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WO2007036194A1 - Systeme de resine epoxyde, matiere moulable produite a partir de ce systeme de resine epoxyde et composant optoelectronique comprenant cette matiere moulable - Google Patents

Systeme de resine epoxyde, matiere moulable produite a partir de ce systeme de resine epoxyde et composant optoelectronique comprenant cette matiere moulable Download PDF

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Publication number
WO2007036194A1
WO2007036194A1 PCT/DE2006/001578 DE2006001578W WO2007036194A1 WO 2007036194 A1 WO2007036194 A1 WO 2007036194A1 DE 2006001578 W DE2006001578 W DE 2006001578W WO 2007036194 A1 WO2007036194 A1 WO 2007036194A1
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WO
WIPO (PCT)
Prior art keywords
component
epoxy resin
resin system
epoxy
cycloaliphatic
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
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PCT/DE2006/001578
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German (de)
English (en)
Inventor
Carsten GÖTTE
Klaus Höhn
Kirstin Petersen
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Ams Osram International GmbH
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Osram Opto Semiconductors GmbH
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Publication of WO2007036194A1 publication Critical patent/WO2007036194A1/fr
Anticipated expiration legal-status Critical
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    • 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

  • Epoxy resin system as well as from the EpoxidharzSystem manufacturable molding material and optoelectronic device with the molding material
  • the object of the present invention is an epoxy resin system to provide a producible from the epoxy resin molding material and an optoelectronic device with the molding material, which is improved in terms of the above-mentioned disadvantages.
  • One embodiment of the invention describes an epoxy resin system comprising an epoxide-containing A component and an acid anhydride-containing B component.
  • the A component contains as the first epoxy component at least one epoxy resin which is selected from cycloaliphatic and aliphatic epoxy resins, which are obtainable by distillation purification.
  • the B component comprises at least one acid anhydride selected from a cyclic aliphatic and aliphatic carboxylic acid, at least one acidic ester of the carboxylic acid, at least one organic zinc 2+ complex compound and at least one organophosphorus compound.
  • the inventors have found that the thermal yellowing stability of epoxy resin systems can surprisingly be improved by further purifying the cycloaliphatic and aliphatic epoxy resins from the corresponding, non-purified products by means of distillative purification.
  • the inventors found that neither purified hardener and accelerator components of the B component of the epoxy resin systems nor washing the cycloaliphatic and aliphatic epoxy resins with water or cleaning these epoxy resins with activated carbon improves the thermal yellowing stability.
  • the improved yellowing stability of the epoxy-containing A component of the epoxy resin systems also leads to curing of the epoxy resin system to epoxy molding materials, which also have improved thermal yellowing stability.
  • the available by distillation purification cycloaliphatic and aliphatic epoxy resins generally have less impurities compared to the non-purified corresponding epoxy resins. These impurities may be selected from the oligomers of the cycloaliphatic and / or aliphatic epoxy resins, clerkpoxid appearing products of the respective epoxy resins and process chemicals, which were used during the synthesis of epoxy resins.
  • a molding material which can be produced from such an epoxy resin system also has the same properties apart from the good thermal yellowing stability a good cracking and delamination behavior with a high glass transition temperature.
  • the epoxy resin according to a further embodiment of the invention may be substantially transparent, so that a producible from the Epoxiharzsystem Epoxidharzformstoff particularly for the encapsulation of optoelectronic devices or for the production of optical elements such. B. lenses is suitable.
  • substantially transparent means that a 1 mm thick sample of an epoxy resin molding material that can be produced from the epoxy resin system> 88% is transparent to radiation in the wavelength range of about 400 to 800 nm. Such measurements may be carried out in a manner known to those skilled in the art by means of a UV spectrometer.
  • the A component can also be solvent-free. This has the advantage that only components are present in the A component, which are incorporated as completely as possible into the molding material during the crosslinking - that is, do not migrate or wash out, with no solubilizing components being necessary.
  • the first epoxide component of the A component selected from cycloaliphatic and aliphatic epoxy resins carries at least one, but preferably two or more epoxide functions. It is possible that these epoxy resins have no or only a very low absorption in the UV-VIS spectrum at wavelengths less than 400 nm, preferably between 300 and 400 nm.
