Semiconductor coating composition, and optical semiconductor apparatus

Abstract

Disclosed in the present invention is a semiconductor coating composition. The composition contains: (A) a copolymer obtained by polymerizing monomers M, the monomers M comprising the following monomers: a monomer M1, the monomer M1 being at least one of acrylate and methacrylate containing more than two vinylsilyl groups per molecule; a monomer M2, the monomer M2 being an organopolysilazane compound containing more than two hydrosilyl groups and more than two nitrogen-hydrogen groups per molecule; and a monomer M3, the monomer M3 being at least one of acrylate and methacrylate not containing a vinylsilyl group; (B) a solvent; and (C) a functional auxiliary agent. Further provided in the present invention is an optical semiconductor apparatus. The coating composition can improve the adhesion performance between a substrate on which a semiconductor element is mounted and a cured product of an addition reaction-curable organosilicon composition used for sealing the optical semiconductor element, and also can prevent metal electrodes formed on the substrate from being corroded.

Description

Semiconductor coating composition and optical semiconductor device Technical Field

[0001] The present invention relates to a semiconductor coating composition and an optical semiconductor device using the same. Background Art

[0002] Light-emitting diodes (LEDs) in optical semiconductor devices are sealed on substrates using a transparent resin sealant. Common sealants are often epoxy-based compositions. With the recent miniaturization of semiconductor packages and the increasing brightness of LEDs, ceramics, such as alumina, are becoming increasingly popular as substrate materials, offering superior heat resistance compared to polyphthalamide resins. However, there is a problem with the substrate made of alumina ceramic and the sealant, which is made of a cured silicone composition. Furthermore, because silicone compositions generally have good gas permeability, the sealed LED is susceptible to environmental influences. When the LED light source is exposed to atmospheric sulfides, exhaust gases, and other substances, these substances can permeate the cured silicone composition, corroding and blackening the metal electrodes, particularly the Ag electrodes, on the sealed substrate.

[0003] Therefore, it is necessary to develop a semiconductor coating composition that can improve the adhesion between a substrate on which a semiconductor element is mounted and a cured product of an addition reaction-curable silicone composition used to seal the optical semiconductor element, while preventing corrosion of the metal electrodes formed on the substrate, and be applied to the Mini-LED and Micro-LED fields.

[0004] Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the defects in the prior art of low adhesion between the substrate of a semiconductor element and the cured product of an addition reaction-curable silicone composition used to seal the optical semiconductor element, and the susceptibility to corrosion of the metal electrodes formed on the substrate, and to provide a semiconductor coating composition and an optical semiconductor device.

[0006] In order to achieve the above object, the present invention provides a semiconductor coating composition, wherein the composition comprises:

[0007] (A) A copolymer obtained by polymerizing monomers M, wherein the monomers M comprise the following monomers:

[0008] - Monomer M1, wherein monomer M1 is at least one of an acrylate and a methacrylate containing two or more silyl vinyl groups in one molecule;

[0009] -Monomer M2, wherein the M2 monomer is an organic polysilazane compound containing two or more silicon-hydrogen groups and two or more nitrogen-hydrogen groups in one molecule;

[0010] -Monomer M3, monomer M3 is at least one of acrylate and methacrylate that does not contain a silicone vinyl group;

[0011] (B) solvent;

[0012] (C) Functional additives.

[0013] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0014] <Semiconductor coating composition>

[0015] The semi-conductive coating composition of the present invention contains the component (A), the component (B), and the component (C) described later as essential components.

[0016] Hereinafter, each component of the semi-conductive coating composition of the present invention will be described.

[0017] (A) Component

[0018] The component (A) contained in the semiconductive coating composition of the present invention is a copolymer obtained by polymerizing a monomer M, wherein the monomer M comprises the following monomers:

[0019] - Monomer M1, wherein monomer M1 is at least one of an acrylate and a methacrylate containing two or more silyl vinyl groups in one molecule;

[0020] -Monomer M2, wherein the M2 monomer is an organic polysilazane compound containing two or more silicon-hydrogen groups and two or more nitrogen-hydrogen groups in one molecule;

[0021] -Monomer M3, monomer M3 is at least one of acrylate and methacrylate that does not contain a silicone vinyl group.

