KR101733960B1 - Curable composition, cured product and photo-semiconductor device - Google Patents
Curable composition, cured product and photo-semiconductor device Download PDFInfo
- Publication number
- KR101733960B1 KR101733960B1 KR1020140001912A KR20140001912A KR101733960B1 KR 101733960 B1 KR101733960 B1 KR 101733960B1 KR 1020140001912 A KR1020140001912 A KR 1020140001912A KR 20140001912 A KR20140001912 A KR 20140001912A KR 101733960 B1 KR101733960 B1 KR 101733960B1
- Authority
- KR
- South Korea
- Prior art keywords
- polysiloxane
- cured product
- curable composition
- group
- semiconductor device
- Prior art date
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73251—Location after the connecting process on different surfaces
- H01L2224/73265—Layer and wire connectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/19—Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
- H01L2924/191—Disposition
- H01L2924/19101—Disposition of discrete passive components
- H01L2924/19107—Disposition of discrete passive components off-chip wires
Abstract
(A) a polysiloxane (A) having at least two alkenyl groups, aryl groups and fluorine atoms per molecule, at least two alkenyl groups and at least two alkenyl groups and aryl groups per molecule and having no fluorine atom (B ), A hydrogensiloxane (C) having at least two hydrogen atoms bonded to silicon atoms per molecule, and a catalyst (D) for hydrosilylation reaction.
(Effect) The curable composition of the present invention can form a cured product that can provide an optical semiconductor device having excellent brightness. The optical semiconductor device having a cured product formed of the curable composition of the present invention as an encapsulating material has excellent brightness.
Description
The present invention relates to a curable composition, a cured product, and an optical semiconductor device.
The semiconductor light emitting element is sealed with an encapsulating material such as a transparent resin in order to protect it from moisture and foreign substances. The light emitted from the semiconductor light emitting element is prevented from being reflected at the interface between the semiconductor light emitting element having a high refractive index and a semiconductor material layer such as GaN or InGaN and the sealing material so that the light extraction efficiency (Brightness), it is necessary to increase the refractive index of the encapsulant (Patent Document 1).
However, if the refractive index of the sealing material is increased, the light extraction efficiency from the light emitting surface of the semiconductor light emitting element to the sealing material is improved. However, if the refractive index of the sealing material is increased, The refractive index difference increases, and light is reflected at the interface between the sealing material and the outside. Therefore, there is a limit to improve the brightness by raising the refractive index of the sealing material.
It is an object of the present invention to provide an optical semiconductor device having excellent brightness, to provide an encapsulant (cured product) used in the optical semiconductor device, and to provide a curable composition for forming the cured product.
The present invention for achieving the above object is as follows.
(1) a polysiloxane (A) having an aryl group, a fluorine atom and at least two alkenyl groups per molecule, a polysiloxane (B) having at least two alkenyl groups and / or aryl groups per molecule and having no fluorine atom, A hydrogen siloxane (C) having at least two hydrogen atoms bonded to silicon atoms per molecule, and a catalyst (D) for hydrosilylation reaction.
[2] The curable composition according to the above [1], wherein the content of the polysiloxane (A) is 30 to 90% by weight based on the total amount of the polysiloxane (A) and the polysiloxane (B).
[3] The curable composition according to [1] or [2], wherein the polysiloxane (A) is a polysiloxane having a group represented by the following formula (1) bonded to a silicon atom in the main chain of the polysiloxane (A)
(In the formula (1), R 1 represents an alkanediyl group having 1 to 20 carbon atoms or a group formed by substituting a hydrogen atom of the alkanediyl group with a fluorine atom).
[4] A cured product obtained by curing the curable composition according to any one of [1] to [3].
[5] A photosemiconductor device having the cured product according to [4] above.
The curable composition of the present invention can form a cured product that can provide an optical semiconductor device having excellent brightness when used as an encapsulating material or the like. The optical semiconductor device having a cured product formed of the curable composition of the present invention as an encapsulating material has excellent brightness.
1 is a schematic view showing one specific example of a photosemiconductor device.