  • the first epoxy resin component of the A component can be selected from hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, diglycidyl ester of adipate and cyclohexane dimethylol diclycidyl ether, epoxycyclohexyl methyl -3 ', 4'-epoxy cyclohexyl carboxylate, diglycidyl ester of hexahydrophthalic acid and methylhexahydrophthalic acid, diglycidyl ethers of tricyclodecanedimethanol, bis (3,4-epoxycyclohexylmethyl) adipate, and reaction products of 1,4-cyclohexanedimethanol (available from Dow Chemical under the designation ERLX-4360) with methyl 3,4-epoxycyclohexanecarboxylate. 3, 4-epoxycyclohexyl-methyl-3 ', 4'-epoxy cyclohexyl carb
  • the at least one saturated Acid anhydride of the B component may be selected from hexahydrophthalic acid anhydride and methyl-hexahydrophthalic anhydride and mixtures thereof.
  • Such acid anhydride hardeners are particularly suitable for colorless, transparent epoxy resin systems which have good yellowing stability since these acid anhydrides are not aromatic but saturated and otherwise have no C-C double bonds.
  • the at least one acidic ester of the aliphatic or cycloaliphatic carboxylic acid can be obtained by reacting the carboxylic acid with a substoichiometric amount of at least one alcohol.
  • the alcohol may be selected from aliphatic, cycloaliphatic and branched mono- or polyfunctional alcohols and polyethers and glycol ethers, for example ethanol, 1, 2-propanediol, 1, 4-butanediol, 1,6-hexanediol, glycerol, dimethylolpropane, trimethylolpropane , Diethylene glycol, ⁇ -diethylene glycol, tricyclodecanedimethylol and ⁇ - ⁇ -dipropylene glycol.
  • the at least one acidic ester of the aliphatic or cycloaliphatic carboxylic acid can improve the curing behavior of the epoxy resin in terms of temperature-time behavior in certain embodiments of the invention and ensure increased compatibility of the individual hardener and accelerator components of the B component and a good storage behavior.
  • modified hardener components improve the thermomechanical behavior and reduce the brittleness of moldings produced therewith.
  • 5 to 30% by weight of the B component is composed the acidic ester of the aliphatic or cycloaliphatic carboxylic acid.
  • zinc octoate is added directly to the B component.
  • Zinc octoate includes 2-ethylhexanoic acid anions and zinc as a double-positive cation.
  • Zinc octoate can serve as a reaction accelerator in the epoxy resin systems and allow rapid cure cycles. These advantages can be realized particularly well in the interaction of the zinc octoate with the acidic esters of the carboxylic acids and phosphorus-organic constituents.
  • the zinc octoate content may be less than 10% by weight in the B component, with the zinc content of the zinc octoate preferably being greater than 18% by weight, preferably between 21.5 and 23.5% by weight.
  • the Zn content of the zinc accelerator, the organic zinc 2+ complex compound may also comprise at least 10 wt%, or preferably at least 20 wt%, most preferably 21.5 to 23.5 wt%.
  • the at least one organophosphorus compound can be selected from triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenyl-diphosphonite , Tris (4'-n-nonylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphonite and diphenyldecyl phosphite.
  • Such organophosphorus compounds are advantageously added in proportions ⁇ 10% by weight of the B component "and can act, for example, as antioxidants and as reaction accelerators and likewise the viscosity of the Epoxy resin system and the thermomechanical behavior of moldings produced therewith advantageously influence.
  • B component which in addition to aliphatic and cycloaliphatic carboxylic acid anhydrides, for example hexahydrophthalic anhydride and / or methyl hexahydrophthalic anhydride, also an organophosphorus compound, for example triphenyl phosphite and the acidic ester of said carboxylic acid anhydrides and zinc octoate with a maximum proportion of 10 weight percent, preferably 3 to 7 percent by weight, since such B-components are solvent-free among other things and good compatibility of the individual components is ensured.
  • organophosphorus compound for example triphenyl phosphite and the acidic ester of said carboxylic acid anhydrides and zinc octoate with a maximum proportion of 10 weight percent, preferably 3 to 7 percent by weight
  • Such a B-component allows particularly fast curing cycles in the minute range at temperatures of 130 0 C to 200 0 C, preferably 160 ° to 190 0 C for a reel-to-reel production. To achieve the final properties so produced components can be post-cured.
  • the cycloaliphatic and aliphatic epoxy resins of the first epoxy component of the A component by means of distillative purification at temperatures of less than 25O 0 C at a pressure ⁇ 10 mbar are available. Further preferred is a distillative purification at temperatures below 200 0 C and pressures ⁇ 1 mbar. It is particularly advantageous if the distillation is carried out under an inert gas atmosphere, for example nitrogen. In such distillation procedures, a relatively gentle distillative purification of the cycloaliphatic and aliphatic epoxy resins under reduced pressure is possible and the epoxide resins produced therewith are as little as possible thermally damaged.
  • the cycloaliphatic and aliphatic epoxy resins of the first epoxy component of the A component may have a purity of at least 91% by weight.
  • a first epoxy component is particularly suitable for epoxy resin systems and resulting epoxy resin moldings which are to have an increased yellowing stability.
  • the purity of the cycloaliphatic and aliphatic epoxy resins of the first epoxide component of the A component is preferably from 91 to 97% by weight, preferably more than 95% by weight.
  • the impurities may be selected, for example, from oligomeric reaction products of the respective cycloaliphatic and aliphatic epoxy resins, partially epoxidized products of these epoxy resins and process chemicals which were used during the synthesis of the epoxy resins.
  • the purity of the cycloaliphatic and aliphatic epoxy resins could be detected, for example, by GPC, HPLC or GCMS methods.
  • non-aromatic epoxy resins as second epoxide component which are different from the first epoxy component of the A component are additionally present in the A component.
  • Such non-aromatic epoxy resins may, for example, be selected from monofunctional and polyfunctional aliphatic alicyclic epoxy resins having oxirane groups, glycidyl ester compounds and glycidyl ether compounds of cycloaliphatic, aliphatic, alicyclic carboxylic anhydrides and carboxylic acids and glycidyl compounds of polyether polyols and polyester polyols.
  • Such an epoxy resin may be, for example, glycidylated castor oil.
  • the epoxy component of the A component may serve to adjust the viscosity and to improve the thermomechanical properties and to adjust the glass transition temperatures.
  • the inventors have recognized that the glass transition temperature of a molding material resulting from curing by the epoxy resin system is lower the more of this second epoxy component is added to the A component.
  • the second epoxide component of the A component is advantageously added in concentrations of less than 30% by weight of the A component.
  • the non-aromatic epoxy resins of the second epoxy component of the A component can be selected, for example, from ce-.omega.-hexanediol diglycidyl ether, 1,4-butanediol dicyclodyl ether, glycidylated trimethylolpropane diglycidyl ether, 2-ethylhexyl diglycidyl ether and glycidylated castor oil ,
  • the non-aromatic epoxy resins of the second epoxy component are also obtainable by means of distillative purification.
  • Such epoxy resin systems and epoxy resin molded articles made therefrom exhibit improved yellowing stability compared to the corresponding unpurified compositions.
  • At least one reaction product of bisphenol A and propylene oxide units of different length with diglycidyl ether functions in ⁇ / ⁇ position may be present in the A component as the third epoxy resin component.
  • a compound is available, for example, from Asahi Denka under the name EP-4005. The inventors have found that such compounds despite their aromatic structures do not lead to an unacceptable yellowing of these containing epoxy resin or epoxy resin molded therefrom. At the same time, however, these compounds can serve as flexibilizers for adjusting the thermomechanical properties of the molding materials and can be added in concentrations of ⁇ 30% by weight of the A component.
  • Epoxy resin systems according to the invention in further embodiments may, apart from this third epoxy resin component, comprise no further aromatic epoxy resin components.
  • more than 50% by weight of the A component consists of the cycloaliphatic and aliphatic epoxy resins as the first epoxide component.
  • less than 30% by weight of the A component may consist of the non-aromatic epoxy resin of the second epoxy component.
  • more than 60% by weight of the B component consists of the at least one acid anhydride of the cycloaliphatic or aliphatic carboxylic acid or mixtures of both.
  • the A component may additionally contain light stabilizers, for example selected from sterically hindered amines, amine oxides and amine oxide derivatives, for example alkoxyamines and aminoethers.
  • light stabilizers for example selected from sterically hindered amines, amine oxides and amine oxide derivatives, for example alkoxyamines and aminoethers.
  • UV absorbers which are for example selected from benzotriazole derivatives, triazines and benzoxazines in further Embodiments of epoxy resin systems according to the invention may be present.
  • R 1 and R 2 are independently alkyl, aryl, or alkylaryl, together form a bivalent radical or together with the N-atom form a heterocyclic ring and R 3 is the above-mentioned alkyl, aryl, alkylaryl or a cycloalkyl group.
  • the group R 3 may have at least one oxygen atom in the chain or may also comprise a plurality of oxygen atoms and thus also, for example, ether groups or ester group.
  • the light stabilizers can be present in concentrations of at most 5% by weight of the A component, preferably at most 2.5% by weight of the A component.
  • At least one antioxidant may additionally be present which is selected from sterically hindered phenol, cresol, phosphite, phosphonite, thioester, tocopherol, 5,7-di-tert-butyl-3 - (3, 4-dimethylphenyl) -3H-benzofuran-2-one, 4,6-bis (octylthiomethyl) -o-cresol, 4-methoxy-phenol, 3-tert-butyl-4-hydroxyanisole and lactone -Links.
  • the 5,7-di-tert-butyl-3- (3, 4-dimethylphenyl) -3H-benzofuran-2-one is available, for example, from Ciba Specialty under the designation HP136.
  • These antioxidants can be used individually or in combinations of different antioxidants, for example in one portion of at most 5% by weight, preferably about a maximum of 2.5% by weight, may be present in the A component.
  • the A component may additionally contain phosphors for the production of luminescence conversion elements.
  • luminescent substances are described for example in the utility model DE 297 24 382 Ul on page 3, lines 1 to 6, page 5, lines 9 to 26 and pages 6, lines 26 to page 7, line 7, the disclosure of which hereby by reference is recorded.
  • the mixing ratio is 100 parts A component to about 80 to 150 parts B component, with a mixing ratio of about 100 parts A component to about 100 to 130 parts B component being preferred.
  • Such epoxy resin systems have a service life of at least 2 h at 25 ° C and allow a particularly good curing at the same time good thermomechanical stability and good yellowing stability.
  • alcohols which are monohydric or polyhydric and may also comprise aliphatic, cycloaliphatic, polyether-polyester alcohols and alcohol ethers may furthermore be present.
  • decane tricyclodecanedimethylol
  • ⁇ - ⁇ -diethylene glycol and ce- ⁇ -dipropylene glycol.
  • Such alcohols can serve to improve the mechanical properties, which usually does not result in a significant deterioration of the moisture absorption. Often, a structural conditional Improvement in cracking behavior, for example, to observe a better solderability.
  • deaerators may be present in particular embodiments of an epoxy resin system according to the invention and thus also in the epoxy resin molding materials obtainable therefrom.
  • thixotropic agents may be added, for example finely divided, fumed silica, titanium dioxide and zirconium dioxides.
  • dyes in the A component.
  • diffuser pigments for example CaF 2 , BaSO 4 , TiO 2 and / or CaCO 3 can be added to the A component.
  • the A component may also contain, as further components, additives which are selected, for example, from fused silica, quartz flour, quartz, Al 2 O 3 , MgO, Y 2 O 3 , ZrO 2 , CeO x , TiO 2 and ZnO and talc.
  • mono-, di- or trifunctionalized alkoxysilanes may also be present as adhesion promoters.
  • these mono-, di- or trifunctionalized alkoxysilyles also have at least one maximum but three substituents with a functional group, for example a glycidyloxyalkyl group, a 0H group or an amine.
  • a coupling agent is, for example, 3-glycidyloxypropyltrimethoxysilane or 3-glycidyloxypropoyltriethoxysilane.
  • Epoxy resin moldings which are obtainable by means of curing of at least some embodiments of the epoxy resin systems according to the invention have a glass transition temperature of at least 125 ° C, preferably> 145 ° C.
  • the epoxy resin systems and epoxy resin molding materials obtainable therefrom can be used for potting, covering, coating and as a mounting material for bonding electronic and optoelectronic components.
  • Particularly suitable are such Epoxidharzformstoffe for optoelectronic devices in which high photochemical loads occur, such as UV emitters, light emitting diodes, photodiodes, phototransistors, photo arrays, optical couplers, optical transmitter-receiving components, optical fibers and lasers.
  • Such photochemical loads occur, for example, amplified by radiation with wavelengths less than 500 nm.
  • Electronic and optoelectronic components which comprise or are encapsulated with the epoxy resin moldings exhibit good stability against moisture and weathering and can also be used in the automotive sector. It is also possible to use the Epoxidharzformstoffe for outdoor applications.
  • the epoxy resin moldings can also be used for the production of optical components, for example lenses, prisms, windows, filters or light-guiding units, as well as for decorative purposes.
  • the subject matter of a further embodiment of the invention is also a process for producing an epoxy resin molding material in which the A and B components of an epoxy resin system are mixed together as mentioned above and the resulting mixture is cured.
  • the curing can be carried out, for example, at temperatures above 100 0 C for rapid processing at temperatures above 140 0 C in the minute range. For example, at temperatures of about 140 0 C. Cured for about 30 minutes or at temperatures above 16O 0 C at correspondingly shorter curing times.
  • Improved molding properties of the Epoxidharzformschers be achieved by post-curing at temperatures greater than 125 0 C. Post-curing under an inert gas atmosphere, for example under nitrogen, further improves the yellowing stability.
  • Figure 1 shows a tabular comparative overview of various purified and non-purified cycloaliphatic epoxy resins.
  • Figures 2A and 2B show the glass transition temperatures Tg of a cured epoxy molding material according to an embodiment of the invention, depending on different curing conditions.
  • FIG. 3 shows the transparency of an epoxy resin molding material according to an embodiment of the invention as a function of the wavelength.
  • Figure 4 shows the UV-VIS shows characteristics of a cycloaliphatic epoxy resin which is purified by distillation, or was not cleaned after four weeks of thermal aging at 7O 0 C (10 mm cell).
  • the A component of embodiment 2 is stable for storage for at least six months at room temperature and can be mixed and dosed bubble-free and homogeneously with a service life vgon min. 2h at 25 ° C with a hardener component, the B component.
  • Component A shows a viscosity of 200 to 500 mPas (25 0 C, 500 1 / sec), preferably 200 to 300 mPas.
  • the viscosity increases after six months storage at room temperature from 215 mPas to 255 mPas. In the thermal resin aging, the viscosity after four weeks at 70 0 C also increases only slightly from 270 to 280 mPas.
  • hexahydrophthalic anhydride based hardener glass transition temperatures of greater than 150 0 C are achieved in the mixing ratio of 100: 104 to 100: 112 parts.
  • the gel times be at 120 0 C and 150 0 C for 3 min 30 sec and 1 min, so that rapid Anhärtungen for fast production cycles can be performed.
  • FIGS. 2A and 2B show differential scanning calorimetry (DSC) results from hardness tests in which an epoxy resin component A according to the second embodiment was cured with a hexahydrophthalic anhydride based hardener at a mixing ratio A: B of 100: 112.
  • the column denoted by 13 of FIG. 2A designates the t-T profile (DSC isothermal), the column denoted by 14 designates the glass transition temperatures Tg resulting from the corresponding profile, and the column denoted by 15 denotes the calculated residual reaction in percent. It can be seen from FIG. 2A that, depending on the curing temperature and the curing time, the glass transition temperature of the resulting molding materials increases the longer and is cured at the higher temperatures.
  • the column denoted by 16 designates the curing conditions (curing time and curing temperature)
  • the post-hardening column denoted by 17 designates the glass transition temperature in 0 C of the resulting molded materials.
  • This 2B it can be seen that can be achieved by very long subsequent hardening at high temperatures between about 150 0 C to 160 0 C improved glass transition temperatures, which are between 162 ° C and 166 ° C.
  • the epoxy resin moldings are colorless and transparent with high permeability in the visible range. After a short-term temperature load of 6 min at 290 0 C, a slight yellowing of the molding material was observed.
  • the molded materials show in the dynamic mechanical analysis at 1 Hz an E modulus at 2O 0 C and 100 0 C of 3,300 MPa and 2,300 MPa, the linear thermal expansion coefficient between -50 0 C and + 50 0 C is 72 ppm / K ,
  • the Epoxidharzformstoffe all show a glass transition temperature greater than 150 0 C.
  • potted Lumineszenzdioden are sufficiently cyclic (1000 x TC (temperature cycle): -40 ° C / + 100 ° C), sufficiently stable against soldering heat in wave soldering (5 x TTW (through the wave) 260 0 C), stable in humidity (85 0 C 85% RH 5 mA, hitherto 500 h) and yellow slightly after short-term temperature stress of 5 x Wellenl ⁇ ten at 260 0 C. in order potted components can below the predetermined quality requirements are economically prepared ,
  • FIG. 1 shows the chemical and physical properties of various cycloaliphatic epoxy resins which have been purified by distillation or have not been purified.
  • the line marked 1 indicates the supplier, the line denoted by 2 the chemical name, line 3 the CAS number, line 4 shows the purity of the respective cycloaliphatic epoxy resins.
  • the uppermost value in line 4 indicates the purity in percent by weight for the particular cycloaliphatic epoxy resin, the value in the middle of the weight fraction of monoepoxides and the lower value the proportion by weight of oligomers contained the respective cycloaliphatic epoxy resin.
  • the epoxy value is given in mol / 100 g.
  • Line 6 indicates the color value (APHA max).
  • ERL-4221 indicates the properties of an epoxy resin obtained from Dow Chemical which was not purified by distillation
  • ERL-4221 E indicates the chemical and physical properties of the corresponding epoxy-based epoxy resin after purification with water
  • ERL-4221 D and ERL-4241 (Opto) characterize the same cycloaliphatic epoxy resins from Dow obtained by distillative purification.
  • EP 4085 S refers to the chemical and physical properties of a 1, 4-Cyclohexandimethyloldiglycidylethers which may also be part of the first component of the A component.
  • the distillatively purified ERI-4221 (the columns denoted D and Opto, respectively) have a greater purity of 91 to 91% by weight, compared to a lower purity of 82 to 89% by weight for that purified ERL-4221 or water-purified ERL-4221 E.
  • the products obtained by means of distillative purification have fewer oligomers of the particular cycloaliphatic epoxy resin, namely less than 4% by weight in comparison with the by distillation purified products containing 8 to 13% by weight of soluble oligomers.
  • the viscosity of the distillatively purified products is lower with simultaneously increased epoxy value. It is noteworthy and important in this context that products purified by distillation continue to have a lower color number (APHA max).
  • FIG. 3 shows the transparency of an epoxy resin molding material obtained by curing the epoxy resin component of the second embodiment with a hexahydrophthalic anhydride-based hardener.
  • the curve denoted by 20 indicates the transmission behavior in% as a function of the wavelength in nm. Measured on a Perkin Elmar Lamda 2 spectrometer, wherein the sample had a layer thickness of 0.8 mm. It can be seen from the figure that from a wavelength of about 400 nm to more than 750 nm, a transmission greater than 88% can be observed with the epoxy resin molding material. This is thus particularly suitable for use in optoelectronic components and optical elements such as lenses and windows.
  • FIG. 4 shows the UV-VTS characteristics of a distillatively purified cycloaliphatic epoxy resin (curve designated 40: ERL-4221 Opto) in comparison to the corresponding UV-VIS characteristics of the same non-distillatively purified epoxy resin (curve designated 30: ERL-4221 Standard quality).
  • the appropriate UV-VIS characteristics were after four weeks of thermal aging at 7O 0 C by means of a Perkin Elmar determined Lamda 2 spectrophotometer and a 10 mm cuvette at room temperature. It can be clearly seen that the non-distillatively purified cycloaliphatic epoxy resin has a higher Yellowing shows as the corresponding distillatively purified product.
  • An epoxy resin molding material was prepared by curing an A component consisting of non-distillatively purified ERL-4221 in an amount of 94.986% by weight, trimethylolpropane in a proportion of 4.750% by weight, Tego-DF48 as a silicone-based internal release agent in a proportion of 0, 25% by weight and masterbatch 09 as optical brightener with a fraction of 0.014% by weight were obtained with a methylhexahydrophthalic anhydride-based hardener.
  • this epoxy resin molded thermal aging is after six weeks of aging at 120 0 C in air as a spectroscopic color locus 17.3. This means a very high thermal yellowing.
  • Distillatively purified aliphatic and / or cycloaliphatic epoxy resins are, above all, able to improve the thermal yellowing stability of the abovementioned epoxy resin molding material.
  • This can be demonstrated by the fact that an epoxy resin molding produced by curing an A-component according to the second embodiment already mentioned above and a hardener component B based on methylhexahydrophthalic anhydride shows a substantially increased thermal yellowing stability.
  • the decrease of the light intensity I v in an LED with a GaN chip as a measure of the yellowing stability after 500 h at 85 ° C and 30 m ⁇ is about 30%.
  • An epoxy resin molding material based on bisphenol A epoxy resin without distillatively purified cycloaliphatic components shows in comparative and simultaneously performed aging tests a total LED yellowing, which is characterized by a decrease in the light intensity I v of about 65%. This result indicates a significant improvement in the yellowing stability as the sum of thermo-oxidative and photochemical component yellowing compared to conventional epoxy resin molding materials.
  • Components that contribute to photochemical yellowing are the wavelength of the light, the intensity and the radiation dose.

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

Abstract

L'invention concerne un système de résine époxyde qui contient un constituant A à groupe époxy comprenant au moins une résine époxyde cycloaliphatique ou aliphatique pouvant être obtenue par purification par distillation, ainsi qu'un constituant B comprenant au moins un anhydride d'un acide carboxylique cycloaliphatique et aliphatique, au moins un ester acide de l'acide carboxylique, au moins un composé complexe zinc<SUP>2+</SUP> organique et au moins un composé organophosphorique. De tels systèmes de résine époxyde et les matières moulables à résine époxyde produites à partir de ces systèmes présentent une résistance accrue au jaunissement.
PCT/DE2006/001578 2005-09-28 2006-09-11 Systeme de resine epoxyde, matiere moulable produite a partir de ce systeme de resine epoxyde et composant optoelectronique comprenant cette matiere moulable Ceased WO2007036194A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102005046444.0 2005-09-28
DE102005046444 2005-09-28
DE102005060348A DE102005060348A1 (de) 2005-09-28 2005-12-16 Epoxidharzsystem sowie aus dem Epoxidharzsystem herstellbarer Formstoff und optoelektronisches Bauelement mit dem Formstoff
DE102005060348.3 2005-12-16

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013045398A1 (fr) * 2011-09-30 2013-04-04 Osram Opto Semiconductors Gmbh Module opto-électronique comprenant une couche d'adhérence, procédé de préparation d'une couche d'adhérence dans un module opto-électronique et utilisation d'une colle pour former des couches d'adhérence dans des modules opto-électroniques
US9096708B2 (en) 2012-10-23 2015-08-04 Industrial Technology Research Institute Partially esterified epoxy resin and epoxy resin composition applied with the same, and method for preparing the composition
WO2017085127A1 (fr) * 2015-11-16 2017-05-26 Osram Opto Semiconductors Gmbh Système de résine époxyde, résine époxyde, utilisation d'un système de résine époxyde, composant comprenant une résine époxyde et procédé pour produire une résine époxyde
