Organosiloxane monomers, ink compositions and methods of making the same, flexible semiconductor devices and methods of thin film encapsulation thereof

Abstract

The application discloses an organic siloxane monomer, an ink composition, a preparation method of the ink composition, a thin film packaging method and a flexible semiconductor device. The organic siloxane monomer has a special dendritic structure. The ink composition with high adhesion comprises the following components in parts by weight, based on 100 parts of total weight: the organic siloxane monomer 5-70 parts, a first photocuring monomer 15-80 parts, a second photocuring monomer 5-50 parts and a photoinitiator 0.1-10 parts. The ink composition is prepared by using the organic siloxane monomer with the special structure as a main component of a flexible semiconductor device packaging material and in cooperation with other components. The ink composition has low water vapor transmission rate, good adhesion and high curing rate, and can be effectively used for thin film packaging of the flexible semiconductor device.

Description

Technical Field

[0001] This application relates to the field of electronic device packaging materials technology, and in particular to an organosiloxane monomer, an ink composition and its preparation method, a flexible semiconductor device and its thin film packaging method. Background Technology

[0002] Thin-film encapsulation technology involves growing single-layer or multi-layer thin films on the substrate of a fabricated flexible semiconductor device, such as an OLED device, to achieve a barrier effect against moisture. This is typically achieved using an organic-inorganic composite thin film approach. A typical example is a three-layer structure, where the first inorganic layer (SiNx) serves as a smooth substrate, the second organic layer is formed by inkjet printing and subsequent curing, and the third inorganic layer (SiNx) is the final inorganic layer. During the deposition process, the inorganic layer is prone to defects such as cracks or shrinkage cavities. Therefore, the organic layer helps stabilize the inorganic layer and extends the water and oxygen permeation pathways. Consequently, the encapsulation materials for flexible semiconductor devices must meet requirements such as high curing rate, low shrinkage rate, and low moisture permeability.

[0003] In existing technologies, organic UV-curable resins are considered a conventional and effective organic encapsulation material due to their excellent curing characteristics, stability, and light transmittance. Commonly used resins typically include acrylic resins, methacrylic resins, isoprene resins, ethylene resins, epoxy resins, polyurethane resins, cellulose resins, perylene resins, imide resins, or mixtures of two or more. However, during prolonged high-temperature exposure, conventional resins of this type are prone to peeling between the organic and inorganic layers; furthermore, they exhibit low curing rates, are susceptible to UV shrinkage and water absorption, and require stringent process environments. Patent CN107068896A discloses an organic light-emitting display panel and its preparation method, using a network structure obtained by cross-linking polyorganosiloxane as the material for the organic encapsulation layer. This panel boasts high light transmittance (over 98%), photocurability, good shock resistance, low surface energy, and advantages such as resistance to temperature changes and yellowing. However, it also exhibits high water vapor transmittance, and its components are primarily monofunctional groups with few curable functional groups, resulting in a low curing rate and poor adhesion to the substrate. Summary of the Invention

[0004] To address the aforementioned problems, this application provides an organosiloxane monomer with a special structure.

[0005] Another object of this application is to provide an ink composition with high adhesion comprising the above-mentioned organosiloxane monomer.

[0006] Another object of this application is to provide a method for preparing the above-mentioned ink composition with high adhesion.

[0007] Another objective of this application is to provide a thin-film packaging method for flexible semiconductor devices.

[0008] Another objective of this application is to provide a flexible semiconductor device prepared using the above-described thin-film encapsulation method.

[0009] To achieve the above objectives, the technical solution of this application is as follows:

[0010] This application provides an organosiloxane monomer with the structural formula shown in general formula (Ⅰ):

[0011]

[0012]

[0013] Among them, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently substituted or unsubstituted C. 1-20 Alkylene, substituted or unsubstituted C 1-30 alkylene ether group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Aryl, substituted or unsubstituted fluoroalkyl, C 1-30 One of the alkyl groups;

[0014] X1, X2, X3, and X4 are each independently substituted or unsubstituted C. 1-20 Alkylene, substituted or unsubstituted C 1-30 alkylene ether group, substituted or unsubstituted C 6-30 aryl or substituted or unsubstituted C 7-30 One of the aryl alkylene groups;

[0015] The structural formulas of Z1, Z2, Z3, and Z4 are shown independently as follows:

[0016]

[0017] Where R is methyl or hydrogen.

[0018] This application also provides an ink composition with high adhesion, which, calculated based on a total weight of 100 parts, comprises the following components in parts by weight: 5-70 parts of the organosiloxane monomer, 15-80 parts of the first photocurable monomer, 5-50 parts of the second photocurable monomer, and 0.1-10 parts of the photoinitiator.

[0019] This application also provides a method for preparing the above-mentioned ink composition with high adhesion, comprising the following steps: mixing the organosiloxane monomer, the first photocurable monomer, the second photocurable monomer and the photoinitiator under a nitrogen atmosphere in a light-protected condition, and immersing the mixture to obtain the ink composition.