(Mode for carrying out the invention)
≪ Curable composition >
The curable composition of the present invention is a curable composition containing at least two alkenyl groups, aryl groups and a polysiloxane (A) having a fluorine atom per molecule, at least two alkenyl groups and an aryl group per molecule, A polysiloxane (B), a hydrogensiloxane (C) having at least two hydrogen atoms bonded to silicon atoms per molecule, and a catalyst (D) for hydrosilylation reaction.
In the present invention, "polysiloxane" means a compound having a molecular skeleton in which two or more siloxane units (Si-O) are bonded.
Polysiloxane (A)
The polysiloxane (A) is a polysiloxane having an aryl group, a fluorine atom and at least two alkenyl groups per molecule. The polysiloxane (A), together with the polysiloxane (B), is the main component of the composition and is cured by the hydrosilylation reaction with the hydrogensiloxane (C) to become the main component of the cured product.
Examples of the alkenyl group of the polysiloxane (A) include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, . Of these, a vinyl group, an allyl group and a hexenyl group are preferable.
The content of the alkenyl group in the polysiloxane (A) is preferably from 3 to 50 mol%, more preferably from 5 to 40 mol%, based on 100 mol% of all the Si atoms contained in the polysiloxane (A) Mol%, and more preferably 10 to 30 mol%. When the content of the alkenyl group is within the above range, the hydrosilylation reaction between the polysiloxane (A) and the polysiloxane (B) and the hydrogensiloxane (C) proceeds appropriately, and a cured product having a high strength is obtained.
Examples of the aryl group of the polysiloxane (A) include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Among them, a phenyl group is preferable. When the polysiloxane (A) has an aryl group, a characteristic that a high luminance is obtained when a cured product obtained from the present composition is used as an encapsulant of an LED is developed.
When the total number of Si atoms contained in the polysiloxane (A) is 100 mol%, the content of the aryl group in the polysiloxane (A) is preferably 30 to 120 mol%, more preferably 50 to 110 mol% %, More preferably 70 to 100 mol%. When the content of the aryl group is within the range of 30 to 120 mol%, a cured product having a high luminance and a high refractive index can be obtained from the composition.
The polysiloxane (A) has a fluorine atom. In this respect, the polysiloxane (A) is different from the polysiloxane (B) described later.
When the total number of Si atoms contained in the polysiloxane (A) is 100 mol%, the content of fluorine atoms in the polysiloxane (A) is preferably 1 to 60 mol%, more preferably 3 to 40 mol% %, More preferably 5 to 30 mol%. When the content of the fluorine atoms is within the above range, when the cured product obtained from the present composition is used as an encapsulating material for LED, a high luminance is exhibited.
The polysiloxane (A) is preferably a polysiloxane having a group represented by the following formula (1) bonded to a silicon atom in the main chain of the polysiloxane (A)
(In the formula (1), R 1 represents an alkanediyl group having 1 to 20 carbon atoms or a group formed by substituting a hydrogen atom of the alkanediyl group with a fluorine atom).
R 1 is an alkanediyl group having 1 to 20 carbon atoms in which the hydrogen atom may be substituted with a fluorine atom, that is, an alkanediyl group having 1 to 20 carbon atoms, or a group formed by substituting a hydrogen atom of the alkanediyl group with a fluorine atom. The number of carbon atoms of the alkanediyl group is more preferably 2 to 8.
As a method for producing the polysiloxane (A), for example, an alkenyl group, an aryl group, and an alkoxysilane having at least one of fluorine atoms are suitably used in combination, and Japanese Unexamined Patent Application Publication No. 6-9659, Japanese Unexamined Patent Application Publication No. 2003-183582, Japanese Unexamined Patent Application Publication No. 2007-008996, Japanese Unexamined Patent Application Publication No. 2007-106798, Japanese Unexamined Patent Publication No. 2007-169427, Japanese Unexamined Patent Application Publication No. 2010-059359, , A method of cohydrolyzing chlorosilane or alkoxysilane having an alkenyl group or an aryl group as each unit source, a method of equilibrating the cohydrolyzate with an alkali metal catalyst or the like, and the like.
Examples of the alkoxysilane having a fluorine atom include an alkoxysilane represented by the following formula (2).
In the formula (2), R 2 is a fluoroalkyl group in which a hydrogen atom of an alkyl group having 1 to 26, preferably 1 to 20 carbon atoms is partially or completely substituted with a fluorine atom, R 3 is a divalent group, - (CH 2 ) n - wherein n is an integer of 2 to 20, - (CH 2 ) n -X- (CH 2 ) p - (-X- is -O- or -C (O) O- (CH 2 ) q - (Q is a divalent group containing at least one oxygen atom, q is 2 or 3, and n is an integer of 0 to 2 and p is an integer of 5 to 25) 3), R 4 and R 5 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms, and r is 0, 1 or 2.
Examples of the alkoxysilane include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane, 3,3,3-trifluoropropyldimethylmethoxysilane, 4,4,4-trifluorobutyltrimethoxysilane, 4,4,4-trifluorobutyltriethoxysilane, 3,3,4 , 4,4-pentafluorobutyltrimethoxysilane, 3,3,4,4,4-pentafluorobutyltriethoxysilane, 3,3,4,4,5,5,6,6,7 , 7,8,8,8-tridecafluorooctyltrimethoxysilane, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooxane Heptadecafluorodecyltrimethoxysilane, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyltrimethoxysilane, 3 , 3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl triethoxysilane, 15- (trifluoro Pentadecyl-15- (trifluoroacetoxy) pentadecylmethyldiethoxysilane, and the like.
The polysiloxane (A) has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography usually in the range of 100 to 50000, and preferably in the range of 500 to 10000. When the weight average molecular weight of the polysiloxane (A) is within the above range, the sealant is easily handled when the sealant is produced using the composition, and the cured product obtained from the composition has sufficient strength as the optical semiconductor encapsulant.
The content of the polysiloxane (A) in the composition is preferably 30 to 90% by weight, more preferably 50 to 90% by weight, and even more preferably 50 to 90% by weight, based on the total amount of the polysiloxane (A) By weight is from 60 to 85% by weight. When the content of the polysiloxane (A) is within the above range, a high luminance is exhibited when the cured product obtained from the composition is used as an encapsulating material for LED.
Polysiloxane (B)
The polysiloxane (B) is a polysiloxane having at least two alkenyl groups and aryl groups per molecule and not having a fluorine atom. The polysiloxane (B), together with the polysiloxane (A), is the main component of the composition and is cured by the hydrosilylation reaction with the hydrogensiloxane (C) to become the main component of the cured product.
The alkenyl group of the polysiloxane (B) is the same as that of the alkenyl group described in the polysiloxane (A).
The aryl group of the polysiloxane (B) is the same as that of the aryl group described in the polysiloxane (A).
The polysiloxane (B) has no fluorine atom. In this respect, the polysiloxane (B) is different from the polysiloxane (A) described above.
The polysiloxane (B) has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography usually in the range of 100 to 50000, and preferably in the range of 500 to 10000. When the weight average molecular weight of the polysiloxane (B) is within the above range, the sealant is easily handled when the sealant is produced using the composition, and the cured product obtained from the composition has sufficient strength as the optical semiconductor encapsulant.
The polysiloxane (B) can be produced by a known method in the same manner as the polysiloxane (A), using an appropriate combination of an alkenyl group, an aryl group and an alkoxysilane having at least one fluorine atom.
Hydrogen siloxane (C)
The hydrogen siloxane (C) has at least two hydrogen atoms bonded to silicon atoms (hereinafter also referred to as silicon atom-bonded hydrogen) per molecule. The hydrogensiloxane (C) is a crosslinking agent for the polysiloxane (A) and the polysiloxane (B) and forms a cured product by hydrosilylation reaction with the polysiloxane (A) and the polysiloxane (B).
Hydrogen siloxane (C) is not particularly limited as long as it is a polysiloxane having at least two silicon atom-bonded hydrogen atoms per molecule, which is used as a crosslinking agent in a conventional hydrosilyl-based polysiloxane composition.