WO2020225249A1 (fr) * 2019-05-09 2020-11-12 Osram Opto Semiconductors Gmbh Composition de résine, utilisation de cette composition de résine, composant optoélectronique et procédé de fabrication d'un composant optolectronique
CN113817286A (zh) * 2021-08-24 2021-12-21 安徽众博新材料有限公司 抗盐雾、抗高压起痕、抗闪污的绝缘件材料
CN116178890A (zh) * 2022-11-30 2023-05-30 深圳伊帕思新材料科技有限公司 热固性树脂组合物、pcb用半固化片及pcb用覆铜板

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011056295B4 (de) * 2011-12-12 2022-02-17 OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung Epoxidharzsystem, Verwendung des Epoxidharzsystems, alterungsbeständiger Epoxidharzformstoff und Bauelement mit dem Epoxidharzformstoff

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2642465A1 (de) * 1976-09-21 1978-03-23 Siemens Ag Giessharzmassen zum verguss von optoelektronischen bauelementen
JPS6312623A (ja) * 1986-07-03 1988-01-20 Daicel Chem Ind Ltd 熱硬化性樹脂組成物
EP0942027A2 (fr) * 1998-03-13 1999-09-15 Mitsui Chemicals, Inc. Composition polymérisable
WO2002004541A2 (fr) * 2000-07-06 2002-01-17 3M Innovative Properties Company Compositions adhesives a fluxage sans ecoulement

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3016097A1 (de) * 1980-04-25 1981-10-29 Siemens AG, 1000 Berlin und 8000 München Schnellhaertende epoxidharzmassen
DD240553B1 (de) * 1985-08-29 1989-11-15 Leuna Werke Veb Verfahren zur herstellung optisch transparenter verkappungsmassen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2642465A1 (de) * 1976-09-21 1978-03-23 Siemens Ag Giessharzmassen zum verguss von optoelektronischen bauelementen
JPS6312623A (ja) * 1986-07-03 1988-01-20 Daicel Chem Ind Ltd 熱硬化性樹脂組成物
EP0942027A2 (fr) * 1998-03-13 1999-09-15 Mitsui Chemicals, Inc. Composition polymérisable
WO2002004541A2 (fr) * 2000-07-06 2002-01-17 3M Innovative Properties Company Compositions adhesives a fluxage sans ecoulement

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 198809, Derwent World Patents Index; AN 1988-058903, XP002416215 *
EDDY V J ET AL: "A NEW ONE-COMPONENT ANHYDRIDE-CURED EPOXY WITH AN ALIPHATIC DISILOXANE DIANHYDRIDE AND METAL-COORDINATED LEWIS BASES", JOURNAL OF POLYMER SCIENCE, POLYMER CHEMISTRY EDITION, INTERSCIENCE POUBLISHERS, NEW YORK, NY, US, vol. 28, no. 9, 1 August 1990 (1990-08-01), pages 2417 - 2426, XP000174863, ISSN: 0360-6376 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013045398A1 (fr) * 2011-09-30 2013-04-04 Osram Opto Semiconductors Gmbh Module opto-électronique comprenant une couche d'adhérence, procédé de préparation d'une couche d'adhérence dans un module opto-électronique et utilisation d'une colle pour former des couches d'adhérence dans des modules opto-électroniques
US9224924B2 (en) 2011-09-30 2015-12-29 Osram Opto Semiconductors Gmbh Optoelectronic component including an adhesive layer and method for producing the same
US9096708B2 (en) 2012-10-23 2015-08-04 Industrial Technology Research Institute Partially esterified epoxy resin and epoxy resin composition applied with the same, and method for preparing the composition
WO2017085127A1 (fr) * 2015-11-16 2017-05-26 Osram Opto Semiconductors Gmbh Système de résine époxyde, résine époxyde, utilisation d'un système de résine époxyde, composant comprenant une résine époxyde et procédé pour produire une résine époxyde
WO2020225249A1 (fr) * 2019-05-09 2020-11-12 Osram Opto Semiconductors Gmbh Composition de résine, utilisation de cette composition de résine, composant optoélectronique et procédé de fabrication d'un composant optolectronique
CN113817286A (zh) * 2021-08-24 2021-12-21 安徽众博新材料有限公司 抗盐雾、抗高压起痕、抗闪污的绝缘件材料
CN116178890A (zh) * 2022-11-30 2023-05-30 深圳伊帕思新材料科技有限公司 热固性树脂组合物、pcb用半固化片及pcb用覆铜板

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