KR20130112761A - Curable composition, cured product and photo-semiconductor device - Google Patents
Curable composition, cured product and photo-semiconductor device Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C—CHEMISTRY; METALLURGY
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- 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
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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- H—ELECTRICITY
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- 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
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- 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
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- 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
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
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- 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
Solution: A curable composition comprising a compound (A) represented by the following formula (1), a polysiloxane (B) represented by the following formula (2), and a catalyst for hydrosilylation reaction (C):
(Wherein n represents an integer of 1 or more; R 1 and R 2 represent an alkyl group having 1 to 4 carbon atoms; Ar represents an aryl group);
(Wherein, R 3 , R 5 and R 6 each independently represent an organic group; provided that at least two of all R 3 and R 6 are alkenyl groups, and R 5 is a silicon atom to which R 5 is bonded); When another R 5 to be bonded is an aryl group, it is not an alkyl group having 1 to 4 carbon atoms and an aryl group; R 4 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group, and at least one of R 4 is an aryl group X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; a, c, e, and f each independently represent an integer of 0 or more; b and d each independently represent an integer of 1 or more; When 0, d is an integer of 2 or more).
(Effect) The curable composition of this invention has high resistance to a thermal shock, etc., and can form the hardened | cured material which is hard to produce a crack even in an excessive environment.
Description
The present invention relates to a curable composition, a cured product, and an optical semiconductor device.
Silicone resins are widely used as sealing materials for semiconductor devices including LED devices. The silicone resin is excellent in heat resistance, transparency, and discoloration resistance compared to the epoxy resins conventionally used as an encapsulating material, and has low mechanical properties such as bending strength, and thus thermal shock and high temperature generated when the LED is energized or lit. There is a problem that cracks are likely to occur due to a high humidity environment or the like.
As a technique for preventing the occurrence of such a crack, Patent Literature 1 has at least two silicon atom-bonded alkenyl groups in one molecule and has a branched organopolysiloxane having a specific siloxane unit, and at least two silicon in one molecule. An organopolysiloxane composition having an atom-bonded hydrogen atom and containing a linear organohydrogenpolysiloxane having a viscosity at 25 ° C. of 1000 mPa · s or less and an addition reaction catalyst is disclosed.
An object of this invention is to provide the curable polysiloxane composition which has high resistance to thermal shock, high temperature, high humidity conditions, etc., and can form hardened | cured material which is hard to generate | occur | produce under severe environment.
This invention is a curable composition containing the compound (A) represented by following formula (1), the polysiloxane (B) represented by following formula (2), and the catalyst for hydrosilylation reaction (C):
(Wherein n represents an integer of 1 or more; R 1 and R 2 represent an alkyl group having 1 to 4 carbon atoms; Ar represents an aryl group);
(Wherein, R 3 , R 5 and R 6 each independently represent an organic group; provided that at least two of all R 3 and R 6 are alkenyl groups, and R 5 is a silicon atom to which R 5 is bonded); When another R 5 to be bonded is an aryl group, it is not an alkyl group having 1 to 4 carbon atoms and an aryl group; R 4 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group, and at least one of R 4 is an aryl group X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; a, c, e, and f each independently represent an integer of 0 or more; b and d each independently represent an integer of 1 or more; When 0, d is an integer of 2 or more).
In the curable composition, it is preferable that R 4 in the formula (2) is an aryl group.
Another invention is hardened | cured material obtained by hardening | curing the said curable composition.
Another invention is an optical semiconductor device having the cured product.
The curable composition of this invention has high resistance to thermal shock, high temperature, high humidity conditions, etc., and can form the hardened | cured material which is hard to produce a crack even in severe environment.
Therefore, the optical semiconductor device obtained by covering a semiconductor light emitting element with the hardened | cured material obtained from this curable composition becomes an optical semiconductor device excellent in reliability.
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 this invention contains the compound (A) represented by following formula (1), the polysiloxane (B) represented by following formula (2), and the catalyst for hydrosilylation reaction (C):
(Wherein n represents an integer of 1 or more; R 1 and R 2 represent an alkyl group having 1 to 4 carbon atoms; Ar represents an aryl group);
(R 3, R 5 and R 6 each independently represents an organic group; also bonded to the end, all of R 3 and R 6, at least two of the pieces is an alkenyl group, R 5 is a silicon atom to which they bind, that R 5 When another R 5 is an aryl group, it is not an alkyl group or an aryl group having 1 to 4 carbon atoms, R 4 each independently represents an alkyl group or an aryl group having 1 to 4 carbon atoms, and at least one of R 4 represents an aryl group; X Represents a hydrogen atom or an alkyl group of 1 to 3 carbon atoms; a, c, e and f each independently represent an integer of 0 or more; b and d each independently represent an integer of 1 or more; provided that when a is 0 , d is an integer of 2 or more).
In addition, in this invention, "polysiloxane" means the siloxane which has the molecular skeleton which two or more siloxane units (Si-O) couple | bonded.
Compound (A)
Compound (A) is a compound represented by said formula (1). Compound (A) is linear polysiloxane and has two silicon atom bonded hydrogen atoms per molecule. Silicon atom bonded hydrogen atoms are present in the siloxane units at both ends of the molecule. Compound (A) is a crosslinking agent with respect to polysiloxane (B), and forms hardened | cured material by hydrosilylation reaction with polysiloxane (B).
R <1> and R <2> represents a C1-C4 alkyl group. That is, compound (A) is a hydrogensiloxane which has one or more siloxane units of the D unit which the aryl group and the C1-C4 alkyl group couple | bonded with the silicon atom. Compound (A) having such a D unit siloxane unit is more than a hydrogen siloxane containing a D unit siloxane unit having two aryl groups or a hydrogen siloxane containing a D unit siloxane unit having two alkyl groups. The crystallinity is lowered. For this reason, the hardened | cured material obtained from the curable composition obtained by using a compound (A) and the following polysiloxane (B) together becomes a partially flexible structure, has high resistance to thermal shock, etc., and it becomes difficult to produce a crack.
Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group and tert-butyl group. Among these, methyl group is preferable. Do.
As an aryl group, heteroaryl groups, such as aromatic hydrocarbon groups, such as a phenyl group and a tolyl group, thienyl group, and pyridyl, are mentioned. Moreover, the group formed by substituting hydrogen atoms of groups, such as a phenyl group previously, by groups, such as a halogen atom and an alkyl group, may be sufficient. In the case where n in Formula (1) is an integer of 2 or more, n Ar in Formula (1) may be the same or different aryl groups.
In said formula (1), n represents the integer of 1 or more, Preferably it is an integer of 1-3.
Compound (A) reacts alkoxysilanes, such as methylphenyldimethoxysilane and diphenyldimethoxysilane, and hydrogensiloxane, such as 1,1,3,3- tetramethyldisiloxane, by a well-known method, for example. Can be obtained.
As content of the compound (A) in the curable composition of this invention, it is preferable that it is a quantity whose molar ratio of the silicon atom bond hydrogen atom amount in a compound (A) with respect to the amount of alkenyl groups in a polysiloxane (B) becomes 0.1-5, and more Preferably it is 0.5-2, More preferably, it is the quantity becoming 0.7-1.4. When content of a compound (A) is in the said range, it has high resistance to a thermal shock, etc., the hardened | cured material which a crack does not produce easily becomes easy, and hardening of a composition advances enough.
Polysiloxane (B)
Polysiloxane (B) is polysiloxane represented by said formula (2). Polysiloxane (B) is a main component of this composition, it hardens by hydrosilylation reaction with a compound (A), and becomes a main body of hardened | cured material.
In said formula (2), R <3> , R <5> and R <6> respectively independently represent an organic group. Three R <3> contained in one siloxane unit may respectively be a different organic group, two may be the same organic group, the other may be a different organic group, and all three may be the same organic group. In addition, when a is an integer of 2 or more, the some siloxane unit containing R <3> may be the same respectively, may differ, respectively, some of them may be the same, and the remainder may differ from it. Two R 5 contained in one siloxane unit may be a different organic group, or may be the same organic group. In addition, when c is an integer of 2 or more, the some siloxane units containing R <5> may be the same respectively, may differ, respectively, some of them may be the same, and the remainder may differ from it. When d is an integer of 2 or more, the some siloxane unit containing R <6> may be the same respectively, may differ, respectively, some of them may be the same, and the remainder may differ from it.
As said organic group, an alkyl group, an alkenyl group, an aryl group, etc. are mentioned.
As an alkyl group, Preferably, they are a C1-C4 alkyl group, A methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, etc. are mentioned. Among these, a methyl group is preferable.
As an alkenyl group, a vinyl group, an allyl group, a propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, heptenyl group, hexenyl group, cyclohexenyl group, etc. are mentioned, for example. Among these, vinyl group, allyl group, and hexenyl group are preferable.
As an aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned, for example, A phenyl group is preferable among these.
The organic group may be a group containing an epoxy group. When polysiloxane (B) has a group containing an epoxy group as an organic group, it is hard to inhibit the hydrosilylation reaction which arises when hardening a curable composition, and hardened | cured material with high adhesiveness to a board | substrate, metal wiring, etc. can be formed. As group which has the said epoxy group, For example, glycidoxy group, such as glycidoxy group and 3-glycidoxy propyl group, and 3, 4- epoxy cyclopentyl group, 3, 4- epoxy cyclohexyl group, 2- And epoxy cycloalkyl groups such as (3,4-epoxycyclopentyl) ethyl group and 2- (3,4-epoxycyclohexyl) ethyl group.
However, at least 2 of all R <3> and R <6> contained in 1 molecule is an alkenyl group, Preferably 2-4 are alkenyl groups. That is, the polysiloxane (B) has two or more alkenyl groups per molecule. At least two of R 3 is an alkenyl group, all of R 6 may be groups other than alkenyl groups, all of R 3 are groups other than alkenyl groups, and at least two of R 6 may be alkenyl groups, and in R 3 One or more may be an alkenyl group, and one or more of R <6> may be an alkenyl group.
In addition, R 5 is, that when R 5 is another one R 5 aryl date that bind to the silicon atom to which they bind, and are not an alkyl group and an aryl group having 1 to 4 carbon atoms. That is, the siloxane unit containing R 5 is not the same as the siloxane unit containing R 4 .
In said Formula (2), two R <4> contained in one siloxane unit each independently represents a C1-C4 alkyl group or an aryl group, and at least 1 of R <4> represents an aryl group. When b is an integer of 2 or more, the some siloxane unit containing R <4> may be the same respectively, may differ, respectively, some of them may be the same, and the remainder may differ from it. That is, the polysiloxane (B) is a siloxane unit containing R 4 , and has at least one D unit having an aryl group and an alkyl group having 1 to 4 carbon atoms bonded to a silicon atom, or only a D unit having two aryl groups bonded to a silicon atom. It has one or more, or has one or more D units which the aryl group and the C1-C4 alkyl group couple | bonded with the silicon atom, and has one or more D units which two aryl groups couple | bonded with the silicon atom. By using together the polysiloxane (B) which has such a siloxane unit of D unit, and the said compound (A), it becomes possible to obtain the curable composition which has high resistance to a thermal shock, etc., and can form the hardened | cured material which a crack does not produce easily.
In addition, if R 4 is an aryl group, that is, if the polysiloxane (B) has only a D unit in which two aryl groups are bonded to a silicon atom as the siloxane unit containing R 4 , cracks are less likely to occur, and further It is preferable at the point which can form hardened | cured material with high gas barrier property.
Examples of the alkyl group having 1 to 4 carbon atoms represented by R 4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group and tert-butyl group, and the like. Especially, a methyl group is preferable.
As an aryl group which R <4> represents, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned, Among these, a phenyl group is especially preferable.
X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
a, c, e and f each independently represent an integer of 0 or more. b and d each independently represent an integer of 1 or more. However, when a is 0, d is an integer of 2 or more. Since d is an integer of 1 or more, since the polysiloxane (B) necessarily has a siloxane unit of T unit, it has a branched structure. Even if polysiloxane which does not have a branched structure and a compound (A) is used together, a composition is hard to harden | cure. Moreover, even when the composition is hardened | cured, the hardened | cured material obtained does not have crack resistance.
a becomes like this. Preferably it is 0-5, More preferably, it is 1-3. b becomes like this. Preferably it is 1-5, More preferably, it is 1-3. c becomes like this. Preferably it is 0-3, More preferably, it is 0-1. d becomes like this. Preferably it is 1-9, More preferably, it is 4-7. e becomes like this. Preferably it is 0-5, More preferably, it is 0-1.
When content of the polysiloxane (B) contained in the curable composition of this invention makes the sum total of (A) component, (B) component, and (C) component contained in this composition 100 mass%, Preferably it is 30- It is 95 mass%, More preferably, it is 40-90 mass%, More preferably, it is 50-80 mass%. When content of polysiloxane (B) is in the said range, it has high resistance to a thermal shock, etc., the hardened | cured material which is hard to produce a crack becomes easy to form, and hardening of a composition advances enough.
It is preferable that the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography of polysiloxane (B) exists in the range of 100-500000, and it is more preferable to exist in the range of 500-5000. The detail of the measurement conditions by gel permeation chromatography is as having described in the Example. When the weight average molecular weight of polysiloxane (B) is in the said range, it is easy to handle when manufacturing a sealing material using this composition, and the hardened | cured material obtained from this composition has sufficient material strength and a characteristic as an optical semiconductor sealing material.
As a manufacturing method of polysiloxane (B), Unexamined-Japanese-Patent No. 6-9659, Unexamined-Japanese-Patent No. 2003-183582, Unexamined-Japanese-Patent No. 2007-008996, Unexamined-Japanese-Patent No. 2007-106798, Unexamined-Japanese-Patent No. Known methods described in 2007-169427 and Japanese Unexamined Patent Publication No. 2010-059359 and the like, for example, a method of cohydrolyzing chlorosilanes or alkoxysilanes serving as unit units, or a cohydrolyzate of an alkali metal The method of equilibrating reaction with a catalyst, etc. are mentioned.
Hydrosilylation Reaction Catalyst (C)
The catalyst for hydrosilylation reaction (C) is a catalyst for hydrosilylation reaction of compound (A) and polysiloxane (B).
The catalyst for hydrosilylation reaction (C) can be used without particular limitation as long as it is a catalyst used as a catalyst for hydrosilylation reaction in the conventional hydrosilylation polysiloxane composition.
Specific examples of the catalyst for hydrosilylation reaction (C) include a platinum catalyst, a rhodium catalyst and a palladium catalyst. Among them, a platinum catalyst is preferable from the viewpoint of promoting the curing of the present composition. As a platinum type catalyst, a platinum-alkenylsiloxane complex etc. are mentioned, for example. As the alkenylsiloxane, for example, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl Cyclotetrasiloxane, and the like. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferable from the viewpoint of the stability of the complex.
The content of the catalyst for hydrosilylation reaction (C) in the curable composition of the present invention is an amount to which the hydrosilylation reaction between the compound (A) and the polysiloxane (B) proceeds in reality.
As long as the objective of this invention is achieved, the curable composition of this invention is inorganic fillers, such as particulate silica, such as fumed silica and quartz powder, titanium oxide, and zinc oxide, cyclone, as needed other than the said component, as needed. -Retarders such as tetramethyltetravinyl tetrasiloxane, diluents such as diphenylbis (dimethylvinylsiloxy) silane and phenyltris (dimethylvinylsiloxy) silane, phosphors, pigments, flame retardants, heat resistant agents, antioxidants and the like can do.
The curable composition of this invention can be prepared by mixing each said component uniformly by well-known methods, such as a mixer.
As viscosity at 25 degrees C of the curable composition of this invention, Preferably it is 1-1 million mPa * s, More preferably, it is 10-10000 mPa * s. If the viscosity is within this range, the operability of the present composition is improved.
The curable composition of this invention can also be prepared as one liquid, can divide into two liquids, and can also mix and use two liquids at the time of use. As needed, you may add a small amount of hardening inhibitors, such as acetylene alcohol.
<Cured product>
A cured product is obtained by curing the curable composition of the present invention. When sealing a semiconductor element with the curable composition of this invention, and hardening it, the hardened | cured material which is a sealing material is obtained.
As a method of hardening the curable composition of this invention, after apply | coating a curable composition on a board | substrate, the method of heating at 100-180 degreeC for 1 to 13 hours, etc. are mentioned, for example.
