EP0081557A1 - Compose de moulage - Google Patents

Compose de moulage

Info

Publication number
EP0081557A1
EP0081557A1 EP82902032A EP82902032A EP0081557A1 EP 0081557 A1 EP0081557 A1 EP 0081557A1 EP 82902032 A EP82902032 A EP 82902032A EP 82902032 A EP82902032 A EP 82902032A EP 0081557 A1 EP0081557 A1 EP 0081557A1
Authority
EP
European Patent Office
Prior art keywords
molding compound
weight
metal
filler
epoxy resin
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP82902032A
Other languages
German (de)
English (en)
Other versions
EP0081557A4 (fr
Inventor
Richard Brian Allen
Mark Markowitz
Robert Alan Wiercinski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
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 General Electric Co filed Critical General Electric Co
Publication of EP0081557A1 publication Critical patent/EP0081557A1/fr
Publication of EP0081557A4 publication Critical patent/EP0081557A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/681—Metal alcoholates, phenolates or carboxylates
    • C08G59/683—Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/70—Chelates

Definitions

  • U. S. Patent No. 3,812,214 of Mark Markowitz describes certain hardenable epoxy resin compositions. Those compositions generally contain: a) an epoxy resin having more than one 1,2-epoxy group per molecule; b) a metal acetylacetonate having solely metal to oxygen bonds; and, if desired, c) a phenolic accelerator.
  • compositions are said to possess outstanding characteristics including rapid cure rates and storage stability.
  • the patent does not, however, describe the use of these compositions as molding compounds.
  • the present invention is directed to improved epoxy molding compounds.
  • These molding compounds comprise an admixture of: a) from about 5 to 90% by weight of epoxy resin having more than one 1,2-epoxy group per molecule; b) from 0.001 to 5% by weight of metal acetylacetonate having solely metal to oxygen bonds; c) from 0.025 to 30% by weight of phenolic accelerator; and d) from about 10 to 95% by weight of filler, based on the total weight of the composition.
  • These compositions which may be in either solid or liquid form, not only exhibit rapid cure rates and storage stability but also superior strength, shrinkage and allied physical properties important to their use as molding compositions.
  • the epoxy resins employed in this invention can be any 1,2-epoxy resin having more than 1 epoxy group per molecule. They include cycloaliphatic epoxy resins such as 3 ,4-epoxycyclohexylmethyl-3(3,4-epoxy)cyclohexane carboxylate (sold under the trademarks ERL 4221 by Union Carbide Plastics Company or Araldite CY 179 by Ciba Products Company); bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate (sold under the trademarks ERL 4289 by Union Carbide Plastics Company or Araldite CY 178 by Ciba Products Company); vinylcyclohexane dioxide (EEL 4206 made by Union Carbide Plastics Company); bis (2,3-epoxycyclopentyl) ether resins (sold under the trademark ERL 4205 by Union Carbide Plastics Company; 2-(3,4-epoxy) cyclohexyl-5,5 spiro (3,4
  • Epon 1004, etc. by Sheel Chemical Company phenol-formaldehyde novolac polyglycidyl ether epoxy resins (such as those sold under the trademarks DEN 431, DEN 438, and DEN 439 by Dow Chemical Company); epoxy cresol novolacs (such as those sold under the trademarks ECN 1235, ECN 1273, ECN 1280 and ECN 1299 by Ciba Products Company); resorcinol glycidyl ether (such as ERE 1359 made by Ciba Products Company); tetraglycidoxy tetraphenylethane (Epon 1031 made by Shell Chemical Company); glycidyl ester epoxy resins such as diglycidyl phthalate (ED-5661 by Celanese Resins Company); diglycidyl tetrahydrophtha late (Aradite CY 182 by Ciba Products Company) and diglycidyl hexahydrophthalate (Araldite CY 183 made by Ciba Products
  • epoxy resins are well known in the art and are set forth for example, in many patents including U.S. Patent Nos . 2 , 324 , 483 ; 2 , 444 , 333 ; 2 , 494 ,295 and 2 ,511 , 913. Moreover, it often is advantageous to employ mixtures of these epoxy resins, e.g., a glycidyl ether epoxy resin such as Epon 828 with a cycloaliphatic epoxy resin such as ERL 4221 to control the cure rate of the thermosetting resin.
  • a glycidyl ether epoxy resin such as Epon 828
  • a cycloaliphatic epoxy resin such as ERL 4221
  • the present compositions ordinarily contain from about 5 to 90%, more preferably from about 5 to 50%, of epoxy resin by total weight. This amount generally provided optimum properties for the present molding compounds.
  • M is a metal ion and n is 1 to 4 corresponding to the valence number of the metal ion. They are characterized by the presence of solely metal to oxygen bonds. Included within the scope of the invention are metal acetylacetonates in which one or more hydrogen atoms of the methyl or methylene groups are substituted by a halogen atom or by an alkyl, aryl, or an alkaryl substituent.
  • An example of a halogen-substituted metal acetylacetonate is a metal hexafluoroacetylacetonate or trifluoracetylacetonate.
  • an alkyl-substituted acetylacetonate is dipIvaloylethane in which the three hydrogen atoms on each of the methyl groups are substituted with a methyl group.
  • the acetylacetonate hardeners of the present invention should not be confused with similar compositions containing a labile halogen atom.
  • the halogens if present, are attached directly to a carbon atom of the methylene or methyl groups and are therefore extremely stable.
  • Labile halogen atoms in epoxy resin curing agents normally form halogen acids, and the presence of such an ionic constituent in the cured resin would raise many problems, including poor electrical properties and corrosive action on metals.
  • Metal acetylacetonates in which the metal is aluminum, titanium, zinc or zirconium are a particularly preferred class of metal acetylacetonates within the scope of the invention.
  • essentially any metallic acetylacetonate may be used, including those aluminum, barium, beryllium, cadmium, calcium, cerous, chromic, cobaltic, cobaltous, cupric, ferric, ferrous, gallium, hafnium, indium, lead, lithium, magnesium, manganic, manganous, molybdenum, molybdenyl, nickel, palladium, platium, potassium, rhodium, rubidium, ruthenium, sodium, strontium, thallium, thorium, titanium, tungstyl, uranyl, vanadium, vanadyl, zinc, and zirconium.
