CN109749459B - Addition-curable silicone composition, cured product, and optical element - Google Patents
Addition-curable silicone composition, cured product, and optical element Download PDFInfo
- Publication number
- CN109749459B CN109749459B CN201811293909.5A CN201811293909A CN109749459B CN 109749459 B CN109749459 B CN 109749459B CN 201811293909 A CN201811293909 A CN 201811293909A CN 109749459 B CN109749459 B CN 109749459B
- Authority
- CN
- China
- Prior art keywords
- formula
- component
- sio
- addition
- curable silicone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- 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
-
- 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
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Abstract
The invention provides an addition curing type organic silicon composition for providing a cured product with high heat discoloration resistance and high vulcanization resistance, and an optical element sealed by the cured product and having high reliability. The addition-curable silicone composition includes: (A-1) a branched organopolysiloxane represented by the average compositional formula (1) (R)1 3SiO1/2)a(R2R1 2SiO1/2)b(R2R1SiO)c(R1 2SiO)d(R2SiO3/2)e(R1SiO3/2)f(SiO4/2)gThe branched organopolysiloxane described in (1) has at least two or more siloxane units represented by the following formula (2) in one molecule as (R) in the average composition formula (1)2R1 2SiO1/2) Unit of [ chemical formula 1]
(A-2) a linear organopolysiloxane represented by the following formula (3): the mass ratio of (A-1) to (A-2) is 100:0 to 50:50 (formula 2)]
(B) An organohydrogenpolysiloxane having at least two or more siloxane units represented by the following formula (4) in one molecule [ chemical formula 3]]
Description
Technical Field
The present invention relates to an addition-curable silicone composition, a cured product thereof, and an optical element sealed with the cured product.
Background
A device having a Light Emitting Diode (LED) as an optical semiconductor element is generally configured by sealing an LED mounted on a substrate with a sealing material made of a transparent resin. Although epoxy resin has been used as the sealing material, cracking and yellowing occur in the resin due to an increase in the amount of heat generation and a reduction in the wavelength of light accompanying the recent reduction in size of semiconductor packages and the increase in luminance of LEDs, resulting in a decrease in reliability.
Therefore, a silicone resin composition has been drawing attention as a sealing material from the viewpoint of heat resistance and heat discoloration resistance, and an addition reaction curing type silicone resin composition can be cured by heating for a short time, and therefore has high productivity and is useful as a sealing material for LEDs (patent document 1).
On the other hand, since silicone resin has a higher gas permeability than epoxy resin, corrosion of the silver substrate of LED due to sulfur compounds present in the air may be caused. When a silicone composition having a main chain composed of dimethylsiloxane units and diphenylsiloxane units or a main chain composed of methylphenylsiloxane units is used (patent document 2), although the silicone composition has excellent heat discoloration resistance and can suppress corrosion of a silver substrate to some extent, the vulcanization resistance is still insufficient.
On the other hand, there have been proposed sealing materials for optical semiconductor elements, which use an organically modified organopolysiloxane composition containing a polycyclic hydrocarbon skeleton component (patent documents 3 and 4). Such a composition has superior resistance to vulcanization compared to a sealing material using a general phenyl silicone, and can suppress corrosion of a silver substrate, but has a large discoloration when exposed to high temperatures and insufficient resistance to thermal discoloration. Thus, a sealing material for an optical semiconductor element which is excellent in transparency and mechanical strength and satisfies both of the resistance to vulcanization and the resistance to thermal discoloration has been desired.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2004-292714
Patent document 2: japanese patent laid-open publication No. 2010-132795
Patent document 3: japanese patent laid-open No. 2008-069210
Patent document 4: japanese patent laid-open No. 2012 and 046604
Disclosure of Invention
Technical problem to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide an addition-curable silicone composition which can provide a cured product having high thermal discoloration resistance and high vulcanization resistance, and an optical element which is sealed with the cured product and has high reliability.
Means for solving the problems
In order to solve the above-mentioned technical problems, the present invention provides an addition-curable silicone composition comprising: (A-1) a branched organopolysiloxane represented by the average compositional formula (1) (R)1 3SiO1/2)a(R2R1 2SiO1/2)b(R2R1SiO)c(R1 2SiO)d(R2SiO3/2)e(R1SiO3/2)f(SiO4/2)g···(1)
In the formula, R1Is an unsubstituted or substituted monovalent hydrocarbon group of the same or different species not containing an alkenyl group, all R1At least 10 mol% of (A) are aryl radicals, R2Is an alkenyl group, wherein a, b, c, d, e, f and g are numbers satisfying a.gtoreq.0, b > 0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0, f.gtoreq.0 and g.gtoreq.0, wherein e + f + g > 0 and a + b + c + d + e + f + g ═ 1, and the branched organopolysiloxane has at least two or more siloxane units represented by the following formula (2) in one molecule as (R) in the average composition formula (1)2R1 2SiO1/2) The unit cell is a unit cell, which is composed of a plurality of unit cells,
[ chemical formula 1]
In the formula, R1And the above-mentioned R1The same;
(A-2) a linear organopolysiloxane represented by the following formula (3): the mass ratio of (A-1) to (A-2) is 100:0 to 50:50, wherein the amount of the component (A-2) is more than 0 part by mass,
[ chemical formula 2]
In the formula, R1’Is a non-substituted or substituted monovalent hydrocarbon radical of the same or different species not containing an alkenyl group, R3Is methyl or phenyl, h is an integer of 0 to 50, i is an integer of 0 to 100, the arrangement order of the siloxane units is arbitrary, wherein, when h is 0, R is3Is phenyl, i is an integer of 1-100, and the arrangement of siloxane units with brackets can be random or block;
(B) an organohydrogenpolysiloxane having at least two or more siloxane units represented by the following formula (4) in one molecule: the number of silicon atom-bonded hydrogen atoms in the component (B) is 0.1 to 5.0 relative to 1 silicon atom-bonded alkenyl group in the components (A-1) and (A-2),
[ chemical formula 3]
(C) a hydrosilylation catalyst comprising a platinum group metal.
