WO2014019195A1 - Curable compositions for LED encapsulants comprising a polycarbosilane and a hydrosilicone - Google Patents

Curable compositions for LED encapsulants comprising a polycarbosilane and a hydrosilicone Download PDF

Info

Publication number
WO2014019195A1
WO2014019195A1 PCT/CN2012/079587 CN2012079587W WO2014019195A1 WO 2014019195 A1 WO2014019195 A1 WO 2014019195A1 CN 2012079587 W CN2012079587 W CN 2012079587W WO 2014019195 A1 WO2014019195 A1 WO 2014019195A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
composition according
polycarbosilane
composition
organopolysiloxane
Prior art date
Application number
PCT/CN2012/079587
Other languages
French (fr)
Inventor
Thomas XING
Liwei Zhang
Zhiming Pasing Li
Yong Zhang
Juan Du
Original Assignee
Henkel (China) Company Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel (China) Company Limited filed Critical Henkel (China) Company Limited
Priority to EP12882183.2A priority Critical patent/EP2880095B1/en
Priority to PCT/CN2012/079587 priority patent/WO2014019195A1/en
Priority to KR20157002623A priority patent/KR20150037952A/en
Priority to CN201280074976.2A priority patent/CN104662098A/en
Priority to JP2015524588A priority patent/JP2015529713A/en
Priority to TW102121024A priority patent/TW201406864A/en
Publication of WO2014019195A1 publication Critical patent/WO2014019195A1/en
Priority to US14/609,984 priority patent/US9359478B2/en

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
    • 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
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • 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
    • C08L83/16—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/16—Coating compositions based on 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; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • 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
    • 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
    • C08G77/60—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C08L2203/162—Applications used for films sealable films

