WO2014017598A1 - Composition d'organopolysiloxane durcissable, son procédé de préparation, procédé de préparation d'organopolysiloxane durci, procédé de condensation d'organopolysiloxane, emballage semi-conducteur optique et catalyseur de condensation destiné à des organopolysiloxanes - Google Patents

Composition d'organopolysiloxane durcissable, son procédé de préparation, procédé de préparation d'organopolysiloxane durci, procédé de condensation d'organopolysiloxane, emballage semi-conducteur optique et catalyseur de condensation destiné à des organopolysiloxanes Download PDF

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WO2014017598A1
WO2014017598A1 PCT/JP2013/070218 JP2013070218W WO2014017598A1 WO 2014017598 A1 WO2014017598 A1 WO 2014017598A1 JP 2013070218 W JP2013070218 W JP 2013070218W WO 2014017598 A1 WO2014017598 A1 WO 2014017598A1
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organopolysiloxane
compound
indium
component
molecule
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PCT/JP2013/070218
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English (en)
Japanese (ja)
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憲章 寺田
滝沢　健一
森　寛
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三菱化学株式会社
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Priority to CN201380038094.5A priority Critical patent/CN104487520B/zh
Priority to JP2014527007A priority patent/JP6277956B2/ja
Priority to KR1020157001008A priority patent/KR20150037830A/ko
Publication of WO2014017598A1 publication Critical patent/WO2014017598A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/057—Metal alcoholates
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy 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
    • C08G77/48—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
    • C08G77/58—Metal-containing linkages
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item

Definitions

  • the present invention relates to a curable organopolysiloxane composition, a method for producing the same, a method for producing a cured organopolysiloxane, a method for condensing organopolysiloxane, a sealed optical semiconductor, and an organopolysiloxane condensation catalyst.
  • a condensation-curable organopolysiloxane composition is used as a sealing material for white LED that requires heat resistance and light resistance.
  • the condensation-curable organopolysiloxane composition typically has a polydiorganopolysiloxane having two or more silicon atoms bonded to a hydroxyl group in one molecule and three or more condensable functional groups in one molecule. It can be obtained by mixing organopolysiloxane or organosilane with a condensation catalyst.
  • condensation catalyst As an example of a condensation catalyst that can be used in a condensation-curable polysiloxane composition, a compound containing a metal such as zirconium, hafnium, tin, zinc, or titanium is known. Tin compounds have been pointed out to corrode electrodes, and in recent years, their use tends to be refrained in consideration of environmental effects. It has also been proposed to use a gallium compound as a condensation catalyst (see Patent Document 1). There has also been proposed a coating composition capable of forming an organopolysiloxane coating film excellent in chemical durability such as water resistance and boiling water resistance that requires a free acid (see Patent Document 2).
  • the main object of the present invention is to provide a curable organopolysiloxane composition using a novel condensation catalyst.
  • the present inventors have found that a specific organic compound containing indium (In) has a high solubility in organopolysiloxane and acts as a condensation catalyst, thereby completing the present invention.
  • Embodiments of the present invention include the following curable organopolysiloxane compositions.
  • a curable organopolysiloxane composition comprising an organopolysiloxane having at least one hydroxyl group or hydrolyzable group bonded to a silicon atom in one molecule and an In compound.
  • the In compound is at least one organic indium compound selected from an indium chelate complex, an alkoxide, and a fatty acid salt.
  • the In compound is preferably soluble in the organopolysiloxane and can act as a condensation catalyst for the organopolysiloxane.
  • an organopolysiloxane in which at least one organic indium compound selected from an indium chelate complex, an alkoxide, and a fatty acid salt has at least one of a hydroxyl group bonded to a silicon atom or a hydrolyzable group in one molecule. It is preferably dissolved in siloxane.
  • the organopolysiloxane preferably contains a polydiorganosiloxane structure.
  • the organopolysiloxane preferably has three or more hydroxyl groups or hydrolyzable groups bonded to silicon atoms in one molecule.
  • this curable organopolysiloxane composition contains the silicon compound which has 3 or more of at least one of the hydroxyl group couple
  • the silicon compound here is preferably polysiloxane or silane.
  • the curable organopolysiloxane composition preferably further contains a polysiloxane having at least three hydrosilyl groups in one molecule.
  • a curable organopolysiloxane composition comprising a step of preparing a mixture containing an organopolysiloxane having at least one of hydroxyl group or hydrolyzable group bonded to a silicon atom in one molecule and an In compound Manufacturing method.
  • the In compound is an organic indium compound of at least one of an indium chelate complex, an alkoxide, and a fatty acid salt.
