Photo-thermal dual-curing organic silicon composition for adhesive film packaging as well as preparation method and application of photo-thermal dual-curing organic silicon composition

Abstract

The invention discloses a photo-thermal dual-curing organic silicon composition for adhesive film packaging as well as a preparation method and application of the photo-thermal dual-curing organic silicon composition. Relates to the technical field of LED packaging. The raw materials of the organic silicon composition comprise the following components: vinyl-terminated methacryloyloxypropyl phenyl polysiloxane; a hydrogen-containing phenyl polysiloxane; a photocatalyst; a hydrosilylation catalyst; the vinyl-terminated methacryloyloxypropyl phenyl polysiloxane is phenyl polysiloxane containing a silicon vinyl bond, and the vinyl-terminated methacryloyloxypropyl phenyl polysiloxane is phenyl polysiloxane containing a silicon vinyl bond; the hydrogen-containing phenyl polysiloxane is phenyl polysiloxane containing a silicon hydrogen group bond. Vinyl-terminated phenyl polysiloxane with methacryloyloxypropyl is used as dual-curing base resin, hydrogen-containing phenyl polysiloxane is used as a cross-linking agent for a hydrosilylation reaction, and meanwhile, a free radical photocatalyst and a hydrosilylation catalyst are added, so that the controllable and multi-stage curing photo-thermal curing organic silicon composition is prepared.

Description

Technical Field

[0001] The present invention relates to the technical field of LED packaging, and in particular to a photothermal dual-curing silicone composition for film packaging, and a preparation method and application thereof. Background Art

[0002] Chip-on-Board Packaging (CSP), an innovative packaging technology, has been widely applied and researched in the LED packaging field in recent years. The CSP package size is only slightly larger than the LED chip, with an area ratio typically around 1.5:1. Therefore, it offers many unique advantages, such as compact size, high assembly density, space savings, and cost savings. These characteristics have made CSP play an increasingly important role in LED lighting, backlighting displays, and other optoelectronic products.

[0003] One of the most widely used CSP packaging methods is phosphor film bonding. This process utilizes a phosphor film premixed and dispersed with phosphor. These films are typically silicone-based semi-cured phase-change materials, also known as B-Stage. B-Stage features adjustable curing properties, allowing it to remain solid at lower temperatures while maintaining fluidity at higher temperatures, facilitating precise bonding and positioning during the packaging process.

[0004] The working principle of B-Stage phosphor film is particularly important in the CSP packaging process. First, B-Stage film remains liquid when uncured, which ensures a long shelf life during transportation and storage. During packaging, the B-Stage film, after undergoing a first-stage cure, is solid at room temperature, making it easy to handle and apply. However, when the temperature reaches the critical phase transition point, the film undergoes a phase change, transitioning from a solid state to a viscous flow state. At this point, the film's fluidity increases, facilitating precise bonding with the LED chip. Finally, through a high-temperature curing process, the film completes a second-stage cure, forming a robust packaging structure. This method allows the phosphor to be evenly dispersed throughout the film, effectively improving the LED's luminous efficiency and stability.

[0005] Despite the importance of B-Stage phosphor films in CSP packaging, practical application still presents challenges. While epoxy resin-based films offer excellent adhesion and mechanical properties, making them widely used in various packaging materials, epoxy resins exhibit poor durability under UV light and can age and yellow after long-term use. Conventional silicone B-Stage films control the degree of crosslinking by controlling the curing temperature and time to ensure a gel-like film. In actual production, the high efficiency of the platinum-catalyzed hydrosilylation reaction leads to demanding film-forming processes and poor batch-to-batch stability. Specifically, the preparation of silicone B-Stage films requires stringent temperature and time conditions, requiring meticulous control and monitoring, which increases production complexity and costs. Furthermore, storage of silicone B-Stage films involves lowering the ambient temperature to inhibit the curing reaction. However, this does not guarantee a complete halt to the curing reaction; even slight variations in the material can lead to performance variations, impacting the quality of the LED package. Summary of the Invention

[0006] The purpose of the present invention is to develop a silicone composition with B-Stage properties and a method for preparing a film of the silicone composition with high curing controllability.

[0007] A first aspect of the present invention is:

[0008] Provided is an organosilicon composition.

[0009] The second aspect of the present invention is:

[0010] The invention relates to a method for preparing the organosilicon composition.

[0011] The third aspect of the present invention is:

[0012] Application of the organosilicon composition.

[0013] Specifically, the technical solution adopted according to the first aspect of the present invention is:

[0014] An organosilicon composition, wherein the raw materials of the organosilicon composition include the following components:

[0015] Vinyl terminated methacryloyloxypropylphenyl polysiloxane;

[0016] Hydrogenated phenyl polysiloxane;

[0017] photocatalysts;

[0018] Hydrosilylation catalysts;

[0019] The vinyl-terminated methacryloyloxypropylphenyl polysiloxane is a phenyl polysiloxane containing a silicon-vinyl bond;

[0020] The hydrogen-containing phenyl polysiloxane is a phenyl polysiloxane containing a silicon-hydrogen bond.

[0021] According to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0022] The present invention uses vinyl-terminated phenyl polysiloxane with methacryloyloxypropyl as a dual-curing base resin, hydrogen-containing phenyl polysiloxane as a crosslinking agent for a hydrosilylation reaction, and simultaneously adds a photocatalyst and a hydrosilylation catalyst to prepare a controllable, multi-stage curing photothermal curing silicone composition.

[0023] Specifically, the vinyl-terminated methacryloyloxypropylphenyl polysiloxane undergoes a silylation reaction with the Si-H bond in the molecular structure of the hydrogenated phenyl polysiloxane serving as a crosslinker through the silicon-vinyl bond (Si-Vi bond) in its molecular structure. Simultaneously, the methacryloyloxypropyl group in the structure can undergo free radical polymerization under a photocatalyst. The silylation reaction and free radical polymerization coexist in the organosilicon composition system, making the organosilicon composition a dual-cure system. When used, thermal curing can be performed first. The adhesive film obtained after thermal curing can be stably stored under light-free conditions, which provides operating space for practical applications and improves the quality stability of the adhesive film. The adhesive film can be further laminated and photocured for packaging when needed.

[0024] According to one embodiment of the present invention, the raw materials of the organosilicon composition include the following components in parts by mass:

[0025] Vinyl-terminated methacryloyloxypropylphenyl polysiloxane, 50-70 parts;

[0026] Hydrogenated phenyl polysiloxane, 15-35 parts;

[0027] Monovinyl methacryloyloxypropylphenyl polysiloxane, 10-30 parts.

[0028] According to one embodiment of the present invention, the raw materials of the organosilicon composition include the following components in parts by mass:

[0029] Vinyl-terminated methacryloyloxypropylphenyl polysiloxane, 60-70 parts;

[0030] Hydrogenated phenyl polysiloxane, 15-35 parts;

[0031] Monovinyl methacryloyloxypropylphenyl polysiloxane, 10-30 parts.

[0032] According to one embodiment of the present invention, the raw materials of the organosilicon composition include the following components in parts by mass:

[0033] Vinyl-terminated methacryloyloxypropylphenyl polysiloxane, 50-70 parts;

[0034] Hydrogenated phenyl polysiloxane, 15-20 parts;

[0035] Monovinyl methacryloyloxypropylphenyl polysiloxane, 10-30 parts.

[0036] According to one embodiment of the present invention, the photocatalyst includes at least one of α-hydroxy aromatic ketone compounds, acylphosphine oxides, benzophenone compounds, benzoin compounds and benzil compounds; and / or the hydrosilylation catalyst is selected from at least one of platinum-containing compounds, rhodium-containing compounds and palladium-containing compounds.

[0037] According to one embodiment of the present invention, the molecular formula of the vinyl-terminated methacryloyloxypropylphenyl polysiloxane is:

[0038] (R 1 SiO 3 / 2 ) x (R 1 2SiO) y (R 2 3SiO 1 / 2 ) m , formula 1;

[0039] In formula 1, R 1 Each independently selected from methacryloyloxypropyl, methyl or phenyl, wherein the number of methacryloyloxypropyl groups is not 0;

[0040] R 2 Each independently selected from vinyl, methyl or phenyl, wherein the number of vinyl groups is not 0;

[0041] x and y are numbers not less than 0 and x and y are not 0 at the same time;

[0042] m is a number greater than 0;

[0043] The mass fraction of the phenyl group in the vinyl-terminated methacryloyloxypropylphenyl polysiloxane is 8 wt % to 55 wt %.

[0044] According to one embodiment of the present invention, the preparation method of the vinyl-terminated methacryloyloxypropylphenyl polysiloxane comprises the following steps:

[0045] A1 mixes the following raw materials at room temperature: γ-methacryloxypropyltrimethoxysilane, diphenyldimethoxysilane, divinyltetramethylsiloxane, hexamethyldisiloxane, trifluoromethanesulfonic acid catalyst and solvent to obtain a mixture;

[0046] A2: add pure water dropwise to the mixture, controlling the addition rate so that the reaction temperature is below 40°C. After the addition is complete, heat the mixture to react, cool, allow to stand, separate the layers and remove the water layer to obtain an oil phase.

[0047] A3 adds an alkali catalyst to the oil phase, raises the temperature for reaction, cools to room temperature, washes with pure water until the pH is neutral, and removes the solvent under reduced pressure to obtain the vinyl-terminated methacryloyloxypropylphenyl polysiloxane.

[0048] According to one embodiment of the present invention, the step A1 further includes the following raw material: phenyltrimethoxysilane.

[0049] According to one embodiment of the present invention, in step A2, the temperature of the temperature-raising reaction is 68-80° C., and the reaction time is 3-4 hours.

[0050] According to one embodiment of the present invention, in step A3, the temperature of the reaction is 115-120°C.

[0051] According to one embodiment of the present invention, the weight ratio of the raw materials in step A1 is:

[0052] γ-methacryloxypropyltrimethoxysilane 109g-307g,

[0053] Phenyltrimethoxysilane 0g-198g,

[0054] Diphenyldimethoxysilane 143-150g,

[0055] Divinyltetramethylsiloxane 16-17g,

[0056] Hexamethyldisiloxane 24-25g,

[0057] Trifluoromethanesulfonic acid 0.67-0.7g,

[0058] Solvent 122-130g.

[0059] According to one embodiment of the present invention, in step A1, the solvent is selected from toluene.

[0060] According to one embodiment of the present invention, the amount of pure water in A2 is 171-180 g, and is added dropwise through a constant pressure dropping funnel with a stirring speed of 150-160 r / min.

[0061] According to one embodiment of the present invention, the base catalyst in step A3 is potassium hydroxide.

[0062] According to one embodiment of the present invention, the conditions for removing the solvent in step A3 include: vacuuming until no large amount of distillate flows out and no obvious bubbles are found, and then continuing vacuuming for 1-2 hours.

[0063] According to one embodiment of the present invention, the raw materials of the silicone composition also include the following component: monovinyl methacryloyloxypropylphenyl polysiloxane. This monovinyl methacryloyloxypropylphenyl polysiloxane acts as a thermal crosslink density modifier in the silicone composition. Its monovinyl structure reduces the crosslink density of the hydrosilylation reaction heat-curing material, rendering the heat-curing material in a gel state and thereby ensuring good adhesion between the adhesive film and the LED chip. This eliminates the need to control the degree of crosslinking through thermal curing conditions, further enabling the photothermally curable silicone composition of the present invention to exhibit a controllable, multi-stage curing property.

[0064] According to one embodiment of the present invention, the raw materials of the organosilicon composition include the following components in parts by mass:

[0065] Vinyl-terminated methacryloyloxypropylphenyl polysiloxane, 50-70 parts;

[0066] Hydrogenated phenyl polysiloxane, 15-35 parts;

[0067] Monovinyl methacryloyloxypropylphenyl polysiloxane, 10-30 parts.

[0068] According to one embodiment of the present invention, the structural formula of the monovinyl methacryloyloxypropylphenyl polysiloxane is:

[0069]

[0070] In Formula 2, each R is independently selected from a methacryloxypropyl group, a glycidyloxypropyl group, an alkoxy group or a methyl group, wherein the number of the methacryloxypropyl group is not 0.

[0071] According to one embodiment of the present invention, the preparation method of the monovinyl methacryloyloxypropylphenyl polysiloxane comprises the following steps:

[0072] B1: Mix methylvinyldimethoxysilane, diphenyldihydroxysilane, dimethyldimethoxysilane, solvent and barium hydroxide at room temperature, raise the temperature to react, cool and wash until neutral, and heat and vacuum to obtain an intermediate product;

[0073] B2: The intermediate product is placed in a reaction flask, a coupling agent, zirconium n-propoxide, and a solvent are added, the temperature is raised for reaction, and the monovinyl methacryloyloxypropylphenyl polysiloxane is obtained by heating and vacuum desolvation.

[0074] According to one embodiment of the present invention, in step B1, the temperature of the temperature-raising reaction is 70-80°C, preferably 70°C.

[0075] According to one embodiment of the present invention, the vinyl silane is selected from methylvinyldimethoxysilane or divinyltetramethyldisiloxane.

[0076] According to one embodiment of the present invention, the hydroxysilane is selected from diphenyldihydroxysilane.

[0077] According to one embodiment of the present invention, the methoxysilane is selected from one of dimethyldimethoxysilane and diphenyldimethoxysilane.

[0078] According to one embodiment of the present invention, the molecular formula of the hydrogen-containing phenyl polysiloxane is:

[0079] (R 1 SiO 3 / 2 ) x (R 1 2SiO) y (R 2 3SiO 1 / 2 ) m , formula 3;

[0080] In formula 3, R 1 Each independently selected from methacryloyloxypropyl, methyl or phenyl;

[0081] R 2 Each independently selected from hydrogen, methyl or phenyl, wherein the hydrogen is not 0;

[0082] x and y are numbers not less than 0 and x and y are not 0 at the same time;

[0083] m is a number greater than 0;

[0084] The mass fraction of the phenyl group in the hydrogen-containing phenyl polysiloxane is 8 wt%-55 wt%.

[0085] According to one embodiment of the present invention, the preparation method of the hydrogen-containing phenyl polysiloxane comprises the following steps:

[0086] C1: Tetramethyldisiloxane and phenyl-substituted silane are mixed, and a strong acid catalyst and toluene solvent are added;

[0087] C2 is added with pure water under stirring, heated to 65-70°C for reaction, cooled and washed to neutrality, the water layer is removed, a strong acid catalyst is added again, heated to 65-70°C for reaction, cooled and washed to neutrality, and heated and vacuumed for desolvation to obtain the hydrogen-containing phenyl polysiloxane.

[0088] According to one embodiment of the present invention, the phenyl-substituted silane is at least one selected from methylphenyldimethoxysilane, diphenyldimethoxysilane and phenyltrimethoxysilane.

[0089] According to one embodiment of the present invention, the strong acid catalyst is selected from trifluoromethanesulfonic acid.

[0090] According to one embodiment of the present invention, the mass fraction of the photocatalyst is 0.01%-1% of the total mass fraction of the vinyl-terminated methacryloxypropylphenyl polysiloxane, hydrogen-containing phenyl polysiloxane and monovinyl methacryloxypropylphenyl polysiloxane.

[0091] According to one embodiment of the present invention, the photocatalyst includes at least one of an α-hydroxy aromatic ketone catalyst, an acylphosphine oxide, a benzophenone catalyst, a benzoin catalyst, a benzyl catalyst and an anthraquinone catalyst. Preferably, the photopolymerization initiator (D) is an α-hydroxy aromatic ketone or an acylphosphine oxide. More preferably, the photocatalyst is 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), 1-hydroxy-cyclohexyl benzophenone (184) or 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO). More preferably, the photocatalyst is 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173). The photocatalyst is used in the organosilicon composition to promote the polymerization reaction of the methacryloyloxypropyl group in the molecular structure of the organopolysiloxane under light conditions.

[0092] According to one embodiment of the present invention, the α-hydroxy aromatic ketone catalyst includes at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) and 1-hydroxy-cyclohexyl benzophenone (184).

[0093] According to one embodiment of the present invention, the acylphosphorus oxide includes at least one of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and 2,4,6-trimethylbenzoyl ethylphosphonate (TPO-L).

[0094] According to one embodiment of the present invention, the benzophenone catalyst includes at least one of benzophenone, tetramethyl Michler's ketone, tetraethyl Michler's ketone, and methyl ethyl Michler's ketone.

[0095] According to one embodiment of the present invention, the benzoin catalyst includes at least one of benzoin dimethyl ether BDK and benzoin dimethyl ether 651.

[0096] According to one embodiment of the present invention, the anthraquinone catalyst includes at least one of 2-isopropylthioxanthone (ITX).

[0097] According to one embodiment of the present invention, the mass fraction of the hydrosilylation catalyst is 1-10 ppm of the total mass fraction of the vinyl-terminated methacryloxypropylphenyl polysiloxane, hydrogen-containing phenyl polysiloxane and monovinyl methacryloxypropylphenyl polysiloxane.

[0098] According to one embodiment of the present invention, the hydrosilylation catalyst is selected from platinum-containing compounds, rhodium-containing compounds and palladium-containing compounds.

[0099] According to one embodiment of the present invention, the hydrosilylation catalyst is selected from at least one of chloroplatinic acid, a reaction product of chloroplatinic acid and an alcohol, a platinum-olefin complex, a platinum-vinylsilane complex, a platinum-ketone complex, a platinum-phosphine complex, a rhodium-phosphine complex, a rhodium-sulfur compound complex, and a palladium-phosphine complex.

[0100] According to one embodiment of the present invention, the hydrosilylation catalyst is preferably a platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.

[0101] According to one embodiment of the present invention, the raw materials of the organosilicon composition further include the following component: a hydrosilylation inhibitor. The type of the hydrosilylation inhibitor is not particularly limited, and any type known in the art can be used.

[0102] According to one embodiment of the present invention, the hydrosilylation inhibitor comprises at least one of a phosphorus-containing compound, a nitrogen-containing compound, a maleic acid derivative, an alkynol, and a vinylsilane. Preferably, the hydrosilylation inhibitor is an alkynol. More preferably, the hydrosilylation inhibitor is at least one of 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, and 3-methylbutynol.

[0103] According to one embodiment of the present invention, the phosphorus-containing compound is preferably triphenylphosphine.

[0104] According to one embodiment of the present invention, the nitrogen-containing compound is at least one selected from tributylamine, tetramethylethylenediamine, and benzotriazole.

[0105] According to one embodiment of the present invention, the maleic acid derivative is preferably dimethyl maleate.

[0106] According to one embodiment of the present invention, the alkynol is selected from at least one of 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, and 3-methylbutynol.

[0107] According to one embodiment of the present invention, the vinylsilane is 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane.

[0108] According to one embodiment of the present invention, the mass fraction of the hydrosilylation inhibitor is 200-3000 ppm based on the total mass fraction of the vinyl-terminated methacryloyloxypropylphenyl polysiloxane, hydrogen-containing phenyl polysiloxane and monovinyl methacryloyloxypropylphenyl polysiloxane.

[0109] Specifically, the technical solution adopted according to the second aspect of the present invention is:

[0110] A method for preparing the organosilicon composition comprises the following steps:

[0111] The vinyl-terminated methacryloyloxypropylphenyl polysiloxane, hydrogen-containing phenyl polysiloxane, photocatalyst and hydrosilylation catalyst are mixed uniformly under light-proof conditions to obtain the organosilicon composition.

[0112] According to one embodiment of the present invention, the preparation method of the silicone composition comprises the following steps: uniformly mixing the vinyl-terminated methacryloyloxypropylphenyl polysiloxane, monovinyl methacryloyloxypropylphenyl polysiloxane, hydrogen-containing phenyl polysiloxane, a photocatalyst, a hydrosilylation catalyst, and an inhibitor under light-proof conditions to obtain the silicone composition.

[0113] According to one embodiment of the present invention, the method for preparing the silicone composition comprises the following steps: dividing the vinyl-terminated methacryloyloxypropylphenyl polysiloxane, monovinyl methacryloyloxypropylphenyl polysiloxane, hydrogen-containing phenyl polysiloxane, photocatalyst, hydrosilylation catalyst, and inhibitor into two components and mixing them separately in a mixing device to prepare the silicone composition in a two-component form.

[0114] Another aspect of the present invention provides a sealant for film encapsulation, comprising the silicone composition described in the embodiment of the first aspect. Because this application utilizes all of the technical solutions of the silicone composition, it possesses at least all of the beneficial effects of the technical solutions of the aforementioned embodiment.

[0115] Another aspect of the present invention provides an application method of a sealant for film encapsulation, comprising the following steps: preparing the silicone composition into a gel-state silicone composition film by thermal curing; attaching the gel-state silicone composition film to a semiconductor device during use; and completing the encapsulation by photocuring.

[0116] According to one embodiment of the present invention, the light curing is performed by irradiation curing with a UV-LED lamp.

[0117] According to one embodiment of the present invention, the wavelength of the light for photocuring is about 365 nm.

[0118] According to one embodiment of the present invention, the light radiation energy of the light curing is 500mJ / cm 2 about.

[0119] According to one embodiment of the present invention, the temperature of the thermal curing is 100-200° C. Preferably, the temperature of the thermal curing is 150° C.

[0120] According to one embodiment of the present invention, the baking time of the thermal curing is 0.5-4 hours. Preferably, the baking time of the thermal curing is 2 hours.

[0121] Other features and advantages of the present invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0122] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the following description of the embodiments with reference to the accompanying drawings, in which:

[0123] Figure 1 1 is the H-NMR spectrum of the high refractive index vinyl-terminated methacryloyloxypropylphenyl polysiloxane (A-1) in the examples.

[0124] Figure 2 This is the H-NMR spectrum of the monovinyl methacryloyloxypropylphenyl polysiloxane (B-1) in the example. DETAILED DESCRIPTION

[0125] The terms "preferably," "more preferably," and the like, used herein refer to embodiments of the present invention that may provide certain benefits under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the present invention.

[0126] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values of the range is included. In addition, when multiple ranges are provided to describe a feature or characteristic, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein are understood to include any and all subranges subsumed therein.

[0127] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts are within the scope of the present invention.

[0128] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0129] The raw materials used in the embodiment are as follows:

[0130] The vinyl-terminated methacryloyloxypropylphenyl polysiloxane of the present invention is synthesized by the following different steps to obtain vinyl-terminated methacryloyloxypropylphenyl polysiloxane products with different refractive indices, which are named A-1, A-2, and A-3 respectively;

[0131] Among them, A-1 is a high refractive index vinyl-terminated methacryloyloxypropylphenyl polysiloxane, and its H NMR spectrum is as follows: Figure 1 As shown, the molecular formula is (PhSiO 3 / 2 )1(R 1 SiO 3 / 2 ) 0.44 (Ph2SiO) 0.58 (Me3SiO 1 / 2 ) 0.3 (Me2ViSiO 1 / 2 ) 0.17 , where R 1 is methacryloyloxypropyl;

[0132] Among them, A-2 is a medium refractive index vinyl-terminated methacryloyloxypropylphenyl polysiloxane. Compared with A-1, A-2 has a lower phenyl content. The molecular formula is (R 1 SiO 3 / 2 ) 1.24 (Ph2SiO) 0.58 (Me3SiO 1 / 2 ) 0.3 (Me2ViSiO 1 / 2 )0.17 , where R 1 is methacryloyloxypropyl;

[0133] Among them, A-3 is a low refractive index vinyl-terminated methacryloyloxypropyl methyl polysiloxane, which does not contain phenyl groups and has the molecular formula (R 1 SiO 3 / 2 ) 1.24 (Me2SiO) 0.58 (Me3SiO 1 / 2 ) 0.3 (Me2ViSiO 1 / 2 ) 0.17 , where R 1 It is methacryloyloxypropyl.

[0134] The preparation method of A-1 comprises the following steps:

[0135] At room temperature, 109 g of γ-methacryloxypropyltrimethoxysilane (KH570), 198 g of phenyltrimethoxysilane, 143 g of diphenyldimethoxysilane, 16.18 g of divinyltetramethylsiloxane, 24 g of hexamethyldisiloxane, 0.67 g of trifluoromethanesulfonic acid, and 122 g of toluene were added to the reaction flask; the speed was set to 150 r / min, and 171 g of pure water was added dropwise to the reaction flask using a constant pressure dropping funnel. The rate of addition was such that the material temperature did not exceed 40 ° C. After the addition was completed, the material temperature was raised to 68 ° C and reacted for 3 h; heating and stirring were stopped, and the water layer was removed after standing. A water separation device was installed, 1.43 g of potassium hydroxide was added to the oil phase, the temperature was raised to separate the water, and the material temperature was maintained at 115°C for 2 h. The reaction was stopped and the temperature was restored to room temperature. The mixture was repeatedly washed with pure water until the pH value was 6-7. The stirring speed was set to 150 r / min, and the vacuum pump was turned on to evacuate the mixture. The temperature was raised to remove the solvent. After no large amount of distillate flowed out and no obvious bubbles were found, the vacuum was continued for 1 h. Then the heating and vacuum were stopped. The material was discharged as a colorless viscous liquid A-1 with a viscosity of 300,000 mPa.S, a double bond content of 2.6 wt%, a refractive index of 1.5471, and a phenyl content of 46.63 wt%.

[0136] The preparation method of A-2 comprises the following steps:

[0137] At room temperature, 307 g of γ-methacryloxypropyltrimethoxysilane (KH570), 143 g of diphenyldimethoxysilane, 16.18 g of divinyltetramethylsiloxane, 24 g of hexamethyldisiloxane, 0.67 g of trifluoromethanesulfonic acid, and 122 g of toluene were added to the reaction flask; the speed was set to 150 r / min, and 171 g of pure water was added dropwise to the reaction flask using a constant pressure dropping funnel. The rate of addition was such that the material temperature did not exceed 40 ° C. After the addition was completed, the material temperature was raised to 68 ° C and reacted for 3 h; heating and stirring were stopped, and the water layer was removed by standing for stratification; a water separator was installed instead. The mixture was placed in a vacuum oven, 1.43 g of potassium hydroxide was added to the oil phase, the temperature was raised to separate the water, and the material temperature was maintained at 115°C for 2 h. The reaction was stopped and the mixture was returned to room temperature. The mixture was repeatedly washed with pure water until the pH value was 6-7. The stirring speed was set to 150 r / min, and the vacuum pump was turned on to evacuate the mixture. The temperature was raised to remove the solvent. After no large amount of distillate flowed out and no obvious bubbles were found, the vacuum was continued for 1 h. Then the heating and vacuum were stopped. The material was discharged as a colorless viscous liquid A-2 with a viscosity of 180,000 mPa.S, a double bond content of 2.55 wt%, a refractive index of 1.4671, and a phenyl content of 27 wt%.

[0138] The preparation method of A-3 comprises the following steps:

[0139] At room temperature, 307 g of γ-methacryloxypropyltrimethoxysilane (KH570), 70 g of dimethyldimethoxysilane, 16.18 g of divinyltetramethylsiloxane, 24 g of hexamethyldisiloxane, 0.67 g of trifluoromethanesulfonic acid, and 122 g of toluene were added to the reaction flask; the speed was set to 150 r / min, and 171 g of pure water was added dropwise to the reaction flask using a constant pressure dropping funnel. The rate of addition was such that the material temperature did not exceed 40 ° C. After the addition was completed, the material temperature was raised to 68 ° C and reacted for 3 h; heating and stirring were stopped, and the water layer was removed by standing for stratification; a water separator was installed. The mixture was placed in a vacuum oven, 1.43 g of potassium hydroxide was added to the oil phase, the temperature was raised to separate the water, and the material temperature was maintained at 115°C for 2 h. The reaction was stopped and the mixture was returned to room temperature. The mixture was repeatedly washed with pure water until the pH value was 6-7. The stirring speed was set to 150 r / min, and the vacuum pump was turned on to evacuate the mixture. The temperature was raised to remove the solvent. After no large amount of distillate flowed out and no obvious bubbles were found, the vacuum was continued for 1 h. Then the heating and vacuum were stopped. The material was discharged as a colorless viscous liquid A-3 with a viscosity of 140,000 mPa.S, a double bond content of 2.9 wt%, a refractive index of 1.4230, and a phenyl content of 0 wt%.

[0140] The monovinyl hydroxy-terminated phenyl polysiloxane of the present invention (denoted as B-0) has the molecular formula:

[0141]

[0142] Monovinyl methacryloyloxypropylphenyl polysiloxane (denoted as B-1), H NMR spectrum as Figure 2 As shown, the molecular formula is:

[0143]

[0144] The preparation method comprises the following steps:

[0145] In a three-necked flask, 81.77 g of methylvinyldimethoxysilane, 400 g of diphenyldihydroxysilane, and 73.56 g of dimethyldimethoxysilane were added at room temperature. After rapid stirring for 10 min, 400 g of toluene and 2.8 g of barium hydroxide were added. The temperature was raised to 70 ° C and the reaction was carried out for 1 h. After cooling and washing until neutral, the mixture was heated and vacuumed to obtain a colorless viscous intermediate product B-0. 34.83 g of the intermediate product was added to a reaction flask, and 5.41 g of KH570, 5.46 g of KH560, 0.03 g of zirconium n-propoxide, and 35 g of toluene were added. The temperature was raised to 60 ° C and the reaction was carried out for 24 h. The mixture was heated and vacuumed to obtain a colorless viscous product B-1 with a viscosity of 300 cPs, a vinyl content of 2.9 wt%, and a refractive index of 1.5310.

[0146] Vinyl-terminated linear phenyl polysiloxane (denoted as B-2), the molecular formula is:

[0147] (Ph2SiO)2(Me2ViSiO 1 / 2 )2;

[0148] The preparation method comprises the following steps:

[0149] In a three-necked flask, 18.6 g of divinyltetramethyldisiloxane and 48.6 g of diphenyldimethoxysilane were added at room temperature. After rapid stirring for 10 min, 100 g of toluene and 0.065 g of trifluoromethanesulfonic acid were added, and stirring was continued for 30 min. Subsequently, 108 g of pure water was added dropwise under stirring. After the addition was completed, the temperature was raised to 65 ° C and the reaction was carried out for 5 h. After cooling and washing to neutrality, the water layer was removed, 0.065 g of trifluoromethanesulfonic acid was added, the temperature was raised to 65 ° C and the reaction was carried out for more than 5 h. The reaction was stopped, the material was returned to room temperature, and the pure water was washed to neutrality. The solution was heated and vacuumed to obtain a colorless viscous liquid B-2 with a viscosity of 80 cPs, a vinyl content of 7.5 wt%, a refractive index of 1.5380, and a phenyl content of 26.4 wt%.

[0150] The hydrogenated phenyl polysiloxane of the present invention is prepared by the following method:

[0151] MDT type hydrogenated phenyl polysiloxane (denoted as C-1), the molecular formula is:

[0152] (PhSiO 3 / 2 ) 0.14 (MePhSiO) 0.21 (Me2HSiO 1 / 2 ) 0.2

[0153] The preparation method comprises the following steps:

[0154] In a three-necked flask, 13.4 g of tetramethyldisiloxane, 38.2 g of methylphenyldimethoxysilane, and 27.7 g of phenyltrimethoxysilane were added at room temperature. After rapid stirring for 10 min, 100 g of toluene and 0.079 g of trifluoromethanesulfonic acid were added, and stirring was continued for 30 min. Subsequently, 20 g of pure water was added dropwise under stirring. After the addition was completed, the temperature was raised to 65 ° C and the reaction was carried out for 5 h. After cooling and washing to neutrality, the water layer was removed, 0.08 g of trifluoromethanesulfonic acid was added, the temperature was raised to 65 ° C and the reaction was carried out for more than 5 h. The reaction was stopped, and the material was returned to room temperature and washed with pure water until neutral. After heating and vacuum desolventizing, a colorless viscous liquid C-1 with a viscosity of 80 cPs, a hydrogen content of 0.29 wt%, a refractive index of 1.5105, and a phenyl content of 18 wt%.

[0155] Linear hydrogen-containing phenyl polysiloxane (denoted as C-2), the molecular formula is:

[0156] (Ph2SiO)2(Me2HSiO 1 / 2 )2

[0157] The preparation method comprises the following steps:

[0158] In a three-necked flask, 13.4 g of tetramethyldisiloxane and 48.6 g of diphenyldimethoxysilane were added at room temperature. After rapid stirring for 10 min, 100 g of toluene and 0.065 g of trifluoromethanesulfonic acid were added, and stirring was continued for 30 min. Subsequently, 108 g of pure water was added dropwise under stirring. After the addition was completed, the temperature was raised to 65 ° C and the reaction was carried out for 5 h. After cooling and washing to neutrality, the water layer was removed, 0.065 g of trifluoromethanesulfonic acid was added, the temperature was raised to 65 ° C and the reaction was carried out for more than 5 h. The reaction was stopped, and the material was returned to room temperature and washed with pure water until neutral. After heating and vacuum desolventizing, a colorless viscous liquid C-2 with a viscosity of 30 cPs, a hydrogen content of 0.32 wt%, a refractive index of 1.5360, and a phenyl content of 30 wt%.

[0159] The photocatalyst is 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), which is commercially available.

[0160] The platinum catalyst is a platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (the platinum content is 0.5 wt%), which is commercially available.

[0161] The inhibitor was acetylene cyclohexanol, which is commercially available.

[0162] The following examples and comparative examples were all cured by the following method to prepare the silicone composition into a sealant, and the components were weighed according to the weight ratios in Table 1;

[0163] Curing method: The composition prepared in each example or comparative example was placed at 150°C for 2 hours to complete the first-stage thermal curing; the thermally cured composition was placed under a UV-LED lamp with a wavelength of 365nm for curing, and the light radiation energy was 500mJ / cm 2 , complete the second-order light curing.

[0164] Table 1

[0165]

[0166] In Table 1, A-1 is a high refractive index vinyl-terminated methacryloyloxypropylphenyl polysiloxane;

[0167] A-2 is a medium refractive index vinyl-terminated methacryloyloxypropylphenyl polysiloxane;

[0168] A-3 is a methyl type (phenyl-free) vinyl-terminated methacryloyloxypropyl polysiloxane;

[0169] B-0 is a monovinyl hydroxyl-terminated phenyl polysiloxane

[0170] B-1 is a monovinyl methacryloyloxypropylphenyl polysiloxane;

[0171] B-2 is a vinyl terminated linear phenyl polysiloxane;

[0172] C-1 is an MDT type hydrogenated phenyl polysiloxane;

[0173] C-2 is a linear hydrogen-containing phenyl polysiloxane;

[0174] D is the photocatalyst 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173);

[0175] E is a platinum catalyst, platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content is 0.5 wt %);

[0176] F is the inhibitor, acetylene cyclohexanol;

[0177] H / Vi is the ratio of hydrogen groups to vinyl groups in the raw material components.

[0178] Performance testing:

[0179] The compositions of Examples 1-4 and Comparative Examples 1-6 were cured and subjected to the following tests. The test results are shown in Table 2.

[0180] Test method:

[0181] Cone penetration: Cone penetration is tested using a SYD-2801C needle penetration tester at 25°C, 1 / 4 cone, 0.1mm.

[0182] Hardness (Shore D): Refer to GB / T 2411-2008;

[0183] Appearance: judged by visual observation;

[0184] Surface adhesion: Comprehensively judged by adhesion to the release film after thermal curing and finger touch;

[0185] Shear Strength (MPa): Referring to the standard GB / T 13936-2014, the composition is first thermally cured on a release film to form a composite film. The film is then used to bond two glass sheets to form a shear specimen. A second light-curing step is then performed, and the shear strength is measured using a universal testing machine. The shear strength determines the adhesive properties of the silicone composition.

[0186] Table 2

[0187]

[0188] 1#: The cured part is a silicone elastomer and does not appear in a silicone gel state. Therefore, it cannot be tested using a cone penetrometer.

[0189] 2#: The more * there are, the stickier it is.

[0190] As shown in Table 2, compared with Examples 1-4, Comparative Example 1 has a lower refractive index due to the lack of phenyl groups in the base resin, which leads to optical incompatibility with other components and cannot present a transparent appearance.

[0191] Compared with Example 1, Comparative Example 2 does not use monovinyl-terminated phenyl polysiloxane to adjust the crosslinking density of thermal curing. Therefore, the crosslinking is too high after the first-stage thermal curing, resulting in the prepared film being non-sticky and unable to have good adhesion to the substrate. Therefore, the shear force value is low after the second-stage photocuring.

[0192] In silicones, vinyl-dicapped linear phenyl polysiloxanes are commonly used to improve material toughness. Adding linear structures to a composition reduces the structural density of the material system, but this does not reduce the crosslink density of the active groups. The experiments in Comparative Example 3 show that this method fails to achieve the same thermally curable silicone gel effect in this composition. Combined with the results of Example 1 and Comparative Example 6, it is clear that the monovinyl-terminated phenyl polysiloxanes proposed in this invention offer significant advantages in reducing crosslink strength.

[0193] Comparative Example 4 has a lower H / Vi ratio than Example 1. Although it can effectively reduce the crosslinking density, the amount of hydrogen-containing crosslinking agent used is too small, so the composition remains liquid after thermal curing, resulting in failure to form a film.

[0194] Compared with Example 1, Comparative Example 5 has a higher H / Vi, and the amount of hydrogen-containing crosslinking agent used in the composition is relatively high. After thermal curing, the composition is an elastomer with a dry surface. The excessively high degree of crosslinking limits the migration of chain segments, resulting in the inability to bond to the substrate during secondary photocuring.

[0195] Compared with Example 1, in Comparative Example 6, the phenyl polysiloxane with a monovinyl structure has no photocurable group and thus cannot participate in the second-stage photocuring, resulting in the hardness of the composition being too low after being fully cured.

[0196] The above are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the contents of the present invention specification, or directly or indirectly applied in related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. An organosilicon composition, characterized in that: The raw materials of the organosilicon composition include the following components: Vinyl terminated methacryloyloxypropylphenyl polysiloxane; Hydrogenated phenyl polysiloxane; photocatalysts; Hydrosilylation catalysts; The vinyl-terminated methacryloyloxypropylphenyl polysiloxane is a phenyl polysiloxane containing a silicon-vinyl bond; The hydrogen-containing phenyl polysiloxane is a phenyl polysiloxane containing a silicon-hydrogen bond.

2. The organosilicon composition according to claim 1, characterized in that: The photocatalyst includes at least one of α-hydroxy aromatic ketone compounds, acylphosphine oxides, benzophenone compounds, benzoin compounds and benzil compounds; and / or the hydrosilylation catalyst is selected from at least one of platinum-containing compounds, rhodium-containing compounds and palladium-containing compounds.

3. The organosilicon composition according to claim 1, wherein: The raw materials of the organic silicon composition further include the following component: monovinyl methacryloyloxypropylphenyl polysiloxane.

4. The organosilicon composition according to claim 3, wherein: The raw materials of the organosilicon composition include the following components in parts by mass: Vinyl-terminated methacryloyloxypropylphenyl polysiloxane, 50-70 parts; Hydrogenated phenyl polysiloxane, 15-35 parts; Monovinyl methacryloyloxypropylphenyl polysiloxane, 10-30 parts.

5. The organosilicon composition according to claim 1, wherein: The molecular formula of the vinyl-terminated methacryloyloxypropylphenyl polysiloxane is: (R 1 SiO 3 / 2 ) x (R 1 2SiO) y (R 2 3SiO 1 / 2 ) m , formula 1; In formula 1, R 1 Each independently selected from methacryloyloxypropyl, methyl or phenyl, wherein the number of methacryloyloxypropyl groups is not 0; R 2 Each independently selected from vinyl, methyl or phenyl, wherein the number of vinyl groups is not 0; x and y are numbers not less than 0 and x and y are not 0 at the same time; m is a number greater than 0; The mass fraction of the phenyl group in the vinyl-terminated methacryloyloxypropylphenyl polysiloxane is 8 wt % to 55 wt %.

6. An organosilicon composition according to any one of claims 1 to 5, characterized in that: The preparation method of the vinyl-terminated methacryloyloxypropylphenyl polysiloxane comprises the following steps: A1 mixes the following raw materials at room temperature: γ-methacryloxypropyltrimethoxysilane, diphenyldimethoxysilane, divinyltetramethylsiloxane, hexamethyldisiloxane, trifluoromethanesulfonic acid catalyst and solvent to obtain a mixture; A2: add pure water dropwise to the mixture, controlling the addition rate to keep the reaction temperature below 40°C, raise the temperature to react after the addition is complete, cool and allow to stand for stratification, and remove the water layer to obtain an oil phase; A3 adds an alkali catalyst to the oil phase, raises the temperature for reaction, cools to room temperature, washes with pure water until the pH is neutral, and removes the solvent under reduced pressure to obtain the vinyl-terminated methacryloyloxypropylphenyl polysiloxane.

7. The organosilicon composition according to claim 3, characterized in that: The structural formula of the monovinyl methacryloyloxypropylphenyl polysiloxane is: In Formula 2, each R is independently selected from a methacryloxypropyl group, a glycidyloxypropyl group, an alkoxy group or a methyl group, wherein the number of the methacryloxypropyl group is not 0.

8. The organosilicon composition according to claim 1, characterized in that: The molecular formula of the hydrogen-containing phenyl polysiloxane is: (R 1 SiO 3 / 2 ) x (R 1 2SiO) y (R 2 3SiO 1 / 2 ) m , formula 3; In formula 3, R 1 Each independently selected from methacryloyloxypropyl, methyl or phenyl; R 2 Each independently selected from hydrogen, methyl or phenyl, wherein the hydrogen is not 0; x and y are numbers not less than 0 and x and y are not 0 at the same time; m is a number greater than 0; The mass fraction of phenyl groups in the hydrogenated phenyl polysiloxane is 8 wt% to 55 wt%.

9. A sealant for film packaging, characterized in that: The method comprises the organosilicon composition according to any one of claims 1 to 5 and 7 to 8.

10. A method for applying a sealant for film packaging, characterized in that: The following steps are involved: The organic silicon composition is prepared into a gel-state organic silicon composition film by heat curing. When in use, the gel-state organic silicon composition film is attached to the semiconductor device and then photocured to complete the encapsulation.

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