EP0805832A1 - Systeme de resine de reaction comprenant un composant contenant du phosphore - Google Patents

Systeme de resine de reaction comprenant un composant contenant du phosphore

Info

Publication number
EP0805832A1
EP0805832A1 EP96900244A EP96900244A EP0805832A1 EP 0805832 A1 EP0805832 A1 EP 0805832A1 EP 96900244 A EP96900244 A EP 96900244A EP 96900244 A EP96900244 A EP 96900244A EP 0805832 A1 EP0805832 A1 EP 0805832A1
Authority
EP
European Patent Office
Prior art keywords
resin system
reaction
component
reaction resin
anhydride
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.)
Ceased
Application number
EP96900244A
Other languages
German (de)
English (en)
Inventor
Ernst Wipfelder
Winfried Plundrich
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.)
Siemens AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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 Siemens AG, Siemens Corp filed Critical Siemens AG
Publication of EP0805832A1 publication Critical patent/EP0805832A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
    • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5304—Acyclic saturated phosphine oxides or thioxides
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents

Definitions

  • Processing-safe, flame-retardant reactive resin molding materials are required for covering and encasing electrical and electronic components.
  • Reaction resins that can be processed by potting are common, particularly in the case of passive components.
  • epoxy resins are used to a large extent, which can withstand high thermal loads and have good mechanical and electrical properties.
  • the low molecular weight or oligomeric starting components can be converted to high-quality thermosetting materials using a wide variety of hardeners such as, for example, carboxylic anhydrides, amines, phenols or isocyanate or by ionic polymerization.
  • the low molecular weight to oligomeric starting state of the epoxy resins is responsible for the advantageous processing behavior of epoxy resins. They can be filled up with inorganic inert fillers and can still be processed as cast resin.
  • No. 5,262,456 proposes a phosphine or phosphonic acid Integrate derivative with alcoholic hydroxyl groups in an epoxy resin molding material.
  • DE 42 37 132 proposes to use phosphorus components based on phosphine oxide or phosphate as reaction resin components which increase the flame retardancy.
  • DE 43 08 185 AI proposes converting polyepoxide compounds into phosphorus-containing epoxy compounds by reaction with a phosphonic acid anhydride and then crosslinking them with known hardener components into flame-retardant molding materials.
  • the common disadvantage of these phosphorus compounds is their relatively low phosphorus content. As a consequence, considerable amounts of these phosphorus-containing compounds are required in order to ensure satisfactory flame protection. Because of the high viscosity of these phosphorus components, which is observed in particular in the case of the phosphorus-modified epoxy resins, there are clear restrictions on the processability of such modified reaction resin systems.
  • the phosphonic acid derivatives are generally less viscous and therefore more advantageous for casting technology. However, they show a weaker flame retardant effect and must therefore be used in higher concentrations, which in turn can adversely affect the properties of the molding material.
  • the object of the present invention is therefore to modify a reaction resin system based on epoxy resin in such a way that a molding material produced therefrom fulfills the flame retardant specifications required for electronic components, without thereby reducing the processability of the reactive resin system, the molding material properties or the reliability of the molding material covered or encased component is negatively influenced, and that the molding material does not produce any decomposition products that are harmful to the environment when burned.
  • the invention is based on the discovery of the half esters of phosphonic acid with alcohols. These phosphorus-containing compounds (component B2) are surprisingly miscible in any ratio with the other components (components A and B1) of a reaction resin system known per se. It is possible to add components B2 directly or particularly advantageously in a mixture with customary, in particular liquid carboxylic acid anhydrides (components B1) to the reaction resin composition.
  • component B2 is also possible to provide component B2 as the sole hardener component.
  • the variety in the selection of the alcohol components D for the phosphorus-containing component B2 makes it possible to specifically set the mechanical, thermal, electrical and chemical properties of a molding material produced therefrom without adversely affecting the curing characteristics of the reaction resin system according to the invention.
  • phosphorus-containing half-esters behave like carboxyl-functional acid esters with regard to hardenability.
  • phosphorus-containing half-esters are easily processable, low-viscosity liquids which generally have a high phosphorus content.
  • product z. B. of propanephosphonic anhydride and 1,5-pentanediol results in a phosphorus content of 15.7 weight percent.
  • phosphorus-containing component B2 For this reason, only small amounts of phosphorus-containing component B2 are required in order to provide adequate flame protection.
  • Table 1 shows the most important parameters of this half ester. In addition, the proportion of the half-ester containing phosphorus is listed for the realization of a sufficiently flame-retardant molding material. So z. B. for a relatively high phosphorus content of 3 percent by weight in the cast resin system, only 16 percent by weight half-ester is required.
  • Table 1 Characteristic characteristics of a half ester made from propanephosphonic anhydride and 1,5-pentanediol.
  • reaction resin system based on epoxy / anhydride in the direction of improved flame protection.
  • the known reaction resin system can have properties optimized for a particular application, which are not impaired by the modification according to the invention (addition of the phosphorus-containing half-ester).