The hydrogensiloxane (C) can be produced, for example, by reacting an alkoxysilane such as phenyltrimethoxysilane or diphenyldimethoxysilane with a hydrogensiloxane such as 1,1,3,3-tetramethyldisiloxane by a known method In a suitable synthetic solvent.
The content of the hydrogen siloxane (C) in the curable composition of the present invention is preferably such that the molar ratio of the silicon atom-bonded hydrogen in the hydrogen siloxane (C) to the total amount of the alkenyl groups in the polysiloxane (A) 5, more preferably 0.5 to 2, and still more preferably 0.7 to 1.4. When the content of the hydrogensiloxane (C) is within the above range, the curing of the composition proceeds sufficiently, and the resulting cured product has sufficient heat resistance.
Hydrosilylation The reaction catalyst (D)
The catalyst (D) for the hydrosilylation reaction is a catalyst for the hydrosilylation reaction of the polysiloxane (A) and the polysiloxane (B) with the hydrogensiloxane (C).
The hydrosilylation reaction catalyst (D) can be used without particular limitation, as long as it is a catalyst that is used as a hydrosilylation reaction catalyst in a conventional hydrosilyl-based polysiloxane composition.
Specific examples of the hydrosilylation reaction catalyst (D) include platinum catalysts, rhodium catalysts and palladium catalysts. Among these, platinum-based catalysts are preferable from the viewpoint of promoting curing of the composition. Examples of the platinum-based catalyst include platinum-alkenylsiloxane complexes and the like. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl Cyclotetrasiloxane, and the like. Particularly, from the viewpoint of stability of the complex, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferable.
The content of the catalyst (D) for hydrosilylation reaction in the curable composition of the present invention is such that the hydrosilylation reaction between the polysiloxane (A) and the polysiloxane (B) and the hydrogensiloxane (C) proceeds practically.
As long as the object of the present invention is achieved, the curable composition of the present invention may contain, in addition to the above components, inorganic fillers such as fine particulate silica such as fumed silica and quartz powder, titanium oxide and zinc oxide, A retarder such as cyclotetramethyltetravinyltetrasiloxane, a diluent such as diphenylbis (dimethylvinylsiloxy) silane or phenyltris (dimethylvinylsiloxy) silane, a phosphor, a pigment, a flame retardant, a heat resistance agent, an antioxidant, And the like, and the like.
The curable composition of the present invention can be prepared by uniformly mixing the above components by a known method such as a mixer.
The viscosity of the curable composition of the present invention at 25 占 폚 is preferably 1 to 1000000 mPa 占 퐏, and more preferably 10 to 10000 mPa 占 퐏. When the viscosity is within this range, the operability of the composition is improved.
The curable composition of the present invention may be prepared as a single solution or divided into two solutions, and two solutions may be mixed at the time of use. If necessary, a small amount of a curing inhibitor such as acetylene alcohol may be added.
When the curable composition of the present invention is applied to a substrate, for example, in that it contains a polysiloxane (A) having a fluorine atom and a polysiloxane (B) having no fluorine atom in the curable composition of the present invention, (A) having a fluorine atom rather than the polysiloxane (B) having no fluorine atom is present on the air side due to the tension. It is presumed that a cured product of a multilayer structure having a layer containing a large amount of fluorine atoms on the air side is obtained by curing the coating film. That is, when the curable composition of the present invention is used, it is presumed that a cured product having a multilayer structure can be obtained by a single coating step. In this multi-layer structure, the refractive index is lowered in the layer closer to the air side due to the effect of the fluorine atoms which lower the refractive index. As a result, the refractive index difference between the air-side layer of the cured product and air is reduced. As a result, it is presumed that the optical semiconductor device having a cured product obtained from the curable composition of the present invention has excellent brightness.