[0022] Examples of the monomer M1 containing at least one of acrylate and methacrylate groups having two or more silyl vinyl groups in one molecule include compounds having the following structure:

[0023] Chemical formula (I):

[0024] In formula (I), R is H or CH3, and n is 0 or 1.

[0025] As the specific structure of the above-mentioned M1, compounds having the following structure can be listed as examples:

[0026] The present invention has no particular limitation on the source of the above-mentioned M1, which can be commercially available or prepared according to methods well known to those skilled in the art. The present invention is preferably prepared according to the following method:

[0027] The silane is prepared by reacting methacryloxypropyltrimethoxysilane or acryloxypropyltrimethoxysilane with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

[0028] Preferably, after methacryloxypropyltrimethoxysilane or acryloxypropyltrimethoxysilane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane are mixed, concentrated sulfuric acid is added under cooling conditions, and then water is added to carry out hydrolysis and equilibrium reaction.

[0029] The organopolysilazane compound M2 containing at least two silicon-hydrogen groups and nitrogen-hydrogen groups in one molecule of the present invention may include compounds having the following structure:

[0030] Chemical formula (II):

[0031] In formula (II), R1, R2, R3, R4, R5 and R6 are each independently selected from CH3, H or CH=CH2, and the total number of H and CH=CH2 in R1-R3 is 1; and the total number of H and CH=CH2 in R4-R6 is 1; and x is an integer from 2 to 30.

[0032] The source of M2 in the present invention is not particularly limited and can be commercially available or prepared according to methods well known to those skilled in the art.

[0033] The source of the acrylate and methacrylate monomers M3 not containing silyl vinyl groups in the present invention is not particularly limited and can be commercially available or prepared according to methods well known to those skilled in the art.

[0034] The acrylate may be one or more of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, isoamyl acrylate, n-hexyl acrylate, n-octyl acrylate, isononyl acrylate, n-decyl acrylate, and isodecyl acrylate;

[0035] The methacrylate is one or more of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, isooctyl methacrylate, n-octyl methacrylate, isononyl methacrylate, n-decyl methacrylate and isodecyl methacrylate.

[0036] Among them, alkyl acrylates and alkyl methacrylates having an alkyl group with 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms, are preferred, and methyl methacrylate is even more preferred.

[0037] The (co)polymerization ratio (by mass ratio) of the acrylate or methacrylate M1 containing two or more silyl vinyl groups per molecule, the organopolysilazane compound M2 containing two or more silyl hydride groups and two or more nitrogen hydride groups per molecule, and the (meth)acrylate M3 containing no silyl vinyl groups in component (A) is preferably More preferably

[0038] The component (A) can be prepared by a well-known method. For example, a copolymer of an acrylic ester monomer containing at least two or more silyl vinyl groups in one molecule, an organic polysilazane compound containing at least two silyl hydrogen groups and two nitrogen hydrogen groups in one molecule, and a methacrylate can be obtained by treating the corresponding target monomers with a free radical polymerization initiator such as 2,2'-azobisisobutyronitrile.

[0039] The molecular weight of the component (A) is preferably More preferably The molecular weight distribution of the component (A) is preferably Mw / Mn of 2.5 or less, more preferably 2 or less.

[0040] The content of component (A) in the composition is preferably % of the total amount of the composition (the total amount of components (A) to (C)). parts by mass, preferably parts by mass, more preferably Mass parts.