[0020] This application also provides a thin-film packaging method for flexible semiconductor devices, comprising the following steps:

[0021] S1: Integrating semiconductor components on a flexible substrate;

[0022] S2: An inorganic material is deposited on the surface of the semiconductor element in S1 to obtain an inorganic layer with a thickness of 5-1000nm;

[0023] S3: Deposit a layer of the ink composition with high adhesion on the surface of the inorganic layer described in S2, and then cure it with ultraviolet light to obtain an organic layer;

[0024] S4: Deposit another layer of inorganic material on the surface of the organic layer described in S3 to obtain another inorganic layer with a thickness of 5-1000nm, thereby realizing the thin film encapsulation of the semiconductor device;

[0025] In steps S2 and S4, the inorganic materials are each independently one or more of silicon nitride, titanium oxide, aluminum oxide, or silicon oxide.

[0026] This application also provides a flexible semiconductor device prepared by the above-described thin-film encapsulation method, comprising: a flexible substrate, a semiconductor element, and a thin-film encapsulation structure. The semiconductor element is disposed on one side of the flexible substrate, and the thin-film encapsulation structure comprises a first inorganic layer, an organic layer, and a second inorganic layer. The first inorganic layer, the organic layer, and the second inorganic layer are sequentially stacked on a surface of the semiconductor element opposite to the flexible substrate.

[0027] Compared with the prior art, the beneficial effects of this application are:

[0028] This application provides an organosiloxane monomer with a special structure containing a large proportion of Si-O bond units, which allows for better bonding and adhesion to the substrate, exhibiting high adhesion. Furthermore, the organosiloxane monomer has low viscosity and good compatibility with other formulation components. By combining it with a first photocurable monomer, a second photocurable monomer, and a photoinitiator, the prepared ink composition can maintain high adhesion and high curing rate while retaining low water vapor transmission rate (<5.8 × 10⁻⁶). -4 g / m 2 • Day, adhesion ≥4B, curing rate ≥95%. Furthermore, the prepared ink composition is suitable for inkjet printing and can be widely used in thin-film encapsulation of flexible semiconductor devices. Attached Figure Description

[0029] Figure 1 This is a schematic diagram of a thin-film encapsulation structure provided in this application.

[0030] Figure 2This is a flowchart illustrating the formation of an organic layer from the ink composition provided in this application.

[0031] Figure 3 This is a schematic diagram of the structure of a flexible semiconductor device provided in this application. Detailed Implementation

[0032] The present invention is further illustrated below with reference to specific embodiments. These embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions in the art or as recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, are all commercially available from the conventional market. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention are within the scope of protection claimed by the present invention.

[0033] One embodiment of this application provides an organosiloxane monomer, the structural formula of which is shown in general formula (Ⅰ):

[0034]

[0035] Among them, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently substituted or unsubstituted C. 1-20 Alkylene, substituted or unsubstituted C 1-30 alkylene ether group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Aryl, substituted or unsubstituted fluoroalkyl, C 1-30 One of the alkyl groups;

[0036] X1, X2, X3, and X4 are each independently substituted or unsubstituted C. 1-20 Alkylene, substituted or unsubstituted C 1-30 alkylene ether group, substituted or unsubstituted C 6-30 aryl or substituted or unsubstituted C 7-30 One of the aryl alkylene groups;

[0037] The structural formulas of Z1, Z2, Z3, and Z4 are shown independently as follows:

[0038]

[0039] Where R is methyl or hydrogen.

[0040] This application provides an organosiloxane monomer with a special structure containing a large proportion of Si-O bond units, which allows for better bonding and adhesion to the substrate, exhibiting high adhesion. Furthermore, the organosiloxane monomer exhibits different properties when R1, R2, R3, R4, R5, R6, R7, and R8 are different substituents. When C... 1-20 When alkylene oxides are used, the organosiloxane monomers exhibit excellent flexibility; when C is used... 6-30 When aryl, it exhibits excellent rigidity; as C 1-30 When the alkylene ether group is present, it not only exhibits excellent water absorption, but its alkoxysilane structure also demonstrates better adhesion to inorganic metal substrates. In the structure, X1, X2, X3, and X4 are each independently substituted or unsubstituted C groups. 1-20 Alkylene, substituted or unsubstituted C 1-30 alkylene ether group, substituted or unsubstituted C 6-30 aryl or substituted or unsubstituted C 7-30 One of the aryl alkyl groups, different structures have different properties, and can work synergistically with R groups to complement or superimpose the properties of materials.

[0041] In addition, active functional groups Z1, Z2, Z3, and Z4 are introduced into the structure of the organosiloxane monomer. These are (meth)acrylates or (meth)acrylamides, which can undergo crosslinking reactions to form films under ultraviolet conditions. In particular, when Z1, Z2, Z3, and Z4 are all (meth)acrylamide structures, the organosiloxane monomer has higher reactivity and can effectively improve the curing rate of the subsequent ink composition.

[0042] In one embodiment, the organosiloxane monomer is one of the following compounds: I-1, I-2, I-3, I-4, I-5, I-6, I-7, and I-8.

[0043]

[0044]

[0045]

[0046]

[0047] This application also provides an ink composition with high adhesion, which, calculated based on a total weight of 100 parts, comprises the following components in parts by weight: 5-70 parts of organosiloxane monomer, 15-80 parts of first photocurable monomer, 5-50 parts of second photocurable monomer, and 0.1-10 parts of photoinitiator.

[0048] The dendritic organosiloxane monomer provided in this application has low viscosity and good compatibility with other formulation components. When combined with a first photocurable monomer, a second photocurable monomer, and a photoinitiator, the resulting ink composition exhibits high adhesion and high curing rate while maintaining low water vapor transmission rate (<5.8 × 10⁻⁶). -4 g / m 2 • Day, adhesion ≥4B, curing rate ≥95%. Furthermore, the prepared ink composition is suitable for inkjet printing and can be widely used in the packaging of flexible semiconductor devices.

[0049] In one embodiment, the ink composition with high adhesion comprises the following components in parts by weight, calculated based on a total weight of 100 parts: 15-30 parts of organosiloxane monomer, 50-60 parts of first photocurable monomer, 10-20 parts of second photocurable monomer, and 1-5 parts of photoinitiator.

[0050] In one embodiment, the structural formula of the first photocurable monomer is shown in general formula (II):

[0051]

[0052] Wherein, R is methyl or hydrogen; L is a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted arylalkylene group, -O- or -N(T)-; T in -N(T)- is hydrogen, a substituted or unsubstituted alkyl group; and n is a positive integer between 2 and 20.

[0053] The first photocurable monomer used in this application is mainly a long-chain aliphatic or long-chain ether-based bifunctional (meth)acrylate or (meth)acrylamide. These structures have low viscosity (providing excellent dilution properties) and high flexibility (viscosity < 30 cps), and the bifunctional groups in the structure can effectively improve the curing rate of the entire ink composition system. In addition, long-chain alkanes also have good spreadability and are beneficial to the leveling properties of the system.

[0054] Specifically, the first photocurable monomer is diethoxylated bisphenol A dimethacrylate, 1,17-heptadecanediol di(meth)acrylate, 1,3-cyclohexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,20-eicosenediol di(meth)acrylate, 1,11-undecanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,15-pentadecanedanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, 1,7-octanediol di(meth)acrylate, 1,2-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,18 - One of the following: octadecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 2,4-diethyl-1,5-pentanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,19-nonadecanediol di(meth)acrylate, or neopentanediol di(meth)acrylate. 1,17-Heptadecanediol di(methyl)acrylamide, 1,3-cyclohexanediol di(methyl)acrylamide, 1,8-octanediol di(methyl)acrylamide, 1,20-eicosenediol di(methyl)acrylamide, 1,11-undecanediol di(methyl)acrylamide, 1,4-butanediol di(methyl)acrylamide, 1,15-pentadecanediol di(methyl)acrylamide, 1,13-tridecanediol di(methyl)acrylamide, 1,7-octanediol di(methyl)acrylamide, 1,2-butanediol di(methyl)acrylamide, 3-methyl-1,5-pentanediol di(methyl)acrylamide, 1,18-octadecanediol di(methyl)acrylamide One of the following: methyl acrylamide, 1,16-hexadecanediol di(methyl)acrylamide, 2,4-diethyl-1,5-pentanediol di(methyl)acrylamide, 1,3-butanediol di(methyl)acrylamide, 1,5-pentanediol di(methyl)acrylamide, 1,6-hexanediol di(methyl)acrylate, 1,7-heptanediol di(methyl)acrylamide, 1,9-nonanediol di(methyl)acrylamide, 1,10-decanediol di(methyl)acrylamide, 1,12-dodecanediol di(methyl)acrylamide, 1,14-tetradecanediol di(methyl)acrylamide, or 1,19-nonadecanediol di(methyl)acrylamide.

[0055] In one embodiment, the structural formula of the second photocurable monomer is shown in general formula (Ⅲ):

[0056]

[0057] Where R3 is hydrogen or methyl; A is C 1-30 alkylene chains or C 1-30 The alkene oxide chain; B is a substituted or unsubstituted cycloalkyl group, and C is a substituted or unsubstituted C. 6-30 Aryl.

[0058] More preferably, in the structural formula of the second photocurable monomer, B is a substituted or unsubstituted cycloalkyl group.

[0059] More preferably, the second photocurable monomer is one of the following compounds: III-1, III-2, III-3, III-4, III-5, III-6, III-7, III-8, III-9, III-10, III-11, III-12, III-13, or III-14.

[0060]

[0061] More preferably, the second photocurable monomer is one of the following compounds: III-4 or III-8:

[0062]

[0063] The second photocurable monomer in this application is an ethoxylated cycloalkanes acrylate compound. Due to the unique hybridization of carbon atoms, cycloalkanes can effectively increase the absorption of the monomer in the ultraviolet region and reduce the absorption in the visible region, thus having the characteristic of fast photocuring rate. In addition, monomers without aromatic structures do not yellow after curing, so the organic film produced has the advantages of high curing rate and high light transmittance.

[0064] In one embodiment, the photoinitiator is one or more of acylphosphine oxide, α-hydroxy ketone, α-amino ketone, or glyoxylate.

[0065] More preferably, the photoinitiator is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4,6-trimethylbenzoyl-dimethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, benzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diethoxyphenylphosphine oxide, benzoyl-diethoxyphosphine oxide, benzophenone and its derivatives, benzoin and its derivatives, anthraquinone and its derivatives, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, diethoxyacetophenone, 4-tert-butyltrichloroacetophenone, 2-dimethylaminoethyl benzoate, p-dimethylaminoethyl benzoate, diphenyl disulfide, thioxanone and its derivatives, camphorquinone, 7,7-dimethyl-2,3-dioxobicyclohexane [2.2.1] Heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1] heptane-1-carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1] heptane-1-carboxyl chloride, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, α-aminoalkylphenyl ketone derivatives, phenyl-glyoxylic acid-methyl ester, oxy-phenyl-acetic acid 2-[2-oxy-2-phenyl-ethoxy-ethoxy]-ethyl ester or oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester.

[0066] This application also provides a method for preparing the above-mentioned ink composition with high adhesion, comprising the following steps: mixing the above-mentioned organosiloxane monomer, first photocurable monomer, second photocurable monomer and photoinitiator under a nitrogen atmosphere in a light-protected condition, and immersing to obtain the ink composition.

[0067] In one embodiment, the mixing time is 2 hours, and the soaking step is soaking in activated 4A molecular sieve for 48 hours.

[0068] In addition, this application also provides a thin-film packaging method for flexible semiconductor devices, comprising the following steps:

[0069] S1: Integrating semiconductor components on a flexible substrate;

[0070] S2: An inorganic material is deposited on the surface of the semiconductor element in S1 to obtain a first inorganic layer with a thickness of 5-1000 nm;

[0071] S3: Deposit a layer of the above-mentioned ink composition with high adhesion on the surface of the inorganic layer described in S2, and then cure it with ultraviolet light to obtain an organic layer;

[0072] S4: Deposit another layer of inorganic material on the surface of the organic layer described in S3 to obtain a second inorganic layer with a thickness of 5-1000nm, thereby realizing the thin film encapsulation of the semiconductor device;

[0073] In steps S2 and S4, the inorganic materials are each independently at least one of silicon nitride, titanium oxide, aluminum oxide, or silicon oxide.

[0074] In one embodiment, the semiconductor element is one of OLED, LED, Micro-LED, silicon-based semiconductor element, AsGa semiconductor element or gallium phosphide semiconductor element.

[0075] This application also provides a flexible semiconductor device prepared using the above-described thin-film encapsulation method, comprising a flexible substrate, a semiconductor element, and a thin-film encapsulation structure. The semiconductor element is disposed on one side of the flexible substrate. The thin-film encapsulation structure includes a first inorganic layer, an organic layer, and a second inorganic layer, which are sequentially stacked on the surface of the semiconductor element facing away from the flexible substrate. A schematic diagram of the thin-film encapsulation structure is shown below. Figure 1 As shown.

[0076] Specifically, firstly, the inorganic material is deposited on the surface of the semiconductor device using chemical vapor deposition to form a first inorganic layer. Then, a layer of the aforementioned highly adhesive ink composition is sprayed onto the first inorganic layer using inkjet printing to obtain the organic layer. Finally, a second inorganic layer is deposited on the organic layer to obtain the flexible semiconductor device. A schematic diagram of the fabricated flexible semiconductor device is shown below. Figure 2 As shown.

[0077] The process of obtaining the organic layer using inkjet printing is as follows: Figure 3 As shown, the inkjet printing step includes using the above-mentioned ink composition with high adhesion as Ink ink, aligning and ejecting ink using a flexible substrate, the ink contacting the flexible substrate, spreading and leveling on the flexible substrate, and then curing into a film under ultraviolet light curing (UV LED) conditions to obtain the organic layer.

[0078] The preparation method and performance of the ink composition with high adhesion provided in this application are described below using specific examples and comparative examples.

[0079] The reagents used in the various embodiments and comparative examples of this application are described below:

[0080] Organosiloxane monomers: see I-1, I-2, I-3, I-4, I-5, I-6, I-7, and I-8 above;

[0081] First photocurable monomer:

[0082] II-1 PEG-200 (EM224, Changxing Chemical)

[0083] II-2SR-262 (Sartoma);

[0084] Second photocurable monomer: see III-4 (Changxing Chemical) and III-8 (TCI) above;

[0085] Photoinitiator: IGM (acylphosphine oxide).

[0086] In the following preparation reaction equation, "Karstedt catalyst" refers to the Karstedt catalyst, D4 is octamethylcyclotetrasiloxane, "rt" means "stirring", and "hydrolysis" means hydrolysis reaction.

[0087] Example 1

[0088] (1) Preparation of organosiloxane monomer I-1

[0089] The reaction equation for the preparation of I-1 is as follows:

[0090]

[0091] The specific preparation process is as follows:

[0092] Under a nitrogen atmosphere, compound b (94.8 g, purchased from TCI), Karstedt catalyst (0.5 g, purchased from TCI), octamethylcyclotetrasiloxane (D4, 490 g, purchased from TCI), and compound a (42.7 g, purchased from TCI) were added to a dry three-necked flask. The mixture was stirred at room temperature for 16 h. After the reaction was completed, the mixture was purified by column chromatography to obtain compound I-1 (74.8 g).

[0093] (2) Preparation of ink compositions with high adhesion

[0094] In a glove box (N2 atmosphere), organosiloxane monomer I-1 (25g), first photocurable monomer II-1 (PEG-200, 57g), second photocurable monomer III-8 (15g), and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0095] Example 2

[0096] (1) Preparation of organosiloxane monomer I-2

[0097] The reaction equation for the preparation of Ⅰ-2 is as follows:

[0098]

[0099] The specific preparation process is as follows:

[0100] In a three-necked round-bottom flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel, compound c (44.04 g, purchased from Alfa), anhydrous ethanol (40 g, purchased from Anage), and deionized water (25 g) were added and stirred for 1 h until homogeneous. Compound d (235 g, purchased from Alfa) was slowly added at -20°C. After the addition was complete, concentrated H₂SO₄ (1 mL) was added, and stirring continued for 30 min to initiate the hydrolysis reaction. After standing, the organic layer was separated using a separatory funnel. The organic layer was washed five times with distilled water until the solution was neutral, then washed with saturated saline solution, and the water was absorbed with sodium sulfate solution. Low-boiling-point substances were removed by vacuum distillation to obtain compound e.

[0101] Under a nitrogen atmosphere, compound b (94.8 g), Karstedt catalyst (0.5 g, purchased from TCI), octamethylcyclotetrasiloxane (D4, 490 g, purchased from TCI), and compound e (108.2 g) were added to a dry three-necked flask. The mixture was stirred at room temperature for 23 h. After the reaction was completed, the mixture was purified by column chromatography to obtain compound I-2 (196 g).

[0102] (2) Preparation of ink compositions with high adhesion

[0103] In a glove box (N2 atmosphere), organosiloxane monomer I-2 (25g), first photocurable monomer II-1 (57g), second photocurable monomer III-8 (15g), and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0104] Example 3

[0105] (1) Preparation of organosiloxane monomer I-3

[0106] The reaction equation for the preparation of Ⅰ-3 is as follows:

[0107]

[0108] The specific preparation process is as follows:

[0109] In a three-necked round-bottom flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel, compound c (44.04 g, purchased from Alfa), anhydrous ethanol (32.5 g, purchased from Anage), and deionized water (20 g) were added and stirred for 1 h until homogeneous. At -5°C, compound f (157 g, purchased from Sigma Aldrich) was slowly added to the mixture (expected to be completed in 5 hours). After the addition was complete, concentrated H₂SO₄ (1 mL) was added, and stirring continued for 30 min. After standing, the organic layer was separated using a separatory funnel. The organic layer was washed five times with distilled water until the solution became neutral. The organic layer was then washed with saturated saline solution, and water was absorbed with sodium sulfate solution. Low-boiling-point substances were removed by vacuum distillation. Compound g was obtained by column chromatography.

[0110] Under a nitrogen atmosphere, compound b (94.8 g, purchased from TCI), Karstedt catalyst (0.5 g, purchased from TCI), octamethylcyclosiloxane (D4, 490 g, purchased from TCI), and compound g (76 g) were added to a dry three-necked flask. The mixture was stirred at room temperature for 20 h. After the reaction was completed, the mixture was purified by column chromatography to obtain compound I-3 (115 g).

[0111] (2) Preparation of ink compositions with high adhesion

[0112] In a glove box (N2 atmosphere), organosiloxane monomer I-3 (25g), first photocurable monomer II-1 (57g), second photocurable monomer III-8 (15g), and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0113] Example 4

[0114] (1) Preparation of organosiloxane monomer I-4

[0115] The reaction equation for the preparation of I-4 is as follows:

[0116]

[0117] The specific preparation process is as follows:

[0118] In a three-necked round-bottom flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel, compound c (44.04 g, purchased from Alfa), anhydrous ethanol (32.5 g, purchased from Anage), and deionized water (20 g) were added and stirred for 1 h to ensure homogeneity. At -5°C, compound f (157 g, purchased from Sigma Aldrich) was slowly added to the mixture (expected to be completed in 5 hours). After the addition was complete, concentrated H₂SO₄ (1 mL) was added, and stirring continued for 30 min. After standing, the organic layer was separated using a separatory funnel. The organic layer was washed five times with distilled water until the solution became neutral. The organic layer was then washed with saturated saline solution, and water was absorbed with sodium sulfate solution. Low-boiling-point substances were removed by vacuum distillation. Compound g was obtained by column chromatography.

[0119] Under a nitrogen atmosphere, compound h (94.8 g, purchased from Hubei Shishun Biotechnology), Karstedt catalyst (0.5 g, purchased from TCI), octamethylcyclotetrasiloxane (D4, 490 g, purchased from TCI), and compound g (76 g) were added to a dry three-necked flask. The mixture was stirred at room temperature for 18 h. After the reaction was completed, the mixture was purified by column chromatography to obtain compound I-4 (108 g).

[0120] (2) Preparation of ink compositions with high adhesion

[0121] In a glove box (N2 atmosphere), organosiloxane monomer I-4 (25g), first photocurable monomer II-1 (57g), second photocurable monomer III-8 (15g), and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0122] Example 5

[0123] (1) Preparation of organosiloxane monomer I-5

[0124] The reaction equation for the preparation of I-5 is as follows:

[0125]

[0126] The specific preparation process is as follows:

[0127] In a three-necked round-bottom flask equipped with a magnetic stirrer, thermometer, condenser, and dropping funnel, compound c (44.04 g, purchased from Alfa), anhydrous ethanol (40 g, purchased from Anage), and deionized water (25 g) were added and stirred for 1 h until homogeneous. At -20°C, compound d (235 g, purchased from Alfa) was slowly added to the mixture. After the addition was complete, concentrated H₂SO₄ (1 mL) was added, and stirring continued for 30 min. After standing, the organic layer was separated using a separatory funnel. The organic layer was washed five times with distilled water until the solution became neutral. The organic layer was then washed with saturated saline solution, and water was absorbed with sodium sulfate solution. Low-boiling-point substances were removed by vacuum distillation to obtain compound e.

[0128] Under a nitrogen atmosphere, compound h (94.8 g, purchased from Hubei Shishun Biotechnology), Karstedt catalyst (0.5 g, purchased from TCI), octamethylcyclotetrasiloxane (D4, 490 g, purchased from TCI), and compound e (108.2 g) were added to a dry three-necked flask. The mixture was stirred at room temperature for 20 h. After the reaction was completed, the mixture was purified by column chromatography to obtain compound I-5 (189 g).

[0129] (2) Preparation of ink compositions with high adhesion

[0130] In a glove box (N2 atmosphere), organosiloxane monomer I-5 (25g), first photocurable monomer II-1 (57g), second photocurable monomer III-8 (15g) and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0131] Example 6

[0132] (1) Preparation of organosiloxane monomer I-6

[0133] The reaction equation for the preparation of I-6 is as follows:

[0134]

[0135] The specific preparation process is as follows:

[0136] Under a nitrogen atmosphere, compound h (92g, purchased from Hubei Shishun Biotechnology), Karstedt catalyst (0.5g, purchased from TCI), octamethylcyclotetrasiloxane (D4, 490g, purchased from TCI) and compound a (42.7g, purchased from TCI) were added to a dry three-necked flask. The mixture was stirred at room temperature for 13 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain compound I-6 (70.2g).

[0137] (2) Preparation of ink compositions with high adhesion

[0138] In a glove box (N2 atmosphere), organosiloxane monomer I-6 (25g), first photocurable monomer II-1 (57g), second photocurable monomer III-8 (15g), and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0139] Example 7

[0140] (1) Preparation of organosiloxane monomer I-7

[0141] The reaction equation for the preparation of I-7 is as follows:

[0142]

[0143] The specific preparation process is as follows:

[0144] BiCl3 (2.9 g, 5 mol%, purchased from TCI), methanol / n-hexane (1:1, 150 mL, both purchased from Anaiji), compound i (59 g, purchased from TCI), and compound j (250 g, purchased from Chongqing Futeng Pharmaceutical Co., Ltd.) were added to a 2 L reaction flask. The mixture was stirred at room temperature for 3 h. After the reaction was completed, the solvent and excess compound j were removed under reduced pressure, and compound k (21.3 g) was obtained by distillation.

[0145] Under a nitrogen atmosphere, compound h (23g, purchased from Hubei Shishun Biotechnology), Karstedt catalyst (0.13g, purchased from TCI), octamethylcyclotetrasiloxane (D4, 120g, purchased from TCI), and compound g (21.3g) were added to a dry three-necked flask. The mixture was stirred at room temperature for 12h. After the reaction was completed, the mixture was purified by column chromatography to obtain compound I-7 (76g).

[0146] (2) Preparation of ink compositions with high adhesion

[0147] In a glove box (N2 atmosphere), organosiloxane monomer I-7 (25g), first photocurable monomer II-1 (57g), second photocurable monomer III-8 (15g), and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0148] Example 8

[0149] (1) Preparation of organosiloxane monomer I-8

[0150] The reaction equation for the preparation of I-8 is as follows:

[0151]

[0152] The specific preparation process is as follows:

[0153] BiCl3 (2.9 g, purchased from TCI), methanol / n-hexane (1:1, 150 mL, both purchased from Anaiji), compound i (59 g, purchased from TCI), and compound j (250 g, purchased from Chongqing Futeng Pharmaceutical Co., Ltd.) were added to a 2 L reaction flask. The mixture was stirred at room temperature for 3 h. After the reaction was completed, the solvent and excess compound j were removed under reduced pressure, and compound k (21.3 g) was obtained by distillation.

[0154] Under a nitrogen atmosphere, compound b (24.6 g, purchased from TCI), Karstedt catalyst (0.13 g, purchased from TCI), octamethylcyclotetrasiloxane (D4, 120 g, purchased from TCI), and compound g (21.3 g) were added to a dry three-necked flask. The mixture was stirred at room temperature for 12 h. After the reaction was completed, the mixture was purified by column chromatography to obtain compound I-8 (71 g).

[0155] (2) Preparation of ink compositions with high adhesion

[0156] In a glove box (N2 atmosphere), organosiloxane monomer I-8 (25g), first photocurable monomer II-1 (57g), second photocurable monomer III-8 (15g), and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0157] Example 9

[0158] In a glove box (N2 atmosphere), organosiloxane monomer I-7 (5g), first photocurable monomer II-1 (57g), second photocurable monomer III-4 (35g), and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0159] Example 10

[0160] In a glove box (N2 atmosphere), organosiloxane monomer I-7 (50g), first photocurable monomer II-1 (32g), second photocurable monomer III-4 (15g), and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0161] Example 11

[0162] In a glove box (N2 atmosphere), organosiloxane monomer I-7 (25g), first photocurable monomer II-1 (57g), second photocurable monomer III-4 (15g), and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0163] Example 12

[0164] In a glove box (N2 atmosphere), organosiloxane monomer I-7 (25g), first photocurable monomer II-1 (37g), second photocurable monomer III-8 (35g) and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0165] Example 13

[0166] In a glove box (N2 atmosphere), organosiloxane monomer I-7 (25g), first photocurable monomer II-2 (57g), second photocurable monomer III-8 (15g), and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0167] Example 14

[0168] In a glove box (N2 atmosphere), organosiloxane monomer I-7 (25g), first photocurable monomer II-1 (50g), second photocurable monomer III-8 (15g), and photoinitiator (acylphosphine oxide, 10g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0169] Example 15

[0170] In a glove box (N2 atmosphere), organosiloxane monomer I-7 (25g), first photocurable monomer II-1 (59.9g), second photocurable monomer III-8 (15g), and photoinitiator (acylphosphine oxide, 0.1g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0171] Comparative Example 1

[0172] The difference between this comparative example and Example 7 is that no organosiloxane monomer is added to the reaction system.

[0173] Specifically, in a glove box (N2 atmosphere), the first photocurable monomer II-1 (85g), the second photocurable monomer III-8 (15g), and the photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration using a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0174] Comparative Example 2

[0175] The difference between this comparative example and Example 7 is that no second photocurable monomer is added to the reaction system.

[0176] In a glove box (N2 atmosphere), organosiloxane monomer I-7 (25g), first photocurable monomer II-1 (72g) and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration through a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0177] Comparative Example 3

[0178] The difference between this comparative example and Example 7 is that no first photocurable monomer is added to the reaction system.

[0179] Specifically, in a glove box (N2 atmosphere), organosiloxane monomer I-7 (25g), second photocurable monomer III-8 (72g), and photoinitiator (acylphosphine oxide, 3g) were added to a 500mL volumetric flask. The mixture was vigorously mixed for 2 hours under light-protected conditions, and then soaked in activated 4A molecular sieve for 48 hours to obtain the composition. After filtration using a 0.45µm needle filter, an ink composition with high adhesion was obtained.

[0180] The formulations of the ink compositions in Examples 1-15 are shown in Table 1, and the formulations of the ink compositions in Comparative Examples 1-3 are shown in Table 2.

[0181] Take a flexible semiconductor substrate with a silicon nitride inorganic layer formed on its surface. Apply the ink compositions prepared in the above examples and comparative examples to the inorganic layer using an inkjet printing method. After UV curing (wavelength 395nm, light intensity 1500mJ / cm²), the ink compositions are cured. 2 A film was formed with a curing time of 30 seconds, and the film thickness was approximately 10 μm. The performance of each cured film obtained above was tested, and the test results are shown in Table 3.

[0182] The performance testing methods and standards are as follows:

[0183] (1) Viscosity: The dynamic viscosity at 25°C was measured using a rheometer (MCR502, Anton Paar);

[0184] (2) Curing rate: The change in peak area of ​​characteristic peaks before and after curing was detected using Fourier transform infrared spectroscopy (FT-IR);

[0185] (3) Transmittance: Ultraviolet-visible spectrophotometer (Lambda 650S, Platinum Elmer);

[0186] (4) Adhesion: Refer to the GB / T 9286-1998 test standard, use the cross-cut adhesion test to test the adhesion of the cured film, and divide the adhesion into 0 to 5B grades. The higher the grade, the stronger the adhesion.

[0187] (5) Water vapor permeability: The water vapor permeability was measured for 24 hours at 40°C and 100% relative humidity using a water permeability measuring instrument (Model3, MOCON).

[0188] Table 1. Formulations (parts) of the ink compositions in Examples 1-15

[0189]

[0190] Table 2. Formulations (parts) of the ink compositions in Comparative Examples 1-3

[0191]

[0192] Table 3 Performance test results of the examples and comparative examples

[0193]

[0194] As can be seen from the performance test results of Examples 1-15 in Table 3, the prepared ink compositions have excellent water vapor permeability resistance, good adhesion, and high curing rate, with a water vapor permeability of <5.8×10⁻⁶. -4 g / m 2 • Day, adhesion ≥4B, curing rate ≥95%. In Example 7, when organosilane monomer I-7 is used as raw material, its water vapor permeability is as low as 3.4 × 10⁻⁶. -4 g / m 2 The ink composition exhibits a high curing rate, achieving an adhesion strength of 5B and a curing rate of up to 99.3%. When applied to OLED encapsulation materials, it demonstrates high curing rate, strong adhesion, and leaves no residue after peeling, while also resisting dust adhesion at room temperature. The excellent film surface ensures that stress concentration and defects are less likely to occur on the upper and lower contact surfaces. Furthermore, the prepared ink composition possesses good light transmittance (≥95%) and low viscosity (<30cps, 25℃). Therefore, when used as an encapsulant, it can enhance the integrity of semiconductor devices, improve resistance to external thermal shocks and vibrations, improve the insulation of internal components and circuitry, prevent direct exposure of components and circuitry, and improve the waterproof and moisture-proof performance of devices.

[0195] In Comparative Example 1, without the addition of organosiloxane monomers, the water vapor permeability increased to 2.1 × 10⁻⁶. -3 g / m 2 • day, and the adhesion decreased to 0B; in Comparative Example 2, without the addition of a second photocurable monomer, i.e., a cyclic hydrocarbon-substituted acrylic monomer, the curing rate decreased, and the water vapor permeability increased to 3.6 × 10⁻⁶. -3 g / m 2 •day, while in Comparative Example 3, without the addition of the second photocurable monomer, the viscosity of the prepared ink composition increased significantly (39cps, 25℃).

[0196] In summary, this application presents an ink composition prepared by designing organosiloxane monomers with specific structures, combined with a first photocurable monomer, a second photocurable monomer, and a photoinitiator. This ink composition exhibits high curing rate and high adhesion while maintaining low moisture permeability, and is suitable for inkjet printing, enabling its widespread application in the packaging of flexible semiconductor devices.

[0197] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application and are not intended to limit it. Although this application has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of this application without departing from the spirit and scope of the technical solutions of this application.

Claims

1. An ink composition with high adhesion, characterized in that, Based on a total weight of 100 parts, the composition includes the following components in parts by weight: 5-70 parts of organosiloxane monomer, 15-80 parts of first photocurable monomer, 5-50 parts of second photocurable monomer, and 0.1-10 parts of photoinitiator, wherein the organosiloxane monomer is one of the following compounds I-1, I-2, I-3, I-4, I-5, I-6, I-7, and I-8: Ⅰ-1 Ⅰ-2 Ⅰ-3 Ⅰ-4 Ⅰ-5 Ⅰ-6 Ⅰ-7 Ⅰ-8， The structural formula of the first photocurable monomer is shown in general formula (II): （Ⅱ） Wherein, R is methyl or hydrogen; L is one of substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, and substituted or unsubstituted arylene; n is a positive integer between 2 and 20; The structural formula of the second photocurable monomer is shown in formula (Ⅲ): （Ⅲ） Where R3 is hydrogen or methyl; A is C 1-30 alkylene chains or C 1-30 The alkene oxide chain; B is a substituted or unsubstituted cycloalkyl group, and C is a substituted or unsubstituted C. 6-30 Aryl.

2. The ink composition with high adhesion as described in claim 1, characterized in that, Based on a total weight of 100 parts, the components include the following parts by weight: 15-30 parts of the organosiloxane monomer, 50-60 parts of the first photocurable monomer, 10-20 parts of the second photocurable monomer, and 1-5 parts of the photoinitiator.

3. The ink composition with high adhesion as described in claim 1, wherein B in the structural formula of the second photocurable monomer is a substituted or unsubstituted cycloalkyl group.

4. The ink composition with high adhesion as described in claim 1, characterized in that, The photoinitiator is one or more of acylphosphine oxide, α-hydroxy ketone, or α-amino ketone.

5. A method for preparing an ink composition with high adhesion as described in any one of claims 1 to 4, characterized in that, The process includes the following steps: Under a nitrogen atmosphere, the organosiloxane monomer, the first photocurable monomer, the second photocurable monomer, and the photoinitiator are mixed under light-protected conditions, and then immersed to obtain the ink composition with high adhesion.

6. The preparation method according to claim 5, characterized in that, The mixing time is 2 hours; the soaking step includes soaking in activated 4A molecular sieves for 48 hours.

7. A thin-film encapsulation method for a flexible semiconductor device, characterized in that, Includes the following steps: S1: Integrating semiconductor components on a flexible substrate; S2: An inorganic material is deposited on the surface of the semiconductor element in S1 to obtain a first inorganic layer with a thickness of 5-1000 nm; S3: Deposit a layer of ink composition with high adhesion as described in any one of claims 1 to 4 on the surface of the inorganic layer described in S2, and then cure it with ultraviolet light to obtain an organic layer; S4: Deposit another layer of inorganic material on the surface of the organic layer described in S3 to obtain a second inorganic layer with a thickness of 5-1000 nm, thereby realizing the thin-film encapsulation of the semiconductor device; In steps S2 and S4, the inorganic materials are each independently one or more of silicon nitride, titanium oxide, aluminum oxide, or silicon oxide.

8. The thin-film encapsulation method as described in claim 7, characterized in that, The semiconductor element is one of LED, silicon-based semiconductor element, AsGa semiconductor element, or gallium phosphide semiconductor element.

9. A flexible semiconductor device, characterized in that, The thin-film encapsulation method described in claim 7 or 8 is used to prepare the following: a flexible substrate, a semiconductor element disposed on one side of the flexible substrate, and a thin-film encapsulation structure. The thin-film encapsulation structure includes a first inorganic layer, an organic layer, and a second inorganic layer, wherein the first inorganic layer, the organic layer, and the second inorganic layer are sequentially stacked on a surface of the semiconductor element opposite to the flexible substrate.

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