  • the In compound is preferably soluble in the organopolysiloxane.
  • the organopolysiloxane preferably contains a polydiorganosiloxane structure.
  • the organopolysiloxane preferably has three or more hydroxyl groups or hydrolyzable groups bonded to silicon atoms in one molecule.
  • the mixture preferably contains a silicon compound having three or more hydroxyl groups bonded to silicon atoms or hydrolyzable groups in one molecule.
  • the silicon compound here is preferably polysiloxane or silane.
  • the mixture preferably further contains polysiloxane having at least three hydrosilyl groups in one molecule.
  • the manufacturing method further includes a step of thickening the mixture by heating.
  • the embodiment of the present invention includes a method for producing a cured organopolysiloxane described below.
  • a method for producing a cured organopolysiloxane comprising a step of condensing organopolysiloxanes having a hydroxyl group and / or a hydrolyzable group using an In compound as a catalyst.
  • the In compound is at least one organic indium compound selected from an indium chelate complex, an alkoxide, and a fatty acid salt.
  • the embodiments of the present invention include the following organopolysiloxane condensation methods.
  • the In compound is at least one organic indium compound selected from an indium chelate complex, an alkoxide, and a fatty acid salt.
  • the optical semiconductor sealing body mentioned below is contained in embodiment of this invention.
  • An optical semiconductor encapsulant obtained by embedding an optical semiconductor chip with the above curable organopolysiloxane composition and then curing the curable organopolysiloxane composition by heating. Includes the following condensation catalysts for organopolysiloxanes. i) a condensation catalyst of an organopolysiloxane containing an organoindium compound soluble in an organopolysiloxane having at least one of a hydroxyl group bonded to a silicon atom or a hydrolyzable group in one molecule; Preferable examples of the organic indium compound are indium chelate complexes, alkoxides and fatty acid salts.
  • the present invention has been found that the In compound can be suitably used for the production of curable organopolysiloxane and the production of cured organopolysiloxane as a catalyst for the condensation reaction.
  • Curable organopolysiloxane composition includes the following components A and B.
  • ⁇ Component A> Organopolysiloxane having two or more hydroxyl groups or hydrolyzable groups bonded to a silicon atom in one molecule
  • ⁇ Component B> In compound
  • suitable examples of the In compound include Indium chelate complexes, alkoxides and fatty acid salts.
  • the In compound is preferably soluble in the organopolysiloxane and can act as a condensation catalyst for the organopolysiloxane.
  • the preferable curable organopolysiloxane composition which concerns on embodiment of this invention contains the following component C and / or D.
  • component C Silicon compound having at least three hydroxyl groups or hydrolyzable groups bonded to silicon atoms in one molecule
  • Component D Polysiloxane having at least three hydrosilyl groups in one molecule
  • Component A is an organopolysiloxane having at least one of a hydroxyl group bonded to a silicon atom or a hydrolyzable group in one molecule. Among these, at least two silicon atoms bonded to a hydroxyl group and / or a hydrolyzable group are included in one molecule in that the cured product of the organopolysiloxane of the present invention is likely to be a coating film having excellent physical and mechanical strength.
  • the organopolysiloxane having is preferable.
  • Component A is an organopolysiloxane having at least two silicon atoms bonded to the hydroxyl group and / or hydrolyzable group in one molecule. It is not limited.
  • hydrolyzable groups include alkoxy groups such as methoxy, ethoxy and propoxy; alkoxyalkoxy groups such as methoxyethoxy, ethoxyethoxy and methoxypropoxy; acetoxy, octanoyloxy and benzoyloxy Acyloxy groups; alkenyloxy groups such as vinyloxy groups, isopropenyloxy groups, 1-ethyl-2-methylvinyloxy groups; ketoxime groups such as dimethyl ketoxime groups, methylethyl ketoxime groups, diethyl ketoxime groups; dimethylamino groups, diethylamino groups Group, amino group such as butylamino group and cyclohexylamino group; aminoxy group such as
  • an alkoxy group is preferable.
  • the component A contains a hydroxyl group bonded to a silicon atom
  • addition of water for hydrolyzing the hydrolyzable group it is also possible not to add a solvent for compatibilizing the added water and component A.
  • the total number of hydroxyl groups or hydrolyzable groups bonded to silicon atoms in the organopolysiloxane of component A is that the cured product of the organopolysiloxane of the present invention is likely to become a coating film having excellent physical and mechanical strength.
  • the curable organopolysiloxane composition of the present invention has a low viscosity and is excellent in workability.
  • the total number is preferably 3 or more, and more preferably 4 or more.
  • examples of commercially available organopolysiloxanes having a total number of 3 or more include “KC89S” (methyltrimethoxysilane oligomer) manufactured by Shin-Etsu Chemical Co., Ltd.
  • the weight average molecular weight of component A when converted to polystyrene by GPC (gel permeation chromatography) is preferably 400 to 100,000, and more preferably 500 to 100,000.
  • the polysiloxane composition is preferably high in that the cured product of the organopolysiloxane of the present invention is likely to become a coating film excellent in physical and mechanical strength. It is preferable that the polysiloxane composition has a low viscosity and is excellent in workability. Therefore, specifically, for example, it is preferably 10 mPa ⁇ s or more, more preferably 20 mPa ⁇ s or more, particularly preferably 30 mPa ⁇ s or more, and 1,000 mPa ⁇ s or more.
  • it is preferably 100,000 mPa ⁇ s or less, more preferably 50,000 mPa ⁇ s or less, still more preferably 10,000 mPa ⁇ s or less, and 8,000 mPa ⁇ s. It is particularly preferably s or less, and most preferably 5,000 mPa ⁇ s or less.
  • the viscosity is usually measured using a rotational viscometer.
  • Component A organopolysiloxane preferably contains a polydiorganosiloxane structure.
  • component A an organopolysiloxane having a polydiorganosiloxane structure represented by the following general formula (1) can be given.
  • each R is a monovalent hydrocarbon group (which may be different from each other)
  • each U is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms (which may be different from each other).
  • Each of Y is a hydroxyl group or a hydrolyzable group (which may be different from each other), m is an integer of 0 to 2, and n is a natural number.
  • R is preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms, specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Alkyl groups such as decyl group and octadecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group; phenyl group, tolyl group, xylyl group, ⁇ Aryl groups such as —, ⁇ -naphthyl group; aralkyl groups such as benzyl group, 2-phenylethyl group, 3-phenylpropyl group; and some or all of hydrogen atoms of these groups are F, Cl, Br Group
  • a methyl group, an ethyl group, and a phenyl group are preferable, and a methyl group and a phenyl group are particularly preferable.
  • the divalent hydrocarbon group for U include — (CH 2 ) p — (p represents 1 to 8), a phenylene group, and the like.
  • U is preferably an oxygen atom or —CH 2 CH 2 —.
  • n is preferably set so that the viscosity of the organopolysiloxane at 25 ° C. falls within the above-mentioned preferable range.
  • n is preferably large in that the cured product of the organopolysiloxane of the present invention is likely to be a coating film excellent in physical and mechanical strength, but the viscosity of the curable organopolysiloxane composition of the present invention is low, In terms of excellent workability, n is preferably small. Specifically, n is preferably 1 or more, more preferably 3 or more, and on the other hand, it is preferably 1000 or less, and more preferably 800 or less.
  • organopolysiloxane represented by the general formula (1) include the following.
  • organopolysiloxanes that can be used as the above formula (2) include, for example, Momentive Performance Materials Japan GK “XC96-723”, “YF3800”, “XF3905”, “YF3057”, “ YF3807 ”,“ YF3802 ”, Shin-Etsu Chemical Co., Ltd.“ X-21-5841 ”,“ KF-9701 ”, Gelest“ DMS-S12 ”,“ DMS-S14 ”,“ DMS-S15 ”,“ DMS-S21 ” ”,“ DMS-S27 ”,“ DMS-S31 ”,“ DMS-S32 ”,“ DMS-S33 ”,“ DMS-S35 ”,“ DMS-S42 ”,“ DMS-S45 ”and the like.
  • the n repeating units (—Si (R) 2 —O) may be the same as or different from each other.
  • Specific examples of the organopolysiloxane represented by the general formula (1) when n repeating units (—Si (R) 2 —O) are different include the following.
  • m, m1, m2, n, M, and N are each an integer of 2 or more, preferably 5 or more.
  • one or both of the terminal hydroxyl groups are replaced with hydrolyzable groups, or a part of the hydrocarbon groups bonded to silicon atoms are replaced with hydroxyl groups or hydrolyzable groups.
  • Those can also be preferably used as component A.
  • Component A is not limited to those exemplified above, but is an M unit represented by the formula R 3 SiO 1/2 (where each R is a hydrocarbon group), and a formula RSiO 3/2 (R is a hydrocarbon group). It may include a T unit represented or a Q unit represented by the formula SiO 4/2 .
  • a vinyl group, a methacryl group, an amino group, an epoxy group, a mercapto group, or the like, which is a reactive group that can be bonded to an organic material may be introduced into a terminal or a side chain.