  • Acetylacetonates of the rare earth elements scandium, cerium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium are known and can reasonably be expected to be useful in the practice of the present invention.
  • the metal acetylacetonates are used in small catalytic quantities of from 0.001 to 5.0 percent, based upon the weight of the epoxy resin. Optimum results have been achieved with from 0.05 to 3.0 percent. It is important to note that the acetylacetonates of the invention are catalytic hardeners, which do not in a significant way become a part of the hardened epoxy molecule as do curing agents added in much larger or near stoichiometric amounts.
  • examples of other phenolic accelerators suitably employed in this invention also include halogenated phenols such as ortho-, meta- and para chloro phenols or bromophenols and ortho-, meta-, and para nitrophenols.
  • the phenolic accelerator may be present in concentrations ranging from 0.025 to 30 percent, with optimum cure rates being produced with phenolic accelerator concentrations between 0.5 and 10 percent by weight of the epoxy resin.
  • the phenolics are added in relatively small amounts because they are accelerators or catalysts rather than curing agents of the stoichiometric type which form a significant reaction with the epoxy resin and become a significant part of the epoxy molecule.
  • the fillers of the present invention are generally chemically inert. They ordinarily will not react with any of the epoxy resins, metal acetylacetonate or accelerator. They instead function by stabilizing the physical properties of the molding compound, particularly during and after resin cure.
  • Any conventional filler may be utilized in the present compositions. Representative fillers include: clays, like kaolin and calcined clays; silica, like novaculities, ground sand and amorphous glass; mica; talc; carbon black; alumina; and wollastonite. Alternatively, or in addition, a structural filler may be employed. These fillers include such fibrous materials as glass fiber, mineral wool and the like which may provide enhanced product strength.
  • the present molding compounds should contain from about 10 to 95% filler by total weight. More preferably, from about 50 to 95% filler is utilized. This optimizes the advantages of the present invention.
  • the various ingredients may simply be admixed, usually at ambient temperatures.
  • Solid molding compounds in particulate form are, for example, generally prepared in this manner.
  • conventional techniques may be employed. For example, a solid composition may be compression, transfer, or injection molded while a liquid one is normally injection or pultrusion molded. While under molding pressure, the composition should be heated, generally to from about
  • the molding compound may contain one or more auxiliary components: For example, up to about 10%, desirably from 1 to 5%, by weight of a flame retardant may be incorporated. Most commercial retardants, including antimony oxide or halogenated hydrocarbon may be utilized. Mold release agents such as wax, ordinarily in an amount of from 0.2 to 4% by weight, are also highly desirable. These and other components may simply be admixed with the composition prior to molding to obtain the benefits for which they are already known.
  • the following examples are given by way of illustration only and are not intended as a limitation on the scope of this invention. Many variations are possible without departing from its spirit and scope. Unless otherwise specified herein, all proportions are provided on a weight basis.
  • Comparative sample molding compounds differing in filler composition are made and tested. In each instance, they are prepared by dissolving the accelerator in one half of the epoxy resin at 130°C under mechanical agitation; the metal acetylacetonate is dissolved in the other half at 110°C under similar agitation. The two halves are then cooled to room temperature and mixed with filler, as indicated, under vacuum in a Ross planetary mixer.
  • Comparative Sample A is totally unsatisfactory is molding compound. In addition to the difference in properties shown, cracking and charring attributed to a higher curing exotherm are apparent. For the other two samples, the improvements in properties are dramatic and are directly related to increasing filler composition.
  • Example 3 A molding composition is made by the method of Example I consisting of 95 parts of EPON 828 epoxy resin, 5 parts of EPON 871 epoxy resin, 2 parts zirconium acetylacetonate catalyst, 7.5 parts of catechol accelerator, 125 parts crystalline silicon filler, 25 parts of OCF 405 BB 1/8 bundled glass fiber. The composition was compression molded Into excellent parts. The molded parts have a flex strength of 10,600 psi, a flex modulus of 1.2 x 10 6 psi and a notched izod impact of 1.1 ft.1b/ in.
  • EXAMPLE 4 5 parts of EPON 1004 epoxy resin and 7.5 parts plastic resin are dissolved in 42.5 parts of ERL 4221 at 120°C while separately, 1 part of aluminum acetylacetonate is dissolved in 42.5 parts of ERL 4221. After cooling, these resins at mixed for minutes in a planetary mixer under vacuum with 108 grams of crystalline silica, 54 parts of milled glass and 0.33 parts of candelilla wax powder as a mold release agent. This composition is compression molded into a 1/8" X 4" disc at 350°F for 3 minutes and gives excellent parts which release from the mold readily. The parts have an average hot rigidity of 96 mils.
  • EXAMPLE 5 Three sample molding compounds are prepared from solid epoxy resins. In each case all ingredients are ground to a fine powder and dryblended in a paint shaker for 5 minutes. They are then melted on a two-roll mill for 2-3 minutes at 150-155°F. The melted sheets are regreund and transfer molded into 4" diameter parts at 175°C for 3 minutes.
  • the compositions and test results are as follows :
  • EXAMPLE 6 Sample molding composition with additive flame retardants, are prepared and tested as in Example 1. The compositions and results are as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

Composes de moulage possedant des proprietes ameliorees comprenant des vitesses elevees de polymerisation ainsi qu'une stabilite au stockage. Ces composes comprennent un melange de: a) d'environ 5 a 90% en poids d'une resine epoxyde possedant plus qu'un groupe 1,2-epoxyde par molecule; b) de 0,001 a 5% en poids d'un acetyle acetonate metallique possedant uniquement des liaisons metal-oxygene; c) de 0,025 a 30% en poids d'un accelerateur phenolique; et d) d'environ 10 a 95% en poids d'un agent de remplissage, par rapport au poids total de la composition.
EP19820902032 1981-06-12 1982-05-17 Compose de moulage. Withdrawn EP0081557A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US27302581A 1981-06-12 1981-06-12
US273025 1981-06-12

Publications (2)

Publication Number Publication Date
EP0081557A1 true EP0081557A1 (fr) 1983-06-22
EP0081557A4 EP0081557A4 (fr) 1983-10-26

Family

ID=23042232

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19820902032 Withdrawn EP0081557A4 (fr) 1981-06-12 1982-05-17 Compose de moulage.

Country Status (3)

Country Link
EP (1) EP0081557A4 (fr)
JP (1) JPS58500898A (fr)
WO (1) WO1982004437A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5261282A (en) * 1992-03-03 1993-11-16 Kraft General Foods, Inc. Method and apparatus for monitoring a continuous cooking process based on particulate residence time
KR101807194B1 (ko) * 2011-07-29 2017-12-08 에이비비 리써치 리미티드 경화성 에폭시 수지 조성물

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1341731A (fr) * 1961-10-05 1963-11-02 Ciba Geigy Perfectionnements aux compositions à base de résine époxy

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2511913A (en) * 1950-06-20 Compositions of resinous epoxides
US3812214A (en) * 1971-10-28 1974-05-21 Gen Electric Hardenable composition consisting of an epoxy resin and a metal acetylacetonate
GB1402899A (en) * 1971-10-28 1975-08-13 Gen Electric Curable epoxy resin compositons
DE2156700C3 (de) * 1971-11-15 1978-04-27 Siemens Ag, 1000 Berlin Und 8000 Muenchen Fließfähige Preßmasse mit definierter elektrischer Leitfähigkeit
JPS5450556A (en) * 1977-09-29 1979-04-20 Hitachi Chem Co Ltd Preparation of epoxy resin molding material
CH637149A5 (de) * 1978-09-18 1983-07-15 Ciba Geigy Ag Epoxidharzformmassen und deren verwendung zur herstellung von formkoerpern.
JPS5650953A (en) * 1979-10-04 1981-05-08 Toshiba Corp Epoxy resin molding material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1341731A (fr) * 1961-10-05 1963-11-02 Ciba Geigy Perfectionnements aux compositions à base de résine époxy

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO8204437A1 *

Also Published As

Publication number Publication date
WO1982004437A1 (fr) 1982-12-23
JPS58500898A (ja) 1983-06-02
EP0081557A4 (fr) 1983-10-26

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Legal Events

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PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

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Designated state(s): DE FR GB NL

17P Request for examination filed

Effective date: 19830616

STAA Information on the status of an ep patent application or granted ep patent

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18D Application deemed to be withdrawn

Effective date: 19851009

RIN1 Information on inventor provided before grant (corrected)

Inventor name: ALLEN, RICHARD BRIAN

Inventor name: WIERCINSKI, ROBERT ALAN

Inventor name: MARKOWITZ, MARK