CN112898781B - Silica gel film with water and gas blocking characteristic - Google Patents

Silica gel film with water and gas blocking characteristic Download PDF

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CN112898781B
CN112898781B CN202011409438.7A CN202011409438A CN112898781B CN 112898781 B CN112898781 B CN 112898781B CN 202011409438 A CN202011409438 A CN 202011409438A CN 112898781 B CN112898781 B CN 112898781B
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moisture
substituted
silica gel
film
sio
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CN112898781A (en
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邓仕杰
黄如慧
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BenQ Materials Corp
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/05—Polysiloxanes containing silicon bound to hydrogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

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Abstract

The invention discloses a silica gel film with water-gas resisting property, which is formed by curing a curable silicon resin composition, wherein the curable silicon resin composition comprises 10-25 parts by weight of linear polysiloxane; 40 to 55 parts by weight of a first silicone resin, wherein the first silicone resin is used to indicateHas an average unit structural formula of at least R1SiO3/2Monomer and R2 2SiO2/2Monomer, and the R1SiO3/2The mole fraction of the monomer in the average unit structural formula is between 0.60 and 0.75; 15 to 30 parts by weight of a second silicone resin; 15 to 25 parts by weight of a polysiloxane containing silicon-hydrogen bonds; 10 to 40 parts by weight of a micro-laminate and a platinum group metal-based catalyst.

Description

Silica gel film with water and gas blocking characteristic
Technical Field
The present invention relates to a bending-resistant silica gel film with moisture-resistant characteristics, which can be used for packaging optical semiconductor devices, and more particularly, to a silica gel film applicable to the packaging of light Emitting diodes (leds).
Background
Compared with the conventional illumination, the Light Emitting Diode (LED) has the advantages of small size, high Light Emitting efficiency, long lifetime, high safety, fast operation response time, rich color, no thermal radiation, no pollution from toxic substances such as silver, and the like, and thus is rapidly developing. Their applications are quite diverse, such as architectural lighting, consumer hand-held lighting, retail display lighting, residential lighting, and the like.
The general LED packaging structure comprises a support, an LED chip arranged on the support and packaging glue. Since silica gel has good characteristics of heat resistance, light resistance, and the like, silica gel is often used as an LED packaging material in the prior art. However, the silica gel film has poor moisture-blocking property due to a large Si-O-Si bond angle in the silica gel, and is prone to color change or light decay caused by moisture of phosphor powder or Quantum dots (Quantum dots) in the LED. Although it is known to increase the crosslinking density of silica gel or to add nanoparticles to increase the gas barrier properties of silica gel, the aforementioned methods have a limited effect on enhancing the gas barrier properties. In addition, since the silica gel has a large Coefficient of Thermal Expansion (CTE), a large thermal stress is generated during the sputtering process of the inorganic thin film, and it is not easy to obtain a dense and flat inorganic thin film on the silica gel surface, so that it is not recommended to sputter the inorganic thin film on the silica gel to improve the water and gas resistance of the silica gel.
The conventional gas barrier film structure is formed by using a polymer material having a good water and gas blocking property, such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), as a substrate and preparing an aluminum oxide film on the polymer substrate by using an atomic layer deposition method. However, the flexibility and plasticity of polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) are not enough to be applied to Chip Scale Package (CSP) in high-end LED products.
Therefore, there is still a need for a novel silicone film with moisture blocking properties, which can provide sufficient moisture blocking properties, has high processability, can be applied to LED packaging processes, and still maintain the optical properties required as an LED packaging material.
Disclosure of Invention
To achieve the above objective, the present invention provides a silicone film with moisture-blocking properties, which can be used to package optical semiconductor devices, and more particularly, to a silicone film applicable to the packaging of light Emitting diodes (leds).
A silica gel film with moisture blocking characteristics is formed by curing a curable silicone resin composition, wherein the curable silicone resin composition comprises: 10 to 25 parts by weight of a linear polysiloxane having an average unit structural formula of at least one silicon atom-bonded aryl group and two silicon atom-bonded alkenyl groups; 40 to 55 parts by weight of a first silicone resin having an average unit structural formula of at least R1SiO3/2Monomer and R2 2SiO2/2Monomer (II) wherein R1And R2Is substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl or substituted or unsubstituted aryl, and the mole fraction of the R1SiO3/2 monomer in the average unit structural formula is between 0.60 and 0.75, and the mole ratio of the alkenyl bonded with silicon atom relative to all the functional groups bonded with silicon atom is 0.03 to 0.15; 15 to 30 parts by weight of a second silicone resin having an average unit structural formula of at least R3SiO3/2And R43SiO1/2Wherein R is3And R4Is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or substituted or unsubstituted aryl; 15 to 25 parts by weight of at least one polysiloxane containing silicon-hydrogen bonds, the chemical structural formula of which is as follows: HR (human HR)5 2SiO(SiR6 2O)nSiR5 2H, wherein R5Is substituted byOr unsubstituted alkyl or hydrogen atom, R6Is a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group, and n is an integer of 0 or more; 10 to 40 parts by weight of a microlayer sheet; and a platinum group metal catalyst, wherein the silica gel film with water vapor blocking property has a Water Vapor Transmission Rate (WVTR) of less than 40gm-2day-1The visible light transmittance is more than 92% and the haze is less than 4%.
According to an embodiment of the present invention, an aspect ratio of the microlayer is between 10 and 200, and a length of the microlayer is between 0.1 micrometers (μm) and 25 micrometers (μm).
According to an embodiment of the present invention, the micro-layer sheet may be at least one of mica, clay, layered double hydroxide, calcium hydrogen phosphate, or a combination thereof.
According to one embodiment of the present invention, the 25-50 ℃ Coefficient of Thermal Expansion (CTE) of the silicone film with water-vapor blocking properties is between 20ppm and 60ppm, the 80-100 ℃ Coefficient of Thermal Expansion (CTE) is between 50ppm and 150ppm, and the arithmetic mean height (Sa) of the surface is between 0.01 micrometers (μm) and 0.15 micrometers (μm).
According to another embodiment of the present invention, the curable silicone composition may optionally further comprise an adhesive, an inhibitor, a thixotropic agent, an anti-settling agent, an inorganic filler, a phosphor, or a combination thereof.
According to an embodiment of the present invention, the inorganic filler in the curable silicone resin composition includes fumed silica.
According to another embodiment of the present invention, the silica gel film with moisture blocking property may further include an inorganic coating layer on a surface of the silica gel film with moisture blocking property.
According to an embodiment of the present invention, the inorganic film is formed on a surface of the silica gel film with a moisture blocking property by a sputtering method (Sputter Deposition) or an Atomic Layer Deposition (ALD).
According to another embodiment of the present invention, the thickness of the inorganic coating layer is between 10 nanometers (nm) and 300 nm.
According to another embodiment of the present invention, the inorganic coating layer comprises silicon dioxide (SiO)2) Aluminum oxide (Al)2O3) Or hafnium oxide (HfO)2)。
According to another embodiment of the present invention, the moisture penetration rate (WVTR) of the aforementioned silicone film with moisture blocking property is less than 0.5gm-2day-1。
The present invention further provides an optical semiconductor device, wherein the optical semiconductor device is packaged by the aforementioned silica gel film with moisture-blocking property.
Detailed Description
In order to make the disclosure of the present invention more detailed and complete, the following description is given for illustrative purposes with respect to embodiments and specific examples of the present invention; it is not intended to be the only form in which an embodiment of the invention may be practiced or utilized. The various embodiments disclosed below may be combined with or substituted for one another where advantageous, and additional embodiments may be added to one embodiment without further recitation or description.
The advantages, features, and technical solutions of the present invention will be described in more detail with reference to exemplary embodiments and may be implemented in different forms, so that the present invention should not be construed as limited to the embodiments set forth herein, but rather should be construed as providing examples that provide a more complete, and complete disclosure of the present invention as defined by the appended claims.
Unless otherwise defined, all terms (including technical and scientific terms) and terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and terms such as those defined in commonly used dictionaries should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an overly idealized or overly formal sense unless expressly so defined herein.
The invention provides a silica gel film with water-blocking characteristic, which is prepared by curing a curable silicone resin composition, wherein the curable silicone resin composition comprises: 10 to 25 parts by weight of a linear polysiloxane having an average unit structural formula of at least one silicon atom-bonded aryl group and two silicon atom-bonded alkenyl groups; 40 to 55 parts by weight of a first silicone resin having an average unit structural formula of at least R1SiO3/2Monomer and R2 2SiO2/2Monomer (II) wherein R1And R2Is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group or a substituted or unsubstituted aryl group, and in this average unit structural formula, the aforementioned R1SiO3/2The mole fraction of the monomer is between 0.60 and 0.75, and the mole ratio of the alkenyl bonded with the silicon atom to all the functional groups bonded with the silicon atom is 0.03 to 0.15; 15 to 30 parts by weight of a second silicone resin having an average unit structural formula of at least R3SiO3/2And R43SiO1/2Wherein R is3And R4Is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or substituted or unsubstituted aryl; 15 to 25 parts by weight of at least one polysiloxane containing silicon-hydrogen bonds, the chemical structural formula of which is as follows: HR (human HR)5 2SiO(SiR6 2O)nSiR5 2H, wherein R5Is a substituted or unsubstituted alkyl group or a hydrogen atom, R6Is a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group, and n is an integer of 0 or more; 10 to 40 parts by weight of a microlayer sheet; and a platinum group metal is the catalyst.
In the curable silicone resin composition of the silicone film with the water-blocking property, the water-blocking property of the silicone film is improved by adding the micro-layer sheets in a specific proportion, and the optical properties and necessary processability required by the LED packaging material such as high visible light transmittance and low haze can be still maintained.
In one embodiment of the present invention, the suitable micro-layer sheet can be at least one of mica, clay, layered double hydroxide, calcium hydrogen phosphate, boron nitride, or a combination thereof. An aspect ratio of the microlayers is suitably between 10 and 200, and preferably between 50 and 200. Suitable microlayers have a length of between 0.1 and 25 micrometers (μm), and preferably between 2 and 25 micrometers (μm). Suitable microlayers have a thickness of from 10 nanometers (nm) to 1000 nanometers (nm), and preferably from 10 nm to 400 nm.
In a preferred embodiment of the present invention, the microlayers in the curable silicone resin may be modified with silicone to improve the hydrophobic properties of the microlayers to prevent the microlayers from aggregating in the curable silicone resin. In a preferred embodiment of the present invention, the microlayers in the curable silicone resin may be methylsilicone-treated mica platelets.
In the curable silicone resin composition of the present invention, the addition amount of the microlayer sheet (microsheet) may be between 10 and 40 parts by weight, and when the addition amount of the microlayer sheet is too high, the haze of the silicone film with moisture blocking properties is too high, which affects the light emitting efficiency of the LED. When the addition amount is too low, the water and gas blocking property of the silica gel film with the water and gas blocking property cannot be effectively improved, and the necessary water and gas blocking property cannot be maintained because the Coefficient of Thermal Expansion (CTE) of the silica gel cannot be effectively reduced and the cracking phenomenon may occur after the inorganic coating layer is subsequently formed when the Coefficient of Thermal Expansion (CTE) is too high.
In one embodiment of the present invention, the average unit structural formula of the first silicone resin at least has R1SiO3/2Monomer and R22SiO2/2Monomer (I) wherein R1And R2Is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. The substituted or unsubstituted aryl group may be, for example, phenyl, tolyl, xylyl or naphthyl, preferably phenyl. The substituted or unsubstituted alkenyl group may be, for example, vinyl, propenyl, allyl, butenyl, pentenyl or hexenyl, preferably vinyl. With the exception of substituted or unsubstituted aryl and substituted or unsubstituted alkenyl radicals, the remaining functions bound to the silicon atomThe functional group may be a substituted or unsubstituted alkyl group, and may be, for example, a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl or decyl group, preferably a methyl group.
In an embodiment of the present invention, in order to improve the heat resistance and hardness of the silicone film with moisture blocking properties, in the average unit structural formula of the first silicone resin, the mole ratio of the aryl groups bonded to the silicon atoms to all the functional groups bonded to the silicon atoms, except the end capping monomer, is at least 0.48. The weight average molecular weight of the first silicone resin may be between 500 and 200,000, and preferably between 1,000 and 190,000.
In a preferred embodiment of the present invention, the average unit structure for the first silicone resin is represented by, for example, (PhSiO)3/2)0.7(Me2SiO2/2)0.15(ViMeSiO2/2)0.15And monomers ViMe for end capping2SiO1/2The composition is as follows. Ph represents a phenyl group, Me represents a methyl group, and Vi represents a vinyl group.
In another preferred embodiment of the present invention, the average unit structure for the first silicone resin is represented by, for example, (PhSiO)3/2)0.7(Me2SiO2/2)0.2(ViMeSiO2/2)0.1And monomers ViMe for end capping2SiO1/2The composition is as follows.
The linear polysiloxane can improve the processability between the first silicon resin and the second silicon resin and the flexibility of the prepared silica gel film with the waterproof and air-proof properties. In one embodiment of the present invention, the average unit structure of the suitable linear polysiloxane has at least one aryl group bonded to a silicon atom and two alkenyl groups bonded to a silicon atom. The aforementioned aryl group may be a substituted or unsubstituted aryl group, and may be, for example, a phenyl group, a tolyl group, a xylyl group or a naphthyl group, preferably a phenyl group. The alkenyl group may be substituted or unsubstituted, and may be, for example, vinyl, propenyl, allyl, butenyl, pentenyl or hexenyl, preferably vinyl. The functional groups bonded to the silicon atom, other than the aryl and alkenyl groups, may be substituted or unsubstituted alkyl groups, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl or decyl, preferably methyl.
In order to improve the heat resistance, hardness and refractive index of the silica gel film with the water-gas blocking characteristic, in the curable silica resin composition, the average unit structural formula of the linear polysiloxane, except the end capping group monomer, the mole ratio of the aryl bonded with the silicon atom relative to all the functional groups bonded with the silicon is at least 0.4. And the linear polysiloxane may be added in an amount of 10 to 25 parts by weight, preferably 14 to 20 parts by weight.
In a preferred embodiment of the present invention, the average unit structural formula for expressing the linear polysiloxane is as follows: prepared from (PhMeSiO)2/2)0.8(Me2SiO2/2)0.1(ViMeSiO2/2)0.1And monomers ViMe for end capping2SiO1/2Wherein Ph represents a phenyl group, Me represents a methyl group, and Vi represents a vinyl group. The linear polysiloxane may have a weight average molecular weight of between 1,000 and 200,000, and preferably between 1,000 and 160,000. The viscosity of the linear polysiloxane at 25 ℃ is not limited, and is preferably in the range of 6,000 to 10,000 mPa.s. In a preferred embodiment of the invention, the linear polysiloxane has a viscosity of 6420mpa.s at 25 ℃.
In the curable silicone resin composition for forming the silicone film with the moisture-blocking characteristic, the average unit structural formula for representing the second silicone resin at least has R3SiO3/2And R4 3SiO1/2Wherein R is3Is a substituted or unsubstituted aryl, substituted or unsubstituted alkyl, or substituted or unsubstituted alkenyl. R4Is a substituted or unsubstituted aryl, substituted or unsubstituted alkyl, or substituted or unsubstituted alkenyl. The above-mentioned substituted or unsubstituted aryl group may be, for example, a phenyl group, a tolyl group, a xylyl group, or a naphthyl group, and is preferably a phenyl group. Substituted or not as described aboveThe substituted alkenyl group can be, for example, vinyl, propenyl, allyl, butenyl, pentenyl or hexenyl, preferably vinyl. The functional groups bonded to the silicon atom, other than the substituted or unsubstituted aryl groups and the substituted or unsubstituted alkenyl groups, are substituted or unsubstituted alkyl groups, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl or decyl, preferably methyl.
In order to improve the heat resistance and hardness of the silica gel film with the water-gas blocking characteristic, in the curable silica resin composition, the mole ratio of the aryl bonded with the silicon atom to all functional groups bonded with the silicon atom in the second silica resin except the end-capping monomer is at least more than 0.25.
In a preferred embodiment of the present invention, the average unit structural formula for representing the second silicone resin is as follows: (PhSiO)3/2)0.5(ViMe2SiO1/2)0.5. Ph represents a phenyl group, Me represents a methyl group, and Vi represents a vinyl group. The weight average molecular weight of the second silicone resin may be between 100 and 10,000, and preferably between 500 and 5,000.
In the curable silicone resin composition for forming a silicone film having moisture blocking properties of the present invention, the chemical structural formula of the polysiloxane used for representing the silicon-hydrogen bond is: HR (human HR)5 2SiO(SiR6 2O)nSiR5 2H, wherein R5Is a substituted or unsubstituted alkyl group or a hydrogen atom, R6Is a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group, and n is an integer of 0 or more.
The above-mentioned substituted or unsubstituted aryl group may be, for example, a phenyl group, a tolyl group, a xylyl group, or a naphthyl group, and is preferably a phenyl group. The substituted or unsubstituted alkyl group may be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, octyl, nonyl or decyl, preferably methyl.
In a preferred embodiment of the present invention,the average unit structural formula for representing the polysiloxane containing silicon-hydrogen bonds is as follows: (Ph)2SiO2/2)1(HMe2SiO1/2)2. Ph represents a phenyl group, and Me represents a methyl group. The polysiloxane containing silicon-hydrogen bonds may have a weight average molecular weight of 100 to 5,000, and preferably 100 to 1,000.
Suitable platinum group metals are catalysts which may be, for example, platinum-type catalysts, rhodium-type catalysts or palladium-type catalysts, preferably platinum-type catalysts, and customary catalysts which may be, for example, H2PtCl6·mH2O，K2PtCl6，KHPtCl6·mH2O，K2PtCl4，K2PtCl4·mH2O or PtO2·mH2O (m is a positive integer), and the like. Or complexes between these catalysts and alkenes, alcohols or vinyl-containing organopolysiloxanes, for example, Platinum (0) -2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane Complex solution (Platinum (0) -2,4,6, 8-tetramethylcyclotetramethoxysiloxane Complex solution) or octyleneplatinum Complex compound (Platinum-Octanal/Octanol Complex), but not limited thereto. These platinum group metals may be used alone or in combination as a catalyst. The platinum group metal is added in an amount of 1ppm to 50ppm, preferably 3ppm to 10ppm, based on the total weight parts of the linear polysiloxane, the first silicone resin, the second silicone resin and the polysiloxane containing silicon-hydrogen bonds.
In a preferred embodiment of the present invention, the platinum group metal used is octyl platinum complex catalyst, which is used in an amount of 4.3ppm based on the sum of the parts by weight of the linear polysiloxane, the first silicone resin, the second silicone resin and the polysiloxane containing silicon-hydrogen bonds.
In addition, the curable silicone resin composition for forming the silicone film with moisture-blocking characteristics of the invention may further comprise a thixotropic agent, an inhibitor, an anti-settling agent, an inorganic filler, a phosphor, quantum dots or a combination thereof.
The inorganic filler is used for increasing the heat resistance of the silica gel film with the moisture-blocking property, can be used as an anti-precipitation agent for preventing the precipitation of the fluorescent powder, and can also be used as a reflecting particle. Examples of the inorganic filler include reinforcing inorganic fillers such as fumed silica and fumed titanium dioxide, and non-reinforcing inorganic fillers such as calcium carbonate, calcium silicate, titanium dioxide, titanium oxide, and zinc oxide.
In an embodiment of the present invention, the curable silicone resin composition for forming a silicone film with moisture barrier properties includes fumed silica, and an amount of the fumed silica added is 0.1 to 5 parts by weight relative to 100 parts by weight of a total of the linear polysiloxane, the first silicone resin, the second silicone resin, and the polysiloxane with silicon-hydrogen bonds.
The silica gel film with the water vapor blocking characteristic provided by the invention has good water vapor blocking property and proper optical property, and the water vapor penetration rate (WVTR) of the silica gel film can be less than 40gm-2day-1The visible light transmittance can be more than 92%, and the haze can be less than 4%. In addition, the silica gel film with the water and gas blocking characteristic has good processability, the Coefficient of Thermal Expansion (CTE) of the silica gel film at 25-50 ℃ can be between 20ppm and 60ppm, the Coefficient of Thermal Expansion (CTE) of the silica gel film at 80-100 ℃ can be between 50ppm and 150ppm, and the arithmetic mean height (Sa) of the surface can be between 0.01 micrometer (mum) and 0.15 micrometer (mum), so that a subsequent inorganic coating layer can be formed.
In another embodiment of the present invention, an inorganic coating layer is further disposed on a surface of the silica gel film with moisture blocking property, so as to further reduce the moisture blocking property of the silica gel film.
The inorganic coating may include, but is not limited to, silicon dioxide (SiO)2) Aluminum oxide (Al)2O3) Or hafnium oxide (HfO)2) In one embodiment of the present invention, the inorganic coating layer may be aluminum oxide (Al)2O3) And (7) coating a film layer. In another embodiment of the present invention, the inorganic coating layer can be aluminum oxide (Al)2O3) Hafnium oxide (HfO)2) And (7) coating a film layer.
The inorganic coating Layer may be formed on a surface of the silica gel film having a moisture blocking property by a sputtering method (Sputter Deposition) or an Atomic Layer Deposition (ALD).
In one embodiment of the present invention, the thickness of the inorganic coating layer may be between 10 nanometers (nm) and 300 nm, and preferably between 20 nm and 30 nm. And the silica gel film with the inorganic coating layer and the water-gas blocking characteristic has a water-gas penetration rate (WVTR) of less than 0.5gm-2day-1。
The present invention provides an optical semiconductor device, wherein the optical semiconductor device is packaged by using the aforementioned silica gel film with moisture-blocking property.
The following examples are intended to further illustrate the invention, but the invention is not limited thereto.
Example (b):
preparation example 1: process for producing linear polysiloxane (Compound 1)
3499.92 g (19.13mole) of methylphenyldimethoxysilane (phenyldimethyldimethoxysilane, obtained from Hengqian industries, Inc., Taiwan, China), 288.48 g (2.4mole) of Dimethyldimethoxysilane (Dimethyldimethoxysilane, obtained from Hengqian industries, Inc., Taiwan, China), and 317.28 g (2.4mole) of Methylvinyldimethoxysilane (Dimethyldimethoxysilane, obtained from Hexa and Chemicals, Inc., Taiwan, China) were added to the reaction tank and stirred at room temperature to form a homogeneous mixture solution. The mixed solution was dropped into a 5% sulfuric acid aqueous solution (5337.4 g) to obtain a reaction solution, then the reaction solution was heated to 75 ℃ to conduct hydrolysis, after completion of the reaction, deionized water was used for extraction to make the organic layer neutral, and finally the solvent was removed to obtain a hydrolysate.
The hydrolysate, 69.52 g (0.374mole) of Divinyltetramethyldisiloxane (Divinyltetramethyldisiloxane, available from Hexa Kagaku K.K., Taiwan), and 5.88 g of tetramethylammonium hydroxide (trade name L09658, available from Alfa Aesar, USA) were placed in a reaction tank, nitrogen gas was introduced into the reaction tank, and the mixture was uniformly stirred at room temperature to prepare a reaction solution. Heating the reaction solution to 95 ℃ until the reaction is completedAnd base removal is performed to complete the preparation of compound 1. The average unit structural formula of the compound 1 is represented by (PhMeSiO)2/2)0.8(Me2SiO2/2)0.1(ViMeSiO2/2)0.1And monomers ViMe for end capping2SiO1/2The composition is as follows. Ph represents a phenyl group, Me represents a methyl group, and Vi represents a vinyl group. Preparation example 2: preparation method of first silicon resin (compound 2)
2685 g (13.5mole) of phenyltrimethoxysilane (phenyl-trimethoxysilane, available from Hexa Ltd., Taiwan, China), 349 g (2.9mole) of Dimethyldimethoxysilane (dimethyldimethyldimethyldimethoxysilane, available from Hexagon industries Ltd., Taiwan, China), and 384 g (2.9mole) of Methylvinyldimethoxysilane (methylvinyldimethilane, available from Hexa Ltd., Taiwan, China) were placed in a reaction tank and stirred at room temperature to prepare a uniformly mixed solution. The mixed solution was dropped into a 5% sulfuric acid aqueous solution (4579 g) to prepare a reaction solution, and then the reaction solution was heated to 75 ℃ to hydrolyze, after completion of the reaction, extraction was performed with deionized water to make the organic layer neutral, and finally the solvent was removed to prepare a hydrolyzate.
The hydrolysate, 21.39 g (0.11mole) of Divinyltetramethyldisiloxane (Divinyltetramethyldisiloxane, available from Hexa Ltd., Taiwan, China), 22.74 g of potassium hydroxide and 2274 g of toluene were placed in a reaction tank, and a reaction solution was prepared by introducing nitrogen gas into the reaction tank and stirring at room temperature. The reaction solution was then heated to 95 ℃. After the reaction was complete, the organic layer was neutralized by extraction with deionized water and finally the solvent was removed to complete the preparation of compound 2. The average unit structural formula of the compound 2 is (PhSiO)3/2)0.7(Me2SiO2/2)0.15(ViMeSiO2/2)0.15And monomeric ViMe for encapsulation2SiO1/2The composition is as follows.
Preparation example 3: method for preparing first silicone resin (compound 3)
2776 g (14mole) phenyltrimethoxysilane (phenyl-trimethoxysilane, available from sixfold ltd., taiwan), 480.88 g (4mole) Dimethyldimethoxysilane (dimethyidimethilane, available from hengqiao industries ltd., taiwan), and 264.46 g (2mole) Methylvinyldimethoxysilane (methyvinyldimethisilne, available from sixfold ltd., taiwan) were placed in a reaction tank and stirred at room temperature to prepare a uniformly mixed solution. Dripping the mixed solution into 5% sulfuric acid water solution to obtain a reaction solution, heating the reaction solution to 75 deg.C for hydrolysis, extracting with deionized water to make the organic layer neutral after the reaction is completed, and removing the solvent to obtain a hydrolysate.
The hydrolysate, 21.39 g (0.11mole) of Divinyltetramethyldisiloxane (Divinyltetramethyldisiloxane, available from Hexa Ltd., Taiwan, China), 22.74 g of potassium hydroxide and 2274 g of toluene were placed in a reaction tank, and a reaction solution was prepared by introducing nitrogen gas into the reaction tank and stirring at room temperature. The reaction solution was then heated to 95 ℃. After the reaction was complete, the organic layer was neutralized by extraction with deionized water and finally the solvent was removed to complete the preparation of compound 3. The average unit structural formula of the compound 3 is (PhSiO)3/2)0.7(Me2SiO2/2)0.2(ViMeSiO2/2)0.1And monomeric ViMe for encapsulation2SiO1/2The composition is as follows.
Preparation example 4: preparation method of second silicone resin (Compound 4)
2379.4 g (12mole) of Phenyltrimethoxysilane (Phenyltrimethoxysilane, available from Liuhe chemical Co., Ltd., Taiwan, China) and 1118.4 g (6mole) of Divinyltetramethyldisiloxane (Divinytetramethidiloxane, available from Liuhe chemical Co., Ltd., Taiwan, China) were placed in a reaction tank and stirred at room temperature to prepare a uniformly mixed solution. The mixed solution was dropped into a 5% sulfuric acid aqueous solution (4547.16 g) to prepare a reaction solution, the reaction solution was heated to 75 ℃ to conduct hydrolysis, after completion of the reaction, the organic layer was extracted with deionized water to make it neutral, and finally the solvent was removed to prepare a hydrolysate.
The hydrolyzate, 1998 g of toluene and 10 g of potassium hydroxide were placed in a reaction vessel, and nitrogen gas was introduced into the reaction vessel, followed by uniform stirring at room temperature to prepare a reaction solution. The reaction solution was heated to 85 ℃. After the reaction was complete, the organic layer was neutralized by extraction with deionized water and finally the solvent was removed to complete the preparation of compound 4. The average unit structural formula of the compound 4 is (PhSiO)3/2)0.5(ViMe2SiO1/2)0.5。
Preparation example 5: preparation method of polysiloxane (compound 5) containing silicon-hydrogen bond
3432.04 g (14mole) of Diphenyldimethoxysilane (Diphenyldimethoxysilane, available from Hexa and Chemicals Co., Ltd., Taiwan, China) and 1880.62 g (14mole) of Tetramethyldisiloxane (1,1,3,3-Tetramethyldisiloxane, available from Hengqiao industries Co., Ltd., Taiwan, China) were placed in a reaction tank and stirred at room temperature to prepare a homogeneous mixed solution. The mixed solution was dropped into a 50% sulfuric acid aqueous solution (2669 g) to prepare a reaction solution, and then the reaction solution was reacted at room temperature for 4 hours to conduct hydrolysis. After the reaction was complete, the organic layer was neutralized by extraction with deionized water and finally the solvent was removed to complete the preparation of compound 5. The average unit structural formula of the compound 5 is (Ph)2SiO2/2)0.33(HMe2SiO1/2)0.67。
Preparation example 6: preparation method of polysiloxane (compound 6) containing silicon-hydrogen bond
2776 g (14mole) of phenyltrimethoxysilane (phenyltrimethoxysilane, available from Liuhe chemical Co., Ltd., Taiwan), and 1880.62 g (14mole) of tetramethyldisiloxane (1,1,3,3-tetramethyldisiloxane, available from Hengqiao industries Ltd., Taiwan) were placed in a reaction tank and stirred at room temperature to prepare a uniformly mixed solution. The mixed solution was dropped into a 50% by mass aqueous sulfuric acid solution (2669 g) to prepare a reaction solution, which was then subjected to distillationThe reaction solution was reacted at room temperature for 4 hours to effect hydrolysis. After the reaction is completed, deionized water is used for extraction to make the pH value of the organic layer reach neutral, and finally the solvent is removed to complete the preparation of polysiloxane (compound 6) containing silicon-hydrogen bonds, wherein the average unit structural formula of the compound 6 is (PhSiO)3/2)0.33(HMe2SiO1/2)0.67。
Example 1
First, 47.3 g of compound 2, 18.4 g of compound 4, 20 g of compound 5, 1000ppm (relative to 100 g of compound 1, the sum of compound 2, compound 4 and compound 5) of 1-ethynylcyclohexanol as an inhibitor, and 1.5 parts by weight of fumed silica (TS-720, available from Cabot corp., usa) were put into a reaction flask to prepare a first solution. In another reaction flask were placed 14.3 g of compound 1 and 4.3ppm (relative to 100 g of the sum of compound 1, compound 2, compound 4 and compound 5) of Octanol Complex platinum compound (PIatinum-Octanal/Octanol Complex, available from Gelest, USA) to form a second solution. The first solution, the second solution, 30 g of a mica sheet (purchased from taiwan, japan), which was treated with methyl silicone, 30 g of toluene as a solvent, and 0.3mm zirconium beads, which were equal in weight to the above-mentioned materials, were uniformly stirred by a vacuum planetary debubbling machine thinly ARV-310 type, and coated on a PET substrate, which was then heated at 80 ℃ for 15 minutes and 150 ℃ for 3 hours to cure, and the PET substrate was torn off to obtain a silica gel film. The silica gel film thickness was about 50 micrometers (μm).
Example 2
A silicone gel film was produced in the same manner as in example 1 except that the amount of the methylsilicone-treated mica layer was changed to 40 parts by weight and the amount of the solvent toluene was changed to 35 parts by weight.
Example 3
First, 47.84 g of compound 3, 19.53 g of compound 4, 15.96 g of compound 5, 2.05 g of compound 6, 1000ppm (relative to 100 g of compound 1, the sum of compound 3, compound 4, compound 5 and compound 6) of 1-ethynylcyclohexanol as an inhibitor, and 1.5 parts by weight of fumed silica (TS-720, available from Cabot corp., usa) were put into a reaction flask to prepare a first solution. In another reaction flask were placed 14.53 g of compound 1, and 4.3ppm (relative to 100 g of the sum of compound 1, compound 3, compound 4, compound 5 and compound 6) of Octanol Complex platinum compound (PIatinum-Octanal/Octanol Complex, available from Gelest, USA) to form a second solution. The first solution, the second solution, 10 g of a mica sheet (purchased from taiwan, japan), which was treated with methyl silicone, 10 g of toluene as a solvent, and 0.3mm zirconium beads, which were equal in weight to the above-mentioned materials, were uniformly stirred by a vacuum planetary debubbling machine thinly ARV-310 type, and coated on a PET substrate, which was then heated at 80 ℃ for 15 minutes and 150 ℃ for 3 hours to cure, and the PET substrate was torn off to obtain a silica gel film. The silica gel film thickness was about 50 micrometers (μm).
Example 4
A silicone gel film was produced in the same manner as in example 3 except that the amount of the methylsilicone-treated mica layer was changed to 30 parts by weight and the amount of the solvent toluene was changed to 37 parts by weight.
Example 5
A silicone rubber film was produced in the same manner as in example 3 except that the amount of the methylsilicone-treated mica layer was changed to 40 parts by weight and the amount of the solvent toluene was changed to 37 parts by weight.
Comparative example 1
A silica gel film was prepared in the same manner as in example 1, except that the methyl silicone-treated mica layer sheet and the solvent toluene were not added.
Comparative example 2
A silica gel film was prepared in the same manner as in example 3, except that the methylsilicone-treated mica layer was not added and the solvent toluene was not added.
Comparative example 3
A silicone gel film was produced in the same manner as in example 1 except that the amount of the methylsilicone-treated mica layer was changed to 50 parts by weight and the amount of the solvent toluene was changed to 45 parts by weight.
Hereinafter, the silica gel film with moisture blocking property according to the present invention is evaluated and tested according to the following method, and the measurement results are shown in the following table 1.
Water Vapor Transmission Rate (WVTR) measurement
The Water Vapor Transmission Rate (WVTR) was measured by Moconaqua tran model 1 (measurement range: 5-5X 10-5gm-2day-1) according to ASTM F1249 rule, measuring area 0.5-5cm2, at 25 deg.C and humidity 90% RH.
Coefficient of Thermal Expansion (CTE)
The CTE in the range of 30 to 100 ℃ was measured with a thermo-mechanical analyzer (TMA from TA instrument) in a nitrogen atmosphere at a temperature rise rate of 10 ℃/min in accordance with ASTM E831 rules, using a tension of 0.0023N.
Penetration rate (T%)
The light transmittance in the wavelength range of 380-700nm was measured by a spectral luminance meter (U4100, available from Hitachi, Japan).
Haze measurement
The haze of the silica gel film was measured by a haze meter (NDH2000, available from Nippon Denshoku industries Co., Ltd.).
Surface Roughness (Sa) measurement
The arithmetic mean height (Sa) of the surface of the silica gel film was measured according to ISO25178 using an Olympus OLS 50003D laser microscope under the principle of laser confocal.
Table 1: results of testing characteristics of silica gel thin films of examples 1 to 5 and comparative examples 1 to 2
Figure GDA0003632007790000131
Figure GDA0003632007790000141
As a result of the tests shown in table 1, the silicone films of examples 1 to 5, which have incorporated the microlayers, all have a lower moisture vapor transmission rate than the silicone films of comparative examples 1 and 2. In addition, the light transmittance of the silicone films of examples 1 to 5 is still greater than 96%, and the haze of the silicone films of examples 1 to 4 is only 0, so that the silicone films still have good optical properties. In addition, the thermal expansion coefficients of the examples 1 to 5 are lower than those of the comparative examples 1 and 2, so that the inorganic coating layer can be formed with better processability.
Example 6
The silica gel thin film obtained in example 3 was further sputtered by using a sputtering apparatus of Syskey Technology, using argon as a working gas, at a working pressure of 0.005Torr, to form an alumina (Al) having a thickness of about 50 nanometers (nm) on the surface of the thin film2O3) And (7) coating a film layer.
Example 7
The silica gel film obtained in example 3 was pretreated with oxygen plasma. Next, using ALD equipment (i-SA, available from Syskey Technology, Taiwan, China), trimethylaluminum (AlCH) was added3)3And tetra (ethylmethylaminonium) hafnium (TEMAHF) as a precursor, water (H)2O) as oxidant, high-purity nitrogen as purge gas and carrier gas, and forming aluminum oxide (Al) with a thickness of about 20 nm on the surface of the silica gel film by atomic layer deposition at 25 deg.C and a working pressure of 9Torr2O3) Hafnium oxide (HfO)2) And (7) coating a film layer.
Example 8
The silica gel film obtained in example 2 was subjected to the same atomic layer deposition method as in example 7 to form aluminum oxide (Al) having a thickness of about 20 nm on the surface of the silica gel film2O3) Hafnium oxide (HfO)2) And (7) coating a film layer.
The detailed test results of the silica gel films having moisture blocking properties of the above examples 6 to 8 are shown in the following table 2.
Table 2: results of testing the characteristics of the silica gel films of examples 6 to 8
Figure GDA0003632007790000151
As can be seen from the test results shown in Table 2, the surface of the silica gel film was again modifiedForming an inorganic coating layer to further reduce the moisture penetration rate. Examples 6 to 8 the water vapor transmission rate after forming the inorganic coating layer was further reduced to 0.5gm- 2day-1The following. Therefore, the silica gel film with the moisture-blocking characteristic of the invention can simultaneously have good moisture-blocking property and excellent processability.
The above description is only for the preferred embodiment of the present invention and should not be construed as limiting the scope of the present invention, and any person skilled in the art can make further modifications and variations without departing from the spirit and scope of the present invention.

Claims (12)

1. A silica gel film with water-gas resistant characteristic, wherein the silica gel film is formed by curing a curable silicone resin composition, the curable silicone resin composition comprising:
10 to 25 parts by weight of a linear polysiloxane having an average unit structural formula of at least one silicon atom-bonded aryl group and two silicon atom-bonded alkenyl groups;
40 to 55 parts by weight of a first silicone resin having an average unit structural formula of at least R1SiO3/2Monomer and R2 2SiO2/2Monomer (II) wherein R1And R2Is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group or a substituted or unsubstituted aryl group, and in this average unit structural formula, the R is1SiO3/2The mole fraction of the monomer is between 0.60 and 0.75, and the mole ratio of the alkenyl bonded with the silicon atom to all the functional groups bonded with the silicon atom is 0.03 to 0.15;
15 to 30 parts by weight of a second silicone resin having an average unit structural formula of at least R3SiO3/2And R4 3SiO1/2Wherein R is3And R4Is a substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or substituted or unsubstituted aryl;
15 to 25 parts by weight of polysiloxane containing at least silicon-hydrogen bond, which has the chemical structural formula: HR (human HR)5 2SiO(SiR6 2O)nSiR5 2H, wherein R5Is a substituted or unsubstituted alkyl group or a hydrogen atom, R6Is a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group, and n is an integer of 0 or more;
10 to 40 parts by weight of a micro-layer sheet, wherein the micro-layer sheet is at least one selected from the group consisting of mica, clay, layered double hydroxide, calcium hydrogen phosphate and boron nitride or a combination thereof; and
the platinum group metal is a catalyst;
wherein, the water vapor penetration rate of the silica gel film with the water vapor blocking characteristic is less than 40gm-2day-1The visible light transmittance is more than 92% and the haze is less than 4%.
2. A silicone film with moisture blocking properties as claimed in claim 1, wherein the microlayer has an aspect ratio of between 10 and 200.
3. A silicone film with moisture blocking properties as recited in claim 1, wherein the length of said microlayers is between 0.1 micron and 25 microns.
4. The moisture-blocking silicone film of claim 1, wherein the moisture-blocking silicone film has a coefficient of thermal expansion between 20ppm and 60ppm at 25 ℃ and between 50ppm and 150ppm at 80 ℃ and 100 ℃, and an arithmetic mean height of the surface between 0.01 micron and 0.15 micron.
5. The moisture resistant silicone film of claim 1 wherein said curable silicone composition further comprises an inhibitor, a thixotropic agent, an anti-settling agent, an inorganic filler, a phosphor, or combinations thereof.
6. A silicone film having moisture blocking properties according to claim 5, wherein the inorganic filler in the curable silicone composition comprises fumed silica.
7. The moisture resistant silicone film of claim 1 further comprising an inorganic coating layer on the surface of the moisture resistant silicone film.
8. The moisture-blocking silicone film according to claim 7, wherein the inorganic coating layer is formed on the surface of the moisture-blocking silicone film by sputtering or atomic layer deposition.
9. The silica gel film with water-blocking property of claim 7, wherein the thickness of the inorganic coating layer is between 10 nm and 300 nm.
10. The silicone film with moisture blocking properties of claim 7, wherein said inorganic coating layer comprises silicon dioxide, aluminum oxide or hafnium oxide.
11. A moisture-blocking silicone film according to claim 7, wherein the moisture permeability of the silicone film is less than 0.5gm-2day-1。
12. An optical semiconductor device, wherein the optical semiconductor device is packaged by the silica gel film with moisture blocking property as claimed in any one of claims 1 to 11.
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Lead, copper, cobalt and nickel removal from water solutions by dynamic ionic exchange in LECA zeolite beds;Roque-Malherbe, Rolando M.等;《INTERNATIONAL JOURNAL OF ENVIRONMENT AND POLLUTION》;20070101;第31卷(第3-4期);第292-303页 *

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