Such an addition-curable silicone composition can provide a cured product having high thermal discoloration resistance and high vulcanization resistance.
Further, R in the formula (2) is preferable1And R in the formula (3)1’Is phenyl or methyl.
Such an addition-curable silicone composition can be suitably used as the component (A-1).
Further, the blending amount of the component (B) is preferably: the number of hydrogen atoms bonded to the silicon atom in the component (B) is 1.0 to 3.0 relative to 1 alkenyl group bonded to the silicon atom in the component (A-1) and the component (A-2).
Such a blending amount can impart high strength and vulcanization resistance to the cured product of the composition.
The organohydrogenpolysiloxane of the component (B) is preferably an organohydrogenpolysiloxane represented by the following formula (5) or (6).
[ chemical formula 4]
In the formula, the order of arrangement of the siloxane units may be random or block.
[ chemical formula 5]
Such an organohydrogenpolysiloxane can be suitably used as the component (B).
The present invention also provides a cured product obtained by curing the addition-curable silicone composition.
Such a cured product has good strength characteristics, high resistance to vulcanization, high resistance to thermal discoloration, and a high refractive index.
Further, the present invention provides an optical element sealed with the cured product.
The cured product of the present invention has good strength characteristics, high resistance to vulcanization, high resistance to thermal discoloration, and a high refractive index. Therefore, the optical element sealed with such a cured product has high reliability.
Effects of the invention
As described above, the addition-curable silicone composition of the present invention can provide a cured product having high transparency, a high refractive index, high vulcanization resistance, and excellent thermal discoloration resistance. Therefore, the cured product of the present invention can be suitably used as an optical element sealing material.
Detailed Description
As described above, there have been demanded an addition curing type silicone composition which can provide a cured product having high thermal discoloration resistance and high vulcanization resistance, and an optical element which is sealed with the cured product and has high reliability.
The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, have found that the above-mentioned problems can be achieved by an addition-curable silicone composition containing the following components (a-1), (a-2), (B) and (C), and have completed the present invention.
Namely, the present invention is an addition-curable silicone composition comprising: (A-1) a branched organopolysiloxane represented by the average compositional formula (1) (R)1 3SiO1/2)a(R2R1 2SiO1/2)b(R2R1SiO)c(R1 2SiO)d(R2SiO3/2)e(R1SiO3/2)f(SiO4/2)g···(1)
In the formula, R1Is an unsubstituted or substituted monovalent hydrocarbon group of the same or different species not containing an alkenyl group, all R1At least 10 mol% of (A) are aryl radicals, R2Is an alkenyl group. Wherein a, b, c, d, e, f and g are numbers satisfying a.gtoreq.0, b > 0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0, f.gtoreq.0 and g.gtoreq.0, wherein e + f + g > 0 and a + b + c + d + e + f + g is 1, and the branched organopolysiloxane has at least two or more siloxane units represented by the following formula (2) in one molecule as (R) in the average composition formula (1)2R1 2SiO1/2) The unit cell is a unit cell, which is composed of a plurality of unit cells,
[ chemical formula 6]
In the formula, R1And the above-mentioned R1The same;
(A-2) a linear organopolysiloxane represented by the following formula (3): the mass ratio of (A-1) to (A-2) is 100:0 to 50:50, wherein the amount of the component (A-2) is more than 0 part by mass,
[ chemical formula 7]
In the formula, R1’Is a non-substituted or substituted monovalent hydrocarbon radical of the same or different species not containing an alkenyl group, R3Is methyl or phenylH is an integer of 0 to 50, i is an integer of 0 to 100, and the order of arrangement of the siloxane units is arbitrary. Wherein, when h is 0, R3Is phenyl, i is an integer of 1-100, and the arrangement of siloxane units with brackets can be random or block;
(B) an organohydrogenpolysiloxane having at least two or more siloxane units represented by the following formula (4) in one molecule: the number of silicon atom-bonded hydrogen atoms in the component (B) is 0.1 to 5.0 relative to 1 silicon atom-bonded alkenyl group in the components (A-1) and (A-2),
[ chemical formula 8]
(C) a hydrosilylation catalyst comprising a platinum group metal.
The present invention will be described in detail below, but the present invention is not limited thereto.
[ addition-curable Silicone composition ]
The addition-curable silicone composition of the present invention contains the following components (A-1), (A-2), (B) and (C). Hereinafter, each component will be described in detail.
(A-1) branched organopolysiloxane
The component (A-1) is a branched organopolysiloxane represented by the average composition formula (1) (R)1 3SiO1/2)a(R2R1 2SiO1/2)b(R2R1SiO)c(R1 2SiO)d(R2SiO3/2)e(R1SiO3/2)f(SiO4/2)g···(1)
In the formula, R1Is an unsubstituted or substituted monovalent hydrocarbon group of the same or different species not containing an alkenyl group, all R1At least 10 mol% of (A) are aryl radicals, R2Is an alkenyl group. Wherein a, b, c, d, e, f and g are numbers respectively satisfying a is more than or equal to 0, b is more than 0, c is more than or equal to 0, d is more than or equal to 0, e is more than or equal to 0, f is more than or equal to 0 and g is more than or equal to 0, wherein the number is e + f + gA number of > 0 and satisfying a + b + c + d + e + f + g ═ 1, wherein the branched organopolysiloxane has at least two or more siloxane units represented by the following formula (2) in one molecule as (R) in the average composition formula (1)2R1 2SiO1/2) And (4) units.
[ chemical formula 9]
In the formula, R1And the above-mentioned R1The same is true.
The component (A-1) is an essential component for obtaining the reinforcement of the silicone composition, and contains SiO3/2Unit and SiO4/2Either one or both of the cells.
The component (A-1) has two or more siloxane units represented by the above formula (2) in one molecule. By having the siloxane unit represented by the above formula (2), a cured product of the silicone composition can be provided with high strength, high refractive index, and high vulcanization resistance.
As the above-mentioned R1The alkenyl group is not particularly limited as long as it is not contained, and examples thereof include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl and phenethyl; and unsubstituted or halogenated monovalent hydrocarbon groups having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, such as halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3, 3-trifluoropropyl groups, and particularly preferably methyl groups.
All R1At least 10 mole% of which are aryl groups. If the aryl group content is less than 10 mol%, higher hardness and higher vulcanization resistance cannot be imparted to the cured product. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group, and a phenyl group is particularly preferable.
R is as defined above2The alkenyl group is preferably a group having 2 to 10 carbon atoms such as a vinyl group, allyl group, ethynyl group, etc., more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably a vinyl group.
The content of the siloxane unit represented by the formula (2) in the component (A-1) is preferably in the range of 0.01 to 1mol, more preferably 0.05 to 0.5mol, per 100g of the component (A-1). By satisfying the above range, a cured product having high hardness and high vulcanization resistance can be obtained.
The component (A-1) is preferably a three-dimensional network organopolysiloxane resin which is waxy or solid at 23 ℃. "wax-like" means a gel-like substance (raw rubber-like substance) which does not exhibit self-fluidity at 23 ℃ at 10,000 pas or more, particularly at 100,000 pas or more.
The component (A-1) may be used singly or in combination of two or more.
< (A-2) straight-chain organopolysiloxane
The component (A-2) is represented by the following formula (3), and is a diorganopolysiloxane having a main chain composed of a repeating unit having a phenyl group in a side chain, and containing vinyl groups and phenyl groups at both ends of the molecular chain, and being blocked by triorganosiloxy groups.
[ chemical formula 10]
In the formula, R1’Is a non-substituted or substituted monovalent hydrocarbon radical of the same or different species not containing an alkenyl group, R3Is methyl or phenyl, h is an integer of 0 to 50, i is an integer of 0 to 100, and the arrangement order of the siloxane units is arbitrary. Wherein, when h is 0, R3The siloxane units are arranged randomly or in blocks, and i is an integer of 1 to 100.
In the component (A-2), R in the formula (3) is1’Can be exemplified by R in the component (A-1)1The same groups.
In the formula (3), h is an integer of 0 to 50, i is an integer of 0 to 100, and R is 03Is phenyl, i is 1 to 100. If h and i are outside the above ranges, high hardness and high vulcanization resistance cannot be imparted to the cured product of the composition.
The viscosity of the component (A-2) at 25 ℃ is preferably 10 to 100,000 mPas, more preferably 10 to 10,000 mPas. If the viscosity is within the above range, there is no fear that the present component excessively acts as a soft segment, and a desired high hardness can be obtained. Further, there is no fear that the viscosity of the composition becomes remarkably high and the workability is poor.
Both ends of the molecular chain of the component (A-2) are blocked with a triorganosiloxy group containing a vinyl group and a phenyl group. This can impart high strength and high vulcanization resistance to the cured product. Specific examples of the component (A-2) include diphenylsiloxane terminated with methylphenylvinyl groups at both ends, diphenylsiloxane terminated with methylphenylvinyl groups at one end and diphenylvinyl groups at one end, diphenylsiloxane terminated with diphenylvinyl groups at both ends, diphenylsiloxane-methylphenylsiloxane copolymers terminated with diphenylvinyl groups at both ends, and the like. The component (A-2) may be used singly or in combination of two or more.
The ratio of the (A-1) component to the (A-2) component is also one of the important factors of the composition of the present invention. The amount of the component (A-1) is an amount of 100:0 to 50:50 by mass of the component (A-1) to the component (A-2) (wherein the amount of the component (A-2) is more than 0 part by mass), and preferably an amount of 80:20 to 60:40 by mass of the component (A-1) to the component (A-2). If the blending amount of the component (A-1) is less than the above range, a cured product having high hardness and high vulcanization resistance is not easily obtained.
(B) Organohydrogenpolysiloxane
(B) The component (A) is an organohydrogenpolysiloxane having at least two siloxane units represented by the following formula (4) in one molecule, which is reacted with the components (A-1) and (A-2) by hydrosilylation and functions as a crosslinking agent. By having the component (B), a cured product of the silicone composition containing the component (B) can be imparted with high hardness and high vulcanization resistance.
[ chemical formula 11]
(B) The molecular structure of the component (a) is not particularly limited, and various organohydrogenpolysiloxanes such as linear, cyclic, branched, and three-dimensional network (resin-like) structures can be used. Further, the component (B) may be in the form of a liquid, wax or solid at 23 ℃.
(B) The organohydrogenpolysiloxane of component (a) has at least 2, preferably 3 to 300, and particularly preferably 3 to 100 hydrogen atoms bonded to silicon atoms (i.e., silicon hydride groups (SiH groups)) in 1 molecule. (B) When the organohydrogenpolysiloxane of component (b) is a linear structure, the SiH group may be located at only one of the molecular chain terminals and the region other than the terminals, or may be located at both of the molecular chain terminals and the region other than the terminals.
(B) The number of silicon atoms (polymerization degree) in 1 molecule of the component (A) is preferably 2 to 300, more preferably 3 to 200, and still more preferably 4 to 150.
As the component (B), for example, an organohydrogenpolysiloxane represented by the following average composition formula (7) can be used.
R4 jHkSiO(4-j-k)/2 (7)
In the formula, R4The monovalent hydrocarbon group bonded to a silicon atom, which is unsubstituted or unsubstituted, identical or different from each other, and does not contain an alkenyl group, has preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms, and R in the component (A-1) is exemplified1And R in the component (A-2)1’The same monovalent hydrocarbon group. Further, j and k are preferably positive numbers such that j is 0.7. ltoreq. j.ltoreq.2.1, k is 0.001. ltoreq.1.0, and j + k is 0.8. ltoreq.j.ltoreq.3.0, and more preferably positive numbers such that j is 1.0. ltoreq. j.ltoreq.2.0, k is 0.01. ltoreq.1.0, and j + k is 1.55. ltoreq. j + k.ltoreq.2.5.
Specific examples of the component (B) include a both-terminal dimethylphenylsiloxy-terminated methylphenylhydrosiloxane-dimethylsiloxane cyclic copolymer, a both-terminal methylphenylhydrosiloxy-terminated diphenylpolysiloxane, a both-terminal methylphenylhydrosiloxy-terminated dimethylsiloxane-diphenylsiloxane-methylhydrosiloxane copolymer, and the like.
More specifically, the component (B) includes an organohydrogenpolysiloxane represented by the following formula (5) or (6).
[ chemical formula 12]
In the formula, the order of arrangement of the siloxane units may be random or block.
[ chemical formula 13]
(B) The blending amount of the components is as follows: the number of silicon atom-bonded hydrogen atoms in the component (B) is 0.1 to 5.0, preferably 0.5 to 3.0, and more preferably 1.0 to 3.0, relative to 1 silicon atom-bonded alkenyl group in the components (A-1) and (A-2). If the blending amount of the component (B) is outside the above range, high hardness and vulcanization resistance cannot be imparted to the cured product of the composition.
(B) The organohydrogenpolysiloxane of component (a) may be used alone or in combination of two or more.
< (C) hydrosilylation catalyst containing platinum group metal
(C) The hydrosilylation catalyst containing a platinum group metal of component (a) functions as an addition reaction catalyst to promote an addition reaction between the alkenyl groups of components (a-1) and (a-2) and the silicon atom-bonded hydrogen atoms of component (B). Specific examples thereof include platinum, palladium, rhodium, etc., chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid with olefins, vinylsiloxanes or acetylene compounds, platinum group metals such as tetrakis (triphenylphosphine) palladium, chlorotris (triphenylphosphine) rhodium, etc., and compounds thereof, with platinum group compounds being particularly preferred.
(C) One of the components may be used alone, or two or more of the components may be used in combination.
(C) The amount of the component (B) may be an effective amount as a catalyst, and is preferably in the range of 1 to 500ppm, more preferably 1 to 100ppm, in terms of the mass of the catalyst metal element, relative to the total amount of the components (A-1), (A-2) and (B). When the amount satisfies the above range, the reaction rate of the addition reaction is appropriate, and a cured product having high strength can be obtained.
< (D) other component
In addition to the above components, an adhesion improver may be added to the composition of the present invention in order to improve adhesion to a resin.
As the adhesion improver, an organic silicon compound such as silane or siloxane, a non-organic silicon organic compound, or the like containing a functional group imparting adhesion can be used from the viewpoint of imparting self-adhesion to the composition of the present invention which is an addition reaction curing type.
Specific examples of the functional group for imparting adhesiveness include an alkenyl group such as a vinyl group or an allyl group bonded to a silicon atom, a hydrogen atom; an epoxy group (e.g., γ -glycidoxypropyl group,. beta. - (3, 4-epoxycyclohexyl) ethyl group, etc.) bonded to a silicon atom via a carbon atom, an acryloxy group (e.g., γ -acryloxypropyl group, etc.) or a methacryloxy group (e.g., γ -methacryloxypropyl group, etc.); and an alkoxysilyl group (for example, an alkoxysilyl group such as a trimethoxysilyl group, triethoxysilyl group, or methyldimethoxysilyl group, which is bonded to a silicon atom through an alkenyl group that may have 1 to 2 ester structures, carbamate structures, or ether structures).
Examples of the organic silicon compound having a functional group for imparting adhesiveness include a silane coupling agent, a siloxane having an alkoxysilyl group and an organic functional group, and a compound obtained by introducing an alkoxysilyl group into an organic compound having a reactive organic group.
Examples of the non-silicone organic compound include allyl organosilicate, an epoxy group ring-opening catalyst, an organotitanium compound, an organozirconium compound, and an organoaluminum compound.
In order to improve the reinforcing property, fine powder silica may be blended in the composition of the present invention. The specific surface area (BET method) of the fine powder silica is preferably 50m2More preferably 50 to 400 m/g2A specific preferred range is 100 to 300m2(ii) in terms of/g. If the specific surface area is 50m2At least g, sufficient reinforcement can be imparted to the cured product.
In the present invention, as such fine powder silica, known fine powder silica conventionally used as a reinforcing filler for silicone rubber can be used, and examples thereof include fumed silica (dry silica), precipitated silica (wet silica), and the like. The fine powder silica may be used as it is, but in order to impart good fluidity to the composition, it is preferable to use silica treated with an organic silicon compound such as methylchlorosilanes such as trimethylchlorosilane, dimethyldichlorosilane and methyltrichlorosilane, and hexaorganodisilazane such as dimethylpolysiloxane, hexamethyldisilazane, divinyltetramethyldisilazane and dimethyltetravinyldisilazane. The reinforcing silica may be used alone or in combination of two or more.
In addition, a reaction inhibitor having a curing-inhibiting effect on the addition reaction catalyst of the component (C) can be used in the composition of the present invention. Examples of the reaction inhibitor include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine and benzotriazole; a sulfur-containing compound; acetylene compounds; a hydroperoxide compound; maleic acid derivatives, and the like.
Since the degree of the curing inhibition effect by the reaction inhibitor varies significantly depending on the chemical structure of the reaction inhibitor, it is preferable to adjust the blending amount of the reaction inhibitor to an optimum amount for the reaction inhibitor to be used. If the amount of the reaction inhibitor is an optimum amount, there is no fear that the long-term storage stability of the composition at room temperature cannot be obtained and the curing of the composition is inhibited. It is usually preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of the organopolysiloxane of the component (A-1), the component (A-2), and the component (B).
Examples of the other optional components include inorganic fillers such as crystalline silica, hollow fillers and silsesquioxane, and fillers obtained by subjecting the above fillers to surface hydrophobization treatment with an organosilicon compound such as an organoalkoxysilane compound, an organochlorosilane compound, an organoazane compound or a low-molecular-weight siloxane compound; silicone rubber powder, silicone resin powder, and the like.
[ cured product ]
The present invention also provides a cured product obtained by curing the addition-curable silicone composition.
The curing method and conditions of the addition-curable silicone composition of the present invention can employ known curing methods and conditions. For example, the resin composition can be cured at 100 to 180 ℃ for 10 minutes to 5 hours.
The cured product obtained by curing the addition-curable silicone composition of the present invention has high strength and refractive index, excellent resistance to vulcanization, and particularly high light transmittance, and therefore can be used as a sealing material for semiconductor devices, an optical component, or a protective coating material for electric and electronic devices.
[ optical element ]
Further, the present invention provides an optical element sealed with the cured product.
As described above, the cured product of the present invention has high strength and refractive index, excellent vulcanization resistance, and particularly high light transmittance. Therefore, the optical element sealed with such a cured product is also highly reliable.
Examples
The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto.
The viscosity in the examples is a value measured at 25 ℃ using a rotary viscometer.
Examples 1 to 3 and comparative examples 1 to 3
The following components were mixed at the blending ratios shown in table 1 to prepare addition-curable silicone compositions. In table 1, parts represent parts by mass.
(A-1) component:
(CH2＝CH(CH3)(C6H5)SiO1/2)2((C6H5)2SiO)3.8(SiO2)4.3branched chain of the formulaeSilicone resin
(A-2) component:
(A-2-a)(CH2＝CH(CH3)(C6H5)SiO1/2)2((C6H5)2SiO)3a linear silicone oil having a viscosity of 2,000 mPas
(A-2-b)(CH2＝CH(CH3)(C6H5)SiO1/2)2((C6H5)2SiO) and having a viscosity of 240 mPas
(A-2-c)(CH2＝CH(CH3)2SiO1/2)2((C6H5)2SiO)3A straight-chain silicone oil having a viscosity of 700 mPas
(B) The components:
(B-a) an organohydrogenpolysiloxane represented by the following formula (8)
[ chemical formula 14]
In the formula, the order of arrangement of the siloxane units is arbitrary.
(B-B) an organohydrogenpolysiloxane represented by the following formula (9)
[ chemical formula 15]
(B-c) an organohydrogenpolysiloxane represented by the following formula (10)
[ chemical formula 16]
(B-d) an organohydrogenpolysiloxane represented by the following formula (11)
[ chemical formula 17]
In the formula, the order of arrangement of the siloxane units is arbitrary.
(B-e) an organohydrogenpolysiloxane represented by the following formula (12)
[ chemical formula 18]
(C) Composition (I)
Platinum catalyst: a complex of hexachloroplatinic acid and 1, 3-divinyltetramethyldisiloxane was diluted with a dimethyl organopolysiloxane having a viscosity of 600mPa · s so that the platinum content was 1.0 mass%.
Other components:
(D) ethynyl cyclohexanol
(E-a) a component for imparting tackiness represented by the following formula (13)
[ chemical formula 19]
(E-b) an adhesive property-imparting component represented by the following formula (14)
[ chemical formula 20]
The following evaluations were made on the addition-curable silicone compositions obtained in examples 1 to 3 and comparative examples 1 to 3, and the results are shown in table 2. In comparative example 4, SCR-1016 manufactured by Shin-Etsu Chemical co., ltd. was used as the organic modified silicone material not having the siloxane unit represented by formula (2).
(hardness)
The composition was poured into a mold so as to be 2mm thick, and cured at 150 ℃ for 4 hours. The TypeD hardness of the cured product was measured in accordance with JIS K6253. If the type d hardness is 50 or more, it can be judged that the hardness is sufficiently high.
(refractive index)
Refractive index the refractive index at a wavelength of 589nm was measured at 25 ℃ using a digital display refractometer RX-5000 manufactured by ATAGO. If the refractive index is 1.5 or more, the material has sufficiently high refractive index.
(fabrication of optical semiconductor Package (PKG))
An LED package substrate having a concave portion on which an optical semiconductor element is mounted and a first lead and a second lead which are plated with silver are provided on a bottom portion thereof [ SMD5050 (I-chip die input co., ltd.) ] is prepared as an LED package substrate, and EV-B35A (manufactured by SemiLEDS Corporation) is prepared as an optical semiconductor element.
A die bond material KER-3000-M2 manufactured by Shin-Etsu Chemical co., ltd. was quantitatively transferred to the silver-plated first leads of the package substrate by punching using a die bonder (AD-830 manufactured by Advanced materials inc., and mounted with an optical semiconductor element thereon. Next, the package substrate was put into an oven, and the die-bonding material was cured by heating (150 ℃ c, 2 hours), whereby the lower electrode of the optical semiconductor element was electrically connected to the first lead. Next, the upper electrode of the optical semiconductor element of the LED package substrate on which the optical semiconductor element was mounted was electrically connected to the second lead by using a gold wire (FA 25 μm manufactured by Tanaka Densi co., ltd.) using a wire bonder, and 1 piece of each LED package substrate on which the optical semiconductor element was mounted was obtained.
(vulcanization test)
The composition was sealed in a predetermined PKG, and cured at 150 ℃ for 4 hours. Next, 0.1g of sulfur powder was charged into a 100g bottle, and after the PKG in which the resin was sealed was charged, the bottle was sealed. The PKG was taken out after 70 ℃ x 48 hours, and the color of the silver substrate was visually observed to evaluate the vulcanization resistance. When the silver substrate of PKG discolored to black, it was marked x, when it did not discolor, it was marked o, and when it was marked o, it indicated that the vulcanization resistance was excellent.
(oxygen permeability)
The composition was poured into a mold with an outer diameter of 100mm Φ and a thickness of 1mm, and cured at 150 ℃ for 4 hours. The oxygen permeability of the cured product was measured using an oxygen permeability measuring apparatus 8000 series manufactured by イリノイ. The lower the numerical value, the more excellent the gas barrier property, and the higher the vulcanization resistance.
(light transmittance)
The composition was poured into a mold so as to be 2mm thick, and cured at 150 ℃ for 4 hours. The transmittance at a wavelength of 400nm of the cured product was measured. When the content is 80% or more, the transparency is sufficiently high.
(resistance to Heat discoloration)
The composition was poured into a mold so as to be 2mm thick, and cured at 150 ℃ for 4 hours. The cured product was exposed to 180 ℃ for 100 hours, and then the transmittance at a wavelength of 400nm was measured. The smaller the difference from the initial light transmittance, the more excellent the heat discoloration resistance was evaluated.
[ Table 1]
1) The number of silicon atom-bonded hydrogen atoms in component (B) relative to 1 silicon atom-bonded alkenyl groups in components (A-1) and (A-2)
[ Table 2]
As shown in Table 2, the cured silicone materials of examples 1 to 3 had high hardness, high strength, high refractive index, and low oxygen permeability, and thus had excellent vulcanization resistance. Further, the material is less discolored at high temperatures, and has high reliability in terms of both resistance to vulcanization and resistance to thermal discoloration.
On the other hand, in comparative example 1 containing no component (B) of the present invention, the strength was poor and the oxygen permeability was as high as 250cc, and along with this, the silver substrate was discolored to black in the vulcanization test and the vulcanization resistance was poor. In comparative examples 2 and 3 which did not contain the component (A) or the component (B) of the present invention, it was confirmed that the oxygen permeability was high and the sulfuration resistance was poor although the thermal discoloration resistance was high. Further, in comparative example 4, which is a conventional organically modified silicone, it is found that although the vulcanization resistance is excellent, the thermal discoloration resistance is poor.
From the above, it was confirmed that the addition-curable silicone composition of the present invention not only has a high refractive index and high strength, but also can provide a cured product which has higher vulcanization resistance than conventional phenyl silicones (comparative examples 1 to 3), has more excellent thermal discoloration resistance than conventional organically-modified silicones (comparative example 4), and is suitable for LED applications.
The present invention is not limited to the above embodiments. The above-described embodiments are illustrative, and any embodiments having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same operational effects are included in the technical scope of the present invention.
Claims (10)
1. An addition-curable silicone composition characterized by comprising:
(A-1) a branched organopolysiloxane represented by the average compositional formula (1) (R)1 3SiO1/2)a(R2R1 2SiO1/2)b(R2R1SiO)c(R1 2SiO)d(R2SiO3/2)e(R1SiO3/2)f(SiO4/2)g ···(1)
In the formula, R1Is an unsubstituted or substituted monovalent hydrocarbon group of the same or different species not containing an alkenyl group, all R1At least 10 mol% of (A) are aryl radicals, R2Is alkenyl, wherein a, b, c, d, e, f, g are independently a ≥ 0, b > 0, c ≥ 0, d ≥ 0, e ═ 0, f ═ 0 and g>0, wherein e + f + g > 0, and a + b + c + d + e + f + g is 1, and the branched organopolysiloxane has at least two or more silicon represented by the following formula (2) in one moleculeAn alkylene oxide unit as (R) in the average composition formula (1)2R1 2SiO1/2) The unit cell is a unit cell, which is composed of a plurality of unit cells,
[ chemical formula 1]
In the formula, R1And said R1The same;
(A-2) a linear organopolysiloxane represented by the following formula (3): the mass ratio of (A-1) to (A-2) is 100:0 to 50:50, wherein the amount of the component (A-2) is more than 0 part by mass,
[ chemical formula 2]
In the formula, R1’Is a non-substituted or substituted monovalent hydrocarbon radical of the same or different species not containing an alkenyl group, R3Is methyl or phenyl, h is an integer of 0 to 50, i is an integer of 0 to 100, the arrangement order of the siloxane units is arbitrary, wherein, when h is 0, R is3Is phenyl, i is an integer of 1-100, and the arrangement of siloxane units with brackets can be random or block;
(B) an organohydrogenpolysiloxane having at least two or more siloxane units represented by the following formula (4) in one molecule: the number of silicon atom-bonded hydrogen atoms in the component (B) is 0.1 to 5.0 relative to 1 silicon atom-bonded alkenyl group in the components (A-1) and (A-2),
[ chemical formula 3]
(C) a hydrosilylation catalyst comprising a platinum group metal.
2. The addition-curable silicone composition according to claim 1A compound characterized in that R in the formula (2)1And R in the formula (3)1’Is phenyl or methyl.
3. The addition-curable silicone composition according to claim 1, wherein the blending amount of component (B) is: the number of hydrogen atoms bonded to the silicon atom in the component (B) is 1.0 to 3.0 relative to 1 alkenyl group bonded to the silicon atom in the component (A-1) and the component (A-2).
4. The addition-curable silicone composition according to claim 2, wherein the blending amount of component (B) is: the number of hydrogen atoms bonded to the silicon atom in the component (B) is 1.0 to 3.0 relative to 1 alkenyl group bonded to the silicon atom in the component (A-1) and the component (A-2).
5. The addition-curable silicone composition according to claim 1, wherein the organohydrogenpolysiloxane of component (B) is an organohydrogenpolysiloxane represented by formula (5) or (6),
[ chemical formula 4]
In the formula, the order of arrangement of the siloxane units may be random or block,
[ chemical formula 5]
6. The addition-curable silicone composition according to claim 2, wherein the organohydrogenpolysiloxane of component (B) is an organohydrogenpolysiloxane represented by formula (5) or (6),
[ chemical formula 6]
In the formula, the order of arrangement of the siloxane units may be random or block,
[ chemical formula 7]
7. The addition-curable silicone composition according to claim 3, wherein the organohydrogenpolysiloxane of component (B) is an organohydrogenpolysiloxane represented by formula (5) or (6),
[ chemical formula 8]
In the formula, the order of arrangement of the siloxane units may be random or block,
[ chemical formula 9]
8. The addition-curable silicone composition according to claim 4, wherein the organohydrogenpolysiloxane of component (B) is an organohydrogenpolysiloxane represented by formula (5) or (6),
[ chemical formula 10]
In the formula, the order of arrangement of the siloxane units may be random or block,
[ chemical formula 11]
