EP1928968A1 - Uv-curing adhesive, preparation process, adhesively bonded semiconductor component, and method of adhesive bonding - Google Patents
Uv-curing adhesive, preparation process, adhesively bonded semiconductor component, and method of adhesive bondingInfo
- Publication number
- EP1928968A1 EP1928968A1 EP06806828A EP06806828A EP1928968A1 EP 1928968 A1 EP1928968 A1 EP 1928968A1 EP 06806828 A EP06806828 A EP 06806828A EP 06806828 A EP06806828 A EP 06806828A EP 1928968 A1 EP1928968 A1 EP 1928968A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- adhesive
- substrate
- resin
- particles
- curable
- 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
Links
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 62
- 239000000853 adhesive Substances 0.000 title claims abstract description 61
- 239000004065 semiconductor Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004026 adhesive bonding Methods 0.000 title abstract 2
- 238000002360 preparation method Methods 0.000 title description 5
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000004927 clay Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims description 30
- 238000005538 encapsulation Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000002318 adhesion promoter Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 2
- 229910000271 hectorite Inorganic materials 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 238000003848 UV Light-Curing Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002734 clay mineral Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000035699 permeability Effects 0.000 description 7
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- -1 ammonium ions Chemical class 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 238000004299 exfoliation Methods 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 230000001473 noxious effect Effects 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004823 Reactive adhesive Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/02—Containers; Seals
- H01L23/10—Containers; Seals characterised by the material or arrangement of seals between parts, e.g. between cap and base of the container or between leads and walls of the container
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12044—OLED
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/13—Discrete devices, e.g. 3 terminal devices
- H01L2924/1304—Transistor
- H01L2924/1306—Field-effect transistor [FET]
- H01L2924/13091—Metal-Oxide-Semiconductor Field-Effect Transistor [MOSFET]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/287—Adhesive compositions including epoxy group or epoxy polymer
Definitions
- UV-curing adhesive for manufacture, bonded semiconductor device and method of bonding
- the invention relates to a UV-curing adhesive with organic clay minerals for bonding and encapsulating semiconductor devices, a process for producing such an adhesive, bonded or encapsulated Halbleiterbau- elements and a method for bonding or encapsulation.
- the adhesives should not only ensure a secure and rapid bonding of the individual components, but they should also reliably prevent the penetration of, for example, water, moisture and harmful gases. This is of particular importance in particular for organic, light-emitting diodes (OLEDs).
- OLEDs organic, light-emitting diodes
- OLEDs comprise organic monomers or polymers interposed between electrodes, with one electrode being transparent. When a voltage is applied to the electrodes, the emission of light takes place.
- OLEDs include an organic electroluminescent material (emitter), an organic hole transporting material, and an organic electron transporting material. These materials, as well as the cathode material, must be protected from degradation by air (oxygen) and water, which requires efficient encapsulation or packaging.
- Various encapsulations are described, for example, in European Patent 1 218 950 Bl, which, however, all have specific disadvantages, as illustrated below.
- the OLEDs are enclosed by a glass housing, wherein the glass parts must be connected to each other.
- Glass soldering i. the bonding of glass parts through a glass solder, has the disadvantage of heating the diode, which may cause the polymer materials can be destroyed.
- EP 1 218 950 B1 also discloses an epoxy adhesive.
- This adhesive is a UV-curable reactive adhesive and does not require any heating of the adhesive to cure. However, it still has the disadvantage that the penetration of noxious gases and moisture can not be reliably prevented.
- US Pat. No. 2003/39812 proposes epoxy resins which are mixed with organic clay materials, so-called organoclays, in order to reduce the permeability to noxious gases and moisture and to reduce the hygroscopic properties of the resin.
- organoclays organic clay minerals
- thermosetting plastics since only by a slow curing process, as in the case of thermosetting plastics
- Plastics is present, a substantial or complete exfoliation of the phyllosilicates is possible.
- the curing in UV-curable resins takes place within a few seconds. This period of time is not sufficient for the exfoliation of the clay minerals.
- Thermosetting plastics in turn have the disadvantage that the parts to be bonded must be heated to cure the plastic. This can cause damage to the partially sensitive components.
- a UV-curable adhesive comprising at least one UV-curable resin and a plurality of organic clay particles having a high aspect ratio with respect to a height to a length of a particle.
- a process for producing a UV-curable resin containing a plurality of organic clay particles having a high aspect ratio with respect to a height to a length of a particle comprising the steps of: a) providing a resin ; b) dispersing an organic clay material in the resin; c) swelling the organic clay in the resin for a predetermined period of time; d) homogeneous mixing of the swollen mixture.
- a semiconductor device having a substrate and a semiconductor structure integrated with the substrate or mounted on a surface of the substrate is provided with a semiconductor structure protection package and an adhesive as claimed in any of claims 1-6 ,
- a method for bonding substrates comprising the following steps:
- Curing in the adhesive to exfoliate Such an adhesive, which already contains exfoliated clay minerals, has a reduced permeability to moisture or noxious gases and is not detrimental to heat-sensitive parts, since curing takes place via UV irradiation.
- the adhesive is well storable. Since at least one dimension of the particles is in the nanometer range, they show no or no significant light scattering and thus do not affect the adhesive with respect to the light transmission.
- the adhesives can be produced solvent-free and are thus very good for the environment. Reducing the volumetric fill of inorganic material over conventional fillers improves adhesion to the substrate surfaces. It also reduces mechanical stress and the modulus of elasticity, which reduces the formation and propagation of cracks.
- the exfoliated clay minerals dispersed in the adhesive have an aspect ratio of greater than 10, preferably greater than 100, more preferably greater than 1000.
- an exfoliated clay mineral particle is characterized by its greatly differing extents. These particles have a height of typically a few nanometers. In contrast, the width and the length of the particles can be in the range of micrometers. To determine the dimensions of a particle, its height, width and length are used. The height is the shortest and the length is the longest extent. The particles correspond to isolated crystal lamellae.
- an epoxy resin is preferably used. This epoxy resin may be an aliphatic and / or cycloaliphatic epoxy resin. The use of bisphenol A has proven particularly advantageous.
- Diglycidyl ether exposed as an epoxy resin.
- the organic clay minerals that form the particles can be obtained from natural and / or synthetic clay mineral. These can be prepared by intercalation and / or exfoliation. During the intercalation, the alkali metal and / or alkaline earth metal ions, which are located between the crystalline layers, are exchanged for suitable ammonium compounds and / or carboxylic acids. During this process, the layer compounds are made oranophilic and thus plastic compatible. The layer compounds prepared in this way are called organoclays.
- Bentonite, hectorite, montmorillonite and / or hydrotalcite are preferably used as organic clay material.
- the adhesive preferably additionally comprises further substances. These may e.g. Adhesion promoter, photoinitiator and / or filler.
- Adhesion promoters can be silane-based, for example.
- alkoxy-functional silanes which are generally methoxy- and ethoxy-functional silanes, can be used to advantage.
- the silanes usually carry at least one other group that over
- the coupling agent may preferably be added to the adhesive in an amount of 0.05 to 2% by mass.
- the photon initiator used is advantageously an onium salt, in particular a triarylsulfonium salt with hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate as anion, for example triphenylsulfonium hexafluoroantimonate.
- the photoinitiator is preferably tiator used in a proportion of 0.01 to 5 mass%.
- fillers may be included. These fillers can be used, for example, to adjust the flow properties.
- suitable fillers are quartz flours or other mineral fine flours, in particular based on silicic acid.
- other known additives or additives can be added. These may include, for example, dyes, pigments, wetting aids, leveling agents, adhesion promoters, thixotropic agents, defoamers, flow modifiers, stabilizers and flame retardants.
- the adhesive can be given additional properties such as color, special rheological properties and high flammability.
- the adhesive may also contain a polyol. The polyols are used to modify the mechanical properties of the cured
- the reaction adhesive may additionally contain a surface-active compound, in particular a surface-active siloxane.
- Such additives serve as defoamers and leveling agents.
- the proportion of surface-active compounds is low. It is generally only 0.1 to 0.5 mass%.
- the process for producing a UV-curable resin involves dispersing the organoclays in the resin. Subsequently, the organoclay is exfoliated in a swelling phase.
- the swelling can be carried out at a temperature in the range of 20-120 0 C, preferably in the range of 40-100 0 C.
- the swelling time is from 1 to 10 hours, preferably from 4 to 12 hours.
- the mixture is then homogenized again. In this case, further substances such as a UV-hardener or photoinitiator can be added.
- the adhesive can be advantageously used in encapsulating semiconductor devices in several embodiments.
- the adhesive may be used to bond a capping be used with a substrate or as encapsulation itself. It can also be used wherever adhesive properties are required together with an airtight or gas-tight seal. Therefore, the adhesives of the present invention can be preferably used in the encapsulation of OLEDs.
- the adhesive is applied to at least one surface of at least one of the substrate parts.
- the UV-curable adhesive is cured by irradiation with UV light.
- light is used here in the absorption maximum or close to the absorption maximum of the UV photoinitiator.
- light in the absorption maximum of the ultraviolet curable resin itself may be used as far as it absorbs in the ultraviolet region. Wavelengths shorter than 400nm are used for this.
- Figure 1 is a cross-sectional view of an encapsulated OLED
- FIG. 2 is a cross-sectional view of a power device encapsulated with an adhesive.
- the filler was first in the desired concentration with the aid of a dispersing machine in 100 parts by mass of a Bisphenol A diglycidyl ether resin dispersed. After a swelling period of 8 hours at a temperature of 80 0 C 3 mass parts of UVI were UCC (Union Carbide Chemicals) as a UV curing agent is added 6974 to the mixture after cooling. The mixture was then stirred for a further 15 minutes at room temperature, degassed and then applied by screen printing on a substrate surface in a layer thickness of about 0.25 mm.
- UCC Union Carbide Chemicals
- the curing takes place under a commercially available UV lamp from Hönle by irradiation for a period of 30 seconds.
- UV curing agent UV 6974
- UV curing agent UV 6974
- the water vapor permeability (WDD) of the epoxy resin nanocomposite molding materials was investigated by means of a Ca-level.
- a Ca-mirror is deposited in a glass cavity with a thickness of about 1 micron.
- the adhesive used is the epoxy resin nanocomposite according to the invention.
- the diffusion takes place through the adhesive layer.
- a measure of the diffusion is the fading of the Ca-level by diffusing moisture when stored in a climate of 70 0 C and 90% relative humidity. The results of the tests are shown in Table 1.
- Table 1 Time to fade of Ca level as a measure of water vapor permeability.
- the water vapor permeability of the samples according to the invention is superior to that of the comparative example.
- FIG. 1 shows a cross-sectional view of an encapsulated OLED.
- two layers 2 and 3 are applied to form the OLED on a substrate 1.
- the two layers are surrounded by an encapsulation 4.
- This encapsulation 4 is bonded to the substrate via an adhesive 5.
- the substrate 1 is the two organic layers 2, 3 for the production the OLED applied.
- an adhesive 5 is applied to the contact region of the encapsulation 4 with the substrate 1.
- the encapsulation 4 is placed on the substrate 1 with the applied adhesive 5, so that the OLED is encapsulated by the encapsulation 4.
- Figure 2 shows a cross-sectional view of an encapsulated with an adhesive power device 6.
- the adhesive 7 is poured over the applied to a substrate 1 device 6, whereby this is encapsulated.
- the power device may be, for example, a MOSFET, a JFET or a thyristor.
- the present invention has been described above with reference to a preferred embodiment, it is not limited thereto, but modifiable in many ways.
- the invention is not limited to the specific structure of an OLED shown in the preceding figure. Rather, the adhesive may also be used to encapsulate other semiconductor devices.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
Beschreibungdescription
UV-härtender Klebstoff, Verfahren zur Herstellung, verklebtes Halbleiterbauelement und Verfahren zum VerklebenUV-curing adhesive, method of manufacture, bonded semiconductor device and method of bonding
Die Erfindung betrifft einen UV-härtenden Klebstoff mit organischen Tonmineralien zur Verklebung und Verkapselung von Halbleiterbauelementen, ein Verfahren zur Herstellung eines solchen Klebstoff, verklebte oder verkapselte Halbleiterbau- elemente sowie ein Verfahren zum Verkleben oder Verkapseln.The invention relates to a UV-curing adhesive with organic clay minerals for bonding and encapsulating semiconductor devices, a process for producing such an adhesive, bonded or encapsulated Halbleiterbau- elements and a method for bonding or encapsulation.
Häufig werden bei der Montage von Halbleiterbauelementen diverse Teile des Halbleiterbauelements durch Klebemassen miteinander verbunden bzw. im Rahmen eines so genannten Bauele- ment-Packaging gekapselt. Mit den steigenden Anforderungen an die Halbleiterbauelemente steigen auch die Anforderungen an derartige Klebemassen. So sollen die Klebstoffe nicht nur ein sicheres und schnelles Verkleben der einzelnen Komponenten sicherstellen, sondern sie sollen des Weiteren auch das Ein- dringen von beispielsweise Wasser, Feuchtigkeit und Schadgasen zuverlässig verhindern. Dies ist insbesondere bei organischen, lichtemittierenden Dioden (OLEDs) von besonderer Bedeutung. Die Erfindung soll nachfolgend am Beispiel von OLEDs beschrieben werden, ist jedoch nicht darauf beschränkt.Frequently, during the assembly of semiconductor components, various parts of the semiconductor component are bonded together by means of adhesives or encapsulated in the context of a so-called component packaging. With the increasing demands on the semiconductor devices, the requirements for such adhesives are also increasing. Thus, the adhesives should not only ensure a secure and rapid bonding of the individual components, but they should also reliably prevent the penetration of, for example, water, moisture and harmful gases. This is of particular importance in particular for organic, light-emitting diodes (OLEDs). The invention will be described below using the example of OLEDs, but is not limited thereto.
OLEDs weisen organische Monomere oder Polymere auf, die zwischen Elektroden angeordnet sind, wobei eine Elektrode transparent ist. Beim Anlegen einer Spannung an die Elektroden erfolgt die Emission von Licht. OLEDs weisen dazu typischerwei- se ein organisches elektrolumineszierendes Material (Emitter) , ein organisches Löcher transportierendes Material und ein organisches Elektronen transportierendes Material auf. Diese Materialien sowie das Kathodenmaterial müssen vor einer Degradation durch Luft (Sauerstoff) und Wasser geschützt wer- den, wozu eine effiziente Kapselung oder ein Gehäuse erforderlich ist. Verschiedene Verkapselungen sind beispielsweise in dem Europäischen Patent 1 218 950 Bl beschrieben, die jedoch alle spezifische Nachteile aufweisen, wie im Folgenden dargestellt wird.OLEDs comprise organic monomers or polymers interposed between electrodes, with one electrode being transparent. When a voltage is applied to the electrodes, the emission of light takes place. Typically, OLEDs include an organic electroluminescent material (emitter), an organic hole transporting material, and an organic electron transporting material. These materials, as well as the cathode material, must be protected from degradation by air (oxygen) and water, which requires efficient encapsulation or packaging. Various encapsulations are described, for example, in European Patent 1 218 950 Bl, which, however, all have specific disadvantages, as illustrated below.
Bevorzugt werden die OLEDs durch ein Glasgehäuse eingefasst, wobei die Glasteile miteinander verbunden werden müssen. Das Glaslöten, d.h. das Verbinden von Glasteilen durch ein Glaslot, hat dabei den Nachteil, die Diode zu erwärmen, wodurch unter Umständen die Polymermaterialien zerstört werden können .Preferably, the OLEDs are enclosed by a glass housing, wherein the glass parts must be connected to each other. Glass soldering, i. the bonding of glass parts through a glass solder, has the disadvantage of heating the diode, which may cause the polymer materials can be destroyed.
Auch die Verklebung von Glasteilen, wie Glassubstraten, Glasplatten oder Glasverkapselungen, mit unterschiedlichen, zu- meist wärmehärtenden Klebstoffen ist bekannt. Die hierfür eingesetzten Klebstoffe weisen jedoch alle den Nachteil auf, dass der Ausschluss von Feuchtigkeit nicht vollständig gewährleistet werden kann. Daher werden oftmals so genannte Gettermaterialien eingesetzt, um eindringende Feuchtigkeit abzufangen und zu binden. Da diese Materialien mit der Zeit verbraucht werden, verlieren sie im Verlauf der Zeit an Effektivität, sodass das OLED nicht mehr vor eindringender Feuchtigkeit geschützt werden kann.The bonding of glass parts, such as glass substrates, glass plates or Glasverkapselungen, with different, mostly thermosetting adhesives is known. However, the adhesives used for this all have the disadvantage that the exclusion of moisture can not be fully guaranteed. Therefore, so-called getter materials are often used to trap and bind ingressing moisture. As these materials are consumed over time, they lose their effectiveness over time, preventing the OLED from being protected from moisture.
In der EP 1 218 950 Bl wird auch ein Epoxidharz-Klebstoff offenbart. Dieser Klebstoff ist ein UV-härtbarer Reaktionsklebstoff und erfordert zum Aushärten keine Erwärmung des Klebstoffs. Er besitzt jedoch nach wie vor den Nachteil, dass ein Eindringen von Schadgasen und Feuchtigkeit nicht zuverlässig verhindert werden kann.EP 1 218 950 B1 also discloses an epoxy adhesive. This adhesive is a UV-curable reactive adhesive and does not require any heating of the adhesive to cure. However, it still has the disadvantage that the penetration of noxious gases and moisture can not be reliably prevented.
In der US-Offenlegungsschrift US 2003/39812 werden dagegen Epoxidharze vorgeschlagen, die mit organischen Tonmaterialien, so genannten Organoclays, versetzt werden, um die Durchlässigkeit für Schadgase und Feuchtigkeit zu vermindern sowie die hygroskopischen Eigenschaften des Harzes zu verringern. Als organophile Tonmineralien oder organische Tonmineralien werden Tonmineralien bezeichnet, bei denen die in den Schichten vorliegenden Alkali- und Erdalkaliionen durch sperrigere Kationen wie substituierte Ammoniumionen ausgetauscht sind. Dies wird allgemein als Interkalation bezeichnete. Durch diese Interkalation wird der Schichtabstand in den Schichtsilikaten vergrößert. Die Schichten können dabei auch vollständig voneinander abgetrennt werden (Exfolierung) .In contrast, US Pat. No. 2003/39812 proposes epoxy resins which are mixed with organic clay materials, so-called organoclays, in order to reduce the permeability to noxious gases and moisture and to reduce the hygroscopic properties of the resin. As organophilic clay minerals or organic clay minerals clay minerals are called, in which the in the Layers present alkali and alkaline earth ions are exchanged by bulkier cations such as substituted ammonium ions. This is commonly referred to as intercalation. This intercalation increases the layer spacing in the layer silicates. The layers can also be completely separated from each other (exfoliation).
Die Verwendung von organischem Ton in Kunststoffen ist bisher jedoch auf wärmehärtbare Kunststoffe beschränkt, da nur durch einen langsamen Aushärtprozess, wie er bei wärmehärtbarenThe use of organic clay in plastics has hitherto, however, been limited to thermosetting plastics, since only by a slow curing process, as in the case of thermosetting plastics
Kunststoffen vorliegt, eine weitgehende oder vollständige Ex- folierung der Schichtsilikate möglich ist. Die Aushärtung in UV-härtbaren Harzen erfolgt jedoch innerhalb weniger Sekunden. Diese Zeitdauer ist für die Exfolierung der Tonminera- lien nicht ausreichend. Wärmehärtbare Kunststoffe weisen wiederum den Nachteil auf, dass die zu verklebenden Teile zum Aushärten des Kunststoffs erhitzt werden müssen. Dadurch kann eine Schädigung der teilweise empfindlichen Bauteile verursacht werden.Plastics is present, a substantial or complete exfoliation of the phyllosilicates is possible. The curing in UV-curable resins, however, takes place within a few seconds. This period of time is not sufficient for the exfoliation of the clay minerals. Thermosetting plastics in turn have the disadvantage that the parts to be bonded must be heated to cure the plastic. This can cause damage to the partially sensitive components.
Derzeit besteht somit der Bedarf nach einem Klebstoff insbesondere für empfindliche Halbleiterbauelemente wie OLEDs, der einen verbesserten Schutz vor Feuchtigkeit aufweist und nicht durch Wärmeeinwirkung ausgehärtet werden muss.There is currently a need for an adhesive, especially for sensitive semiconductor devices such as OLEDs, which has improved protection against moisture and does not have to be cured by the action of heat.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein UV-härtbares Harz und ein entsprechendes Herstellungsverfahren für das Harz bereitzustellen, wobei das Harz eine verminderte Durchlässigkeit für Feuchtigkeit aufweist. Eine weitere Aufgabe der vorliegenden Erfindung ist es, ein Verfahren zum Verkleben von Materialien sowie ein verklebtes Material bereitzustellen, wobei ein UV-härtbares Harz, das eine verminderte Durchlässigkeit für Feuchtigkeit aufweist, als Klebstoff verwendet wird.It is an object of the present invention to provide a UV-curable resin and a corresponding method for producing the resin, wherein the resin has a reduced permeability to moisture. Another object of the present invention is to provide a method for bonding materials and a bonded material wherein a UV-curable resin having a reduced permeability to moisture is used as an adhesive.
Erfindungsgemäß wird zumindest eine diese Aufgaben durch einen Klebstoff mit den Merkmalen des Patentanspruchs 1 sowie ein Verfahren mit den Merkmalen des Patentanspruchs 7 gelöst. Eine weitere Aufgaben wird durch das Verfahren zum Verkleben von Materialien nach Anspruch 10 sowie ein Substrat nach Anspruch 11 gelöst.According to the invention, at least one of these objects is achieved by an adhesive having the features of patent claim 1 and a method having the features of patent claim 7. Another object is achieved by the method of bonding materials of claim 10 and a substrate of claim 11.
Gemäß eines ersten Aspekts ist ein UV-härtender Klebstoff vorgesehen, der zumindest ein UV-härtbares Harz und eine Vielzahl von Partikeln aus organischem Tonmaterial, welche ein hohes Aspektverhältnis bezogen auf eine Höhe zu einer Länge eines Partikels aufweisen, enthält.According to a first aspect, there is provided a UV-curable adhesive comprising at least one UV-curable resin and a plurality of organic clay particles having a high aspect ratio with respect to a height to a length of a particle.
Nach einem weiteren Aspekt ist ein Verfahren zum Herstellen eines UV-härtbaren Harzes vorgesehen, das eine Vielzahl von Partikeln aus organischem Tonmaterial enthält, welches ein hohes Aspektverhältnis bezogen auf eine Höhe zu einer Länge eines Partikels aufweisen, mit den Schritten: a) Bereitstellen eines Harzes; b) Dispergieren eines organischen Tonmaterials in dem Harz; c) Quellen des organischen Tons in dem Harz für eine vor- gegebene Zeitdauer; d) homogenes Vermischen der gequollenen Mischung.According to another aspect, there is provided a process for producing a UV-curable resin containing a plurality of organic clay particles having a high aspect ratio with respect to a height to a length of a particle, comprising the steps of: a) providing a resin ; b) dispersing an organic clay material in the resin; c) swelling the organic clay in the resin for a predetermined period of time; d) homogeneous mixing of the swollen mixture.
Nach noch einem weiteren Aspekt ist ein Halbleiterbauelement mit einem Substrat und mit einer Halbleiterstruktur, die in dem Substrat integriert ist oder auf einer Oberfläche des Substrats angebracht ist, mit einem Gehäuse zum Schutz der Halbleiterstruktur und mit einem Klebstoff nach einem der Ansprüche 1-6 vorgesehen.In yet another aspect, a semiconductor device having a substrate and a semiconductor structure integrated with the substrate or mounted on a surface of the substrate is provided with a semiconductor structure protection package and an adhesive as claimed in any of claims 1-6 ,
Gemäß einem vierten Aspekt ist ein Verfahren zum Verkleben von Substraten vorgesehen, das folgende Schritte aufweist:According to a fourth aspect, a method for bonding substrates is provided, comprising the following steps:
(A) Bereitstellen eines ersten Substrates;(A) providing a first substrate;
(B) Aufbringen eines Klebstoffes nach einem der Ansprüche 1-6 auf das Substrat; (C) Aufbringen eines zweiten Substrates auf das erste(B) applying an adhesive according to any one of claims 1-6 to the substrate; (C) applying a second substrate to the first
Substrat; (D) Aushärten zumindest des Klebstoffes durch UV-Licht. Die der vorliegenden Erfindung zugrunde liegende Idee besteht darin, einen Klebstoff durch das Einbringen von interkalier- tem bzw. exfoliertem organischem Tonmaterial undurchlässig für Feuchtigkeit bzw. Wasser und/oder Schadgase zu machen. Es wurde ein Verfahren entwickelt, die Tonmineralien vor dersubstrate; (D) curing at least the adhesive by UV light. The idea on which the present invention is based is to make an adhesive impermeable to moisture or water and / or noxious gases by introducing intercalated or exfoliated organic clay material. A process has been developed which includes clay minerals before the
Aushärtung in dem Klebstoff zu exfolieren. Ein solcher Klebstoff, der bereits exfolierte Tonmineralien enthält, besitzt eine verminderte Durchlässigkeit für Feuchtigkeit bzw. Schadgase und ist für wärmeempfindliche Teile nicht abträglich, da eine Aushärtung über UV-Bestrahlung erfolgt. Zudem ist der Klebstoff gut lagerfähig. Da mindestens eine Dimension der Partikel im Nanometerbereich liegt, zeigen sie keine oder keine wesentliche Lichtstreuung und beeinträchtigen somit den Klebstoff bezüglich der Lichtdurchlässigkeit nicht. Die Kleb- Stoffe könne lösungsmittelfrei hergestellt werden und sind damit sehr gut umweltverträglich. Die Verringerung des Volumenfüllgrades an anorganischem Material gegenüber den herkömmlichen Füllmitteln verbessert die Haftung gegenüber den Substratoberflächen. Ebenso werden dadurch mechanische Span- nungen und der E-Modul gesenkt, wodurch die Bildung und Ausbreitung von Rissen reduziert wird.Curing in the adhesive to exfoliate. Such an adhesive, which already contains exfoliated clay minerals, has a reduced permeability to moisture or noxious gases and is not detrimental to heat-sensitive parts, since curing takes place via UV irradiation. In addition, the adhesive is well storable. Since at least one dimension of the particles is in the nanometer range, they show no or no significant light scattering and thus do not affect the adhesive with respect to the light transmission. The adhesives can be produced solvent-free and are thus very good for the environment. Reducing the volumetric fill of inorganic material over conventional fillers improves adhesion to the substrate surfaces. It also reduces mechanical stress and the modulus of elasticity, which reduces the formation and propagation of cracks.
