CN113372728B - Silicone resin composition, cured product thereof, and LED element - Google Patents
Silicone resin composition, cured product thereof, and LED element Download PDFInfo
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- CN113372728B CN113372728B CN202110921804.5A CN202110921804A CN113372728B CN 113372728 B CN113372728 B CN 113372728B CN 202110921804 A CN202110921804 A CN 202110921804A CN 113372728 B CN113372728 B CN 113372728B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/005—Processes relating to semiconductor body packages relating to encapsulations
Abstract
The invention provides a silicone resin composition, a cured product thereof and an LED element. In the invention, cerium-containing vinyl branched polysiloxane with phenyl is used as matrix resin and is matched with linear organohydrogenpolysiloxane with phenyl, and a cured product of the prepared organic silicon resin composition can have proper hardness and strength, high light transmittance, low yellowness and low light attenuation, particularly, the Shore D hardness is not lower than 50, the 450nm light transmittance is not lower than 98%, the yellowness b value is not higher than 1, the elongation at break is not lower than 40%, the tensile strength is not lower than 5.0MPa, and the 500-hour light attenuation is not higher than 1%.
Description
Technical Field
The present invention relates to a silicone resin composition, and more particularly to a silicone resin composition for encapsulating an LED chip, a cured product thereof, and an LED element having an encapsulating layer formed from the cured product.
Background
In recent years, as the brightness and power of LED products are increasing, more severe requirements are put on the performance of LED packaging materials. LED packaging materials that exhibit good overall performance in terms of hardness, strength, yellowness, light transmittance, light decay, and the like, are receiving increasing attention.
There have been prior reports of using silicone resins as LED encapsulation materials and making technical improvements around the above performance requirements. For example, chinese patent application CN105121556A discloses that the addition of cerium-containing organopolysiloxane as a heat-resistant additive to a silicone resin matrix can inhibit the deterioration of the properties of the cured product, such as hardness, light transmittance, and yellowness, in the heat aging test to some extent. However, the LED element encapsulated with the cured product exhibited a poor lifetime, in which the light decay was at least 5% or more after continuous light emission for 300 hours under the conditions of an operating temperature of 85 ℃ and an operating current of 700 mA.
For this reason, development of a silicone resin encapsulating material having suitable hardness and strength, high light transmittance, low yellowness, and low light decay has been demanded as soon as possible.
Disclosure of Invention
An object of the present invention is to provide a silicone resin composition, a cured product of which can combine appropriate hardness and strength, high light transmittance, low yellowness, and low light attenuation.
Another object of the present invention is to provide a cured product obtained by curing the silicone resin composition.
It is a further object of the present invention to provide an LED element comprising an encapsulating layer composed of the cured product.
In one aspect, the present invention provides a silicone resin composition comprising:
(A) 100 parts by weight of a cerium-containing vinyl-branched polysiloxane having a cerium content of 40ppm to 200ppm, the preparation method comprising the steps of:
(S1) reacting a vinyl-branched polysiloxane (I) represented by the following formula (1) with a hydroxide (II) of an alkali metal or an alkaline earth metal to obtain a silicon alkoxide (III) of the vinyl-branched polysiloxane;
(ViMe2SiO1/2)a(Me2SiO2/2)b(MeSiO3/2)c(PhSiO3/2)d（1）
in the formula (1), Vi represents a vinyl group, Me represents a methyl group, and Ph represents a phenyl group; a. b, c, d represent molar ratios, respectively, and a is 0.05 to 0.5, b is 0.05 to 0.5, c is 0.4 to 0.9, d is 0.4 to 0.9;
(S2) reacting a silicon alkoxide (III) of the vinyl-branched polysiloxane with a cerium salt (IV) to obtain the cerium-containing vinyl-branched polysiloxane (a);
(B) 1 to 40 parts by weight of a linear organohydrogenpolysiloxane represented by the following formula (2):
(HMe2SiO1/2)(Ph2SiO2/2)n(HMe2SiO1/2) （2）
in the formula (2), Me represents a methyl group, and Ph represents a phenyl group; n represents a degree of polymerization, and n is an integer of 1 to 20; and
(C) a catalytically effective amount of a hydrosilylation catalyst.
According to the silicone resin composition of the present invention, preferably, in step (S1), the hydroxide of an alkali metal or alkaline earth metal (II) is lithium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, or a combination thereof.
According to the silicone resin composition of the present invention, preferably, in step (S1), the alkali metal or alkaline earth metal hydroxide (II) is used in an amount of 1ppm to 2000ppm by mass of the vinyl-branched polysiloxane (I).
According to the silicone resin composition of the present invention, preferably, in step (S2), the cerium salt (IV) is cerium chloride, cerium 2-ethylhexanoate, cerium naphthenate, cerium oleate, cerium laurate, cerium stearate, or a combination thereof.