  • a sufficiently high flame retardancy is achieved with a phosphorus content of the reaction resin system of 1 to 5 percent by weight.
  • the reactivity of such phosphorus-modified reaction resin systems can be specifically adjusted by adding accelerators.
  • the low adjustable viscosity of the reaction resin system according to the invention enables a high proportion of filler, which can reach up to 70 percent by weight for a cast resin application.
  • the carboxylic anhydride is derived from an aromatic di- or tetracarboxylic acid.
  • the aromatic skeleton of the carboxylic acid can be a mono- or polynuclear aromatic.
  • the simplest species in this group of compounds is phthalic anhydride.
  • aromatic anhydrides are benzene-1,2,4,5-tetracarboxylic acid dianhydride, benzophenonetetracarboxylic acid dianhydride or perylene-3,4,9,10-tetracarboxylic acid-3,4,9,10-dianhydride, naphthalene-1,8 -dicarboxylic acid anhydride, benzoic acid anhydride or biphenyltetracarboxylic acid dianhydride.
  • aromatic anhydrides also cycloaliphatic, aliphatic and olefinic anhydrides such as hexahydrophthalic anhydride, phthalic anhydride Methylhexahydro-, succinic anhydride, Valerian Text- anhydride, isovaleric anhydride, hexanoic anhydride, PI valinTexreanhydrid, 5-norbornene-2,3-dicarboxylic anhydride, maleic anhydride , 2-dodecen-l-yl succinic anhydride and methyl tetrahydrophthalic anhydride.
  • cycloaliphatic, aliphatic and olefinic anhydrides such as hexahydrophthalic anhydride, phthalic anhydride Methylhexahydro-, succinic anhydride, Valeriankla- anhydride, isovaleric anhydride, hexanoic anhydride, PI valinklareanhydr
  • a commercially available epoxy resin or a mixture of commercially available epoxy resins can be selected as the epoxy resin component (component A).
  • the polyglycidyl ethers based on bisphenol-A and bisphenol-F have proven particularly advantageous.
  • those of aliphatic alcohols are also suitable.
  • such tiger alcohols 1,4-butanediol, 1,6 hexanediol, polyalkylene glycols, glycerol, trimethylolpropane, bis- (4-hydroxycyclo-clohexyl) -2, 2-propane and pentaerythritol may be mentioned.
  • Polyglycidyl esters which are obtained by reacting, for example, epichlorohydrin or similar epoxy compounds with aliphatic, cycloaliphatic or aromatic polycarboxylic acids are also suitable. Also suitable for the epoxy component are those polyepoxides which are obtained by epoxidizing polyalkenes.
  • Component D in the reactive resin system according to the invention can be a linear, branched or cyclic mono- or polyhydric alcohol. It can be selected from alkanol, alkenol and corresponding aromatically substituted derivatives.
  • Suitable components D are, for example, monohydric alcohols from propanol to hexadecanol.
  • Suitable unsaturated alcohols are, for example, allyl alcohol, propargyl alcohol and others.
  • Suitable diols range from glycol to pentanediol to decanediol.
  • a suitable aromatically substituted alcohol is, for example, bisphenol A bis (hydroxyethyl ether).
  • Polyvalent alcohols are, for example, pentaerythritol or trimethylolpropane.
  • Longer-chain or oligomeric to polymeric alcohols have a flexibilizing effect in the reactive resin system according to the invention.
  • Such oligomeric to polymeric alcohols can be polyether polyols, polyester polyols or polyester ether polyols.
  • Cyclic and polycyclic alcohols as component D can improve the thermal mechanical properties of the reactive resin system or of the molding material produced therefrom.
  • the only representative here is the TCD alcohol derived from cyclopentadiene chemistry
  • Such alcohols can be selected from hydroxyalkyl-substituted phosphine oxide and hydroxyl-containing phosphinic, phosphonic and phosphoric acid esters.
  • Suitable and readily available compounds are, for example, sec-butyl bis (3-hydroxypropyl) phosphine oxide, diethyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphonate, 2-hydroxyethanephosphonic acid dimethyl ester or tris (hydroxymethyl) - phosphine oxide.
  • Table 2 shows the essential characteristics of the half-ester
  • Propanephosphonic anhydride and sec-butyl bis (3-hydroxypropyl) phosphine oxide Table 2: Characteristic values of the half ester from propanephosphonic anhydride and sec-butyl-bis- (3-hydroxypropyl) phosphine oxide.
  • component E can be contained in the reaction resin system according to the invention.
  • components E additives known per se for epoxy resins which influence the processability, the color or the properties of the hardened molding materials and which can be selected as a function of the desired application.
  • Such additives can be: reaction accelerators, reactive diluents, leveling aids, defoamers, adhesion promoters, thixotropic agents, dyes, pigments and in particular fillers.
  • the flame resistance can also be increased by means of fillers. Although this is already achieved with a high filler content and thus a reduction in the proportion of the organic resin matrix, the flame resistance can also be improved by selecting the filler material.
  • Well-compatible filler with a flame retardant effect is, for example, aluminum hydroxide.
  • Phosphonic acid anhydride are used to produce the phosphonic acid half-esters
  • a phosphonic anhydride solution is preferably slowly added dropwise at room temperature and with the exclusion of moisture to component D presented in bulk or in solution.
  • the solvent is drawn off and components B2 which can be used directly in the reaction resin system are obtained as adducts.
  • R -CH - CH - CH
  • the phosphonic acid half-ester adduct obtained has a viscosity of 4300 mPas at 80 ° C. and gives an acid value of 0.64 mol / 100 g. 2nd example
  • the production of the phosphonic acid half ester • II consisting of 1,5-pentanediol (POL) and propanephosphonic anhydride (PPA), is carried out in the same manner as described in Example 1.
  • POL 1,5-pentanediol
  • PPA propanephosphonic anhydride
  • This phosphonic acid half-ester has a phosphorus content of 19% and a viscosity at 60 ° C of 540 mPas. E ⁇ results in an acid value of 0.65 mol / 100 g.
  • This phosphorus-modified adduct shows a shelf life of R.T. of over 1 year with exclusion of moisture.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