Definitions

  • Curable compositions for LED encapsulants comprising a polycarbosilane and a hydrosilicone
  • the present invention relates to curable compositions comprising a combination of at least one polycarbosilane comprising vinyl functionality and at least one organopoly- siloxane comprising hydrogen functionality, and light emitting devices encapsulated with products prepared by curing these compositions. More particularly, the invention relates to hydrosilylation-curable compositions that cure to form polycarbosilane/polysiloxane products having optical clarity, resistance to high temperature, and very good moisture and gas barrier properties. This invention further relates to reliable light emitting devices encapsulated with these compositions.
  • LEDs Light emitting diodes
  • LEDs have a variety of favorable properties including long life, high brightness, low voltage, and small size, an almost complete absence of heat rays during use, and good retention of light emitting efficiency even at low temperature.
  • a composition for sealing a light emitting element is required not only to protect the light emitting element from external influences but also to provide satisfactory and stable adhesiveness of the light emitting element to a support substrate of polyphthalamide, ceramics, or the like, supporting the light emitting element.
  • the composition needs also to have high transparency so as not to decrease luminance of the light emitting element.
  • a sealing composition for example, epoxy resin and the like have been conventionally used.
  • LEDs have become more and more efficient, resulting in increased luminance, increased heat generation during use and emission of light of shorter wavelength, and thus the use of the epoxy resin has been a cause of cracking and yellowing. Therefore, organopolysiloxane compositions (silicone compositions) have been used because of their excellence in heat resistance and ultraviolet resistance.
  • addition-reaction type silicone compositions curing via hydrosilylation reaction have been widely used since they are excellent in productivity because of their quick curability by heating and avoidance of formation of any byproduct when cured.
  • WO 2008023537 A1 describes a curable organopolysiloxane composition comprising at least the following components: (A) a linear diorganopolysiloxane with a mass average molecular weight of at least 3,000, (B) a branched organopolysiloxane, (C) an
  • organopolysiloxane having, on average, at least two silicon-bonded aryl groups and, on average, at least two silicon-bonded hydrogen atoms in one molecule, and (D) a hydrosilylation reaction catalyst;
  • this composition has excellent curability and, when cured, forms a flexible cured product of high refractive index, optical transmissivity, excellent adherence to various substrates, high hardness and slight surface tack.
  • EP 2032653 B1 discloses a curable organopolysiloxane composition
  • a curable organopolysiloxane composition comprising at least the following components: an organopolysiloxane (A) represented by the following general formula: R 3 SiO(R 2 SiO) m SiR 3 (where R is a monovalent hydrocarbon group, and "m” is an integer from 0 to 100); an organopolysiloxane (B) represented by the following average unit formula: (R 2 Si0 3 2)a(R 2 2Si0 2 2) (R 2 3Si0 1 2)c (where R 2 is a monovalent hydrocarbon group, and "a", "b", and “c” are specific numbers); an organopolysiloxane (C) having in one molecule on average at least two silicon-bonded aryl groups and on average at least two silicon-bonded hydrogen atoms; and a hydrosilylation-reaction catalyst (D); this composition is characterized by good gap filling properties and cur
  • US 20070249790 A1 describes a colorless transparent silicone lens produced by thermally curing a silicone resin composition
  • a silicone resin composition comprising (A) an organopolysiloxane having a resin structure comprising R SiOi. 5 units, R 2 2 SiO units, and R 3 a R 4 b SiO(4-a-b)/2 units, wherein R , R 2 , and R 3 are independently a methyl group, an ethyl group, a propyl group, a cyclohexyl group, or a phenyl group, R 4 is a vinyl group or an allyl group, a is 0, 1 , or 2, b is 1 or 2, and a+b is 2 or 3, and wherein the number of repetition of the R 2 2 SiO unit is 5 to 300, (B) an organohydrogen polysiloxane having a resin structure comprising R Si0 1 5 units, R 2 2 SiO units, and R 3 c H d SiO (4-c
  • US 20080160322 A1 describes a silicone composition for sealing a light emitting element including (A) a vinyl group-containing organopolysiloxane having a three-dimensional network structure represented by the average unit formula
  • EP 1767580 A1 discloses an addition reaction curing silicone composition, comprising an organopolysiloxane, wherein some of the silicon atoms may be linked via bivalent hydrocarbon groups of 2 to 10 carbon atoms. However, at least 80 mol-% of all groups bridging two silicon atoms have to be oxygen atoms, i.e. the polymeric backbone predominantly consists of siloxane units with only few silalkylene or silarylene units being allowed.
  • the composition is said to be particularly useful as a sealing material for photo devices such as LEDs, as well as lens material or hard coating agent or the like.
  • KR 20100030959 A teaches polysiloxanes for sealing materials or a lens of a LED.
  • the polysiloxanes comprise a repeating unit [-Si(R1 )(R2)-X1-C 6 H 4 -Y1-] m , wherein R1 and R2 are independently H, methyl, ethyl, phenyl or C2-C6 alkenyl; X1 and Y1 are independently C0-C6 alkylene, C2-C6 alkenylene, C2-C6 alkynylene, NH or O; and m is 1 or more.
  • the presence of siloxane units is not excluded.
  • the silicon-containing polymers further comprise siloxane units. The molar amount of units comprising said
  • the polymers may be used in curable polymer compositions suitable for obtaining a cured product characterized by a high index of refraction. Such compositions are useful as a sealant for optical devices such as LEDs and for use in optical instruments.
  • silicone compositions are widely used as LED encapsulant material.
  • silicone compositions have large free volume as an inherent property, they show much worse gas and moisture barrier properties than epoxy based materials. Thus, moisture penetrates more easily through the encapsulating material resulting in the corrosion of LED chips, which greatly influences the durability of LEDs.
  • the object of the invention is to provide a composition, which is curable via hydrosilylation and after curing exhibits high transparency, heat stability, and very good gas and moisture barrier properties.
  • the inventors found that Si-[bivalent hydrocarbon group]-Si bonds, and in particular Si-C 2 H 4 -Si bonds and Si-C 6 H 4 -Si bonds are very stable even at high temperature, and hence, such bonds are used to build up the backbones of polymers useful for this invention.
  • Such polymers comprise in the backbone solely silicon atoms which are linked via said bivalent hydrocarbon groups and, hence, such polymers are called in the following polycarbosilanes.
  • the objects of the invention are achieved by providing a composition as set forth hereinafter.
  • the invention relates to a curable composition, in particular a transparent LED encapsulant composition, comprising:
  • R , R 2 , R 3 , R 4 , R 5 , and R 6 each independently designates a methyl group, an ethyl group, a vinyl group, or a phenyl group, with the proviso that each molecule comprises at least 2 vinyl groups; each X independently designates a bivalent C 2 H 4 hydrocarbon group or phenylene; and M, D, T, and Q each represents a number ranging from 0 to less than 1 , provided that M+D+T+Q is 1 ,
  • the organopolysiloxane B comprises hydrogen atoms directly bonded to silicon and, hence, may also be called organohydrogenpolysiloxane or hydrosilicone.
  • the present invention relates to a cured composition obtainable by heating a composition according to the present invention, as well as to the use of a composition according to the present invention as semiconductor encapsulating material and/or electronic elements packaging material.
  • composition according to the invention comprises a polycarbosilane A represented by formula (1 ) and a organopolysiloxane B represented by formula (2).
  • the polymer comprises different "units", wherein a unit is understood to be a structural motive which is formed of 1 silicon-atom and - according to the number of valencies at the silicon-atom - 4 bridging groups X or O and remaining groups R, respectively, being directly bonded to the silicon-atom.
  • a unit having only one bridging group is also called mono-functional or M-unit.
  • a unit having two bridging groups is called di-functional or D-unit, a unit having three bridging groups tri-functional or T-unit, and a unit having four bridging groups tetra-functional or Q-unit.
  • the number of specific units being present in a particular polymer is represented by the indices M and M', D and D', T and T', and Q and Q".
  • bridging units X can be different not only within the various types of units of a particular polycarbosilane but also within various units of one and the same type and even within one single unit.
  • a D-unit comprising two bridging groups like the [R 4 R3 ⁇ 4iX 2 /2] unit in formula (1 ) may contain two identical bridging groups, namely 2/2 bivalent C 2 H 4 groups or 2/2 phenylene groups.
  • such unit may also comprise 1/2 bivalent C 2 H 4 group and 1/2 phenylene group.
  • the polycarbosilane A substantially is a liquid or solid polycarbosilane with linear or branched structure represented by the average compositional formula (1 ) as set forth above.
  • the polycarbosilane A has a branched structure, i.e. corresponds to formula (1 ), wherein T+Q is greater than 0.
  • the weight average molecular weight of the polycarbosilane according to the present invention is 100-300,000 g/mol, preferably 1 ,000-50,000 g/mol (GPC, standard: polystyrene).
  • Their viscosity is preferably 0.1-100 Pa s at 25°C and more preferably 0.5-50 Pa s at 25°C (Brookfield DV-+Digital Viscometer/LV, (spindle S64, rotation speed 50 rpm)).
  • X preferably designates a bivalent C 2 H 4 hydrocarbon group.
  • a "curable composition” is understood to be a mixture of two or more substances which mixture can be converted from a soft state into a harder state by means of physical or chemical actions. Those physical or chemical actions can consist, for example, in the delivery of energy in the form of heat, light, or other electromagnetic radiation, but also in simply bringing into contact with atmospheric moisture, water, or a reactive component.
  • the composition of the present invention is heat-curable.
  • the curable composition of the invention further comprises at least an organopolysiloxane B represented by formula (2).
  • organopolysiloxane comprises at least two hydrogen atoms directly bonded to silicon per molecule.
  • the organopolysiloxane B substantially is a liquid or solid polycarbosilane with linear or branched structure. Preferably, it has a linear structure, i.e. corresponds to formula (2), wherein T'+Q' is 0, and D' is greater than 0.
  • the weight average molecular weight of the organopolysiloxane B is 1 ,000-300,000 g/mol, and more preferred 10,000-100,000 g/mol (GPC, standard:
  • polystyrene polystyrene
  • Their viscosity is preferably 0.1-100 Pa s at 25°C and more preferably 0.5-50 Pa s at 25°C (Brookfield DV-+Digital Viscometer/LV, (spindle S64, rotation speed 50 rpm)).
  • the curable composition preferably comprises an organopolysiloxane B comprising 0.8-8 mmol/g silicon-bonded hydrogen atoms.
  • the curable composition preferably comprises polycarbosilane A and organopolysiloxane B in respective amounts to provide a molar ratio of silicon-bonded hydrogen atoms (i.e. SiH groups) resulting from the presence of any organopolysiloxane B to silicon-bonded vinyl groups resulting from the presence of any poylcarbosilane A in the range of 0.5 to 10, more preferably of 0.8 to 4, and most preferably of 1 to 3.
  • SiH groups silicon-bonded hydrogen atoms
  • Si-H/Si-Vinyl ratio is preferably 0.5-10, more preferably 0.8-4.0, and most preferably 1.0-3.0.
  • the curable composition furthermore comprises at least a catalyst.
  • catalyst any compound may be used which is able to promote the hydrosilylation addition reaction between vinyl and/or allyl groups in polycarbosilane A and Si-H groups in oraganopoly- siloxane B.
  • Typical addition reaction catalysts are platinum group metal catalysts including platinum catalysts, such as the reaction products of chloroplatinic acid with monohydric alcohols, complexes of chloroplatinic acid with olefins, and platinum bisacetoacetate, as well as palladium catalysts and rhodium catalysts.
  • the catalyst is one or more compound selected from the group consisting of platinum group metal catalysts.
  • the amount of the catalyst used preferably is used in such an amount to give about 1 to 500 ppm, especially about 2 to 100 ppm of metal, especially of platinum group metal, based on the total weight of the curable composition.
  • the term "metal” or “platinum group metal”, respectively, only refers to the content of the metal itself, even if in the curable composition the metal is present as a complex compound.
  • the curable composition of the invention may be prepared by simply mixing all ingredients. A thus prepared mixture is ready to be applied and to be cured, e.g. by applying heat.
  • the composition is a two-component preparation consisting of component 1 and component 2, wherein component 1 comprises polycarbosilane A and the total amount of catalyst being present and component 2 comprises the total amount of organopolysiloxane B being present and optionally further polycarbosilane A.
  • component 1 comprises polycarbosilane A and the total amount of catalyst being present
  • component 2 comprises the total amount of organopolysiloxane B being present and optionally further polycarbosilane A.
  • Each component may be filled in a different container, e.g. a tube or jar, or a different compartment of a two-compartment container, e.g. a two-chamber tube. This allows to safely storing the composition without causing premature curing.
  • Component 1 and component 2 are kept separately until application.
  • component 1 and component 2 are mixed and the mixture is applied to the desired place.
  • composition according to the present invention may further comprise optional components insofar as the objects of the invention are not compromised.
  • optional components include addition reaction inhibitors for adjusting curing time and imparting a pot life, and adhesion promoters to improve the adhesive properties of the composition.
  • Suitable reaction inhibitors include ethynylcyclohexanol, 2-methyl-3-butyn-2-ol,
  • adhesion promoter is understood to mean a substance that improves the adhesion properties of the composition on surfaces.
  • Conventional adhesion promoters tackifiers known to the person skilled in the art can be used individually or as a combination of several compounds. Suitable examples include resins, terpene oligomers,
  • coumarone/indene resins aliphatic petrochemical resins and modified phenolic resins.
  • Suitable within the framework of the present invention are, for example, hydrocarbon resins, as obtained by polymerization of terpenes, mainly a- or ⁇ -pinene, dipentene or limonene. Polymerization of these monomers is usually cationic with initiation using Friedel-Crafts catalysts.
  • the terpene resins also include copolymers of terpenes and other monomers, such as styrene, a-methylstyrene, isoprene and the like.
  • the above-mentioned resins are used, for example, as adhesion promoters for
  • the composition comprises an aminosilane of the general formula (3)
  • R' and R" are, independently of one another, hydrogen or d - C 8 alkyl residues
  • R is a divalent hydrocarbon residue having 1 - 12 C atoms optionally containing a heteroatom
  • X', Y', Z' are, independently of one another, d - C 8 alkyl, d - C 8 alkoxy or d - C 8 acyloxy residues, at least one of the residues being a d - C 8 alkoxy or d - C 8 acyloxy group.
  • Such compounds inherently exhibit a high affinity to the binding polymer components of the curable composition according to the invention, but also to a wide range of polar and non-polar surfaces and therefore contribute to the formation of particularly stable adhesion between the cured composition and the substrates to be bonded or encapsulated in each case.
  • the linking group R can be, for example, a straight-chained or branched or cyclic, substituted or unsubstituted alkylene residue. As a heteroatom, nitrogen (N) or oxygen (O) is optionally contained therein. If X', Y' and/or Z' are an acyloxy group, this can be, for example, the acetoxy group -OCO-CH 3 .
  • inorganic fillers for enhancing the strength of the composition.
  • Suitable fillers for the composition according to the invention are, for example, chalk, lime powder, precipitated and/or pyrogenic silica, zeolites, bentonites, magnesium carbonate, kieselguhr, alumina, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder and other ground minerals.
  • organic fillers especially carbon black, graphite, wood fibers, wood flour, sawdust, wood pulp, cotton, pulp, wood chips, chopped straw, chaff, ground walnut shells and other chopped fibers, can also be used.
  • short fibers such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber or polyethylene fibers can also be added.
  • Aluminum powder is also suitable as filler.
  • hollow spheres with a mineral shell or a plastic shell are suitable as fillers. These can be, for example, hollow glass spheres, which are commercially available with the trade names Glass Bubbles ® . Hollow spheres based on plastics are available for example under the trade names Expancel ® or Dualite ® . These are composed of inorganic or organic substances, each having a diameter of 1 mm or less, preferably of 500 ⁇ or less. For some applications, fillers which impart thixotropy to the preparations are preferred. Such fillers are also described as rheological auxiliaries, e.g. hydrogenated castor oil, fatty acid amides or swellable plastics such as PVC.
  • rheological auxiliaries e.g. hydrogenated castor oil, fatty acid amides or swellable plastics such as PVC.
  • such preparations have a viscosity of 3,000 to 15,000, preferably 4,000 to 8,000 mPas or 5,000 to 6,000 mPas.
  • the fillers may be used in a quantity of 1 to 80 wt.%, based on the total weight of the composition. A single filler or a combination of several fillers can be used.
  • the filler is highly dispersed silica having a BET surface area of from 10 to 90 m 2 /g, in particular from 35 to 65 m 2 /g.
  • silica of this type it does not cause a substantial increase in the viscosity of the composition according to the invention but contributes to a reinforcement of the cured composition.
  • this reinforcement for example, the initial strengths, shear strengths and the adhesion of the adhesives, sealants or coating compositions in which the composition according to the invention is used are improved.
  • highly dispersed silica having a BET surface area of 45 to 55 m 2 /g, in particular having a BET surface area of about 50 m 2 /g, is used.
  • Such silicas have the added advantage of a 30 to 50% shorter incorporation time in comparison to silicas with a higher BET surface area.
  • Another advantage lies in the fact that said highly dispersed silica can be incorporated at a considerably higher concentration without the
  • the filler is highly dispersed silica with a mean particle size d 50 , measured by laser diffraction, of less than 25 ⁇ , preferably from 5 to 20 ⁇ .
  • a filler of this type is especially suitable where highly transparent, clear compositions are needed for particularly demanding applications.
  • pyrogenic and/or precipitated silicas with a relatively high BET surface area, advantageously with 100 - 250 m 2 /g, in particular 1 10 - 170 m 2 /g, as filler.
  • the incorporation of such silicas takes a comparatively long time and is therefore more costly.
  • significant quantities of air are introduced into the product, which has to be removed again in a complicated and time-consuming manner.
  • a basic filler for example calcium carbonates (chalks) are suitable, in which case cubic, non-cubic, amorphous and other modifications can be used.
  • the chalks used are surface treated or coated.
  • a coating agent preferably fatty acids, fatty acid soaps and fatty acid esters are used, for example lauric acid, palmitic acid or stearic acid, sodium or potassium salts of such acids or their alkyl esters.
  • the surface treatment of chalks is often associated with an improvement in processability and adhesive strength and also the weathering resistance of the compositions.
  • the coating composition is usually used in a proportion of 0.1 to 20 wt%, preferably 1 to 5 wt%, based on the total weight of the crude chalk.
  • ground chalks can be produced, for example, from natural lime, limestone or marble by mechanical grinding, using either dry or wet methods. Depending on the grinding process, fractions having different average particle sizes can be obtained.
  • Advantageous specific surface area values (BET) are between 1.5 m 2 /g and 50 m 2 /g.
  • phosphor and antidegradants may also be added.
  • auxiliary substances and additives include plasticizers, stabilizers, antioxidants, reactive diluents, drying agents, UV stabilizers, anti-ageing agents, rheological auxiliaries, fungicides and/or flame retardants.
  • Curing of the compositions according to the invention typically involves heating at 50 to 200°C, and particularly at 70 to 160°C, for 1 to 60 minutes, and particularly for 2 to 30 minutes. Furthermore, post-curing may also be conducted at 50 to 200°C, and particularly at 70 to 160°C, for 0.1 to 10 hours, and particularly for 1 to 4 hours.
  • the invention relates to cured products obtainable by heating a curable composition according to the invention.
  • a further subject matter of the present invention is the use of a curable composition according to the invention in encapsulation, sealing, protection, bonding and/or lens formation materials, in particular as semiconductor encapsulating material and/or electronic elements packaging material.
  • the composition of the invention can provide enhanced barrier properties against moisture and gases.
  • the composition according to the invention is advantageously used in encapsulation materials for the encapsulation of semiconductor devices, especially of light emitting devices (LEDs).
  • weight average molecular weight values are polystyrene-equivalent values measured using gel permeation chromatography (GPC).
  • Hydrogen content was titrated as disclosed in Feng S. Y.; Zhang, J.; Li, M. J.; Zhu, Q. Z.; Organosilicon Polymer and Application Thereof, p. 400-401 ; Chemical Industry Press. Transmittance was measured by an UV-Visible spectrum analyzer Lambda 650S manufactured by PerkinElmer Corporation. The transmittance was measured for the range from 300 nm to 800 nm, and the value at 450 nm was recorded as the
  • Divinyldimethylsilane (CAS 10519-87-6) was purchased from Ruilijie Chemical Company.
  • Platinum catalyst SIP 6832.2 (2.0 - 2.3% platinum concentration in cyclic methylvinylsiloxanes, CAS: 68585-32-0) was purchased from Gelest.
  • HPM-502 (a hydride terminated methylhydrosiloxane-phenylmethylsiloxane copolymer having a viscosity of 100 mPa*S, and a weight average weight of 1359 g/mol, a hydrogen content of 6.06 mmol/g, and a phenyl content of 35.4 weight-%) was purchased from Gelest.
  • the obtained polymer has an average formula of
  • the resulting cured product was evaluated regarding permeation, cracking, adhesion/lamination, initial transparency at 450 nm (T@450nm (initial)), and
  • cured products according to the invention show improved permeation behavior compared to cured products obtainable from commercially available encapsulating materials based solely on organopoly- siloxanes. Thermal stabilities are comparable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Sealing Material Composition (AREA)
  • Silicon Polymers (AREA)

Abstract

The present invention provides a curable composition, comprising: (A) at least one polycarbosilane A represented by the following formula (1 ) [R1R2R3SiX1/2]M[R4R5SiX2/2]D[R6SiX3/2]T[SiX4/2]Q (1 ), wherein R1, R2, R3, R4, R5, and R6, each independently designates a methyl group, an ethyl group, a vinyl group, or a phenyl group, with the proviso that each molecule comprises at least 2 vinyl groups; each X independently designates a bivalent C2H4 hydrocarbon group or phenylene; and M, D, T, and Q each represents a number ranging from 0 to less than 1, provided that M+D+T+Q is 1, (B) at least one organopolysiloxane B represented by the following formula (2): [R7R8R9SiO1/2)M'(R10R11SiO2/2)D'(R12SiO3/2)T'(SiO4/2)Q', (2), wherein R7, R8, R9, R10, R11, and R12, each independently designates a methyl group, an ethyl group, a vinyl group, a phenyl group, or hydrogen, with the proviso that each molecule comprises at least 2 hydrogen atoms directly bonded to silicon; and M', D', T', and Q' each represents a number ranging from 0 to less than 1, provided that M'+D'+T'+Q' is 1, and (C) at least a catalyst, as well as a cured product obtainable by heating such composition, and the use of the composition as semiconductor encapsulating material and/or electronic elements packaging material.

Description

Curable compositions for LED encapsulants comprising a polycarbosilane and a hydrosilicone
Field of the Invention
The present invention relates to curable compositions comprising a combination of at least one polycarbosilane comprising vinyl functionality and at least one organopoly- siloxane comprising hydrogen functionality, and light emitting devices encapsulated with products prepared by curing these compositions. More particularly, the invention relates to hydrosilylation-curable compositions that cure to form polycarbosilane/polysiloxane products having optical clarity, resistance to high temperature, and very good moisture and gas barrier properties. This invention further relates to reliable light emitting devices encapsulated with these compositions.
Background Art
Light emitting diodes (LEDs) have a variety of favorable properties including long life, high brightness, low voltage, and small size, an almost complete absence of heat rays during use, and good retention of light emitting efficiency even at low temperature.
In a light emitting device such as a light emitting diode (LED), a composition for sealing a light emitting element is required not only to protect the light emitting element from external influences but also to provide satisfactory and stable adhesiveness of the light emitting element to a support substrate of polyphthalamide, ceramics, or the like, supporting the light emitting element. The composition needs also to have high transparency so as not to decrease luminance of the light emitting element.
As such a sealing composition, for example, epoxy resin and the like have been conventionally used. However, recently LEDs have become more and more efficient, resulting in increased luminance, increased heat generation during use and emission of light of shorter wavelength, and thus the use of the epoxy resin has been a cause of cracking and yellowing. Therefore, organopolysiloxane compositions (silicone compositions) have been used because of their excellence in heat resistance and ultraviolet resistance. In particular, addition-reaction type silicone compositions curing via hydrosilylation reaction have been widely used since they are excellent in productivity because of their quick curability by heating and avoidance of formation of any byproduct when cured.
Many references deal with such silicone compositions and their use for LED
manufacturing.
WO 2008023537 A1 describes a curable organopolysiloxane composition comprising at least the following components: (A) a linear diorganopolysiloxane with a mass average molecular weight of at least 3,000, (B) a branched organopolysiloxane, (C) an
organopolysiloxane having, on average, at least two silicon-bonded aryl groups and, on average, at least two silicon-bonded hydrogen atoms in one molecule, and (D) a hydrosilylation reaction catalyst; this composition has excellent curability and, when cured, forms a flexible cured product of high refractive index, optical transmissivity, excellent adherence to various substrates, high hardness and slight surface tack.
EP 2032653 B1 discloses a curable organopolysiloxane composition comprising at least the following components: an organopolysiloxane (A) represented by the following general formula: R 3SiO(R 2SiO)mSiR 3 (where R is a monovalent hydrocarbon group, and "m" is an integer from 0 to 100); an organopolysiloxane (B) represented by the following average unit formula: (R2Si03 2)a(R22Si02 2) (R23Si01 2)c (where R2 is a monovalent hydrocarbon group, and "a", "b", and "c" are specific numbers); an organopolysiloxane (C) having in one molecule on average at least two silicon-bonded aryl groups and on average at least two silicon-bonded hydrogen atoms; and a hydrosilylation-reaction catalyst (D); this composition is characterized by good gap filling properties and curability and, upon curing, forms a cured body that possesses a high refractive index, high light transmissivity, and strong adhesion to various substrates.
US 20070249790 A1 describes a colorless transparent silicone lens produced by thermally curing a silicone resin composition comprising (A) an organopolysiloxane having a resin structure comprising R SiOi.5 units, R2 2SiO units, and R3 aR4 bSiO(4-a-b)/2 units, wherein R , R2, and R3 are independently a methyl group, an ethyl group, a propyl group, a cyclohexyl group, or a phenyl group, R4 is a vinyl group or an allyl group, a is 0, 1 , or 2, b is 1 or 2, and a+b is 2 or 3, and wherein the number of repetition of the R2 2SiO unit is 5 to 300, (B) an organohydrogen polysiloxane having a resin structure comprising R Si01 5 units, R2 2SiO units, and R3 cHdSiO (4-c d) 2 units, wherein c is 0, 1 , or 2, d is 1 or 2, and c+d is 2 or 3, and wherein the number of repetition of the R2 2SiO unit is 5 to 300, and (C) a platinum group catalyst. This composition shows excellent flexibility, transparency, and moldability as well as reduced surface tackiness is provided.
US 20080160322 A1 describes a silicone composition for sealing a light emitting element including (A) a vinyl group-containing organopolysiloxane having a three-dimensional network structure represented by the average unit formula
(Si04 2)a(ViR2Si01 2) (R3Si01 2)c, wherein Vi represents a vinyl group, R's are identical or different substituted or unsubstituted monovalent hydrocarbon groups other than alkenyl groups, and a, b, and c are positive numbers satisfying that a/(a+b+c) is 0.2 to 0.6 and b/(a+b+c) is 0.001 to 0.2; (B) an organohydrogenpolysiloxane containing at least two hydrogen atoms per molecule, each hydrogen atom being bonded to a silicon atom, the organohydrogenpolysiloxane being contained in such an amount that the amount of hydrogen atoms bonded to a silicon atom is 0.3 to 3.0 mol per 1 mol of a vinyl group bonded to a silicon atom in the component (A); and (C) a catalytic amount of a hydrosilylation catalyst, wherein the coefficient of linear expansion of the composition after curing is 10 <10~6to 290x 10~6/°C. It is possible to obtain a cured product whose residual stress with a support substrate is reduced and which has long-term satisfactory and stable adhesiveness.
EP 1767580 A1 discloses an addition reaction curing silicone composition, comprising an organopolysiloxane, wherein some of the silicon atoms may be linked via bivalent hydrocarbon groups of 2 to 10 carbon atoms. However, at least 80 mol-% of all groups bridging two silicon atoms have to be oxygen atoms, i.e. the polymeric backbone predominantly consists of siloxane units with only few silalkylene or silarylene units being allowed. The composition is said to be particularly useful as a sealing material for photo devices such as LEDs, as well as lens material or hard coating agent or the like.
KR 20100030959 A teaches polysiloxanes for sealing materials or a lens of a LED. The polysiloxanes comprise a repeating unit [-Si(R1 )(R2)-X1-C6H4-Y1-]m, wherein R1 and R2 are independently H, methyl, ethyl, phenyl or C2-C6 alkenyl; X1 and Y1 are independently C0-C6 alkylene, C2-C6 alkenylene, C2-C6 alkynylene, NH or O; and m is 1 or more. The presence of siloxane units is not excluded.
From WO 2009/131023 A1 silicon-containing polymers are known comprising
-R2-C6H4-R2- units bridging neighboring silicon atoms, wherein R2 designates identical or different, substituted or unsubstituted alkylene groups. The silicon-containing polymers further comprise siloxane units. The molar amount of units comprising said
-R2-C6H4-R2- bridges within the silicon-containing polymer is below 10 %. The polymers may be used in curable polymer compositions suitable for obtaining a cured product characterized by a high index of refraction. Such compositions are useful as a sealant for optical devices such as LEDs and for use in optical instruments.
From the above documents, it can be seen that silicone compositions are widely used as LED encapsulant material. However, since silicone compositions have large free volume as an inherent property, they show much worse gas and moisture barrier properties than epoxy based materials. Thus, moisture penetrates more easily through the encapsulating material resulting in the corrosion of LED chips, which greatly influences the durability of LEDs.
Therefore, it is a great challenge to develop an LED encapsulant with both very good gas and moisture barrier properties and at the same time thermal stability equal to the stability of silicone compositions.
Summary of the Invention
The object of the invention is to provide a composition, which is curable via hydrosilylation and after curing exhibits high transparency, heat stability, and very good gas and moisture barrier properties. The inventors found that Si-[bivalent hydrocarbon group]-Si bonds, and in particular Si-C2H4-Si bonds and Si-C6H4-Si bonds are very stable even at high temperature, and hence, such bonds are used to build up the backbones of polymers useful for this invention. Such polymers comprise in the backbone solely silicon atoms which are linked via said bivalent hydrocarbon groups and, hence, such polymers are called in the following polycarbosilanes. The objects of the invention are achieved by providing a composition as set forth hereinafter. In a first aspect the invention relates to a curable composition, in particular a transparent LED encapsulant composition, comprising:
(A) at least one polycarbosilane A represented by the following formula (1 ):
[R R2 R3SiX1/2]M[R4R5SiX2/2]D[R6SiX3/2]-r[SiX4/2]Q (1 ), wherein R , R2, R3, R4, R5, and R6, each independently designates a methyl group, an ethyl group, a vinyl group, or a phenyl group, with the proviso that each molecule comprises at least 2 vinyl groups; each X independently designates a bivalent C2H4 hydrocarbon group or phenylene; and M, D, T, and Q each represents a number ranging from 0 to less than 1 , provided that M+D+T+Q is 1 ,
(B) at least one organopolysiloxane B represented by the following formula (2):
[R7R8 R9SiOi/dM-[R10R11SiOM]D-[R12SiO3e]r[SiO4/2]Q-, (2), wherein R7, R8, R9, R 0, R , and R 2, each independently designates a methyl group, an ethyl group, a vinyl group, a phenyl group, or hydrogen, with the proviso that each molecule comprises at least 2 hydrogen atoms directly bonded to silicon; and M', D', T', and Q' each represents a number ranging from 0 to less than 1 , provided that M'+D'+T'+Q' is 1 , and
(C) at least a catalyst.
The organopolysiloxane B comprises hydrogen atoms directly bonded to silicon and, hence, may also be called organohydrogenpolysiloxane or hydrosilicone.
Furthermore, the present invention relates to a cured composition obtainable by heating a composition according to the present invention, as well as to the use of a composition according to the present invention as semiconductor encapsulating material and/or electronic elements packaging material. Detailed Description
The composition according to the invention comprises a polycarbosilane A represented by formula (1 ) and a organopolysiloxane B represented by formula (2). In both cases the polymer comprises different "units", wherein a unit is understood to be a structural motive which is formed of 1 silicon-atom and - according to the number of valencies at the silicon-atom - 4 bridging groups X or O and remaining groups R, respectively, being directly bonded to the silicon-atom. A unit having only one bridging group is also called mono-functional or M-unit. A unit having two bridging groups is called di-functional or D-unit, a unit having three bridging groups tri-functional or T-unit, and a unit having four bridging groups tetra-functional or Q-unit. The number of specific units being present in a particular polymer is represented by the indices M and M', D and D', T and T', and Q and Q".
It is understood that the bridging units X can be different not only within the various types of units of a particular polycarbosilane but also within various units of one and the same type and even within one single unit. Thus, e. g. a D-unit comprising two bridging groups, like the [R4R¾iX2/2] unit in formula (1 ), may contain two identical bridging groups, namely 2/2 bivalent C2H4 groups or 2/2 phenylene groups. However, such unit may also comprise 1/2 bivalent C2H4 group and 1/2 phenylene group. The corresponding applies to the bridging groups in T-, and Q-units.
The polycarbosilane A substantially is a liquid or solid polycarbosilane with linear or branched structure represented by the average compositional formula (1 ) as set forth above.
Preferably, the polycarbosilane A has a branched structure, i.e. corresponds to formula (1 ), wherein T+Q is greater than 0.
It is preferred that the weight average molecular weight of the polycarbosilane according to the present invention is 100-300,000 g/mol, preferably 1 ,000-50,000 g/mol (GPC, standard: polystyrene). Their viscosity is preferably 0.1-100 Pa s at 25°C and more preferably 0.5-50 Pa s at 25°C (Brookfield DV-+Digital Viscometer/LV, (spindle S64, rotation speed 50 rpm)). In formula (1 ) X preferably designates a bivalent C2H4 hydrocarbon group.
A "curable composition" is understood to be a mixture of two or more substances which mixture can be converted from a soft state into a harder state by means of physical or chemical actions. Those physical or chemical actions can consist, for example, in the delivery of energy in the form of heat, light, or other electromagnetic radiation, but also in simply bringing into contact with atmospheric moisture, water, or a reactive component. Preferably, the composition of the present invention is heat-curable.
The curable composition of the invention further comprises at least an organopolysiloxane B represented by formula (2). Such organopolysiloxane comprises at least two hydrogen atoms directly bonded to silicon per molecule.
The organopolysiloxane B substantially is a liquid or solid polycarbosilane with linear or branched structure. Preferably, it has a linear structure, i.e. corresponds to formula (2), wherein T'+Q' is 0, and D' is greater than 0.
It is preferred that the weight average molecular weight of the organopolysiloxane B is 1 ,000-300,000 g/mol, and more preferred 10,000-100,000 g/mol (GPC, standard:
polystyrene). Their viscosity is preferably 0.1-100 Pa s at 25°C and more preferably 0.5-50 Pa s at 25°C (Brookfield DV-+Digital Viscometer/LV, (spindle S64, rotation speed 50 rpm)).
The curable composition preferably comprises an organopolysiloxane B comprising 0.8-8 mmol/g silicon-bonded hydrogen atoms.
The curable composition preferably comprises polycarbosilane A and organopolysiloxane B in respective amounts to provide a molar ratio of silicon-bonded hydrogen atoms (i.e. SiH groups) resulting from the presence of any organopolysiloxane B to silicon-bonded vinyl groups resulting from the presence of any poylcarbosilane A in the range of 0.5 to 10, more preferably of 0.8 to 4, and most preferably of 1 to 3. In other words the
Si-H/Si-Vinyl ratio is preferably 0.5-10, more preferably 0.8-4.0, and most preferably 1.0-3.0. The curable composition furthermore comprises at least a catalyst. As catalyst any compound may be used which is able to promote the hydrosilylation addition reaction between vinyl and/or allyl groups in polycarbosilane A and Si-H groups in oraganopoly- siloxane B. Typical addition reaction catalysts are platinum group metal catalysts including platinum catalysts, such as the reaction products of chloroplatinic acid with monohydric alcohols, complexes of chloroplatinic acid with olefins, and platinum bisacetoacetate, as well as palladium catalysts and rhodium catalysts.
Preferably, the catalyst is one or more compound selected from the group consisting of platinum group metal catalysts.
There are no specific restrictions with regard to the amount of the catalyst used, provided that it is added in a catalytic amount sufficient for accelerating the desired hydrosilylation reaction. The addition reaction catalyst preferably is used in such an amount to give about 1 to 500 ppm, especially about 2 to 100 ppm of metal, especially of platinum group metal, based on the total weight of the curable composition. The term "metal" or "platinum group metal", respectively, only refers to the content of the metal itself, even if in the curable composition the metal is present as a complex compound.
The curable composition of the invention may be prepared by simply mixing all ingredients. A thus prepared mixture is ready to be applied and to be cured, e.g. by applying heat.
However, in one embodiment of the invention the composition is a two-component preparation consisting of component 1 and component 2, wherein component 1 comprises polycarbosilane A and the total amount of catalyst being present and component 2 comprises the total amount of organopolysiloxane B being present and optionally further polycarbosilane A. Each component may be filled in a different container, e.g. a tube or jar, or a different compartment of a two-compartment container, e.g. a two-chamber tube. This allows to safely storing the composition without causing premature curing. Component 1 and component 2 are kept separately until application. To apply the composition, component 1 and component 2 are mixed and the mixture is applied to the desired place.
In addition to the components (A) to (C) described above, the composition according to the present invention may further comprise optional components insofar as the objects of the invention are not compromised. Possible optional components include addition reaction inhibitors for adjusting curing time and imparting a pot life, and adhesion promoters to improve the adhesive properties of the composition.
Suitable reaction inhibitors include ethynylcyclohexanol, 2-methyl-3-butyn-2-ol,
3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, or similar alkyne alcohols;
3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, or a similar enyne compound; 1 ,3,5,7-tetramethyl-1 ,3,5,7-tetravinyl-cyclotetrasiloxane, 1 ,3,5,7-tetramethyl- 1 ,3,5,7-tetrahexenyl-cyclotetrasiloxane, benzotriazole, or the like. There are no special restrictions with regard to the quantities in which these inhibitors can be added but it is preferred that in term of weight units these inhibitors are added in a quantity of 10 to 1 ,000 ppm per weight of the composition.
An adhesion promoter is understood to mean a substance that improves the adhesion properties of the composition on surfaces. Conventional adhesion promoters (tackifiers) known to the person skilled in the art can be used individually or as a combination of several compounds. Suitable examples include resins, terpene oligomers,
coumarone/indene resins, aliphatic petrochemical resins and modified phenolic resins. Suitable within the framework of the present invention are, for example, hydrocarbon resins, as obtained by polymerization of terpenes, mainly a- or β-pinene, dipentene or limonene. Polymerization of these monomers is usually cationic with initiation using Friedel-Crafts catalysts. The terpene resins also include copolymers of terpenes and other monomers, such as styrene, a-methylstyrene, isoprene and the like. The above-mentioned resins are used, for example, as adhesion promoters for
pressure-sensitive adhesives and coating materials. Also suitable are the terpene phenolic resins, which are produced by acid-catalyzed addition of phenols to terpenes or rosin. Terpene phenolic resins are soluble in most organic solvents and oils and miscible with other resins, waxes and rubber. Also suitable as adhesion promoters within the framework of the present invention in the above sense are the rosins and their derivatives, such as esters or alcohols thereof. Particularly suitable are silane adhesion promoters, in particular aminosilanes and epoxysilanes, for example 3,4-epoxycyclohexylethyl trimethoxysilane. In a specific embodiment of the curable composition according to the invention, the composition comprises an aminosilane of the general formula (3)
R'R"N-R-SiX'Y'Z' (3) as an adhesion promoter, in which
R' and R" are, independently of one another, hydrogen or d - C8 alkyl residues,
R is a divalent hydrocarbon residue having 1 - 12 C atoms optionally containing a heteroatom, and
X', Y', Z' are, independently of one another, d - C8 alkyl, d - C8 alkoxy or d - C8 acyloxy residues, at least one of the residues being a d - C8 alkoxy or d - C8 acyloxy group. Such compounds inherently exhibit a high affinity to the binding polymer components of the curable composition according to the invention, but also to a wide range of polar and non-polar surfaces and therefore contribute to the formation of particularly stable adhesion between the cured composition and the substrates to be bonded or encapsulated in each case.
The linking group R can be, for example, a straight-chained or branched or cyclic, substituted or unsubstituted alkylene residue. As a heteroatom, nitrogen (N) or oxygen (O) is optionally contained therein. If X', Y' and/or Z' are an acyloxy group, this can be, for example, the acetoxy group -OCO-CH3.
Insofar as transparency is not impaired, there may be blended inorganic fillers for enhancing the strength of the composition.
Suitable fillers for the composition according to the invention are, for example, chalk, lime powder, precipitated and/or pyrogenic silica, zeolites, bentonites, magnesium carbonate, kieselguhr, alumina, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder and other ground minerals. In addition, organic fillers, especially carbon black, graphite, wood fibers, wood flour, sawdust, wood pulp, cotton, pulp, wood chips, chopped straw, chaff, ground walnut shells and other chopped fibers, can also be used. Furthermore, short fibers such as glass fiber, glass filament, polyacrylonitrile, carbon fiber, Kevlar fiber or polyethylene fibers can also be added. Aluminum powder is also suitable as filler. In addition, hollow spheres with a mineral shell or a plastic shell are suitable as fillers. These can be, for example, hollow glass spheres, which are commercially available with the trade names Glass Bubbles®. Hollow spheres based on plastics are available for example under the trade names Expancel® or Dualite®. These are composed of inorganic or organic substances, each having a diameter of 1 mm or less, preferably of 500 μηι or less. For some applications, fillers which impart thixotropy to the preparations are preferred. Such fillers are also described as rheological auxiliaries, e.g. hydrogenated castor oil, fatty acid amides or swellable plastics such as PVC. So that they can be pressed out readily from a suitable metering device (e.g. tube), such preparations have a viscosity of 3,000 to 15,000, preferably 4,000 to 8,000 mPas or 5,000 to 6,000 mPas.
The fillers may be used in a quantity of 1 to 80 wt.%, based on the total weight of the composition. A single filler or a combination of several fillers can be used.
In a preferred embodiment of the composition according to the invention, the filler is highly dispersed silica having a BET surface area of from 10 to 90 m2/g, in particular from 35 to 65 m2/g. When silica of this type is used, it does not cause a substantial increase in the viscosity of the composition according to the invention but contributes to a reinforcement of the cured composition. By means of this reinforcement, for example, the initial strengths, shear strengths and the adhesion of the adhesives, sealants or coating compositions in which the composition according to the invention is used are improved.
Particularly preferably, highly dispersed silica having a BET surface area of 45 to 55 m2/g, in particular having a BET surface area of about 50 m2/g, is used. Such silicas have the added advantage of a 30 to 50% shorter incorporation time in comparison to silicas with a higher BET surface area. Another advantage lies in the fact that said highly dispersed silica can be incorporated at a considerably higher concentration without the
transparency and the flow properties of the compositions being impaired. Particular preference is also given to an embodiment of the composition according to the invention in which the filler is highly dispersed silica with a mean particle size d50, measured by laser diffraction, of less than 25 μηι, preferably from 5 to 20 μηι. A filler of this type is especially suitable where highly transparent, clear compositions are needed for particularly demanding applications. It is also conceivable to use pyrogenic and/or precipitated silicas with a relatively high BET surface area, advantageously with 100 - 250 m2/g, in particular 1 10 - 170 m2/g, as filler. The incorporation of such silicas, however, takes a comparatively long time and is therefore more costly. In addition, significant quantities of air are introduced into the product, which has to be removed again in a complicated and time-consuming manner. On the other hand, the effect of a
reinforcement of the cured composition due to the higher BET surface area can be achieved with a smaller proportion by weight of silica. In this way, additional substances can be introduced to improve the preparation according to the invention with regard to other requirements.
In the event that a basic filler is to be used instead of acidic fillers, for example calcium carbonates (chalks) are suitable, in which case cubic, non-cubic, amorphous and other modifications can be used. Preferably, the chalks used are surface treated or coated. As a coating agent, preferably fatty acids, fatty acid soaps and fatty acid esters are used, for example lauric acid, palmitic acid or stearic acid, sodium or potassium salts of such acids or their alkyl esters. In addition, however, other surface-active substances, such as sulfate esters of long-chain alcohols or alkylbenzenesulfonic acids or their sodium or potassium salts or coupling reagents based on silanes or titanates, are also suitable. The surface treatment of chalks is often associated with an improvement in processability and adhesive strength and also the weathering resistance of the compositions. The coating composition is usually used in a proportion of 0.1 to 20 wt%, preferably 1 to 5 wt%, based on the total weight of the crude chalk.
Depending on the desired property profile, precipitated or ground chalks can be used. Ground chalks can be produced, for example, from natural lime, limestone or marble by mechanical grinding, using either dry or wet methods. Depending on the grinding process, fractions having different average particle sizes can be obtained. Advantageous specific surface area values (BET) are between 1.5 m2/g and 50 m2/g.
If desired, phosphor and antidegradants may also be added.
Further auxiliary substances and additives include plasticizers, stabilizers, antioxidants, reactive diluents, drying agents, UV stabilizers, anti-ageing agents, rheological auxiliaries, fungicides and/or flame retardants. Curing of the compositions according to the invention typically involves heating at 50 to 200°C, and particularly at 70 to 160°C, for 1 to 60 minutes, and particularly for 2 to 30 minutes. Furthermore, post-curing may also be conducted at 50 to 200°C, and particularly at 70 to 160°C, for 0.1 to 10 hours, and particularly for 1 to 4 hours.
Furthermore, the invention relates to cured products obtainable by heating a curable composition according to the invention.
A further subject matter of the present invention is the use of a curable composition according to the invention in encapsulation, sealing, protection, bonding and/or lens formation materials, in particular as semiconductor encapsulating material and/or electronic elements packaging material. The composition of the invention can provide enhanced barrier properties against moisture and gases. In particular, the composition according to the invention is advantageously used in encapsulation materials for the encapsulation of semiconductor devices, especially of light emitting devices (LEDs).
Examples
In the following particular aspects of the present invention are further described using a series of examples, however, the present invention is in no way restricted to these examples.
Test methods:
The evaluations were conducted in the manner described below.
In the following examples, weight average molecular weight values (g/mol) are polystyrene-equivalent values measured using gel permeation chromatography (GPC).
Vinyl content was titrated according to Chinese Chemical Industry Standard HG/T
3312-2000.
Hydrogen content was titrated as disclosed in Feng S. Y.; Zhang, J.; Li, M. J.; Zhu, Q. Z.; Organosilicon Polymer and Application Thereof, p. 400-401 ; Chemical Industry Press. Transmittance was measured by an UV-Visible spectrum analyzer Lambda 650S manufactured by PerkinElmer Corporation. The transmittance was measured for the range from 300 nm to 800 nm, and the value at 450 nm was recorded as the
transmittance.
Permeation was measured by Mocon Permatran-W® model 3/33 at 50°C/100%RH (RH = relative humidity).
To test cracking and lamination behavior 3 samples of each composition to be tested were used. Each sample was prepared by curing the composition in an LED cup under below mentioned conditions. If one or more of the samples cracked during hardening, the composition was evaluated as "poor", if no sample cracked, the composition was evaluated as "good". If one or more of the test pieces was found delaminated from the LED cup, the composition was evaluated as "delamination", if no test piece delaminated, the composition was evaluated as "no delamination"
Raw Materials:
Divinyldimethylsilane (CAS 10519-87-6) was purchased from Ruilijie Chemical Company. Diphenylsilane (CAS: 775-12-2) and trivinylmethylsilane (CAS: 18244-95-6) was purchased from Gelest. Platinum catalyst SIP 6832.2 (2.0 - 2.3% platinum concentration in cyclic methylvinylsiloxanes, CAS: 68585-32-0) was purchased from Gelest. HPM-502 (a hydride terminated methylhydrosiloxane-phenylmethylsiloxane copolymer having a viscosity of 100 mPa*S, and a weight average weight of 1359 g/mol, a hydrogen content of 6.06 mmol/g, and a phenyl content of 35.4 weight-%) was purchased from Gelest.
Synthesis Example 1 (Vinylpolycarbosilane (VPCS), linear)
Into a 100 mL dry and clean two-neck round bottom flask were added 9.22 g
diphenylsilane, 6.16 g divinyldimethylsilane, 0.008 g platinum catalyst SI P 6832.2 and 6.28 g xylene. A magnetic stirrer was added and the flask was capped with a stopper and a condenser. With stirring the mixture was heated to 75°C and kept at this temperature for 1 h, followed by further heating to 130°C for 6 h. The unreacted monomer was removed by rotary evaporation at 1 15°C and 20 mbar for 1 h and subsequently at 135°C and 5 mbar for another hour. The obtained liquid had a weight average molecule weight of 3072 g/mol, and its vinyl content was 0.65 mmol/g.
The obtained polymer has an average formula of
[Vi(CH3)2Si(C2H4)1 2]o.095[ Ph2Si(C2H4)22] 0.47β[ (CH3)2Si(C2H4)2/2]o.429-
Synthesis Example 2 (VPCS, branched)
Into a 100 mL dry and clean two-neck round bottom flask were added 9.22 g
diphenylsilane, 7.44 g trivinylmethylsilane, 0.016 g platinum catalyst SIP 6832.2 and 6.28 g toluene. A magnetic stirrer was added and the flask was capped with a stopper and a condenser. With stirring the mixture was heated to 75°C and kept at this temperature for 1 h, followed by further heating to 130°C for 6 h. The unreacted monomer was removed by rotary evaporation at 1 15°C and 20 mbar for 1 h and subsequently at 135°C and 5 mbar for another hour. The obtained liquid polymer has a branched structure, a weight average molecule weight of 1662 g/mol, and its vinyl content was 3.6 mmol/g.
Application Example 1
100 g vinylpolycarbosilane of synthesis example 1 , 21.5 g organohydrogenpolysiloxan HPM-502, 0.001 g platinum catalyst SIP 6832.2, and 0.001 g of the inhibitor
3,5-dimethyl-1 hexyn-3-ol were mixed. The resulting mixture was heated at 150 °C for 2 hours to yield a cured product. The product was evaluated regarding permeation, cracking, adhesion/lamination, initial transparency at 450 nm (T@450nm (initial)), and transparency at 450 nm after heat treatment of the product at 150 °C for 100 hours (T@450nm (150°C, 100 hours)). The results are shown in Table 1. Application Example 2
100 g vinylpolycarbosilane of synthesis example 2, 55 g organohydrogenpolysiloxan HPM-502, 0.001 g platinum catalyst SIP 6832.2, and 0.001 g of the inhibitor
3,5-dimethyl-1 hexyn-3-ol were mixed. The resulting mixture was heated at 150 °C for 2 hours to yield a cured product. The resulting mixture was heated at 150 °C for 2 hours to yield a cured product. The product was evaluated regarding permeation, cracking, adhesion/lamination, initial transparency at 450 nm (T@450nm (initial)), and
transparency at 450 nm after heat treatment of the product at 150 °C for 100 hours (T@450nm (150°C, 100 hours)). The results are shown in Table 1.
Comparative Example 1
The two components A and B of a high Rl (refractive index) encapsulating material commercially available from Dow Corning under the name 6636 were mixed at a weight ratio of A : B = 1 : 2 and heated at 70 °C for 1 hour, 120°C for 1 hour and finally 150 °C for 1 hour. The resulting cured product was evaluated regarding permeation, cracking, adhesion/lamination, initial transparency at 450 nm (T@450nm (initial)), and
transparency at 450 nm after heat treatment of the product at 150 °C for 100 hours (T@450nm (150°C, 100 hours)). The results are shown in Table 1.
Table 1 :
Figure imgf000017_0001
As can be seen from the results given in Table 1 cured products according to the invention show improved permeation behavior compared to cured products obtainable from commercially available encapsulating materials based solely on organopoly- siloxanes. Thermal stabilities are comparable.

Claims

Claims: rable composition, comprising least one polycarbosilane A represented by the following formula (1 )
[R R2 R3SiXi 2]M[R4R5SiX2 2] D[R6SiX32]T[SiX42] (1 ), wherein R , R2, R3, R4, R5, and R6, each independently designates a methyl group, an ethyl group, a vinyl group, or a phenyl group, with the proviso that each molecule comprises at least 2 vinyl groups; each X independently designates a bivalent C2H4 hydrocarbon group or phenylene; and M, D, T, and Q each represents a number ranging from 0 to less than 1 , provided that M+D+T+Q is 1 ,
(B) at least one organopolysiloxane B represented by the following formula (2):
[R7R8 R^id/^M R^R^SiO^D R^SiOs^T SiO^Q-, (2), wherein R7, R8, R9, R 0, R , and R 2, each independently designates a methyl group, an ethyl group, a vinyl group, a phenyl group, or hydrogen, with the proviso that each molecule comprises at least 2 hydrogen atoms directly bonded to silicon; and M', D', T, and Q' each represents a number ranging from 0 to less than 1 , provided that M'+D'+T'+Q' is 1 , and
(C) at least a catalyst.
2. The composition according to claim 1 , comprising a polycarbosilane A represented by the formula (1 ), wherein T+Q is greater than 0.
3. The composition according to claim 1 , wherein the weight average molecular weight of the polycarbosilane A is 100-300,000 g/mol, preferably 1 ,000-50,000 g/mol.
4. The composition according to claim 1 , comprising an organopolysiloxane B represented by the formula (2), wherein D' is greater than 0.
5. The composition according to claim 1 , wherein polycarbosilane A and organopoly- siloxane B is present in respective amounts to provide a molar Si-H/Si-Vinyl ratio of 0.5-10, preferably 1 .0-3.0.
6. The composition according to claim 1 , wherein the weight average molecular weight of the organopolysiloxane B is 1 ,000-300,000 g/mol, preferably 10,000-100,000 g/mol.
7. The composition according to claim 1 , wherein the catalyst is one or more selected from the group consisting of platinum group metal catalysts.
8. The composition according to claim 1 , wherein the catalyst is present in such an amount that the content of the catalytic metal is in the range of 1 to 500 ppm, preferably 2 to 100 ppm, based on the total weight of the curable composition.
9. The composition according to claim 1 , wherein the composition is a two-component preparation consisting of component 1 and component 2, wherein component 1 comprises polycarbosilane A and the total amount of catalyst being present and component 2 comprises the total amount of organopolysiloxane B being present and optionally further polycarbosilane A.
10. A cured product obtainable by heating a curable composition according to any one of claims 1 to 9.
1 1 . Use of the composition according to any one of claims 1 to 9 as semiconductor encapsulating material and/or electronic elements packaging material.
PCT/CN2012/079587 2012-08-02 2012-08-02 Curable compositions for LED encapsulants comprising a polycarbosilane and a hydrosilicone WO2014019195A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP12882183.2A EP2880095B1 (en) 2012-08-02 2012-08-02 Curable compositions for led encapsulants comprising a polycarbosilane and a hydrosilicone
PCT/CN2012/079587 WO2014019195A1 (en) 2012-08-02 2012-08-02 Curable compositions for LED encapsulants comprising a polycarbosilane and a hydrosilicone
KR20157002623A KR20150037952A (en) 2012-08-02 2012-08-02 Curable compositions for LED encapsulants comprising a polycarbosilane and a hydrosilicone
CN201280074976.2A CN104662098A (en) 2012-08-02 2012-08-02 Curable compositions for led encapsulants comprising a polycarbosilane and a hydrosilicone
JP2015524588A JP2015529713A (en) 2012-08-02 2012-08-02 Curable composition for LED encapsulant comprising polycarbosilane and hydrosilicone
TW102121024A TW201406864A (en) 2012-08-02 2013-06-14 Curable compositions for LED encapsulants comprising a polycarbosilane and a hydrosilicone
US14/609,984 US9359478B2 (en) 2012-08-02 2015-01-30 Curable compositions for LED encapsulants comprising a polycarbosilane and a hydrosilicone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2012/079587 WO2014019195A1 (en) 2012-08-02 2012-08-02 Curable compositions for LED encapsulants comprising a polycarbosilane and a hydrosilicone

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/609,984 Continuation US9359478B2 (en) 2012-08-02 2015-01-30 Curable compositions for LED encapsulants comprising a polycarbosilane and a hydrosilicone

Publications (1)

Publication Number Publication Date
WO2014019195A1 true WO2014019195A1 (en) 2014-02-06

Family

ID=50027119

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2012/079587 WO2014019195A1 (en) 2012-08-02 2012-08-02 Curable compositions for LED encapsulants comprising a polycarbosilane and a hydrosilicone

Country Status (7)

Country Link
US (1) US9359478B2 (en)
EP (1) EP2880095B1 (en)
JP (1) JP2015529713A (en)
KR (1) KR20150037952A (en)
CN (1) CN104662098A (en)
TW (1) TW201406864A (en)
WO (1) WO2014019195A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104151835A (en) * 2014-07-04 2014-11-19 江苏嘉娜泰有机硅有限公司 Organic silicon composition with main chain containing phenylene structure and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023222203A1 (en) * 2022-05-17 2023-11-23 Wacker Chemie Ag Silphenylene polymers

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006013066A2 (en) * 2004-08-04 2006-02-09 Wacker Chemie Ag Resin-encapsulated light emitting diode and method for encapsulating light emitting diode
WO2006055231A1 (en) * 2004-11-19 2006-05-26 Dow Corning Corporation Silicone composition and cured silicone resin

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69427275T2 (en) * 1993-12-28 2001-10-25 Kanegafuchi Chemical Ind Silicon containing polymer, method of manufacture and monomer
JP3537204B2 (en) * 1993-12-28 2004-06-14 鐘淵化学工業株式会社 Reactive silicon-based polymer and curable composition using the same
JPH07330874A (en) * 1994-06-01 1995-12-19 Toshiba Corp Resin composition and resin-encapsulated semiconductor device
US5907899A (en) * 1996-06-11 1999-06-01 Dow Corning Corporation Method of forming electrodes for lithium ion batteries using polycarbosilanes
JPH10140009A (en) * 1996-11-06 1998-05-26 Kanegafuchi Chem Ind Co Ltd Thermoset resin composition for electrical insulating material
JPH10152616A (en) * 1996-11-25 1998-06-09 Kanegafuchi Chem Ind Co Ltd Thermosetting resin composition for electrical insulation material
JPH1180362A (en) * 1997-08-29 1999-03-26 Toray Dow Corning Silicone Co Ltd Production of silphenylenealkylene polymer
US6072016A (en) 1997-12-29 2000-06-06 Dow Corning Toray Silicone Co., Ltd. Silphenylene polymer and composition containing same
US6017587A (en) * 1998-07-09 2000-01-25 Dow Corning Corporation Electrically conductive silicone compositions
WO2006077667A1 (en) 2005-01-24 2006-07-27 Momentive Performance Materials Japan Llc. Silicone composition for encapsulating luminescent element and luminescent device
JP4648146B2 (en) 2005-09-26 2011-03-09 信越化学工業株式会社 Addition-curing silicone composition with excellent crack resistance
KR100902852B1 (en) 2006-04-24 2009-06-16 신에쓰 가가꾸 고교 가부시끼가이샤 Silicone Lens and Silicone Resin Composition for Molding Lens
JP5202822B2 (en) 2006-06-23 2013-06-05 東レ・ダウコーニング株式会社 Curable organopolysiloxane composition and semiconductor device
JP5148088B2 (en) 2006-08-25 2013-02-20 東レ・ダウコーニング株式会社 Curable organopolysiloxane composition and semiconductor device
CN101240070B (en) * 2007-02-09 2012-05-30 中国人民解放军国防科学技术大学 Method for synthesizing supercritical fluid of ceramic precursor polycarbosilane
JP5350602B2 (en) * 2007-04-19 2013-11-27 大阪瓦斯株式会社 Polysilane and method for producing the same
JP5579371B2 (en) 2008-04-23 2014-08-27 東レ・ダウコーニング株式会社 Silicon-containing polymer and curable polymer composition
KR101271584B1 (en) 2008-09-11 2013-06-11 주식회사 엘지화학 Polysiloxane for sealing material or lens of Light-Emitting Diode and Polymer Composition Comprising The Same
JP5176976B2 (en) * 2009-01-21 2013-04-03 Ｊｓｒ株式会社 Curable composition
US8026331B2 (en) * 2009-04-21 2011-09-27 The United States Of America As Represented By The Secretary Of The Navy Polymers made from polyhedral oligomeric silsesquioxanes and diacetylene-containing compounds
JP5170471B2 (en) * 2010-09-02 2013-03-27 信越化学工業株式会社 Low gas permeable silicone resin composition and optical semiconductor device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006013066A2 (en) * 2004-08-04 2006-02-09 Wacker Chemie Ag Resin-encapsulated light emitting diode and method for encapsulating light emitting diode
WO2006055231A1 (en) * 2004-11-19 2006-05-26 Dow Corning Corporation Silicone composition and cured silicone resin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2880095A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104151835A (en) * 2014-07-04 2014-11-19 江苏嘉娜泰有机硅有限公司 Organic silicon composition with main chain containing phenylene structure and preparation method thereof
CN104151835B (en) * 2014-07-04 2017-01-04 江苏矽时代材料科技有限公司 A kind of main chain silicon composition containing penylene structure and preparation method thereof

Also Published As

Publication number Publication date
TW201406864A (en) 2014-02-16
KR20150037952A (en) 2015-04-08
US9359478B2 (en) 2016-06-07
EP2880095A1 (en) 2015-06-10
EP2880095B1 (en) 2017-03-29
CN104662098A (en) 2015-05-27
US20150148510A1 (en) 2015-05-28
JP2015529713A (en) 2015-10-08
EP2880095A4 (en) 2016-01-13

Similar Documents

Publication Publication Date Title
US9410019B2 (en) Polycarbosilane and curable compositions for LED encapsulants comprising same
JP5247979B2 (en) Polyorganosiloxane composition giving a transparent cured product
US8178642B2 (en) Curable organopolysiloxane composition and cured product thereof
US20160372641A1 (en) Polycarbosiloxane containing curable compositions for led encapsulants
EP2892953B1 (en) Curable silicone composition and cured product thereof
JP6347237B2 (en) Addition-curing organopolysiloxane composition and semiconductor device
EP3184589B1 (en) Addition-curable silicone resin composition and a semiconductor device
JP2017115116A (en) Addition-curable silicone resin composition and semiconductor device
EP2271700B1 (en) Organopolysiloxane, method of manufacturing thereof, curable silicone composition, and cured product thereof
US9359478B2 (en) Curable compositions for LED encapsulants comprising a polycarbosilane and a hydrosilicone
JP6428595B2 (en) Addition-curable resin composition and semiconductor device
TWI825270B (en) Organically modified silicone resin composition for die bonding, its hardened product and optical semiconductor element

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12882183

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2012882183

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2012882183

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20157002623

Country of ref document: KR

Kind code of ref document: A

Ref document number: 2015524588

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE