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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—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 at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/54—Nitrogen-containing linkages
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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  • 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
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  • 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
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  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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  • 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
  • C08L83/14—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 at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
• • H—ELECTRICITY
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  • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
  • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
  • H10H20/80—Constructional details
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• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F21—LIGHTING
  • F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
  • F21Y2115/00—Light-generating elements of semiconductor light sources
  • F21Y2115/10—Light-emitting diodes [LED]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
  • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
  • H10H20/01—Manufacture or treatment
  • H10H20/036—Manufacture or treatment of packages
  • H10H20/0362—Manufacture or treatment of packages of encapsulations

Definitions

• the present invention relates to silazane-siloxane random copolymers as well as their production and their uses, particularly in LEDs.
• LEDs light emitting diodes
• the lifetime of incandescent light bulbs is generally on the order of a few thousand hours, while LEDs claim lifetimes of several tens of thousands of hours. These long lifetimes are only made possible if the light emitting materials in an LED can effectively be protected from degradation by environmental factors, such as oxygen and moisture. Frequently this is done by encapsulating the LED in a polymer. However, such encapsulating polymers need to fulfill a number of further requirements:
• the polymer has to withstand high temperatures without degradation of mechanical and/or optical properties
• the polymer in addition to optical clarity and high service temperature the polymer needs to have a high refractive index
• the polymer is required to have a high resistance to radiation of high intensity
• Such copolymers are for example disclosed in WO 02/068535 Al.
• these polymers as well as their methods of production still leave room for improvement, particularly in respect to the balance between mechanical properties and thermal and/or light stability. While they show good thermal and light stability, current polysilazanes tend, for example, towards severe crack formation, particularly the formation of micro-cracks, and also exhibit limited compatibility with additives.
• the present application therefore provides for a polymer comprising a first monomer unit M 1 and a second monomer unit M 2 in random sequence, wherein the first monomer unit M 1 is of formula (I) and the second monomer unit M 2 is of formula (II)
• a is an integer of at least 1 and at most 10.
• the present application therefore provides for a method comprising the step of obtaining a silazane-siloxane random copolymer by reacting an organosilane, an amine and an organosiloxane, wherein the organosilane comprises two halogen end groups and the organosiloxane is of formula (11-3)
• X 3 and X 4 are identical and are at each occurrence independently selected from the group consisting of OH, CI, Br, I;
• R 3 , R 4 and R 5 are at each occurrence independently H or a carbyl group; and a is an integer of at least 1 and at most 10.
• organosilane is used to denote an organyl derivative of a silane, i.e. a silane wherein one or more hydrogen is replaced by the corresponding number of organyl groups.
• organosiloxane is used to denote an organyl derivative of a siloxane, i.e. a siloxane wherein one or more hydrogen is replaced by the corresponding number of organyl groups.
• organic is used to denote any organic substituent group, regardless of functional type, having one free valence at a carbon atom.
• organoheteryl is used to denote any univalent group containing carbon, which is thus organic, but which has the free valence at an atom other than carbon.
• the term “carbyl group” includes both, organyl groups and organoheteryl groups.
• the term “carbyl group” will be understood to mean any monovalent or multivalent organic radical moiety which comprises at least one carbon atom either without any non-carbon atoms (like for example -G ⁇ C-), or optionally comprising one or more heteroatoms (for example carbonyl etc.).
• hydrocarbyl group will be understood to mean a carbyl group that does additionally contain one or more H atoms and optionally contains one or more hetero atoms.
• hetero atom will be understood to mean an atom in an organic compound that is not a H- or C-atom, and preferably will be understood to mean N, O, S, P, Si, Se, As, Te or Ge.
• a carbyl or hydrocarbyl group comprising a chain of 3 or more C atoms may be straight-chain, branched and/or cyclic, including spiro and/or fused rings.
• Preferred carbyl and hydrocarbyl groups include alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy, each of which is optionally substituted and has 1 to 40, preferably 1 to 25, very preferably 1 to 18 C atoms, furthermore optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25 C atoms, furthermore alkylaryloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy, each of which is optionally substituted and has 6 to 40, preferably 7 to 40 C atoms, wherein all these groups do optionally contain one or more hetero atoms, preferably selected from N, O, S, P, Si, Se, As, Te and Ge.