As mentioned above, the hardened | cured material obtained by hardening | curing the curable composition of this invention has high resistance to a thermal shock, etc., and it is hard to generate a crack even in an extreme environment.
<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 for curing the curable composition is as described above.
As an optical semiconductor device, LED (Light Emitting Diode), LD (Laser Diode), etc. are mentioned.
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 mentioned above, since the hardened | cured material obtained by hardening | curing the curable composition of this invention is hard to generate | occur | produce a crack under severe environment, the optical semiconductor device which has the said hardened | cured material as a sealing material is a condition in which thermal shock is applied, but high temperature. It can be used also under high humidity conditions.
(Example)
1. Preparation of Curable Composition
1-1. Structural analysis
The structure of the synthesized compound was calculated by 29 Si NMR and 13 C NMR.
1-2. Weight average molecular weight
The weight average molecular weight (Mw) was measured on the following conditions by gel permeation chromatography (GPC), and it calculated | required as polystyrene conversion value.
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 listed below are represented by the following symbols:
M (Vi): (ViMe 2 SiO 1/2)
D (MePh): (MePhSiO 2 /2)
D (MeEp): (MeEpSiO 2 /2)
D (Ph): (Ph 2 SiO 2/2)
T (Ph): (PhSiO 3 /2)
(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 Compound (A1)
455 g of methylphenyldimethoxysilane, 0.1 g of trifluoromethanesulfonic acid, and 336 g of 1,1,3,3-tetramethyldisiloxane were added to the reaction vessel, followed by addition of 180 g of acetic acid, followed by reaction at 50 ° C for 3 hours. After completion | finish of reaction, liquid-liquid extraction was carried out using toluene and water, and the compound (A1) shown below was obtained.
Synthesis Example 2 Synthesis of Compound (A2)
300 g of methylphenyldimethoxysilane, 0.1 g of trifluoromethanesulfonic acid, and 450 g of 1,1,3,3-tetramethyldisiloxane were added to the reaction vessel, and then 100 g of acetic acid was added, followed by reaction at 50 ° C for 3 hours. After completion | finish of reaction, liquid-liquid extraction was carried out using toluene and water, and the compound (A2) shown below was obtained.
Synthesis Example 3 Synthesis of Compound (A3)
656 g of methylphenyldimethoxysilane, 0.1 g of trifluoromethanesulfonic acid, and 188 g of 1,1,3,3-tetramethyldisiloxane were added to the reaction vessel, and then 280 g of acetic acid was added, followed by reaction at 50 ° C for 3 hours. After completion | finish of reaction, liquid-liquid extraction was carried out using toluene and water, and the compound (A3) shown below was obtained.
Synthesis Example 4 Synthesis of Compound (D1)
403 g of diphenyldimethoxysilane, 0.1 g of trifluoromethanesulfonic acid, and 450 g of 1,1,3,3-tetramethyldisiloxane were added to the reaction vessel, and then 130 g of acetic acid was added, followed by reaction at 50 ° C for 3 hours. After completion | finish of reaction, liquid-liquid extraction was carried out using toluene and water, and the compound (D1) shown below was obtained.
Synthesis Example 5 Synthesis of Compound (D2)
403 g of diphenyldimethoxysilane, 40 g of dimethoxydimethylsiloxane, 0.1 g of trifluoromethanesulfonic acid, 450 g of 1,1,3,3-tetramethyldisiloxane were added to the reaction vessel, and then 130 g of acetic acid was added, followed by 50 ° C. Reaction was carried out for 3 hours. After completion | finish of reaction, liquid-liquid extraction was carried out using toluene and water, and the compound (D2) shown below was obtained.
Synthesis Example 6 Synthesis of Polysiloxane (B1)
186 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 594 g of phenyltrimethoxysilane, 182 g of methylphenyldimethoxysilane, 180 g of water, 0.8 g of trifluoromethanesulfonic acid and 650 g of toluene Was added and heated to reflux for 1 hour. Subsequently, 1 g of 3-glycidoxypropylmethyldimethoxysilane and 0.6 g of potassium hydroxide were added, and the mixture was heated to reflux for 5 hours. After neutralizing with an acid, water washing was performed to obtain polysiloxane (B1) containing 60 mol of T (Ph), 20 mol of D (MePh), and 0.1 mol of D (MeEp) with respect to 20 mol of M (Vi). The weight average molecular weight of polysiloxane (B1) was 1,400.
