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WO1997034709A1 - Procede pour la preparation d'articles thermodurcis avec revetement electrostatique, contenant des charges - Google Patents

Procede pour la preparation d'articles thermodurcis avec revetement electrostatique, contenant des charges Download PDF

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Publication number
WO1997034709A1
WO1997034709A1 PCT/US1997/004148 US9704148W WO9734709A1 WO 1997034709 A1 WO1997034709 A1 WO 1997034709A1 US 9704148 W US9704148 W US 9704148W WO 9734709 A1 WO9734709 A1 WO 9734709A1
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WO
WIPO (PCT)
Prior art keywords
percent
composition
carbon black
article
volume
Prior art date
Application number
PCT/US1997/004148
Other languages
English (en)
Inventor
Richard A. Lundgard
Original Assignee
The Dow Chemical Company
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 The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to AU23287/97A priority Critical patent/AU2328797A/en
Publication of WO1997034709A1 publication Critical patent/WO1997034709A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • B05D1/045—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field on non-conductive substrates

Definitions

  • This invention relates to electrostatically coatable compositions based on thermosetting polymers and, more particularly, relates to such compositions based on sheet molding compound or bulk molding compound.
  • conductive fillers are known for the incorporation of conductive fillers into polymers in order to improve their conductivity for use in electrostatic coating applications.
  • the conductivity of articles made therefrom, as well as the physical, and/or surface appearance properties of the coated articles may be less than desirable for certain applications.
  • the use of conductive primer compositions to prime the article in order to increase its conductivity is also known.
  • the cured primer may have adhesion, surface smoothness, hydrolytic stability, and durability characteristics which are less than desirable for a particular application.
  • such primers typically contain volatile organic solvents, the emission of which during the priming process may be undesirable.
  • U.S. Patent 5,490,893 illustrates a method for making a laminate of a thermoformable conductive material and an article of sheet molding compound (SMC) to provide an SMC-based article having good surface conductivity for use in electrostatic coating applications.
  • SMC sheet molding compound
  • this invention is a process comprising electromotively coating an article molded from a composition comprising a mixture of (a) a thermosetting resin, (b) a filler, a reinforcing material, or a combination thereof, and (c) a carbon black having a primary particle size of less than 125 nm, a nitrogen surface area of at least 50 m 2 /g, and a dibutyl phthalate abso ⁇ tion of at least 50 cc/100 g; wherein (i) component (b) is present in an amount, based on the volume of the composition, of at least 30 percent; (ii) component (c) is present in an amount, based on the weight of the composition, in the range of from 0.15 percent to 3 percent; and (iii) the article has a conductivity of at least 10 ' 4 Siemens/cm (S/cm).
  • thermosetting resins, reinforcing materials, and fillers which may be employed in the composition of the invention include materials which are employed in the preparation of SMC and BMC.
  • thermosetting resins include oligomers or polymers having a molecular weight of greater than 1000 and having pendant functional groups which will react with a crosslinking compound to provide a crosslinked polymer. Further, an article consisting of the crosslinked compound will have a tensile strength of at least 13 MPa (2000 psi).
  • thermosetting resins include unsaturated polyesters, epoxy resins, vinyl ester resins, and thermosetting phenolic resins.
  • Preferred crosslinking compounds include styrene (for polyester resins), amines (for epoxy resins), styrene or vinyl toluene (for vinyl ester resins), and hexamethylenetetraamine (for phenolic resins).
  • unsaturated polyester resins are described in U.S. Patent 5,491 ,184.
  • vinyl ester resins are described in U.S. Patent 5,034,437.
  • epoxy resins and thermosetting phenolic resins are described in the Encyclopedia of Polvmer Science and Engineering. Vol. 6, pp. 322-382 (1988) and Vol. 11 , pp. 45-93 (1988), respectively.
  • the thermosetting resin is preferably employed in an amount, based on the weight of the composition, of at least 5 percent, more preferably at least 8 percent, but is preferably no greater than 50 percent, more preferably no greater than 35 percent.
  • filler refers to particulate matenals having a size in the range of from 0.1 ⁇ m to 50 ⁇ m and an aspect ratio of less than 5, which are wholly
  • inorganic particulate matenals particles of inorganic materials which have been surface- treated with an organic material which increases its wettabihty or dispersibility, carbon blacks (other than the carbon blacks referred as component (c) above), and mixtures thereof.
  • inorganic particulate matenals include glass particles and minerals such as calcium carbonate, dolomite, clays, talc, zinc borate, perlite, vermiculite, alumina trihydrate, l o and solid or hollow glass microspheres.
  • reinforcing material refers to glass fibers, boron fibers, and fibers of extruded polymers, having an aspect ratio greater than 5 and a length in the range of from 0 1 ⁇ m to 3 cm
  • Suitable polymer-based fibers should comprise polymers which are solid at 25°C.
  • polymer-based fibers include nylon, polyester, 15 polybenzoxazole, and aramid fibers. Fibers may be woven or nonwoven, chopped (if desired), or may be used in the form of fiber bundles coated with a sizing agent.
  • the reinforcing material is present in an amount, based on the total volume of the composition, of at least 10 percent by volume, and more preferably at least 15 percent by volume.
  • the combined volume percentage of fillers and reinforcing agents present in the composition is preferably at least 30 percent, more preferably at least 40 percent, but is preferably no greater than 80 percent, more preferably no greater than 70 percent.
  • suitable carbon blacks include particles of carbon having an 25 average primary particle diameter of less than 125 nm, more preferably less than 60 nm.
  • the carbon black is preferably utilized as an aggregate or agglomerate of primary particles, the aggregate or agglomerate having a size of 5 to 10 times the primary particle size
  • the carbon black preferably does not comprise a graphite form of carbon.
  • the carbon black preferably has a nitrogen surface area of at least 125 m7g, more preferably at least 200 m 2 /g, and most preferably at least 750 m7g.
  • the nitrogen surface area of the carbon black may be determined using ASTM Method No. D 3037-93.
  • the dibutyl phthalate absorption of the carbon is preferably at least 75 cc/100 g, more preferably at least 150 cc/100 g, most preferably at least 250 cc 100 g, and may be measured according to ASTM Method No. D 2414-93.
  • the carbon black is preferably employed in an amount, based on the weight of the composition of at least 0.25 percent, but preferably no greater than 2.5 percent, more preferably no greater than 2.0 percent.
  • ingredients which may also be present in the composition include crosslinking compounds; viscosity-modifying agents such as magnesium oxide; initiators; mold release agents; free-radical inhibitors such as benzoquinone or hydroquinone; catalysts such as organic peroxides or hydroperoxides; colorants; and "low profile" thermoplastic additives such as polyvinyl acetate, saturated polyesters, polystyrene, polyacrylates or polymethacrylates, and saturated polyester urethanes.
  • electronically conductive additives other than carbon black may also be utilized in the preparation of the compositions.
  • the carbon black and other conductive additives are employed in an amount sufficient to provide a conductivity of at least 10 " S/cm, but the combined weight percentage of the carbon black and other conductive additives may not exceed 3 percent, based on the weight of the composition.
  • Such additives include conductive salts, carbon fibers, graphite fibers, and particles of conductive polyaniline.
  • the composition may be prepared by any method suitable for mixing the components and curing the thermosetting resin.
  • the resin, fillers, carbon black, curing agents, and all other components except for the reinforcing materials are thoroughly mixed together in two separate batches having similar volumes, one containing the thermosetting agent and the other containing any initiators or crosslinking compounds. Sheets of the batches are extruded separately. The reinforcing material is then deposited between the sheets and compressed, forming a composite of the sheets and the material. The sheets are stored for several days to permit the composition to thicken, and then cut into a suitable shape and heated and/or molded under conditions sufficient to cure the thermosetting resin.
  • the composition preferably has a conductivity of at least 10 9 S/cm, and more preferably at least 10 7 S/cm, but is preferably no greater than 10 ' S/cm.
  • the conductivity of the composition may be measured according to the procedure set forth below.
  • the electronically conductive article can be painted or coated on at least one of its surfaces using any suitable electromotive coating process.
  • electromotive coating process refers to any coating process wherein an electrical potential exists between the substrate being coated and the coating material.
  • electromotive coating processes include electrostatic coating of liquids or powders, electrodeposition ( ⁇ -Coaf ) processes, electromotive vapor deposition, and electroplating processes.
  • the article may be painted or coated with any suitable water-based or organic-based composition (or water/organic mixture), including conductive primer compositions which further enhance the electronic conductivity of the article, or with a solventless organic composition by a powder coating or vapor deposition method.
  • the distinctness-of-image gloss characteristics of the coated article may be measured by ASTM Test Method No. E 430-91.
  • the physical properties of the coated or uncoated article may be determined by ASTM Test Method Nos. D 638 (Tensile Strength, Tensile Elongation, and Tensile Modulus); D 790 (Fiexural Stress, Flexural Strain, Flexural Modulus); D 3763 (Dynatup Impact); and D256 (Notched Izod).
  • coated articles prepared by the process of the invention are useful in any application for coated plastic articles, but are particularly useful as components in applications where the use of a lightweight non-corrosive material is desirable, such as automotive and other transportation applications, as well as static-dissipation and shielding applications.
  • a mixture containing 0.5 weight percent carbon black was prepared by mixing 180 g of an unsaturated polyester resin styrene mixture (Aropol Q-6585, available from Ashland Chemical, which contained 70 percent by weight polyester resin), 120 g of low profile additive (LP40A, a solution of polyvinyl acetate containing styrene, available from Union Carbide), 3.0 g of a peroxybenzoate initiator (Trigonox C, available from Akzo Nobel), 14.1 g of a 38 weight percent dispersion of MgO (PG 9033, available from Plasticolors (Ashtabula, OH)), 14.4 g of a mold release compound (S-1058, zinc stearate, available from Synpro (Cleveland, OH)), 441.3 g of calcium carbonate (Atomite, available from E.C.C. International (Atlanta, GA)), and 6.0 g of a conducting carbon black (BP-2000, available from Cabot
  • Example 1 was repeated using the amounts of carbon black and the particular carbon blacks shown in Table I.
  • “XE 2” refers to Printex XE-2, a conducting carbon black available from Degussa Corp.
  • XC 72 refers to a conducting carbon black available from Cabot Corp.
  • the amount of calcium carbonate was adjusted in order to keep the total volume of carbon black and calcium carbonate the same as in Example 1.
  • the amount of calcium carbonate is 150 parts by weight per 100 parts of polyester resin (which is a 60/40 weight percent mixture of Aropol Q-6585 and LP40A, respectively).
  • the plaques were prepared and tested in accordance with the procedure described in Example 1 , and the results are shown in Table I. Examples 11-14
  • Example 1 was repeated four times using the same carbon black, except that the carbon black was utilized in the amounts of 0.54, 0.81 , 1.1 , and 1.4 percent of the total composition, respectively, for each example, and the amount of calcium carbonate utilized in each example is 150 parts by weight per 100 parts of polyester resin (which is a 60/40 weight percent mixture of Aropol Q-6585 and LP40A, respectively). Plaques of the compositions were prepared and their conductivity tested in accordance with the procedure described in Example 1. The conductivities of the plaques are 8.1 by 10 ⁇ 1.9 by 10 "4 , 3.2 by 10" ⁇ and 1.2 by 10 '3 , respectively.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention se rapporte à un procédé pour appliquer un revêtement électromoteur sur un article moulé à partir d'une composition contenant un mélange, constitué par (a) une résine thermodurcissante, (b) une charge, un matériau de renforcement ou une combinaison de ceux-ci et (c) un noir de carbone ayant une taille de particules primaires inférieure à 125 nm, une superficie azotée d'au moins 50 mm2/g, et une absorbtion du dibutylphtalate d'au moins 50 cm3/100 g. Dans ce procédé, (i) le constituant (b) est présent selon une quantité d'au moins 30 %, calculée sur la base du volume de la composition; (ii) le constituant (c) est présent selon une quantité comprise entre 0,15 et 3 %, calculée sur la base du poids de la composition; et (iii) cet article possède une conductivité d'au moins 10-14 Siemens/cm (S/cm).
PCT/US1997/004148 1996-03-21 1997-03-18 Procede pour la preparation d'articles thermodurcis avec revetement electrostatique, contenant des charges WO1997034709A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU23287/97A AU2328797A (en) 1996-03-21 1997-03-18 Process for the preparation of electromotively coated, thermoset articles containing fillers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US61941396A 1996-03-21 1996-03-21
US08/619,413 1996-03-21

Publications (1)

Publication Number Publication Date
WO1997034709A1 true WO1997034709A1 (fr) 1997-09-25

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AU (1) AU2328797A (fr)
WO (1) WO1997034709A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6001919A (en) * 1998-04-06 1999-12-14 The Budd Company Conductive sheet molding compound
WO2000016911A1 (fr) * 1998-09-24 2000-03-30 The Dow Chemical Company Procede de production d'articles thermodurcis renfermant une charge et revetus par voie electromotrice
DE202018006104U1 (de) 2017-12-08 2019-04-18 Ensinger Gmbh Polymer-basierendes Substrat

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4515710A (en) * 1983-07-18 1985-05-07 Gencorp Inc. In-mold coating composition
EP0283108A1 (fr) * 1987-03-16 1988-09-21 Gencorp Inc. Procédé pour mouler des matières synthétiques renforcées de fibres de verre
EP0622386A1 (fr) * 1993-04-26 1994-11-02 Gencorp Inc. Revêtements conductrices dans une moule
EP0623782A2 (fr) * 1993-04-08 1994-11-09 Robert Bosch Gmbh Réflecteur pour phare de véhicule et procédé pour sa fabrication
EP0685527A1 (fr) * 1994-06-01 1995-12-06 General Electric Company Composition thermoplastique de mélanges compatibilisés de polyphenylenether-polyamide et noir de carbon conducteur d'électricité

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4515710A (en) * 1983-07-18 1985-05-07 Gencorp Inc. In-mold coating composition
EP0283108A1 (fr) * 1987-03-16 1988-09-21 Gencorp Inc. Procédé pour mouler des matières synthétiques renforcées de fibres de verre
EP0623782A2 (fr) * 1993-04-08 1994-11-09 Robert Bosch Gmbh Réflecteur pour phare de véhicule et procédé pour sa fabrication
EP0622386A1 (fr) * 1993-04-26 1994-11-02 Gencorp Inc. Revêtements conductrices dans une moule
US5614581A (en) * 1993-04-26 1997-03-25 Gencorp Inc. Conductive gray in-mold coating
EP0685527A1 (fr) * 1994-06-01 1995-12-06 General Electric Company Composition thermoplastique de mélanges compatibilisés de polyphenylenether-polyamide et noir de carbon conducteur d'électricité

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6001919A (en) * 1998-04-06 1999-12-14 The Budd Company Conductive sheet molding compound
WO2000016911A1 (fr) * 1998-09-24 2000-03-30 The Dow Chemical Company Procede de production d'articles thermodurcis renfermant une charge et revetus par voie electromotrice
US6174427B1 (en) 1998-09-24 2001-01-16 The Dow Chemical Company Process for the preparation of electromotively coated filled thermoset articles
DE202018006104U1 (de) 2017-12-08 2019-04-18 Ensinger Gmbh Polymer-basierendes Substrat
DE102017129353A1 (de) 2017-12-08 2019-06-13 Ensinger Gmbh Polymer-basierendes Substrat sowie Verfahren zu dessen Herstellung
WO2019110181A1 (fr) 2017-12-08 2019-06-13 Ensinger Gmbh Substrat à base de polymère, ainsi que procédé pour la fabrication de ce dernier
US11898056B2 (en) 2017-12-08 2024-02-13 Ensinger Gmbh Polymer-based substrate and method for producing the same

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Publication number Publication date
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