According to the silicone resin composition of the present invention, preferably, in step (S2), the cerium salt (IV) is used in an amount of 1ppm to 2000ppm by mass of the vinyl-branched polysiloxane (I).
The silicone resin composition according to the present invention preferably further comprises: (D) 0.001 to 2 parts by weight of a hydrosilylation reaction inhibitor.
The silicone resin composition according to the present invention preferably further comprises: (E) 0.1 to 10 parts by weight of an adhesion promoter.
In another aspect, the present invention provides a cured product obtained by curing the silicone resin composition of the present invention.
The cured product according to the present invention preferably has the following properties:
(i) shore D hardness is not lower than 50;
(ii) the 450nm light transmittance is not lower than 98 percent;
(iii) yellowness b is not higher than 1;
(iv) the elongation at break is not less than 40 percent;
(v) the tensile strength is not lower than 5.0 MPa; and
(vi) the light decay is not higher than 1% in 500 hours, wherein the light decay determination method comprises the following steps: manufacturing an LED element comprising an LED chip and an encapsulating layer covering the LED chip, wherein the LED chip has a main emission center peak of 450nm and a size of 36mil × 26mil, and the encapsulating layer is composed of the cured product of the present invention and has a thickness of 0.6 mm; at an operating temperature of 105 ℃ and operatingThe LED element was lighted at a current of 800mA, and its initial luminous flux F was measured0And luminous flux F after continuous emission for 500 hours500In which F is0And F500All units of (a) are lm; the 500-hour light attenuation is calculated by the following formula:
500-hour light decay = [ (F)0-F500)/F0]×100%。
In yet another aspect, the present invention also provides an LED element comprising:
an LED chip; and
an encapsulation layer covering the LED chip;
wherein the encapsulating layer is composed of the cured product of the present invention.
The invention unexpectedly discovers that a cured product of the organic silicon resin composition prepared by taking the cerium-containing vinyl branched polysiloxane with the phenyl as a matrix resin and matching with the linear organohydrogenpolysiloxane with the phenyl can combine proper hardness and strength, high light transmittance, low yellowness and low light attenuation, particularly the Shore D hardness of the organic silicon resin composition is not less than 50, the light transmittance at 450nm is not less than 98%, the yellowness b x value is not more than 1, the elongation at break is not less than 40%, the tensile strength is not less than 5.0MPa and the light attenuation at 500 hours is not more than 1%.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the scope of the present invention is not limited thereto.
< interpretation of terms >
The "curing" or "curing reaction" mentioned in the description of the silicone resin composition in the present invention has substantially the same meaning as the hydrosilylation reaction, unless otherwise specified.
The properties mentioned in the description of the silicone-sealing resin composition in the present invention are obtained by measuring the cured product of the silicone resin composition after curing, unless otherwise specified. Of course, in order to better illustrate the beneficial properties of the silicone resin compositions of the present invention during formulation or prior to curing, the properties of the silicone resin compositions are sometimes also measured prior to curing.
The parts by weight mentioned in the description of the contents of the components of the silicone resin composition in the present invention are, unless otherwise specified, relative to 100 parts by weight of the content of the cerium-containing vinyl-branched polysiloxane (a).
As used herein, "ppm" refers to parts per million by weight (or concentration).
The term "catalytically effective amount" as referred to herein has its art-recognized meaning, i.e., the amount of catalyst that is effective to catalyze the hydrosilylation reaction.
< Silicone resin composition >
The silicone resin composition of the present invention comprises:
(A) 100 parts by weight of a cerium-containing vinyl-branched polysiloxane having a cerium content of 40ppm to 200ppm, the preparation method comprising the steps of:
(S1) reacting a vinyl-branched polysiloxane (I) represented by the following formula (1) with a hydroxide (II) of an alkali metal or an alkaline earth metal to obtain a silicon alkoxide (III) of the vinyl-branched polysiloxane;
(ViMe2SiO1/2)a(Me2SiO2/2)b(MeSiO3/2)c(PhSiO3/2)d（1）
in the formula (1), Vi represents a vinyl group, Me represents a methyl group, and Ph represents a phenyl group; a. b, c, d represent molar ratios, respectively, and a is 0.05 to 0.5, b is 0.05 to 0.5, c is 0.4 to 0.9, d is 0.4 to 0.9;
(S2) reacting a silicon alkoxide (III) of the vinyl-branched polysiloxane with a cerium salt (IV) to obtain the cerium-containing vinyl-branched polysiloxane (a);
(B) 1 to 40 parts by weight of a linear organohydrogenpolysiloxane represented by the following formula (2):
(HMe2SiO1/2)(Ph2SiO2/2)n(HMe2SiO1/2) （2）
in the formula (2), Me represents a methyl group, and Ph represents a phenyl group; n represents a degree of polymerization, and n is an integer of 1 to 20; and
(C) a catalytically effective amount of a hydrosilylation catalyst.
The invention unexpectedly discovers that a cured product of the organic silicon resin composition prepared by taking the cerium-containing vinyl branched polysiloxane (A) with the phenyl as a matrix resin and matching with the linear organohydrogenpolysiloxane (B) with the phenyl has proper hardness and strength, high light transmittance, low yellowness and low light attenuation, and particularly has Shore D hardness of not less than 50, light transmittance of not less than 450nm of not less than 98%, yellowness B value of not more than 1, elongation at break of not less than 40%, tensile strength of not less than 5.0MPa and light attenuation of not more than 1% in 500 hours.
Vinyl branched polysiloxane containing cerium (A)
The silicone resin composition of the present invention comprises: a cerium-containing vinyl branched polysiloxane (A).
The cerium-containing vinyl-branched polysiloxane (a) has a phenyl group, and is compounded with the linear organohydrogenpolysiloxane (B) as a base resin, and a cured product of the silicone resin composition prepared therefrom can combine appropriate hardness and strength, high light transmittance, low yellowness and low light attenuation.
In the present invention, the preparation method of the cerium-containing vinyl-branched polysiloxane (a) comprises the steps of:
(S1) reacting a vinyl-branched polysiloxane (I) represented by the following formula (1) with a hydroxide (II) of an alkali metal or an alkaline earth metal to obtain a silicon alkoxide (III) of the vinyl-branched polysiloxane;
(ViMe2SiO1/2)a(Me2SiO2/2)b(MeSiO3/2)c(PhSiO3/2)d（1）
in the formula (1), Vi represents a vinyl group, Me represents a methyl group, and Ph represents a phenyl group; a. b, c, d represent molar ratios, respectively, and a is 0.05 to 0.5, b is 0.05 to 0.5, c is 0.4 to 0.9, d is 0.4 to 0.9;
(S2) reacting the silanolate (III) of the vinyl-branched polysiloxane with a cerium salt (IV) to obtain the cerium-containing vinyl-branched polysiloxane (A).
In the formula (1), a is preferably 0.2 to 0.4; b is preferably from 0.2 to 0.4; c is preferably from 0.6 to 0.8; d is preferably 0.6 to 0.8.
In the step (S1), the hydroxide of an alkali metal or an alkaline earth metal (II) is preferably lithium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, or a combination thereof, and more preferably potassium hydroxide or sodium hydroxide.
In step (S1), the alkali metal or alkaline earth metal hydroxide (II) is preferably used in an amount of 1ppm to 2000ppm by mass of the branched polysiloxane (I), more preferably 10ppm to 1000ppm by mass of the vinyl branched polysiloxane (I), and most preferably 50ppm to 500ppm by mass of the vinyl branched polysiloxane (I).
In step (S1), the reaction of the vinyl-branched polysiloxane (I) with the hydroxide of an alkali metal or alkaline earth metal (II) is preferably carried out in an organic solvent. The organic solvent is preferably hexane, cyclohexane, toluene, xylene, methanol, ethanol, isopropanol or a combination thereof, more preferably toluene or toluene.
In the step (S1), the reaction temperature of the vinyl-branched polysiloxane (I) with the hydroxide of an alkali metal or alkaline earth metal (II) is preferably 80 ℃ to 180 ℃, more preferably 100 ℃ to 150 ℃.
In the step (S1), the reaction time of the vinyl-branched polysiloxane (I) with the hydroxide of an alkali metal or alkaline earth metal (II) is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.
In the step (S2), the cerium salt (IV) is preferably cerium chloride, cerium 2-ethylhexanoate, cerium naphthenate, cerium oleate, cerium laurate, cerium stearate, or a combination thereof, and more preferably cerium chloride.
In step (S2), the cerium salt (IV) is preferably used in an amount of 10ppm to 2000ppm by mass of the vinyl-branched polysiloxane (I), more preferably 10ppm to 1000ppm by mass of the vinyl-branched polysiloxane (I), and most preferably 50ppm to 500ppm by mass of the vinyl-branched polysiloxane (I).
In the step (S2), the reaction of the silicon alkoxide salt of vinyl-branched polysiloxane (III) with the cerium salt (IV) is preferably carried out in an organic solvent. The organic solvent is preferably hexane, cyclohexane, toluene, xylene, methanol, ethanol, isopropanol or a combination thereof, more preferably toluene or toluene.
In the step (S2), the reaction temperature of the silicon alkoxide salt (III) of vinyl-branched polysiloxane with the cerium salt (IV) is preferably 80 ℃ to 180 ℃, more preferably 100 ℃ to 150 ℃.
In the step (S2), the reaction time of the silicon alkoxide salt (III) of vinyl-branched polysiloxane with the cerium salt (IV) is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.
In step (S2), optionally, after the reaction of the silanolate (III) of the vinyl-branched polysiloxane with the cerium salt (IV) is completed, filtration and/or desolventization is performed.
In the present invention, the cerium content of the cerium-containing vinyl-branched polysiloxane (a) is from 40ppm to 200ppm, preferably from 50ppm to 160ppm, more preferably from 60ppm to 100 ppm.
Linear organohydrogenpolysiloxane (B)
The silicone resin composition of the present invention further comprises: linear organohydrogenpolysiloxane (B).
The linear organohydrogenpolysiloxane (B) has a phenyl group, which is compounded with the cerium-containing vinyl-branched polysiloxane (a) as a base resin, and a cured product of the silicone resin composition prepared therefrom can combine appropriate hardness and strength, high light transmittance, low yellowness, and low light attenuation.
In the present invention, the linear organohydrogenpolysiloxane (B) has a structure represented by the following formula (2):
(HMe2SiO1/2)(Ph2SiO2/2)n(HMe2SiO1/2) （2）
in the formula (2), Me represents a methyl group, and Ph represents a phenyl group; n represents a degree of polymerization, and n is an integer of 1 to 20, preferably an integer of 1 to 10, more preferably an integer of 1 to 5.
In the present invention, the linear organohydrogenpolysiloxane (B) is contained in the silicone resin composition in an amount of 1 to 40 parts by weight, preferably 10 to 30 parts by weight, relative to 100 parts by weight of the cerium-containing vinyl-branched polysiloxane (a).
Hydrosilylation catalyst (C)
The silicone resin composition of the present invention further comprises: a hydrosilylation catalyst (C).
The hydrosilation catalyst (C) is capable of catalyzing the hydrosilation reaction between the vinyl groups of the cerium-containing vinyl-branched polysiloxane (a) and the hydrogen atoms of the linear organohydrogenpolysiloxane (B), thereby achieving curing of the silicone resin composition of the present invention.
In the present invention, the type of the hydrosilylation catalyst (C) is not particularly limited, and a type known in the art can be used. Examples of the hydrosilation catalyst (C) include, but are not limited to: platinum-containing compounds such as chloroplatinic acid, reaction products of chloroplatinic acid with alcohols, platinum-olefin complexes, platinum-vinylsilane complexes, platinum-ketone complexes, platinum-phosphine complexes; rhodium-containing compounds, such as rhodium-phosphine complexes, rhodium-sulfur compound complexes; palladium-containing compounds, such as palladium-phosphine complexes. In order to improve the catalytic activity, the hydrosilylation catalyst (C) may be supported on a carrier. Examples of such supports include, but are not limited to, silica, alumina, carbon black, and the like. Preferably, the hydrosilylation catalyst (C) is a complex of platinum and vinylsiloxane, more preferably a platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex.
In the present invention, the hydrosilylation catalyst (C) is contained in the silicone resin composition in a catalytically effective amount. Preferably, the content of the hydrosilylation catalyst (C) in the silicone resin composition is 0.5ppm to 100ppm, preferably 1ppm to 50ppm, relative to 100 parts by weight of the cerium-containing vinyl-branched polysiloxane (a).
Hydrosilylation inhibitor (D)
The silicone resin composition of the present invention may further comprise: a hydrosilylation reaction inhibitor (D).
The hydrosilylation reaction inhibitor (D) can be used to regulate the rate of hydrosilylation reaction of the vinyl group of the cerium-containing vinyl-branched polysiloxane (a) with the hydrogen atom of the linear organohydrogenpolysiloxane (B), thereby regulating the curing rate of the silicone resin composition of the present invention.
In the present invention, the type of the hydrosilylation inhibitor (D) is not particularly limited, and a type known in the art may be used. Examples of the hydrosilylation reaction inhibitor (D) include, but are not limited to: phosphorus-containing compounds, such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, benzotriazole, and the like; maleic acid derivatives such as dimethyl maleate and the like; alkynols such as 1-ethynylcyclohexanol, 3, 5-dimethyl-1-hexyn-3-ol, 3-methylbutynol and the like; vinyl silanes, such as 1,3,5, 7-tetramethyl-1, 3,5, 7-tetravinyl cyclotetrasiloxane and the like. Preferably, the hydrosilylation inhibitor (D) is 1-ethynylcyclohexanol or 1,3,5, 7-tetramethyl-1, 3,5, 7-tetravinylcyclotetrasiloxane.
In the present invention, the content of the hydrosilylation reaction inhibitor (D) in the silicone resin composition is not particularly limited, but the content of the hydrosilylation reaction inhibitor (D) in the silicone resin composition is preferably 0.001 to 2 parts by weight, more preferably 0.01 to 1 part by weight, relative to 100 parts by weight of the cerium-containing vinyl-branched polysiloxane (a), from the viewpoint of facilitating control of the curing rate of the silicone resin composition.
Adhesion promoter (E)
The silicone resin composition of the present invention may further comprise: an adhesion promoter (E).
The adhesion promoter can improve the adhesion performance of the silicone resin composition and the cured product thereof.
In the present invention, the type of the adhesion promoter (E) is not particularly limited, and a type known in the art may be used. Preferably, the adhesion promoter (E) is a silane coupling agent. Examples of the silane coupling agent include, but are not limited to: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, acryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, isocyanatopropyltrimethoxysilane, isocyanatopropyltriethoxysilane, and the like. Preferably, the adhesion promoter (E) is 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, or a combination thereof.
In the present invention, the content of the adhesion promoter (E) in the silicone resin composition is not particularly limited, but from the viewpoint of facilitating control of the adhesion properties of the silicone resin composition and its cured product, the content of the adhesion promoter (E) in the silicone resin composition is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the cerium-containing vinyl-branched polysiloxane (a).
< cured product >
The cured product of the present invention is formed by curing the silicone resin composition of the present invention.
The present inventors have surprisingly found that a cured product of a silicone resin composition prepared by using a cerium-containing vinyl-branched polysiloxane (a) having a phenyl group as a base resin and blending a linear organohydrogenpolysiloxane (B) having a phenyl group can combine suitable hardness and strength, high light transmittance, low yellowness and low light attenuation.
In the present invention, the curing time and curing temperature of the curing are not particularly limited, but from the viewpoint of facilitating the formation of a sufficiently cured product, the curing time of the curing is preferably 0.5 to 10 hours, more preferably 1 to 5 hours; the curing temperature of the curing is preferably from 80 ℃ to 200 ℃, more preferably from 100 ℃ to 160 ℃.
The cured product disclosed by the invention has proper hardness and strength, high light transmittance, low yellowness and low light attenuation. Preferably, the cured product of the present invention has the following properties:
(i) shore D hardness is not lower than 50;
(ii) the 450nm light transmittance is not lower than 98 percent;
(iii) yellowness b is not higher than 1;
(iv) the elongation at break is not less than 40 percent;
(v) the tensile strength is not lower than 5.0 MPa; and
(vi) the light decay is not higher than 1% in 500 hours, wherein the light decay determination method comprises the following steps: manufacturing an LED element comprising an LED chip and an encapsulating layer covering the LED chip, wherein the LED chip has a main emission center peak of 450nm and a size of 36mil × 26mil, and the encapsulating layer is composed of the cured product of the present invention and has a thickness of 0.6 mm; the LED element was lighted at an operating temperature of 105 ℃ and an operating current of 800mA, and its initial luminous flux F was measured0And luminous flux F after continuous emission for 500 hours500In which F is0And F500All units of (a) are lm; the 500-hour light attenuation is calculated by the following formula:
500-hour light decay = [ (F)0-F500)/F0]×100%。
< LED element >
The LED element of the present invention comprises:
an LED chip; and
an encapsulation layer covering the LED chip;
wherein the encapsulating layer is composed of the cured product of the present invention.
In the present invention, the type of the LED chip is not particularly limited, and a type commonly used in the art may be used. Examples of the LED chip include, but are not limited to: the LED chip comprises a blue LED chip, a blue-violet LED chip, a yellow LED chip, a green LED chip, a yellow-green LE chip, a red LED chip, an orange-red LED chip and the like.
In the present invention, the encapsulating layer is composed of the cured product of the present invention. The formation process of the encapsulation layer is not particularly limited, and a process known in the art may be used. For example, the forming process may include the steps of: applying the silicone resin composition of the present invention over the LED chip, and then curing the silicone resin composition of the present invention to form the encapsulation layer. The manner of application is not particularly limited and processes well known in the art may be employed. The curing time and curing temperature of the curing are not particularly limited, but from the viewpoint of facilitating the formation of a sufficiently cured product, the curing time of the curing is preferably 0.5 to 10 hours, more preferably 1 to 5 hours; the curing temperature of the curing is preferably from 80 ℃ to 200 ℃, more preferably from 100 ℃ to 160 ℃.
In the present invention, the thickness of the encapsulation layer is not particularly limited, and a thickness known in the art may be used. For example, the thickness of the encapsulation layer may be 0.1 μm to 1000 μm.
Examples
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited by these examples.
< test methods >
The hardness measuring method comprises the following steps: the silicone resin composition was cured at 150 ℃ for 2 hours to prepare a cured sheet having a thickness of 2 mm. According to the determination method specified in the national standard GB/T2411-2008, the Shore D hardness of the cured tablet is determined by an EHS5D type digital Shore durometer.
Tensile strength and elongation determination methods: the silicone resin composition was cured at 150 ℃ for 2 hours to prepare a cured sheet having a thickness of 2 mm. The cured sheet was cut into a tensile specimen of a predetermined size according to the measurement method specified in the national standard GB/T1701-2001, and the tensile strength and elongation of the tensile specimen were measured by an Instron 2367 type universal material tester.
The light transmittance determination method comprises the following steps: the silicone resin composition was cured at 150 ℃ for 2 hours to prepare a cured sheet having a thickness of 1 mm. The transmittance of the cured sheet at 450nm was measured using a UV-3100PC scanning type UV/Vis spectrophotometer.
Yellowness b-value determination method: the silicone resin composition was cured at 150 ℃ for 2 hours to prepare a cured sheet having a thickness of 1 mm. The yellowness b of the cured sheet was measured using a CM-3600 type spectrocolorimeter.
The light attenuation measuring method comprises the following steps: manufacturing an LED element comprising an LED chip and an encapsulation layer covering the LED chip, wherein the LED chip has a main emission center peak of 450nm and a size of 36mil × 26 mil; the encapsulating layer is composed of a cured product formed by curing the organic silicon resin composition, and the thickness of the encapsulating layer is 0.6 mm; the LED element was lighted at an operating temperature of 105 ℃ and an operating current of 800mA, and its initial luminous flux F was measured0And luminous flux F after continuous emission for 500 hours500In which F is0And F500All units of (a) are lm; the 500-hour light attenuation is calculated by the following formula:
500-hour light decay = [ (F)0-F500)/F0]×100%。
Synthesis example 1 preparation of cerium-containing vinyl-branched polysiloxane (A1)
100 g of a vinyl-branched polysiloxane (a 1) represented by the following formula (1-1) was dissolved in 100ml of xylene to prepare a solution. After adding 0.005 g of potassium hydroxide to the solution, the solution was heated to 140 ℃ and refluxed at 140 ℃ for 2 hours. Then, without separation, 0.0075 g of cerium trichloride was added to the resultant reaction solution while it was hot, and the reaction was continued under reflux at 140 ℃ for 2 hours. After the reaction is finished, the obtained reaction product is cooled to room temperature, and the solvent is removed through filtration and rotary evaporation, so that the cerium-containing vinyl branched polysiloxane (A1) with the cerium content of 40ppm is obtained.
(ViMe2SiO1/2)0.26(Me2SiO2/2)0.3(MeSiO3/2)0.75(PhSiO3/2)0.75（1-1）
Synthesis example 2 preparation of cerium-containing vinyl-branched polysiloxane (A2)
100 g of the vinyl-branched polysiloxane (a 1) represented by the above formula (1-1) in Synthesis example 1 was dissolved in 100ml of xylene to prepare a solution. After adding 0.01 g of potassium hydroxide to the solution, the solution was heated to 140 ℃ and refluxed at 140 ℃ for 2 hours. Then, without separation, 0.015 g of cerium trichloride was added to the obtained reaction solution while it was hot, and the reflux reaction was continued at 140 ℃ for 2 hours. After the reaction is finished, the obtained reaction product is cooled to room temperature, and the solvent is removed through filtration and rotary evaporation, so that the cerium-containing vinyl branched polysiloxane (A2) with the cerium content of 80ppm is obtained.
Synthesis example 3 preparation of cerium-containing vinyl-branched polysiloxane (A3)
100 g of the vinyl-branched polysiloxane (a 1) represented by the above formula (1-1) in Synthesis example 1 was dissolved in 100ml of xylene to prepare a solution. After adding 0.03 g of potassium hydroxide to the solution, the solution was heated to 140 ℃ and the reaction was refluxed for 2 hours while maintaining the temperature at 140 ℃. Then, without separation, 0.045 g of cerium trichloride was added to the resultant reaction solution while it was hot, and the reaction was continued under reflux at 140 ℃ for 2 hours. After the reaction is finished, the obtained reaction product is cooled to room temperature, and the solvent is removed through filtration and rotary evaporation, so that the cerium-containing vinyl branched polysiloxane (A3) with the cerium content of 200ppm is obtained.
< comparative Synthesis example 1 preparation of cerium-containing vinyl-branched polysiloxane (A1') >
100 g of the vinyl-branched polysiloxane (a 1) represented by the above formula (1-1) in Synthesis example 1 was dissolved in 100ml of xylene to prepare a solution. After 0.015 g of potassium hydroxide was added to the solution, the solution was heated to 140 ℃ and the reaction was refluxed for 2 hours while maintaining the temperature at 140 ℃. Then, without separation, 0.002 g of cerium trichloride was added to the obtained reaction solution while it was hot, and the reflux reaction was continued at 140 ℃ for 2 hours. After the reaction was completed, the obtained reaction product was cooled to room temperature, and the solvent was removed by filtration and rotary evaporation to obtain a cerium-containing vinyl-branched polysiloxane (a 1') having a cerium content of 10 ppm.
< comparative Synthesis example 2 preparation of cerium-containing vinyl-branched polysiloxane (A2') >
100 g of the vinyl-branched polysiloxane (a 1) represented by the above formula (1-1) in Synthesis example 1 was dissolved in 100ml of xylene to prepare a solution. After 0.036 g of potassium hydroxide was added to the solution, the solution was heated to 140 ℃ and the reaction was refluxed for 2 hours while maintaining the temperature at 140 ℃. Then, without separation, 0.054 g of cerium trichloride was added to the obtained reaction solution while it was hot, and the reflux reaction was continued at 140 ℃ for 2 hours. After the reaction was completed, the obtained reaction product was cooled to room temperature, and the solvent was removed by filtration and rotary evaporation to obtain cerium-containing vinyl-branched polysiloxane (a 2') having a cerium content of 240 ppm.