Vorteilhafte Ausgestaltungen und Weiterbildungen der Erfindung sind Gegenstand der Unteransprüche sowie der Beschrei- bung unter Bezugnahme auf die Zeichnung.Advantageous embodiments and further developments of the invention are the subject matter of the subclaims and the description with reference to the drawing.
Die exfolierten Tonmineralien, die in dem Klebstoff disper- giert sind, besitzen ein Aspektverhältnis von größer als 10, bevorzugt größer als 100, noch bevorzugter größer als 1000. Ein exfoliertes Tonmineralpartikel zeichnet sich also durch seine stark unterschiedlichen Ausdehnungen aus. Diese Partikel besitzen eine Höhe von typischerweise wenigen Nanometern. Dagegen können die Breite und die Länge der Partikel im Bereich von Mikrometern liegen. Zur Bestimmung der Ausmaße ei- nes Partikels werden dessen Höhe, Breite und Länge verwendet. Dabei ist die Höhe die kürzeste und die Länge die längste Ausdehnung. Die Partikel entsprechen vereinzelten Kristalllamellen . Als UV-härtbares bzw. UV-härtendes Harz wird bevorzugt ein Epoxidharz verwendet. Dieses Epoxidharz kann ein aliphati- sches und/oder cycloaliphatisches Epoxidharz sein. Als beson- ders vorteilhaft hat sich die Verwendung von Bisphenol-A-The exfoliated clay minerals dispersed in the adhesive have an aspect ratio of greater than 10, preferably greater than 100, more preferably greater than 1000. Thus, an exfoliated clay mineral particle is characterized by its greatly differing extents. These particles have a height of typically a few nanometers. In contrast, the width and the length of the particles can be in the range of micrometers. To determine the dimensions of a particle, its height, width and length are used. The height is the shortest and the length is the longest extent. The particles correspond to isolated crystal lamellae. As the UV-curable or UV-curing resin, an epoxy resin is preferably used. This epoxy resin may be an aliphatic and / or cycloaliphatic epoxy resin. The use of bisphenol A has proven particularly advantageous.
Diglycidylether als Epoxidharz herausgestellt. Es lassen sich jedoch auch andere bekannte Epoxidharze oder auch andere Duroplasten verwenden.Diglycidyl ether exposed as an epoxy resin. However, it is also possible to use other known epoxy resins or else other thermosets.
Die organischen Tonmineralien, die die Partikel bilden, können aus natürlichen und/oder synthetischen Tonmineral gewonnen werden. Diese können durch Interkalation und/oder Exfo- lierung aufbereitet werden. Bei der Interkalation werden die Alkali- und/oder Erdalkaliionen, die sich zwischen den kri- stallinen Schichten befinden, durch geeignete Ammoniumverbindungen und/oder Carbonsäuren ausgetauscht. Während dieses Vorgangs werden die Schichtverbindungen oranophil und damit kunststoffverträglich gemacht. Die derart hergestellten Schichtverbindungen bezeichnet man als Organoclays.The organic clay minerals that form the particles can be obtained from natural and / or synthetic clay mineral. These can be prepared by intercalation and / or exfoliation. During the intercalation, the alkali metal and / or alkaline earth metal ions, which are located between the crystalline layers, are exchanged for suitable ammonium compounds and / or carboxylic acids. During this process, the layer compounds are made oranophilic and thus plastic compatible. The layer compounds prepared in this way are called organoclays.
Bevorzugt werden Bentonit, Hectorit, Montmorillonit und/oder Hydrotalcit als organisches Tonmaterial verwendet.Bentonite, hectorite, montmorillonite and / or hydrotalcite are preferably used as organic clay material.
Der Klebstoff weist vorzugsweise zusätzlich weitere Stoffe auf. Diese können z.B. Haftvermittler, Photoinitiator und/oder Füllstoff sein. Haftvermittler können beispielsweise silanbasiert sein. Insbesondere alkoxyfunktionelle Silane, die im Allgemeinen methoxy- und ethoxyfunktionelle Silane sind, können vorteilhaft verwendet werden. Die Silane tragen üblicherweise mindestens eine weitere Gruppe, die über einThe adhesive preferably additionally comprises further substances. These may e.g. Adhesion promoter, photoinitiator and / or filler. Adhesion promoters can be silane-based, for example. In particular, alkoxy-functional silanes, which are generally methoxy- and ethoxy-functional silanes, can be used to advantage. The silanes usually carry at least one other group that over
Si-C-Bindung gebunden ist, wie dies beispielsweise bei Glyci- dyloxipropyltrimethoxysilan der Fall ist. Der Haftvermittler kann dem Klebstoff vorzugsweise in einer Menge von 0,05 bis 2 Masse-% zugesetzt werden. Als Photoninitiator wird vorteil- hafterweise ein Oniumsalz, insbesondere ein Triarylsulfonium- salz mit Hexafluorophosphat, Hexafluoroarsenat oder Hexafluo- roantimonat als Anion, wie beispielsweise Triphenylsulfonium- hexafluoroantimonat, eingesetzt. Bevorzugt wird der Photoini- tiator in einem Anteil von 0,01 bis 5 Masse-% eingesetzt. Weiterhin können Füllstoffe enthalten sein. Diese Füllstoffe können beispielsweise zur Anpassung der Fließeigenschaften verwendet werden. Als Füllstoffe eignen sich beispielsweise Quarzmehle oder andere mineralische Feinmehle, insbesondere auf Kieselsaurebasis . Daneben können weitere bekannte Zusatzstoffe bzw. Additive zugefugt werden. Diese können beispielsweise Farbstoffe, Pigmente, Netzhilfsmittel, Verlaufshilfsmittel, Haftvermittler, Thixotropierungsmittel, Entschäumer, Fließmodifikatoren, Stabilisatoren und Flammschutzmittel umfassen. Dadurch können dem Klebstoff zusatzliche Eigenschaften, wie Farbe, spezielle rheologische Eigenschaften und schwere Entflammbarkeit verliehen werden. Der Klebstoff kann auch zusatzlich ein Polyol enthalten. Die Polyole dienen zur Modifizierung der mechanischen Eigenschaften des gehartetenSi-C bond is bound, as is the case for example with glycidyloxipropyltrimethoxysilane. The coupling agent may preferably be added to the adhesive in an amount of 0.05 to 2% by mass. The photon initiator used is advantageously an onium salt, in particular a triarylsulfonium salt with hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate as anion, for example triphenylsulfonium hexafluoroantimonate. The photoinitiator is preferably tiator used in a proportion of 0.01 to 5 mass%. Furthermore, fillers may be included. These fillers can be used, for example, to adjust the flow properties. Examples of suitable fillers are quartz flours or other mineral fine flours, in particular based on silicic acid. In addition, other known additives or additives can be added. These may include, for example, dyes, pigments, wetting aids, leveling agents, adhesion promoters, thixotropic agents, defoamers, flow modifiers, stabilizers and flame retardants. As a result, the adhesive can be given additional properties such as color, special rheological properties and high flammability. The adhesive may also contain a polyol. The polyols are used to modify the mechanical properties of the cured
Klebstoffs und werden je nach Molmasse und OH-Gehalt in einer derartigen Menge eingesetzt, dass kein Uberschuss von OH- Gruppen über Epoxidgruppen besteht. Ferner kann der Reaktionsklebstoff zusatzlich eine oberflächenaktive Verbindung enthalten, insbesondere ein oberflächenaktives Siloxan. Derartige Additive dienen als Entschäumer und Verlaufshilfsmittel. Der Anteil an oberflächenaktiven Verbindungen ist gering. Er betragt im Allgemeinen lediglich 0,1 bis 0, 5 Masse-% .Adhesive and are used depending on the molecular weight and OH content in an amount such that there is no excess of OH groups on epoxy groups. Furthermore, the reaction adhesive may additionally contain a surface-active compound, in particular a surface-active siloxane. Such additives serve as defoamers and leveling agents. The proportion of surface-active compounds is low. It is generally only 0.1 to 0.5 mass%.
