WO2010027351A1 - Articles moulés par injection assistée par un fluide et procédé associé - Google Patents

Articles moulés par injection assistée par un fluide et procédé associé Download PDF

Info

Publication number
WO2010027351A1
WO2010027351A1 PCT/US2008/074994 US2008074994W WO2010027351A1 WO 2010027351 A1 WO2010027351 A1 WO 2010027351A1 US 2008074994 W US2008074994 W US 2008074994W WO 2010027351 A1 WO2010027351 A1 WO 2010027351A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
amount
weight
terephthalate
fluid
Prior art date
Application number
PCT/US2008/074994
Other languages
English (en)
Inventor
Kenneth Leon Price
Original Assignee
Ticona, Llc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ticona, Llc. filed Critical Ticona, Llc.
Priority to PCT/US2008/074994 priority Critical patent/WO2010027351A1/fr
Publication of WO2010027351A1 publication Critical patent/WO2010027351A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/1703—Introducing an auxiliary fluid into the mould
    • B29C45/1704—Introducing an auxiliary fluid into the mould the fluid being introduced into the interior of the injected material which is still in a molten state, e.g. for producing hollow articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0094—Condition, form or state of moulded material or of the material to be shaped having particular viscosity

Definitions

  • Semi-crystalline polymers are useful as engineering thermoplastics because they possess advantageous chemical, physical and electrical properties.
  • Semi- crystalline thermoplastic polymers for instance, can be readily processed by thermal means and formed into numerous and different shapes.
  • thermoplastic polymers can be formed into various articles through one of many different molding processes such as extrusion, rotational molding, blow molding, and injection molding.
  • fluid-assisted injection molding One particular type of injection molding that is used to produce plastic articles is typically referred to in the art as fluid-assisted injection molding.
  • a molten polymer composition is injected into a mold in conjunction with a fluid, such as a gas.
  • the fluid is injected into the mold under pressure placing a force on the molten polymer composition.
  • the fluid not only forces the polymeric composition into the extremities of the mold, but also creates an internal hollow cavity or void space in the resulting article.
  • a single fluid can be introduced into the mold or multiple fluids.
  • a gas is injected into the mold followed by a liquid. The fluid maintains pressure against the polymeric composition until the polymeric composition substantially cools. Once the article is cooled, the fluid pressure is reduced and the article is removed from the mold.
  • the fluid provides numerous benefits. For instance, by forming a hollow cavity or void on the interior of the article, less plastic is used to produce the article and the resulting article is lighter.
  • the fluid can also be used to speed up the cycle time or the time it takes to produce the article.
  • the fluid also forces the polymer composition into the different parts of the mold and potentially improves the surface characteristics of the resulting article.
  • the present disclosure is directed to further improvements in fluid-assisted injection molding processes.
  • fluid-assisted injection molding can produce products having relatively favorable surface characteristics, pitting on the surface still remains a problem, especially when producing fiber reinforced articles.
  • the present disclosure is directed particularly to the production of fluid-assisted injection molding articles that have reduced surface imperfections, such as pits or glass fiber on the surface.
  • the present disclosure is directed to improved fluid-assisted injection molded articles and to corresponding processes for producing the articles. More particularly, the present disclosure is directed to a fluid-assist injection molded article having low surface imperfections by way of a combination of increased gloss and low incidence of surface pits.
  • the fluid-assist molded article is molded from a composition comprising particular polyester(s) and from 10 wt.% to 25 wt.%, preferably from 10 wt.
  • polyester polymers include from 99% to 60% by weight a polyethylene terephthalate polymer characterized in that in addition to terephthalic acid and/or napthalenedicarboxylic acid there may also be from 0.25 mol% to 10 mol% (based on total acid content), such as from about 2.5 mol% to about 10 mol%, of isophthalic acid and/or 2,6- napthalene dicarboxylate including combinations; and from 1 wt.% to 40 wt.% of a second polyester polymer selected from polybutylene terephthalate, polytrimethylene terephthalate, polycyclohexylene dimethyl
  • the filled polyester compositions defined herein being processed under fluid- assist injection conditions to result in hollow molded articles showing significant and unexpected improvement in surface quality, as measured by instrumented gloss readings and reduced surface imperfections as evaluated by ImagePro® digitized micrograph analysis of the exterior molded surface of the formed article which is shaped by the interior mold cavity.
  • the invention further provides a balance to minimize sacrifices in melt flow rate, and the rate of crystallization while providing improved surface quality.
  • Figure 1 is one embodiment of a schematic diagram of a fluid-assisted injection molding process that may be used in accordance with the present disclosure.
  • Figures 2 to 12 are micrographs illustrating the surface of samples made in the Examples. Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the present invention.
  • the present disclosure is directed to filled polyester compounds processed via the fluid-assisted injection molding process to make superior shaped articles.
  • the articles in accordance with the invention exhibit dramatically improved surface characteristics compared to controls derived from filled compounds containing PET homopolymer, a PET copolymer only, and embodiments comprising a filled mixture of polyester resins characterized by a major amount of polyester derived from butane diol ("PBT").
  • PBT butane diol
  • a fluid-assisted injection molded article is formed from a filled polymeric composition containing a polymer mixture of a polyethylene terephthalate copolymer and another polyester polymer other than one derived from a diol solely comprised of ethylene glycol.
  • the polymer mixture in one embodiment, may contain a polyethylene terephthalate copolymer in an amount from about 55% by weight to about 99% by weight based on 100% of the total weight of the polyester polymers present.
  • the polyethylene terephthalate copolymer may be present in the polymer mixture in an amount from about 60% to about 90% by weight, such as in an amount from about 65% to about 75% by weight of the total polyester polymers present.
  • the polyethylene terephthalate suitable under the invention is one which exhibits a comparatively slower crystallization half-time versus a PET homopolymer, in the compounded formulation.
  • the crystallization half-time at 220 0 C is 0.32 min.
  • the crystallization half-time at 22O 0 C is 2.35 min.
  • the crystallization half time can be important in delaying the onset of polymer skin formation during the fluid injection stage after the molten compound has been introduced by the short-shot method.
  • a polymer is used having a crystallization half-time of greater than 0.75 min, such as greater than 1.5 min, such as greater than 2 min.
  • the polyester copolymer comprises, but is not limited to the following diacids: terephthalic acid, isophthalic acid, 2,6-napthalenedicarboxylic acid, phthalic acid, adipic acid, sebacic acid, decanedicarboxylic acid, azelaic acid, and cyclohexanedicarboxylic acid; and diols: ethylene glycol, diethylene glycol, propylene glycol, neopentyl glyol, butanediol, pentanediol, hexanediol, 2-methyl-1 ,3- propane diol, bisphenol A, polyethylene glycol and polypropylene glycol, and cyclohexane dimethanol; and combinations of multiple diacids and diols
  • the polyethylene terephthalate may be copolymerized with isophthalic acid.
  • a copolymer of polyethylene terephthalate and isophthalic acid may be used wherein the copolymer is formed from primarily ethylene glycol, terephthalic acid copolymerized with isophthalic acid; the isophthalic acid being present in the copolymer in an amount from about 0.25 mole percent to about 10 mole percent, such as from about 2.5 mole percent to about 7 mole percent, such as from about 3 mole percent to about 6 mole percent.
  • the polymer mixture may further contain another polyester, such as polytrimethylene terephthalate, polypropylene terephthalate, polycyclohexylene dimethyl terephthalate, polybutylene terephthalate, polybutylene napthalate, or mixtures thereof.
  • another polyester such as polytrimethylene terephthalate, polypropylene terephthalate, polycyclohexylene dimethyl terephthalate, polybutylene terephthalate, polybutylene napthalate, or mixtures thereof.
  • One or more of the above polyesters may be contained in the polymer mixture, in one embodiment, in an amount from about 1 % by weight to about 40% by weight with about from 99% to 60% polyethylene terephthalate copolymer, such as from about 10% to about 30% by weight of another polyester and 90% to 70% polyethylene terephthalate of copolymer.
  • polybutylene terephthalate may be used in an amount from about 18% to about 25% by weight, with about 82% to about 75% polyethylene terephthalate copolymer.
  • the other polyester may be present in the polymer mixture in an amount less than about 10% by weight, such as from about 3% by weight to about 1 % by weight.
  • the polymer mixture may be formulated so as to have a melt viscosity at 265°C of less than about 300 Pa-s, such as less than about 250 Pa-s, such as less than about 225 Pa-s, such as even less than about 200 Pa-s.
  • the melt viscosity may be from about 120 Pa-s to about 225 Pa-s at 265°C .
  • the crystallization rate of the polymer mixture can also be adjusted based upon the relative amounts of the components.
  • the crystallization half-time is an indication of the crystallization rate and is measured using a Differential Scanning Calorimeter (DSC) by raising the material above its melt point and then reducing the temperature to a set point and holding it constant.
  • DSC Differential Scanning Calorimeter
  • the time between the onset of crystallization and the peak of crystallization is the crystallization half-time.
  • the crystallization half-time at 220 0 C of the polymer mixture for instance, can be adjusted so as to be between about 0.32 minutes in the case where a PET homopolymer comprises 98.5% of the total polyester polymers present to about 2.35 minutes in the case where a PET copolymer comprises 98.5% of the total polyester polymers present.
  • the composition used to form the fluid-assisted injection molded article can contain various other ingredients and components, for example, platelet shaped filler particles, and mixtures thereof.
  • Exemplary fibers include carbon fibers, wollastonite fibers, and particularly glass fibers.
  • Exemplary platelet fillers are talc and mica.
  • Glass fibers that may be used include, for instance, fibers comprised of lime-aluminum borosilicate glass. Fibers are typically employed in an amount from about 5% to about 50% by weight, such as in an amount from about 10% to about 35% by weight.
  • Chopped fibers can generally have an initial length before compounding of from about 3 mm to about 5 mm.
  • Nonreinforcing fillers may be incorporated into the composition for various purposes.
  • suitable particulate filler include various mineral fillers such as, clay, silica, calcium silicate (wollastonite), mica, calcium carbonate, titanium dioxide, and the like.
  • the fillers may be present in the composition in an amount from about 0.5% to about 50% by weight, such as from about 0.5% to about 15% by weight.
  • One or more coloring and/or opacifying pigments may also be incorporated into the composition, for instance, titanium dioxide, iron oxide and other metallic pigments.
  • Metallic pigments can include, for instance, aluminum pigments, gold pigments, copper pigments, bronze pigments, and the like.
  • Metallic pigments provide the article with a brushed or polished metal appearance. Pigment particles are effective typically in an amount from about 0.1 % to about 5% by weight.
  • compositions further comprise a stabilizer.
  • a stabilizer Preferred are phosphorous-containing stabilizers.
  • the phosphite stabilizer may be obtained from GE Specialty Chemicals under the trade name ULTRANOX 626.
  • a useful phosphite stabilizer is bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite.
  • Other phosphorous-containing stabilizers include phosphates or phosphonates. Phosphorous stabilizers are effectively employed in an amount from about 0.1 % to about 5% by weight, such as in an amount from about 0.1 % to about 1 % by weight.
  • a lubricant can be used in order to facilitate mold release.
  • a lubricant that may be used includes any suitable wax, such as an amide wax, a montan wax, esters of montan wax, stearic acide, stearyl alcohol, stearamides, and the like.
  • articles made according to the present invention can have pits appearing on the exterior surface of the article in an amount less than 3% of the surface area, such as in an amount less than about 2.5% of the surface area, such as in an amount less than about 2% of the surface area, such as in an amount less than about 1.5% of the surface area, such as even in an amount less than about 1 % of the surface area of the article.
  • the above results can be obtained even when the composition used to form the article contains a significant amount of reinforcing fibers or fillers, such as even when the composition contains fibers or reinforcing fillers in an amount greater than 10% by weight.
  • surface imperfections are minimized without adversely interfering with the mechanical properties of the molded part.
  • any suitable fluid-assisted injection molding process may be used to produce articles in accordance with the present disclosure.
  • Fluid-assisted injection molding processes for instance, are disclosed in U.S. Patent No.
  • the polymeric composition is introduced into a mold cavity in the form of a molten stream.
  • One or more fluids at one or more selected locations is injected into the mold cavity and applies pressure against the molten polymeric composition.
  • the pressure of the fluid is controlled so as to create a fluid containing cavity surrounded by the molten polymeric material.
  • the pressurized fluid is then continuously injected into the mold cavity at a controlled rate and pressure causing the molten polymer to flow through the mold space, into all of the extremities of the mold, and be pushed against the walls of the mold cavity.
  • a blowing agent may be premixed with the polymeric material.
  • the rate of introduction of the polymeric material and the rate of injection of the fluid are controlled one relative to the other whereby the pressure of the fluid injected fluctuates with the pressure of the polymeric material. During this process, however, the pressure of the fluid remains higher than the pressure of the polymeric material to ensure a uniform injection during the process.
  • the fluid may be initially introduced at a relatively high pressure in conjunction with the polymeric material in order to create a hollow cavity within the mold.
  • the fluid pressure can then be subsequently decreased as the cavity extends within the inner region of the flowing polymeric material.
  • the injection molding system includes a polymer supply 10 which introduces molten polymeric material into a mold 12 that defines a mold cavity 14.
  • the polymer supply 10 may comprise an extruder that receives the polymer material from a hopper in the form of pellets or a powder.
  • the system can further include at least one fluid supply.
  • the system includes a first fluid supply 16 and a second fluid supply 18.
  • the process involves the step of injecting the molten polymeric material into the mold cavity 14.
  • a first fluid such as a liquid or a gas, is also injected into the mold cavity 14 with the polymeric material. Initially, the fluid assists in the movement of the polymeric material into the mold cavity 14, forcing the polymeric material into the extremities of the mold.
  • the fluid also forms a void or cavity on the interior of the article being formed. Forming a cavity within the polymeric article significantly reduces the amount of polymeric material needed to produce the article, thus reducing the material cost and the weight of the finished part.
  • the fluid entering the mold cavity 14 from the fluid supply 16 can be a gas or a liquid.
  • a gas such as nitrogen, air, or an inert gas.
  • the fluid pressure is maintained against the polymeric material until the polymeric material hardens sufficiently to form a self-supporting article. The pressure can then be reduced and the article may be removed from the mold cavity 14.
  • a first fluid such as a gas
  • a second fluid from the second fluid supply 18 can then be injected into the mold cavity for cooling the polymeric article.
  • the second fluid may comprise a liquid, such as water.
  • the second fluid injected into the mold cavity may comprise a liquid that vaporizes as the polymeric article cools.
  • liquid carbon dioxide can be injected into the mold cavity. Once contacted with the polymeric material, the carbon dioxide evaporates into a vapor which increases the fluid pressure and further forces the polymeric material against the walls of the mold cavity.
  • Fluid-assisted molding processes provide numerous advantages and benefits. As described above, for instance, less polymeric material may be needed to produce the polymeric article. Depending upon the pressure of the fluid against the polymeric material, for instance, an article can be formed having relatively thin walls. For instance, the average wall thickness of the resulting article can be less than 0.5 inches, such as less than 0.25 inches, such as even less than 0.1 inches. The actual wall thickness, however, will depend upon the intended use of the article being formed. Another advantage to fluid-assisted injection molding is that the fluid prevents the polymeric material from shrinking away from the mold cavity during cooling. In addition, the fluid facilitates flowing the polymeric material throughout the mold so that the polymeric material is evenly distributed. In addition, the fluid also can minimize cycle times by serving to cool the polymeric material once injected into the mold cavity.
  • compositions that were formulated and tested include the following:
  • Comparative Sample C is intended to represent a current commercial embodiment that is believed to contain a polyethylene terephthalate copolymer combined with 15% by weight fiberglass.
  • the polyethylene terephthalate copolymer is believed to contain polyethylene terephthalate copolymerized with isophthalic acid.
  • the isophthalic acid is present in the polymer in relatively low amounts, such as in an amount of 2.3 mol%. It is unknown what other additives may be contained in the polymer.
  • Comparative Sample C displays a greater amount of surface pitting, surface fibers and other surface imperfections in comparison to the samples made according to the present disclosure.
  • Example 2 quantitatively demonstrates the reduction of surface pitting when producing fluid-assisted injection molded articles in accordance with the present disclosure.
  • Two polymeric compositions were formulated and formed into fluid-assisted injection molded articles using the process described in Example 1.
  • the polymeric compositions that were formulated included the following:
  • Example 2 To assess the relative area of pitting on the surface the same technique of reflected light optical microscopy presented in Example 1 was used to obtain micrographs. Images were taken from about 3 cm areas from the middle and from the end near the gate of each handle. The micrographs were imaged using Image Pro software. The pits were identified using color sensitivity, with the dark areas representing surface pits. The total area counts for all the pits in the micrograph was divided by the total area count of the entire micrograph to determine the percent relative area of pitting. The results of 12 micrographs were averaged. The following results were obtained.
  • the flexural strength of a sample is defined as its ability to resist deformation under load. More particularly, the flexural test was conducted according to ISO Test No.178 and measures the force required to bend the specimen under three point loading conditions. The flexural strength as well as the flexural modulus were recorded.
  • the test was performed at 23 0 C and measures energy absorbed by the sample material during impact.
  • the impact resistances of a sample were tested according to ISO Test No. 179. The test was performed at 23 0 C and measures energy absorbed by the sample material during fracture.
  • EXAMPLE 3 The mechanical property tests as described in Example 2 were used to test injection molded samples with varying PET/PBT ratios. Tests were also conducted to measure the melt viscosity at 265 0 C and melt flow rate at 265 0 C of the polymeric compositions. The melt viscosity test was performed using a capillary rheometer with an orifice of 1.0160 mm diameter and 15.240 mm length. Melt flow rate was determined according to ISO Test No. 1 133. The compositions tested and the results of the mechanical property tests as well as the physical property tests are shown in the following table.
  • Example further demonstrates how polymer compositions made in accordance with the present disclosure reduce surface pitting in fluid- assisted injection molded samples. Reduction of the microscopic surface pitting is advantageous because it produces a surface that appears to have an improved finish.
  • samples were produced containing primarily a PET copolymer in the polymer mixture.
  • the PET copolymer used contained from 2 mole percent to 4 mole percent isophthalic acid.
  • the type of PET polymer used influences the surface appearance.
  • the data above demonstrates that a mixture of PBT with PET copolymer (isophthalic acid co-monomer) shows an improved surface appearance compared with a PET homopolymer alone and is believed to be improved over certain PET copolymers alone.
  • Table 7 shows a PET homopolymer (see e.g., Comparative N) having a lower pitted area per square millimeter percentage value than the PET copolymer of Sample K, the micrographs were observed to have more glass fibers at the surface and physical observation of the molded samples with the naked eye indicates that Sample K has a superior surface versus Sample N. Micrograph images of each sample were taken using a reflected light optical microscopy. The results were illustrated in Figs. 7 through 12.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention porte sur des articles de moulage par injection assistée par un fluide et sur un procédé de production des articles. Dans un mode de réalisation, un article moulé par injection assistée par un fluide est formé à partir d'une composition polymère contenant un polymère de téréphtalate de polyéthylène en combinaison avec un autre polymère de polyester, tel que le téréphtalate de polybutylène. Le polymère de téréphtalate de polyéthylène peut comprendre un copolymère de téréphtalate de polyéthylène avec de l'acide isophtalique. La composition polymère peut également contenir un agent de renforcement, tel que des fibres de verre. Des produits fabriqués selon la présente invention ont présenté des caractéristiques de surface améliorées de façon remarquable. En particulier, l'érosion sur la surface de l'article moulé est rendue minimale.
PCT/US2008/074994 2008-09-02 2008-09-02 Articles moulés par injection assistée par un fluide et procédé associé WO2010027351A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2008/074994 WO2010027351A1 (fr) 2008-09-02 2008-09-02 Articles moulés par injection assistée par un fluide et procédé associé

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2008/074994 WO2010027351A1 (fr) 2008-09-02 2008-09-02 Articles moulés par injection assistée par un fluide et procédé associé

Publications (1)

Publication Number Publication Date
WO2010027351A1 true WO2010027351A1 (fr) 2010-03-11

Family

ID=40627398

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2008/074994 WO2010027351A1 (fr) 2008-09-02 2008-09-02 Articles moulés par injection assistée par un fluide et procédé associé

Country Status (1)

Country Link
WO (1) WO2010027351A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120082811A1 (en) * 2010-09-30 2012-04-05 Ticona Llc Fluid-Assisted Injection Molded Articles and Process
WO2012135829A1 (fr) * 2011-04-01 2012-10-04 Sabic Innovative Plastics Ip B.V. Articles creux comportant des compositions polyester à renfort de fibres, leurs procédés de fabrication, et leurs utilisations
EP2607043A1 (fr) * 2011-12-20 2013-06-26 Linde Aktiengesellschaft Refroidissement de dioxyde de carbone liquide d'un canal de gaz formé avec un moulage par injection de gaz

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990000466A1 (fr) * 1988-07-11 1990-01-25 Ladney, Michael Procede de moulage par injection et article en plastique creux ainsi produit
EP0612807A2 (fr) * 1993-02-26 1994-08-31 Bayer Ag Masses à mouler thermoplastiques de polytéréphtalate d'alkylène
US5589530A (en) * 1992-12-22 1996-12-31 General Electric Company Stabilization of low molecular weight polybutylene terephthalate/polyester blends with phosphorus compounds
JPH1149937A (ja) * 1997-07-30 1999-02-23 Polyplastics Co ガスアシスト射出成形用樹脂組成物および成形方法
US6579489B1 (en) * 1999-07-01 2003-06-17 Alliance Gas Systems, Inc. Process for gas assisted and water assisted injection molding
EP1449871A2 (fr) * 2003-02-12 2004-08-25 Mitsubishi Engineering-Plastics Corporation Composition thermoplastique ignifuge de resine polyester et produits moules a partir de celle-ci
US20040167277A1 (en) * 2003-02-26 2004-08-26 Chang Moh-Ching Oliver Thermoplastic molding compositions having good properties
EP1645394A2 (fr) * 2004-10-11 2006-04-12 Battenfeld GmbH Procédé et dispositif pour la fabrication de pièces moulées par injection assistée par gaz
WO2007089517A1 (fr) * 2006-01-27 2007-08-09 General Electric Company Compositions de moulage contenant des copolymeres aleatoires de polybutylene terephtalate (pbt) modifie derives de polyetheylene terephtalate (pet)
WO2008033767A1 (fr) * 2006-09-15 2008-03-20 The Coca-Cola Company Outillage sous pression pour le moulage par injection et procédé d'utilisation correspondant
US20080161468A1 (en) * 2006-12-28 2008-07-03 Vishvajit Chandrakant Juikar Polyester molding compositions

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990000466A1 (fr) * 1988-07-11 1990-01-25 Ladney, Michael Procede de moulage par injection et article en plastique creux ainsi produit
US5589530A (en) * 1992-12-22 1996-12-31 General Electric Company Stabilization of low molecular weight polybutylene terephthalate/polyester blends with phosphorus compounds
EP0612807A2 (fr) * 1993-02-26 1994-08-31 Bayer Ag Masses à mouler thermoplastiques de polytéréphtalate d'alkylène
JPH1149937A (ja) * 1997-07-30 1999-02-23 Polyplastics Co ガスアシスト射出成形用樹脂組成物および成形方法
US6579489B1 (en) * 1999-07-01 2003-06-17 Alliance Gas Systems, Inc. Process for gas assisted and water assisted injection molding
EP1449871A2 (fr) * 2003-02-12 2004-08-25 Mitsubishi Engineering-Plastics Corporation Composition thermoplastique ignifuge de resine polyester et produits moules a partir de celle-ci
US20040167277A1 (en) * 2003-02-26 2004-08-26 Chang Moh-Ching Oliver Thermoplastic molding compositions having good properties
EP1645394A2 (fr) * 2004-10-11 2006-04-12 Battenfeld GmbH Procédé et dispositif pour la fabrication de pièces moulées par injection assistée par gaz
WO2007089517A1 (fr) * 2006-01-27 2007-08-09 General Electric Company Compositions de moulage contenant des copolymeres aleatoires de polybutylene terephtalate (pbt) modifie derives de polyetheylene terephtalate (pet)
WO2008033767A1 (fr) * 2006-09-15 2008-03-20 The Coca-Cola Company Outillage sous pression pour le moulage par injection et procédé d'utilisation correspondant
US20080161468A1 (en) * 2006-12-28 2008-07-03 Vishvajit Chandrakant Juikar Polyester molding compositions

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120082811A1 (en) * 2010-09-30 2012-04-05 Ticona Llc Fluid-Assisted Injection Molded Articles and Process
WO2012044362A1 (fr) * 2010-09-30 2012-04-05 Ticona Llc Articles moulés par injection à l'aide d'un fluide et procédés associés
US8883279B2 (en) * 2010-09-30 2014-11-11 Ticona Llc Fluid-assisted injection molded articles and process
WO2012135829A1 (fr) * 2011-04-01 2012-10-04 Sabic Innovative Plastics Ip B.V. Articles creux comportant des compositions polyester à renfort de fibres, leurs procédés de fabrication, et leurs utilisations
EP2607043A1 (fr) * 2011-12-20 2013-06-26 Linde Aktiengesellschaft Refroidissement de dioxyde de carbone liquide d'un canal de gaz formé avec un moulage par injection de gaz

Similar Documents

Publication Publication Date Title
Bourmaud et al. Observation of the structure of a composite polypropylene/flax and damage mechanisms under stress
EP1990369B1 (fr) Composition de resine thermoplastique renforcee par des fibres de verre et article moulé à base de celle-ci
US3368995A (en) Fiberglass reinforced polyethylene terephthalate
KR101896072B1 (ko) 섬유 충전된 폴리에스테르 조성물을 포함하는 중공 성형품, 그 제조 방법 및 그 용도
CA1105637A (fr) Melanges de moulage a base de pbt
JP7277368B2 (ja) ポリアミドの制御された粘度調整のための添加剤
JP5500986B2 (ja) ガラス繊維強化ポリアミド樹脂組成物
US20080076880A1 (en) Polylactic acid based resin molded articles
Teymoorzadeh et al. Biocomposites of wood flour and polylactic acid: Processing and properties
Deshmukh et al. Evaluation of mechanical and thermal properties of Poly (butylene terephthalate)(PBT) composites reinforced with wollastonite
Franciszczak et al. Short-fibre hybrid polypropylene composites reinforced with PET and Rayon fibres–Effects of SSP and interphase tailoring
US8883279B2 (en) Fluid-assisted injection molded articles and process
WO2010027351A1 (fr) Articles moulés par injection assistée par un fluide et procédé associé
Kráčalík et al. Recycled poly (ethylene terephthalate) reinforced with basalt fibres: Rheology, structure, and utility properties
US20210246303A1 (en) Biodegradable polymer blend
CN111171541A (zh) 用于3d打印的改性pc/abs组合物及制备方法
CN111566161A (zh) 用于3d打印的改进的长丝
KR102268612B1 (ko) 표면 특성이 우수한 유리섬유-강화 폴리프로필렌 수지 조성물 및 이를 포함하는 성형품
JP2007091790A (ja) 有機繊維強化ポリ乳酸樹脂組成物および成形品
JPS58101146A (ja) 強化熱可塑性樹脂組成物
Zhou et al. Injection‐molded porous hydroxyapatite/polyamide‐66 scaffold for bone repair and investigations on the experimental conditions
CA1104732A (fr) Compositions de moulage par injection
JP3929889B2 (ja) ポリブチレンテレフタレート樹脂組成物及び成形品
Pisharath et al. Development of the morphology and crystalline state due to hybridization of reinforced toughened nylon containing a liquid‐crystalline polymer
JP2001279070A (ja) ポリエステル樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08821047

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08821047

Country of ref document: EP

Kind code of ref document: A1