Recherche Images Maps Play YouTube Actualités Gmail Drive Plus »
Connexion
Les utilisateurs de lecteurs d'écran peuvent cliquer sur ce lien pour activer le mode d'accessibilité. Celui-ci propose les mêmes fonctionnalités principales, mais il est optimisé pour votre lecteur d'écran.

Brevets

  1. Recherche avancée dans les brevets
Numéro de publicationUS20060223978 A1
Type de publicationDemande
Numéro de demandeUS 11/098,116
Date de publication5 oct. 2006
Date de dépôt4 avr. 2005
Date de priorité4 avr. 2005
Autre référence de publicationCN101155853A, CN101891945A, CN101891945B, EP1866360A2, EP1866360B1, EP1992654A1, EP1992654B1, US7887716, US7902305, US20070034515, US20080272328, US20080296159, WO2006107803A2, WO2006107803A3
Numéro de publication098116, 11098116, US 2006/0223978 A1, US 2006/223978 A1, US 20060223978 A1, US 20060223978A1, US 2006223978 A1, US 2006223978A1, US-A1-20060223978, US-A1-2006223978, US2006/0223978A1, US2006/223978A1, US20060223978 A1, US20060223978A1, US2006223978 A1, US2006223978A1
InventeursShengqian Kong
Cessionnaire d'origineShengqian Kong
Exporter la citationBiBTeX, EndNote, RefMan
Liens externes: USPTO, Cession USPTO, Espacenet
Radiation- or thermally-curable oxetane barrier sealants
US 20060223978 A1
Résumé
This invention relates to cationically curable sealants that provide low moisture permeability and good adhesive strength after cure. The composition consists essentially of an oxetane compound and a cationic initiator.
Images(1)
Previous page
Next page
Revendications(19)
1. A cationically curable barrier composition consisting essentially of
(a) an oxetane compound,
(b) a cationic initiator,
(c) optionally, one or more fillers,
(d) optionally one or more adhesion promoters, or one or more epoxy resins.
2. The cationically curable barrier composition in accordance with claim 1, in which the oxetane compound has the structure:
in which R1, R2, R3, R4, R5, R6 are selected from the group consisting hydrogen, and alkyl, haloalkyl, alkoxy, aryloxy, aryl, ester, thio-ester, and sulfide groups.
3. The cationically curable barrier composition in accordance with claim 1, in which the oxetane compound is selected from the group of oxetane compounds having the structures:
4. The cationically curable barrier composition in accordance with claim 1, in which the oxetane compound has an aromatic core, onto which aromatic core are substituted in a meta-position with each other, the oxetane functionality and an additional polymerizable functionality.
5. The cationically curable barrier composition in accordance with claim 1, in which the oxetane compound has the structure:
in which
R7, R8, R9, R10 and R11 are independently selected from the group consisting of hydrogen, alkyl, haloalkyl, alkoxy, aryloxy, aryl, alkyloyl and aryloyl groups;
n is 0, 1, 2, 3, or 4;
Z is a cationically reactive functionality selected from the group consisting of
in which
R11 and R12 are independently selected from the group consisting of hydrogen, alkyl, haloalkyl, alkoxy, aryloxy, aryl, alkyloyl and aryloyl groups; and
R13 is a linking group selected from the group consisting of alkyl, haloalkyl, aryl, ether, thio-ether, ester, thio-ester, silane, carbonate, or ketone.
6. The cationically curable barrier composition in accordance with claim 5, in which the oxetane compound is selected from the group having the structures:
7. The cationically curable barrier composition in accordance with claim 1, in which the oxetane compound is a hybrid compound having both an oxetane and a second reactive functionality extending from a cycloaliphatic backbone.
8. The cationically curable barrier composition in accordance with claim 1, in which the oxetane compound has the structure
in which
L, L′, L″ and L′″ are linking groups independently selected from the group consisting of
R and R′ independently are selected from the group consisting of linear alkyl, branched alkyl, cycloalkyl, aryl, heteroaryl, silane or siloxane groups;
R″ is independently selected from the group consisting of hydrogen, alkyl, haloalkyl, alkoxy, aryloxy, aryl, alkyloyl and aryloyl groups;
X is a reactive group independently selected from the group consisting of glycidyl epoxy, aliphatic epoxy, and cycloaliphatic epoxy; oxetane; vinyl, propenyl, crotyl, allyl, and propargyl ether and thio-ethers of those groups; acrylate and methacrylate; itaconate; maleimide; maleate, fumarate, and cinnamate esters; styrenic; acrylamide and methacrylamide; chalcone; thiol; allyl, alkenyl, and cycloalkenyl groups;
n, k, l, n′, k′, and l′ are 0 or 1; and
y is 1 to 10.
9. The cationically curable barrier composition in accordance with claim 8, in which the oxetane compound has the structure selected from the group consisting of:
10. The cationically curable barrier composition in accordance with any of claims 1 through 9 in which the cationic initiator is a Brφnsted acid, a Lewis acid, or a photo or thermal acid generator.
11. The cationically curable barrier composition in accordance with any of claims 1 through 9 in which one or more fillers are present.
12. The cationically curable barrier composition in accordance with any of claims 1 through 9 in which one or more fillers are present and are selected from the group consisting of ground quartz, fused silica, amorphous silica, talc, glass beads, graphite, carbon black, alumina, clays, mica, vermiculite, aluminum nitride, boron nitride; silver, copper, gold, tin, tin/lead alloys, poly(tetrachloroethylene), poly(chlorotriflouroethylene), poly(vinylidene chloride), CaO, BaO, Na2SO4, CaSO4, MgSO4, zeolites, silica gel, P2O5, CaCl2, and Al2O3
13. The cationically curable barrier composition in accordance with any of claims 1 through 9 in which one or more epoxy resins are present.
14. The cationically curable barrier composition in accordance with any of claims 1 through 9 in which one or more epoxy resins are present and are selected from the group consisting of bisphenol F diglycidyl ether, resorcinol diglycidyl ether, novolac glycidyl ethers, and halogenated glycidyl ethers.
15. The cationically curable barrier composition in accordance with any of claims 1 through 9 in which one or more adhesion promoters are present.
16. The cationically curable barrier composition in accordance with any of claims 1 through 9 in which an adhesion promoter is present and is a silane.
17. A hybrid compound containing both oxetane and epoxy functionality selected from the group consisting of:
18. An electronic or optoelectronic device sealed with the cationically-curable barrier sealant according to any one of claims 1 to 9.
19. The electronic or optoelectronic device according to claim 18 in which the device is an OLED.
Description
  • [0001]
    This Invention was made with support from the Government of the United States of America under Agreement No. MDA972-93-2-0014 awarded by the Army Research Laboratories. The Government has certain rights in the Invention.
  • FIELD OF THE INVENTION
  • [0002]
    This invention relates to barrier sealants, adhesives, encapsulants, and coatings for use in electronic and optoelectronic devices. (As used in this specification and claims, adhesives, sealants, encapsulants, and coatings are similar materials, all having adhesive, sealant, and coating properties and functions. When any one is recited, the others are deemed to be included.)
  • BACKGROUND
  • [0003]
    Radiation curable materials have found increased use as coatings, adhesives, and sealants over the past three decades for reasons including low energy consumption during cure, rapid cure speed through either radical or cationic mechanisms, low curing temperature, wide availability of curable materials, and the availability of solvent-free products. These benefits have made such products especially suited for rapidly adhering and sealing electronic and optoelectronic devices that are temperature sensitive or cannot conveniently withstand prolonged curing times. Optoelectronic devices particularly are often thermally sensitive and may need to be optically aligned and spatially immobilized through curing in a very short time period.
  • [0004]
    Numerous optoelectronic devices are also moisture or oxygen sensitive and need to be protected from exposure during their functional lifetime. A common approach is to seal the device between an impermeable substrate on which it is positioned and an impermeable glass or metal lid, and seal or adhere the perimeter of the lid to the bottom substrate using a radiation curable adhesive or sealant.
  • [0005]
    A common manifestation of this package geometry is exemplified in FIG. 1, which discloses the use of a radiation curable perimeter sealant (1) to bond a metal or glass lid (2) over an organic light emitting diode (OLED) stack (3) fabricated on a glass substrate (4). Although various configurations exist, a typical device also contains an anode (5), a cathode (6), and some form of electrical interconnect between the OLED pixel/device and external circuitry (7). For the purposes of this invention, no particular device geometry is specified or required aside from one which incorporates an adhesive/sealant material such as a perimeter sealant (1).
  • [0006]
    In many configurations, as for the example in FIG. 1, both the glass substrate and the metal/glass lid are essentially impermeable to oxygen and moisture, and the sealant is the only material that surrounds the device with any appreciable permeability. For electronic and optoelectronic devices, moisture permeability is very often more critical than oxygen permeability; consequently, the oxygen barrier requirements are much less stringent, and it is the moisture barrier properties of the perimeter sealant that are critical to successful performance of the device.
  • [0007]
    Good barrier sealants will exhibit low bulk moisture permeability, good adhesion, and strong interfacial adhesive/substrate interactions. If the quality of the substrate to sealant interface is poor, the interface may function as a weak boundary, which allows rapid moisture ingress into the device regardless of the bulk moisture permeability of the sealant. If the interface is at least as continuous as the bulk sealant, then the permeation of moisture typically will be dominated by the bulk moisture permeability of the sealant itself.
  • [0008]
    It is important to note that one must examine moisture permeability (P) as the measure of effective barrier properties and not merely water vapor transmission rate (WVTR), as the latter is not normalized to a defined path thickness or path length for permeation. Generally, permeability can be defined as WVTR multiplied by unit permeation path length, and is, thus, the preferred way to evaluate whether a sealant is inherently a good barrier material.
  • [0009]
    The most common ways to express permeability are the permeability coefficient (e.g. g-mil/(100 in2·day·atm)), which applies to any set of experimental conditions, or the permeation coefficient (e.g. g·mil/(100 in2·day) at a given temperature and relative humidity), which must be quoted with the experimental conditions in order to define the partial pressure/concentration of permeant present in the barrier material. In general, the penetration of a permeant through some barrier material (permeability, P) can be described as the product of a diffusion term (D) and a solubility term (S): P=DS
  • [0010]
    The solubility term reflects the affinity of the barrier for the permeant, and, in relation to water vapor, a low S term is obtained from hydrophobic materials. The diffusion term is a measure of the mobility of a permeant in the barrier matrix and is directly related to material properties of the barrier, such as free volume and molecular mobility. Often, a low D term is obtained from highly crosslinked or crystalline materials (in contrast to less crosslinked or amorphous analogs). Permeability will increase drastically as molecular motion increases (for example as temperature is increased, and particularly when the Tg of a polymer is exceeded).
  • [0011]
    Logical chemical approaches to producing improved barriers must consider these two fundamental factors (D and S) affecting the permeability of water vapor and oxygen. Superimposed on such chemical factors are physical variables: long permeation pathways and flawless adhesive bondlines (good wetting of the adhesive onto the substrate), which improve barrier performance and should be applied whenever possible. The ideal barrier sealant will exhibit low D and S terms while providing excellent adhesion to all device substrates.
  • [0012]
    It is not sufficient to have only a low solubility (S) term or only a low diffusivity (D) term in order to obtain high performance barrier materials. A classic example can be found in common siloxane elastomers. Such materials are extremely hydrophobic (low solubility term, S), yet they are quite poor barriers due to their high molecular mobility due to unhindered rotation about the Si—O bonds (which produces a high diffusivity term (D). Thus, many systems that are merely hydrophobic are not good barrier materials despite the fact that they exhibit low moisture solubility. Low moisture solubility must be combined with low molecular mobility and, thus, low permeant mobility or diffusivity.
  • [0013]
    For liquid materials that are cured to solid sealants, such as the inventive compositions, the attainment of lower molecular mobility within the cured matrix is approached through high crosslink density, microcrystallinity, or close packing of molecular backbones between the crosslinked portions of the matrix.
  • BRIEF DESCRIPTION OF THE DRAWING
  • [0014]
    FIG. 1 is a perimeter sealed optoelectronic device.
  • SUMMARY OF THE INVENTION
  • [0015]
    The inventors have discovered that certain resin and resin/filler systems provide superior barrier performance, particularly to moisture, through the incorporation of an oxetane resin and a cationic initiator into the barrier composition. The oxetane resin in general will have the structure which the oxetane compound has the structure:
    in which R1, R2, R3, R4, R5, R6 are selected from the group consisting hydrogen, and alkyl, haloalkyl, alkoxy, aryloxy, aryl, ester, thio-ester, and sulfide groups. Such barrier materials may be used alone or in combination with other curable resins and various fillers. The resulting compositions exhibit a commercially acceptable cure rate, a balance of high crosslink density and molecular packing (low permeant mobility/diffusivity term, D), hydrophobicity (low water solubility term, S), and adhesion (strong adhesive/substrate interfaces) to make them effective for use in sealing and encapsulating electronic, optoelectronic, and MEMS devices.
  • DETAILED DESCRIPTION OF THE INVENTION
  • [0016]
    This invention is a cationically curable barrier sealant consisting essentially of (a) an oxetane compound and (b) a cationic initiator. The barrier adhesive or sealant optionally contains (c) one or more fillers and optionally, (d) one or more adhesion promoters or one or more epoxy resins. When one or more epoxy resins are present, preferably they are selected from the group consisting of bisphenol F diglycidyl ether, resorcinol diglycidyl ether, novolac glycidyl ethers, and halogenated glycidyl ethers, although other epoxies may be used. The use of a cationic photoinitiator results in a radiation-curable formulation; however, the use of a cationic catalyst that can trigger polymerization at room or elevated temperatures may be used for thermal cure. The resulting compositions are suitable for use in sealing and encapsulating electronic and optoelectronic devices.
  • [0017]
    Within this specification, the term radiation is used to describe actinic electromagnetic radiation. Actinic radiation is defined as electromagnetic radiation that induces a chemical change in a material, and for purposes within this specification will also include electron-beam curing. In most cases electromagnetic radiation with wavelengths in the ultraviolet (UV) and/or visible regions of the spectrum are most useful.
  • [0018]
    Within this specification, the term oxetane compound refers to any small molecule, oligomer, or polymer carrying an oxetane functionality. The oxetane compound in general will have the structure
    in which R1, R2, R3, R4, R5, and R6 are selected from the group consisting of hydrogen, and alkyl, haloalkyl, alkoxy, aryloxy, aryl, ester, thio-ester, and sulfide groups. In one embodiment, the oxetane compounds are selected from the group of oxetane compounds having the structures:
  • [0019]
    In another embodiment, the oxetane compound will have an aromatic core, onto which aromatic core are substituted in a meta-position with each other, the oxetane functionality and an additional polymerizable functionality. In this embodiment, the oxetane compound will have the structure:
    in which R7, R8, R9, R10, and R11 are independently selected from the group consisting of hydrogen, alkyl, haloalkyl, alkoxy, aryloxy, aryl, alkyloyl and aryloyl groups; n is 0, 1, 2, 3, or 4; Z is a cationically reactive functionality selected from the group consisting of, but not limited to:
    in which R11 and R12 are independently selected from the group consisting of hydrogen, alkyl, haloalkyl, alkoxy, aryloxy, aryl, alkyloyl and aryloyl groups; and R13 is a linking group selected from the group consisting of alkyl, haloalkyl, aryl, ether, thio-ether, ester, thio-ester, silane, carbonate, or ketone.
  • [0020]
    Exemplary oxetane compounds meeting the above description include, but are not limited to,
  • [0021]
    In another embodiment the oxetane compound is a hybrid compound having both oxetane and a second reactive functionality extending from a cycloaliphatic backbone. In general, such compounds will have the structure
    in which L, L′, L″ and L′″ are linking groups independently selected from the group consisting of
    R and R′ independently are selected from the group consisting of linear alkyl, branched alkyl, cycloalkyl, aryl, heteroaryl, silane or siloxane groups; R″ is independently selected from the group consisting of hydrogen, alkyl, haloalkyl, alkoxy, aryloxy, aryl, alkyloyl and aryloyl groups; X is a reactive group independently selected from the group consisting of glycidyl epoxy, aliphatic epoxy, and cycloaliphatic epoxy; oxetane; vinyl, propenyl, crotyl, allyl, and propargyl ether and thio-ethers of those groups; acrylate and methacrylate; itaconate; maleimide; maleate, fumarate, and cinnamate esters; styrenic; acrylamide and methacrylamide; chalcone; thiol; allyl, alkenyl, and cycloalkenyl groups; n, k, l, n′, k′, and l′ are 0 or 1; and y is 1 to 10.
  • [0022]
    When n, k, and l in the above structures are 0, and X is a form of epoxy, X can be attached to the cycloaliphatic backbone by a direct bond or can be a part of the cycloaliphatic backbone. Exemplary embodiments of the cycloaliphatic hybrid compounds include, but are not limited to,
  • [0023]
    Within this specification, the terms cycloaliphatic or alicyclic refer generally to a class of organic compounds containing carbon and hydrogen atoms joined to form one or more rings, which may contain other atoms, such as, halogens (e.g. Cl, Br, I), substituent atoms (e.g. O, S, N), or substituent groups (e.g. OR, SR, NR2 in which R is a linear or branched alkyl or cycloalkyl or aryl group). In general, cycloaliphatic resins are defined as resins that contain a cyclic carbon-based ring structure in their backbone, which cyclic carbon backbone may have heteroatoms within the backbone or attached to it. It is preferable that the cycloaliphatic resin backbone be composed primarily of carbon, hydrogen and halogen atoms.
  • [0024]
    The selection of an initiator for the inventive radiation curable barrier materials is familiar to those skilled in the art of radiation curing. For photocuring, the curing initiator be a photoinitiator. The selection of an appropriate photoinitiator is highly dependent on the specific application in which the barrier sealant is to be used. A suitable photoinitiator is one that exhibits a light absorption spectrum that is distinct from that of the resins, fillers, and other additives in the radiation curable system. If the sealant must be cured through a cover or substrate, the photoinitiator will be one capable of absorbing radiation at wavelengths for which the cover or substrate is transparent. For example, if a barrier sealant is to be cured through a sodalime glass coverplate, the photoinitiator must have significant UV absorbance above ca. 320 nm. UV radiation below 320 nm will be absorbed by the sodalime glass coverplate and not reach the photoinitiator. In this example, it would be beneficial to include a photosensitizer with the photoinitiator into the photoinitiating system, to augment the transfer of energy to the photoinitiator.
  • [0025]
    Exemplary cationic photoinitiators are disclosed in Ionic Polymerizations and Related processes, 45-60, 1999, Kluwer Academic Publishers; Netherlands; J. E. Puskas et al. (eds.). Preferred cationic photoinitiators include diaryliodonium salts and triarylsulfonium salts. Well known commercially available examples include UV9380C (GE Silicones), PC2506 (Polyset), SR1012 (Sartomer), Rhodorsil 2074 (Rhodia), and UVI-6974 (Dow). Preferred sensitizers for diaryliodonium salts are isopropylthioxanthone (referred to herein as ITX, often sold as a mixture of 2- and 4-isomers) and 2-chloro-4-propoxythioxanthone. The selection of an efficient cationic photoinitiating system for a particular curing geometry and resin system is known to those skilled in the art of cationic UV curing, and is not limited within the scope of this invention.
  • [0026]
    Less common initiating systems, such as thermally generated acids are also anticipated in cases where such catalysts, initiators, and curing agents are appropriate. Exemplary catalysts include Brφnsted acids, Lewis acids, and latent thermal acid generators. Representative examples of Brφnsted and Lewis acids may be found in literature sources such as Smith, M. B. and March, J. in March's Advanced Organic Chemistry, Reactions, Mechanisms, and Structures, 5th Edition, 2001, John Wiley & Sons, Inc., New York, N.Y. pp. 327-362. Examples of latent thermal acid generators include, but not limited to, diaryliodonium salts, benzylsulfonium salts, phenacylsulfonium salts, N-benzylpyridinium salts, N-benzylpyrazinium salts, N-benzylammonium salts, phosphonium salts, hydrazinium salts, ammonium borate salts, etc.
  • [0027]
    Common fillers include, but are not limited to ground quartz, fused silica, amorphous silica, talc, glass beads, graphite, carbon black, alumina, clays, mica, vermiculite, aluminum nitride, and boron nitride. Metal powders and flakes consisting of silver, copper, gold, tin, tin/lead alloys, and other alloys are contemplated. Organic filler powders such as poly(tetrachloroethylene), poly(chlorotriflouroethylene), and poly(vinylidene chloride) may also be used. Fillers that act as desiccants or oxygen scavengers, including but not limited to, CaO, BaO, Na2SO4, CaSO4, MgSO4, zeolites, silica gel, P2O5, CaCl2, and Al2O3 may also be utilized.
  • EXAMPLES Example 1 Synthesis of Oxetane, 3,3′-[1,3-Phenylenebis (Methyleneoxymethylene)]bis[3-Methyl-
  • [0028]
  • [0029]
    Into a 250 mL three-neck round bottom flask equipped with a reflux condenser, a mechanic stirrer were added 12.0 g NaOH (0.3 mol), 0.6 g n-Bu4N+Br (0.0019 mol), 30.0 g 3-methyl-3-hydroxymethyl-oxetane (0.29 mol), 25.0 g α, α′-dibromo-m-xylene (0.095 mol), and 100 mL of toluene. The reaction was brought to 110° C. for 3.5 hours. The organic phase was collected by filtration and the solvents were removed. The light yellow crude product was redissolved in 200 mL of toluene and washed with deionized water three times. After drying over magnesium sulfate, the toluene solution was passed through a short column of neutral alumina to remove trace amount of the ammonium salt phase transfer catalyst. Finally, the solvents were removed with rotary evaporator and Kugelrohr and the sample was purified by distillation. 1H NMR (CDCl3): δ ppm 1.36 (6H), 3.56 (4H), 4.38-4.55 (8H), 4.60 (4H), 7.18-7.38 (4H).
  • Example 2 Synthesis of Oxetane, 3,3′-[1,4-Phenylenebis(Methyleneoxymethylene)]bis[3-Methyl-
  • [0030]
  • [0031]
    The reaction conditions of Example 1 were adopted except 25.0 g α, α′-dibromo-p-xylene (0.095 mol) was used instead of 25.0 g a,a′-dibromo-m-xylene (0.095 mol). 1H NMR (CDCl3): δ ppm 1.36 (6H), 3.55 (4H), 4.37-4.55 (8H), 4.59 (4H), 7.36 (4H)
  • Example 3 Synthesis of Oxetane, 3,3′-[1,3-Phenylenebis(Methyleneoxymethylene)]bis[3-Ethyl-
  • [0032]
  • [0033]
    The reaction conditions of Example 1 were adopted except 34.1 g 3-ethyl-3-hydroxymethyl-oxetane (0.29 mol) was used instead of 30.0 g 3-methyl-3-hydroxymethyl-oxetane (0.29 mol). 1H NMR (CDCl3): δ ppm 0.87-0.91 (6H), 1.77-1.83 (4H), 3.61 (4H), 4.40-4.49 (8H), 4.59 (4H), 7.28-7.38 (4H).
  • Example 4 Synthesis of Oxetane, 3,3′-[1,4-Phenylenebis (Methyleneoxymethylene)]bis[3-Ethyl-
  • [0034]
  • [0035]
    The reaction conditions of Example 3 were adopted except 25.0 g α, α′-dibromo-p-xylene (0.095 mol) was used instead of 25.0 g α, α′-dibromo-m-xylene (0.095 mol). 1H NMR (CDCl3): δ ppm 0.89-0.92 (6H), 1.77-1.83 (4H) 3.61 (4H), 4.40-4.49 (8H), 4.58 (4H), 7.34 (4H).
  • Example 5 Oxetane-Based Barrier Sealant 1
  • [0036]
    The oxetane from example 3, a photoinitiating system (cationic photoinitiator and ITX) were placed in a plastic jar and mixed with a vortex mixer for one hour until clear. Micron sized silica and a nanosilica rheology modifier were then added to the jar and the whole sample was mixed for another hour with the vortex mixer. The resulting paste was further mixed with a ceramic three-roll mill and degassed in a vacuum chamber. The components and parts by weight are disclosed in Table 1.
    TABLE 1
    BARRIER SEALANT # 1
    COMPONENT PARTS BY WEIGHT
    Oxetane in Example 3 35.3
    Photoinitiator 0.7
    ITX 0.1
    Micron sized silica 63.1
    Nanosilica rheology modifier 0.9
    Total: 100.0
  • [0037]
    After the formulation was thoroughly mixed, 1-2 grams of formulation material were placed on a TEFLON coated aluminum plate. An eight-path variable scraper was used to cast an even thickness of film. The sample was then placed inside a Dymax stationary curing unit and cured for 70 seconds (3.3 J/cm2 UVA) with a medium pressure mercury lamp. Irradiance on the sample surface was measured with a UV Power Puck high energy UV radiometer (EIT Inc., Sterling, Va.) and was found to be 47 (UVA), 32 (UVB), 3 (UVC), 35 (UW) mW/cm2 respectively. Moisture permeation coefficient (50° C., 100% relative humidity) of the above film was measured with Mocon Permeatran 3/33 and was found to be 3.1 g·mil/100 in2·day.
  • [0038]
    Adhesion performance was tested by applying two pieces of tape (˜5 mils) approximately a quarter of an inch apart on TEFLON coated aluminum plates. Using a blade, the formulation was drawn into a film between the tapes. The glass slides and the dies were wiped clean with isopropanol and sonicated for ten minutes in isopropanol. The slides and dies were removed from the isopropanol and air-dried followed by 5 min UV ozone cleaning. The dies were then placed in the film of formulation and slightly tapped to wet out the entire die. The dies were picked from the formulation coating and placed onto the slides. The dies were slightly tapped to allow the formulation to wet out between the die and the slide. The sealant formulations were cured in a Dymax UV curing unit with 3.3 J/cm2 UVA. The shear adhesion of the cured samples was tested using a Royce Instrument 552 100K equipped with a 100 kg head and a 300 mil die tool. The adhesion was found to be 44.7±1.6 kg.
  • [0039]
    In another embodiment, the cationically curable barrier composition will further consist essentially of an adhesion promoter, preferably a silane adhesion promoter. The effect of the addition of a silane adhesion promoter was investigated by adding 3.5 wt % Silquest A-186 silane (based on the total formulation) to the formulation in Table 1. Moisture permeation of the cured sample (3.3 J/cm2 UVA) was found to be 3.1 g·mil/100 in2·day and the die shear was 17.0±4.0 kg, sufficient for some commercial applications.
  • Example 6 Oxetane-Based Barrier Sealant 2
  • [0040]
    Oxetane resins may be combined with platelet fillers such as talc in order to reduce moisture permeability. A formulation was prepared similarly to Example 5. The components and parts by weight are disclosed in Table 2. After curing with 6.0 J/cm2 UVA, the permeation coefficient was 4.2 g-mil/100 in2·day at 50° C., 100% relative humidity.
    TABLE 2
    BARRIER SEALANT #2
    COMPONENT PARTS BY WEIGHT
    Oxetane in Example 3 58.8
    Photoinitiator 1.2
    ITX 0.2
    Filler: Vertal 410 talc 39.8
    Total: 100.0
  • Example 7 Synthesis and Performance of an Aromatic Epoxy-Oxetane Hybrid
  • [0041]
  • [0042]
    3-Hydroxybenzyl alcohol (24.8 g, 0.2 mol), 3-methyl-3-bromomethyl oxetane (36.3 g, 0.22 mol), potassium carbonate fine powder (30.4 g, 0.22 mol), and 200 mL methyl ethyl ketone were combined in a four neck, 1000 mL round bottom flask equipped with a condenser and mechanical stirrer. The reaction was heated to 65° C. in an oil bath with stirring, and heating and stirring were continued for a total of five days. The solid was filtered off and the liquid portion was washed with 3% aqueous NaOH solution followed by water. Solvent removal by rotary evaporator gave a low viscosity liquid.
  • [0043]
    This liquid (40.0 g, 0.19 mol) was combined with allyl bromide (36.3 g, 0.3 mol), NaOH (12.0 g, 0.3 mol), tetrabutylammonium bromide (0.82 g, 0.0025 mol), and 100 mL toluene in a four-neck, 1000 mL round bottom flask equipped with a mechanical stirrer and condenser. The reaction was heated to 65° C. with stirring, and the color changed from brown to orange within ten minutes. Heating and stirring were continued overnight. Finally, the solid was filtered off and toluene was removed to give the allylated oxetane product, which was purified by vacuum distillation.
  • [0044]
    Epoxidation of the allylated oxetane was conducted by combining 17.5 g (0.1 mol) of 3-chloroperoxybenzoic acid in 225 mL of dichloromethane in a four-neck, 500 mL round bottom flask equipped with a mechanical stirrer and thermometer. The flask was chilled to 0° C. in an ice/water bath, and 20.5 g of the above allylated oxetane product dissolved in 50 mL of CH2Cl2 was added dropwise over 2.5 hours. The flask was warmed to room temperature one hour later, and stirring continued for three days. The solid was filtered off to obtain a clear, orange liquid. The CH2Cl2 solution was washed with saturated NaHCO3 solution in water and then three times with water.
  • [0045]
    The organic layer was collected and dried over sodium sulfate. The CH2Cl2 was removed by rotary evaporation. Purification by vacuum distillation gave 1.5 g of pure hybrid epoxy-oxetane product at 155° C./147 micron. This product was a clear, colorless liquid. 1H NMR (CDCl3): δ ppm 1.45 (3H), 2.61-2.82 (2H), 3.19 (1H), 3.43-3.80 (2H), 4.04 (2H), 4.45 (2H), 4.46-4.58 (2H), 4.62-4.64 (2H), 6.86-6.95 (3H), 7.25-7.29 (1H). This product was mixed with a photoinitiating system (2.0 wt % cationic photoinitiator SR1012 and 0.12% ITX) and cured with 3.3 J/cm2 UVA. Permeation of the cured film was 6.3 g·mil/100 in2·day at 50° C., 100% relative humidity.
  • Example 8 Synthesis and Performance of a Cycloaliphatic Epoxy-Oxetane Hybrid
  • [0046]
  • [0047]
    A four-neck, 500 mL round bottom flask equipped with mechanical stirrer and condenser was charged with 150.0 g (0.2 mol) hydroxycyclopentadiene (TCI America), 165.0 g (0.24 mol) 3-methyl-3-bromomethyl oxetane (Chemada), 9.6 g (0.24 mol) sodium hydroxide, 0.64 g (1.0 mol %) tetrabutylammonium bromide (TBAB), and 100 mL toluene. The reaction mixture was heated at 80° C. in an oil bath for two hours, and the temperature was then increased to 110° C. for 24 hours. An additional 26.4 g (0.16 mol) 3-methyl-3-bromomethyl oxetane, 6.4 g (0.16 mol) sodium hydroxide, and 0.64 g TBAB were added and stirring continued for 24 hours. The mixture was filtered and toluene was removed by rotary evaporation, and the oxetane product was separated by vacuum distillation.
  • [0048]
    Next, 13.8 g (0.061 mol) of 77% m-chloroperoxybenzoic acid (mCPBA) and 200 mL dichloromethane were combined to form a 0.4 M solution in a 500 mL round bottom flask equipped with mechanical stirrer and thermometer, and chilled to 0° C. in an ice/water bath. Using an additional funnel, 12.3 g (0.0525 mol) above oxetane product dissolved in 65 mL dichloromethane was added dropwise to the mCPBA solution over 1.5 hours. The mixture was warmed to room temperature and allowed to stir for another 24 hours.
  • [0049]
    After the reaction, the mixture was filtered, and the dichloromethane solution was washed with 70 mL saturated NaHCO3 solution, and then with 70 mL water three times. The organic layer was collected and dried over sodium sulfate, and the dichloromethane was removed by rotary evaporation. Vacuum distillation gave the desired product as a colorless liquid in 10.5% yield. 1H NMR (CDCl3): δ ppm 1.29 (3H), 1.27-2.32 (11H), 3.24-3.41 (2H), 3.43-3.50 (2H), 4.32-4.34 (2H), 4.46-4.50 (2H). The resin was combined with a photoinitiating system (2.0 wt % cationic photoinitiator SR1012 and 0.24 wt % ITX). The formulation cured well and the moisture permeation coefficient was 6.6 mil·g/100 in2 day at 50° C., 100% relative humidity.
  • Example 9 Effect of Aromatic Substitution on Permeation Coefficient
  • [0050]
    The oxetanes in Examples 1 to 4 were each blended with a photoinitiating system (2 wt % photoinitiator GE 9380C) and cured with 6.0 J/cm2 UVA followed by annealing at 175° C. for one hour. The permeation coefficient of the cured films were measured and are reported in Table 3. As the data indicate, the meta-substituted oxetanes in examples 1 and 3 are better moisture barrier materials than their para-substituted counterparts, examples 2 and 4.
  • [0051]
    The permeation coefficient of a 50/50 (wt/wt) solution of the oxetane in example 3 and an aromatic epoxy (EPON 862) using a photoinitiating system of 2 wt % cationic photoinitiator (UV 9380C) was compared with the permeation coefficient of the oxetane in example 4. Again, the meta-substituted oxetane formulation resulted in lower permeation coefficient. As shown in table 3, one may also tailor the moisture barrier performance of the cured samples by choosing different epoxies.
  • [0052]
    In the following formulations brominated BPADGE is brominated bisphenol A diglycidyl ether and has the structure:
    EPON 862 has the structure:
  • [0053]
    EPON 828 has the structure
    TABLE 3
    PERMEATION COEFFICIENT
    (g · mil/100 in2 · day at 50° C., 100% relative humidity)
    OF VARIOUS FORMULATIONS
    50/50 50/50 50/50 (WT)
    (WT) WITH (WT) WITH WITH
    BY EPON EPON BROMINATED
    OXETANE ITSELF 862 828 BPADGE
    Oxetane in 7.0
    example 1
    Oxetane in 9.4
    example 2
    Oxetane in 5.9  6.2
    example 3
    Oxetane in 9.5 10.5 11.0 9.1
    example 4
  • Example 10 Oxetane/Epoxy Blends with Various Fillers
  • [0054]
    In this example, epoxy/oxetane formulations with different fillers were tested and compared. The results are reported in Table 4 and indicate that, in general, platy fillers such as talc work better at reducing moisture permeation (formulations A, B, C in table 4) than nanosilica fillers (formulation D), on an equal weight basis. The results further indicate that aromatic epoxy EPON 862 in formulation D is a better barrier material than aromatic epoxy EPON 828 in formulation E, when used in cationic UV curable systems. It is also possible to use both talc and silica as fillers for better barrier performance as shown in formulations F and G. No difference in permeation was observed when nanosilica filler was replaced with micron sized silica.
    TABLE 4
    PERMEATION COEFFICIENTS OF
    OXETANE/EPOXY BLENDS WITH VARIOUS FILLERS
    FORMULATION
    COMPONENTS A B C D E F G
    Oxetane in example 3 24.7 24.7
    Oxetane in example 4 32.9 32.9 32.9 32.9 32.9
    Aromatic epoxy 32.9 32.9 32.9 32.9 24.7 24.7
    Epon 862
    Aromatic epoxy 32.9
    EPON 828
    Cationic photoinitiator 1.0 1.0
    SR1012
    Cationic photoinitiator 1.3 1.3 1.3 1.3 1.3
    UV 9380C
    Photosensitizer 0.1 0.1
    ITX
    Filler 32.9
    Vertal 7 talc
    Filler 32.9
    FDC talc
    Filler 32.9 33.0 33.0
    Mistrofil P403 talc
    Filler 32.9 32.9 16.5
    Nanosilica
    Filler 16.5
    Micron sized silica
    Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0
    Permeation Coefficient 5.7 9.3 5.4 7.7 8.8 3.5 3.5
    g · mil/100
    in2 · day at
    50° C., 100% RH
  • Example 11 Oxetane/Vinyl Ether Formulation
  • [0055]
    Oxetanes may be blended with diluents, such as vinyl ethers, in UV curable cationic formulations. In this example, a cycloaliphatic vinyl ether (CAVE) having the below structure was used as a reactive diluent and the resulting formulation exhibited a very low moisture permeation coefficient. The formulation and results are reported in Table 5.
    TABLE 5
    PERMEATION COEFFICIENT OF
    OXETANE/VINYL ETHER FORMULATION
    COMPONENTS PARTS BY WEIGHT
    Oxetane in example 3 17.5
    CAVE 11.7
    Photoinitiator (GE9380C) 0.87
    Photosensitizer (ITX) 0.045
    Micron sized silica 69.9
    Total 100.0
    Viscosity (cP)
    10 rpm 6,676
     1 rpm 9,420
    Permeation Coefficient 2.8
    g · mil/100 in2 · day at (3 J/cm2 UVA)
    50° C., 100% RH
  • Example 12 Oxetane/Epoxy Blends with Different Additives
  • [0056]
    Oxetane/epoxy resin mixtures may also be blended with diluents, such as vinyl ethers or alcohols in UV curable cationic formulations. The formulation and results are reported in Table 6. Cure speed was measured with a Perkin Elmer Differential Scanning Calorimetry 7 equipped with a UV light source.
    TABLE 6
    OXETANE/EPOXY BLENDS WITH DIFFERENT ADDITIVES
    COMPONENTS PARTS BY WEIGHT
    Oxetane in example 3 4.0 4.0 4.0
    Aromatic epoxy 4.0 4.0 4.0
    EPON 862
    Cationic Photoinitiator SR1012 0.16 0.16 0.16
    CAVE 0.82
    Tricyclodecane dimethanol (Aldrich) 0.82
    Curing Speed Excellent Excellent Fair
    Time to Peak Exotherm(min) 0.13 0.12 0.78
    Time to 90% Total Exotherm (min) 0.69 0.69 1.78
    ΔH (J/g) 294 271 328
    Permeation Coefficient 6.3 6.4 7.2
    g · mil/100 in2 · day at
    50° C., 100% RH
    (cured with 3 J/cm2 UVA)
  • Example 13 Properties and Performances of Oxetane/Epoxy/Talc Formulations with Various Oxetane/Epoxy Ratios
  • [0057]
    UV cure speed and the reactivity of a perimeter sealant is critical to production throughput, and the minimization of thermal processing is generally required for many display applications. UV curing kinetics and thermodynamics can be measured using differential photocalorimetry (“photo DSC”). The cure speed for a series of oxetane/epoxy/talc formulations with various oxetane/epoxy ratios are reported in Table 7. Differential photocalorimetry was performed on the samples using a Perkin-Elmer Differential Scanning Calorimeter 7 equipped with a Hg-arc lamp UV light source. All samples were cured through an indium/tin oxide (ITO)-coated sodalime glass.
  • [0058]
    Each of the resin combinations contains oxetane (OXT-121, Toagosei), EPON 862 aromatic epoxy, 35 wt % talc (Mistrofil P403 talc), and a photoinitiating system of 2.0 wt % cationic photoinitiator (SR1012), and 0.21 wt % ITX (all based on total weight). For each barrier sealant, the time from UV initiation to maximum curing exotherm was recorded, as well as the time taken to reach 90% of the observed UV curing exotherm. Shorter time to peak and time to 90% conversion are indications of good curing performance.
  • [0059]
    As the table indicates, good curing performance and good die shear adhesion were observed for formulations K, L, M where the oxetane/epoxy ratio ranged from 75:25 to 25:75. Most significantly, the fastest UV cure speed came from a 50:50 mole ratio of the oxetane and epoxy, which has the sharpest and narrowest exothermic peak. In addition, die shear adhesion of the oxetane rich (H, I) formulations were found to be better than epoxy rich (M, N) formulations.
    TABLE 7
    PROPERTIES AND PERFORMANCES OF OXETANE/EPOXY/TALC
    FORMULATIONS WITH VARIOUS OXETANE/EPOXY RATIOS
    OXT 121: Cure
    EPON Viscosity Speed (min) Die shear
    862 (cPs) Time to Time to Adhesion
    Formula (mole) 1.0 rpm 10.0 rpm Peak 90% (kg)
    H 100:0  2,867 1,597 0.43 3.92 40.9
    I 95:5  4,096 2,252 0.27 4.44 40.9
    J 75:25 8,601 4,198 0.17 0.93 45.2
    K 50:50 7,987 4,301 0.12 0.70 44.4
    L 25:75 11,870 6,553 0.13 1.73 44.2
    M  5:95 15,560 9,093 0.15 2.04 33.1
    N  0:100 18,020 10,420 0.20 2.34 35.5
  • Example 14 Permeability of Oxetane/Epoxy Blends with Various Photoinitiators
  • [0060]
    Several cationic photoinitiators were used to cure 50/50 (by weight) blends of OXT-121 oxetane and EPON 862 epoxy. The results are reported in Table 8 and indicate there is little difference in the permeabilities obtained using these different photoinitiators. The loading of the photoinitiators were normalized so that equal molar amounts of the active catalyst were used. The sulfonium salt catalyst is proprietary to National Starch and Chemical Company.
    TABLE 8
    PERMEABILITY OF OXETANE/EPOXY BLENDS WITH VARIOUS
    PHOTOINITIATORS
    PERMEATION
    FOR- LOADING (g · mil/
    MULA PHOTOINITIATOR (WT %) 100 in2 · day)
    O solid iodonium SR1012 1.0 10.1
    salt
    P solid iodonium SR1012 1.0 10.3
    salt with a perylene 0.1
    sensitizer
    Q sulfonium salt proprietary 1.1 9.9
    R liquid UV 9380C 2.0 9.1
    iodonium
    salt I
  • [0061]
    Different levels of photoinitiator SR 1012 were also explored using 50/50 (by weight) blends of OXT-121 oxetane and EPON 862 epoxy and the results are reported in Table 9. Within experimental error, the change in the photoinitiator level did not show significant impact on the moisture permeation performance of the sealant. This clearly demonstrates that the barrier performance of the sealants is mostly dominated by the choice of resins and less affected by ways of curing.
    TABLE 9
    VARIATIONS IN PHOTOINITIATOR LEVEL
    PHOTOINITIATOR PERMEATION
    LOADING (WT %) (g · mil/100 in2 · day)
    0.25 9.6
    0.50 9.3
    1.00 10.1
    2.00 9.7
    3.00 10.1
  • Example 15 Curing of Oxetane/Epoxy Blends by Heat
  • [0062]
    A series of oxetane (OXT-121) and epoxy (EPON 862) resin blends were prepared and cured by heat. The oxetane and epoxy blends at different weight ratios were polymerized using DSC ramp from room temperature to 300° C. at 10° C./min. Each sample contained 2.0% cationic photoinitiator (SR1012). The onset, peak temperatures and total heat of polymerization are reported in Table 10.
    TABLE 10
    CURING OF OXETANE/EPOXY BLENDS BY HEAT
    RATIO OXETANE:EPOXY
    100:0 67:33 50:50 33:67 0:100
    ONSET (° C.) 138 135 133 138 171
    PEAK (° C.) 158 153 158 203 214
    ΔH (J/G) 627 724 681 637 646
Citations de brevets
Brevet cité Date de dépôt Date de publication Déposant Titre
US20398 *1 juin 1858 Telephonic indicator for steam-boilers
US37677 *17 févr. 1863 Improvements breast-pumps
US62125 *19 févr. 1867 Improvement in apparatus for lighting gas by electricity
US111519 *7 févr. 1871F OneImprovement in clothes-driers
US191566 *2 sept. 18765 juin 1877 Improvement in limekilns
US225025 *7 mai 18792 mars 1880 Bill-file
US2830721 *28 mars 195615 avr. 1958Plax CorpPlastic coated articles
US3704806 *6 janv. 19715 déc. 1972Le T Im LensovetaDehumidifying composition and a method for preparing the same
US3835003 *19 oct. 197210 sept. 1974American Can CoPhotopolymerization of oxetanes
US4013566 *7 avr. 197522 mars 1977Adsorbex, IncorporatedFlexible desiccant body
US4036360 *12 nov. 197519 juil. 1977Graham Magnetics IncorporatedPackage having dessicant composition
US4081397 *3 déc. 197128 mars 1978P. R. Mallory & Co. Inc.Desiccant for electrical and electronic devices
US4265976 *17 sept. 19795 mai 1981Celanese CorporationRadiation-curable coated article having moisture barrier propetes
US4394403 *2 avr. 197519 juil. 1983Minnesota Mining And Manufacturing CompanyPhotopolymerizable compositions
US5008137 *19 juin 198916 avr. 1991Ppg Industries, Inc.Barrier coatings
US5122403 *3 avr. 198916 juin 1992Ppg Industries, Inc.Windshield edge seal
US5171760 *21 déc. 199015 déc. 1992Edison Polymer Innovation Corp.UV curable polymer formulation
US5300541 *30 sept. 19915 avr. 1994Ppg Industries, Inc.Polyamine-polyepoxide gas barrier coatings
US5304419 *9 mars 199219 avr. 1994Alpha Fry LtdMoisture and particle getter for enclosures
US5401536 *24 juin 199328 mars 1995Shores; A. AndrewMethod of providing moisture-free enclosure for electronic device
US5463084 *1 févr. 199331 oct. 1995Rensselaer Polytechnic InstitutePhotocurable silicone oxetanes
US5491204 *27 avr. 199513 févr. 1996Ppg Industries, Inc.Gas barrier coating from reacting polyamine, alkanolamine and polyepoxide
US5591379 *2 août 19937 janv. 1997Alpha Fry LimitedMoisture getting composition for hermetic microelectronic devices
US5665823 *30 août 19969 sept. 1997Dow Corning CorporationPolyisobutylene polymers having acrylic functionality
US5703394 *10 juin 199630 déc. 1997MotorolaIntegrated electro-optical package
US5747363 *8 juil. 19975 mai 1998Motorola, Inc.Method of manufacturing an integrated electro-optical package
US5827908 *6 févr. 199727 oct. 1998Shin-Etsu Chemical Co., Ltd.Naphthalene and or biphenyl skeleton containing epoxy resin composition
US5882842 *12 févr. 199716 mars 1999Kansai Paint Co., Ltd.Active energy ray-curable resin composition
US6054549 *25 nov. 199825 avr. 2000Dow Corning Asia, Ltd.Alkenyl ether functional polyisobutylenes and methods for the preparation thereof
US6081071 *18 mai 199827 juin 2000Motorola, Inc.Electroluminescent apparatus and methods of manufacturing and encapsulating
US6084004 *21 août 19984 juil. 2000Espe Dental AgCompositions which undergo light-induced cationic curing and their use
US6121358 *22 sept. 199719 sept. 2000The Dexter CorporationHydrophobic vinyl monomers, formulations containing same, and uses therefor
US6150479 *23 nov. 199821 nov. 2000Loctite CorporationRadical-curable adhesive compositions, reaction products of which demonstrate superior resistance to thermal degradation
US6166101 *23 nov. 199826 déc. 2000Kansai Paint Co., Ltd.Ultraviolet-curing coating composition for cans
US6211320 *28 juil. 19993 avr. 2001Dexter CorporationLow viscosity acrylate monomers formulations containing same and uses therefor
US6226890 *7 avr. 20008 mai 2001Eastman Kodak CompanyDesiccation of moisture-sensitive electronic devices
US6521731 *7 févr. 200118 févr. 2003Henkel Loctite CorporationRadical polymerizable compositions containing polycyclic olefins
US6569532 *20 nov. 200127 mai 2003Sony CorporationEpoxy resin compositions and premolded semiconductor packages
US6586496 *9 août 20001 juil. 2003Mitsui Chemicals, Inc.Photocurable resin composition for sealing material and method of sealing
US6692610 *26 juil. 200117 févr. 2004Osram Opto Semiconductors GmbhOled packaging
US6692986 *6 sept. 200017 févr. 2004Osram Opto Semiconductors GmbhMethod for encapsulating components
US6706779 *27 août 200116 mars 2004Dow Corning CorporationRadiation curable compositions containing alkenyl ether functional polyisobutylenes
US6780898 *18 janv. 200124 août 2004Sony Chemicals CorporationAdhesive composition
US6833668 *7 sept. 200021 déc. 2004Sanyo Electric Co., Ltd.Electroluminescence display device having a desiccant
US6835950 *12 avr. 200228 déc. 2004Universal Display CorporationOrganic electronic devices with pressure sensitive adhesive layer
US6897474 *4 avr. 200324 mai 2005Universal Display CorporationProtected organic electronic devices and methods for making the same
US6936131 *31 janv. 200230 août 20053M Innovative Properties CompanyEncapsulation of organic electronic devices using adsorbent loaded adhesives
US20010018477 *18 janv. 200130 août 2001Sony Chemical Corp.Adhesive composition
US20030062125 *16 juil. 20023 avr. 2003Yasushi TakamatsuPhotocationic-curable resin composition and uses thereof
US20040084686 *1 mai 20036 mai 2004Ping-Song WangPackaging material used for a display device and method of forming thereof
US20040225025 *2 févr. 200411 nov. 2004Sullivan Michael G.Curable compositions for display devices
US20060162771 *18 févr. 200427 juil. 2006Nippon Kayaku Kabushiki KaishaSealing agent for photoelectric conversion element and photoelectric conversion device element using the same
Référencé par
Brevet citant Date de dépôt Date de publication Déposant Titre
US793230118 août 200826 avr. 2011Industrial Technology Research InstituteEncapsulant composition and method for fabricating encapsulant material
US8278401 *29 mars 20062 oct. 2012Henkel Ag & Co. KgaaRadiation or thermally curable barrier sealants
US836776816 déc. 20095 févr. 2013Industrial Technology Research InstituteEncapsulant compositions and method for fabricating encapsulant materials
US901827617 mars 201128 avr. 2015Industrial Technology Research InstituteEncapsulant composition and method for fabricating encapsulant material
US921224425 févr. 201015 déc. 2015Merck Patent Gesellschaft Mit Beschrankter HaftungPolymers made from mixtures comprising vinyl ether monomers
US20090270526 *18 août 200829 oct. 2009Industrial Technology Research InstituteEncapsulant composition and method for fabricating encapsulant material
US20100148666 *16 déc. 200917 juin 2010Industrial Technology Research InstituteEncapsulant compositions and method for fabricating encapsulant materials
US20100155247 *29 mars 200624 juin 2010Jie CaoRadiation-curable rubber adhesive/sealant
US20100164368 *29 mars 20061 juil. 2010National Starch And Chemical Investment Holding CoRadiation- or thermally-curable barrier sealants
US20110166246 *17 mars 20117 juil. 2011Industrial Technology Research InstituteEncapsulant composition and method for fabricating encapsulant material
US20110200918 *28 oct. 200918 août 2011Tomoya MizutaPhotosensitive composition for volume hologram recording and producing method thereof
EP2108688A1 *11 janv. 200814 oct. 2009Sekisui Chemical Co., Ltd.Adhesive for electronic components
EP2108688A4 *11 janv. 20087 sept. 2011Sekisui Chemical Co LtdAdhesive for electronic components
Classifications
Classification aux États-Unis528/417, 528/421, 525/523
Classification internationaleC08G59/08, C08L63/00, C08G59/06
Classification coopérativeC08G65/18, G03F7/038
Classification européenneC08G65/18
Événements juridiques
DateCodeÉvénementDescription
17 mai 2005ASAssignment
Owner name: NATIONAL STARCH AND CHEMICAL INVESTMENT HOLDING CO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:KONG, SHENGQIAN;REEL/FRAME:016220/0474
Effective date: 20050513
19 nov. 2008ASAssignment
Owner name: HENKEL KGAA, GERMANY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NATIONAL STARCH AND CHEMICAL INVESTMENT HOLDING CORPORATION;INDOPCO, INC.;REEL/FRAME:021912/0634
Effective date: 20080401
Owner name: HENKEL KGAA,GERMANY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NATIONAL STARCH AND CHEMICAL INVESTMENT HOLDING CORPORATION;INDOPCO, INC.;REEL/FRAME:021912/0634
Effective date: 20080401
3 déc. 2008ASAssignment
Owner name: HENKEL AG & CO. KGAA, GERMANY
Free format text: CHANGE OF NAME;ASSIGNOR:HENKEL KGAA;REEL/FRAME:022309/0718
Effective date: 20080415
Owner name: HENKEL AG & CO. KGAA,GERMANY
Free format text: CHANGE OF NAME;ASSIGNOR:HENKEL KGAA;REEL/FRAME:022309/0718
Effective date: 20080415