Das Verfahren zur Herstellung eines UV-hartbaren Harzes beinhaltet das Dispergieren des Organoclays in dem Harz. Anschließend wird in einer Quellphase der Organoclay exfoliert. Das Quellen kann bei einer Temperatur im Bereich von 20-1200C, bevorzugt im Bereich von 40-1000C durchgeführt werden. Die Quelldauer betragt von 1-10 Stunden, bevorzugt von 4-12 Stunden. Anschließend wird die Mischung erneut homogenisiert. Dabei können weitere Stoffe wie z.B. ein UV-Harter bzw. Photoinitiator zugegeben werden.The process for producing a UV-curable resin involves dispersing the organoclays in the resin. Subsequently, the organoclay is exfoliated in a swelling phase. The swelling can be carried out at a temperature in the range of 20-120 0 C, preferably in the range of 40-100 0 C. The swelling time is from 1 to 10 hours, preferably from 4 to 12 hours. The mixture is then homogenized again. In this case, further substances such as a UV-hardener or photoinitiator can be added.
Der Klebstoff kann beim Verkapseln von Halbleiterbauelementen vorteilhaft in mehreren Ausgestaltungen verwendet werden. Beispielsweise kann der Klebstoff zum Verkleben einer Verkap- seiung mit einem Substrat oder auch als Verkapselung selbst verwendet werden. Eine Verwendung ist auch überall dort möglich, wo klebende Eigenschaften zusammen mit einem luft- oder gasdichten Verschluss nötig sind. Daher können die Klebstoffe der vorliegenden Erfindung bevorzugt bei der Verkapselung von OLEDs eingesetzt werden.The adhesive can be advantageously used in encapsulating semiconductor devices in several embodiments. For example, the adhesive may be used to bond a capping be used with a substrate or as encapsulation itself. It can also be used wherever adhesive properties are required together with an airtight or gas-tight seal. Therefore, the adhesives of the present invention can be preferably used in the encapsulation of OLEDs.
Zum Verkleben von Substraten wird der Klebstoff auf mindestens eine Oberfläche mindestens eines der Substratteile auf- gebracht. Nach Zusammenbringen und Ausrichten der Oberflächen wird der UV-härtbare Klebstoff durch Bestrahlung mit UV-Licht ausgehärtet. Bevorzugt wird hier Licht im Absorptionsmaximum oder nahe bei dem Absorptionsmaximum des UV-Photoinitiators verwendet. Es kann jedoch auch Licht im Absorptionsmaximum des UV-härtbaren Harzes selbst verwendet werden, sofern dieses im ultravioletten Bereich absorbiert. Hierfür werden Wellenlängen kürzer als 400nm verwendet.For bonding substrates, the adhesive is applied to at least one surface of at least one of the substrate parts. After contacting and aligning the surfaces of the UV-curable adhesive is cured by irradiation with UV light. Preferably, light is used here in the absorption maximum or close to the absorption maximum of the UV photoinitiator. However, light in the absorption maximum of the ultraviolet curable resin itself may be used as far as it absorbs in the ultraviolet region. Wavelengths shorter than 400nm are used for this.
Die Erfindung wird nachfolgend anhand von Ausführungsbeispie- len und anhand der schematischen Figuren der Zeichnung näher erläutert. Es zeigt dabei:The invention will be explained in more detail by means of exemplary embodiments and with reference to the schematic figures of the drawing. It shows:
Figur 1 eine Querschnittsansicht einer verkapselten OLED; Figur 2 eine Querschnittsansicht eines mit einem Klebstoff verkapselten Leistungsbauelement.Figure 1 is a cross-sectional view of an encapsulated OLED; FIG. 2 is a cross-sectional view of a power device encapsulated with an adhesive.
Die Erfindung wird nachfolgend anhand von Ausführungsbeispielen näher erläutert.The invention will be explained in more detail with reference to embodiments.
Zur Herstellung von Epoxidharz-Nanocompositen wurde als Nano- composite-Füllstoff (Organoclay) der synthetische Bentonit EXM 857 der Firma Süd-Chemie AG, Moosburg, verwendet. Als organische Modifizierung ist in diesem Produkt ein Ammoiniumka- tion enthalten. Epoxidharz-Bentonit-Mischungen mit verschie- denen EXM 857-Konzentrationen wurden wie folgt hergestellt.For the production of epoxy resin nanocomposites, the synthetic bentonite EXM 857 from Süd-Chemie AG, Moosburg, was used as nanocomposite filler (organoclay). The organic modification contained in this product is an ammoinium cation. Epoxy-bentonite blends with various EXM 857 concentrations were prepared as follows.
Der Füllstoff wurde zunächst in der gewünschten Konzentration mit Hilfe eines Dispergiergerätes in 100 Masseteile eines Bisphenol-A-diglycidylether-Harz dispergiert. Nach einer Quellphase von 8 Stunden bei einer Temperatur von 800C wurden zu der Mischung nach Abkühlung 3 Massenteile UVI 6974 der Firma UCC (Union Carbide Chemicals) als UV-Härter zugegeben. Die Mischung wurde dann weitere 15 Minuten bei Raumtemperatur gerührt, entgast und anschließend mittels Siebdruck auf einer Substratoberflächen in einer Schichtdicke von ca. 0,25 mm appliziert .The filler was first in the desired concentration with the aid of a dispersing machine in 100 parts by mass of a Bisphenol A diglycidyl ether resin dispersed. After a swelling period of 8 hours at a temperature of 80 0 C 3 mass parts of UVI were UCC (Union Carbide Chemicals) as a UV curing agent is added 6974 to the mixture after cooling. The mixture was then stirred for a further 15 minutes at room temperature, degassed and then applied by screen printing on a substrate surface in a layer thickness of about 0.25 mm.
Die Aushärtung erfolgt unter einer kommerziell erhältlichen UV-Lampe der Firma Hönle durch Bestrahlung für die Dauer von 30 Sekunden.The curing takes place under a commercially available UV lamp from Hönle by irradiation for a period of 30 seconds.
Es wurden verschiedene Formulierungen hergestellt.Various formulations were prepared.
Probe 1 :Sample 1:
Präparation wie oben beschrieben.Preparation as described above.
Formulierung:Formulation:
5 Massenteile Organoclays (EXM 857) 100 Massenteile Bisphenol-A-Diglycidylether (EP 0162)5 parts by mass of organoclays (EXM 857) 100 parts by mass of bisphenol A diglycidyl ether (EP 0162)
3 Massenteile UV-Härter (UVI 6974)3 parts by mass UV curing agent (UVI 6974)
Probe 2:Sample 2:
Präparation wie oben beschrieben. Formulierung:Preparation as described above. Formulation:
10 Massenteile Organoclays (EXM 857)10 parts by mass of organoclays (EXM 857)
100 Massenteile Bisphenol-A-Diglycidylether (EP 0162;100 parts by mass of bisphenol A diglycidyl ether (EP 0162;
3 Massenteile UV-Härter (UVI 6974)3 parts by mass UV curing agent (UVI 6974)
Probe3:Sample 3:
Präparation wie oben beschrieben. Formulierung:Preparation as described above. Formulation:
10 Massenteile Organoclays (EXM 857)10 parts by mass of organoclays (EXM 857)
100 Massenteile Bisphenol-A-Diglycidylether (EP 0162) 10 Massenteile Bisphenol-A-Diglycidylether modifiziert (77- 02, Fa. Leuna-Harze) 3 Massenteile UV-Härter (UVI 6974) Probe 4 :100 parts by mass of bisphenol A diglycidyl ether (EP 0162) 10 parts by mass of bisphenol A diglycidyl ether modified (77-02, Leuna resins) 3 parts by mass UV curing agent (UVI 6974) Sample 4:
Präparation wie oben beschrieben. Formulierung :Preparation as described above. Formulation:
10 Massenteile Organoclays (EXM 857) 100 Massenteile Bisphenol-A-Diglycidylether (EP 0162)10 parts by mass of organoclays (EXM 857) 100 parts by mass of bisphenol A diglycidyl ether (EP 0162)
10 Massenteile Epoxyphenol-Novolak (DEN 438, Dow Chemical) 3 Massenteile UV-Härter (UVI 6974)10 parts by mass of epoxy phenol novolac (DEN 438, Dow Chemical) 3 parts by mass UV curing agent (UVI 6974)
Die Wasserdampfdurchlässigkeit (WDD) der Epoxidharz- Nanocomposite-Formstoffe wurde mittels eines Ca-Spiegels untersucht. Dabei wird in einer Glaskavität ein Ca-Spiegel mit einer Dicke von ca. 1 μm abgeschieden. Auf diese wird ein Glasdeckel geklebt. Als Klebstoff wird das erfindungsgemäße Epoxidharz-Nanocomposite eingesetzt. Die Diffusion erfolgt durch die KlebstoffSchicht . Als Maß für die Diffusion dient das Verblassen des Ca-Spiegels durch eindiffundierende Feuchtigkeit bei Lagerung in einem Klima von 700C und 90 % relativer Feuchte. Die Ergebnisse der Untersuchungen sind in Tabelle 1 dargestellt.The water vapor permeability (WDD) of the epoxy resin nanocomposite molding materials was investigated by means of a Ca-level. In this case, a Ca-mirror is deposited in a glass cavity with a thickness of about 1 micron. On this a glass lid is glued. The adhesive used is the epoxy resin nanocomposite according to the invention. The diffusion takes place through the adhesive layer. As a measure of the diffusion is the fading of the Ca-level by diffusing moisture when stored in a climate of 70 0 C and 90% relative humidity. The results of the tests are shown in Table 1.
Tabelle 1: Zeit bis zum Verblassen des Ca-Spiegels als Maß für die Wasserdampfdurchlässigkeit .Table 1: Time to fade of Ca level as a measure of water vapor permeability.
Wie aus dem Vergleichsbeispiel ersichtlich ist, ist die Wasserdampfdurchlässigkeit der erfindungsgemäß hergestellten Proben der des Vergleichsbeispiels überlegen.As can be seen from the comparative example, the water vapor permeability of the samples according to the invention is superior to that of the comparative example.
Figur 1 zeigt eine Querschnittsansicht einer verkapselten OLED. Dabei sind auf einem Substrat 1 zwei Schichten 2 und 3 zur Ausbildung des OLEDs aufgebracht. Die beiden Schichten sind von einer Verkapselung 4 umgeben. Diese Verkapselung 4 ist mit dem Substrat über einen Klebstoff 5 verklebt.FIG. 1 shows a cross-sectional view of an encapsulated OLED. In this case, two layers 2 and 3 are applied to form the OLED on a substrate 1. The two layers are surrounded by an encapsulation 4. This encapsulation 4 is bonded to the substrate via an adhesive 5.
Zur Herstellung einer solchen verkapselten OLED wird das Substrat 1 die beiden organischen Schichten 2, 3 zur Erzeugung der OLED aufgebracht. Zur Verkapselung der Anordnung wird ein Klebstoff 5 auf den Kontaktbereich der Verkapselung 4 mit dem Substrat 1 aufgebracht. Anschließend wird die Verkapselung 4 mit dem aufgebrachten Klebstoff 5 auf das Substrat 1 aufge- setzt, so dass das OLED durch die Verkapselung 4 verkapselt wird.To produce such an encapsulated OLED, the substrate 1 is the two organic layers 2, 3 for the production the OLED applied. To encapsulate the arrangement, an adhesive 5 is applied to the contact region of the encapsulation 4 with the substrate 1. Subsequently, the encapsulation 4 is placed on the substrate 1 with the applied adhesive 5, so that the OLED is encapsulated by the encapsulation 4.
Figur 2 zeigt eine Querschnittsansicht eines mit einem Klebstoff verkapselten Leistungsbauelement 6. Dabei wird der Klebstoff 7 über das auf einem Substrat 1 aufgebrachte Bauelement 6 gegossen, wodurch dieses verkapselt wird. Das Leistungsbauelement kann beispielsweise ein MOSFET, ein JFET oder ein Thyristor sein.Figure 2 shows a cross-sectional view of an encapsulated with an adhesive power device 6. In this case, the adhesive 7 is poured over the applied to a substrate 1 device 6, whereby this is encapsulated. The power device may be, for example, a MOSFET, a JFET or a thyristor.
Obgleich die vorliegende Erfindung vorstehend anhand eines bevorzugten Ausführungsbeispiels beschrieben wurde, ist sie darauf nicht beschränkt, sondern auf vielfältige Art und Weise modifizierbar. So sei die Erfindung nicht auf den in der vorstehenden Figur dargestellten, speziellen Aufbau einer OLED beschränkt. Vielmehr kann der Klebstoff auch zum Verkapseln anderer Halbleiterbauelemente verwendet werden. Although the present invention has been described above with reference to a preferred embodiment, it is not limited thereto, but modifiable in many ways. Thus, the invention is not limited to the specific structure of an OLED shown in the preceding figure. Rather, the adhesive may also be used to encapsulate other semiconductor devices.
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005046439 | 2005-09-28 | ||
DE102005062946 | 2005-12-29 | ||
PCT/EP2006/066745 WO2007036524A1 (en) | 2005-09-28 | 2006-09-26 | Uv-curing adhesive, preparation process, adhesively bonded semiconductor component, and method of adhesive bonding |
Publications (1)
Publication Number | Publication Date |
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EP1928968A1 true EP1928968A1 (en) | 2008-06-11 |
Family
ID=37478819
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06806828A Ceased EP1928968A1 (en) | 2005-09-28 | 2006-09-26 | Uv-curing adhesive, preparation process, adhesively bonded semiconductor component, and method of adhesive bonding |
Country Status (4)
Country | Link |
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US (1) | US20080193751A1 (en) |
EP (1) | EP1928968A1 (en) |
JP (1) | JP2009510202A (en) |
WO (1) | WO2007036524A1 (en) |
Families Citing this family (6)
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TWI352714B (en) * | 2007-12-05 | 2011-11-21 | Ind Tech Res Inst | Transparent flexible film and fabrication method t |
TWI375837B (en) * | 2007-12-31 | 2012-11-01 | Ind Tech Res Inst | Method for forming optical compensating films, optical compensating films formed thereby, structure of optical compensating films, and polarizing plates |
JP5815965B2 (en) * | 2011-03-29 | 2015-11-17 | デンカ株式会社 | Protection sheet for solar cell module |
JP2016154368A (en) * | 2011-03-30 | 2016-08-25 | 日本電波工業株式会社 | Piezoelectric device and manufacturing method of the same |
JP6122724B2 (en) * | 2013-07-23 | 2017-04-26 | 積水化学工業株式会社 | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element |
EP3421567B1 (en) * | 2017-06-28 | 2024-09-18 | Henkel AG & Co. KGaA | Uv pre-curable epoxide composition for two stage process of assembly |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1218950A1 (en) * | 1999-09-09 | 2002-07-03 | Siemens Aktiengesellschaft | Method for encapsulating components |
Family Cites Families (14)
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JPH10251488A (en) * | 1997-03-07 | 1998-09-22 | Sony Corp | Curable resin composition for semiconductor device |
AU1837000A (en) * | 1998-12-07 | 2000-06-26 | Eastman Chemical Company | A polymer/clay nanocomposite comprising a clay mixture and process for making same |
US6648959B1 (en) * | 1999-07-13 | 2003-11-18 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Coloring pigment |
SE516817C2 (en) * | 1999-09-07 | 2002-03-05 | Tetra Laval Holdings & Finance | Process for producing a laminated packaging material, packaging material made according to this procedure, and packaging made from this packaging material |
DE19961063A1 (en) * | 1999-12-17 | 2001-07-12 | Basf Ag | Process for the preparation of a polymeric reaction product |
WO2002016479A1 (en) * | 2000-08-25 | 2002-02-28 | Sekisui Chemical Co., Ltd. | Sheet-form molding |
WO2002032832A1 (en) * | 2000-10-16 | 2002-04-25 | 3M Innovative Properties Company | Method of making abrasive agglomerate particles and abrasive articles therefrom |
US6521004B1 (en) * | 2000-10-16 | 2003-02-18 | 3M Innovative Properties Company | Method of making an abrasive agglomerate particle |
TW523532B (en) | 2001-08-09 | 2003-03-11 | Ind Tech Res Inst | Epoxy/clay nanocomposite for copper clad laminate applications |
US6936131B2 (en) * | 2002-01-31 | 2005-08-30 | 3M Innovative Properties Company | Encapsulation of organic electronic devices using adsorbent loaded adhesives |
JP4159081B2 (en) * | 2002-07-09 | 2008-10-01 | ダイセル化学工業株式会社 | Moisture-proof laminated film, laminate and package |
WO2005047370A2 (en) * | 2003-10-15 | 2005-05-26 | Michigan State University | Bio-based epoxy, their nanocomposites and methods for making those |
JP4799416B2 (en) * | 2003-11-04 | 2011-10-26 | ハンツマン・アドヴァンスト・マテリアルズ・(スイッツランド)・ゲーエムベーハー | Two-component curable composition |
WO2005061620A1 (en) * | 2003-12-23 | 2005-07-07 | Valorbec Societe En Commandite | Method and system for making high performance epoxies, and high performance epoxies obtained therewith |
-
2006
- 2006-09-26 EP EP06806828A patent/EP1928968A1/en not_active Ceased
- 2006-09-26 JP JP2008532766A patent/JP2009510202A/en active Pending
- 2006-09-26 US US12/067,839 patent/US20080193751A1/en not_active Abandoned
- 2006-09-26 WO PCT/EP2006/066745 patent/WO2007036524A1/en active Application Filing
Patent Citations (1)
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EP1218950A1 (en) * | 1999-09-09 | 2002-07-03 | Siemens Aktiengesellschaft | Method for encapsulating components |
Non-Patent Citations (5)
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HIROAKI MIYAGAWA ET AL: "Amine-cured epoxy/clay nanocomposites. II. The effect of the nanoclay aspect ratio", JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS, vol. 42, no. 23, 1 January 2004 (2004-01-01), pages 4391 - 4400, XP055051658, ISSN: 0887-6266, DOI: 10.1002/polb.20289 * |
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JP2009510202A (en) | 2009-03-12 |
US20080193751A1 (en) | 2008-08-14 |
WO2007036524A1 (en) | 2007-04-05 |
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