< comparative Synthesis example 3 preparation of cerium-containing vinyl-branched polysiloxane (A3') >
100 g of a vinyl-branched polysiloxane (a 1 ') represented by the following formula (1-1') was dissolved in 100ml of xylene to prepare a solution. After adding 0.01 g of potassium hydroxide to the solution, the solution was heated to 140 ℃ and refluxed at 140 ℃ for 2 hours. Then, without separation, 0.015 g of cerium trichloride was added to the obtained reaction solution while it was hot, and the reflux reaction was continued at 140 ℃ for 2 hours. After the reaction was completed, the obtained reaction product was cooled to room temperature, and the solvent was removed by filtration and rotary evaporation to obtain cerium-containing vinyl-branched polysiloxane (a 3') having a cerium content of 80 ppm.
（1-1′）(ViMe2SiO1/2)0.26(Me2SiO2/2)0.3(MeSiO3/2)1.5。
< examples 1 to 3 and comparative examples 1 to 5>
The raw materials used in inventive examples 1 to 3 and comparative examples 1 to 5 were as follows:
vinyl-branched polysiloxane:
a1：(ViMe2SiO1/2)0.26(Me2SiO2/2)0.3(MeSiO3/2)0.75(PhSiO3/2)0.75。
cerium-containing vinyl branched polysiloxane:
a1: synthesis example 1 prepared cerium-containing vinyl-branched polysiloxane (cerium content 40 ppm).
A2: synthesis example 2 prepared cerium-containing vinyl-branched polysiloxane (cerium content: 80 ppm).
A3: synthesis example 3 prepared cerium-containing vinyl-branched polysiloxane (cerium content 200 ppm).
A1': the cerium-containing vinyl-branched polysiloxane prepared in comparative Synthesis example 1 (cerium content: 10 ppm).
A2': the cerium-containing vinyl-branched polysiloxane prepared in comparative Synthesis example 2 (cerium content 240 ppm).
A3': the cerium-containing vinyl-branched polysiloxane prepared in comparative Synthesis example 3 (cerium content: 80 ppm).
Linear organohydrogenpolysiloxane:
B1：(Me2HSiO1/2)(Ph2SiO2/2)(Me2HSiO1/2)。
B1′：(Me2HSiO1/2)(Me2SiO2/2)2.67(Me2HSiO1/2)。
hydrosilylation reaction catalyst:
c: platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex.
Hydrosilylation reaction inhibitor:
d: 1-ethynylcyclohexanol.
Adhesion promoter:
e: 3- (2, 3-epoxypropoxy) propyltrimethoxysilane.
The silicone resin compositions of examples 1 to 3 of the present invention and comparative examples 1 to 5 were respectively formulated in accordance with the compositions shown in table 1 and allowed to cure at 150 ℃ for 2 hours to prepare corresponding cured products. The cured product properties of the silicone resin compositions formulated in examples 1 to 3 of the present invention and comparative examples 1 to 5 were tested and are shown in table 1.
TABLE 1
As can be seen from table 1, the silicone resin compositions of examples 1 to 3 of the present invention, which have a cerium-containing vinyl-branched polysiloxane having a cerium content of 40ppm to 200ppm as a base resin, exhibited lower light attenuation, in particular, their 500-hour light attenuation was less than 1%, as compared to comparative example 1, which uses a branched polysiloxane containing no cerium as a base resin.
The silicone resin composition of example 2 of the present invention, which had the same cerium-containing vinyl-branched polysiloxane as the base resin, exhibited lower light attenuation, in particular, it had a 500-hour light attenuation of less than 1%, as compared to comparative example 2, which had the cerium-containing vinyl-branched polysiloxane as an auxiliary additive (in an amount of only 10 parts by weight).
The silicone resin compositions of examples 1 to 3 of the present invention having a cerium-containing vinyl-branched polysiloxane as a base resin having a cerium content of 40ppm to 200ppm exhibited lower light attenuation, in particular, 500-hour light attenuation thereof was less than 1%, as compared to comparative example 3 having a cerium-containing vinyl-branched polysiloxane as a base resin having a cerium content of less than 40 ppm.
The silicone resin compositions of examples 1 to 3 of the present invention having a cerium-containing vinyl-branched polysiloxane having a cerium content of 40ppm to 200ppm as a base resin exhibited: lower light attenuation, especially less than 1% in 500 hours; lower yellowness b values, in particular lower than 1; and higher light transmittance, particularly light transmittance at 450nm of not less than 98%.
In comparison with comparative example 5, in which the base resin has the same cerium content but neither the cerium-containing vinyl-branched polysiloxane nor the linear organohydrogenpolysiloxane has a phenyl group, example 2, which uses the cerium-containing vinyl-branched polysiloxane having a phenyl group and the linear organohydrogenpolysiloxane having a phenyl group, shows: higher Shore D hardness, especially Shore D hardness not less than 50; higher tensile strength, particularly not less than 5.0 MPa.
In summary, the invention takes the phenyl-containing cerium vinyl branched polysiloxane as the matrix resin and is matched with the phenyl-containing linear organohydrogenpolysiloxane, and the cured product of the prepared organic silicon resin composition has appropriate hardness and strength, high light transmittance, low yellowness and low light attenuation, particularly, the Shore D hardness is not lower than 50, the light transmittance at 450nm is not lower than 98%, the yellowness b x value is not higher than 1, the elongation at break is not lower than 40%, the tensile strength is not lower than 5.0MPa and the light attenuation is not higher than 1%.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (10)
1. A silicone resin composition characterized in that it comprises:
(A) 100 parts by weight of a cerium-containing vinyl-branched polysiloxane having a cerium content of 40ppm to 200ppm, the preparation method comprising the steps of:
(S1) reacting a vinyl-branched polysiloxane (I) represented by the following formula (1) with a hydroxide (II) of an alkali metal or an alkaline earth metal to obtain a silicon alkoxide (III) of the vinyl-branched polysiloxane;
(ViMe2SiO1/2)a(Me2SiO2/2)b(MeSiO3/2)c(PhSiO3/2)d （1）
in the formula (1), Vi represents a vinyl group, Me represents a methyl group, and Ph represents a phenyl group; a. b, c, d represent molar ratios, respectively, and a is 0.05 to 0.5, b is 0.05 to 0.5, c is 0.4 to 0.9, d is 0.4 to 0.9;
(S2) reacting a silicon alkoxide (III) of the vinyl-branched polysiloxane with a cerium salt (IV) to obtain the cerium-containing vinyl-branched polysiloxane (a);
(B) 1 to 40 parts by weight of a linear organohydrogenpolysiloxane represented by the following formula (2):
(HMe2SiO1/2)(Ph2SiO2/2)n(HMe2SiO1/2) （2）
in the formula (2), Me represents a methyl group, and Ph represents a phenyl group; n represents a degree of polymerization, and n is an integer of 1 to 20; and
(C) a catalytically effective amount of a hydrosilylation catalyst.
2. The silicone resin composition according to claim 1, wherein in step (S1), the hydroxide of an alkali metal or alkaline earth metal (II) is lithium hydroxide, potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, or a combination thereof.
3. The silicone resin composition according to claim 1, wherein in step (S1), the alkali metal or alkaline earth metal hydroxide (II) is used in an amount of 1ppm to 2000ppm based on the mass of the vinyl-branched polysiloxane (I).
4. The silicone resin composition according to claim 1, wherein in step (S2), the cerium salt (IV) is cerium chloride, cerium 2-ethylhexanoate, cerium naphthenate, cerium oleate, cerium laurate, cerium stearate, or a combination thereof.
5. The silicone resin composition according to claim 1, wherein in step (S2), the cerium salt (IV) is used in an amount of 1ppm to 2000ppm by mass of the vinyl-branched polysiloxane (I).
6. The silicone resin composition according to claim 1, characterized in that it further comprises: (D) 0.001 to 2 parts by weight of a hydrosilylation reaction inhibitor.
7. The silicone resin composition according to claim 1, characterized in that it further comprises: (E) 0.1 to 10 parts by weight of an adhesion promoter.
8. A cured product obtained by curing the silicone resin composition according to any one of claims 1 to 7.
9. The cured product according to claim 8, which has the following properties:
(i) shore D hardness is not lower than 50;
(ii) the 450nm light transmittance is not lower than 98 percent;
(iii) yellowness b is not higher than 1;
(iv) the elongation at break is not less than 40 percent;
(v) the tensile strength is not lower than 5.0 MPa; and
(vi) the light decay is not higher than 1% in 500 hours, wherein the light decay determination method comprises the following steps: manufacturing an LED element comprising an LED chip having a main emission center peak of 450nm and a size of 36mil × 26mil, and an encapsulating layer covering the LED chip, the encapsulating layer being composed of the cured product and having a thickness of 0.6 mm; the LED element was lighted at an operating temperature of 105 ℃ and an operating current of 800mA, and its initial luminous flux F was measured0And luminous flux F after continuous emission for 500 hours500In which F is0And F500All units of (a) are lm; the 500-hour light attenuation is calculated by the following formula:
500-hour light decay = [ (F)0-F500)/F0]×100%。
10. An LED element, comprising:
an LED chip; and
an encapsulation layer covering the LED chip;
wherein the encapsulating layer is composed of the cured product according to claim 8 or 9.
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