Photocurable silicone composition and cured product, laminated structure and optical device including the same
Patent Information
- Application Number
- PCT/EP2025/056631
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2025-03-11
- Publication Date
- 2026-09-17
Smart Images
Figure IMGF000002_0001 
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Abstract
Description
[0001] WA12503S
[0002] PHOTOCURABLE SILICONE COMPOSITION AND CURED PRODUCT, LAMINATED
[0003] STRUCTURE AND OPTICAL DEVICE INCLUDING THE SAME
[0004] [Technical Field]
[0005] The present invention relates to a photocurable silicone composition and a cured product, laminated structure and optical device including the same.
[0006] [Background Art]
[0007] Optical adhesive formulations are used to improve visibility, readability and durability by filling an air gap between a screen panel and a display module.
[0008] As materials for optical adhesive formulations, acrylates and silicones are used. Acrylates are widely used as optical adhesive formulations for small displays, but when the size of a display increases, problems such as yellowing mura and bubbles occur.
[0009] Although silicone can provide high thermal stability, the problem of gelation occurs because storage stability is not secured according to temperature conditions. In addition, even when additives were added to ensure storage stability, there was still a problem of poor storage stability at temperatures above room temperature, and problems of deterioration of physical properties such as delayed curing rate also occurred.
[0010] [Disclosure]
[0011] [Technical Problem]
[0012] Therefore, the present invention has been made in view of the above problems, and it is one object of the present invention to provide a photocurable silicone composition with easy workability, improved high-temperature storage stability, and consistent physical properties and a cured product, laminated structure and optical device including the photocurable silicone composition.WA12503S
[0013] [Technical Solution]
[0014] In accordance with an aspect of the present invention, the above and other objects can be accomplished by the provision of a photocurable silicone composition, including: a polysiloxane resin; a curing catalyst; and a stabilizer including an aliphatic phosphite compound.
[0015] In an embodiment of the present invention, the photocurable silicone composition may be a one-component.
[0016] In an embodiment of the present invention, the stabilizer may be liquid at room temperature.
[0017] In an embodiment of the present invention, the aliphatic phosphite compound may be represented by Formula 1 below:
[0018] [Formula 1]
[0019]
[0020] where Ri to R3 are each independently an alkyl group having 4 to 15 carbon atoms. In an embodiment of the present invention, the stabilizer may include a borate compound. In an embodiment of the present invention, a weight ratio of the aliphatic phosphite compound:the borate compound included in the photocurable silicone composition may be 1:2 to 1:100.
[0021] In an embodiment of the present invention, the content of the stabilizer may be 10 ppm to 10,000 ppm based on the total weight of the photocurable silicone composition.
[0022] In an embodiment of the present invention, the polysiloxane resin may include an organopolysiloxane containing an alkenyl group; and an organohydrogenpolysiloxane containing one or more hydrogens bonded to a silicon atom.
[0023] In accordance with another aspect of the present invention, provided is a cured product made by curing a photocurable silicone composition, wherein the photocurable siliconeWA12503S
[0024] composition includes: a poly siloxane resin; a curing catalyst; and a stabilizer including an aliphatic phosphite compound.
[0025] In accordance with still another aspect of the present invention, provided is a laminated structure, including an adhesive layer arranged between a first optical member and a second optical member, wherein the adhesive layer includes a cured product made by curing a photocurable silicone composition including a polysiloxane resin, a curing catalyst, and a stabilizer including an aliphatic phosphite compound.
[0026] In accordance with yet another aspect of the present invention, provided is an optical device, including: a substrate; an electronic component arranged on the substrate; and an encapsulant for protecting at least a portion of the electronic component, wherein the encapsulant includes a cured product made by curing a photocurable silicone composition including a polysiloxane resin, a curing catalyst, and a stabilizer including an aliphatic phosphite compound.
[0027] [Advantageous effects]
[0028] A composition according to the present invention is a one-component composition, so sufficient working time can be secured before UV exposure. Accordingly, working efficiency can be improved. In addition, since a polysiloxane resin, a crosslinking agent, and a catalyst are included in one product, a stable system can be constructed.
[0029] The composition according to the present invention includes a stabilizer containing an aliphatic phosphite compound, so that the electron donating group (EDG) effect can be exhibited, and the active site of a catalyst can be effectively blocked due to its small molecular weight and simple structure. Accordingly, the high-temperature storage stability can be improved, compared to an existing stabilizer containing an aromatic phosphite compound. In addition, the aliphatic phosphite compound exhibits a liquid phase at room temperature, confirming that it can be easily processed, compared to an aromatic phosphite compound that is solid at room temperature.
[0030] The stabilizer can further include a borate compound. The borate compound can be adsorbed on a catalyst surface to form a physical force or induce a structural change in the catalyst. Accordingly, the chemical stability of the composition can be improved, and the catalyst can be controlled so as not to be activated.WA12503S
[0031] In addition, the borate compound can maintain physical properties, such as curing rate, hardness, adhesive force, and optical properties, at constant levels even when its content increases. Therefore, when used in combination with the aliphatic phosphite compound, the physical properties can be maintained constant while the high-temperature storage stability can be improved
[0032] [Best Mode]
[0033] Structural or functional descriptions of embodiments disclosed in the present specification or application are merely illustrated for the purpose of explaining embodiments according to the technical idea of the present invention, embodiments according to the technical idea of the present invention may be implemented in various forms other than the embodiments disclosed in the present specification or application, and it is not to be construed that the technical idea of the present invention is limited to the embodiments described in the present specification or application.
[0034] In the present specification or application, when a certain component is “included,” this indicates that only the component is included or the component may further include another component unless there is no different disclosure. In addition, it should be understood that all numerical ranges representing physical property values, dimensions, etc. of components described in the present specification or application are modified by the term 'about' in all cases unless otherwise specified. Additionally, the description of “A and / or B” in this specification or application means “A, B, or, A and B.”
[0035] The meaning of each term described in this specification or application is as follows. Siloxane: It may refer to a compound having a Si-O-Si bond.
[0036] Polysiloxane: It may refer to a compound having a plurality of Si-O-Si bonds.
[0037] Polysiloxane resin: It may refer to a composition composed of only a polysiloxane compound, or a composition including polysiloxane and mixed with additional compounds for implementing specific performance.
[0038] Main chain: It may refer to a relatively longest chain in a polysiloxane resin.
[0039] Side chain: It may refer to a structure branched from the main chain in the polysiloxane resin.WA12503S
[0040] M unit: It may refer to a so-called monofunctional siloxane unit, which is sometimes expressed as RsSiOi / 2.
[0041] D unit: It may refer to a so-called difunctional siloxane unit, which is sometimes expressed as R2SiO2 / 2
[0042] T unit: It may refer to a so-called trifunctional siloxane unit, which is sometimes expressed as RSiO3 / 2.
[0043] Q unit: It may refer to a so-called tetrafunctional siloxane unit, which is sometimes expressed as SiC
[0044] Monovalent hydrocarbon group: It may refer to a monovalent residue derived from a compound composed of carbon and hydrogen or a derivative of such a compound. For example, a monovalent hydrocarbon group may contain 1 to 25 carbon atoms. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and the like.
[0045] Alkyl group: It may refer to an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic. In addition, the alkyl group may be optionally substituted with one or more substituents.
[0046] Alkenyl group: It may refer to an alkenyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. The alkenyl group may be linear, branched or cyclic, and may be optionally substituted with one or more substituents.
[0047] Aryl group: It may refer to a monovalent residue derived from a compound or its derivative containing a benzene ring or a structure in which two or more benzene rings are condensed or bonded. The scope of an aryl group may include functional groups commonly referred to as an aryl group, as well as a so-called aralkyl group or arylalkyl group, etc. The aryl group may be, for example, an aryl group having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group, dichlorophenyl, chlorophenyl, a phenylethyl group, a phenylpropyl group, a benzyl group, a tolyl group, a xylyl group, a naphthyl group, and the like.
[0048] Linear polysiloxane resin: For the main chain (-Si-O-Si-O-) of poly siloxane, it may referWA12503S
[0049] to a polysiloxane that does not have a structure in which the siloxane chain is connected by an atomic linker on the Si atom.
[0050] Branched polysiloxane resin: It may refer to polysiloxane containing at least one T-shaped or cross-shaped branch point.
[0051] Organopolysiloxane: It may refer to polysiloxane that has a structure in which an organic group is bonded to a Si atom forming a Si-O-Si bond.
[0052] A photocurable silicone composition according to the present invention may include a polysiloxane resin. The polysiloxane resin may include an organopolysiloxane containing an alkenyl group; and an organohydrogenpolysiloxane containing one or more hydrogens bonded to a silicon atom.
[0053] The composition containing organopolysiloxane may have excellent moldability and may improve viscoelasticity, transparency, and light transmission.
[0054] The organopolysiloxane may have a structure wherein the alkenyl group is included at the end of its main chain.
[0055] The alkenyl group may be vinyl, allyl, methallyl, butenyl, pentenyl, or hexenyl. Preferably, the alkenyl group may be vinyl.
[0056] The organopolysiloxane may include a first organopolysiloxane and second organopolysiloxane having different weight average molecular weights.
[0057] The first organopolysiloxane may include a siloxane unit having an average chain length of less than 150 and may have a weight average molecular weight of 8,000 g / mol or less. The first organopolysiloxane may include a siloxane unit having an average chain length of less than 130 and may have a weight average molecular weight of 7,800 g / mol or less. The first organopolysiloxane may include a siloxane unit having an average chain length of less than 110 and may have a weight average molecular weight of 7,600 g / mol or less.
[0058] The second organopolysiloxane may include a siloxane unit having an average chain length of 150 to 1,200 and may have a weight average molecular weight of 40,000 g / mol to 80,000 g / mol. The second organopolysiloxane may include a siloxane unit having an average chain length of 150 to 1,150 and may have a weight average molecular weight of 40,000 g / mol to 78,000WA12503S
[0059] g / mol. The second organopoly siloxane may include a siloxane unit having an average chain length of 150 to 1,100 and may have a weight average molecular weight of 47,000 g / mol to 76,000 g / mol.
[0060] A weight ratio of the first organopolysiloxane:the second organopolysiloxane may be 100:1 to 1:1, 80:1 to 1:1, 70:1 to 1:1, or 50:1 to 1:1. When the ranges are satisfied, the range of process options is expanded, so an adhesive layer may be formed efficiently on an optical device.
[0061] The content of the organopolysiloxane may be 10 % by weight to 98 % by weight, 20 % by weight to 98 % by weight, 30 % by weight to 98 % by weight, or 50 % by weight to 90 % by weight based on the total weight of the photocurable silicone composition. When the ranges are satisfied, the photocurable silicone composition may have appropriate flowability, so processability may be improved.
[0062] The organopolysiloxane may include a siloxane M unit represented by Average Unit Formula 1 below:
[0063] [Average Unit Formula 1]
[0064] (R SiOi^)
[0065] In Average Unit Formula 1, R1may be each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 20 carbon atoms.
[0066] At least one of R1may include an alkenyl group having 2 carbon atoms. As the alkenyl group having 2 carbon atoms is included, a higher crosslinking density may be provided during a curing reaction, so mechanical strength, thermal stability, and durability may be improved.
[0067] The organopolysiloxane resin may include the M unit represented by Average Unit Formula 1 in an amount of 10 mol % to 25 mol %, 10 mol % to 22 mol %, 10 mol % to 20 mol %, or 10 mol % to 15 mol % of the total siloxane units. When the ranges are satisfied, the photocurable silicone composition may have appropriate flexibility, hydrophobicity and crosslinking density, so mechanical properties may be improved and chemical resistance may be imparted.
[0068] The organopolysiloxane may include a siloxane D unit represented by Average Unit Formula 2 below:
[0069] [Average Unit Formula 2]WA12503S
[0070] (R22SiO22)
[0071] In Average Unit Formula 2, R2may be each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms. In Average Unit Formula 2, R2may be each independently an alkyl group having 1 to 6 carbon atoms. In Average Unit Formula 2, all of R2may be an alkyl group having 1 to 6 carbon atoms. In Average Unit Formula 2, all of R2may be a methyl group. As the methyl group is included, the light transmittance and chemical resistance of the photocurable silicone composition may be improved, and the physical and chemical properties thereof may be maintained even in a high-temperature environment.
[0072] The organopolysiloxane resin may include the D unit represented by Average Unit Formula 2 in an amount of 40 mol% or more, 41 mol% or more, 43 mol% or more, or 41 mol% or more to 45 mol% or less of the total siloxane units. When the ranges are satisfied, the flexibility and elasticity of the photocurable silicone composition may increase, so that shrinkage or expansion due to temperature change may be facilitated. Accordingly, thermal shock characteristics may be improved. In addition, mechanical strength and hardness may be maintained, and the occurrence of micro-cracks in a cured product due to stress concentration may be suppressed.
[0073] The organopolysiloxane may include a siloxane T unit represented by Average Unit Formula 3 below:
[0074] [Average Unit Formula 3]
[0075] (R3SiO3 / 2)
[0076] In Average Unit Formula 3, R3may be an aryl group having 6 to 12 carbon atoms. In Average Unit Formula 3, R3may be a phenyl group.
[0077] The organopolysiloxane resin may include the T unit represented by Average Unit Formula 3 in an amount of 25 mol % to 35 mol %, 26 mol % to 35 mol %, 27 mol % to 35 mol %, or 27 mol % to 33 mol % of the total siloxane units.
[0078] As the ranges are satisfied and the phenyl group is included, the electron density is increased by the delocalized 7t-electron system of the phenyl group, which has a large molecular size and high density compared to an alkyl group, so that the refractive index may be improved. Accordingly, excellent optical properties may be realized. In addition, the influence of the steric hindrance of the phenyl group may be minimized, so that the curing rate and the mechanicalWA12503S
[0079] properties may not be deteriorated.
[0080] The polysiloxane resin may not include the T unit containing an alkenyl group. The T unit containing the alkenyl group may cause poor curing rate of the photocurable silicone composition due to steric hindrance, compared to the M unit including an alkenyl group.
[0081] The polysiloxane resin may not include the T unit containing an alkenyl group. The T unit containing the alkenyl group may cause a lower curing rate of the photocurable silicone composition, compared to the M unit containing an alkenyl group, due to steric hindrance.
[0082] The organopolysiloxane resin may include a siloxane Q unit represented by Average Unit Formula 4 below:
[0083] [Average Unit Formula 4]
[0084] (SiO4 / 2)
[0085] The organopolysiloxane resin may include the siloxane unit represented by Average Unit Formula 4 in an amount of 5 mol % to 25 mol %, 7 mol % to 25 mol %, 7 mol % to 20 mol %, or 10 mol % to 15 mol % of the total siloxane units. When the ranges are satisfied, the impact resistance and processability of the photocurable silicone composition may be maintained, and its mechanical strength and heat resistance may be improved due to increased crosslinking density.
[0086] The organohydrogenpolysiloxane may be a crosslinking agent for crosslinking the organopolysiloxane.
[0087] The organohydrogenpolysiloxane may react with the organopolysiloxane to cause a crosslinking reaction. The crosslinking reaction may be performed by a hydrosilylation reaction in which the Si-H of the organohydrogenpolysiloxane and the alkenyl group of the organopolysiloxane are combined with each other and cured by UV irradiation in the presence of the curing catalyst.
[0088] The organohydrogenpolysiloxane may have one or more Si-bonded hydrogens and one or more Si-bonded aryl groups per its molecule.
[0089] The organohydrogenpolysiloxane may include a branched polysiloxane compound having -Si-O-Si-O-(polysiloxane) as a main chain and having at least one T-shaped or cross-shaped branch point per its molecule.
[0090] The organohydrogenpolysiloxane may contain only the branched polysiloxane compoundWA12503S
[0091] and may not contain the linear polysiloxane compound. Since the organohydrogenpolysiloxane does not contain the linear polysiloxane compound, the mechanical properties and transparency of the photocurable silicone composition may be improved.
[0092] The aryl group may be phenyl, naphthyl, anthryl, phenanthryl, indenyl, benzophenyl, fluorenyl, xanthenyl, antronyl, aryloxyaryl, o-phenoxy -phenyl, p-phenoxy -phenyl, alkaryl, o-tolyl, m -tolyl, p-tolyl, xylyl, ethylphenyl, aralkyl, benzyl, a-phenyl ethyl, or P -phenyl ethyl. Preferably, the aryl group may be phenyl.
[0093] The Si-bonded organic group other than the hydrogen and the aryl group may be a substituted or unsubstituted monovalent hydrocarbon group, and specifically may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or halogenated alkyl. Preferably, it may be methyl.
[0094] The organohydrogenpolysiloxane may be represented by Average Unit Formula 5 below:
[0095] [Average Unit Formula 5]
[0096] (R4R5R6SiOl / 2)a(R7SiO3 / 2)b(R8SiO3 / 2)c
[0097] In Average Unit Formula 5, R4, R5and R6are each independently selected from a substituted or unsubstituted monovalent hydrocarbon group, at least one of R4, R5and R6is a hydrogen, R7is a substituted or unsubstituted monovalent hydrocarbon group, R8is an aryl group having 6 to 12 carbon atoms, 0 < a< 1, 0 < b < 1, 0 < c < 1, and a + b + c = 1.
[0098] A substituent of the monovalent hydrocarbon group may be alkyl, alkenyl, aryl, aralkyl, or halogenated alkyl.
[0099] The aryl group having 6 to 12 carbon atoms may be phenyl or naphthyl.
[0100] a may be 0 < a< l, 0 < a < 0.8, 0.1 < a < 0.8, 0.2 < a < 0.7, or 0.2 < a < 0.6. b may be 0 <b < l, O <b < 0.8, 0 < b < 0.7, 0 < b < 0.6, or 0 < b < 0.5. c may be 0 < c < l, 0 < c < 0.9, 0.1 < c < 0.9, 0.1 < c < 0.8, or 0.2 < c < 0.8.
[0101] The content of the hydrogen may be 0.1 mol% to 40 mol%, 1 mol% to 40 mol%, 3 mol% to 40 mol%, 3 mol% to 40 mol%, or 5 mol% to 40 mol% based on the total amount of R4, R5, R6, R7, and R8. When the ranges are satisfied, a hydrosilylation reaction with the organopolysiloxane may be efficiently performed.
[0102] The content of the aryl group may be 10 mol% to 90 mol%, 20 mol% to 90 mol%, 30 mol% to 90 mol%, 30 mol% to 80 mol%, or 40 mol% to 70 mol% based on the total amount of R4, R5,WA12503S
[0103] R6, R7, and R8. When the ranges are satisfied, phenomena, such as light refraction, reflection, and scattering, of the photocurable silicone composition may be reduced, so its optical properties may be improved.
[0104] The content of the organohydrogenpolysiloxane may be 5 % by weight to 50 % by weight, 5 % by weight to 30 % by weight, 5 % by weight to 20 % by weight, or 5 % by weight to 15 % by weight based on the total weight of the photocurable silicone composition. When the ranges are satisfied, the photocurable silicone composition may maintain high tackiness for a long time after UV energy irradiation, so processability may be improved.
[0105] The photocurable silicone composition may include a curing catalyst.
[0106] An addition reaction between the organopolysiloxane and the organohydrogenpolysiloxane may be promoted by the curing catalyst. The curing catalyst may include a platinum catalyst, a rhodium catalyst, a palladium catalyst, or a complex compound. The complex compound may be a platinum / alkenylsiloxane complex compound, a platinum / olefin complex compound, or a platinum / carbonyl complex compound.
[0107] The content of the curing catalyst may be 0.001 % by weight to 1 % by weight, 0.001 % by weight to 0.5 % by weight, 0.001 % by weight to 0.3 % by weight, or 0.01 % by weight to 0.3 % by weight based on the total weight of the photocurable silicone composition.
[0108] the photocurable silicone composition may include a chain extender that extends the chain of the organopolysiloxane.
[0109] Before the organopolysiloxane forms a cross-linked structure by the chain extender, the chain length of the organopolysiloxane may be extended, so that a polymer network structure may be controlled and the physical properties of the polymer may be adjusted.
[0110] The type of the chain extender is not particularly limited, but diphenyltetrasiloxane may be used to maintain optical transparency.
[0111] The content of the chain extender may be 0.1 % by weight to 30 % by weight, 0.1 % by weight to 20 % by weight, 0.1 % by weight to 15 % by weight, or 0.1 % by weight to 10 % by weight based on the total weight of the photocurable silicone composition. When the ranges are satisfied, the photocurable silicone composition may be imparted with appropriate mechanical strength, brittleness, and flexibility.WA12503S
[0112] The photocurable silicone composition may include an adhesion promoter to improve the adhesive force between the photocurable silicone composition and an adherend.
[0113] A chemical bond is formed between the organic group of the photocurable silicone composition and the functional group of the adherend by the adhesion promoter, so that the adhesive force of the photocurable silicone composition to the adherend may be improved.
[0114] The type of adhesion promoter is not particularly limited, but a high refractive index may be provided, and a silane coupling agent may be used to maintain stability under high-temperature conditions.
[0115] The adhesion promoter may be one or more selected from the group consisting of an epoxy silane such as glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropyltri ethoxy silane or glycidoxypropylmethyldi ethoxy silane, 2-(3-tri ethoxy silylpropyl)maleic anhydride, N-(3 -trimethoxy silylpropyl)urea, N-(3-triethoxysilylpropyl)urea, N-(trimethoxysilylmethyl)urea, N-(methyldimethoxysilylmethyl)urea, O-(methylcarbamatomethyl)methyldimethoxysilane, O- (methylcarbamatomethyl)trimethoxysilane, O-(ethylcarbamatomethyl)methyldiethoxysilane, O-(ethylcarbamatomethyl)triethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethylmethyldimethoxysilane, methacryloyloxymethyltri ethoxy silane, methacryloyloxymethylmethyldi ethoxy silane, 3-acryloyloxypropyltrimethoxysilane, acryloyloxymethyltrimethoxysilane, and acryloyloxymethylmethyldimethoxysilane.
[0116] The content of the adhesion promoter may be 1.5 % by weight to 2.5 % by weight, 1.5 % by weight to 2.4 % by weight, 1.5 % by weight to 2.3 % by weight, or 1.5 % by weight to 2 % by weight based on the total weight of the photocurable silicone composition. When the ranges are satisfied, the adhesive force to an adherend may be improved without deteriorating the mechanical properties of the photocurable silicone composition.
[0117] The photocurable silicone composition according to the present invention may be a one-component. The one-component may refer to a curable silicone composition consisting of only one component, and may refer to a silicone composition in a form that can be used without a separate mixing step. The photocurable silicone composition according to the present invention is a one-component composition, so sufficient working time may be secured before UV exposure.WA12503S
[0118] Accordingly, working efficiency may be improved. In addition, since a polysiloxane resin, a crosslinking agent, and a catalyst are included in one product, a stable system may be constructed.
[0119] The photocurable silicone composition according to the present invention may include a stabilizer including an aliphatic phosphite compound. The stabilizer may be liquid at room temperature.
[0120] Conventionally, an aromatic phosphite compound such as tris(2,3-di-tert-butylphenyl)phosphite (TDBPP) was used as a phosphite stabilizer. However, the aromatic phosphite compound has a complex structure, which limits its adsorption on a catalyst surface due to steric hindrance. In addition, there was a problem that the electron donating group (EDG) effect was dispersed due to the large volume, and the speed of bonding between the unshared electron pair on the phosphorus (P) atom and the catalyst was reduced.
[0121] Accordingly, the present inventors confirmed that, when an aliphatic phosphite compound is used as a stabilizer, the molecular weight is small and the structure is simple, so it may effectively block the active site of the catalyst. In addition, it was confirmed that, since it does not contain an aromatic structure and has a small volume, the electron donating group effect (EDG) may be stably exhibited, and the unshared electron pair existing on the phosphorus (P) atom and the catalyst may be more easily combined. In addition, the aliphatic phosphite compound exhibits a liquid phase at room temperature, confirming that it may be easily processed, compared to an aromatic phosphite compound that is solid at room temperature.
[0122] Accordingly, since the photocurable silicone composition includes an aliphatic phosphite compound as a stabilizer, the active site of the catalyst may be effectively blocked, so that the storage stability may be improved even under high-temperature conditions.
[0123] The aliphatic phosphite compound may include dialkyl phosphite. The dialkyl phosphite may be one or more selected from the group consisting of dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, dioctyl phosphite, didecyl phosphite, didodecyl phosphite, diisopropyl phosphite, di-tert-butyl phosphite, di-2-ethylhexyl phosphite, dicyclopropyl phosphite, dicyclobutyl phosphite, dicyclopentyl phosphite, dicyclohexyl phosphite, methyl ethyl phosphite, methyl butyl phosphite, and ethyl octyl phosphite.
[0124] The aliphatic phosphite compound may include trialkyl phosphite. The trialkyl phosphite may be one or more selected from the group consisting of trimethyl phosphite, triethylWA12503S
[0125] phosphite, tripropyl phosphite, tributyl phosphite, tripentyl phosphite, tnhexyl phosphite, trioctyl phosphite, tridecyl phosphite, triisopropyl phosphite, tri-sec-butyl phosphite, tri -tert-butyl phosphite, tri-2-ethylhexyl phosphite, tricyclo propylphosphite, tricyclobutyl phosphite, tricyclopentyl phosphite, tricyclohexyl phosphite, methyldiethyl phosphite, ethyldimethyl phosphite, methylbutylethyl phosphite, and butylethylhexyl phosphite.
[0126] The aliphatic phosphite compound may have a boiling point of 200 °C to 450 °C, 200 °C to 410 °C, 230 °C to 410 °C, 230 °C to 350 °C, or 230 °C to 300 °C.
[0127] The aliphatic phosphite compound may have a molecular weight of 200 g / mol to 500 g / mol, 220 g / mol to 500 g / mol, 220 g / mol to 450 g / mol, or 220 g / mol to 280 g / mol.
[0128] The aliphatic phosphite compound may be represented by Formula 1 below:
[0129] [Formula 1]
[0130]
[0131] In Formula 1, Ri to R3 are each independently an alkyl group having 4 to 15 carbon atoms. In Formula 1, Ri to R3 may be each independently an alkyl group having 4 to 8 carbon atoms.
[0132] The stabilizer may include a borate compound. The borate compound may be adsorbed on a catalyst surface to form a physical force or induce a structural change in the catalyst. Accordingly, the chemical stability of the photocurable silicone composition may be improved, and the catalyst may be controlled so as not to be activated.
[0133] The borate compound may include borate ester.
[0134] The borate ester may be one or more selected from the group consisting of trimethylborate, triethylborate, tripropylborate, tributylborate, tripentylborate, trihexylborate, tri octylborate, triisopropylborate, tri -sec-buty lb orate, tri -tert-buty lb orate, tri-2-ethylhexylborate, methyl ethylborate, methylpropylborate, ethylbutylborate, triphenylborate, phenyldimethylborate, diphenylmethylborate, triphenoxyborate, tricyclopentylborate, and tricyclohexylborate.
[0135] The borate compound may include a pinacol structure.WA12503S
[0136] The borate compound including a pinacol structure may be one or more selected from the group consisting of methyl pinacol borate, ethyl pinacol borate, butyl pinacol borate, hexyl pinacol borate, isopropyl pinacol borate, phenyl pinacol borate, benzyl pinacol borate, naphthyl pinacol borate, diphenyl pinacol borate, hydroxy pinacol borate, chloro pinacol borate, methoxy pinacol borate, amino pinacol borate, methylethyl pinacol borate, and phenylmethyl pinacol borate.
[0137] The borate compound including the pinacol structure may have improved hydrolytic resistance and may have the characteristic of not being easily converted into boric acid. Accordingly, even in a high-temperature and humid environment, conversion to boric acid due to hydrolysis may be suppressed, so that the function of preventing the activity of the catalyst may be maintained.
[0138] The borate compound may maintain physical properties, such as curing rate, hardness, adhesive force, and optical properties, at constant levels even when its content increases. Accordingly, when used in combination with the aliphatic phosphite compound, the physical properties may be maintained constant while the high-temperature storage stability may be improved.
[0139] The borate compound may have a boiling point of 100 °C to 200 °C, 110 °C to 200 °C, 110 °C to 150 °C, 120 °C to 150 °C, or 130 °C to 150 °C.
[0140] The borate compound may have a molecular weight of 100 g / mol to 500 g / mol, 100 g / mol to 400 g / mol, 100 g / mol to 300 g / mol, 100 g / mol to 200 g / mol, or 150 g / mol to 200 g / mol.
[0141] A weight ratio of the aliphatic phosphite compound:the borate compound which are included in the photocurable silicone composition may be 1:2 to 1:100, 1:2 to 1:90, 1:2 to 1:80, or 1:2 to 1:70.
[0142] The content of the stabilizer may be 10 ppm to 10,000 ppm, 10 ppm to 8,000 ppm, 10 ppm to 5,000 ppm, or 10 ppm to 3,000 ppm based on the total weight of the photocurable silicone composition.
[0143] When the ranges are satisfied, high-temperature storage stability may be improved while maintaining physical properties, such as curing rate, hardness, adhesive force, and optical properties, at constant levels.
[0144] The photocurable silicone composition may satisfy Condition 1 or 2 below:WA12503S
[0145] [Condition 1]
[0146] In Vi < 3,000 mPa.s, 1 ppm < Pi < 1,000 ppm,
[0147] [Condition 2]
[0148] In V2 > 3,000 mPa.s, 1 ppm < P2 < 500 ppm,
[0149] Vi and V2 are each independently the viscosity of the photocurable silicone composition measured at 25°C according to DIN ISO 3219, and Pi and P2 are each independently the content of the aliphatic phosphite compound based on the total weight of the photocurable silicone composition.
[0150] As the content of the aliphatic phosphite compound increases, the effect of suppressing the curing rate of the photocurable silicone composition may increase. In addition, the decrease in the curing rate of the photocurable silicone composition may be related to the molecular weight, viscosity, etc. of the photocurable silicone composition. Accordingly, when the photocurable silicone composition has a viscosity range that satisfies Condition 1 or 2, the aliphatic phosphite compound included in the photocurable silicone composition may be adjusted to have a content range that satisfies Condition 1 or 2. Accordingly, the high-temperature storage stability may be improved while constantly maintaining the physical properties of the photocurable silicone composition.
[0151] A cured product according to the present invention is prepared by curing a photocurable silicone composition that includes a polysiloxane resin, a curing catalyst, and a stabilizer including an aliphatic phosphite compound.
[0152] The photocurable silicone composition may be the same as the above-described photocurable silicone composition. The cured product may be made by curing the photocurable silicone composition by UV irradiation. The shape of the cured product may be a sheet, a film, or a tape, and is not particularly limited.
[0153] The film may be a functional film applicable to a liquid crystal display (LCD), an organic light emitting display (OLED), an electronic paper (e-paper) display, a surface-conduction electron-emitter display (SED), a light emitting diode (LED) display, or an electroluminescent display (ELD).
[0154] The cured product may be used as an optical clear resin (OCR) with functions such asWA12503S
[0155] protection, sealing, adhesion, and sticking. The cured product may be formed by applying the photocurable silicone composition to a film-like substrate, a tape-like substrate, or a sheet-like substrate, and then curing it by UV irradiation.
[0156] A laminated structure according to the present invention includes an adhesive layer arranged between a first optical member and a second optical member, and the adhesive layer may include a cured product formed by curing the photocurable silicone composition that includes the polysiloxane resin, the curing catalyst, and the stabilizer including the aliphatic phosphite compound.
[0157] The photocurable silicone composition may be the same as the above-described photocurable silicone composition.
[0158] The first and second optical members may be bonded by the adhesive layer.
[0159] The first and second optical members may be transparent or opaque. One or more optical members on one side or both sides of the first and second optical members may be a single substrate, and may be an optical member having an independent laminated structure in itself, like a backlight unit.
[0160] The first and second optical members included in the laminated structure may have a plateshaped portion having a planar widening, or the plate-shaped portion or the member itself may be curved.
[0161] The first and second optical members may be generally used as components of an optical display. The first and second optical members may include an image display panel, an optical panel, a front panel, a backlight unit, a touch panel unit, etc.
[0162] The materials of the first and second optical members may be an inorganic optical material such as glass, indium tin oxide (ITO), or an organic optical material such as polycarbonate resin, acrylic resin, epoxy resin, polystyrene resin, polyamide resin, polyimide resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol (PVA) resin, polyethylene terephthalate (PET) resin, cyclopolyolefin resin, polyether ether ketone resin, polyethylene naphthalate (PEN) resin, liquid crystal polyarylate resin, polyamideimide resin, polyether sulfone resin, or a mixture thereof.
[0163] An optical device according to the present invention includes a substrate, an electronic component disposed on the substrate, and an encapsulant protecting at least a portion of theWA12503S
[0164] electronic component. The encapsulant may include a cured product made by curing a photocurable silicone composition including a polysiloxane resin, a curing catalyst, and a stabilizer including an aliphatic phosphite compound.
[0165] The photocurable silicone composition may be the same as the above-described photocurable silicone composition.
[0166] The optical device may be an optical semiconductor device. The optical semiconductor device may be a light emitting diode (LED), a photocoupler, or a charge-coupled device (CCD). The optical device may be an LED device.
[0167] Hereinafter, the present invention is described in more detail based on Examples and Comparative Examples. However, the following Examples and Comparative Examples are only examples for explaining the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.
[0168] First example
[0169] Example 1
[0170] 300 ml of a photocurable silicone composition was prepared by mixing a poly siloxane resin, platinum (CAS 94442-22-5) as a curing catalyst, and the first trialkyl phosphite (boiling point: about 242 °C, molecular weight: about 250 g / mol) as a stabilizer.
[0171] Example 2
[0172] A photocurable silicone composition was prepared using the same content and process as in Example 1, except that the second trialkyl phosphite (boiling point: about 375 °C, molecular weight: about 334 g / mol) was mixed instead of the first trialkyl phosphite of Example 1 as a stabilizer.
[0173] Example 3
[0174] A photocurable silicone composition was prepared using the same content and process as in Example 1, except that the third trialkyl phosphite (boiling point: about 300 °C, molecular weight: about 419 g / mol) was mixed instead of the first trialkyl phosphite of Example 1 as aWA12503S
[0175] stabilizer.
[0176] Comparative Example 1
[0177] A photocurable silicone composition was prepared using the same content and process as in Example 1 , except that triarylphosphite (CAS 31570-04-4) was mixed instead of the first trialkyl phosphite of Example 1 as a stabilizer.
[0178] First experimental example
[0179] Each of the photocurable silicone compositions according to Examples 1 to 3 and Comparative Example 1 was subjected to storage stability evaluation at 30°C and 40°C under conditions of no UV light exposure. Storage stability can be evaluated as excellent when the photocurable silicone composition does not change from a liquid state to a gel state and the viscosity increase rate of the photocurable silicone composition is low. In addition, when the photocurable silicone composition changed from a liquid to a gel, it was classified as gelation. Viscosity changes at 30°C are shown in Table 1 below, and viscosity changes at 40°C are shown in Table 2 below.
[0180] [Table 1]
[0181]
[0182] WA12503S
[0183]
[0184] [Table 2]
[0185]
[0186] Referring to Tables 1 and 2, it can be confirmed that the compositions of Examples 1 to 3 containing an aliphatic phosphite compound according to the present invention exhibit improvedWA12503S
[0187] high-temperature storage stability, compared to the composition of Comparative Example 1 containing an aromatic phosphite compound.
[0188] Second example
[0189] Example 4
[0190] 300 ml of a photocurable silicone composition was prepared by mixing a poly siloxane resin, platinum (CAS 94442-22-5) as a curing catalyst, and the first trialkyl phosphite, used in Example 1, and borate ester (boiling point: about 140 °C, molecular weight: about 185 g / mol) as stabilizers.
[0191] Example 5
[0192] A photocurable silicone composition was prepared using the same content and process as in Example 4, except that a photocurable silicone composition having an initial viscosity of 3,500 mPa.s was used instead of the photocurable silicone composition having an initial viscosity of 2,000 mPa.s of Example 4.
[0193] Comparative Example 2
[0194] A photocurable silicone composition was prepared using the same content and process as in Comparative Example 1, except that a photocurable silicone composition having an initial viscosity of 3,500 mPa.s was used instead of the photocurable silicone composition having an initial viscosity of 1,996 mPa.s of Comparative Example 1.
[0195] Second experimental example
[0196] The photocurable silicone composition of each of Examples 4 and 5 and Comparative Example 2 was subjected to storage stability evaluation at 40°C under conditions of no UV light exposure. Storage stability can be evaluated as excellent when the photocurable silicone composition does not change from a liquid state to a gel state and the viscosity increase rate of the photocurable silicone composition is low. In addition, when the photocurable silicone composition changes from a liquid to a gel, it was classified as gelation. Results are shown in Table 3 below.WA12503S
[0197] [Table 3]
[0198]
[0199] Referring to Table 3, it can be confirmed that the compositions of Examples 4 and 5 containing an aliphatic phosphite compound and a borate compound according to the present invention exhibit improved high-temperature storage stability, compared to the composition of Comparative Example 2 including an aromatic phosphite compound.
[0200] Third example
[0201] Example 6
[0202] The photocurable silicone composition according to Example 1 was prepared. The viscosity of the photocurable silicone composition at room temperature was 2,000 mPa.s. TheWA12503S
[0203] photocurable silicone composition, was irradiated with UV energy of 3,000 mJ / cm2using a 365 nm LED lamp. Next, the photocurable silicone composition was aged at room temperature for 24 hours to manufacture a cured product.
[0204] Example 7
[0205] The photocurable silicone composition according to Example 6 was stored at room temperature for 24 weeks under conditions of no LTV light exposure. Next, the photocurable silicone composition was manufactured into a cured product in the same process as in Example 6.
[0206] Example 8
[0207] The photocurable silicone composition according to Example 4 was prepared. The viscosity of the photocurable silicone composition at room temperature was 2,000 mPa.s. Next, the photocurable silicone composition was manufactured into a cured product in the same process as in Example 6.
[0208] Example 9
[0209] The photocurable silicone composition according to Example 8 was stored at room temperature for 24 weeks under conditions of no LTV light exposure. Next, the photocurable silicone composition was manufactured into a cured product in the same process as in Example 8.
[0210] Example 10
[0211] The photocurable silicone composition according to Example 3 was prepared. The viscosity of the photocurable silicone composition at room temperature was 2,000 mPa.s. Next, the photocurable silicone composition was manufactured into a cured product in the same process as in Example 6.
[0212] Example 11
[0213] The photocurable silicone composition according to Example 10 was stored at room temperature for 24 weeks under conditions of no LTV light exposure. Next, the photocurable silicone composition was manufactured into a cured product in the same process as in Example 10.
[0214] Example 12
[0215] 300 ml of a photocurable silicone composition was prepared by mixing a poly siloxaneWA12503S
[0216] resin, platinum (CAS 94442-22-5) as a curing catalyst with the third trialkyl phosphite and borate ester (boiling point: about 140 °C, molecular weight: about 185 g / mol) used in Example 3 as stabilizers. The viscosity of the photocurable silicone composition at room temperature was 2,000 mPa.s. Next, Next, the photocurable silicone composition was manufactured into a cured product in the same process as in Example 6.
[0217] Example 13
[0218] The photocurable silicone composition according to Example 12 was stored at room temperature for 24 weeks under conditions of no UV light exposure. Next, the photocurable silicone composition was manufactured into a cured product in the same process as in Example 12.
[0219] Example 14
[0220] A cured product was manufactured in the same process as in Example 6, except that a photocurable silicone composition having a viscosity of 3,500 mPa.s at room temperature was used instead of the photocurable silicone composition having a viscosity of 2,000 mPa.s at room temperature of Example 6.
[0221] Example 15
[0222] The photocurable silicone composition according to Example 14 was stored at room temperature for 24 weeks under conditions of no UV light exposure. Next, the photocurable silicone composition was manufactured into a cured product in the same process as in Example 14.
[0223] Example 16
[0224] A cured product was manufactured in the same process as in Example 8, except that a photocurable silicone composition having a viscosity of 3,500 mPa.s at room temperature was used instead of the photocurable silicone composition having a viscosity of 2,000 mPa.s at room temperature of Example 8.
[0225] Example 17
[0226] The photocurable silicone composition according to Example 16 was stored at room temperature for 24 weeks under conditions of no UV light exposure. Next, the photocurable silicone composition was manufactured into a cured product in the same process as in ExampleWA12503S
[0227] 16.
[0228] Example 18
[0229] A cured product was manufactured in the same process as in Example 10, except that a photocurable silicone composition having a viscosity of 3,500 mPa.s at room temperature was used instead of the photocurable silicone composition having a viscosity of 2,000 mPa.s at room temperature of Example 10.
[0230] Example 19
[0231] The photocurable silicone composition according to Example 18 was stored at room temperature for 24 weeks under conditions of no UV light exposure. Next, the photocurable silicone composition was manufactured into a cured product in the same process as in Example 18.
[0232] Example 20
[0233] A cured product was manufactured in the same process as in Example 12, except that a photocurable silicone composition having a viscosity of 3,500 mPa.s at room temperature was used instead of the photocurable silicone composition having a viscosity of 2,000 mPa.s at room temperature of Example 12.
[0234] Example 21
[0235] The photocurable silicone composition according to Example 20 was stored at room temperature for 24 weeks under conditions of no UV light exposure. Next, the photocurable silicone composition was manufactured into a cured product in the same process as in Example 20.
[0236] Third experimental example
[0237] The physical property evaluation results of Examples 6 to 13 are shown in Table 4 below, and the physical property evaluation results of Examples 14 to 21 are shown in Table 5 below.
[0238] [Table 4]WA12503S
[0239]
[0240] [Table 5]
[0241]
[0242] WA12503S
[0243]
[0244] Referring to Tables 4 and 5, it can be confirmed that the viscosity was practically the same
[0245] after the change in time, and the physical properties, such as curing rate, hardness, adhesive force,
[0246] and optical properties, are maintained constant.
Claims
WA12503S[CLAIMS]
1. A photocurable silicone composition, comprising:a polysiloxane resin;a curing catalyst; anda stabilizer comprising an aliphatic phosphite compound.
2. The photocurable silicone composition according to claim 1, wherein the photocurable silicone composition is a one-component.
3. The photocurable silicone composition according to claim 1, wherein the stabilizer is liquid at room temperature.
4. The photocurable silicone composition according to claim 1, wherein the aliphatic phosphite compound is represented by Formula 1 below:[Formula 1]where Ri to R3 are each independently an alkyl group having 4 to 15 carbon atoms.WA12503S
5. The photocurable silicone composition according to claim 1, wherein the stabilizer comprises a borate compound.
6. The photocurable silicone composition according to claim 5, wherein a weight ratio of the aliphatic phosphite compound:the borate compound comprised in the photocurable silicone composition is 1:2 to 1:100.
7. The photocurable silicone composition according to claim 5, wherein a content of the stabilizer is 10 ppm to 10,000 ppm based on a total weight of the photocurable silicone composition.
8. The photocurable silicone composition according to claim 1, wherein the poly siloxane resin comprises an organopolysiloxane containing an alkenyl group; and an organohydrogenpoly siloxane containing one or more hydrogens bonded to a silicon atom.
9. A cured product made by curing a photocurable silicone composition, wherein the photocurable silicone composition comprises:a polysiloxane resin;a curing catalyst; anda stabilizer comprising an aliphatic phosphite compound.
10. WA12503SA laminated structure, comprising an adhesive layer arranged between a first optical member and a second optical member,wherein the adhesive layer comprises a cured product made by curing a photocurable silicone composition comprising a polysiloxane resin, a curing catalyst, and a stabilizer comprising an aliphatic phosphite compound.
11. An optical device, comprising:a substrate;an electronic component arranged on the substrate; andan encapsulant for protecting at least a portion of the electronic component, wherein the encapsulant comprises a cured product made by curing a photocurable silicone composition comprising a polysiloxane resin, a curing catalyst, and a stabilizer comprising an aliphatic phosphite compound.