[0041] (B) Component

[0042] The solvent for component (B) is not particularly limited as long as it can dissolve component (A) and any of the components described below as needed to obtain a uniform solution of the present composition. Known organic solvents can be used. Examples include aromatic hydrocarbon solvents such as xylene, toluene, and benzene; aliphatic hydrocarbon solvents such as heptane and hexane; halogenated hydrocarbon solvents such as trichloroethylene, tetrachloroethylene, and dichloromethane; ester solvents such as ethyl acetate; ketone solvents such as methyl isobutyl ketone and methyl ethyl ketone; alcohol solvents such as ethanol, isopropyl alcohol, and butanol; ether solvents such as n-butyl ether, petroleum ether, and diethyl ether; cyclohexanone, rubber solvents, and silicone solvents. Of these, at least one of ether solvents, ester solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and ketone solvents is preferred; more preferably, at least one of ethyl acetate, diethyl ether, n-butyl ether, xylene, heptane, methyl isobutyl ketone, and isopropyl alcohol is preferred. A combination of two or more solvents can be selected for use as a mixed solvent, depending on the desired evaporation rate during the coating application process. The amount of component (B) added can be arbitrarily selected within the range that does not affect the coating operability and drying operability. Preferably, the amount of component (B) added is 80% by mass or more of the entire coating composition. parts by mass, more preferably 95-99 parts by mass.

[0043] (C) Component

[0044] (C) is a functional auxiliary agent, i.e., a silane coupling agent. The silane coupling agent used in the present invention is selected from one or more of trimethylethoxysilane, methyltrimethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, or mercaptopropyltrimethoxysilane, with trimethylethoxysilane and / or methyltrimethoxysilane being preferred.

[0045] The amount of the silane coupling agent is preferably 0.05-0.5 parts by mass, more preferably 0.05-0.3 parts by mass, based on the total amount of the composition (the total amount of components (A) to (C)).

[0046] The silane coupling agent can further improve the adhesion of the coating composition.

[0047] In a specific embodiment, the coating composition comprises, in parts by mass:

[0048] (A) 0.5-50 parts of copolymer; preferably 0.5-30 parts, more preferably 10-14 parts

[0049] (B) 85-100 parts of solvent; preferably 95-99 parts

[0050] (C) Functional additives 0.05-0.5 parts, preferably 0.05-0.3 parts.

[0051] The semiconductor coating composition of the present invention may be prepared by uniformly mixing the components (A), (B), and (C) and any optional components added as needed using a mixer at room temperature. The resulting composition comprises, in parts by mass:

[0052] (A) 0.5-50 parts of copolymer; preferably 0.5-30 parts, more preferably 10-14 parts

[0053] (B) 85-100 parts of solvent; preferably 95-99 parts

[0054] (C) Functional additives 0.05-0.5 parts, preferably 0.05-0.3 parts.

[0055] A second object of the present invention is to provide an optical semiconductor device, preferably formed by bonding a substrate having an optical semiconductor element mounted thereon and a cured product of an addition reaction-curable silicone composition that seals the optical semiconductor element, using the semiconductor coating composition.

[0056] The material constituting the substrate is preferably any of polyamide, ceramic, silicone, silicone-modified polymers, and liquid crystal polymers. In the present invention, ceramic is more preferred due to its excellent heat resistance, and alumina ceramic is particularly preferred. Conventionally, substrates composed of these materials have had problems with adhesion to the cured product of the addition reaction-curable silicone composition described later, resulting in delamination. However, by using the semiconductor coating composition of the present invention for bonding, a strong bond is achieved without delamination, allowing the above-mentioned materials, which exhibit excellent mechanical strength and heat resistance, to be used as substrates for the production of optical semiconductor devices.

[0057] The cured product of an addition reaction-curable silicone composition is obtained by curing the addition reaction-curable silicone composition and is preferably transparent and rubber-like. Examples of such addition reaction-curable silicone compositions include well-known vinyl-containing organopolysiloxanes, silicone compositions containing organohydrogenpolysiloxanes as crosslinking agents, and platinum-based catalysts as addition reaction catalysts. Furthermore, such silicone compositions may contain reaction inhibitors, colorants, flame retardants, heat resistance enhancers, plasticizers, reinforcing silica, and adhesion-imparting agents as other optional components.

[0058] As a method for manufacturing an optical semiconductor device (LED lamp), the following method can be exemplified.

[0059] In advance, an optical semiconductor element such as an LED is bonded to a substrate plated with Ag and having a metal electrode such as an Ag electrode formed thereon using an adhesive. The electrode terminals of the LED are electrically connected to the metal electrode using bonding wires. The substrate with the LED mounted thereon is then cleaned as needed, and a semiconductor coating composition is applied to the substrate using a coating device such as a spinner or a sprayer. The solvent in the coating composition is then evaporated by heating or air drying to form a coating film preferably having a thickness of 10 μm or less, more preferably 0.1 to 5 μm. After the primer coating film is formed, an addition reaction-curable silicone composition is applied using a dispenser, etc., and cured by leaving it at room temperature or heating it. The LED is then sealed with the rubber-like cured product.

[0060] Thus, by using the semiconductor coating composition of the present invention containing the aforementioned components (A), (B), and (C), a substrate equipped with an optical semiconductor element such as an LED can be firmly bonded to a cured product of the addition reaction-curable silicone composition, thereby providing a highly reliable optical semiconductor device, particularly an LED lamp. Specifically, the method employed in the present invention for protecting an optical semiconductor element substrate and a metal electrode such as silver using the coating composition may include the following steps:

[0061] Step 1: Apply the coating composition of the present invention to the surface of the substrate or device to be protected by brushing, dipping, dispensing, etc., and let it stand at room temperature for 30 minutes;

[0062] Step 2: Place the protected substrate or device coated with the coating composition of the present invention in a forced air drying oven at 150° C. for 30 minutes to completely cure.

[0063] Furthermore, even when LED lamps are exposed to a harsh external environment and sulfides in the atmosphere penetrate into the cured silicone composition, the use of this semiconductor coating composition can suppress corrosion of metal electrodes, especially Ag electrodes, on the substrate.

[0064] Moreover, the optical semiconductor device of the present invention can be suitably used as an LED, including Mini-LED and Micro-LED. In the above-mentioned embodiment, a semiconductor device for LED is used as an example of an optical semiconductor element, but in addition to this, it can also be applied to, for example, photosensitive transistors, photodiodes, charge-coupled devices (CCDs), solar cell modules, erasable programmable read-only memories (EPROMs), and photocouplers.

[0065] The semiconductor coating composition of the present invention is used to protect optical semiconductor element substrates and metal electrodes such as silver, and can also improve the adhesion between the substrate and the cured product of the addition reaction curable silicone composition used to seal the optical semiconductor element.

[0066] The coating composition and the optical semiconductor device using the coating composition provided by the present invention have the following advantages:

[0067] 1. The present invention introduces an acrylic ester monomer containing at least two or more silyl vinyl groups in each molecule and an organic polysilazane compound containing at least two silicon hydrogen groups and two nitrogen hydrogen groups in one molecule into the polymer, giving it better high temperature resistance and toughness than epoxy resin.

[0068] 2. Adding an organic polysilazane compound containing at least two silicon-hydrogen groups and two nitrogen-hydrogen groups in one molecule to the coating composition of the present invention can significantly improve the adhesion of the coating composition.

[0069] 3. The coating composition of the present invention can firmly bond a substrate on which an optical semiconductor element is mounted to a cured product of an addition reaction-curable silicone composition used to seal the optical semiconductor element, while also preventing corrosion of metal electrodes, particularly Ag electrodes, formed on the substrate. Consequently, the optical semiconductor device of the present invention has high reliability.

[0070] Therefore, the coating composition of the present invention has more excellent performance and is suitable for large-scale production applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] FIG1 shows an addition-type liquid silicone rubber encapsulated lamp bead prepared in Example 1 for the adhesion test, which has a yellow appearance.

[0072] FIG2 shows the addition-type liquid silicone rubber encapsulated lamp bead prepared in Comparative Example 1 for the adhesion test, which has a yellow appearance.

[0073] FIG3 is a photograph of Example 1 after high temperature resistance testing. The coating has almost no discoloration, indicating that Example 1 has good high temperature resistance.

[0074] FIG4 is a photograph of Comparative Example 1 after high temperature resistance testing. The coating turns yellow, indicating that Comparative Example 1 has poor high temperature resistance. DETAILED DESCRIPTION

[0075] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended to illustrate the present invention only and are not intended to limit the scope of the invention. The experimental methods in the following examples, for which specific conditions are not specified, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.

[0076] Example

[0077] (1) Preparation method of component A:

[0078] Synthesis Example 1: Acrylate Monomer M1 Containing Two or More Silicon Vinyl Groups

[0079] In a 500ml four-necked flask equipped with a straight condenser and a thermometer, 100.15g of methacryloxymethyltrimethoxysilane and 158.44g of 1,3-divinyltetramethyldisiloxane were added and the temperature was adjusted to below 10°C by ice bath. After cooling, 14.7g of concentrated sulfuric acid was added and mixed for 30 minutes. After mixing, 14.4g of water was added dropwise for hydrolysis and equilibrium reaction. After reacting for 5 hours, 5.0g of water was added, the liquid was separated and the acid was removed, 200g of 10% Glauber's salt water and 200g of toluene were added, and the mixture was further purified by water washing. The solvent was removed by concentration at 100°C / 5mmHg to obtain methacryloxymethyltris(dimethylvinylsiloxy)silane of the following structure.

[0080] Synthesis Example 2: Synthesis of a methacrylate polymer solution containing a silyl vinyl group and an organic polysilazane compound

[0081] In a four-necked flask equipped with a straight condenser and a thermometer, 60 parts by mass of methyl methacrylate, 20 parts by mass of the acrylate monomer M1 of Synthesis Example 1, 10 parts by mass of the organopolysilazane compound M2IOTA 9108 of chemical formula (II), 400 parts by mass of a mixed solvent of isopropanol and ethyl acetate, and 0.3 parts by mass of 2,2'-azobisisobutyronitrile were added, and the mixture was stirred at 80°C-85°C for 5-6 hours, and the temperature was lowered to below 50°C to prepare a solution of a methacrylate polymer containing a silyl vinyl group and an organopolysilazane compound. The weight average molecular weight of the obtained polymer was 10,000-20,000, and the molecular weight distribution was 1.5 <Mw / Mn<2。

[0082] Comparative Synthesis Example 1:

[0083] In a four-necked flask equipped with a vertical condenser and a thermometer, 70 parts by mass of methyl methacrylate, 20 parts by mass of the organopolysilazane compound IOTA 9108 of chemical formula (II), 400 parts by mass of a mixed solvent of isopropyl alcohol and ethyl acetate, and 0.3 parts by mass of 2,2'-azobisisobutyronitrile were added. The mixture was stirred at 80°C-85°C for 5-6 hours, and the temperature was lowered to below 50°C to prepare a solution of a methacrylate polymer containing the organopolysilazane compound.

[0084] Comparative Synthesis Example 2:

[0085] In a four-necked flask equipped with a vertical condenser and a thermometer, 70 parts by mass of methyl methacrylate, 20 parts by mass of the acrylate monomer of Synthesis Example 1, 400 parts by mass of a mixed solvent of isopropanol and ethyl acetate, and 0.3 parts by mass of 2,2'-azobisisobutyronitrile were added. The mixture was stirred at 80°C-85°C for 5-6 hours, and the temperature was lowered to below 50°C to prepare a solution of a methacrylate polymer containing a silyl vinyl group.

[0086] Comparative Synthesis Example 3:

[0087] In a four-necked flask equipped with a vertical condenser and a thermometer, 70 parts by mass of methyl methacrylate, 20 parts by mass of butyl acrylate monomer, 400 parts by mass of a mixed solvent of isopropyl alcohol and ethyl acetate, and 0.3 parts by mass of 2,2'-azobisisobutyronitrile were added. The mixture was stirred at 80°C-85°C for 5-6 hours, and the temperature was lowered to below 50°C to prepare a solution containing a methacrylate polymer.

[0088] (2) Preparation method of semiconductor coating composition:

[0089] Step 1: An acrylate monomer M1 containing at least two or more silyl groups per molecule and an organopolysilazane compound M2 containing at least two silicon-hydrogen groups and two nitrogen-hydrogen groups per molecule undergo a free radical reaction with an acrylate and / or methacrylate monomer M3 under the action of a free radical polymerization initiator to prepare an organopolysilazane-modified acrylate polymer;

[0090] Step 2: Add solvent (B) and stir for 0.5-2h;

[0091] Step 3: Add the functional additive (C) and mix and stir for 0.5-2 hours to obtain the semiconductor coating composition.

[0092] Example 1:

[0093] To 12 parts by mass of the methacrylate polymer solution containing silyl vinyl and organic polysilazane compounds prepared in Synthesis Example 2 above, 55 parts by mass of ethyl acetate and 40 parts by mass of n-butyl ether were added, and the mixture was stirred for 0.5-2 hours. Then, 0.2 parts by mass of a functional auxiliary agent, trimethylethoxysilane, was added, and the mixture was stirred for 0.5-2 hours to obtain the semiconductor coating composition.

[0094] Example 2:

[0095] 90 parts by mass of ethyl acetate as a solvent were added to 1 part by mass of the methacrylate polymer solution containing silyl vinyl and organic polysilazane compounds prepared in Synthesis Example 2, and the mixture was stirred for 0.5-2 hours. 0.5 parts by mass of methyltrimethoxysilane as a functional auxiliary agent was then added and stirred for 0.5-2 hours to obtain the semiconductor coating composition.

[0096] Example 3:

[0097] To 30 parts by mass of the methacrylate polymer solution containing silyl vinyl and organic polysilazane compounds prepared in Synthesis Example 2 above, 70 parts by mass of ethyl acetate and 15 parts by mass of diethyl ether were added, and the mixture was stirred for 0.5-2 hours. Then, 0.05 parts by mass of a functional auxiliary agent, glycidyloxypropyltrimethoxysilane, was added, and the mixture was stirred for 0.5-2 hours to obtain the semiconductor coating composition.

[0098] Example 4:

[0099] To 15 parts by mass of the methacrylate polymer solution containing both silyl vinyl and organic polysilazane compounds prepared in Synthesis Example 2 above, 55 parts by mass of ethyl acetate and 45 parts by mass of xylene were added, and the mixture was stirred for 0.5-2 hours. 0.1 parts by mass of a functional auxiliary agent, methacryloyloxypropyltrimethoxysilane, was then added and stirred for 0.5-2 hours to obtain the semiconductor coating composition.

[0100] Example 5:

[0101] To 2 parts by mass of the methacrylate polymer solution containing silyl vinyl and organic polysilazane compounds prepared in Synthesis Example 2 above, 60 parts by mass of ethyl acetate and 39 parts by mass of heptane were added, and the mixture was stirred for 0.5-2 hours. Then, 0.3 parts by mass of a functional auxiliary agent acryloxypropyltrimethoxysilane was added, and the mixture was stirred for 0.5-2 hours to obtain the semiconductor coating composition.

[0102] Example 6:

[0103] To 50 parts by mass of the methacrylate polymer solution containing silyl vinyl and organic polysilazane compounds prepared in Synthesis Example 2 above, 90 parts by mass of methyl isobutyl ketone (MIBK) was added and stirred for 0.5-2 hours, and then 0.05 parts by mass of a functional auxiliary agent, glycidyloxypropyltrimethoxysilane, was added and stirred for 0.5-2 hours to obtain the semiconductor coating composition.

[0104] Example 7:

[0105] To 0.5 parts by mass of the methacrylate polymer solution containing silyl vinyl and organic polysilazane compounds prepared in Synthesis Example 2 above, 99 parts by mass of isopropyl alcohol was added and the mixture was stirred for 0.5-2 hours. Then, 0.3 parts by mass of a functional auxiliary agent, methacryloyloxypropyltrimethoxysilane, was added and the mixture was stirred for 0.5-2 hours to obtain the semiconductor coating composition.

[0106] Example 8:

[0107] To 8 parts by mass of the methacrylate polymer solution containing silyl vinyl and organic polysilazane compounds prepared in the above-mentioned Synthesis Example 2, 75 parts by mass of solvent xylene and 20 parts by mass of solvent ethyl acetate were added and stirred for 0.5-2 hours, and then 0.05 parts by mass of functional auxiliary agent acryloxypropyltrimethoxysilane was added and stirred for 0.5-2 hours to obtain the semiconductor coating composition.

[0108] Comparative Example 1:

[0109] To 12 parts by mass of the methacrylate polymer solution containing the organic polysilazane compound prepared in the above comparative synthesis example 1, 55 parts by mass of ethyl acetate and 40 parts by mass of n-butyl ether were added, and the mixture was stirred for 0.5-2 hours. Then, 0.2 parts by mass of trimethylethoxysilane, a functional auxiliary agent, was added, and the mixture was stirred for 0.5-2 hours to obtain the semiconductor coating composition.

[0110] Comparative Example 2:

[0111] To 12 parts by mass of the methacrylate polymer solution containing methyl acrylate containing silicon vinyl groups prepared in the comparative synthesis example 2, 55 parts by mass of ethyl acetate and 40 parts by mass of n-butyl ether were added, and the mixture was stirred for 0.5-2 hours. Then, 0.2 parts by mass of trimethylethoxysilane as a functional auxiliary agent was added, and the mixture was stirred for 0.5-2 hours to obtain the semiconductor coating composition.

[0112] Comparative Example 3:

[0113] To 12 parts by mass of the methacrylate polymer solution prepared in the comparative synthesis example 3, 55 parts by mass of ethyl acetate and 40 parts by mass of n-butyl ether were added, and the mixture was stirred for 0.5-2 hours. Then, 0.2 parts by mass of trimethylethoxysilane as a functional auxiliary agent was added, and the mixture was stirred for 0.5-2 hours to obtain the semiconductor coating composition.

[0114] Appearance, light transmittance, adhesion (permeability), and high-temperature resistance were measured using the following test methods. Various physical properties (appearance, light transmittance, adhesion (adhesion strength), and corrosion resistance) were measured using the evaluation methods shown below. The results are shown in Table 1. The physical properties shown in Table 1 are values ​​measured at room temperature.

[0115] Performance 1: Appearance: 0.5 g of the obtained silicone coating composition was injected into an LED device, allowed to dry at 25°C for 30 minutes, and then baked at 150°C for 30 minutes. Yellow fluorescent glue was added to the coating composition and heated at 80°C for 1 hour, followed by 150°C for 3 hours. This produced an addition-type liquid silicone rubber-encapsulated lamp bead for adhesion testing, and its appearance was observed.

[0116] Performance 2: Light Transmittance: 0.5 g of the obtained silicone coating composition was brush-coated onto a glass slide, allowed to dry at 25°C for 30 minutes, and then baked at 150°C for 30 minutes. Measurements were performed using a glass slide coated with light transmittance at a wavelength of 400 nm, with air as a blank (control). The transparency of the silicone coating film was confirmed.

[0117] Performance 3: Adhesion: The packaged LEDs were baked at 260°C for 30 minutes, then placed in ink to observe ink penetration. Adhesion was then evaluated according to the following criteria.

[0118] Permeability <10%, excellent adhesion;

[0119] Permeability ≥10, poor adhesion.

[0120] Performance 4: High-Temperature Resistance: 0.07 g of the obtained organosilicon coating composition was spot-coated on a silver-plated disc, allowed to dry at 25°C for 30 minutes, and then baked at 150°C for 30 minutes. The silver-plated disc containing the cured organosilicon coating composition was then placed on a heating plate and baked at 300°C for 1 hour to evaluate its high-temperature resistance.

[0121] The measured results are shown in Table 1 below:

[0122] Table 1 Performance test results

[0123] As can be seen from the results in Table 1, Examples 1-8, which use semiconductor coating compositions containing polymers of acrylates and methacrylates containing two or more silylene groups in one molecule and organic polysilazane compounds containing two or more silicon hydride groups and two or more nitrogen hydride groups in one molecule, have excellent light transmittance, permeability, and heat resistance.

[0124] On the other hand, it can be seen from the results in Table 1 that the light transmittance, permeability, high temperature resistance and heat resistance of Comparative Examples 1-3 are relatively low.

[0125] Based on the above results, it can be seen that if the semiconductor coating composition of the present invention is used, the adhesion between the substrate on which the optical semiconductor element is mounted and the cured product of the addition reaction-curing silicone composition that seals the optical semiconductor element can be improved, while at the same time preventing the corrosion of the metal electrode on the substrate and improving the heat resistance of the primer.

[0126] It should be understood that the purpose of these embodiments is only to illustrate the present invention and is not intended to limit the scope of protection of the present invention. In addition, it should also be understood that after reading the technical content of the present invention, those skilled in the art may make various changes, modifications and / or variations to the present invention, and all of these equivalent forms also fall within the scope of protection defined by the claims appended hereto.

Claims

1. A semiconductor coating composition, characterized in that The composition contains: (A) A copolymer obtained by polymerizing a monomer M, wherein the monomer M comprises the following monomers: - Monomer M1, wherein monomer M1 is at least one of acrylate and methacrylate containing two or more silyl vinyl groups in one molecule; -monomer M2, wherein the M2 monomer is an organic polysilazane compound containing two or more silicon-hydrogen groups and two or more nitrogen-hydrogen groups in one molecule; -monomer M3, monomer M3 is at least one of acrylate and methacrylate that does not contain silicone vinyl; (B) a solvent; (C) Functional additives.

2. The coating composition according to claim 1, characterized in that The content of the component (B) is 80% by mass or more of the total mass of the coating composition.

3. The coating composition according to claim 2, characterized in that The composition comprises, by weight: (A) 0.5-50 parts of copolymer; preferably 0.5-30 parts, more preferably 10-14 parts (B) 85-100 parts of solvent; preferably 95-99 parts (C) Functional additives 0.05-0.5 parts; preferably 0.05-0.3 parts.

4. The coating composition according to claim 1, characterized in that The structural formula of the monomer M1 is: In formula (I), R is H or CH3, and n is 0 or 1.

5. The coating composition according to claim 1 or 4, characterized in that The structural formula of the monomer M1 is:

6. The coating composition according to claim 1, characterized in that The monomer M2 is a compound having the structure shown below: In formula (II), R1, R2, R3, R4, R5 and R6 are each independently selected from CH3, H or CH=CH2, and the total number of H and CH=CH2 in R1-R3 is 1; and the total number of H and CH=CH2 in R4-R6 is 1; and X is an integer of 2-30.

7. The coating composition according to claim 1, characterized in that The functional auxiliary agent is selected from at least one of trimethylethoxysilane, methyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane and mercaptopropyltrimethoxysilane.

8. The coating composition according to claim 1, characterized in that the solvent is selected from at least one of aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ester solvents, ketone solvents, alcohol solvents, ether solvents or silicone solvents; preferably at least one of ether solvents, ester solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents or ketone solvents.

9. The coating composition according to claim 1, characterized in that In component A, the mass ratio of the monomer M1, the monomer M2 and the monomer M3 is: Preferably and / or, The molecular weight of component A is calculated as weight average molecular weight. 10,000, preferably and / or, The molecular weight distribution Mw / Mn of component A is 2.5 or less, preferably 2 or less.

10. An optical semiconductor device, characterized in that: A substrate on which an optical semiconductor element is mounted and a cured product of an addition reaction curable silicone composition that seals the optical semiconductor element are bonded together by the coating composition according to any one of claims 1 to 9.

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