679.9 dated Aug. 27, 2012, pp. 1-5. |
| European Search Report in commonly owned European Application No. 10194938.6 dated Jul. 21, 2011, pp. 1-5. |
| Notice of Allowance in commonly owned U.S. Appl. No. 12/961,877 mailed Jun. 19, 2013, pp. 1-10. |
| Final Office Action in commonly owned U.S. Appl. No. 12/961,877 mailed Nov. 28, 2012, pp. 1-10. |
| Advisory Action in commonly owned U.S. Appl. No. 12/961,877 mailed Mar. 12, 2013, pp. 1-2. |
| European Search Report in commonly owned European Application No. 08862371 dated Dec. 7, 2010, pp. 1-6. |
| International Search Report in commonly owned International Application No. PCT/KR2008/006870, dated May 28, 2009, pp. 1-2. |
| Office Action in commonly owned U.S. Appl. No. 12/631,018 mailed Nov. 8, 2011, pp. 1-10. |
| Chinese Office Action in commonly owned Chinese Application No. 200910211954 dated Jun. 23, 2011, pp. 1-5. |
| English translation of Chinese Office Action in commonly owned Chinese Application No. 200910211954 dated Jun. 23, 2011, pp. 1-5. |
| Katrizky et al., “Correlation and Prediction of the Refractive Indices of Polymers by QSPR”, Journal of Chemical Information and Computer Sciences, pp. 1171-1176, (1998). |
| Office Action in commonly owned U.S. Appl. No. 12/642,904 mailed Dec. 14, 2011, pp. 1-9. |
| European Search Report in commonly owned European Application No. 09180634 dated Feb. 2, 2010, pp. 1-3. |
| Xu, “Predicition of Refractive Indices of Linear Polymers by a four-descriptor QSPR model”, Polymer, 45 (2004) pp. 8651-8659. |
| European Search Report in commonly owned European Application No. 10196806 dated Apr. 27, 2011, pp. 1-5. |
| Japanese Office Action in commonly owned Japanese Application No. 2010-539284, dated Sep. 11, 2012, pp. 1-3. |
| Office Action in commonly owned U.S. Appl. No. 12/631,018 mailed Apr. 26, 2012, pp. 1-12. |
| Office Action in commonly owned U.S. Appl. No. 12/642,904 mailed Mar. 27, 2012, pp. 1-7. |
| Notice of Allowance in commonly owned U.S. Appl. No. 12/642,904 mailed Jul. 2, 2012, pp. 1-8. |
| Office Action in commonly owned U.S. Appl. No. 12/817,302 mailed Mar. 29, 2012, pp. 1-5. |
| Office Action in commonly owned U.S. Appl. No. 12/884,549 mailed Aug. 21, 2012, pp. 1-12. |
| Mark, Physical Properties of Polymers Handbook, 2nd Edition, Polymer Research Center and Department of Chemistry, University of Cincinnati, OH, (2007) Springer, pp. 5-7. |
| Polysciences, Inc., data sheet for benzyl acrylate, no date, pp. 1-2. |
| Guidechem, data sheet for RUBA-93, no date, pp. 1-2. |
| European Search Report in commonly owned European Application No. 08873329.0 dated Dec. 14, 2012, pp. 1-7. |
| Office Action in commonly owned U.S. Appl. No. 12/972,795 mailed Jan. 18, 2013, pp. 1-9. |
| International Search Report in commonly owned International Application No. PCT/KR2008/07825 dated Aug. 28, 2009, pp. 1-2. |
| Machine translation of JP 2006-257284, pp. 1-27. |
| Office Action in commonly owned U.S. Appl. No. 12/880,209 mailed Feb. 16, 2011, pp. 1-10. |
| International Search Report in commonly owned International Application No. PCT/KR2008/07820 dated Jul. 28, 2009, pp. 1-2. |
| Final Office Action in commonly owned U.S. Appl. No. 12/880,209 mailed Jul. 29, 2011, pp. 1-9. |
| Advisory Action in commonly owned U.S. Appl. No. 12/880,209 mailed Nov. 4, 2011, pp. 1-4. |
| International Search Report in commonly owned International Application No. PCT/KR2008/007157, dated May 28, 2009. |
| Final Office Action in commonly owned U.S. Appl. No. 12/792,176 mailed Apr. 19, 2012, pp. 1-10. |
| Advisory Action in commonly owned U.S. Appl. No. 12/792,176 mailed Aug. 23, 2012, pp. 1-4. |
| European Search Report in commonly owned European Application No. 08873425.6 dated May 29, 2012, pp. 1-5. |
| Office Action in commonly owned U.S. Appl. No. 12/792,176 mailed Nov. 16, 2011, pp. 1-12. |
| Notice of Allowance in commonly owned U.S. Appl. No. 12/880,209 mailed Oct. 10, 2013, pp. 1-10. |
| Search Report in commonly owned European Patent Application No. EP 01 27 4302 dated Mar. 4, 2005, pp. 1-4. |
| Office Action in commonly owned U.S. Appl. No. 11/768,592 mailed Apr. 8, 2009, pp. 1-9. |
| Notice of Allowance in commonly owned U.S. Appl. No. 11/647,101 mailed Dec. 29, 2008, pp. 1-7. |
| International Search Report in commonly owned International Application No. PCT/KR2006/005752, dated Mar. 27, 2007, pp. 1-2. |
| International Search Report dated Jul. 14, 2005 in commonly owned international publication No. PCT/KR2004/003457, pp. 1. |
| International Preliminary Report on Patentability dated Jan. 25, 2007 in commonly owned international publication No. PCT/KR2004/003457, pp. 1-23. |
| Office Action in commonly owned U.S. Appl. No. 12/961,877 mailed Jul. 30, 2012, pp. 1-14. |
| Search Report in counterpart European Application No. 14194463.7 dated Apr. 23, 2015, pp. 1-2. |
| Paris et al. “Glass Transition Temperature of Allyl Methacrylate-n-Butyl Acrylate Gradient Copolymers in Dependence on Chemical Composition and Molecular Weight”, Journal of Polymer Science Part A, pp. 1845-1855. |
| Wunderlich, “Thermal Analysis of Polymeric Materials”, 2005, Springer, New York, p. 698. |
| Extended European Search Report in commonly owned European Application No. 09180865.9, dated Apr. 16, 2010. |
| Number | Date | Country | |
|---|---|---|---|
| 20150152205 A1 | Jun 2015 | US |