Pour augmenter l'ininflammabilité et l'aptitude au traitement d'un système de résine de réaction époxyde-anhydride, il est proposé de compléter le système de résine de réaction avec des semi-esters d'acide phosphonique comme composants réactifs additionnels. Ces esters sont produits par réaction d'anhydride d'acide phosphonique avec des alcools monovalents ou polyvalents. Les propriétés déjà avantageuses de la matière de moulage ainsi modifiée peuvent être déterminées de façon ciblée par le choix des composants alcools, cela sans que la caractéristique de durcissement n'en soit altérée. Les pièces moulées constituées d'une telle matière présentent, déjà avec de petites proportions de semi-ester d'acide phosphonique, une ininflammabilité suffisante, leurs autres propriétés restant inchangées.
EP96900244A 1995-01-26 1996-01-02 Systeme de resine de reaction comprenant un composant contenant du phosphore Ceased EP0805832A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19502410 1995-01-26
DE19502410 1995-01-26
PCT/DE1996/000003 WO1996023018A1 (fr) 1995-01-26 1996-01-02 Systeme de resine de reaction comprenant un composant contenant du phosphore

Publications (1)

Publication Number Publication Date
EP0805832A1 true EP0805832A1 (fr) 1997-11-12

Family

ID=7752381

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96900244A Ceased EP0805832A1 (fr) 1995-01-26 1996-01-02 Systeme de resine de reaction comprenant un composant contenant du phosphore

Country Status (4)

Country Link
US (1) US5811486A (fr)
EP (1) EP0805832A1 (fr)
JP (1) JPH11500150A (fr)
WO (1) WO1996023018A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SK32699A3 (en) 1996-09-26 2000-06-12 Siemens Ag Epoxy resin mixtures
WO2005121220A2 (fr) * 2004-06-04 2005-12-22 Triton Systems, Inc. Preparation de polyphosphonates par transesterification sans catalyseur

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1300695B (de) * 1963-12-21 1969-08-07 Henkel & Cie Gmbh Verfahren zur Herstellung von Formkoerpern, UEberzuegen und Verklebungen auf der Basis von Epoxydpolyaddukten
US3373231A (en) * 1965-11-24 1968-03-12 Hooker Chemical Corp Monoesters of phosphonic acids
FR1503429A (fr) * 1965-12-14 1967-11-24 Ciba Geigy Procédé de préparation d'esters cycliques de l'acide phosphonique
US5262456A (en) * 1989-08-11 1993-11-16 Siemens Aktiengesellschaft Fire retardant casting resin molding compounds based on epoxy resins and acidic esters of hydroxy-functional phosphors
ATE145222T1 (de) * 1989-08-11 1996-11-15 Siemens Ag Flammwidrige giessharzformstoffe
GB9007515D0 (en) * 1990-04-03 1990-05-30 Ciba Geigy Ag Products
DE4308187A1 (de) * 1993-03-15 1994-09-22 Siemens Ag Epoxidharzmischungen
DE4447277A1 (de) * 1994-12-30 1996-07-04 Hoechst Ag Stabilisierte, phosphormodifizierte Epoxidharze und ihre Verwendung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9623018A1 *

Also Published As

Publication number Publication date
US5811486A (en) 1998-09-22
WO1996023018A1 (fr) 1996-08-01
JPH11500150A (ja) 1999-01-06

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