• the carbyl or hydrocarbyl group may be a saturated or unsaturated acyclic group, or a saturated or unsaturated cyclic group. Unsaturated acyclic or cyclic groups are preferred, especially aryl, alkenyl and alkynyl groups (especially ethynyl). Where the C1-C40 carbyl or hydrocarbyl group is acyclic, the group may be straight-chain or branched.
• the C1-C40 carbyl or hydrocarbyl group includes for example: a C1-C40 alkyl group, a C1-C40 fluoroalkyl group, a C1-C40 alkoxy or oxaalkyi group, a C2-C40 alkenyl group, a C2-C40 alkynyl group, a C3-C40 allyl group, a C4-C40 alkyldienyl group, a C4-C40 polyenyl group, a C2-C40 ketone group, a C 2 -C 40 ester group, a C 6 -Ci 8 aryl group, a C6-C40 alkylaryi group, a C6-C 0 arylalkyi group, a C4-C40 cydoalkyi group, a C4-C40 cycloalkenyl group, and the like.
• Preferred among the foregoing groups are a C1-C20 alkyl group, a C1-C20 fluoroalkyl group, a C2-C20 alkenyl group, a C2 -C 20 alkynyl group, a C3-C20 allyl group, a C4-C20 alkyldienyl group, a C2-C20 ketone group, a C2-C20 ester group, a C 6 -Ci 2 aryl group, and a C4-C20 polyenyl group, respectively.
• groups having carbon atoms and groups having hetero atoms like e.g. an alkynyl group, preferably ethynyl, that is substituted with a silyl group, preferably a trialkylsilyl group.
• Very preferred substituents L are selected from halogen, most preferably F, or alkyl, alkoxy, oxaalkyi, thioalkyl, fluoroalkyl and fluoroalkoxy with 1 to 12 C atoms or alkenyl, and alkynyl with 2 to 12 C atoms.
• aryl and heteroaryl groups are phenyl, phenyl wherein one or more CH groups are replaced by N, naphthalene, thiophene, selenophene, thienothiophene, dithienothiophene, fluorene and oxazole, all of which can be unsubstituted, mono- or polysubstituted with L as defined above.
• Very preferred rings are selected from pyrrole, preferably N-pyrrole, furan, pyridine, preferably 2- or 3-pyridine, pyrimidine, pyridazine, pyrazine, triazole, tetrazole, pyrazole, imidazole, isothiazole, thiazole, thiadiazole, isoxazole, oxazole, oxadiazole, thiophene, preferably 2-thiophene, selenophene, preferably 2-selenophene, thieno[3,2-b]thiophene, thieno[2,3-b]thiophene, furo[3,2-b]furan, furo[2,3- b]furan, seleno[3,2-b]selenophene, seleno[2,3-b]selenophene, thieno[3,2-b]furan, in
• alkyl or alkoxy radical i.e. where the terminal CH 2 group is replaced by -0-, can be straight-chain or branched. It is preferably straight-chain (or linear). Suitable examples of such alkyl and alkoxy radical are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.
• Preferred alkyl and alkoxy radicals have 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.
• Suitable examples of such preferred alkyl and alkoxy radicals may be selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy and decoxy.
• alkenyl groups are C 2 -C7-lE-alkenyl, C4-C7-3E-alkenyl, C5-C7-4- alkenyl, C6-C7-5-alkenyl and C7-6-alkenyl, in particular C 2 -C 7 -lE-alkenyl, C4-C7-3E- alkenyl and Cs-C7-4-alkenyl.
• alkenyl grou ps are vinyl, ⁇ -propenyl, lE-butenyl, lE-pentenyl, lE-hexenyl, lE-heptenyl, 3-butenyl, 9
• 6- 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-,7-, 8- or 9-oxadecyl, for example.
• these radicals are preferably neighboured. Accordingly these radicals together form a carbonyloxy group -C(0)-0- or an oxycarbonyl group -O-C(O)-. Preferably this group is straight-chain and has 2 to 6 C atoms.
• acetyloxy propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyl)ethyl, 3-(methoxycarbonyl)prop
• An alkyl group wherein two or more CH 2 groups are replaced by -O- and/or -C(0)0- can be straight-chain or branched. It is preferably straight-chain and has 3 to 12 C atoms. Accordingly it is preferably selected from the group consisting of bis- carboxy-methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy- butyl, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl, 8,8-bis-carboxy-octyl, 9,9-bis-carboxy-nonyl, 10,10-bis-carboxy-decyl, bis- (methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl)-ethyl, 3,3-bis-
• a fluoroalkyl group is preferably perfluoroalkyl, CiF 2l+ i, wherein i is an integer from 1 to 15, in particular CF3, C 2 Fs, C3F7, C4F9, C5F11, C6F13, C7F15 or CsFi7, very preferably C6F13, or partially fluorinated alkyl, in particular 1,1-difluoroalkyl, all of which are straight-chain or branched.
• the hydrocarbyl groups are independently of each other selected from primary, secondary or tertiary alkyl or alkoxy with 1 to 30 C atoms, wherein one or more H atoms are optionally replaced by F, or aryl, aryloxy, heteroaryl or heteroaryloxy that is optionally alkylated or alkoxylated and has 4 to 30 ring atoms.
• Very preferred groups of this type are selected from the group consisting of the following formulae
• ALK denotes optionally fluorinated, preferably linear, alkyl or alkoxy with 1 to 20, preferably 1 to 12 C-atoms, in case of tertiary groups very preferably 1 to 9 C atoms, and the dashed line denotes the link to the ring to which these groups are attached.
• tertiary groups very preferably 1 to 9 C atoms
• the dashed line denotes the link to the ring to which these groups are attached.
• Especially preferred among these groups are those wherein all ALK subgroups are identical.
• halogen includes F, CI, Br or I, preferably F, CI or Br.
• substituted is used to denote that one or more hydrogen present is replaced by a group R s as defined herein.
• R s is at each occurrence independently selected from the group consisting of any group R T as defined herein, hydrocarbyl having from 1 to 40 carbon atoms wherein the hydrocarbyl may be further substituted with one or more groups R T and hydrocarbyl having from 1 to 40 carbon atoms comprising one or more heteroatoms selected from the group consisting of N, O, S, P, Si, Se, As, Te or Ge, with N, O and S being preferred heteroatoms, wherein the hydrocarbyl may be further substituted with one or more groups R T .
• hydrocarbyl suitable as R s may at each occurrence be independently selected from phenyl, phenyl substituted with one or more groups R T , alkyl and alkyl substituted with one or more groups R T , wherein the alkyl has at least 1, preferably at least 5, more preferably at least 10 and most preferably at least 15 carbon atoms and/or has at most 40, more preferably at most 30, even more preferably at most 25 and most preferably at most 20 carbon atoms.
• alkyl suitable as R s also includes fluorinated alkyl, i.e. alkyl wherein one or more hydrogen is replaced by fluorine, and perfluorinated alkyl, i.e. alkyl wherein all of the hydrogen are replaced by fluorine.
• R T is at each occurrence independently selected from the group consisting of F, Br, CI, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(0)NR°R°°, -C(O)X 0 , -C(O)R 0 , -NH 2 , - R°R 00 , - SH, -SR°, -SO3H, -SO2R 0 , -OH, -OR 0 , -NO2, -SF 5 and -SiR°R 00 R 000 .
• Preferred R T are selected from the group consisting of F, Br, CI, -CN, -NC, -NCO, -NCS, -OCN, -SCN, - C(0)NR°R°°, -C(0)X°, -C(0)R°, -NH 2 , -NR°R 00 , -SH, -SR°, -OH, -OR 0 and -SiR°R 00 R 000 .
• R°, R 00 and R 000 are at each occurrence independently of each other selected from the group consisting of H, F, hydrocarbyl having from 1 to 40 carbon atoms. Said hydrocarbyl preferably have at least 5, more preferably at least 10 and most preferably at least 15 carbon atoms. Said hydrocarbyl preferably have at most 30, even more preferably at most 25 and most preferably at most 20 carbon atoms. Preferably, R°, R 00 and R 000 are at each occurrence independently of each other selected from the group consisting of H, F, alkyl, fluorinated alkyl, alkenyl, alkynyl, phenyl and fluorinated phenyl.
• R°, R 00 and R 000 are at each occurrence independently of each other selected from the group consisting of H, F, alkyl, fluorinated, preferably perfluorinated, alkyl, phenyl and fluorinated, preferably perfluorinated, phenyl.
• alkyl suitable as R°, R 00 and R 000 also includes perfluorinated alkyl, i.e. alkyl wherein all of the hydrogen are replaced by fluorine.
• alkyls may be selected from the group consisting of methyl, ethyl, n- propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl (or "t-butyl”), pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl (-C 2 oH 4 i).
• X° is halogen.
• X° is selected from the group consisting of F, CI and Br.
• the present application is directed to a polymer, herein generally referred to as "silazane-siloxane random copolymer", comprising a first monomer unit M 1 and a second monomer unit M 2 in random sequence.
• Said first monomer unit M 1 is of formula (I)
• a is an integer of at least 1 and of at most 10.
• a may be any one of the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10.
• R 1 , R 2 , R 3 , R 4 and R 5 are at each occurrence independently H or a carbyl group, preferably H or a carbyl group as defined above.
• R ⁇ R 2 , R 3 , R 4 and R 5 preferred carbyl groups may at each occurrence independently be selected from the group consisting of alkyi, substituted alkyi, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, alkadienyl, substituted alkadienyl, aryl, and substituted aryl.
• R ⁇ R 2 , R 3 , R 4 and R 5 more preferred carbyl groups may at each occurrence independently be selected from the group consisting of alkyi, substituted alkyl, cycloalkyi, substituted cycloalkyi, alkenyl, substituted alkenyl, alkadienyl and substituted alkadienyl.
• R 1 , R 2 , R 3 , R 4 and R 5 even more preferred carbyl groups may at each occurrence independently be selected from the group consisting of alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkadienyl and substituted alkadienyl.
• R 1 , R 2 , R 3 , R 4 and R 5 still even more preferred carbyl groups may at each occurrence independently be selected from the group consisting of alkyl and substituted alkyl.
• R ⁇ R 2 , R 3 , R 4 and R 5 most preferred carbyl groups may at each occurrence independently be selected from the group consisting of alkyl.
• preferred alkyl may be selected from alkyls having at least 1 carbon atom and at most 40 carbon atoms, preferably at most 30 or 20 carbon atoms, more preferably at most 15 carbon atoms, still even more preferably at most 10 carbon atoms and most preferably at most 5 carbon atoms.
• R 1 , R 2 , R 3 , R 4 and R 5 alkyl having at least 1 carbon atom and at most 5 carbon atoms may, for example, independently be selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n- pentyl, iso-pentyl (2,2-methyl-butyl) and neo-pentyl (2,2-dimethyl-propyl); preferably from the group consisting of methyl, ethyl, n-propyl and iso-propyl; more preferably is methyl or ethyl; and most preferably is methyl.
• preferred cycloalkyi may be selected from cycloalkyi having at least 3, preferably at least 4 and most preferably at least 5 carbon atoms.
• preferred cycloalkyi may be selected from cycloalkyi having at most 30, preferably at most 25, more preferably at most 20, even more preferably at most 15, and most preferably at most 10 carbon atoms.
• R 1 , R 2 , R 3 , R 4 and R 5 preferred examples of cycloalkyi may be selected from the group consisting of cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
• preferred alkenyl may be selected from alkenyl having at least 2 carbon atoms and at most 20, more preferably at most 15, even more preferably at most 10, and most preferably at most 6 carbon atoms.
• alkenyl having at least 2 and at most 10 carbon atoms may be vinyl or allyl, preferably vinyl.
• preferred alkadienyl may be selected from alkadienyl having at least 4 and at most 20, more preferably at most 15, even more preferably at most 10, and most preferably at most 6 carbon atoms.
• alkadienyl having at least 4 and at most 6 carbon atoms may, for example, be butadiene or hexadiene.
• preferred aryl may be selected from aryl having at least 6 carbon atoms, and at most 30, preferably at most 24 carbon atoms.
• aryl may be selected from the group consisting of phenyl, naphthyl, phenanthrenyl, anthracenyl, tetracenyl, benz[a]anthracenyl, pentacenyl, chrysenyl, benzo[a]pyrenyl, azulenyl, perylenyl, indenyl, fluorenyl and any of these wherein one or more (for example 2, 3 or 4) CH groups are replaced by N. Of these phenyl, naphthyl and any of these wherein one or more (for example 2, 3 or 4) CH groups are replaced by N. Phenyl is most preferred.
• the present silazane-siloxane random copolymers have a molecular weight Mw, as determined by GPC, of at least 1,000 g/mol, more preferably of at least 2,000 g/mol, even more preferably of at least 3,000 g/mol.
• the molecular weight of the present silazane-siloxane random copolymers may be modified, preferably increased, by fluoride-catalyzed crosslinking or by base-catalyzed crosslinking. These methods are well known to the skilled person. Further details can be found in the examples.
• the present silazane-siloxane random copolymers are characterized by excellent temperature resistance and/or longevity as compared to currently used standard materials, such as phenylsilicone or organopolysilazanes.
• the improved performance of the present silazane-siloxane random copolymers is believed to be due to their specific random structure, which avoids the formation of rigid regions and thereby is believed to lead to a reduction in the formation of cracks, particularly micro-cracks.
• the present application is also directed to a method comprising the step of obtaining the silazane-siloxane random copolymer as defined herein by reacting one or more organosilane, an amine and one or more organosiloxane.
• the one or more organosilane comprises two halogen end groups, i.e. is an ⁇ , ⁇ - dihalo-organosilane.
• the end groups may be the same or different; preferably they are the same.
• Preferably the two halogen end groups are both CI.
• said organosilane is of formula (l-a)
• X 1 and X 2 are at each occurrence independently of each other selected from th group consisting of CI, Br, I.
• X 1 and X 2 are CI.
• the organosiloxane comprises two halogen end groups, preferably two CI en groups, or two hydroxy (-OH) end groups.
• organosiloxane is of formula (II)
• a is an integer of at least 1 and of at most 10.
• a may be any one of the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10.
• X 3 and X 4 are identical and are at each occurrence independently preferably selected from the group consisting of CI, Br, I and OH, more preferably are CI or OH.
• said amine is of formula (III)
• R 5 is H or methyl, most preferably H.
• said amine may also be a blend of amines with different groups R 5 .
• Preferred methods of obtaining a silazane-siloxane random copolymer in accordance with the present application may, for example, be represented by the following Routes (A) and (B) n C SiR ⁇ 2 + m HO-[SiR 3 R 4 -0-] a -SiR 3 R 4 -OH + 2m+3(n-m) NH 2 R 5
• the conditions for reacting the organosilane, the amine and the organosiloxane are not particularly limited. It is, however, preferred to conduct the reaction within specific ranges of conditions, for example, in respect to temperature and solvent.
• said solvent is an aprotic organic solvent such as a hydrocarbon, an aromatic compound, an ester or an ether. Examples of such solvents are n-heptane, cyclohexane, xylene, pyridine, tetrahydrofuran, 1,4-dioxane, methyl-acetate or ethyl-acetate.
• the present reaction is performed at a temperature of at least -30°C and of at most 120°C, more preferably of at least -20°C and of at most 110°C and most preferably of at least -10°C and of at most 100°C.
• Another preferred synthetic method is to perform the reaction in liquid amine, for example in liquid ammonia. Then the amine is solvent and reactant at the same time. If liquid ammonia is used, the preferred reaction conditions are a temperature of at least -20°C and of at most 40°C and a pressure of at most 20 bar.
• the present application is also directed to a method for producing an electronic device, said process, in addition to the step of reacting the organosilane, the amine and the organosiloxane thus obtaining a silazane-siloxane random copolymer, comprising the steps of providing a composition comprising the so-obtained silazane-siloxane random copolymer and applying it to a substrate in an electronic device.
• the method for producing an electronic device thus comprises the steps of
• step (b) providing a composition comprising the silazane-siloxane random copolymer obtained in step (a), and
• said composition further comprises one or more selected from the group consisting of light emitting material, viscosity modifier, surfactant, additive influencing film formation, additive influencing evaporation behavior, crosslinker and solvent.
• said composition further comprises a light emitting material.
• said light emitting materia! is a phosphor, i.e. a substance that has luminescent properties.
• the term "luminescent” is intended to include both, phosphorescent as well as fluorescent.
• the type of phosphor is not particularly limited. Suitable phosphors are well known to the skilled person and can easily be obtained from commercial sources.
• the term "phosphor" is intended to include materials that absorb in one wavelength of the electromagnetic spectrum and emit at a different wavelength.
• suitable phosphors are inorganic fluorescent materials in particle form comprising one or more emitting centers.
• emitting centers may, for example, be formed by the use of so-called activators, which are preferably atoms or ions selected from the group consisting of rare earth elements, transition metal elements, main group elements and any combination of any of these.
• suitable rare earth elements may be selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
• suitable transition metal elements may be selected from the group consisting of Cr, n, Fe, Co, Ni, Cu, Ag, Au and Zn.
• suitable main group elements may be selected from the group consisting of Na, Tl, Sn, Pb, Sb and Bi.
• suitable phosphors include phosphors based on garnet, silicate, orthosilicate, thiogallate, sulfide, nitride, silicon-based oxynitride, nitridosilicate, nitridoaluminumsilicate, oxonitridosilicate, oxonitridoaluminumsilicate and rare earth doped sialon.
• Suitable yellow phosphors may, for example, comprise or be based on (Gd,Y)3(Al, Ga) 5 0i 2 doped with Ce, such as the commercially available cerium-doped yttrium aluminum garnet (frequently abbreviated as "Ce:YAG” or "YAG:Ce”); or Th 3 - xM x Oi 2 :Ce (TAG) (0 ⁇ x ⁇ 3) with M being selected from the group consisting of Y, Gd, La and Lu; or Sr 2 -x-yBa x Ca y Si0 4 :Eu (0 ⁇ x ⁇ 2; and 0 ⁇ y ⁇ 2).
• green phosphors may be selected from the group of SrGa 2 S :Eu;
• Suitable phosphors may be selected from the following: Ba 2 Si0 4 :Eu 2+ , BaSi 2 0 5 :Pb 2+ , Ba x Sri- x F 2 :Eu 2+ (0 ⁇ x ⁇ 1), BaSrMgSi 2 0 7 :Eu 2+ , BaTiP 2 0 7 , (Ba,Ti) 2 P 2 0 7 :Ti, BasWOeiU, BaY 2 F 8 :Er 3+ ,Yb + , Be 2 Si0 4 :Mn 2+ , Bi 4 Ge 3 0i 2 , CaAI 2 0 :Ce 3+ , CaLa 4 0 7 :Ce 3+ , CaAl 2 0 4 :Eu 2+ , CaAl 2 0 4 :Mn 2+ , CaAl 4 0 7 :Pb 2+ , Mn 2+ , CaAI 2 0 4 :Tb 3+ , Ca 3 Al 2
• the solvent comprised in said composition comprising the silazane-siloxane random copolymer is not particularly limited provided that the components of said composition have a certain solubility therein.
• said solvent may be a non- polar or polar non-protic, preferably organic, solvent.
• suitable solvents may be selected from the group consisting of ethers, cyclic ethers, esters, hydrocarbons, aromatic solvents and any mixture of any of these.
• ethers are l-methoxy-2-propylacetate and di-n-butylether.
• a preferred example of a cyclic ether is tetrahydrofuran (THF).
• ester are ethyl-acetate and n-butyl-acetate.
• hydrocarbons are n-heptane and cyclohexane.
• a preferred example of an aromatic solvent may be selected from the group consisting of toluene, ortho-xylene, meta-xylene, para-xylene and any mixture of any of these.
• Said substrate may be any layer or material on which the composition of the present application as defined above may be deposited. Suitable substrates are not particularly limited in terms of material or shape.
• An exemplary substrate is an LED chip, i.e. the composition of the present application is directly applied onto an LED chip.
• composition comprising said silazane-siloxane random copolymer may be deposited on the substrate by any suitable method, for example with an industrial dispensing system.
• the substrate is an LED chip
• the composition preferably comprises at least 90 wt% or 95 wt% or 99 wt% or consists, with wt% relative to the total weight of said composition, of the silazane-siloxane random copolymer and the light emitting material and is applied directly to the LED chip.
• Suitable compositions preferably have a viscosity of at least 100 mPa ⁇ s and of at most 100,000 mPa ⁇ s, determined as described in the test methods.
• the viscosity of the composition may optionally be modified by changing the temperature at which the composition is deposited, for example, between 10°C and 60°C.
• a typical spray coating formulation consists of 2-10 wt% silazane-siloxane random copolymer, 10- 25 wt% light emitting material, 63-88 wt% solvent and 0-2 wt% other additives, with the respective weight percentages of the components of the spray coating formulation adding up to 100 wt%.
• the solvent is either a pure solvent or a mixture of several solvents, usually a mixture of at least one high boiling and one low boiling solvent.
• the silazane-siloxane random copolymer and the light emitting material may be applied by any other suitable method, such as screen printing or ink-jet printing.
• the silazane-siloxane random copolymer is preferably subjected to a heating step, wherein the material is heated to a temperature of from 100°C to 250°C, preferably from 150X to 220°C, for a period of from 2 to 48 h, preferably of from 4 to 48 h.
• the silazane-siloxane random copolymer may be subjected to a hydrolyzing step in a climate chamber.
• Preferred hydrolyzing conditions in a climate chamber are 4-24 h at 70-90°C and a relative humidity of 70-90 %.
• said present process may be applied to a wide range of electronic devices.
• said electronic device may be selected from the group consisting of field-effect transistors (FETs), thin-film transistors (TFTs), integrated circuits (ICs), logic circuits, capacitors, RFID tags (radio frequency identification tags), light emitting diodes (OLEDs), photovoltaic cells (PVs), photodetectors, laser diodes, photoconductors, electrophotographic devices, organic memory devices, sensor devices, charge injection layers, Schottky diodes, planarising layers, antistatic films, conducting substrates and conducting patterns.
• said electronic device is a light emitting diode.
• Such light emitting diode may, for example, be used for backlights for liquid crystal displays, traffic light, outdoor displays, billboards, to name only a few non-limiting examples.
• a typical LED package according to the invention comprises an LED chip, and/or a lead frame and/or gold wire and/or solder (flip chip) and/or the filling material, converter, an encapsulation material comprising the present silazane-siloxane random copolymer and a primary and secondary optic.
• the encapsulation material has the function of a surface protection material against external environmental influences and guarantees long term reliability in particular aging stability.
• a light emitting diode is constructed similarly to the ones described in US 6,274,924 and 6,204,523.
• Molecular weights of the polymers were determined by GPC against a polystyrene standard.
• eluent a mixture of tetrahydrofuran and 1.45 wt% (relative to the total weight of the eluent) hexamethyldisilazane was used.
• Columns were Shodex KS-804 and 2 x KS-802 and KS-801.
• the detector was an Agilent 1260 refractive index detector.
• Viscosity was determined using a Brookfield Rheometer R/S plus with a Brookfield cone-type spindle RC3-50-1 at a rotation speed of 3 rpm and a temperature of 25°C.
• ⁇ , ⁇ -dichloro-dimethylsilicones may be prepared by reacting water with an excess of dichlorodimethylsilane in an inert solvent, such as for example tetrahydrofuran or 1,4-dioxane. Using the dichlorodimethylsilane in an excess will lead to incomplete hydrolysis and therefore to Si-CI groups remaining. Solvent and unreacted dichlorodimethylsilane may be removed by distillation under reduced pressure to yield a colorless oil, which may be used without further purification or may further be purified by column chromatography or other methods.
• an inert solvent such as for example tetrahydrofuran or 1,4-dioxane.
• a 4 I pressure vessel was charged with 1500 g of liquid ammonia at 0°C and a pressure of between 3 bar and 5 bar.
• a mixture of 359 g dichlorosilane and 442 g 1,3-dichloro-tetramethyldisiloxane was slowly added over a period of 3 h. After stirring the resulting reaction mixture for an additional 3 h the stirrer was stopped and the lower phase isolated and evaporated to remove dissolved ammonia. After filtration 409 g of a colorless viscous oil remained.
• a 4 I pressure vessel was charged with 1500 g of liquid ammonia at 0°C and a pressure of between 3 bar and 5 bar.
• a mixture of 168 g dichlorosilane, 231 g dichloro-methylsilane and 419 g 1,3-dichloro-tetramethyldisiloxane were slowly added over a period of 3 h. After stirring the resulting reaction mixture for an additional 3 h the stirrer was stopped and the lower phase was isolated and evaporated to remove dissolved ammonia. After filtration 422 g of a colorless viscous oil remained.
• a 4 I pressure vessel was charged with 1500 g of liquid ammonia at 0°C and a pressure of between 3 bar and 5 bar.
• a mixture of 168 g dichlorosilane, 237 g dichloromethylsilane and 556 g 1,5-dichloro-hexamethyltrisiloxane were slowly added over a period of 3 h. After stirring the resulting reaction mixture for an additional 3 h the stirrer was stopped and the lower phase was isolated and evaporated to remove dissolved ammonia. After filtration 545 g of a colorless viscous oil remained.
• a 4 I pressure vessel was charged with 1500 g of liquid ammonia at 0°C and a pressure of between 3 bar and 5 bar.
• a mixture of 442 g dichloromethylsilane and 384 g 1,3-dichlorotetramethyldisiloxane were slowly added over a period of 3 h. After stirring the resulting reaction mixture for an additional 3 h the stirrer was stopped and the lower phase was isolated and evaporated to remove dissolved ammonia. After filtration 429 g of a colorless viscous oil remained.
• a 4 I pressure vessel was charged with 1500 g of liquid ammonia at 0°C and a pressure of between 3 bar and 5 bar.
• a mixture of 244 g dichloromethylsilane, 266 g dichlorodimethylsilane and 429 g 1,5-dichlorohexamethyltrisiloxane were slowly added over a period of 3 h. After stirring the resulting reaction mixture for an additional 3 h the stirrer was stopped and the lower phase was isolated and evaporated to remove dissolved ammonia. After filtration 526 g of a colorless viscous oil remained.
• a 4 I pressure vessel was charged with 1500 g of liquid ammonia at 0°C and a pressure of between 3 bar and 5 bar.
• a mixture of 503 g dichloromethylsilane and 645 g 1,7-dichlorooctamethyltetrasiloxane were slowly added over a period of 3 h. After stirring the resulting reaction mixture for an additional 3 h the stirrer was stopped and the lower phase was isolated and evaporated to remove dissolved ammonia. After filtration 703 g of a colorless viscous oil remained.
• the polymer obtained in the examples were blended with phosphor light converter particles (available from Merck KGaA) in weight ratios ranging from 1 : 1 to 1 : 3, and the blend then coated as a 40 pm to 80 pm thick layer onto an LED chip mounted onto an LED package (available from Excelitas). For curing the polymer the LED was then placed on a hotplate at 150°C for 8 hours.
• phosphor light converter particles available from Merck KGaA
• the finished LED was first operated for 24 hours at a starting current of 0.5 A. If no crack formation in the coating of the LED could be detected by microscope the current was raised in steps of 0.1 A, the LED operated for another 24 hours and inspected by microscope until the current for which crack formation could be observed. Because the LED current relates to the temperature of the chip this method gives an indication to the temperature resistance and the longevity of the so-produced LEDs.
• Table 2 shows the highest LED currents at which no crack formation had occurred for the LEDs produced with the polymers of the examples as well as for LEDs produced with phenylsilicone, Durazane 1033 and Durazane 1066 as reference materials.
• An example of a phenylsilicone is QE-6550, commercially available from Dow Coming, USA.
• Durazane 1033 and Durazane 1066 are organopolysilazanes, commercially available from Merck, Darmstadt, Germany.

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