Patent Description:
As engineering plastics, polycarbonate resins have good properties in terms of impact resistance, heat resistance, dimensional stability, weather resistance, flame retardancy, electrical properties, transparency and the like, and are usefully applied to housings of electric/electronic products, interior/exterior materials of office equipment, and the like. In addition, various fillers are used to improve various properties of the polycarbonate resins.

However, fillers, such as glass fiber, talc, and wollastonite, which are applied to improve dimensional stability of the polycarbonate resins, have different physical properties depending on the kind of fillers and can cause deterioration in properties when added in a certain amount or more, thereby making it difficult to realize metal-level dimensional stability.

Therefore, there is a need for development of a thermoplastic resin composition that can realize metal-level dimensional stability and exhibits good properties in terms of flame retardancy, impact resistance, and the like.

The background technique of the present invention is disclosed in <CIT> and <CIT>.

It is an aspect of the present invention to provide a thermoplastic resin composition that exhibits good properties in terms of dimensional stability, flame retardancy, impact resistance, and the like.

It is another aspect of the present invention to provide a molded product produced from the thermoplastic resin composition.

The above and other aspects of the present invention can be achieved by the present invention described below.

The present invention relates to a thermoplastic resin composition according to claims <NUM> to <NUM>, and a molded product produced from the thermoplastic resin composition according to claim <NUM>.

The present invention provides a thermoplastic resin composition that has good properties in terms of dimensional stability, flame retardancy, impact resistance, and the like, and a molded product produced therefrom.

A thermoplastic resin composition according to the present invention comprises: (A) a polycarbonate resin; (B) a polyester resin; (C) a chain extender; (D) glass fibers; (E) a phosphorus flame retardant; and (F) a modified polyolefin.

The polycarbonate resin according to one embodiment of the present invention may comprise any polycarbonate resin used in typical thermoplastic resin compositions. For example, the polycarbonate resin may be an aromatic polycarbonate resin prepared by reacting diphenols (aromatic diol compounds) with a precursor, such as phosgene, halogen formate, or carbonate diester.

In some embodiments, the diphenols may comprise, for example, <NUM>,<NUM>'-biphenol, <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl)propane, <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl)-<NUM>-methylbutane, <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl)cyclohexane, <NUM>,<NUM>-bis(<NUM>-chloro-<NUM>-hydroxyphenyl)propane, and <NUM>,<NUM>-bis-(<NUM>,<NUM>-dichloro-<NUM>-hydroxyphenyl)propane, without being limited thereto. For example, the diphenols may be <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl)propane, <NUM>,<NUM>-bis(<NUM>,<NUM>-dichloro-<NUM>-hydroxyphenyl)propane, <NUM>,<NUM>-bis(<NUM>-methyl-<NUM>-hydroxyphenyl)propane, or <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl)cyclohexane, specifically <NUM>,<NUM>-bis(<NUM>-hydroxyphenyl)propane, which is also referred to as bisphenol-A.

In some embodiments, the polycarbonate resin may be a branched polycarbonate resin. For example, the polycarbonate resin may be a polycarbonate resin prepared by adding a tri- or higher polyfunctional compound, specifically, a trior higher valent phenol group-containing compound, in an amount of about <NUM> mol% to about <NUM> mol% based on the total number of moles of the diphenols used in polymerization.

In some embodiments, the polycarbonate resin may be a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. In addition, the polycarbonate resin may be partly or completely replaced by an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, for example, a bifunctional carboxylic acid.

In some embodiments, the polycarbonate resin may have a weight average molecular weight (Mw) of about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, for example, about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, as measured by gel permeation chromatography (GPC). Within this range, the thermoplastic resin composition can have good fluidity (processability).

According to the present invention, the polyester resin serves to realize metal-level dimensional stability of the thermoplastic resin composition together with the chain extender, the glass fibers, and the like without deterioration in other properties, such as flame retardancy, impact resistance, and the like, and may be selected from any polyester resins used in a typical thermoplastic resin composition. For example, the polyester resin may be obtained by polycondensation of a dicarboxylic acid component and a diol component, in which the dicarboxylic acid component may comprise: aromatic dicarboxylic acids, such as terephthalic acid (TPA), isophthalic acid (IPA), <NUM>,<NUM>-naphthalene dicarboxylic acid, <NUM>,<NUM>-naphthalene dicarboxylic acid, <NUM>,<NUM>-naphthalene dicarboxylic acid, <NUM>,<NUM>-naphthalene dicarboxylic acid, <NUM>,<NUM>-naphthalene dicarboxylic acid, <NUM>,<NUM>-naphthalene dicarboxylic acid, <NUM>,<NUM>-naphthalene dicarboxylic acid, <NUM>,<NUM>-naphthalene dicarboxylic acid, <NUM>,<NUM>-naphthalenedicarboxylic acid, and the like; and aromatic dicarboxylates, such as dimethyl terephthalate (DMT), dimethyl isophthalate, dimethyl-<NUM>,<NUM>-naphthalate, dimethyl-<NUM>,<NUM>-naphthalate, dimethyl-<NUM>,<NUM>-naphthalate, dimethyl-<NUM>,<NUM>-naphthalate, dimethyl-<NUM>,<NUM>-naphthalate, dimethyl-<NUM>,<NUM>-naphthalate, dimethyl-<NUM>,<NUM>-naphthalate, dimethyl-<NUM>,<NUM>-naphthalate, and the like, and in which the diol component may comprise ethylene glycol, <NUM>,<NUM>-propylene glycol, <NUM>,<NUM>-propylene glycol, <NUM>,<NUM>-dimethyl-<NUM>,<NUM>-propanediol, <NUM>,<NUM>-butanediol, <NUM>,<NUM>-butanediol, <NUM>,<NUM>-pentanediol, <NUM>,<NUM>-pentanediol, <NUM>,<NUM>-hexanediol, and a cycloalkylene diol.

In some embodiments, the polyester resin may comprise polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polytrimethylene terephthalate (PTT), polycyclohexylene terephthalate, and combinations thereof. For example, the polyester resin may be polyethylene terephthalate, polybutylene terephthalate, or a combination thereof.

In some embodiments, the polyester resin may have an inherent viscosity of about <NUM> dl/g to about <NUM> dl/g, as measured using an o-chloro phenol solution (concentration: <NUM>/dl) at <NUM> using an Ubbelohde viscometer (capillary viscometer). Within this range, the thermoplastic resin composition can exhibit good processability, dimensional stability, and the like.

In some embodiments, the polyester resin may be present in an amount of about <NUM> parts by weight to about <NUM> parts by weight, for example, about <NUM> parts by weight to about <NUM> parts by weight, relative to about <NUM> parts by weight of the polycarbonate resin. If the content of the polyester resin is less than about <NUM> parts by weight relative to about <NUM> parts by weight of the polycarbonate resin, the thermoplastic resin composition can suffer from deterioration in dimensional stability and the like, and if the content of the polyester resin exceeds about <NUM> parts by weight, the thermoplastic resin composition can suffer from deterioration in flame retardancy, impact resistance, and the like.

According to the present invention, the chain extender serves to improve impact resistance, flame retardancy and dimensional stability of the thermoplastic resin composition together with the polyester resin and may comprise at least one of a composite (phenoxy resin) of an aromatic diol compound and epichlorohydrin, and a modified acrylic copolymer.

In some embodiments, the compound of the aromatic diol compound and epichlorohydrin may comprise bisphenol A-type epoxy resin (phenol, <NUM>,<NUM>'-(<NUM>-methylethylidene)bis-, polymer with <NUM>-(chloromethyl)oxirane), which is a compound of bisphenol A and epichlorohydrin.

In some embodiments, the modified acrylic copolymer may be an acrylic copolymer having an epoxy group.

In some embodiments, the chain extender may have a weight average molecular weight (Mw) of about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, for example, about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol, as measured by GPC (gel permeation chromatography). Within this range, the thermoplastic resin composition can exhibit good properties in terms of impact resistance, dimensional stability, and the like.

In some embodiments, the chain extender may be present in an amount of about <NUM> parts by weight to about <NUM> part by weight, for example, about <NUM> parts by weight to about <NUM> parts by weight. If the content of the chain extender is less than about <NUM> parts by weight relative to about <NUM> parts by weight of the polycarbonate resin, the thermoplastic resin composition can suffer from deterioration in impact resistance, dimensional stability, and the like, and if the content of the chain extender exceeds about <NUM> part by weight, the thermoplastic resin composition can suffer from deterioration in fluidity, flame retardancy, and the like.

In some embodiments, the polyester resin (B) and the chain extender (C) may be present in a weight ratio (B:C) of about <NUM>:<NUM> to about <NUM>:<NUM>, for example, about <NUM>:<NUM> to about <NUM>:<NUM>. If the weight ratio of the polyester resin to the chain extender is less than about <NUM>:<NUM>, the thermoplastic resin composition can suffer from deterioration in dimensional stability, impact resistance, and the like, and if the weight ratio thereof exceeds about <NUM>:<NUM>, the thermoplastic resin composition can suffer from deterioration in fluidity, flame retardancy, and the like.

According to the present invention, the glass fibers serve to realize metal-level dimensional stability of the thermoplastic resin composition together with the polyester resin, the chain extender, and the like without deterioration in other properties, such as flame retardancy, impact resistance, and the like, and may be selected from glass fibers used in a typical thermoplastic resin composition.

In some embodiments, the glass fibers may have a fibrous shape and may have various cross-sectional shapes, such as circular, elliptical, and rectangular shapes. For example, fibrous glass fibers having circular and/or rectangular cross-sectional shapes may be preferred in terms of mechanical properties.

In some embodiments, the glass fibers having a circular cross-section may have a cross-sectional diameter of about <NUM> to about <NUM> and a pre-processing length of about <NUM> to about <NUM>, and the glass fibers having a rectangular cross-section may have an aspect ratio (a ratio of a long-side length to a short-side length in a cross-section of the glass fiber) of about <NUM> to about <NUM>, a short-side length of about <NUM> to about <NUM>, and a pre-processing length of about <NUM> to about <NUM>. Within this range, the thermoplastic resin composition can have good properties in terms of dimensional stability, rigidity and processability.

In some embodiments, the glass fibers may be subjected to surface treatment with a typical surface treatment agent.

In some embodiments, the glass fibers may be present in an amount of about <NUM> parts by weight to about <NUM> parts by weight, for example, about <NUM> parts by weight to about <NUM> parts by weight, relative to about <NUM> parts by weight of the polycarbonate resin. If the content of the glass fibers is less than about <NUM> parts by weight relative to about <NUM> parts by weight of the polycarbonate resin, the thermoplastic resin composition can suffer from deterioration in dimensional stability and the like, and if the content of the glass fibers exceeds about <NUM> parts by weight, the thermoplastic resin composition can suffer from deterioration in impact resistance, flame retardancy, and the like.

In some embodiments, the polyester resin (B) and the glass fibers (D) may be present in a weight ratio (B:D) of about <NUM>:<NUM> to about <NUM>:<NUM>, for example, about <NUM>:<NUM> to about <NUM>:<NUM>. Within this range, the thermoplastic resin composition can exhibit good properties in terms of dimensional stability, impact resistance, and the like.

According to the present invention, the phosphorus flame retardant serves to improve flame retardancy and the like of the thermoplastic resin composition and may be a phosphorus flame retardant used in typical flame retardant thermoplastic resin compositions. For example, the phosphorus flame retardant may comprise a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound, a phosphazene compound, and metal salts thereof. These compounds may be used alone or as a mixture thereof.

In some embodiments, the phosphorus flame retardant may comprise a phosphazene compound represented by Formula <NUM>. <CHM>
where R<NUM>, R<NUM>, R<NUM>, R<NUM>, R<NUM> and R<NUM> are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C<NUM> to C<NUM> alkyl group, a substituted or unsubstituted C<NUM> to C<NUM> alkenyl group, a substituted or unsubstituted C<NUM> to C<NUM> cycloalkyl group, a substituted or unsubstituted C<NUM> to C<NUM> heterocycloalkyl group, a C<NUM> to C<NUM> alkoxy group, a C<NUM> to C<NUM> aryl group or aryloxy group, a C<NUM> to C<NUM> heteroaryl group, a substituted or unsubstituted C<NUM> to C<NUM> alkoxy carbonyl alkyl group, a substituted or unsubstituted C<NUM> to C<NUM> carbonyl alkyl group, an amino group, or a hydroxyl group.

Here, "substituted" means that a hydrogen atom is substituted with a substituent, for example, a C<NUM> to C<NUM> alkyl group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a C<NUM> to C<NUM> aryl group, a C<NUM> to C<NUM> cycloalkyl group, a C<NUM> to C<NUM> heterocycloalkyl group, a C<NUM> to C<NUM> heteroaryl group, and combinations thereof.

In addition, "alkyl", "alkoxy" and other substituents containing an "alkyl" moiety comprise linear or branched structures, and "alkenyl" comprises linear or branched structures having <NUM> to <NUM> carbon atoms and containing at least one double bond. In addition, "cycloalkyl" comprises saturated monocyclic or saturated bicyclic structures having <NUM> to <NUM> carbon atoms. Further, "aryl" is an organic radical derived from an aromatic hydrocarbon through removal of one hydrogen atom therefrom and comprises single or fused ring systems containing suitably <NUM> to <NUM>, preferably <NUM> or <NUM> atoms in each ring. Specifically, "aryl" may comprise phenyl, naphthyl, biphenyl, tolyl, and the like.

Here, "heterocycloalkyl" means a cycloalkyl group containing <NUM> to <NUM> heteroatoms selected from N, O, and S as saturated cyclic hydrocarbon backbone atoms, in which the remaining saturated monocyclic or bicyclic ring backbone atoms are carbon atoms, and may comprise pyrrolidinyl, azetidinyl, pyrazolidinyl, oxazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, hydantoinyl, valerolactamyl, oxylanyl, oxetanyl, dioxolanyl, dioxanyl, oxathiolanyl, oxathianyl, dithianyl, dihydrofuranyl, tetrahydrofuranyl, dihydropyranyl, tetrahydropyranyl, tetrahydropyridinyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, diazepanyl, azepanyl, and the like.

In addition, "heteroaryl" means an aryl group containing <NUM> to <NUM> heteroatoms selected from N, O, and S as aromatic ring backbone atoms, in which the remaining ring backbone atoms are carbon atoms. The heteroaryl group may comprise a divalent aryl group in which a heteroatom in the ring is oxidized or quaternized to form, for example, an N-oxide or a quaternary salt. Specifically, the heteroaryl group may comprise furyl, thiophenyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and the like.

In some embodiments, the phosphorus flame retardant may be present in an amount of about <NUM> parts by weight to about <NUM> parts by weight, for example, about <NUM> parts by weight to about <NUM> parts by weight, relative to about <NUM> parts by weight of the polycarbonate resin. If the content of the phosphorus flame retardant is less than about <NUM> parts by weight relative to about <NUM> parts by weight of the polycarbonate resin, the thermoplastic resin composition can suffer from deterioration in flame retardancy, fluidity, and the like, and if the content of the phosphorus flame retardant exceeds about <NUM> parts by weight, the thermoplastic resin composition can suffer from deterioration in impact resistance, dimensional stability, and the like.

According to the present invention, the modified polyolefin serves to improve impact resistance of the thermoplastic resin composition.

The modified polyolefin comprises ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA).

In some embodiments, the modified polyolefin may be provided in the form of a random copolymer, a block copolymer, a multi-block copolymer, or a combination thereof.

In some embodiments, the modified polyolefin may have a melt-flow index of about <NUM>/<NUM> to about <NUM>/<NUM>, for example, about <NUM>/<NUM> to about <NUM>/<NUM>, as measured under conditions of <NUM> and <NUM> kgf in accordance with ASTM D1238. Within this range, the thermoplastic resin composition can have good impact resistance and the like.

In some embodiments, the modified polyolefin may be present in an amount of about <NUM> part by weight to about <NUM> parts by weight, for example, about <NUM> parts by weight to about <NUM> parts by weight, relative to about <NUM> parts by weight of the polycarbonate resin. If the content of the modified polyolefin is less than about <NUM> part by weight relative to about <NUM> parts by weight of the polycarbonate resin, the thermoplastic resin composition can suffer from deterioration in impact resistance and the like, and if the content of the modified polyolefin exceeds about <NUM> parts by weight, the thermoplastic resin composition can suffer from deterioration in dimensional stability, flame retardancy, and the like.

In some embodiments, the thermoplastic resin composition may further comprise additives used for typical thermoplastic resin compositions. Examples of the additives may comprise antioxidants, anti-dripping agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, and mixtures thereof, without being limited thereto. The additives may be present in an amount of about <NUM> parts by weight to about <NUM> parts by weight, for example, about <NUM> parts by weight to about <NUM> parts by weight, relative to about <NUM> parts by weight of the polycarbonate resin.

In some embodiments, the thermoplastic resin composition may be prepared in pellet form by mixing the aforementioned components, followed by melt extrusion at about <NUM> to about <NUM>, for example, about <NUM> to about <NUM>, using a typical twin-screw extruder.

In some embodiments, the polyester resin and the glass fibers may be fed through a side feeder in preparation (mixing) of the thermoplastic resin composition. As a result, the thermoplastic resin composition has good dimensional stability.

In some embodiments, the thermoplastic resin composition may have a coefficient of linear expansion of about <NUM>/m·°C to about <NUM>/m·°C, for example, about <NUM>/m·°C to about <NUM>/m·°C, as measured on an injection-molded specimen having a size of <NUM> × <NUM> × <NUM> while heating the specimen from <NUM> to <NUM> at <NUM> /min using a thermo-mechanical analyzer in accordance with ASTM D696.

In some embodiments, the thermoplastic resin composition may have a flame retardancy of V-<NUM>, as measured on a <NUM> thick injection-molded specimen by a UL-<NUM>50W vertical test method.

In some embodiments, the thermoplastic resin composition may have a notched Izod impact strength of about <NUM> kgf·cm/cm to about <NUM> kgf·cm/cm, for example, about <NUM> kgf·cm/cm to about <NUM> kgf·cm/cm, as measured on a <NUM>/<NUM>" thick specimen in accordance with ASTM D256.

A molded product according to the present invention is produced from the thermoplastic resin composition set forth above. The thermoplastic resin composition may be prepared in pellet form. The prepared pellets may be produced into various molded products by various molding methods, such as injection molding, extrusion molding, vacuum molding, and casting. These molding methods are well known to those skilled in the art. The molded product has good properties in terms of dimensional stability, flame retardancy, impact resistance, and balance therebetween, and thus can be advantageously used for interior/exterior materials for electrical/electronic products, thin sheets, and the like.

Next, the present invention will be described in more detail with reference to some examples.

Details of components used in Examples and Comparative Examples are as follows.

A bisphenol-A polycarbonate resin having a weight average molecular weight (Mw) of <NUM>,<NUM>/mol was used.

(B1) Polyethylene terephthalate (PET, Manufacturer: SK Chemical, Product Name: SKYPET <NUM>, Inherent viscosity: <NUM> dl/g) was used.

(B2) Polybutylene terephthalate (PBT, Manufacturer: Shinkong, Product Name: Shinite K006, Inherent viscosity: <NUM> dl/g) was used.

(C1) A bisphenol A-type epoxy resin (Phenol, <NUM>,<NUM>'-(<NUM>-methylethylidene)bis-, polymer with <NUM>-(chloromethyl)oxirane, Manufacturer: InChemRez, Product Name: PKHH) was used.

(C2) An epoxy group-containing acrylic copolymer (Manufacturer: BASF, Product Name: ADR-<NUM>) was used.

(D1) Glass fibers (Manufacturer: KCC, Product Name: CS321-EC10-<NUM>).

(D2) Talc (Manufacturer: KOCH, Product Name: KCP-<NUM>).

A phosphazene compound (Manufacturer: Fushimi Pharmaceutical, Product Name: FP-<NUM>) was used.

(F1) An ethylene-methyl acrylate copolymer (EMA, Manufacturer: Dupont, Product Name: Elvaroy AC <NUM>) was used.

(F2) MBS (Manufacturer: Mitsubishi chemical, Product Name: C-223A).

The above components were mixed in amounts as listed in Tables <NUM> and <NUM> and subjected to extrusion under conditions of <NUM>, thereby preparing a thermoplastic resin composition in pellet form. Here, components other than the polyester resin and the glass fibers were fed to a main feeder and the polyester resin and the glass fibers were fed to a side feeder. Extrusion was performed using a twin-screw extruder (L/D=<NUM>, Φ: <NUM>) and the prepared pellets were dried at <NUM> for <NUM> hours or more and injection-molded in a <NUM> oz. injection molding machine (molding temperature: <NUM>, mold temperature: <NUM>), thereby preparing specimens. The prepared specimens were evaluated as to the following properties by the following method, and results are shown in Tables <NUM> and <NUM>.

From the result, it could be seen that the thermoplastic resin composition according to the present invention had good properties in terms of dimensional stability, flame retardancy, impact resistance, and the like.

Claim 1:
A thermoplastic resin composition comprising:
<NUM> parts by weight of a polycarbonate resin;
<NUM> parts by weight to <NUM> parts by weight of a polyester resin;
<NUM> parts by weight to <NUM> part by weight of a chain extender;
<NUM> parts by weight to <NUM> parts by weight of glass fibers;
<NUM> parts by weight to <NUM> parts by weight of a phosphorus flame retardant; and
<NUM> part by weight to <NUM> parts by weight of a modified polyolefin,
wherein the polyester resin and the chain extender are present in a weight ratio of <NUM>:<NUM> to <NUM>:<NUM>,
wherein the modified polyolefin comprises at least one of ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-butyl acrylate (EBA).