Low dielectric constant UV-curable silicone composition
A UV-curable silicone composition with a combination of mono-epoxy and di-epoxy functional siloxanes, a photoacid generator, and di-tert-butyl dicarbonate achieves a dielectric constant below 2.80, addressing the limitations of existing compositions by curing at low temperatures and being suitable for OLED applications.
Patent Information
- Application Number
- PCT/CN2023/132706
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2023-11-20
- Publication Date
- 2025-05-30
AI Technical Summary
Existing UV-curable silicone compositions for OLED applications have dielectric constants above 2.8, which is not low enough for optimal touch sensitivity, and require high temperatures for pore introduction, potentially damaging OLED articles.
A UV-curable silicone composition comprising a combination of mono-epoxy and di-epoxy functional siloxanes, a photoacid generator, and di-tert-butyl dicarbonate, which cures at temperatures below 100°C to achieve a dielectric constant below 2.80, and is free of organic solvents.
The composition achieves a significantly lower dielectric constant than previous compositions, is inkjet printable with a viscosity of 5-25 mPa*s, and can be used as a low Dk encapsulant layer in OLED structures without damaging them.
Smart Images

Figure PCTCN2023132706-FTAPPB-I100001 
Figure PCTCN2023132706-FTAPPB-I100002 
Figure PCTCN2023132706-FTAPPB-I100003
Abstract
Description
LOW DIELECTRIC CONSTANT UV-CURABLE SILICONE COMPOSITIONFIELD
[0001] The present invention relates to ultra-violet (UV) light curable silicon compositions that, upon curing, have a particularly low dielectric constant (Dk) and that can be cured at temperatures below 100 degrees Celsius (℃) .
[0002] INTRODUCTION
[0003] Silicone compositions that are curable to low dielectric constant (low Dk) polysiloxanes are useful in organic light-emitting diode (OLED) applications. Low Dk polysiloxanes are useful, for example, as an encapsulant in multilayer OLED articles. Low Dk properties are desirable to improve touch sensitivity by reducing parasitic capacitance of OLED articles. Therefore, lowering Dk in polysiloxanes suitable for application to OLED article fabrication is particularly desirable.
[0004] US20220348722 discloses a UV curable organopolysiloxane composition that is useful for preparing low Dk films for OLED articles. While the materials of US20220348722 reportedly produce a desirable Dk value below 2.8, it is desirable to identify compositions that can achieve even lower Dk values than those disclosed in US20220348722.
[0005] One method for lowering Dk in material is to introduce pores into the material. US7485362, for instance, discloses nanoporous substrates by thermal decomposition of functionalized organic resins at temperatures of 120 degrees Celsius (℃) and higher. Polymer Chemistry Volume 3, Issue 2, pages 369-376 (2012) discloses low Dk materials of poly (p-phenylene benzobisoxazole) ( “PPBO” ) films that incorporate pores in the PPBO films through thermal decomposition of t-butoxycarbonyl moieties at temperatures of approximately 200 ℃. While introducing pores into a polymer material can lower Dk, processes of introducing pores at temperatures above 100 ℃ are not suitable for using in OLED fabrication because such high temperatures can damage other parts of an OLED article.
[0006] It is desirable to identify a silicone composition that is ultraviolet (UV) curable and that achieves a Dk below 2.80 and lower than compositions of US20220348722 and that can be prepared at temperatures below 100 ℃. Even more desirable is such a composition that is free of organic solvents.SUMMARY
[0007] The present invention provides a UV-curable silicone composition that cures to a composition having a Dk below 2.80 and lower than compositions of US20220348722 and that can be prepared at temperatures below 100 ℃. Even more, the UV-curable silicone composition of the present invention typically has a viscosity in a range of 5-25 milliPascals*seconds (mPa*s) , which means it is inkjet printable. The compositions can be, and desirably are, free of organic solvents.
[0008] The present invention is a result of discovering a UV-curable siloxane composition that comprises a photoacid generator (PAG) and a specific concentration of di-tert-butyl dicarbonate that allows the siloxane composition to produce a polysiloxane with an unexpectedly low Dk value considering it is prepared at a maximum temperature of 70-90 ℃. Upon exposure to UV light during photopolymerization, the PAG decomposes to produce an acid and the acid triggers decomposition of the di-tert-butyl dicarbonate to generate bubbles (pores) in the polysiloxane matrix as it cures. Surprisingly, decreased Dk values (attributed to trapped bubbles) only occurs at in a specific concentration range of di-tert-butyl dicarbonate and only when the UV curing occurs in a temperature range of 70-90 ℃.
[0009] In a first aspect, the present invention is an ultraviolet light curable silicone composition, the ultraviolet light curable silicone composition the comprising the following components: (a) 94 to 98.7 weight-percent of a combination of mono-epoxy functional siloxane and di-epoxy functional siloxane, where the weight-ratio of mono-epoxy functional siloxane to di-epoxy functional siloxane is in a range of 20∶80 to 50∶50; (b) 0.3 to 5 weight-percent of a photoacid generator; and (c) 1 to 4 weight-percent of di-tert-butyl dicarbonate; where weight-percent is relative to the weight of ultraviolet light curable silicone composition.
[0010] In a second aspect, the present invention is a process of curing the ultraviolet light curable silicone composition of the first aspect, wherein the process comprises the following steps: (a) combining the components of the ultraviolet light curable silicone composition together to form the ultraviolet light curable silicone composition; (b) warming the ultraviolet light curable silicone composition to a temperature in a range of 70 to 90 degrees Celsius if it is not already in that temperature range; (c) exposing the ultraviolet light curable silicone composition to ultraviolet light while the curable silicone composition is at a temperature in a range of 70 to 90 degrees Celsius to form a cured ultraviolet light curable silicone composition; and (d) optionally, maintaining the cured ultraviolet light curable silicone composition at a temperature in a range of 70 to 90 degrees Celsius to a period of time after exposing to ultraviolet light as a post-baking step.
[0011] In a third aspect, the present invention is an article comprising a cured polysiloxane composition that contains entrapped gas bubbles in a cured matrix of mono=epoxy functional and di=epoxy functional siloxanes.
[0012] The present invention is useful to prepare a cured polysiloxane composition that is useful for, as an example, a low Dk encapsulant layer in OLED structures.DETAILED DESCRIPTION
[0013] Products identified by their tradename refer to the compositions available under those tradenames on the priority date of this document.
[0014] “Multiple” means two or more. “And / or” means “and, or as an alternative” . All ranges include endpoints unless otherwise indicated.
[0015] Weight-percent (wt%) herein is relative to composition weight unless otherwise stated.
[0016] “Solvent” refers to a non-polymerizable organic material having a boiling point of 120 ℃ or lower at 101 kiloPascals pressure.
[0017] UV Light Curable Silicone Composition
[0018] In a first aspect the present invention is an ultraviolet (UV) light curable silicone composition. In that regard, the silicone composition is curable upon exposure to UV light. The composition may be curable upon exposure to other forms or frequencies of radiation, as long as it is curable upon exposure to UV light. The UV light curable silicone composition comprises: (a) a combination of mono-epoxy functional siloxane and di-epoxy functional siloxane; (b) a photoacid generator (PAG) ; and (c) di-tert-butyl dicarbonate.
[0019] (a) Combination of mono-epoxy functional siloxane and di-epoxy functional siloxane.
[0020] In the broadest scope of the invention, the epoxy functional siloxanes can be any type of siloxane. Desirably, one or both of the mono-epoxy functional siloxane and di-epoxy functional siloxane is a linear siloxane. When the epoxy functional siloxane is linear it is desirable that the epoxy functionality is on one or both ends of the siloxane (that is, the epoxy is a “terminal” functional group) . For the di-epoxy functional siloxane, it is desirable that the siloxane is linear with an epoxy functional group on each end of the linear siloxane. The mono-epoxy functional siloxane can be an epoxy-functional trisloxane. The di-epoxy functional siloxane can be a disiloxane with terminal epoxy groups on opposing ends of the disiloxane.
[0021] In the broadest scope of the invention, the epoxy functionality can be any epoxy group. Desirably, the epoxy group in the epoxy functionality is separated from the silicone to which the functionality attaches by a carbon atom or a chain of carbon atoms. Desirably, each epoxy functionality is a [2- (7-oxabicyclo [4.1.0] heptan-3-yl) ethyl] group having the following structure where the dotted line is a bond to a silicon atom of the functionalized siloxane:
[0022] One suitable mono-epoxy functional siloxane is 1, 1, 1, 3, 5, 5, 5-heptamethyl-3- [2- (7-oxabicyclo [4.1.0] heptan-3-yl) ethyl] trisiloxane:
[0023] One suitable di-epoxy functional siloxane is 1, 3, -Bis [7-oxabicylco [4.1.0] heptan-3-yl] -1, 1, 3, 3-tetramethyldisiloxane:
[0024] The weight ratio of mono-epoxy functional siloxane to di-epoxy functional siloxane is desirably 20∶80 or more, preferably 25∶75 or more, 29∶71 or more, even 30∶70 or more while at the same time is typically 50∶50 or less, and can be 35∶65 or less, even 30∶70 or less.
[0025] The concentration of the combination of mono-epoxy functional siloxane and di-epoxy functional siloxane in the ultraviolet light curable silicone composition is desirably 94 weight-percent (wt%) or more, and can be 95 wt%or more, 96 wt%or more, 97 wt%or more, even 98 wt%or more while at the same time is typically 98.7 wt%or less, 98 wt%or less, even 97 wt%or less relative to weight of the ultraviolet light curable silicone composition.
[0026] (b) Photoacid generator (PAG)
[0027] PAGs become acidic upon exposure to light and, as such, act as photo initiators for acid catalyzed reactions. PAGs typically become acidic by dissociating to form strong acids or dissociated protons upon exposure to light. One common type of PAG include triphenyl sulfonium salts. Examples of PAGs include 4-isopropyl-4'-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-dodecylphenyl) iodonium hexafluoroantimonate; (p-dodecylphenyl) (p-methylphenyl) iodonium hexafluoroantimonate; (p-isopropylphenyl) (p-methylphenyl) iodonium tetrakis (pentafluorophenyl) borate; diphenyliodonium nitrate, diphenyliodonium hexafluorophosphate, (4-fluorophenyl) diphenylsulfonium triflate, N-hydroxynaphthalimide triflate, (4-iodophenyl) diphenylsulfonium triflate, (4-methoxyphenyl) diphenylsulfonium triflate, (4-phenoxyphenyl) diphenylsulfonium triflate, triarylsulfonium hexafluorophosphate, triphenyl sulfonium perfluoro-1-butanesulfanate, triphenyl sulfonium triflate, tris (4-tert-buityphenyl) sulfonium perflulro-1-butanesulfonate, bis (4-tert-butylphenyl) iodonium perfluoro-1-butanesulfonate, and bis (4-tert-butylphenyl) iodonium p-toluenesulfonate.
[0028] The concentration of PAG in the UV light curable silicone composition is 0.3 wt%or more, and can be 0.4 wt%or more, 0.5 wt%or more, even 0.6 wt%or more and at the same time is typically 5 wt%or less and can be 4 wt%or less, 3 wt%or less, 2 wt%or less, one wt%or less, 0.9 wt%or less, 0.8 wt%or less, 0.7 wt%or less with wt%relative to weight of the UV light curable silicone composition.
[0029] (c) Di-tert-butyl dicarbonate
[0030] Di-tert-butyl dicarbonate serves to generate gas when exposed to acid. Upon exposure to UV light, PAG in the UV light curable silicone composition of the present invention forms acid. The acid reacts with the di-tert-butyl dicarbonate to generate gas. The present invention is at least partially the result of discovering that when the concentration of di-tert-butyl dicarbonate is in a particular range of 1 to 4 wt%of the UV light curable silicone composition and UV light exposure generating the gas producing reaction with di-tert-butyl dicarbonate occurs in a temperature range of 70 to 90 degrees Celsius (℃) then the resulting cured silicone composition achieves particularly low dielectric constant properties. Presumably, the concentration of di-tert-butyl dicarbonate and the decomposition temperature range is necessary to trap small bubbles (likely nanometer sized bubbles) in the cured composition and those trapped bubbles lower the dielectric constant relative to the same composition process with a different concentration of di- tert-butyl dicarbonate and / or where the UV light exposure generating the gas producing reaction with di-tert-butyl dicarbonate occurs in a temperature range outside of the 70 to 90 ℃ range.
[0031] The concentration of di-tert-butyl dicarbonate is one wt%or more, and can be 1.5 wt%or more, 2 wt%or more, 2.5 wt%or more, 3 wt%or more, even 3.5 wt%or more while at the same time is 4 wt%or less, and can be 3.5 wt%or less, 3 wt%or less, even 1.5 wt%or less with wt%relative to weight of UV light curable silicone composition. Surprisingly, if the concentration is less than one wt%or greater than 4 wt%of the UV light curable silicone composition then a reduction of dielectric constant does not occur.
[0032] (d) Additional Components
[0033] The UV light curable silicone composition of the present invention can optionally comprise a sensitizer. Sensitizers can be desirable to help absorb UV light and accelerate PAG acid release -basically, increase photo efficiency of the composition. Examples of suitable sensitizers include any one or any combination of more than one thioxanthone and / or substituted thioxanthone materials. Suitable sensitizers include 2-isopropylthoxanthone (CAS#5495-84-1) . The concentration of sensitizer in the UV curable epoxy-based composition is zero wt%or more, and can be 0.01 wt%or more, 0.03 wt%or more, 0.05 wt%or more, 0.10 wt%or more, even 0.15 wt%or more, while at the same time is typically 0.20 wt%or less, 0.15 wt%or less, 0.10 wt%or less, 0.05 wt%or less, or even 0.04 wt%or less, with wt%based on weight of UV light curable silicone composition.
[0034] The UV light curable silicone composition can contain 10 wt%or less, even 5 wt%or less, 3 wt%or less, 2 wt%or less, one wt%or less, 0.5 wt%or less or even can be free of organic solvent.
[0035] The UV light curable silicone composition can contain 10 wt%or less, even 5 wt%or less, 3 wt%or less, 2 wt%or less, one wt%or less, 0.5 wt%or less or even can be free of bis-o-nitrophenol based derivatives, polybenzoxazoles, or a combination thereof. The term “bis-o-nitrophenols” refers to compounds that include two pairs of hydroxyl and nitro groups, which are arranged in the ortho position with respect to one another and which are bonded to phenyl rings, wherein the pairs respectively formed by a hydroxyl group and a nitro group may be arranged on different phenyl rings or on the same phenyl ring.
[0036] Process for Curing the UV Light Curable Silicone Composition
[0037] In a second aspect, the present invention is a process for curing the UV light curable silicone composition of the first aspect of the present invention. As described hereinabove, the concentration of di-tert-butyl dicarbonate is important for achieving a cured UV light curable silicone composition having reduced dielectric constant. However, the process is also important in that the UV light curable silicone composition must be exposed to UV light in a temperature range of 70 to 90 ℃ to realize the reduced dielectric constant. Moreover, surprisingly, curing of the UV light curable silicone composition can be surprisingly completed at temperatures below 100 ℃.
[0038] The process of the present invention comprises the following steps: (a) combining the components of the ultraviolet light curable silicone composition together to form the ultraviolet light curable silicone composition; (b) warming the ultraviolet light curable silicone composition to a temperature in a range of 70 to 90 degrees Celsius if it is not already in that temperature range; (c) exposing the ultraviolet light curable silicone composition to ultraviolet light while the curable silicone composition is at a temperature in a range of 70 to 90 degrees Celsius to form a cured ultraviolet light curable silicone composition; and (d) optionally, maintaining the cured ultraviolet light curable silicone composition at a temperature in a range of 70 to 90 degrees Celsius to a period of time after exposing to ultraviolet light as a post-baking step.
[0039] Step (a) generally occurs at a temperature below 70 ℃ and warming to a temperature in a range of 70 to 90 ℃ in step (b) occurs prior to step (c) . Once the UV light curable silicone composition reaches a temperature in a range of 70 to 90 ℃, it is desirably held in that temperature range for a period of time in a “pre-baking” step as part of step (b) . Desirably, the pre-baking step lasts anywhere from one to 10 minutes, preferably approximately 5 minutes. Prior to step (c) . Notably, the components of the UV light curable silicone composition can be combined already at a temperature in a range of 70 to 90 ℃ thereby rending “warming” in step (b) optional yet a pre-baking step can still be desirable upon forming the UV light curable silicone composition. The method for combining components of the UV light curable silicone composition together is not critical, though it is desirable to achieve as uniform of a mixture of components as possible prior to step (c) .
[0040] It is desirable to deposit the UV light curable silicone composition onto a substrate prior to, or conceivably during, step (c) . For instance, it is desirable to form a film of the UV light curable silicone composition onto a substrate prior to curing. The substrate can be a single composition or can comprise multiple components (for example, an electronic circuit board) . As an example, the process of the present invention can comprise a step spin-coating step after step (a) and before step (c) where the spin-coating step comprises spin coating the UV light curable silicone composition onto a substrate for form a film of the ultraviolet light curable silicone composition on the substrate and it is the film of the ultraviolet light curable silicone composition that cures in subsequent steps.
[0041] The process can further comprise a post-baking step, and desirably does include a post-baking step, after curing by exposure to UV light. During post-baking the UV light curable composition (which should be essentially cured) is held at a temperature in a range of 70 to 90 ℃ for a period of time, typically for a period of time in a range of 20 to 60 minutes. While the post-baking step is not required to achieve lower dielectric constant values for the cured composition, post-baking can further reduce the dielectric constant for the cured composition.
[0042] The process of the present invention can comprise 10 wt%or less, even 5 wt%or less, 3 wt%or less, 2 wt%or less, one wt%or less, 0.5 wt%or less or even can be free of organic solvent.
[0043] The process of the present invention can comprise 10 wt%or less, even 5 wt%or less, 3 wt%or less, 2 wt%or less, one wt%or less, 0.5 wt%or less or even can be free of bis-o-nitrophenol based derivatives, polybenzoxazoles, or a combination thereof. The term “bis-o-nitrophenols” refers to compounds that include two pairs of hydroxyl and nitro groups, which are arranged in the ortho position with respect to one another and which are bonded to phenyl rings, wherein the pairs respectively formed by a hydroxyl group and a nitro group may be arranged on different phenyl rings or on the same phenyl ring.
[0044] Article Comprising Cured UV Light Curable Silicone Composition
[0045] In a third aspect, the present invention is an article comprising the cured UV light curable silicone composition of the first aspect. The cured UV light curable silicone composition is characterized by containing entrapped gas bubbles in a cured matrix of mono-epoxy functional and di-epoxy functional siloxanes. The cured UV light curable silicone composition is obtainable by curing the UV light curable silicone composition according to the process of the second aspect of the present invention.
[0046] The article can comprise solely the cured UV light curable silicone composition. Alternatively, the article can comprise the cured UV light curable silicone composition in combination with other elements to form the article. For instance, the article can comprise cured UV light curable silicone composition coated on a substrate. One desirably article is an organic light-emitting diode comprising cured UV light curable silicone composition as an encapsulant layer in the organic light-emitting diode. The encapsulant layer of an organic light-emitting diode cover an emitting layer of the organic light-emitting diode.
[0047] EXAMPLES
[0048] Table 1 lists the materials for making the samples in this section.
[0049] Table 1
[0050] Synthesis of 1, 1, 1, 3, 5, 5, 5-heptamethyl-3 [2- (7-oxabicyclo [4.1.0] heptan-3-yl) ethyl] trisiloxanePlace 133.6 g of 1, 1, 1, 3, 5, 5, 5-heptamethyltrisiloxane (Millipore Sigma) , 0.01 g Karstedt catalyst (Millipore Sigma) and 0.034 g of 2, 6-ditertbutyl-4-methylphenol (Fisher Scientific) into a three-neck flask. Purge the three-neck flask repeatedly with nitrogen gas to obtain an inert atmosphere. Add dropwise to the three-neck flask 80.72 g of vinylcylcohexene mono-oxide (BOC Sciences) at 100 ℃ over a period of 110 minutes. Heat the contents of the three-neck flask to 110 ℃ for hours. Remove volatile component in vacuo to achieve a 94%yield (195.35 g) of a pale yellow oil having a viscosity of 7milliPascal*seconds. Characterize the produce with 13C and 29Si NMR spectroscopy.
[0051] Sample Preparation and Characterization
[0052] Prepare samples using the formulations in Table 2, where values of each component for each sample are in units of grams (g) . Mix together all of the components of a sample formulation and then spin coat the sample formulation onto a fluorine-doped tin oxide (FTO) glass substrate (50 millimeter by 50 millimeter) at 1000 revolutions per minute for 20 seconds. Pre-bake for the specified period of time (see Table 2) in a temperature range of 70 to 90 ℃ and then immediately expose to 365 nanometer wavelength UV light with an exposure corresponding to 2 Joules per square centimeter of energy. Post-bake for the specified period of time (see Table 2) at a temperature in a range of 70 to 90 ℃.
[0053] Dk Evaluation Technique
[0054] Measure the dielectric constant (Dk) for each cured sample using the following Dk Evaluation Technique. Values for Dk for a material depend on the method of measuring them. The present Dk Evaluation Technique utilizes a method of affixing an aluminum electrode directly to the cured silicone material, which has proven to be a more reproducible (+ / -0.02) than other methods that utilize an aluminum electrode affixed to cured silicone material by means of a film of oil. Dk values from the two different techniques differ slightly are not directly comparable.
[0055] Map the thickness of the spin coated cured film (sample width=50 millimeters (mm) , sample height= 40 mm) using a F50 Film Thickness Measurement Mapping Instrument from Filmetrics use 85 points over the area of the sample except exclude 3 mm along the edges using a wavelength of light fixed in a wavelength range from 832.6 to 958.667 nanometers. The thickness should be 8 micrometers + / -80%over the measurement area.
[0056] At a location on the sample that is 13 mm in diameter and that has a uniform thickness (thickness variation of less than 0.2 micrometers from the mapping evaluation) , use a polyethylene terephthalate mask to deposit a 13 mm diameter aluminum electrode.
[0057] Using the 13 mm diameter electrode, measure the capacitance between the aluminum electrode and the FTO glass substrate using an Agilent E4980A LCR Meter at 100 Herz and one volt. Calculate the Dk for the cured silicone film using the following equation and values: C=εS / d
[0058] where “C” is the capacitance of the film, ε is the permittivity where ε=ε0εr where ε0 is permittivity of a vacuum and εr is Dk, S is the area of the electrode, and d is the thickness of the cured silicone film.
[0059] Sample Viscosity
[0060] Determine the viscosity for a sample in mPa*s at 25℃ using an AR2000ex rheometer from TA instruments with a 40 millimeter diameter aluminum plate and shear rate of 100 s-1. Collect data over a temperature ramp of 20 to 50 ℃ at a ramp rate of 3 ℃ / minute and report the value at 25 ℃.
[0061] Table 2
[0062] NM -not measured. Viscosity was only measured for representative samples. The viscosity values for those samples with measured values should be representative of the viscosity of the remaining samples.
[0063] The data in Table 2 illustrates that Samples within the scope of the present invention (Samples 1-6) all achieve a Dk value below 2.80.
[0064] Sample A corresponds to a formulation within the scope of US2022 / 0348722 (without the Di-tert-butyl-dicarbonate porogen, which US2022 / 0348722 does not mention) and is processed comparable to Samples 1-3, which are in scope of the present invention. Notably, the Dk value for Sample A is slightly higher than that reported in US2022 / 0348722 and that difference is attributed to different methods for measuring Dk. A comparison of Sample A to Samples 1-3 illustrates that when the porogen is present at the claimed concentration range then the Dk value for the resulting cured silicone film is lower than the composition corresponding to the teaching in US2022 / 0348722.
[0065] A comparison of Samples B and C to Samples 1-3 illustrate that when the porogen concentration is lower than 1 wt%or greater than 4 wt%then the Dk value is similar to Sample A (no porogen) yet when the porogen concentration is in a range of 1 to 4 wt%then the Dk value is significantly lower than Sample A. These illustrate the importance of the porogen concentration being in a range of 1 to 4 wt%of the composition weight.
[0066] Samples D, E and F illustrate that essentially regardless of the concentration of porogen, the Dk value remains similar to Sample A (no porogen) without heating the UV light curable silicone composition to a temperature in a range of 70 to 90 ℃ prior to UV curing. These Samples illustrate the importance of UV curing at a temperature of 70 to 90 ℃ in order for the porogen to result in a decrease in Dk value for the cured silicone.
[0067] Confirmation of Bubble Formation
[0068] Samples 1-6 have lower Dk values than Samples A-F presumably due to the presence of gas bubbles in the cured silicone composition. Curing (and concomitantly triggering gas formation by decomposition of the porogen) at a temperature in a range of 70 to 90 ℃ appears to be necessary to both generate and trap the gas bubbles in the cured composition. The gas bubbles are presumably nanometer in size.
[0069] The following experiment demonstrates that the composition, used in the process of the present invention, generates gas bubbles in a cured silicone composition.
[0070] Prepare a UV light curable silicone composition using the composition of Sample 2 in Table 2. Filter the composition through a polytetrafluoroethylene filter (0.45 micrometer, hydrophilic) into a flat bottom aluminum pan (3-5 centimeter in diameter) for obtain a sample of a film of UV light curable silicone composition that is one millimeter thick in the aluminum pan. Pre-bake the sample at a temperature in a range of 70 to 90 ℃ for 5 minutes and then immediately expose to 365 nanometer wavelength UV light with an exposure of 2 Joules per square centimeter. The resulting cured silicone film has visible bubbles trapped in it from the gas generated by acid decomposition of the porogen during UV exposure of the UV light curable silicone composition. The thicker sample makes visualization of the bubbles easier with an unaided eye.
Claims
1.An ultraviolet light curable silicone composition, the ultraviolet light curable silicone composition the comprising the following components:(a) 94 to 98.7 weight-percent of a combination of mono-epoxy functional siloxane and di-epoxy functional siloxane, where the weight-ratio of mono-epoxy functional siloxane to di-epoxy functional siloxane is in a range of 20∶80 to 50∶ 50;(b) 0.3 to 5 weight-percent of a photoacid generator; and(c) 1 to 4 weight-percent of di-tert-butyl dicarbonate;where weight-percent is relative to the weight of ultraviolet light curable silicone composition.2.The ultraviolet light curable silicone composition of claim 1, wherein the ultraviolet light curable silicone composition further comprises a sensitizer.3.The ultraviolet light curable silicone composition of claim 1 or claim 2, wherein the mono-epoxy functional siloxane is an epoxy-functional trisiloxane and the di-epoxy functional siloxane is a disiloxane with terminal epoxy groups on opposing ends of the disiloxane.4.The ultraviolet light curable silicone composition of claim 3, wherein each epoxy group on the mono-epoxy functional siloxane and the di-epoxy functional siloxane are 2- (7-oxabicyclo [4.1.0] heptan-3-yl] groups.5.A process of curing the ultraviolet light curable silicone composition of any one previous claim, wherein the process comprises the following steps:(a) combining the components of the ultraviolet light curable silicone composition together to form the ultraviolet light curable silicone composition;(b) warming the ultraviolet light curable silicone composition to a temperature in a range of 70 to 90 degrees Celsius if it is not already in that temperature range;(c) exposing the ultraviolet light curable silicone composition to ultraviolet light while the curable silicone composition is at a temperature in a range of 70 to 90 degrees Celsius to form a cured ultraviolet light curable silicone composition; and(d) optionally, maintaining the cured ultraviolet light curable silicone composition at a temperature in a range of 70 to 90 degrees Celsius to a period of time after exposing to ultraviolet light as a post-baking step.6.The process of claim 5, wherein the process comprises a step spin-coating step after step (a) and before step (b) where the spin-coating step comprises spin coating the ultraviolet light curable silicone composition onto a substrate for form a film of the ultraviolet light curable silicone composition on the substrate and it is the film of the ultraviolet light curable silicone composition that cures in subsequent steps.7.The process of claim 5 or claim 6, wherein the warming of step (b) occurs in a pre-baking step prior to exposing to ultraviolet light in step (c) .8.The process of claim 5 or claim 6 or claim 7, wherein the process includes the post-baking step and the period of time after exposing the ultraviolet light curable silicone composition to ultraviolet light in the post-baking step is done for a period of time of 20 to 60 minutes.9.An article comprising a cured polysiloxane composition that contains entrapped gas bubbles in a cured matrix of mono-epoxy functional and di-epoxy functional siloxanes.10.The article of claim 9, wherein the article is an organic light-emitting diode and the cured ultraviolet light curable silicone composition is an encapsulant layer in the organic light-emitting diode.
Citation Information
Patent Citations
UV-curable organopolysiloxane composition and use thereof
US20220348722A1
Nanoporous laminates
US7485362B2
Dental composition based on silicone crosslinkable by cation process
US20060178444A1
Chemically amplified positive resist composition and pattern forming process
US20140087294A1
Solventless photocurable liquid composition, cured product thereof, optical filler containing same, and display device including layer comprising said cured product
US20230107203A1