A method of obtaining a cured product of a multilayer structure by repeating a coating step every time one layer is formed is (1) complicated and expensive; (2) when a composition for forming the second layer is applied on the first layer, There is a problem in that the coating property may be deteriorated depending on the surface tension of the composition and there is a possibility that a uniform coating film can not be formed. Particularly, since the surface tension of the liquid is greatly lowered in a composition containing fluorine, there is a high possibility that the fluorine-containing composition is likely to be aggregated at the time of coating and there is a possibility of bubbling. The curable composition of the present invention is excellent in that it is less likely to cause the above problems.
Further, in a conventional composition containing a fluorine atom-containing component and a fluorine atom-free component which form a cured product of a multi-layer structure, after a cured product is formed, It is conceivable to bleed out, and therefore problems such as (1) lack of curability and consequently insufficient crack resistance of the cured product, and (2) insufficient gas barrier property of the cured product are expected. On the other hand, the curable composition of the present invention is excellent in that it is less likely to cause such a problem.
<Hard goods>
A cured product is obtained by curing the curable composition of the present invention. When the semiconductor element is encapsulated with the curable composition of the present invention and cured, a cured product which is an encapsulating material is obtained.
Examples of the method for curing the curable composition of the present invention include a method in which the curable composition is coated on a substrate and then heated at 100 to 180 캜 for 1 to 13 hours.
As described above, it is assumed that the cured product obtained by curing the curable composition of the present invention has a multilayer structure. In the cured product formed by applying the curable composition of the present invention to a substrate and curing, a plurality of layers differing in the content ratio of the component derived from the polysiloxane (A) and the component derived from the polysiloxane (B) are formed. Specifically, a first layer having a low content of components derived from polysiloxane (A) and a high content ratio of components derived from polysiloxane (B) is formed on the substrate surface, and a content ratio of components derived from polysiloxane (A) And the second layer having a low content ratio of the polysiloxane (B) -derived component is formed on the first layer. That is, the concentration of fluorine atoms in the first layer formed on the substrate surface is low, and the concentration of fluorine atoms in the second layer formed on the first layer is high. When the cured product of the present invention has such a plurality of layers, it is presumed that a high-luminance optical semiconductor device can be obtained when the cured product is used as an encapsulating material for a semiconductor light emitting device.
<Optical Semiconductor Device>
The optical semiconductor device of the present invention has a cured product obtained by curing the above-mentioned curable composition. For example, the optical semiconductor device of the present invention has a semiconductor light emitting element and the cured product covering the semiconductor light emitting element. The optical semiconductor device of the present invention is obtained by covering the curable composition with a semiconductor light emitting element and curing the composition. The method of curing the curable composition is as described above.
Examples of the optical semiconductor device include an LED (Light Emitting Diode) and an LD (Laser Diode).
1 is a schematic view of one embodiment of the optical semiconductor device of the present invention. The optical semiconductor device 1 includes an
As described above, the optical semiconductor device having the cured product as a sealing material has a high luminance.
[Example]
1. Preparation of Curable Composition
1-1. Structural analysis
The structure of the synthesized compound was calculated by 29 Si NMR and 1 H NMR.
1-2. Weight average molecular weight
The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions, and the polystyrene reduced value was obtained.
Apparatus: HLC-8120C (manufactured by Toso Co., Ltd.)
Column: TSK-gel Multipore HXL-M (manufactured by Tosoh Corporation)
Eluent: THF, flow rate 0.5 mL / min, loading 5.0%, 100 μL
1-3. Synthesis of each component
The siloxane units exemplified below are represented by the following symbols:
M (Vi): (ViMe 2 SiO 1/2)
M (H): (HMe 2 SiO 1/2)
D (Ph): (Ph 2 SiO 2/2)
D (PhMe): (PhMeSiO 2 /2)
D (Ep): (MeEpSiO 2 /2)
T (Ph): (PhSiO 3 /2)
T (F): (CF 3
(Me represents a methyl group, Ph represents a phenyl group, Vi represents a vinyl group, and Ep represents an epoxy 3-glycidoxypropyl group).
[Synthesis Example 1] Synthesis of polysiloxane (A1)
112 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 476 g of phenyltrimethoxysilane, 293 g of diphenyldimethoxysilane, 262 g of trifluoropropyltrimethoxysilane, 236 g of water , 0.9 g of trifluoromethanesulfonic acid and 460 g of toluene were placed, and the mixture was heated under reflux for 1 hour. Subsequently, 0.6 g of potassium hydroxide was added, and the mixture was refluxed for 5 hours. After neutralization with acetic acid, water was filtered to obtain polysiloxane (A1) containing 20 mol of M (Vi), 40 mol of T (Ph), 20 mol of D (Ph) and 20 mol of T (F). The weight average molecular weight of the polysiloxane (A1) was 1,700.
[Synthesis Example 2] Synthesis of polysiloxane (B1)
The reaction vessel was charged with 37.3 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 234 g of phenyltrimethoxysilane, 97.7 g of methylphenyldimethoxysilane, 55 g of water, 0.3 g of trifluoromethanesulfonic acid, 146 g of toluene was placed, and the mixture was heated under reflux for 1 hour. Then, 4.4 g of 3-glycidoxypropylmethyldimethoxysilane and 0.3 g of potassium hydroxide were added, and the mixture was heated under reflux for 5 hours. The mixture was neutralized with an acid and subjected to liquid fraction extraction using toluene and water to obtain a polysiloxane B1 containing 20 mol of M (Vi), 59 mol of T (Ph), 20 mol of D (PhMe) and 1 mol of D (Ep) . The polysiloxane (B1) had a weight average molecular weight of 1,600.
[Synthesis Example 3] Synthesis of polysiloxane (B2)
149 g of phenyltrimethoxysilane, 183 g of diphenyldimethoxysilane, 0.6 g of trifluoromethanesulfonic acid and 653 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added to the reaction vessel, After adding 40 g of acetic acid, the mixture was heated at 50 DEG C for 3 hours. After heating, the liquid was subjected to liquid extraction using toluene and water to obtain a polysiloxane (B2) containing 70 mol of M (Vi), 15 mol of T (Ph) and 15 mol of D (Ph). The polysiloxane (B2) had a weight average molecular weight of 500.
[Synthesis Example 4] Synthesis of polysiloxane (B3)
82 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 525 g of phenyltrimethoxysilane, 143 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were placed in a reaction vessel and heated for 1 hour Refluxed. Subsequently, 314 g of 3-glycidoxypropylmethyldimethoxysilane, 130 g of water and 0.5 g of potassium hydroxide were added, and the mixture was refluxed for 1 hour. The mixture was neutralized with an acid and subjected to liquid separation using toluene and water to obtain a polysiloxane (B3) containing 25 mol of M (Vi), 75 mol of T (Ph) and 40 mol of D (Ep). The weight average molecular weight of the polysiloxane (B3) was 2,800.
[Synthesis Example 5] Synthesis of polysiloxane (C1)
220 g of diphenyldimethoxysilane, 0.6 g of trifluoromethanesulfonic acid and 60.5 g of 1,1,3,3-tetramethyldisiloxane were placed in a reaction vessel, and 108 g of acetic acid was added dropwise over 30 minutes while stirring at room temperature. After completion of dropwise addition, the mixed solution was heated at 50 캜 for 3 hours while stirring, and then heated at 80 캜 for 2 hours. After heating, the mixture was subjected to liquid separation using toluene and water to obtain a polysiloxane (C1) represented by the following formula (3).
[Synthesis Example 6] Synthesis of polysiloxane (C2)
40 g of phenyltrimethoxysilane, 0.06 g of trifluoromethanesulfonic acid and 20.3 g of 1,1,3,3-tetramethyldisiloxane were placed in a reaction vessel, and while stirring at room temperature, 54 g of acetic acid was added dropwise over 30 minutes. After completion of dropwise addition, the mixture was heated at 50 캜 for 3 hours while stirring. After heating, the mixture was subjected to liquid separation using toluene and water to obtain a polysiloxane (C2) containing 60 mol of M (H) and 40 mol of T (Ph). The weight average molecular weight of the polysiloxane (C2) was 800.
2. Preparation of a curable composition
[Examples 1 to 6 and Comparative Examples 1 to 3]
The components shown in Table 1 below were mixed in the amounts shown in Table 1 to obtain the curable compositions of Examples 1 to 6 and Comparative Examples 1 to 3. &Quot; Parts " in Table 1 indicate parts by weight. The molar ratio of the silicon atom-bonded hydrogen atoms in the compound (A) to the alkenyl group in the polysiloxane (B) is all 1.05. Details of each component in Table 1 are as follows.
(D1): complex of platinum with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (amount of platinum metal: 4% by weight)
Compound (E1): Ethynyl cyclohexanol
Compound (E2): 3-methyl-1-butyn-3-ol
Compound (E3): 3,5-Dimethyl-1-hexyn-3-ol
3. Evaluation of the curable composition
The curable compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were evaluated by the following methods (3-1) to (3-5). The evaluation results are shown in Table 1.
3-1. Luminance increase rate
The curable composition is applied to a package of a surface mounting type (top view type, the semiconductor
The radial flux measurement of the sample for evaluation was carried out using a radiant flux measuring device (MCPD-3700, instantaneous multi-photometry detector, Φ300 mm integral sphere (hemispherical integral sphere)). The rate of increase of the curable composition of Comparative Example 1 from the ratio of the curable composition in the radial direction was evaluated by calculating the percentage of the evaluation sample in the radial direction of the evaluation sample with respect to the initial radial flux measured by energizing the package prior to the application of the sealing material.
3-2. After high temperature and high humidity test crack tolerance
2 " Preparation of Curable Composition "was introduced into an LED package (surface mounting type, top view type), and heated at 100 占 폚 for 1 hour and then at 150 占 폚 for 5 hours to obtain a sample in which a cured product was formed in the LED package Quot; evaluation sample 1 "). The obtained evaluation sample 1 was placed in a thermo-hygrostat (SP-3KP, trade name, manufactured by Espace Co., Ltd.) and kept for 8 hours under the atmosphere of 85 ° C and 85% RH. Then, a solder reflow apparatus (manufactured by Senju Metal Industry Co., , Trade name " STR-2010 ") at 260 占 폚 for 20 seconds (high temperature and high humidity test). The presence or absence of cracks in the cured product after the high temperature and high humidity test was observed with an optical microscope to evaluate the crack resistance after the high temperature and high humidity test. Evaluation was made based on the following criteria.
A: None of the 10 samples were cracked.
B: Cracks were observed in 1 to 4 samples out of 10 samples.
C: There were cracks in more than 5 samples out of 10 samples.
3-3. Gas for hydrogen sulphide Barrier property
2 " Preparation of Curable Composition "was introduced into an LED package (surface mounting type, top view type), and heated at 100 占 폚 for 1 hour and then at 150 占 폚 for 5 hours to obtain a sample in which a cured product was formed in the LED package Quot;
A: There was no color change of silver electrode before and after heating.
B: After heating, the silver electrode portion became yellowish yellow.
C: After heating, the silver electrode portion became black.
3-4. Hardness
2 " Preparation of Curable Composition " The curable composition obtained above was coated on a flat plate of Teflon with a 2 mm thick frame so as to have a height of a frame, and heated in a hot air circulating oven at 150 캜 for 5 hours, 5 mm, and a height of 1 mm. The hardness of the cured product was measured by a Type D durometer specified in JIS K6253.
3-5. Viscosity
The curable composition was measured at 25 캜 using an E-type viscometer.
1: optical semiconductor device
2: Semiconductor light emitting element
3: Reflector
4: Encapsulation material
5: Particle
6: Electrode
7: Wire
Claims (5)
Wherein the content of the polysiloxane (A) is 30 to 90% by weight based on the total amount of the polysiloxane (A) and the polysiloxane (B).
Wherein the polysiloxane (A) is a polysiloxane having a group represented by the following formula (1) bonded to a silicon atom in the main chain of the polysiloxane (A):
(In the formula (1), R 1 represents an alkanediyl group having 1 to 20 carbon atoms or a group formed by substituting a hydrogen atom of the alkanediyl group with a fluorine atom).
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013045254 | 2013-03-07 | ||
JPJP-P-2013-045254 | 2013-03-07 | ||
JPJP-P-2013-234025 | 2013-11-12 | ||
JP2013234025A JP5858027B2 (en) | 2013-03-07 | 2013-11-12 | Curable composition, cured product, and optical semiconductor device |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20140110718A KR20140110718A (en) | 2014-09-17 |
KR101733960B1 true KR101733960B1 (en) | 2017-05-10 |
Family
ID=51756668
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1020140001912A KR101733960B1 (en) | 2013-03-07 | 2014-01-07 | Curable composition, cured product and photo-semiconductor device |
Country Status (2)
Country | Link |
---|---|
KR (1) | KR101733960B1 (en) |
TW (1) | TWI582169B (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003192900A (en) * | 2001-11-06 | 2003-07-09 | Natl Starch & Chem Investment Holding Corp | Fluid-resistant silicone encapsulant |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101880396B (en) * | 2010-06-03 | 2011-11-23 | 杭州师范大学 | Preparation method of organic silicon rubber for encapsulating LED being convenient for vacuum defoamation |
JP5603837B2 (en) * | 2011-06-30 | 2014-10-08 | 信越化学工業株式会社 | Addition-curing silicone composition and optical element |
-
2014
- 2014-01-07 KR KR1020140001912A patent/KR101733960B1/en active IP Right Grant
- 2014-02-18 TW TW103105182A patent/TWI582169B/en active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003192900A (en) * | 2001-11-06 | 2003-07-09 | Natl Starch & Chem Investment Holding Corp | Fluid-resistant silicone encapsulant |
Also Published As
Publication number | Publication date |
---|---|
TWI582169B (en) | 2017-05-11 |
KR20140110718A (en) | 2014-09-17 |
TW201434991A (en) | 2014-09-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105121556B (en) | Curable silicone composition, cured product thereof, and optical semiconductor device | |
TWI661007B (en) | Curable silicone composition, curable hot-melt silicone, and optical device | |
JP6915954B2 (en) | Curable silicone compositions, cured products thereof, and opto-semiconductor devices | |
KR101472829B1 (en) | Curable composition, cured product, photo-semiconductor device, and polysiloxane | |
KR20160104559A (en) | Addition-curable silicone resin composition and die attach material for optical semiconductor device | |
JP2013139547A (en) | Curable composition, cured product, and optical semiconductor device | |
JP5858027B2 (en) | Curable composition, cured product, and optical semiconductor device | |
JP2014125624A (en) | Low gas-permeable silicone resin composition and optical semiconductor device | |
KR20180127647A (en) | Curable resin composition, cured product thereof, and semiconductor device | |
CN103059568A (en) | Silicone resin sheet, cured silicone sheet, light emitting diode device and producing method thereof | |
WO2015178475A1 (en) | Branched-chain polyorganosiloxycyl alkylene, method for producing same, curable resin composition, and semiconductor device | |
KR20180113602A (en) | Curable resin composition, cured product thereof, and semiconductor device | |
JP5696798B2 (en) | Polysiloxane | |
JP5660145B2 (en) | Curable composition, cured product, and optical semiconductor device | |
KR101733960B1 (en) | Curable composition, cured product and photo-semiconductor device | |
KR20130062869A (en) | Curable composition, cured product, and optical semiconductor device | |
CN114181535B (en) | Curable organopolysiloxane composition and preparation method thereof | |
JP7360910B2 (en) | A curable composition and a semiconductor device using the composition as a sealant. | |
TWI829640B (en) | Curable silicone composition and optical semiconductor device | |
KR101594343B1 (en) | Curable composition and method for producing thereof, cured product, and optical semiconductor device | |
JP2022104216A (en) | Curable silicone composition, sealant, and photo-semiconductor device | |
KR20130112761A (en) | Curable composition, cured product and photo-semiconductor device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
E902 | Notification of reason for refusal | ||
E701 | Decision to grant or registration of patent right | ||
GRNT | Written decision to grant |