Synthesis Example 7 Synthesis of Polysiloxane (B2)
186 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 595 g of phenyltrimethoxysilane, 244 g of diphenyldimethoxysilane, 200 g of water, 0.8 g of trifluoromethanesulfonic acid and toluene 700 g was added and it heated and refluxed for 1 hour. Then, 0.6 g of potassium hydroxide was added and refluxed for 5 hours. After neutralization with acetic acid, water washing was performed to obtain polysiloxane (B2) containing 60 mol of T (Ph) and 20 mol of D (Ph) with respect to 20 mol of M (Vi). The weight average molecular weight of polysiloxane (B2) was 1,500.
Synthesis Example 8 Synthesis of Compound (D3)
183 g of diphenyldimethoxysilane, 0.6 g of trifluoromethanesulfonic acid, and 140 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added to the reaction vessel, and then 50 g of acetic acid was added thereto. It was made to react at 3 degreeC. After completion | finish of reaction, liquid-liquid extraction was carried out using toluene and water, and the compound (D3) shown below was obtained.
Synthesis Example 9 Synthesis of Polysiloxane (B3)
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 reacted at 50 ° C for 3 hours. After completion | finish of reaction, liquid-liquid extraction was carried out using toluene and water, and polysiloxane (B3) containing 15 mol of T (Ph) and 15 mol of D (Ph) was obtained with respect to 70 mol of M (Vi). The weight average molecular weight of polysiloxane (B3) was 500.
2. Preparation of a curable composition
[Examples 1 to 5 and Comparative Examples 1 to 3]
The components shown in following Table 1 were mixed by the compounding quantity shown in Table 1, and the curable compositions of Examples 1-5 and Comparative Examples 1-3 were obtained. "Part" in Table 1 represents a mass part. In addition, the molar ratio of the silicon atom bonded hydrogen atom amount in a compound (A) with respect to the amount of alkenyl groups in polysiloxane (B) is all 1.05. In addition, the detail of each component of Table 1 is as follows.
Catalyst for hydrosilylation reaction (C1): A complex of platinum with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (4 mass% of platinum metal)
Compound (D4): Cyclo-tetramethyltetravinyltetrasiloxane
Compound (D5): Diphenylbis (dimethylvinylsiloxy) silane
Compound (D6): Phenyltris (dimethylvinylsiloxy) silane
3. Evaluation of the curable composition
About the curable composition of Examples 1-5 and Comparative Examples 1-3, it evaluated by the method of (3-1)-(3-6) below. The evaluation results are shown in Table 2.
3-1. Heat resistance
Said "2. After apply | coating the curable composition obtained by "preparation of a curable composition" on quartz glass, it heated at 100 degreeC for 1 hour, and then 150 degreeC for 5 hours, and formed the hardened | cured material of the film thickness of 1 mm on quartz glass. The external appearance before and after storing this hardened | cured material at 150 degreeC for 500 hours was visually observed, and heat resistance was evaluated. Evaluation was made based on the following criteria.
A: There is no color change before and after storage.
B: After storage, it was pale yellow.
C: Clearly yellowed after storage.
3-2. After high temperature and high humidity test crack tolerance
Said "2. The curable composition obtained in "Preparation of a curable composition" was injected into an LED package (surface mounted type, top view type), heated at 100 degreeC for 1 hour, and then 150 degreeC for 5 hours, and the sample in which hardened | cured material was formed in the LED package (hereinafter, 10 pieces called "sample 1 for evaluation" were produced. The obtained sample for evaluation 1 was placed in a constant temperature and humidity chamber (the specifications, brand name "PL-3KP"), and preserve | saved for 8 hours in 85 degreeC 85% RH atmosphere, Then, a solder reflow apparatus (Senju Metal Industries, Ltd. make) And the brand name "STR-2010" were heated at 260 degreeC for 20 second (high temperature, 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: There were no cracks in any of the 10 samples.
B: One to four samples out of ten had cracks.
C: Five or more of the ten samples had cracks.
3-3. Heat cycle ( Heat Cycle ) After the test crack tolerance
Said "2. The curable composition obtained in "Preparation of a curable composition" was injected into an LED package (surface mounted type, top view type), heated at 100 degreeC for 1 hour, and then 150 degreeC for 5 hours, and the sample in which hardened | cured material was formed in the LED package (hereinafter, 10 pieces called
A: There were no cracks in any of the 10 samples.
B: One to four samples out of ten had cracks.
C: Five or more of the ten samples had cracks.
3-4. Gas for hydrogen sulfide Barrier property
Said "2. The curable composition obtained in "Preparation of a curable composition" was injected into an LED package (surface mounted type, top view type), heated at 100 degreeC for 1 hour, and then 150 degreeC for 5 hours, and the sample in which hardened | cured material was formed in the LED package (hereinafter, Was called sample 3 for evaluation). Sample 3 for evaluation was put into the heating container filled with the gas containing 90 volume% of air and 10 volume% of hydrogen sulfide, and the evaluation sample 3 was heated at 80 degreeC for 24 hours. The external appearance of the silver electrode of the LED package of the sample 3 for evaluation before and after heating was observed with the optical microscope, and the gas barrier property with respect to hydrogen sulfide was evaluated. Evaluation was made based on the following criteria.
A: There was no color change of the silver electrode before and after heating.
B: After heating, the silver electrode part was pale yellow.
C: After heating, the silver electrode part was blackened.
3-5. Gas for water vapor Barrier property
Said "2. After apply | coating the curable composition obtained by "Preparation of a curable composition" on a peeling film, it heats at 100 degreeC for 1 hour, and then 150 degreeC for 5 hours, and peels a peeling film, and forms the film-form hardened | cured material of a film thickness of 200 micrometers. did. The gas barrier property against water vapor was measured by measuring the water vapor permeation amount using a MOCON water vapor permeability measuring device (manufactured by MOCON, trade name "PERMATRAN-W3 / 31"), and calculating the diffusion coefficient from (water vapor permeation amount x film thickness). Evaluated. Evaluation was made based on the following criteria.
A: The water vapor diffusion coefficient is less than 16.
B: The water vapor diffusion coefficient is 16-20.
C: The water vapor diffusion coefficient is greater than 20.
Since the curable composition of the present invention has high resistance to thermal shock, high temperature, high humidity environment, and the like, and can form a hardened product that is hard to generate cracks, the sealing agent, the adhesive, the potting agent of the optical semiconductor element and the optical semiconductor member, It is useful as a protective coating agent, an underfill agent, etc.
1: optical semiconductor device
2: semiconductor light emitting element
3: reflector
4: encapsulant
5: particle
6: electrode
7: Wire
Claims (4)
(Wherein n represents an integer of 1 or more; R 1 and R 2 represent an alkyl group having 1 to 4 carbon atoms; Ar represents an aryl group);
(Wherein, R 3 , R 5 and R 6 each independently represent an organic group; provided that at least two of all R 3 and R 6 are alkenyl groups, and R 5 is a silicon atom to which R 5 is bonded); When another R 5 to be bonded is an aryl group, it is not an alkyl group having 1 to 4 carbon atoms and an aryl group; R 4 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group, and at least one of R 4 is an aryl group X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; a, c, e, and f each independently represent an integer of 0 or more; b and d each independently represent an integer of 1 or more; When 0, d is an integer of 2 or more).
Curable composition whose said R <4> of the said General formula (2) is an aryl group.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP-P-2012-084723 | 2012-04-03 | ||
| JP2012084723 | 2012-04-03 | ||
| JPJP-P-2013-007112 | 2013-01-18 | ||
| JP2013007112A JP5660145B2 (en) | 2012-04-03 | 2013-01-18 | Curable composition, cured product, and optical semiconductor device |
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| Publication Number | Publication Date |
|---|---|
| KR20130112761A true KR20130112761A (en) | 2013-10-14 |
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|---|---|---|---|
| KR1020130035075A KR20130112761A (en) | 2012-04-03 | 2013-04-01 | Curable composition, cured product and photo-semiconductor device |
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| Country | Link |
|---|---|
| KR (1) | KR20130112761A (en) |
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2013
- 2013-04-01 KR KR1020130035075A patent/KR20130112761A/en not_active Application Discontinuation
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