WO2004052991A1 - High flow engineering theremoplastic compositions and products made therefrom - Google Patents
High flow engineering theremoplastic compositions and products made therefrom Download PDFInfo
- Publication number
- WO2004052991A1 WO2004052991A1 PCT/US2003/037006 US0337006W WO2004052991A1 WO 2004052991 A1 WO2004052991 A1 WO 2004052991A1 US 0337006 W US0337006 W US 0337006W WO 2004052991 A1 WO2004052991 A1 WO 2004052991A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- flow
- polymer
- thermoplastic composition
- high flow
- less
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
Definitions
- the present invention relates to flow modified thermoplastic compositions for molding applications made from thermoplastic polymers and low molecular weight vinyl aromatic/(meth)acrylate polymeric modifiers.
- Thermoplastics and thermoplastic blends for use in various engineering applications should exhibit a variety of favorable physical properties such as high heat resistance, high impact strength, high moldability and processability, and in some instances, good transparency.
- Polycarbonates, polyamides, polyesters and polyethers among other engineering thermoplastics are particularly popular components due to their toughness and relatively high softening temperatures. These favorable mechanical, and thermal properties, as well as their good electrical properties make these resins widely applicable for engineering plastics in various fields, including the field of housings for electronic equipment and automobile parts. Due to their relatively poor melt flow characteristics, however, polycarbonates and other engineering plastics, are often blended with one or more additional polymers and • additives to improve their melt flow properties.
- thermoplastic composition that exhibits increased moldability and processability while retaining other desirable physical properties such as high heat resistance and impact strength.
- the present invention makes use of low molecular weight, vinyl aromatic/(meth)acrylate polymers as flow enhancers for thermoplastics and thermoplastic blends to provide thermoplastic compositions with improved moldability and flowability for molding applications, while maintaining a good balance of impact and heat resistance.
- the thermoplastic compositions of the present invention are suitable for molding opaque and transparent housings for electronic devices, automobile parts, appliances, and other articles, particularly those exposed to high shear during molding. Typical applications are large molded parts or molded parts with thin walls, such as housings for mobile phones, laptop computers, personal computer CPU's and monitors, and other electronic devices, and housings for automobile control and indicator panels, mirrors, headlamps, etc.
- the compositions ensure excellent fluidity and moldability, and excellent surface appearance as well as high mechanical, thermal, and impact properties, without the incidence of delamination or additive juicing, and in some cases, without detriment to the transparency of the composition.
- One aspect of the present invention provides a high flow thermoplastic composition made from a host polymer and a flow modifier polymer having a low molecular weight, wherein the flow modifier polymer has a weight-average molecular weight of less than 15,000 and is made from at least one (meth)acrylate and optionally at least one vinyl aromatic monomer and the relative energy difference (R.E.D.) between the flow modifier and host polymer is less than 2.2 Preferred embodiments have an .E.D. of less than 1.75. Additionally, in preferred embodiments the weight average molecular weight of the flow modifier is less than 10,000. Highly preferred embodiments include flow modifiers having a weight average molecular weight of 5,000.
- Another aspect of the present invention provides a high flow thermoplastic composition made from a flow modifier polymer and a host polymer selected from the group consisting of polycarbonates, polycarbonate/acrylonitrile-butadiene-styrene blends, polyamides, polyesters, polyphenylene ethers, transparent-ABS resins, and combinations thereof.
- a host polymer selected from the group consisting of polycarbonates, polycarbonate/acrylonitrile-butadiene-styrene blends, polyamides, polyesters, polyphenylene ethers, transparent-ABS resins, and combinations thereof.
- Highly preferred embodiments include polycarbonate host polymers or polycarbonate acrylonitrile-butadiene-styrene blend.
- the host polymer is selected from the group consisting of polyamide, poly(butylene terephthalate), poly(propylene terephthalate), poly(ethylene terephthalate), PETG, polyethylene naphthalate, polyphenylene oxide, and
- the host polymer is present in an amount of from about 50 to about 99 weight percent and the flow modifier polymer is present in an amount of from about 1 to about 20 weight percent.
- Still another aspect of the present invention provides a high flow polymer composition made from a flow modifier polymer and a host polymer wherein the flow modifier polymer comprises (bl) l-100 % ofa (meth)acrylate monomer, (b2) 0 - 99% of at least one vinyl aromatic monomer, and (b3) 0-99% of another monomer or mix of monomers able to copolymerize with (bl) and (b2).
- Preferred embodiments include a flow modifier polymer comprising from about 1 to about 70 weight percent of at least one (meth)acrylate monomer and from about 30 to about 99 weight percent of at least one vinyl aromatic monomer.
- Still another aspect of the present invention provides a high flow polymer composition made from a flow modifier polymer and a host polymer, wherein the
- Vicat softening temperature of the composition differs by no more than 10°C from the Vicat softening temperature of the host polymer.
- Still another aspect of the present invention provides a high flow polymer composition made from a flow modifier polymer and a host polymer, wherein the composition is a transparent composition having a haze percentage that differs by less than about 1 % from the haze percentage of the host polymer.
- Still another aspect of the present invention provides a high flow polymer composition made from a flow modifier polymer and a host polymer, wherein the composition further comprises at least one additive wherein the additive is an impact modifier, a mineral filler, a pigment, a dye, or a fire retardant.
- a further aspect of the invention provides a flow thermoplastic composition wherein at least one vinyl aromatic monomer is styrene or a styrene derivative and the at least one (meth)acrylate monomer is selected from the group consisting of butyl methacrylate, methyl methacrylate, glycidyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, acrylic acid and maleic anhydride.
- a suitable composition according to the present invention contains (A) 50-99 % of an engineering thermoplastic chosen from the families of polycarbonates (PCs), polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS) blends, polyesters and polyester based blends, polyamides and polyamide based blends, polyphenylene ether (PPE) based blends and transparent ABS, (B) 1- 20 % of a low molecular weight polymer obtained by polymerizing (bl) 1-100 % of a (meth)acrylate monomer, (b2) 0 - 99% of at least one vinyl aromatic monomer, and (b3) 0-99% of other monomer or mix of monomers able to copolymerize with (bl) and (b2), (C) 0-20% of an impact modifier, (D) 0-50% of a mineral filler or reinforcing agent, (E) 0-10% of a suitable pigment or dye, and (F) 0-2
- PCs poly
- Another aspect of the invention provides a method for increasing the flow of a host polymer by mixing therewith a flow modifier polymer having a weight average molecular weight (M w ) of less than about 15;000.
- the flow modifier polymer is made from at least one (meth)acrylate monomer and optionally at least one vinyl aromatic monomer and the relative energy difference between the flow modifier and host polymer is less than 2.2.
- Still another aspect of this invention provides a molded article made from the high flow composition made from the host polymer and the flow modifier polymer. Another aspect of this invention provides a method for manufacture of a molded article wherein the article is an automobile part or a housing for a piece of electronic equipment.
- the article may also be a housing for a computer, a computer monitor, a keyboard, a printer, a fax machine, a telephone, a mobile communications device, such as a mobile phone, a camera, a power plug, an electrical switch, an electrical connector, an electrical control panel, a telecommunication connector, a telecommunication switch, an automobile control panel, an automobile indicator ⁇ panel, a mount for a mirror, an automobile headlamp, an automotive bumper, automotive fascia, an automotive hood, an engine cover, a generator cover, a battery cover, an air manifold, automotive hoses and connectors, a tractor hood, an automotive panel, a tractor panel, a lawn mower deck, a lawn tool, a piece of office equipment, including a photocopier, a tray for a photocopier, household electronics, such as coffee makers, irons, vacuum cleaners, and fans, large appliances, such as televisions, DVD players, refrigerators, washing machines, and dryers; or parts for a computer, a computer monitor, a
- a generator cover a battery cover, an air manifold, automotive hoses and connectors, a tractor hood, an automotive panel, a tractor panel, a lawn mower deck, a lawn tool, a piece of office equipment, including a photocopier, a tray for a photocopier, household electronics, such as coffee makers, irons, vacuum cleaners, and fans, large appliances, such as televisions, DVD players, refrigerators, washing machines, and dryers.
- Another aspect of this invention provides high flow thermoplastic compositions comprising of a host polymer and low molecular weight flow modifier polymer wherein the flow modifier polymer is substantially free of acrylonitrile.
- Another aspect of this invention provides a method for increasing the flow of a host polymer comprising mixing the host polymer with a flow modifier polymer having a weight average molecular weight of less than about 15,000, the flow modifier polymer comprising at least one vinyl aromatic monomer and at least one (meth)acrylate monomer wherein the said composition is characterized by a relative energy difference ( .E.D.) between the flow modifier polymer and the host polymer of less than 2.2.
- Another aspect of the invention provides a method for manufacturing high flow engineering thermoplastic compositions by mixing a host polymer and a low molecular weight flow modifier polymer, the flow modifier polymer comprising at least one (meth)acrylate monomer and optionally at least one vinyl aromatic monomer, to form a flow modified thermoplastic composition; and molding the flow modified thermoplastic composition, wherein the mixing and molding steps have a maximum processing temperature, and further wherein the flow modifier polymer undergoes a weight loss of less than about 10 % at the maximum processing temperature.
- the weight average molecular weight of the flow modifier polymer is less than about 15,000 and the maximum processing temperature is at least 180°C.
- Another aspect of this invention provides a method for processing a high flow thermoplastic composition
- a method for processing a high flow thermoplastic composition comprising mixing a host polymer and a flow modifier polymer having a weight average molecular weight of less than about 15,000, the flow modifier polymer comprising at least one vinyl aromatic monomer and at least one (meth)acrylate monomer to form a flow modified thermoplastic composition wherein the said composition is characterized by a relative energy difference (R.E.D.) between the flow modifier polymer and the host polymer of less than 2.2; and molding the flow modified thermoplastic composition, wherein the mixing and molding steps have a maximum processing temperature of up to about 350°C, and further wherein the flow modifier polymer undergoes a weight loss of less than about 10 % at the maximum processing temperature. It is preferred that the maximum processing temperature be above 180°C.
- Another aspect of this invention provides a method for processing a high flow thermoplastic composition wherein the mixing and molding steps are carried out at shear rates in excess of 100,000 sec "1 ' Alternative methods can be carried out at shear rates in excess of 300,000 sec “1 or 500,000 sec "1 .
- a first aspect of the invention provides a high flow thermoplastic composition made from a host polymer blended with a low molecular weight vinyl aromatic/(meth) acrylate flow modifier polymer.
- the invention is based on the inventors' discovery that low M w vinyl aromatic/(meth) acrylate resins maybe used as flow enhancers in engineering thermoplastic compositions, providing such compositions with improved moldability (a.k.a. flowability) for injection molding applications, particularly those exposed to very high shear rates. Very high shear rates greater than 10,000s "1 are included.
- Very high shear rates also include shear rates greater than 50,000s "1 , shear rates greater than 100,000s “1 , shear rates greater than 200,000s “1 , shear rates greater than 300,000s “1 , shear rates greater than 400,000s “1 , shear rates greater than 500,000s “1 , and shear rates greater than 1,000,000 " ⁇ Molded products made from the modified thermoplastics maintain a good balance of impact, mechanical, and heat resistance properties without delamination, additive juicing or blooming problems or detriment to the transparency when applicable.
- thermoplastic compositions are useful for housings for electronics and automobile parts which require thinner and ti ⁇ nner walls without losing a satisfactory balance of mechanical, impact and thermal properties, and transparency when required. Additionally, molding thin walled or large intricate parts requires minimization of the viscosity, and thus the shear rates in the mold, by employing extreme temperature conditions.
- the flow modifiers of this invention provide formulations with much lower melt viscosity at given temperatures than other presently available flow modifiers. This provides decreased shear rates and stresses during the molding process and/or allows for lower temperature molding, thus offering energy cost savings.
- FMs flow modifiers
- Compatibility and/or miscibility are controlled in this invention by optimizing the intermolecular interactions between the flow modifiers and the host polymers. These interactions include but are not limited to Van der Waals forces, including London Dispersion forces and dipole-dipole interactions, and/or hydrogen bonding.
- a flow modifier having a combination of suitably high intermolecular interactions with a given host polymer and a suitably low molecular weight appears to
- the flow modifier polymers are low molecular weight polymers made by polymerizing at least one (meth)acrylate monomer and optionally at least one vinyl aromatic monomer.
- a low molecular weight flow modifier polymer may be any flow modifier polymer having a sufficiently low molecular weight to act as a flow
- the flow modifiers are polymers having a M w , as measured using gel permeation chromatography, of less than 15,000.
- low molecular weight flow modifier polymers also include polymers having a M w of less than 10,000, polymers having a M w of less than 9,000, polymers having a M w of less than 8,000, polymers having a M w of less than 7,000, polymers having a M w of less than 6,000, polymers having a M w of less than 5,000, polymers having a M w of less than 4,000, polymers having a M w of less than 3,000, polymers having a M w of less than 2,000, polymers having a M w of less than 1,000, and polymers having a M w of less than 500.
- Rij [4( ⁇ Di - ⁇ Dj ) 2 + ( ⁇ pi - ⁇ Pj) 2 + ( ⁇ Hi- ⁇ Hj) 2 ] 0 5
- i refers to the flow modifier
- j refers to the host plastic
- ⁇ D refers to dispersion solubility parameter
- ⁇ p to the polar solubility parameter
- ⁇ to the hydrogen bonding solubility parameter
- thermoplastic compositions are maximized and the adverse affects of delamination, blooming, juicing and other phase-separation type problems are minimized by decreasing the solubility parameter differences between host polymer and flow modifier.
- a very good measure of compatibility is determined by the Relative Energy Difference (R.E.D. number) between the flow modifiers and the host plastics as defined in Hansen Solubility Parameters - A Users Handbook, C. M. Hansen, CRC Press, 2000, pp. 1 - 13.
- the R.E.D. number is defined as: where R o is the radius of interaction for the host plastic as defined in Hansen Solubility Parameters - A Users Handbook, C. M. Hansen, CRC Press, 2000, pp.
- the mechanical properties of the thermoplastic compositions are maximized and the adverse affects of delamination, blooming, juicing and other phase-separation type problems are minimized by decreasing the R.E.D. number.
- the compositions may have a R.E.D. number of less than about 2.2.
- the R.E.D. number is less than 1.75.This includes embodiments where the R.E.D. number is less than about 1.0, less than about 0.8, less than about 0.6, or even less than about 0.5.
- the improved flow characteristics of the modified thermoplastic compositions may be shown by the increase in the melt flow index (MFI) of the modified host polymer (i.e.
- the MFI provides a measure of the rate of extrusion of a thermoplastic through an orifice at a prescribed temperature and load.
- the ASTM D-1238 test for MFI provides a common and standardized test for measuring the MFI for a given specimen.
- the host polymer plus the flow modifier polymer as compared to the unmodified thermoplastic by at least 5 %.
- the MFI as measured by ASTM D-1238
- the high flow thermoplastic compositions will contain from about 1 to about 20 weight percent of the flow modifier polymer. This includes compositions that contain from about 1 to about 10 weigh percent of the flow modifier polymer, and compositions that contain from about 1 to about 5 weigh percent of the flow modifier polymer.
- An advantage of the flow modifiers of this invention is that they provide improved flowability, and therefore processability, without sacrificing impact strength or heat resistance. This may be demonstrated by the high impact strengths of the modified thermoplastic compositions and the products made therefrom.
- the impact strength of a material is simply a measure of the amount of energy required to break a specimen of the material.
- the ASTM D-256 test for impact strength provides a common and standardized test for measuring the impact strength of a notched specimen (i.e. the "notched impact strength").
- the notched impact strength of the modified thermoplastics of this invention may vary depending on a variety of factors, including the nature of the host plastic and the flow modifier, as well as the intended application for the modified thermoplastic itself and processing conditions.
- the modified host polymers and the compositions made therefrom demonstrate a notched impact strength which is changed when compared to the unmodified host plastic by as little as -40%.
- the impact resistance, measured according to ASTM D- 256 is changed by -30%, -20%, -10%, and 0%.
- the modified host polymers and the compositions made therefrom demonstrate a notched impact strength which is changed when compared to the unmodified host plastic by +40%. This includes embodiments where the impact resistance, measured according to ASTM D-256 is changed by +30%, +20%, +10% and 0%.
- the heat resistance of the modified thermoplastic compositions may be measured by the heat deflection temperature (HDT) or by the Vicat Softening temperature (VST) of the compositions.
- the HDT or VST provides a measure of the temperature at which an arbitrary deformation occurs when a specimen of the material of interest is subjected to a flexural load.
- the ASTM D-648 test for HDT and VST provides a common and standardized test for measuring the HDT of a specimen.
- the HDT or VST of the modified thermoplastics of this invention may vary depending on a variety of factors, including the nature of the host plastic and the flow modifier, as well as the intended application for the modified thermoplastic itself and processing conditions.
- the modified host polymer and compositions made therefrom demonstrate an HDT or VST, measured according to ASTM D-648 which is changed when compared to the unmodified host plastic by as little as -10°C.
- the HDT measured according to ASTM D-648 is changed by - 7°C, -5°C, -2°C, and 0°C.
- the modified host polymers demonstrate an HDT or VST, measured according to ASTM D-648 which is changed when compared to the unmodified host plastic by up to +10°C. This includes embodiments where the HDT, measured according to ASTM D-648 is changed by +7°C, +5°C, +2°C, and 0°C.
- the flow enhancers of the present invention do not significantly degrade the transparency of transparent thermoplastic host polymers, such as polycarbonates, transparent polyesters, and transparent ABS resins.
- transparent thermoplastic host polymers such as polycarbonates, transparent polyesters, and transparent ABS resins.
- high flow transparent thermoplastics may be achieved when starting with transparent engineering thermoplastics and adding the low molecular weight flow agents.
- the transparency of the flow modified thermoplastics may be measured by the haze of the material. Haze is a measure of the scattering of light as it passes through a transparent material.
- the ASTM D-1003 test for haze provides a common and standardized test for measuring the haze of a specimen.
- Using the flow modifiers of the present invention in combination with transparent host polymers may provide high flow, transparent thermoplastic compositions having a haze, as measured by ASTM D-1003 which is changed when compared to the haze of the unmodified host plastic by as little as +1.0%.
- the host polymer may be any engineering thermoplastic or blend of thermoplastics for use in molding applications.
- suitable host polymers include, but are not limited to, polycarbonates, polyamides, polyesters, polyphenylene ethers, and transparent ABS resins. Due to their favorable mechanical properties, polycarbonates or blends of polycarbonates with elastomeric graft polymer resins, such as acrylonitrile-butadiene-styrene (ABS) resins, are particularly suitable host polymers.
- ABS acrylonitrile-butadiene-styrene
- Polycarbonate host polymers included in the compositions may be any aliphatic or aromatic homopolycarbonate or copolycarbonate known in the art. These . polycarbonates may be manufactured according to conventional processes.
- Thermoplastic aromatic polycarbonates suitable for use in the compositions of the present invention include polycarbonates generally prepared by the reaction of dihydric phenols with a carbonate precursor, such as phosgene or carbonate compounds.
- dihydric phenols include, but are not limited to, dihydroxy diphenyls, bis-(hydroxy ⁇ henyl)-alkanes, bis-(hydroxy phenyl)- cycloalkanes, bis-(hydroxy phenyl)-sulphides, bis-(hydroxy phenyl)-ethers, bis- (hydroxy phenyl)-ketones, bis-(hydroxy ⁇ henyl)-sulfoxides, bis-(hydroxy phenyl)- sulphones, ⁇ , ⁇ -bis-(hydroxy phenyl)-diisopropyl benzenes, and combinations thereof.
- suitable dihydric phenols include, but are not limited to, 2,2-bis (4-hydroxypheny ⁇ )propane (bisphenol A), bis (hydroxyaryl) alkanes such as bis (4-hydroxyphenyl)methane, l,l-bis(4-hydroxyphenyl)ethane, 2,2-bis(4- hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(4- .
- bisphenol A 2,2-bis (4-hydroxypheny ⁇ )propane
- bis (hydroxyaryl) alkanes such as bis (4-hydroxyphenyl)methane, l,l-bis(4-hydroxyphenyl)ethane, 2,2-bis(4- hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(4- .
- hydroxyphenyl)phenylmethane 2,2-bis(4-hydroxy-l-methylphenyl)propane, bis(4- hydroxyphenyl)naphthylmethane, 1 , 1 -bis(4-hydroxy-t-butylphenyl) ⁇ ropane, 2,2- bis(4-hydroxy-3,5-tetramethylphenyl)propane; bis(hydroxyaryl)cycloalkanes such as 1,1 -bis (4-hydroxyphenyl)cyclopentane, l,l-bis(4-hydroxyphenyl)cyclohexane, 1,1- bis(4-hydroxyphenyl)-3,5,5-trimethylcyclohexane; dihydroxyaryl ethers such as 4,4'- dihydroxyphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether; dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4
- ABS resins for use in PC/ABS or transparent-ABS host polymers are well- known in the art.
- the ABS resins suitable for use in the host polymers are generally formed from a rigid graft polymer grafted to a diene rubber.
- the ABS resins have a continuous phase made from styrene and acrylonitrile monomers on a discontinuous elastomer phase based on a butadiene elastomer.
- the two phases are generally linked by grafting the styrene/acrylonitrile copolymer onto the polybutadiene.
- ABS resins suitable for use in the present invention also encompasses elastomeric resins formed from a monovinylidene aromatic monomer other than styrene and from acrylate or methacrylate monomers rather than or in addition to the acrylonitrile monomer.
- diene rubbers are not limited to butadiene rubbers.
- the relative proportions of the PC and the ABS in the PC/ABS host polymer blends may vary over a wide range and will depend in part on the intended application of the composition. In one exemplary embodiment, the PC/ABS host polymer blends contain from about 95 to about 50 weight percent PC and from about 5 to about 50 weight percent ABS.
- transparent-ABS is a particularly suitable host polymer.
- Conventional transparent ABS resins are rabber-reinforced resins produced by graft-polymerizing methyl methacrylate (MMA), styrene (ST) and acrylonitrile (AN) in the presence of polybutadiene.
- MMA methyl methacrylate
- ST styrene
- AN acrylonitrile
- the MMA/ST/AN terpolymer obtained by the graft polymerization exhibits a refractive index close to that of polybutadiene.
- Polyamides are another example of a suitable host polymer for use in the present compositions.
- Polyamides (PAs) are well known and commercially available. These thermoplastic polymers cover a range of polymers containing recurring amide groups in the main polymer chain. Mixtures of various polyamides, as well as various polyamide copolymers, are also useful as host polymers.
- the polyamides can be obtained by a number of well known processes such as those described in U.S. Patent Nos. 2,071,250; 2,071,251; 2,130,523; 2,130,948; 2,241,322; 2,312,966; and 2,512,606, which are incorporated herein by reference.
- Nylon-6 for example, is a polymerization product of caprolactam.
- Nylon-6,6 is a condensation product of adipic acid and l,6- ⁇ fiaminohexane.
- nylon 4,6 is a condensation product between adipic acid and 1,4-diaminobutane.
- other useful diacids for the preparation of nylons include azelaic acid, sebacic acid, dodecane diacid, as well as terephthalic and isophthalic acids, and the like.
- diamines include m-xylyene diamine, di-(4-aminophenyl)methane, di-(4-aminocyclohexyl)methane; 2,2-di-(4-aminophenyl)propane, 2,2-di-(4-aminocyclohexyl)propane, among others.
- Copolymers of caprolactam with diacids and diamines are also useful.
- polyamides suitable for use in the present invention include, but are not limited to, those polyamides known as PA 6, PA 6,6; PA 6,12; PA 11; PA 12; and PA 6,9. Polyesters may also be used as the host polymer in the compositions.
- Polyesters are well known in the art and include a variety of polymers produced through the polycondensation of hydroxycarboxylic acids or dicarboxylic acids with dihydroxy compounds.
- Polyesters suitable for use in the present invention are thermoplastic polyesters and include all heterochain macromolecular compounds that possess repeat carboxylate ester groups in the backbone of the polymer. Mixtures of various polyesters, as well as various polyester copolymers, are also useful as host polymers.
- polyesters include, but are not limited to, ⁇ oly(butylene terephthalate) (PBT), polyethylene terephthalate) (PET), PETG, poly(ethylene-co-cyclohexyldimethanol terephthalate), amorphous polyesters, polyethylene naphthalate (PEN), and poly(propylene terephthalate) (PPT).
- PBT ⁇ oly(butylene terephthalate)
- PET polyethylene terephthalate
- PETG poly(ethylene-co-cyclohexyldimethanol terephthalate)
- PEN polyethylene naphthalate
- PPT poly(propylene terephthalate)
- Polyphenylene ethers are also suitable for use as the host polymers in the compositions of the present invention.
- the term polyphenylene ether resin includes unsubstituted polyphenylene ether polymers, substituted polyphenylene ether polymers wherein the aromatic ring is substituted, and blends thereof. Mixtures of various polyphenylene ethers, as well as various polyphenylene copolymers, are also useful as host polymers.
- Polyphenylene oxide (PPO) is one non-limiting example of a polyphenylene ether.
- Blends of two or more of the thermoplastic polymers listed above or blends of the thermoplastic polymers listed above with other polymers may also be used as host polymers.
- suitable blends include polycarbonate/polyester blends, such as PC/PBT, PC/PET blends, blends of polyacrylates with polystyrenes, blends including polyolefins or ABS resins such as polyamide/ABS and polyarnide/polyolefines, such as polyethylene, or polypropylene, and blends of polyphenylene ethers with polystyrenes (including high impact polystyrene), or polyamides.
- the host polymer is itself a blend of two or more polymers, the weight percentages quoted throughout this specification refer to total weight percentages for the multipolymer blends.
- the flow modifiers of the present invention are low molecular weight polymers and copolymers made by polymerizing at least one (meth)acrylate monomer and optionally at least one vinyl aromatic monomer.
- the term (meth)acrylate is intended to indicate both acrylate and methacrylate monomers.
- the low molecular weight flow modifiers are distinct components of the compositions of this invention.
- the flow modifiers are not diene-based graft polymers or other rubber based polymers.
- the flow modifier polymer contains only (meth)acrylate monomers.
- the flow modifier polymer contains from about 1 to about 99 weight percent (meth)acrylate monomer and from about 99 to about 1 weight percent vinyl aromatic monomer. This includes embodiments containing from about 1 and about 70 weight percent of (meth)acrylate monomers and from about 30 to about 99 weight percent vinyl aromatic monomers, and further includes embodiments containing from about 1 to about 80 weight percent (meth)acrylate monomers and from about 20 to about 99 weight percent vinyl aromatic monomers. In some embodiments the flow modifier polymer also contains from about 0 to about 99 weight percent of at least one other monomer or a mixture of other monomers capable of polymerizing with the (meth)acrylate monomers and/or the vinyl aromatic monomers.
- exemplary (meth)acrylate monomers include both functional and nonfunctional monomers.
- Suitable acrylate and methacrylate monomers include, but are not limited to, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n- butyl acrylate, s-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-amyl acrylate, i- amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, methylcyclohexyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate
- Examples of epoxy-functional (meth)acrylate monomers for use in the present invention include both acrylates and methacrylates. Examples of these monomers include, but are not limited to, those containing 1,2-epoxy groups such as glycidyl acrylate and glycidyl methacrylate.
- the epoxy-functional monomer glycidyl methacrylate is a particularly suitable monomer.
- Examples of acid functional monomers include, but are not limited to, acrylic acid and methacrylic acid.
- Examples of hydroxy functional monomers include, but are not limited to, hydroxyethyl acrylate (HEA) and hydroxyethyl methacrylate (HEMA).
- Examples of amine functional monomers include, but are not limited to, dimethylaminoethyl methacrylate (DMAEMA) and dimethylaminoethyl acrylate (DMAEA).
- Vinyl aromatic monomers include both styrene and styrene derivatives, such as styrene, ⁇ -methylstyrene, p-methylstyrene, 3,4-dimethylstyrene, o- and p-divinyl benzene, ⁇ -chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene and p-chloro- ⁇ - methylstyrene, o, m or p-bromostyrene, and di-bromostyrene.
- Vinyl toluene is an additional example of a suitable aromatic monomer for use in the flow modifiers.
- the modifier polymer may include other monomers which are able to copolymerize with the aromatic vinyl monomers and the methacrylate monomers.
- additional monomers include, but are not limited to, maleic anhydride, maleic acid and its mono and diesters, fumaric acid and its mono and diesters, vinyl acetate and the esters of vinyl alcohol, ⁇ -olefmes and diene monomers, vinyl chloride, acrylonotrile.
- the modifier polymer does not include nitrile or acrylonitrile monomers. This is advantageous because many nitrile and acrylonitrile monomers are toxic.
- the high-flow ⁇ thermoplastic compositions may optionally include other additives such as impact modifiers, inorganic or mineral fillers, reinforcing agents, pigments, dyes, and fire retardants.
- impact modifiers for thermoplastic compositions are well known in the art and are commercially available.
- impact modifiers include thermoplastic elastomer based modifiers, including acrylic impact modifiers, such as methyl methacrylate-butadiene-styrene (MBS) impact modifiers, styrene-butadiene (SB) impact modifiers, styrene-butadiene-styrene (SBS) impact modifiers, and styrene- isoprene-styrene (SIS) impact modifiers.
- MFS methyl methacrylate-butadiene-styrene
- SB styrene-butadiene
- SBS styrene-butadiene-styrene
- SIS styrene- isoprene-styrene
- thermoplastic resins such as polycarbonate resins
- examples • include, but are not limited to, glass fibers, carbon fibers, glass beads, carbon black, calcium sulfate, calcium carbonate, calcium silicate, titanium oxide, alumina silica asbestos, talc, clay mica and quartz powder. In addition, a mixture of any of the above may be used.
- thermoplastic compositions are also well known. Perhaps the most popular of these are phosphate and phosphonate based flame retardants. Examples of well-known flame retardants from the prior art include organic phosphate esters such as triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, resorcinol diphenyl phosphate and various other oligomeric phosphates. Tetraflurorethylene polymers are also used in combination with such phosphate esters in order to provide flame retardancy. Many of these phosphorous based flame retardants incidentally act as flow enhancers. Unfortunately, while these phosphate based flame retardants can improve flame retardancy and flow, at high .
- compositions of the present invention over the compositions of the prior art is that by the using flow modifiers disclosed herein, the amount of phosphate flame retardant maybe reduced without sacrificing flame retardancy, impact strength, or heat resistance.
- Another advantage of the flow modifiers of the present invention is that they are flame neutral, that is, they neither improve nor decrease the flame retardancy of the compositions.
- Another advantage of the flow modifiers of the present invention is that they do not increase dripping under UL-94 testing even in the highest flow • compositions.
- the flow modifiers may be used in either flame retardant. or non- flame retardant compositions.
- thermoplastics of the present invention are well suited for a variety of applications.
- examples of products that maybe manufactured from the thermoplastics include, but are not limited to, housings for electronic equipment, business machines, such as computers, momtors, keyboards, printers, fax machines, telephones, notebook and handheld computers, and cameras, power plugs, electrical switches and controls, and telecommunication connectors and switches.
- the compositions may be used to make a variety of parts in the automotive industry, including, control and indicator panels, mirrors, headlamps, automotive bumpers and fascia, tractor hoods and panels, lawn mower decks, lawn and garden tool housings, and various other large structural parts.
- Another aspect of the invention provides a method for increasing the flow of a • host polymer by mixing therewith a flow modifier polymer.
- the modifier polymer is made from at least one (meth)acrylate monomer and optionally at least one vinyl aromatic monomer.
- Suitable host polymers and flow modifier polymers are described in detail above.
- the low molecular weight flow modifier polymers may by produced according to standard techniques well known in the art. Such techniques include, but are not limited to, continuous bulk polymerization processes, batch, and semi-batch polymerization processes.
- a production technique that is well suited for the low molecular weight flow modifier polymers is described in US Patent 6,605,681, the entire disclosure of which is incorporated herein by reference. Briefly, this process involves continuously charging into a reactor at least one (meth)acrylate monomer, optionally at least one vinyl aromatic monomer, and optionally one or more other monomers that are polymerizable with the vinyl aromatic and (meth)acrylate
- the proportion of monomers charged into the reactor may be the same as those proportions that go into the flow modifier polymers discussed above.
- the reactor may be charged with only (meth)acrylate monomers.
- the reactor may be charged with from about 1 to about 99 weight percent (meth)acrylate monomer and from about 99 to about 1 weight percent vinyl aromatic monomer. This includes embodiments where the reactor is charged with from about 1 and about 70 weight percent of (meth)acrylate monomers and from about 30 to about 99 weight percent vinyl aromatic monomers, and further includes embodiments where the reactor is charged with from about 1 to about 80 weight percent (meth)acrylate monomers and from about 20 to about 99 weight percent vinyl aromatic monomers.
- the reactor is also charged with from about 0 to about 99 weight percent of at least one other monomer or a mixture of other monomers capable of polymerizing with the (meth)acrylate monomers and or the vinyl aromatic monomers. This includes embodiments where the reactor is charged with about 1 to about 70 weight percent of at least one other monomer or a mixture of other monomers capable of polymerizing with the (meth)acrylate monomers and/or the vinyl aromatic monomers.
- the reactor may also optionally be charged with at least one free radical polymerization initiator and/or one or more solvents. Examples of suitable initiators and solvents are provided in US patent 6,605,681.
- the initiators suitable for carrying out the process according to the present invention are compounds which decompose thermally into radicals in a first order reaction, although this is not a critical factor.
- Suitable initiators include those with half-life periods in the radical decomposition process of about 1 hour at temperatures greater or equal to 90°C and further include those with half-life periods in the radical decomposition process of about 10 hours at temperatures greater or equal to 100°C. Others with about 10 hour half-lives at temperatures significantly lower than 100°C may also be used.
- Suitable initiators are, for example, aliphatic azo compounds such as 1-t-amylazo-l- cyanocyclohexane, azo-bis-isobutyronitrile and 1-t-butylazo-cyanocyclohexane, 2,2'- azo-bis-(2-methyl)butyronitrile and peroxides and hydroperoxides, such as t- butylperoctoate, t-butyl perbenzoate, dicumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-amyl peroxide and the like.
- aliphatic azo compounds such as 1-t-amylazo-l- cyanocyclohexane, azo-bis-isobutyronitrile and 1-t-butylazo-cyanocyclohexane, 2,2'- azo-bis-(2-methyl)butyronitrile and
- di-peroxide initiators may be used alone or in combination with other initiators.
- Such di-peroxide initiators include, but are not limited to, l,4-bis-(t-butyl peroxycarbo)cyclohexane, l,2-di(t-butyl peroxy)cyclohexane, and 2,5-di(t-butyl peroxy)hexyne-3, and other similar initiators well known in the art.
- the initiators are di-t-butyl peroxide and di-t-amyl peroxide are particularly suited for use in the invention.
- the initiator may be added with the monomers.
- the initiators may be added in any appropriate amount, but preferably the total initiators are added in an amount of about 0.0005 to about 0.06 moles initiator(s) per mole of monomers in the feed.
- initiator is either admixed with the monomer feed or added to the process as a separate feed.
- the solvent may be fed into the reactor together with the monomers, or in a separate feed.
- the solvent may be any solvent well known in the art, including those that do not react with the epoxy functionality on the epoxy-functional acrylic monomer(s) at the high temperatures of the continuous process described herein. The proper selection of solvent may decrease the gel particle formation during the continuous, high temperature reaction of the present invention.
- Such solvents include, but are not limited to, xylene, toluene, ethyl-benzene, Aromatic- lOO ⁇ , Aromatic 150 ⁇ , Aromatic 200 ⁇ (all Aromatics available from Exxon), acetone, methylethyl ketone, methyl amyl ketone, methyl-isobutyl ketone, n-methyl pyrrolidinone, and combinations thereof.
- the solvents are present in any amount desired, taking into account reactor conditions and monomer feed. In one embodiment, one or more solvents are present in an amount of up to 40% by weight, up to 15% by weight in a certain embodiment, based on the total weight of the monomers.
- the reactor is maintained at an effective temperature for an effective period of time to cause polymerization of the monomers to produce a polymeric product from the monomers.
- the continuous process of the present invention allows for a short residence time within the reactor.
- the residence time is generally less than one hour, and may be less than 15 minutes. In another embodiment, the residence time is generally less than 30 minutes, and may be less than 20 minutes.
- the process of the present invention may be conducted using any type of reactor well-known in the art, in a continuous configuration.
- reactors include, but are not limited to, continuous stirred tank reactors ("CSTRs"), tube reactors, loop reactors, extruder reactors, or any reactor suitable for continuous operation.
- CSTRs continuous stirred tank reactors
- tube reactors tube reactors
- loop reactors loop reactors
- extruder reactors or any reactor suitable for continuous operation.
- a form of CSTR which has been found suitable for carrying out the process is a tank reactor provided with cooling coils and/or cooling jackets sufficient to remove any heat of polymerization not taken up by raising the temperature of the continuously charged monomer composition so as to maintain a preselected temperature for polymerization therein.
- a CSTR may be provided with at least one, and usually more, agitators to provide a well-mixed reaction zone.
- Such CSTR may be operated at varying filling levels from 20 to 100% full (liquid full reactor LFR). In one embodiment the reactor is more than 50% full but less than 100%o full. In another embodiment the reactor is 100% liquid full.
- the low molecular weight flow modifier polymers of the present invention possess high thermal stability. Therefore, it is possible to process these polymers at higher temperatures than other flow modifiers.
- the high thermal stability of the flow modifiers of this invention is related to the fact that the process of the present invention is itself conducted in a continuous process at high temperatures. In one embodiment, the temperatures range from about 180°C to about 350°C, this included embodiments where the temperatures range from about 190°C to about 325 °C, and more further included embodiment where the temperatures range from about 200°C to about 300°C. In another embodiment, the temperature may range from about 200°C to about 275°C. Due to their high temperature synthesis the flow modifiers of this invention show high thermal stability when used later in compounding and molding applications in engineering thermoplastic compositions processed at similar temperature ranges. In contrast other flow modifiers presently available undergo degradation and gas evolution at these conditions.
- thermogravimetric analysis TGA monitors the weight loss of a polymeric specimen as a function of temperature.
- the flow modifiers of the present invention are characterized by less than a 10 percent weight loss at the highest processing temperatures utilized in the processing of the modified thermoplastic compositions. This includes embodiments where the weight loss of the flow modifier is less than 5 percent and further includes embodiments where the weight loss of the flow modifier is less than 3 percent at the highest processing temperature for the modified thermoplastic compositions. In some embodiments, the weight loss of the flow modifier is less than 1 percent at the highest processing temperature for the modified thermoplastic compositions. In some embodiments, zero weight loss of the flow modifier is measured at the highest processing temperature for the modified thermoplastic compositions.
- the host polymers, the flow modifiers, and any optional ingredients can be blended according to any conventional techniques.
- the components may be blended in a mixing and compounding apparatus, including, but not limited to, a single or twin screw extruder, mixing roll, ribbon blender or co-kneader.
- the thermoplastic compositions may be molded by various well-known molding techniques, such as injection molding, blow molding, compression molding, and extrusion molding.
- the highest processing temperature realized during processing of the flow modified thermoplastic compositions will be at least 180°C, and, in some cases, will be from about 180 to about 350°C. This includes instances where the highest processing temperature realized is at least 190°C, and in some cases is from about 190 to about 325°C.
- the maximum processing temperature is at least 200°C, and may be from about 200 to about 300°C, or even from about 200 to about 275°C.
- STY styrene
- BMA butyl methacrylate
- MMA methyl methacrylate
- GMA glycidyl methacrylate
- BA butyl acrylate
- DTBP di-tertiary butyl peroxide
- A-100 Aromatic 100 solvent (Exxon).
- Example 1 Enhanced Flow Formulations for Transparent Polycarbonate Injection Molding Applications
- polycarbonate Long 141 G.E. Plastics (GEP)
- GEP G.E. Plastics
- Said formulations were injection molded into ASTM test specimens maintaining the barrel and nozzle temperature of the injection molder extruder between 275°C and 280°C, an injection pressure of 9.31 MPa, and the mold temperature was controlled at 88°C.
- Resulting products showed outstanding balance of moldability, impact strength, HDT, mechanical properties and transparency in comparison to the unmodified plastic.
- Example 2 Enhanced Flow and Impact Formulations for Opaque Polycarbonate Injection Molding Applications of Thin Wall Pieces.
- the compound and the unmodified control were then injection molded into a 5x5x1 mm radial flow mold at the abusively high shear rates provided by a 90% injection speed, 8.2 MPa injection pressure and a temperature profile from 280°C to 305°C.
- the moldings showed outstanding moldability and impact resistance without signs of delamination or additive juicing. These compounds are useful in injection molding applications involving high shear (thin wall or large pieces) where high impact and high crack resistance are needed, such as housings for electronic devices. Comparative results are shown below in Table 3. Table 3. Evaluation of Flow Modifiers in Thin Wall Polycarbonate Formulations
- STY styrene
- BMA butyl methacrylate
- BA butyl acrylate
- AMS alpha-methyl styrene
- AA acrylic acid
- MAH maleic anhydride
- DTBP di-tertiary butyl peroxide
- A- 100 Aromatic 100 solvent (Exxon)
- MAK methyl amyl ketone.
- Example 3 Enhanced Flow Formulations for PC/ABS (low ABS) Injection Molding Applications with Outstanding Balance of Flow, Vicat Softening Temperature (VST) and Impact Resistance To obtain enhanced flow formulations 95 to 97 parts of a low ABS content
- PC/ABS blend (Cycoloy 1200 from GEP) were dry-blended and compounded using a ⁇ temperature profile from 260°C to 275°C with 3 to 5 parts of flow modifiers E, F and G of this invention.
- Said formulations were injection molded into ASTM test specimens using a temperature profile from zone 1 to nozzle between 275 °C and 280°C at an injection pressure of 5.17 MPa. Mold temperature was controlled at 88°C.
- the melt viscosity of said formulations were determined by capillary rheometry, using the method described in ASTM D3835-96.
- a Goettfert Rheolgraph 2003 Capillary Rheometer was used, having a 12mm barrel diameter, a 0.5mm inner diameter, a die length of 20mm, and a 180° die entry angle. The measurements were performed at 300°C, using a six minute preheating time. The resulting products showed outstanding balance of moldability, impact strength, and VST, in comparison to the unmodified plastic. These compounds are useful in injection molding applications involving high shear (thin wall or large pieces) where outstanding impact resistance and VST are requirements. Such applications include housings for mobile phones and other electronic devices. Comparative results are shown below in Table 5.
- Example 4 Enhanced Flow Formulations for PC/ABS (high ABS) Injection Molding Applications with Outstanding Balance of Flow, VST and Impact Resistance
- Example 5 Enhanced Flow Formulations for PC/ABS (low ABS) Fire Retardant Injection Molding Applications.
- Said formulations were injection molded using a Battenfeld 29M ton injection Molding Machine into ASTM test specimens maintaining the barrel and nozzle temperature of the injection molder extruder between 240°C and 265°C, an injection pressure of 14.0 MPa, and the mold temperature was controlled at 54°C.
- the molded parts showed an outstanding balance of moldability, impact strength, VST, and mechanical properties in comparison to the unmodified plastic without signs of delamination or juicing. These compounds are useful in injection molding applications requiring high shear (thin wall or large pieces) and fire retardancy, such as housings for electronic devices, personal care items, and household appliances. Comparative results are shown below in Table 7. Table 7. Evaluation of Flow Modifiers in FR PC/ABS (low ABS) Formulations
- Example 6 Enhanced Flow Formulations for PC/ABS (high ABS) Fire Retardant Injection Molding Applications.
- the molded parts showed an outstanding balance of moldability, impact strength, VST, and mechanical properties in comparison to the unmodified plastic without signs of delamination or juicing. These compounds are useful in injection molding applications requiring high shear (thin wall or large pieces) and fire retardancy, such as housings for electronic devices, personal care items, and household appliances. Comparative results are shown below in Table 8. Table 8. Evaluation of Flow Modifiers in FR PC/ABS (high ABS) Formulations
- flow modifiers C and F of this invention were evaluated along with two different styrene-acrylic flow modifiers, labeled FM J and K below, which were designed, and then prepared in a 2 gallon free radical continuous polymerization reactor system according to the teachings of US patent 6,605,681.
- the specific synthesis conditions and characterization parameters are given in Table 9 below.
- STY styrene
- MMA methyl methacrylate
- BA butyl acrylate
- IPA iso-propyl alcohol
- DTAP di-tertiary amyl peroxide
- DTBP di-tertiary butyl peroxide
- A- 100 Aromatic 100 solvent (Exxon).
- Example 7 Enhanced Flow Formulations for Polyester Injection Molding Applications
- PBT ⁇ oly(butylene terephthalate)
- Valox 325 from GEP
- Said formulations were injection molded into ASTM test specimens using a temperature profile from zone 1 to nozzle between 270°C and 280°C at an injection pressure of 4.14 MPa, mold temperature was controlled at 65°C.
- the resulting products show outstanding balance of moldability, impact strength, VST, and mechanical properties in comparison to the unmodified plastic.
- Example 8 Enhanced Flow Formulations for Glass Fiber Reinforced Polyester Injection Molding Applications
- flow modifier K of this invention was evaluated along with three other styrene-acrylic flow modifiers, labeled FM L, M, and N below, which were designed, and then prepared in a 2 gallon free radical continuous polymerization reactor system according to the teachings of U.S. Patent Application 09/354,350.
- the specific synthesis conditions and characterization parameters are given in Table 12 below.
- Example 9 Enhanced Flow Formulations for Polyamide Injection Molding Applications. To obtain enhanced flow formulations 95 and 97 parts of polyamide 6
- Example 10 Enhanced Flow Formulations for Polyamide Injection Molding Applications.
- Example 11 Enhanced Flow Formulations for Reinforced Polyamide Injection Molding Applications To obtain enhanced flow formulations 82 parts of polyamide 6,6 (PA 6,6)
- flow modifiers A and H of this invention was evaluated along with another styrene-acrylic flow modifier, labeled FM O below, which was designed, and then prepared in a 2 gallon free radical continuous polymerization reactor system according to the teachings of U.S. Patent 6,605,681.
- Example 12 Enhanced Flow Formulations for Poly(phenylene ether) Based Blends for Injection Molding Applications
- styrenic blend Noryl N190, GEP
- styrenic blend Noryl N190, GEP
- Said compositions were injection molded using a Meiki 50 ton injection molding machine into ASTM test specimens maintaining the barrel and nozzle temperature of the injection molder between 230°C and 250°C, an injection pressure of 0.82 MPa, and the mold temperature was controlled at 40°C.
- Example 13 Enhanced Flow Formulations for Transparent-ABS Injection Molding Applications To obtain enhanced flow formulations 100 parts of transparent-ABS (Starex
- CT- 0520 from Cheil Chemicals
- flow modifiers J, P, Q, and R of this invention were formulated, dry-blended with 3 to 9 parts of flow modifiers J, P, Q, and R of this invention and then compounded in a 30 mm twin screw extruder using a temperature profile from 180°C to 200°C.
- Said formulations were injection molded into ASTM test specimens using a DM Mekei Co, M-50A injection molding machine (50 metric tons of clamping force) fitted with a 28 mm screw.
- the temperature profile used from zone 1 to nozzle was controlled between 200°C and 190°C.
- the resulting compounds showed outstanding MFI increases.
- the resulting molding products showed outstanding balance of moldability, impact strength, HDT, mechanical properties and transparency in comparison to the unmodified plastic.
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE60330042T DE60330042D1 (en) | 2002-12-10 | 2003-11-18 | THERMOPLASTIC CONSTRUCTION COMPOSITION WITH HIGH FLOW AND PRODUCTS MANUFACTURED THEREFROM |
BR0317090-0A BR0317090A (en) | 2002-12-10 | 2003-11-18 | Engineered high flow thermoplastic compositions and fabricated products thereof |
EP03786872A EP1570001B1 (en) | 2002-12-10 | 2003-11-18 | High flow engineering thermoplastic compositions and products made therefrom |
CA2508794A CA2508794C (en) | 2002-12-10 | 2003-11-18 | High flow engineering thermoplastic compositions and products made therefrom |
JP2004559140A JP2006509862A (en) | 2002-12-10 | 2003-11-18 | High flow engineering thermoplastic compositions and products produced therefrom |
AU2003295672A AU2003295672B2 (en) | 2002-12-10 | 2003-11-18 | High flow engineering theremoplastic compositions and products made therefrom |
AT03786872T ATE448275T1 (en) | 2002-12-10 | 2003-11-18 | HIGH FLOW THERMOPLASTIC CONSTRUCTION RESIN COMPOSITION AND PRODUCTS MADE THEREFROM |
MXPA05006179A MXPA05006179A (en) | 2002-12-10 | 2003-11-18 | High flow engineering theremoplastic compositions and products made therefrom. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US43226902P | 2002-12-10 | 2002-12-10 | |
US60/432,269 | 2002-12-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004052991A1 true WO2004052991A1 (en) | 2004-06-24 |
Family
ID=32507879
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2003/037006 WO2004052991A1 (en) | 2002-12-10 | 2003-11-18 | High flow engineering theremoplastic compositions and products made therefrom |
Country Status (14)
Country | Link |
---|---|
US (1) | US20040108623A1 (en) |
EP (1) | EP1570001B1 (en) |
JP (1) | JP2006509862A (en) |
KR (1) | KR101020353B1 (en) |
CN (1) | CN1723247A (en) |
AT (1) | ATE448275T1 (en) |
AU (1) | AU2003295672B2 (en) |
BR (1) | BR0317090A (en) |
CA (1) | CA2508794C (en) |
DE (1) | DE60330042D1 (en) |
ES (1) | ES2334910T3 (en) |
MX (1) | MXPA05006179A (en) |
TW (1) | TW200418925A (en) |
WO (1) | WO2004052991A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005121245A1 (en) * | 2004-06-08 | 2005-12-22 | Lanxess Deutschland Gmbh | Molding compounds based on a thermoplastic polyester having improved flowability |
JP2006257126A (en) * | 2005-03-15 | 2006-09-28 | Teijin Chem Ltd | Flame-retardant aromatic polycarbonate resin composition |
CN101155875B (en) * | 2005-04-06 | 2012-07-04 | 朗盛德国有限责任公司 | Molding compounds based on a thermoplastic polycarbonate |
US9353216B2 (en) | 2011-05-19 | 2016-05-31 | Mitsubishi Gas Chemical Company, Inc. | High-fluidity polycarbonate copolymer, process for production highly polymerized aromatic polycarbonate resin and aromatic polycarbonate compound |
WO2019201784A1 (en) | 2018-04-16 | 2019-10-24 | Ineos Styrolution Group Gmbh | Ultra-high flow acrylonitrile butadiene styrene copolymer compositions |
Families Citing this family (64)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2428173B1 (en) | 2001-09-24 | 2014-07-16 | Applied Medical Resources Corporation | Obturator |
EP1503677B1 (en) | 2002-05-16 | 2011-05-04 | Applied Medical Resources Corporation | Cone tip obturator |
WO2005032348A2 (en) | 2003-10-03 | 2005-04-14 | Applied Medical Resources Corporation | Bladeless optical obturator |
EP2545871B1 (en) | 2004-06-29 | 2015-02-11 | Applied Medical Resources Corporation | Insufflating optical surgical instrument |
US7955674B2 (en) | 2005-03-02 | 2011-06-07 | Eastman Chemical Company | Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
US7959836B2 (en) | 2005-03-02 | 2011-06-14 | Eastman Chemical Company | Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol |
US7812112B2 (en) * | 2005-06-17 | 2010-10-12 | Eastman Chemical Company | Outdoor signs comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US20100184940A1 (en) * | 2005-03-02 | 2010-07-22 | Eastman Chemical Company | Polyester Compositions Which Comprise Cyclobutanediol and Certain Thermal Stabilizers, and/or Reaction Products Thereof |
US7959998B2 (en) | 2005-03-02 | 2011-06-14 | Eastman Chemical Company | Transparent, oxygen-scavenging compositions containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
WO2007053548A2 (en) * | 2005-10-28 | 2007-05-10 | Eastman Chemical Company | Polyester compositions comprising minimal amounts of cyclobutanediol |
JP4817678B2 (en) * | 2005-03-11 | 2011-11-16 | 帝人化成株式会社 | Light highly reflective aromatic polycarbonate resin composition |
JP4817679B2 (en) * | 2005-03-11 | 2011-11-16 | 帝人化成株式会社 | Antistatic aromatic polycarbonate resin composition |
JP4817680B2 (en) * | 2005-03-11 | 2011-11-16 | 帝人化成株式会社 | Glass-reinforced polycarbonate resin composition |
JP2006249292A (en) * | 2005-03-11 | 2006-09-21 | Teijin Chem Ltd | Polycarbonate resin composition |
JP4870367B2 (en) * | 2005-03-11 | 2012-02-08 | 帝人化成株式会社 | Reinforced aromatic polycarbonate resin composition |
JP4817681B2 (en) * | 2005-03-15 | 2011-11-16 | 帝人化成株式会社 | Aromatic polycarbonate resin composition |
JP4817684B2 (en) * | 2005-03-16 | 2011-11-16 | 帝人化成株式会社 | Polycarbonate resin composition |
JP4817685B2 (en) * | 2005-03-17 | 2011-11-16 | 帝人化成株式会社 | Aromatic polycarbonate resin composition |
US7704605B2 (en) | 2006-03-28 | 2010-04-27 | Eastman Chemical Company | Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein |
US7794644B2 (en) * | 2005-10-05 | 2010-09-14 | Applied Medical Resources Corporation | Thin-walled optical obturator |
US20100087574A1 (en) * | 2005-10-28 | 2010-04-08 | Emmett Dudley Crawford | Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom |
US20070106054A1 (en) * | 2005-10-28 | 2007-05-10 | Crawford Emmett D | Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom |
US8586701B2 (en) | 2005-10-28 | 2013-11-19 | Eastman Chemical Company | Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US8193302B2 (en) | 2005-10-28 | 2012-06-05 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol and certain phosphate thermal stabilizers, and/or reaction products thereof |
US9598533B2 (en) | 2005-11-22 | 2017-03-21 | Eastman Chemical Company | Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom |
US7737246B2 (en) | 2005-12-15 | 2010-06-15 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol, cyclohexanedimethanol, and ethylene glycol and manufacturing processes therefor |
US9169388B2 (en) | 2006-03-28 | 2015-10-27 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof |
US20080317987A1 (en) * | 2006-07-21 | 2008-12-25 | David Abecassis | Nanocomposite materials for ethanol, methanol and hydrocarbon transportation use and storage |
EP2984993B1 (en) | 2006-10-06 | 2019-09-11 | Applied Medical Resources Corporation | Visual insufflation port |
DE102006057822A1 (en) * | 2006-12-06 | 2008-06-26 | Basell Poliolefine Italia S.R.L. | Solvent-free multilayer laminated material for production of, e.g. floor coverings, includes thermoplastic polymers, flexible material, fibrous intermediate layer comprising plastic and adhesive material, and metal, plastic, or wood |
DE102006060459A1 (en) * | 2006-12-19 | 2008-06-26 | Basell Poliolefine Italia S.R.L. | Multilayer laminated material for Electrical and electronic component, has glass layer, lower substrate layer of plastic, metal or plastic and metal, intermediate layer, plastic fibrous intermediate layer and glass top layer |
GB0711017D0 (en) * | 2007-06-08 | 2007-07-18 | Lucite Int Uk Ltd | Polymer Composition |
US8501287B2 (en) | 2007-11-21 | 2013-08-06 | Eastman Chemical Company | Plastic baby bottles, other blow molded articles, and processes for their manufacture |
JP5635411B2 (en) | 2007-11-21 | 2014-12-03 | イーストマン ケミカル カンパニー | Plastic baby bottles, other blow-molded articles and methods for producing them |
EP2837344B1 (en) | 2008-01-25 | 2016-07-13 | Applied Medical Resources Corporation | Insufflating access system |
JP5357019B2 (en) * | 2008-03-11 | 2013-12-04 | 三菱レイヨン株式会社 | Fluidity improver for aromatic polycarbonate resin and method for producing the same, aromatic polycarbonate resin composition, and molded article |
US8198371B2 (en) | 2008-06-27 | 2012-06-12 | Eastman Chemical Company | Blends of polyesters and ABS copolymers |
DE102008040152A1 (en) | 2008-07-03 | 2010-01-07 | Evonik Röhm Gmbh | rheology modifiers |
EP3545883B1 (en) | 2008-09-29 | 2021-01-13 | Applied Medical Resources Corporation | First-entry trocar system |
US20100099828A1 (en) * | 2008-10-21 | 2010-04-22 | Eastman Chemical Company | Clear Binary Blends of Aliphatic Polyesters and Aliphatic-Aromatic Polyesters |
US8895654B2 (en) | 2008-12-18 | 2014-11-25 | Eastman Chemical Company | Polyester compositions which comprise spiro-glycol, cyclohexanedimethanol, and terephthalic acid |
US8283390B2 (en) * | 2009-09-10 | 2012-10-09 | Sabic Innovative Plastics Ip B.V. | Siloxane block copolymer nanoporous foams, methods of manufacture thereof and articles comprising the same |
KR101334464B1 (en) * | 2010-05-28 | 2013-11-29 | 주식회사 엘지화학 | Resin blend for melting process, pellet and preparation method of resin molded article using the same |
KR101293899B1 (en) * | 2010-09-17 | 2013-08-06 | (주)엘지하우시스 | Low-birefringent resin composition for injection molding and tv panel fabricated using the same |
US8420868B2 (en) | 2010-12-09 | 2013-04-16 | Eastman Chemical Company | Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols |
US8394997B2 (en) | 2010-12-09 | 2013-03-12 | Eastman Chemical Company | Process for the isomerization of 2,2,4,4-tetraalkylcyclobutane-1,3-diols |
US8420869B2 (en) | 2010-12-09 | 2013-04-16 | Eastman Chemical Company | Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols |
JP5759240B2 (en) * | 2011-04-14 | 2015-08-05 | 東洋スチレン株式会社 | Flame retardant styrene resin composition and liquid crystal TV back cover using the same |
US9254148B2 (en) | 2011-05-02 | 2016-02-09 | Applied Medical Resources Corporation | Low-profile surgical universal access port |
CN102391437B (en) * | 2011-10-09 | 2013-04-24 | 深圳市科聚新材料有限公司 | Multi-grafted acrylonitrile-butadiene-styrene (ABS) copolymer and preparation method thereof |
KR20130074427A (en) * | 2011-12-26 | 2013-07-04 | 제일모직주식회사 | Thermoplastic resin composition with excellent flowability and transparency |
TWI450930B (en) * | 2011-12-30 | 2014-09-01 | Chi Mei Corp | Carbonate-based polymer composition and products made from said carbonate-based polymer composition |
JP5884102B2 (en) * | 2012-01-30 | 2016-03-15 | オリヱント化学工業株式会社 | Laser welding resin composition and welded body thereof |
US20130217830A1 (en) | 2012-02-16 | 2013-08-22 | Eastman Chemical Company | Clear Semi-Crystalline Articles with Improved Heat Resistance |
JP6097096B2 (en) * | 2013-03-01 | 2017-03-15 | ウィンテックポリマー株式会社 | Method for producing polybutylene terephthalate resin composition |
KR101342832B1 (en) * | 2013-04-19 | 2013-12-17 | (주)비피케미칼 | Rheology modifier composition comprising acrylic polymer |
US20140370218A1 (en) * | 2013-06-14 | 2014-12-18 | Eastman Chemical Company | Foamed articles with deep undercuts |
EP3303463B1 (en) * | 2015-05-25 | 2019-11-06 | SABIC Global Technologies B.V. | Poly (phenylene ether) composition and article |
CN105131589A (en) * | 2015-08-31 | 2015-12-09 | 宁波海雨新材料科技有限公司 | Gas-assisted molding glass fiber reinforced nylon 6 engineering plastic and preparation method thereof |
US9840989B2 (en) | 2015-11-30 | 2017-12-12 | Ford Global Technologies, Llc | Soft engine cover for intake manifold |
KR102177828B1 (en) * | 2016-12-14 | 2020-11-11 | 주식회사 엘지화학 | Thermoplastic resin composition, method for preparing the resin composition and molding product comprising the resin composition |
CN108864674A (en) * | 2017-05-11 | 2018-11-23 | 上海奥塞尔材料科技有限公司 | Lighting polycarbonate compound and preparation method thereof |
CN109486154B (en) * | 2018-11-27 | 2021-03-23 | 江苏万纳普新材料科技有限公司 | Efficient halogen-free enhanced flame-retardant functional master batch for direct injection molding of PC-ABS (polycarbonate-acrylonitrile butadiene styrene) alloy and preparation method thereof |
CN114369347B (en) * | 2022-02-08 | 2023-12-19 | 北京纳通医学研究院有限公司 | Degradable flow modification auxiliary agent and preparation method and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4740553A (en) * | 1985-10-08 | 1988-04-26 | Denki Kagaku Kogyo Kabushiki Kaisha | Molding composition containing an elastomer-containing styrene resin, a polycarbonate resin, and a polymer of an acrylate monomer possessing environmental stress cracking resistance |
JPH01186312A (en) * | 1988-01-20 | 1989-07-25 | Aron Kasei Co Ltd | Injection molding method |
JP2000129135A (en) * | 1998-10-26 | 2000-05-09 | Sanyo Chem Ind Ltd | Antistatic resin composition |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3948674A (en) * | 1968-04-15 | 1976-04-06 | Monsanto Company | Lubricated thermoplastic resin compositions |
US4286021A (en) * | 1971-01-22 | 1981-08-25 | Rohm And Haas Company | Powder coatings containing copolymer containing isobornyl methacrylate as melt flow modifier |
CA1015084A (en) * | 1972-05-10 | 1977-08-02 | Rohm And Haas Company | Acrylic oligomers as melt flow modifiers of thermoplastic coatings and powders |
JPS602335B2 (en) * | 1974-12-13 | 1985-01-21 | ローム アンド ハース カンパニー | Blend composition of thermoplastic polymer and multiphase acrylic composite polymer |
JPH11181197A (en) * | 1997-10-13 | 1999-07-06 | Arakawa Chem Ind Co Ltd | Flowability improver for polycarbonate and polycarbonate resin composition |
JP3398595B2 (en) * | 1998-05-20 | 2003-04-21 | 出光石油化学株式会社 | Polycarbonate resin composition and equipment housing using the same |
JP4071623B2 (en) | 2000-10-17 | 2008-04-02 | ゼネラル・エレクトリック・カンパニイ | Translucent and transparent polycarbonate thermoplastic resin alloy and method for producing the same |
-
2003
- 2003-11-18 BR BR0317090-0A patent/BR0317090A/en not_active IP Right Cessation
- 2003-11-18 JP JP2004559140A patent/JP2006509862A/en active Pending
- 2003-11-18 CN CNA2003801054259A patent/CN1723247A/en active Pending
- 2003-11-18 AT AT03786872T patent/ATE448275T1/en not_active IP Right Cessation
- 2003-11-18 DE DE60330042T patent/DE60330042D1/en not_active Expired - Lifetime
- 2003-11-18 WO PCT/US2003/037006 patent/WO2004052991A1/en active Application Filing
- 2003-11-18 US US10/707,052 patent/US20040108623A1/en not_active Abandoned
- 2003-11-18 AU AU2003295672A patent/AU2003295672B2/en not_active Ceased
- 2003-11-18 EP EP03786872A patent/EP1570001B1/en not_active Expired - Lifetime
- 2003-11-18 CA CA2508794A patent/CA2508794C/en not_active Expired - Fee Related
- 2003-11-18 MX MXPA05006179A patent/MXPA05006179A/en active IP Right Grant
- 2003-11-18 KR KR1020057010401A patent/KR101020353B1/en active IP Right Grant
- 2003-11-18 ES ES03786872T patent/ES2334910T3/en not_active Expired - Lifetime
- 2003-12-10 TW TW092134854A patent/TW200418925A/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4740553A (en) * | 1985-10-08 | 1988-04-26 | Denki Kagaku Kogyo Kabushiki Kaisha | Molding composition containing an elastomer-containing styrene resin, a polycarbonate resin, and a polymer of an acrylate monomer possessing environmental stress cracking resistance |
JPH01186312A (en) * | 1988-01-20 | 1989-07-25 | Aron Kasei Co Ltd | Injection molding method |
JP2000129135A (en) * | 1998-10-26 | 2000-05-09 | Sanyo Chem Ind Ltd | Antistatic resin composition |
Non-Patent Citations (2)
Title |
---|
DATABASE WPI Section Ch Week 198950, Derwent World Patents Index; Class A18, AN 1989-366552, XP002276331 * |
DATABASE WPI Section Ch Week 200034, Derwent World Patents Index; Class A18, AN 2000-390139, XP002276330 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005121245A1 (en) * | 2004-06-08 | 2005-12-22 | Lanxess Deutschland Gmbh | Molding compounds based on a thermoplastic polyester having improved flowability |
KR100888532B1 (en) | 2004-06-08 | 2009-03-11 | 란세스 도이치란트 게엠베하 | Molding compounds based on a thermoplastic polyester having improved flowability |
JP2006257126A (en) * | 2005-03-15 | 2006-09-28 | Teijin Chem Ltd | Flame-retardant aromatic polycarbonate resin composition |
CN101155875B (en) * | 2005-04-06 | 2012-07-04 | 朗盛德国有限责任公司 | Molding compounds based on a thermoplastic polycarbonate |
US9353216B2 (en) | 2011-05-19 | 2016-05-31 | Mitsubishi Gas Chemical Company, Inc. | High-fluidity polycarbonate copolymer, process for production highly polymerized aromatic polycarbonate resin and aromatic polycarbonate compound |
US10053537B2 (en) | 2011-05-19 | 2018-08-21 | Mitsubishi Gas Chemical Company, Inc. | High-fluidity polycarbonate copolymer, process for production highly polymerized aromatic polycarbonate resin and aromatic polycarbonate compound |
WO2019201784A1 (en) | 2018-04-16 | 2019-10-24 | Ineos Styrolution Group Gmbh | Ultra-high flow acrylonitrile butadiene styrene copolymer compositions |
US11390736B2 (en) | 2018-04-16 | 2022-07-19 | Ineos Styrolution Group Gmbh | Ultra-high flow acrylonitrile butadiene styrene copolymer compositions |
Also Published As
Publication number | Publication date |
---|---|
BR0317090A (en) | 2005-10-25 |
EP1570001B1 (en) | 2009-11-11 |
MXPA05006179A (en) | 2005-08-26 |
EP1570001A1 (en) | 2005-09-07 |
KR101020353B1 (en) | 2011-03-08 |
ES2334910T3 (en) | 2010-03-17 |
DE60330042D1 (en) | 2009-12-24 |
JP2006509862A (en) | 2006-03-23 |
US20040108623A1 (en) | 2004-06-10 |
CN1723247A (en) | 2006-01-18 |
CA2508794C (en) | 2012-09-25 |
KR20050085454A (en) | 2005-08-29 |
AU2003295672B2 (en) | 2008-05-22 |
TW200418925A (en) | 2004-10-01 |
AU2003295672A1 (en) | 2004-06-30 |
CA2508794A1 (en) | 2004-06-24 |
ATE448275T1 (en) | 2009-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2508794C (en) | High flow engineering thermoplastic compositions and products made therefrom | |
JPWO2005030819A1 (en) | Fluidity improver for engineering plastics, thermoplastic resin composition containing the same, and molded article thereof | |
US9382369B2 (en) | Rubber-modified vinyl-based graft copolymer, and thermoplastic resin composition including the same | |
US8383720B2 (en) | Thermoplastic composition | |
JP5107163B2 (en) | Thermoplastic resin composition and injection molded product using the same | |
US10100193B2 (en) | Polymer resin composition and molded article thereof | |
JP2004189805A (en) | Polycarbonate resin composition | |
CN111378268A (en) | Thermoplastic resin composition and molded article formed therefrom | |
TWI478974B (en) | Resin composite | |
KR101492032B1 (en) | Heat-Resistant ABS Resin Composition With Excellent Processability and Resistance for Discoloration at High Temperature and Method for Preparing the Same | |
JP3080217B2 (en) | Thermoplastic copolymer and thermoplastic resin composition using the same | |
JPS62209157A (en) | Thermoplastic resin composition | |
JP3628445B2 (en) | Thermoplastic resin composition | |
JPH0326748A (en) | Thermoplastic resin composition having improved impact resistance | |
JPH08143737A (en) | Thermoplastic resin composition | |
KR101240323B1 (en) | Low gloss thermoplastic resin composition with high weatherability and high thermo-resistance | |
JPH06299021A (en) | Thermoplastic resin composition | |
KR101466275B1 (en) | Thermoplastic resin composition | |
JPH02263852A (en) | Low lustrous thermoplastic resin composition | |
JPH0726100A (en) | Flame-retardant resin composition | |
JPH1017747A (en) | Thermoplastic resin composition | |
JPH04348158A (en) | Resin composition having excellent matte effect | |
JPS6218458A (en) | Creep-and heat-resistant thermoplastic resin composition | |
JPS63135445A (en) | Polyester resin composition | |
JPH0726093A (en) | Flame-retardant resin composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2003786872 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2003295672 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2508794 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 20038A54259 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2005/006179 Country of ref document: MX Ref document number: 1020057010401 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2004559140 Country of ref document: JP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020057010401 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 2003786872 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: PI0317090 Country of ref document: BR |