9. A cured product obtained by curing the addition-curable silicone composition according to any one of claims 1 to 8.
10. An optical element sealed with the cured product according to claim 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-213193 | 2017-11-02 | ||
| JP2017213193A JP6823578B2 (en) | 2017-11-02 | 2017-11-02 | Additive-curable silicone composition, cured product, optical element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109749459A CN109749459A (en) | 2019-05-14 |
| CN109749459B true CN109749459B (en) | 2021-08-27 |
Family
ID=66402483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811293909.5A Active CN109749459B (en) | 2017-11-02 | 2018-11-01 | Addition-curable silicone composition, cured product, and optical element |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6823578B2 (en) |
| KR (1) | KR102640805B1 (en) |
| CN (1) | CN109749459B (en) |
| TW (1) | TWI798283B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7256700B2 (en) * | 2019-06-18 | 2023-04-12 | 信越化学工業株式会社 | Addition-curable silicone coating composition, silicone cured product, and optical semiconductor device |
| JP2021021038A (en) * | 2019-07-30 | 2021-02-18 | デュポン・東レ・スペシャルティ・マテリアル株式会社 | Curable silicone composition, optical semiconductor device and method of manufacturing the optical semiconductor device |
| JP7457604B2 (en) * | 2019-09-12 | 2024-03-28 | 信越化学工業株式会社 | Addition-curable silicone compositions, cured products, sheets, and optical components |
| CN116134104A (en) * | 2020-07-22 | 2023-05-16 | 信越化学工业株式会社 | Anti-vulcanization coating material, cured product of anti-vulcanization coating material, and electronic device |
| WO2023136227A1 (en) * | 2022-01-12 | 2023-07-20 | 信越化学工業株式会社 | Thixotropic silicone gel composition, silicone gel cured product, and electrical/electronic components |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921488A (en) * | 2009-06-15 | 2010-12-22 | 信越化学工业株式会社 | Silicone resin composite for die bonding |
| CN104812841A (en) * | 2012-10-30 | 2015-07-29 | 道康宁东丽株式会社 | Curable silicone composition, cured product thereof, and optical semiconductor device |
| CN104968711A (en) * | 2012-12-28 | 2015-10-07 | 道康宁东丽株式会社 | Curable silicone composition, cured product thereof, and optical semiconductor device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004292714A (en) | 2003-03-28 | 2004-10-21 | Kanegafuchi Chem Ind Co Ltd | Curable composition, cured product, its manufacturing method and light emitting diode encapsulated by cured product |
| JP2008069210A (en) | 2006-09-12 | 2008-03-27 | Shin Etsu Chem Co Ltd | Polycyclic hydrocarbon group-containing silicone-based curable composition |
| JP4862032B2 (en) | 2008-12-05 | 2012-01-25 | 信越化学工業株式会社 | Addition-curable silicone composition that provides a cured product having a high refractive index, and an optical element sealing material comprising the composition |
| JP2012046604A (en) | 2010-08-26 | 2012-03-08 | Shin-Etsu Chemical Co Ltd | Curable silicone-based composition containing polycyclic hydrocarbon skeleton component |
| JP6096087B2 (en) * | 2012-12-21 | 2017-03-15 | 信越化学工業株式会社 | Curable silicone resin composition, cured product thereof and optical semiconductor device |
-
2017
- 2017-11-02 JP JP2017213193A patent/JP6823578B2/en active Active
-
2018
- 2018-10-30 KR KR1020180130423A patent/KR102640805B1/en active IP Right Grant
- 2018-11-01 CN CN201811293909.5A patent/CN109749459B/en active Active
- 2018-11-01 TW TW107138752A patent/TWI798283B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921488A (en) * | 2009-06-15 | 2010-12-22 | 信越化学工业株式会社 | Silicone resin composite for die bonding |
| CN104812841A (en) * | 2012-10-30 | 2015-07-29 | 道康宁东丽株式会社 | Curable silicone composition, cured product thereof, and optical semiconductor device |
| CN104968711A (en) * | 2012-12-28 | 2015-10-07 | 道康宁东丽株式会社 | Curable silicone composition, cured product thereof, and optical semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6823578B2 (en) | 2021-02-03 |
| TWI798283B (en) | 2023-04-11 |
| KR20190050283A (en) | 2019-05-10 |
| KR102640805B1 (en) | 2024-02-27 |
| CN109749459A (en) | 2019-05-14 |
| TW201930474A (en) | 2019-08-01 |
| JP2019085467A (en) | 2019-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109749459B (en) | Addition-curable silicone composition, cured product, and optical element | |
| EP2032653B1 (en) | Curable organopolysiloxane composition and semiconductor device | |
| KR101499709B1 (en) | curable organopolysiloxane composition and semiconductor device | |
| JP5524424B1 (en) | Silicone composition for optical semiconductor element sealing and optical semiconductor device | |
| CN108795053B (en) | Addition-curable silicone composition, method for producing same, silicone cured product, and optical element | |
| JP2008019385A (en) | Curable silicone rubber composition and its cured product | |
| EP3587498A1 (en) | Curable organopolysiloxane composition and semiconductor device | |
| CN111574839B (en) | Silicone resin composition for die bonding, cured product, and optical semiconductor device | |
| CN111138860B (en) | Addition-curable silicone resin composition, cured product thereof, and optical semiconductor device | |
| CN112442276A (en) | Addition-curable silicone composition and optical element | |
| KR20230042272A (en) | Anti-sulfur coating materials, cured products thereof, and electronic devices | |
| TWI837415B (en) | Addition hardening polysiloxane compositions and optical components | |
| JP7270574B2 (en) | Addition-curable silicone composition, cured silicone product, and optical element | |
| JP2020070324A (en) | Addition-curable silicone resin composition, cured product of the same, and optical semiconductor device | |
| KR20200096871A (en) | Organomodified silicone resin composition for die-bonding, cured product thereof, and optical semiconductor element | |
| CN111073297A (en) | Addition-curable silicone composition, silicone cured product, and optical element | |
| KR20160049539A (en) | One-part curable silicone composition and optical semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |