WO2013087317A1

WO2013087317A1 - Epoxy resin system, aging-resistant molding material which can be produced from the epoxy resin system, and electronic component comprising the molding material

Info

Publication number: WO2013087317A1
Application number: PCT/EP2012/072287
Authority: WO
Inventors: Klaus Höhn; Christina Keith
Original assignee: Osram Opto Semiconductors Gmbh
Priority date: 2011-12-12
Filing date: 2012-11-09
Publication date: 2013-06-20
Also published as: DE102011056295B4; DE102011056295A1; TW201331253A

Abstract

The invention relates to at least one epoxy resin system. According to at least one embodiment of the invention, the epoxy resin system comprises a component A and a component B. The component A contains a first epoxy compound and a second epoxy compound, said first epoxy compound comprising an aromatic compound with at least two epoxy functions. The second epoxy compound is selected from a group comprising hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether oligomers, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol F diglycidyl ether oligomers, substituted hydrogenated bisphenol A diglycidyl ether, substituted hydrogenated bisphenol A diglycidyl ether oligomers, substituted hydrogenated bisphenol F diglycidyl ether, substituted hydrogenated bisphenol F diglycidyl ether oligomers, or a combination thereof. The component B comprises a carboxylic acid anhydride.

Description

description

EPOXY RESIN SYSTEM AND MADE OF THE EPOXY RESIN SYSTEM

AGING-RESISTANT MOLDING AND ELECTRONIC CONSTRUCTION ELEMENT WITH THE MOLDING MATERIAL

This patent application claims the priority of German Patent Application 10 2011 056 295.8, the disclosure of which is hereby incorporated by reference.

The invention relates to an epoxy resin system and the

Use of the epoxy resin system. Furthermore, the invention relates to an aging-resistant epoxy molding material obtainable from the epoxy resin system, as well as a

Component comprising the epoxy resin molding material.

For the functionally reliable and reliable use of electronic components, in particular of optoelectronic components or products, they must be protected against harmful environmental influences such as moisture or air. For this are common

Casting compounds of epoxy anhydride compounds used. It turns out, however, that well-known casting compounds, which - in addition to reactive diluents - for example, contain only aromatic epoxy resins as epoxy, are not sufficient to aging ^¬ stable. They still show signs of yellowing within the life of the component or of the product and can become brittle and thus have an increasing mechanical instability resulting in cracks or fractures as well as a reduced bond strength, for example

Delamination leads. The yellowing phenomena are due in particular to the aromatic groups of the epoxide compounds used. These impairments can in particular occur in so-called SMD components (SMD = Surface Mounted Device), which are attached, for example by soldering on a support. When soldering caused by the sudden increase in temperature, a high

thermal or thermomechanical stress for a casting.

It is therefore desirable epoxy resin systems from which epoxy resin moldings with high aging resistance, high yellowing stability and good low-stress properties can be produced. The low-stress properties include, for example, a high glass transition temperature T _G with a simultaneously low storage modulus, a low one

Expansion change during heating and a high thermal stability and thermal shock resistance. Good low-stress properties are therefore associated with high-strength and crack-resistant epoxy resin molding materials or

Associated material. Therefore, an object to be solved is to provide an epoxy resin ^¬ system, from the epoxy resin molding materials

improved properties can be produced. The improved properties include, in particular, increased aging resistance, increased yellowing resistance and improved low-stress properties. Other problems to be solved are to provide a use for the epoxy resin, an epoxy resin molded material, which is available from the epoxide ^¬ resin system, and an electronic,

opto-electronic or optical component comprising such an epoxy molding material.

At least one of these objects is achieved by an epoxy resin system according to at least one embodiment of the application solved. Further objects are achieved by the use of the epoxy resin system, an epoxy resin molding material as well as an electronic, optoelectronic or optical component in each case according to at least one embodiment of the application.

An epoxy resin system is specified. After at least one

Embodiment includes the epoxy resin system

an A component comprising a first epoxy compound and a second epoxy compound,

wherein the first epoxy compound is an aromatic

Compound with at least two epoxide functions includes and

wherein the second epoxide compound is selected from the group consisting of hydrogenated bisphenol A digylcidyl ethers, hydrogenated bisphenol A diglycidyl ether oligomers, hydrogenated ones

Bisphenol F digylcidyl ether, hydrogenated bisphenol F digylcidyl ether oligomers, hydrogenated substituted ones

Bisphenol A digylcidyl ether, hydrogenated substituted

Bisphenol A digylcidyl ether oligomers, hydrogenated

substituted bisphenol-F-digylcidyl ether, hydrogenated substituted bisphenol-F-digylcidyl ether oligomers or a combination thereof, and

a B component comprising a carboxylic acid anhydride.

The first and the second epoxy compound differ according to the application. The epoxy resin system may also be referred to as an epoxy anhydride compound or casting resin composition.

The term "aromatic compound" means that the corresponding compound has at least one aromatic ring contains. Such a compound may also have ^non-¬ aromatic structures.

According to the application, the term "combination" is understood as far as possible. In a combination, but not all elements (here usually chemical

Compounds) of a group may be included. One element or several elements of the group can also be present several times in different modifications.

According to the application, the second epoxy compound, as stated above, a hydrogenated bisphenol A derivative and / or a hydrogenated bisphenol F derivative, wherein the hydrogenated

Bisphenol A derivative is selected from a group that

hydrogenated bisphenol A digylcidyl ether, hydrogenated bisphenol A diglycidyl ether oligomers, hydrogenated substituted

Bisphenol A digylcidyl ether, hydrogenated substituted

Bisphenol A diglycidyl ether oligomers or a combination thereof, and wherein the hydrogenated bisphenol F derivative is selected from the group consisting of hydrogenated bisphenol F digylcidyl ethers, hydrogenated bisphenol F diglycidyl ether oligomers, hydrogenated substituted bisphenol F diglycidyl ether, hydrogenated substituted bisphenol F-digylcidyl ether oligomers, or a combination thereof. Here, the term "hydrogenated" in the "hydrogenated

Bisphenol-A-derivatives "or" hydrogenated bisphenol F derivatives "that these formal hydrogenation of the corresponding aromatic bisphenol A derivatives are ^¬ relationship, bisphenol-F derivatives. That is, in these compounds, the benzene units of bisphenol A derivatives or bisphenol F derivatives formally by

Cyclohexane units are replaced. The hydrogenated bisphenol derivatives or bisphenol F derivatives may need but not necessarily have been prepared using hydrogenation ^¬ reactions, in the case of

Hydrogenation reaction, the hydrogenation reactions are ideally carried out completely.

Under hydrogenated bisphenol A digylcidyl ether

According to the application, a compound which is represented by the following structure of the formula I where n = 0,

Understood. For hydrogenated bisphenol A-digylcidyl ether oligomers, n = 1 to 30, in particular n = 1 to 20. n is especially chosen so that the compounds are liquid or meltable up to 60 ° C. It is also possible to use compounds with a low value for n, for example n = 1 to 10,

in particular n = 0 to 1, are used.

I

Under hydrogenated bisphenol F digylcidyl ether

According to the application, a compound which is represented by the following structure of the formula II where n = 0,

Understood. For hydrogenated bisphenol F-digylcidyl ether oligomers, n = 1 to 30, in particular n = 1 to 20. n is especially chosen so that the compounds are liquid or meltable up to 60 ° C. It is also possible to use compounds with a low value for n, for example n = 1 to 10,

in particular n = 0 to 1, are used.

II

The corresponding substituted compounds can

For example, have substituents on the cyclohexane rings of the hydrogenated bisphenol A units or bisphenol F units. These substituents are selected, for example, from halogen, in particular fluorine, and / or alkyl groups having 1 to 6 carbon atoms. The cyclohexane groups are substituted especially or only in the 2 and 2 'positions (ortho and ortho' positions) to the oxygen atoms, wherein one, two, three or even all four positions of the bisphenol A units or bisphenol F units can be substituted. These positions preferably have an H atom and a substituent selected from fluorine and / or alkyl group having 1 to 6 carbon atoms.

Preferably, all four positions are the same. In a further substitution variant, the methyl groups of the hydrogenated bisphenol A units are fluorinated, in particular perfluorinated.

The A component and the B component are usually stored separately from each other and before hardening of the

Epoxy resin mixed together. By curing the epoxy resin system, a molding material is available, also referred to herein as "epoxy resin molding material". The

Composition of the epoxy resin system therefore requires

largely or completely the properties of

Epoxy resin molding material. An epoxy resin molding material, which from the application according to

Epoxy resin system is produced, has on the one hand a very high resistance to aging and yellowing stability and on the other hand, very good low-stress properties. Such an epoxy resin molding material is characterized in particular by high strength, high thermal shock resistance, high dimensional stability and by a low tendency to brittleness, porosity or cracks. This also applies to composite materials with the epoxy molding material, which are not prone to delamination. The improved low-stress properties are accompanied by a high glass transition temperature T _G and a low storage modulus of the epoxy resin molding material. The epoxy molding material is therefore solder resistant, so that the epoxy resin system is also suitable for use in SMD components, for example LEDs (LED = light emitting diode). This compared to conventional

Epoxy resin molded materials improved properties are mainly due to the application according to the combination of first and second epoxy compound in the A component.

According to another embodiment, the first

Selected from the group consisting of bisphenol A diglycidyl ether, bisphenol A diglycidyl ether oligomers, bisphenol F diglycidyl ether, bisphenol F diglycidyl ether oligomers, epoxy novolacs, substituted bisphenol A diglycidyl ether, substituted bisphenol A, and the like diglycidyl ether oligomers, substituted bisphenol F diglycidyl ethers, substituted bisphenol F diglycidyl ether oligomers, or a combination thereof. Bisphenol A diglycidyl ether is represented by a structure of formula III where n = 0. In the case of bisphenol A diglycidyl ether oligomers, n = 1 to 30, in particular n = 1 to 20. Bisphenol F diglycidyl ether is represented by a structure of the formula IV where n = 0. In the case of bisphenol F diglycidyl ether oligomers, n = 1 to 30, in particular n = 1 to 20. It is also possible to use compounds of low value for n (formula III or IV), for example n = 1 to 10, in particular n = 0 to 1, are used. It can, for example, Araldit MY790-1 the Fa.

Huntsman can be used as the first epoxy compound. Other commercial first epoxide compounds are, for example, D.E.R. 332 from Dow Chemical and Epilox A 17-01 from Leuna Resins.

III

IV

The corresponding substituted compounds can

for example, substituents on the benzene rings of

Bisphenol A or bisphenol F units have. These substituents are selected, for example, from fluorine and / or alkyl groups having 1 to 6 carbon atoms. The

Benzene groups are substituted especially or only in the ortho and ortho 'positions to the oxygen atoms, wherein one, two, three or even all four positions may be substituted. Preferably, all four of these positions are the same. In a further substitution variant, the methyl groups of the bisphenol A units are fluorinated, in particular perfluorinated. In another embodiment, the first epoxide compound is selected from a group consisting of bisphenol A digylcidyl ethers, bisphenol A digylcidyl ether oligomers

Methyl and / or fluoro-substituted bisphenol A digylcidyl ether, methyl and / or fluoro substituted bisphenol A diglycidyl ether oligomers, or a combination thereof.

Surprisingly, according to the application, it has been found that these first epoxide compounds, although containing aromatic groups, are suitable for producing a yellowing-resistant epoxy resin molding material having very good low-stress properties. The increased yellowing resistance is due in particular to the presence of the second epoxy compound, with which the first

Epoxy compound is present together in the A component. In contrast, show conventional casting compounds, their underlying epoxy compounds (in addition to any

Reaktivverdünnern) are selected only from aromatic polyfunctional compounds, a significantly higher tendency to yellowing.

Furthermore, it is also possible to dispense with the addition of cycloaliphatic epoxide compounds, which is advantageous, since they are comparatively expensive and have a carcinogenic potential in admixture with aromatic diglycidyl ethers. In addition, a high proportion of cycloaliphatic epoxy compounds leads to brittle, less cyclic molding materials. Among cycloaliphatic epoxy compounds

according to the application understood compounds in which a

Epoxide function is part of a cycloaliphatic group. An example of a cycloaliphatic epoxide compound is 3,4- An epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate having the following structure (Formula V).

V

In contrast to cycloaliphatic epoxide compounds, the aromatic first epoxide compounds contribute to the high

mechanical resistance of an epoxy resin molding material. Epoxidharzformstoffe according to the invention therefore have a lower moisture absorption, are characterized by higher bond strength and higher stability to chemicals. However, proportionally cycloaliphatic epoxide compounds may possibly be present in the A component. This proportion can be less than 20% by weight

(Wt% = weight percent), in particular less than 10% by weight. Advantageously, it is also possible to dispense entirely with cycloaliphatic epoxide compounds.

According to another embodiment, the first

Epoxy compound bisphenol A digylcidyl ether, a bisphenyl A diglycidyl ether oligomer or a combination thereof. These compounds may have a viscosity of up to 20000 mPa * s at room temperature, which is accompanied by a low value for n in formula III. The value for n can therefore be n = 1 to 10, in particular n = 0 to 1. With this first epoxy compound in the A component epoxy resin molding materials can be obtained with very good properties in conjunction with the second epoxy compound, which are also due to the inexpensive bisphenol A diglycidyl ether very low in the production. According to another embodiment, the second

Selected from the group consisting of hydrogenated bisphenol A digylcidyl ethers, hydrogenated bisphenol A diglycidyl ether oligomers, hydrogenated bisphenol F digylcidyl ethers, hydrogenated bisphenol F-digylcidyl ether oligomers, hydrogenated methyl and / or fluoro-substituted bisphenol -A digylcidyl ether, hydrogenated methyl and / or

Fluoro-substituted bisphenol A diglycidyl ether oligomers, hydrogenated methyl and / or fluoro-substituted bisphenol F digylcidyl ethers, hydrogenated methyl and / or fluoro substituted bisphenol F diglycidyl ether oligomers, or a combination thereof. As the second epoxy compounds, for example, the commercially available compounds YX8000 or YX8034 from Mitsubishi Chemical Corporation can be used.

For example, a methyl and / or fluorine substitution can increase the stability of the epoxy resin molding material since these substituents can inhibit any possible decomposition reactions. Furthermore, in particular fluorine substituents can lead to an advantageous, further increased yellowing stability. This applies to both the first and the second epoxy compound.

According to a further embodiment, the second

Epoxy compound hydrogenated bisphenol A digylcidyl ether, a hydrogenated bisphenol A digylcidyl ether oligomer, or a combination thereof. These compounds can be added

Room temperature have a viscosity of up to 20,000 mPa * s, which is associated with a low value of n in formula I. The value for n can be n = 1 to 10, in particular n = 0 to 1. These connections are due to their advantageous price-performance ratio preferred.

In particular, with this second epoxy compound in

Combination with bisphenol A digylcidyl ether as the first

Epoxy compound an aging and yellowing-resistant epoxy resin molding material with very good thermomechanical properties

Properties are obtained.

In another embodiment, the A component contains from 5 to 90% by weight of the second epoxy compound. The A component may contain 10 to 80% by weight, in particular 10 to 60, preferably 10 to 45% by weight, of the second epoxide compound. Such a content of the second epoxy compound in the A component makes it possible, even in combination with first epoxy compounds having aromatic groups

Produce epoxy resin molding material with very good low-stress properties and improved yellowing resistance.

According to the application it was found that even with a proportion of 15 to 30% by weight of the second epoxide compound in the

A component is already a very advantageous Epoxidharzform- fabric can be produced. This is advantageous because the second epoxy compounds are usually more expensive than the first epoxy compounds, because usually an additional

Step, such as a hydrogenation reaction, for

Manufacturing is needed.

According to a further embodiment, the A component contains at least 20% by weight, in particular at least 40% by weight, of the first epoxide compound. The A component may contain, for example, 20 to 90% by weight of the first epoxy compound. The A component may in particular be 50 to 90% by weight, preferably

55 to 85% by weight of the first epoxy compound. Such a share of the A component can cheaper epoxy resin molded with a high glass transition temperature T _G ^¬ be obtained.

In another embodiment, the carboxylic acid anhydride is selected from the group consisting of an anhydride of a cycloaliphatic or aromatic dicarboxylic acid

Dianhydride of a cycloaliphatic or aromatic

Tetracarboxylic acid or a combination thereof. The carboxylic acid anhydride is particularly selected from hexahydrophthalic anhydride, methylhexahydrophthalic anhydride or a combination thereof. The preferred cycloaliphatic carboxylic acid anhydrides are advantageously liquid, have a low intrinsic color and lead to a better yellowing resistance than aromatic

Carboxylic.

According to a further embodiment, the B-component contains 55 to 95% by weight, in particular 60 to 90% by weight, carboxylic acid anhydride ^¬. The B component may contain, for example, at least 75% by weight of carboxylic acid anhydride. Such a content of carboxylic acid anhydride may be the epoxy resin molding material

necessary strength and impart a sufficiently high glass transition temperature T _G ^¬. According to a further embodiment, the B-component additionally contains at least one acidic carboxylic acid ester. Such an acidic carboxylic ester contains at least one free carboxylic acid group and at least one ester group. In particular, acidic carboxylic acid esters are used which, by alcoholysis, are one of those used according to the application

Carboxylic anhydrides with an alcohol are available. However, they can also be produced by other means. By the acidic carboxylic acid esters, in particular, the curing of the epoxy resin system are accelerated to epoxy resin molding material.

As alcohols in particular aliphatic and / or cycloaliphatic alcohols are used. The alcohols together with a carboxyl group form the at least one

Ester group of the acidic carboxylic acid ester. These

Aliphatic and / or cycloaliphatic alcohols may be selected, for example, from monoalcohols having 1 to 12 carbon atoms, diols, polyhydric alcohols, polyether polyols or a combination thereof. The choice of diols, polyhydric alcohols and polyether polyols is not particularly limited. For example, 1,2-propanediol, glycols or even aliphatic diols linked together through one, several or even numerous functional groups such as ether groups can be used. Examples of alcohols used are ethanol, 1, 2-propanediol, 1, 4-butanediol, 1, 6-hexanediol,

Isorbide (CAS 652-67-5), glycerol, diethylene glycol,

Polyethylene glycol, cyclohexanedimethanol, tricyclodecanedimethylol (CAS 26896-48-0) and trimethylolpropane.

According to a further embodiment, the B component contains from 5 to 40% by weight, in particular from 10 to 25% by weight, of acid

Carbonsäureester. For example, the B component may contain up to 20% by weight of acidic carboxylic acid ester.

According to a further embodiment, the B-component additionally contains an organic phosphorus compound and / or a metal salt. With one or more of these compounds, the hardening process can be accelerated and it will

in particular a bubble-free curing at high temperatures, for example above 150 ° C, allows. According to a further embodiment, the organic

Phosphorus compound selected from alkyl phosphites and / or aromatic phosphites. It can, for example

Triphenylphoshpit be used. With the organic phosphorus compounds in addition to the acceleration of the

Hardening process also the oxidation stability of the

Epoxy resin system or the corresponding

Increased molding material. The B component may contain, for example, 1 to 12% by weight, in particular 3 to 10% by weight, of one or more organic phosphorus compounds. The B component may, for example, up to 5% by weight

containing organic phosphorus compound.

According to another embodiment, the metal salt is selected from a group comprising alkoxides and / or carboxylates of zinc, yttrium, zirconium or a combination of these salts. The metal salt used is in particular zinc octoate. According to the application, the B component can contain 1 to 12% by weight, in particular 3 to 10% by weight, of metal salt. The B-component may contain, for example up to 5% by weight of metal salt ^¬. Like the organic phosphorus compound, the metal salt acts as a reaction accelerator, resulting in rapid, bubble-free curing of the epoxy resin system

is possible. This can be done advantageously in short cure cycles.

In another embodiment, the A component contains a third epoxy compound selected from glycidyl ethers of aliphatic alcohols and / or polyether polyols. The third epoxy compound can act as a reactive diluent. The third epoxide compound may in particular consist of glycidyl ethers of monoalcohols having 1 to 12 carbon atoms. from diglycidyl ethers of aliphatic diols having 1 to 12 carbon atoms, from glycidyl ethers of

Polyether polyols or a combination thereof may be selected. Examples of third epoxide compounds are

Butanediol diglycidyl ether or hexanediol diglycidyl ether. Via the third epoxy compound, the viscosity of the epoxy resin system ^¬ can be adjusted. The third epoxy compound can be used as a so-called reactive diluent. A reactive diluent is a diluent used in the

Hardening process becomes part of the plastic. The

For example, A component may contain 1 to 20% by weight of the third epoxy compound.

According to a further embodiment, the A-component contains at least one of an alcohol, an adhesion promoter, a deaerator, an internal release agent, yellowing stabilizer, thixotropic agents, diffuser pigments,

Converter materials, aggregates, dyes and / or optical brighteners. For these additives conventional compounds can be used. Examples of adhesion promoters are silanes such as Trialkoxypropylsilane the

Structure (RO) 3Si-propyl-X, wherein R = alkyl and X is an atom or a group on the propyl radical, in particular

Glycidoxypropyltrimethoxysilane (ie X = glycidoxy), which is commercially available as silanes A-187 from ABCR GmbH. The so-called deaerators can be used as active substances in small proportions of fluoroorganic and / or

containing siloxane-containing compounds. For example, BYK A-506 from BYK Chemie can be used as deaerator. For example, Masterbatch 09 from CIBASCININ can be used as an optical brightener. As diffuser pigments white pigments, in particular white pigments based on, for example, CaF ₂ , TiO ₂ , Al ₂ O 3, ZrO _2, etc., can be used. According to another embodiment of the epoxy resin system, the A component has the following composition:

In this specified composition, one or more components may not be included. For example, the statement "<3% by weight" means 0 to 3% by weight inclusive. For the rest of the information applies

corresponding.

According to another embodiment of the epoxy resin, the A-component contains 20 to 90 wt% of the first epoxy ^¬ compound and 10 to 80% by weight of the second epoxy compound and the B-component contains 60 to 90% by weight Cabonsäure- anhydride and from 5 to 40% by weight of an acid carboxylic ester. The A component may in particular 55 to 90% by weight of the first epoxy compound and 10 to 45% by weight of the second

Contain epoxy compound and the B component can in particular 60 to 90% by weight of carboxylic acid anhydride and 5 to 40% by weight of an acid carboxylic ester. Optionally, an A component of this embodiment may contain 1 to 20% by weight of the third epoxy compound. In particular, in these specified areas of the epoxy resin system by curing a molding material is formed, which has a very high resistance to aging and yellowing and very good low-stress properties, so that the components can be preferably used in these areas.

In another embodiment, the epoxy resin system contains A component and B component in a ratio of 100: 60 to 100: 120. The ratio of A component to B component is given as a mass ratio.

The A component and B component according to the application are included separately for at least six months

Room temperature (equivalent to 25 ° C) storable without noticeable by-products or decomposition products are formed. An epoxy resin system according to the application, comprising A and B components, can be stored at room temperature for at least three hours, in particular at least four hours, without the viscosity of the epoxy resin system being increased by more than 50%. As a result, for example, the industrial use of the epoxy resin system is facilitated.

According to a further embodiment, the epoxy resin system at 25 ° C has a viscosity of <5000 mPa * s. The viscosity is in particular ^ 3000 mPa * s. By a

Viscosity in this range is the epoxy resin system for use in a reel-to-reel process, as a quick dosing of the epoxy resin system is possible. According to a further embodiment, the epoxy resin system at temperatures of> 125 ° C within a maximum of 30 minutes can be hardened (so-called precuring). The epoxy resin system can be cured at temperatures of> 145 ° C, in particular> 150 ° C. This can happen, for example, within a maximum of 15 minutes, in particular a maximum of 8 minutes. The hardening of the epoxy resin system may be, for example, in

so-called curing cycles take place. A fast

Curing of the epoxy resin system is in particular by a combination of acidic carboxylic ester, organic

Phosphorus compound and / or metal salt allows. The

Hardening takes place advantageously bubble-free. These fast curing times make it suitable

Epoxy resin system, in particular for the series production of electronic components, in particular optoelectronic components, or for the production or attachment of optical components. Such serial production can be realized, for example, in a reel-to-reel process. With the above conditions for curing the

Epoxy resin system is obtained by the crosslinking in particular a no longer flowable molding material. A complete curing or crosslinking to the epoxy resin molding material is usually in a subsequent curing step

(so-called postcuring) received. For example, four hours is heated to> 140 ° C.

According to another embodiment, the epoxy resin system has a chlorine content of <900 ppm. The chlorine content can even be <600 ppm. A low chlorine content is in particular desirable in order to reduce the formation of health ^¬ harmful compounds upon thermal decomposition, for example during a fire. As a further aspect of the application, an epoxy resin molding material is specified. The Epoxidharzformstoff according to the application may in particular comprise a hardened epoxy resin according to at least one embodiment of the application, consist thereof or be obtainable therefrom. For this purpose, the epoxy resin system may have been cured as described above. The composition and properties of the epoxy molding material therefore result substantially or wholly from the underlying epoxy resin system and the underlying curing process.

According to a further embodiment, the epoxy resin molding material has a glass transition temperature T _G of> 130 ° C. The glass transition temperature T _G can be> 135 ° C. The

Glass transition temperature T _G remains even after up to six DSC measurements (DSC = Dynamic Scanning Calorimetry)

Temperatures of up to 260 ° C and heating rates of 10 K / min almost unchanged. Almost unchanged means that the glass transition temperature T _G is less than 5 ° C,

especially less than 2 ° C, changes.

Furthermore, the high thermal dimensional stability of the Epoxidharzformstoff according to the application shows in a low weight loss at high temperatures. In thermogravimetric analyzes (TGA) at 260 ° C in air and a

Heating rate of 10 K / min may be the weight loss of a sample <1.0%, in particular <0.5%. The weight loss of a sample can be less than 0.3% SθϊΠ.

According to a further embodiment, the epoxy resin molding material has a thermal expansion coefficient of <80 ppm / K. The thermal expansion coefficient can <70 ppm / K and especially <65 ppm / K. The data refer to the temperature range from -50 ° C to + 50 ° C and are determined in thermomechanical analyzes (TMA).

According to a further embodiment, the epoxy resin molding material has a storage modulus at 20 ° C. of <2600 MPa,

in particular of <2500 MPa, up. The memory module is determined according to the application in dynamic mechanical measurements (DMTA, dynamic mechanical thermal analysis) in the tensile mode with a measuring frequency of 1 Hz.

The low memory module expresses the very good low-stress properties of the epoxy resin molding material. In particular, a low storage modulus is achieved with a high glass transition temperature T _G of> 130 ° C. Conventional Epoxidharzformstoffe, for example, apart from reactive ^¬ thinners, were prepared using only aromatic epoxy compounds, however, have a significantly higher storage modulus at 20 ° C, for example, about 2800 MPa. Thus, according to the application

Epoxy resin molding material exhibits improved aging resistance in the component, for example with mechanically sensitive LED chips, and is, in particular, insensitive to thermomechanical stress, as occurs, for example, during soldering, with the result that epoxy resin molding material is also suitable for SMD-capable components. The Epoxidharzformstoff according to the application therefore does not tend to brittleness, cracks or cracks, so that, for example, an electronic device over a long period of time very well against air and moisture

can be protected.

The Epoxidharzformstoff according to the application shows in itself a low moisture absorption. The cold water intake at 14 days storage in cold water at 23 C can be 0.55 "6 for Example <0.48%, amount. As a result, an effective protection of electronic components is made possible. Of the

Epoxidharzformstoff is therefore also suitable for a

Use for components or components used outside enclosed spaces.

In another embodiment, the epoxy resin molding material is transparent to visible light. The epoxy ^¬ form material can thereby also be colorless. This is especially the case when no converter materials, dyes or color pigments with a distinct body color in the

underlying epoxy resin system were included. Of the

Epoxidharzformstoff can, for example in the range of 400 to 800 nm wavelength, a transmission of> 85%,

in particular of> 88%. The epoxy resin system or the Epoxidharzformstoff is therefore also suitable for arrangement in the beam path of optoelectronic devices. Furthermore, an epoxy resin molding material according to the application can have a very high yellowing resistance. Even with a three-day UV broadband irradiation with a

Intensity of 60 mW / cm ² can be according to the application

Epoxy resin molding material have only slight discoloration. The yellowing is especially lower than at

conventional mold materials of epoxy resins based only on aromatic epoxy compounds.

As a further aspect of the application, the use of an epoxy resin system is specified. An epoxy resin system according to at least one embodiment of the application can be used in the field of electronics as well as for the production and / or attachment of optical components. It can do that Epoxy resin system for example for potting, covering,

Coating, wrapping, encapsulating, gluing, fixing or the like of electronic and opto-electronic

Components and optical components serve. Optical components or components associated with the

Epoxy resin system can be attached or produced, for example, lenses, prisms, filters, optical windows, reflector elements, reflector housing, etc. A

Component can be called according to the application as a component. As the reflector element or reflector housing, the epoxy resin ^{molding material} or the epoxy resin system can contain white pigments. These white pigments are based in particular on CaF ₂ , TiO ₂ , Al ₂ O 3, ZrO ₂ or the like. The field of electronics, in which the according to the application

Epoxy resin system or the resulting

Epoxy resin molding material is not limited. Since the epoxy resin system can be used to produce an aging-resistant and yellowing-resistant epoxy resin molding material having very good low-stress properties, the epoxy resin system according to the application is suitable, for example, for SMD-compatible materials

electronic components, in particular optoelectronic components such as LEDs. It can be used for example as potting, housing and / or as a reflector of components such as LEDs. Furthermore, the epoxy resin system can also be used in component applications as well as groups of

Components are used in the automotive sector and in outdoor applications. Another example of the use of the epoxy resin system is its use as a conversion element in

optoelectronic components such as LEDs, in particular in white-luminescent LEDs. For this, the epoxy resin system

Converter materials included.

As a further aspect of the application, an electronic, opto-electronic or optical device is provided which comprises a epoxy resin molded material according to at least one execution ^¬ form of the application. This can also from the

Epoxy resin molded consist.

According to a further embodiment, the component is a light-emitting diode, a photodiode, a phototransistor, a photoarray, an optical coupler, an SMD component or an SMD-capable component. The component is preferably an optoelectronic component. The component can be used, for example, for the automotive sector and / or for

Outdoor applications are suitable. It can also be one of the other components mentioned, for which the epoxy resin system is used.

According to a further embodiment, the optical

Component or component, a lens, a prism, a filter, an optical window, a reflector element, a reflector housing or a conversion element.

Exemplary embodiments:

1st embodiment:

It became an A component

Araldite MY790-1 79, 685% by weight

YX8000 20% by weight

BYK A-506 0.30% by weight

Masterbatch 09 0.015% by weight mixed with a B component according to the application and cured as described above. Araldit MY790-1 is a first epoxy compound, YX8000 a second epoxy compound, BYK A-506 a deaerator and Masterbatch 09 an optical brightener. The B component contains> 75% by weight

Methylhexahydrophthalic anhydride, <20% by weight acid

Carboxylic esters, <8% by weight of zinc octoate and <5% by weight

Triphenyl phosphite. The epoxy resin molding thus prepared has a

Glass transition temperature T _G of 137 ° C, which remains stable over six DSC measurements. Was measured from 40 to 260 ° C at a heating rate of 10 K / min. The storage modulus at 20 ° C is 2424 MPa. The weight loss at 260 ° C is less than 0.3%, being heated from room temperature to 10 K / min (TGA measurement). The thermal

Coefficient of expansion between -50 ° C and + 50 ° C is 63 ppm / K (TMA measurement). The chlorine content is 515 ppm. The moisture absorption after 14 days cold water storage at 23 ° C was determined to be 0.48%.

2nd embodiment:

It became an A component

mixed with a B component according to the application and cured as described above. The B component contains> 75% by weight of methyl hexahydrophthalic anhydride, <20% by weight of acidic carboxylic acid ester, <8% by weight of zinc octoate and <5% by weight of triphenyl phosphite. The epoxy resin molding thus prepared has a glass transition temperature T _G of 139 ° C, which remains stable over six DSC measurements. Was measured from 40 to 260 ° C at a heating rate of 10 K / min. The storage modulus at 20 ° C is 2213 MPa. The weight loss at 260 ° C is less than 0.3%, being heated from room temperature to 10 K / min (TGA measurement). The thermal expansion coefficient ^¬ between -50 ° C and + 50 ° C is 65 ppm / C (TMA measurement).

Further advantages, advantageous embodiments and

Further developments of the invention will become apparent from the im

Following embodiments described in connection with the figures and examples.

Show it

Figures 1 to 3 a DMTA spectrum, a TMA spectrum

or a TGA spectrum of an epoxy resin molding material according to FIG. 1.

Embodiment, and

Figures 4 to 6 a DMTA spectrum, a TMA spectrum

or a TGA spectrum of a

Epoxidharzformstoffs after the 2nd

Embodiment.

FIG. 1 shows a DMTA measurement for an epoxy resin molding material produced according to the first exemplary embodiment. In the curve 1 shows the course of the memory module with increasing temperature, with a heating rate of

3 K / min is heated. At 0 ° C will have a memory module of 2535 MPa, at 20 ° C a storage modulus of 2424 MPa and at 100 ° C a storage modulus of 1633 MPa measured. The curve 2

describes the Tan Delta (Tan Δ), after which the glass transition temperature T _G can be determined, here 139 ° C.

The Epoxidharzformstoff according to the first embodiment thus has a high glass transition temperature and a low storage modulus, resulting in a very good

Aging resistance and excellent low-stress properties expresses.

FIG. 2 shows a TMA measurement for an epoxy resin molding material produced according to the first exemplary embodiment.

This results in a thermal expansion coefficient between -50 ° C and + 50 ° C of 63 ppm / K. The expansion is essentially linear in this area. The measurement was made for a 2.02 mm thick sample.

FIG. 3 shows a TGA measurement for an epoxy resin molding material produced according to the first exemplary embodiment. Here, the residual mass of the sample is plotted in% over time (curve 3). It was heated from room temperature to 320 ° C at a heating rate of 10 K / min in air. The temperature profile is shown in curve 4. At a temperature of 260 ° C, a mass loss of <0.3 ~ 6 is measured.

FIGS. 4 to 6 show spectra for the corresponding measurements with an epoxy resin molding material which, according to FIG.

Embodiment was made.

It can be seen from the DMTA measurement of FIG. 4 that at 0 ° C. a storage modulus of 2332 MPa, at 20 ° C. a storage modulus of 2213 MPa and at 100 ° C. a storage modulus of 1729 MPa present (curve 5). The heating rate was again 3 K / min. The curve 6 describes the Tan Delta, after which the

Glass transition temperature T _{G was determined} to 139 ° C. Also, the epoxy resin molding material according to the second embodiment thus has a high glass transition temperature T _G and a low storage modulus, which manifests itself in particular in a very good aging resistance and excellent low-stress properties.

From the TMA measurement of Figure 5 results in a thermal expansion coefficient between -50 ° C and + 50 ° C of 65 ppm / K. Here too, a substantially linear expansion is evident in this temperature range. The measurement was made for a 4.27 mm thick sample.

From the TGA measurement to Figure 6 results in a mass loss of <0.3% at a temperature of 260 ° C. It was by

Room temperature heated to 320 ° C at a heating rate of 10 K / min in air. Again, the residual mass over time (curve 7) and the temperature curve (curve 8) are shown.

The invention is not limited by the description based on the embodiments of these. Rather, the invention includes every new feature as well as any combination of

Features, which includes in particular any combination of features in the claims, even if this feature or this combination itself is not explicitly in the

Claims or embodiments is given.

Claims

claims

An epoxy resin system comprising

an A component comprising a first epoxy compound and a second epoxy compound,

wherein the first epoxy compound is an aromatic

Comprises compound having at least two epoxide functions,

wherein the second epoxide is selected from the group consisting of hydrogenated bisphenol-A-digylcidyl ^¬ ether, hydrogenated bisphenol-A-digylcidylether- oligomers, hydrogenated bisphenol F diglycidyl ether, hydrogenated, hydrogenated bisphenol F diglycidyl ether oligomers substituted bisphenol-A diglycidyl ether, hydrogenated substituted bisphenol A digylcidyl ether oligomers, hydrogenated substituted bisphenol F digylcidyl ethers, hydrogenated substituted bisphenol F digylcidyl ether oligomers or a combination thereof, and

a B component comprising a carboxylic acid anhydride.

2. Epoxy resin system according to claim 1,

wherein the first epoxide compound is selected from the group consisting of bisphenol A diglycidyl ethers, bisphenol A diglycidyl ether oligomers, bisphenol F diglycidyl ethers, bisphenol F diglycidyl ether oligomers, epoxy novolacs, substituted bisphenol A diglycidyl ethers, substituted bisphenol A diglycidyl ether oligomers, substituted bisphenol F diglycidyl ethers, substituted bisphenol F diglycidyl ether oligomers, or a combination thereof.

3. Epoxy resin system according to claim 1 or 2,

wherein the first epoxide compound is selected from the group consisting of bisphenol A digylcidyl ethers, bisphenol A digylcidyl ether oligomers, methyl- and / or fluoro-substituted bisphenol A digylcidyl ethers, methyl- and / or fluoro-substituted bisphenol-A di-glycidyl ether oligomers or a combination thereof.

4. Epoxy resin system according to one of the preceding claims, wherein the A component contains 5 to 90% by weight of the second epoxy compound ^¬ .

5. Epoxy resin system according to one of the preceding claims, wherein the A component contains at least 20% by weight of the first epoxy compound.

6. Epoxy resin system according to one of the preceding claims, wherein the B component additionally contains at least one acidic carboxylic acid ester.

7. Epoxy resin system according to one of the preceding claims, wherein the B component additionally an organic

Phosphorus compound and / or a metal salt.

The epoxy resin system of any one of the preceding claims, wherein the A component comprises a third epoxy compound selected from glycidyl ethers of aliphatic

Alcohols and / or polyether polyols is selected.

9. Epoxy resin system according to one of the preceding claims, wherein the A component

From 20 to 90% by weight of the first epoxide compound,

10 to 80% by weight of the second epoxide compound contains, and

where the B component

- 60 to 90% by weight of carboxylic acid anhydride

5 to 40% by weight of an acid carboxylic ester

contains.

10. Epoxy resin system according to one of the preceding claims, wherein the epoxy resin at 25 ° C, a viscosity of

<5000 mPa * s.

11. Epoxy resin system according to one of the preceding claims, wherein the epoxy resin system at temperatures of> 125 ° C within a maximum of 30 minutes can be hardened.

12. Epoxidharzformstoff comprising a cured epoxy resin system according to any one of claims 1 to 11.

13. Use of an epoxy resin system according to one of

Claims 1 to 11 in the field of electronics and for the production and / or attachment of optical

Building elements.

14. Electronic, optoelectronic or optical

A device comprising an epoxy molding material according to claim 12.

15. The component according to claim 14, wherein the component is a light-emitting diode, a photodiode, a phototransistor, a photoarray, an optical coupler, an SMD component or an SMD-capable component.