  • Another example of component A is an organopolysiloxane represented by the following formula (12).
  • m is an integer.
  • the organopolysiloxane of the formula (12) has a linear structure and has silicon atoms at both ends to which two methoxy groups which are hydrolyzable groups are bonded. That is, it has four hydrolyzable groups in one molecule.
  • component A is a polysiloxane compound obtained by condensing one or more silane compounds selected from silane compounds represented by the following formulas (13) and (14). . That is, it is possible to use the In compound as a catalyst for this condensation reaction.
  • the condensation reaction catalyst used for obtaining Component A known acid catalysts, base catalysts, organometallic compound catalysts, and the like can be used.
  • the curing property of the curable organopolysiloxane composition of the present invention becomes unstable or the curable organopolysiloxane composition of the present invention is applied by the acid catalyst or the base catalyst remaining in the component A. It is preferable to remove the remaining acid catalyst or base catalyst in advance so that the object is not corroded.
  • X represents a hydrolyzable group
  • Y represents a monovalent hydrocarbon group
  • n is 3 or 4.
  • the hydrocarbon group may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • X represents a hydrolyzable group
  • Y represents a monovalent hydrocarbon group.
  • the hydrocarbon group may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • the monovalent hydrocarbon group is preferably the same as the above monovalent hydrocarbon group.
  • compound of formula (13) examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -glycidoxy.
  • the compound of formula (14) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethyldichlorosilane, and methylphenyldimethoxysilane.
  • a polydiorganosiloxane having a hydroxyl group and / or a hydrolyzable group at both ends is replaced with a silane compound represented by formula (13)
  • a polysiloxane obtained by condensation with is also a suitable example of Component A.
  • Examples of commercially available organopolysiloxanes that can be used as component A include the following. ⁇ Products of Shin-Etsu Chemical Co., Ltd.> “KC-89S”, “KR-500”, “X-40-9225”, “X-40-9246”, “X-40-9250”, etc. (above, methyl / methoxy type), “KR-217” Etc. (above phenyl / methoxy type), “KR-9218”, “KR-213”, “KR-510”, “X-40-9227”, “X-40-9247”, “KR-401N” (above , Methylphenyl / methoxy type) and the like. ⁇ Products of Toray Dow Corning Co., Ltd.> “DC-3074”, “DC-3037 Intermediate”, etc. ⁇ Products of Momentive Performance Materials Japan GK> “TSR-165”, “YR3204”, etc.
  • the curable organopolysiloxane composition according to the embodiment of the present invention may contain, as Component A, a polysiloxane represented by a different general formula. Specifically, for example, it may contain a both-end silanol-modified dimethylsiloxane oligomer which is an organopolysiloxane represented by the above formula (2) and a methyltrimethoxysilane oligomer (Examples described later). 3). That is, the curable organopolysiloxane composition according to the embodiment of the present invention contains, for example, both the polysiloxane represented by the above formula (2) and the polysiloxane represented by the formula (3) as component A.
  • the curable organopolysiloxane composition of the present invention contains a compound having at least three hydroxyl groups or hydrolyzable groups bonded to silicon atoms in one molecule for curing by crosslinking. .
  • the organopolysiloxane of component A has at least three hydroxyl groups or hydrolyzable groups bonded to silicon atoms in one molecule. It may be.
  • the curable organopolysiloxane composition of the present invention has at least one of a hydroxyl group or a hydrolyzable group bonded to a silicon atom (not corresponding to the organopolysiloxane of component A) separately from the organopolysiloxane of component A.
  • Compound having 3 or more per molecule in a molecule (hereinafter not corresponding to the organopolysiloxane of component A, a compound having 3 or more hydroxyl groups or hydrolyzable groups bonded to silicon atoms in one molecule) May be referred to as a “silicon compound according to the present invention”).
  • an organopolysiloxane obtained by reacting an organopolysiloxane having at least one of a hydroxyl group bonded to a silicon atom or a hydrolyzable group in one molecule with the silicon compound according to the present invention.
  • examples include the case of using polysiloxane.
  • the reaction for obtaining this organopolysiloxane can be carried out using a component B described later as a catalyst.
  • the silicon compound according to the present invention will be described later as component C.
  • Organopolysiloxane obtained by reacting silanol-modified dimethylsiloxane oligomer, which is an organopolysiloxane represented by the above formula (2), with methyltrimethoxysilane, which is a silicon compound (Example 1 described later) See ii) a both-end silanol-modified dimethylsiloxane oligomer that is an organopolysiloxane represented by the above formula (2), and a both-end silanol-modified methylphenylsiloxane oligomer that is an organopolysiloxane represented by the above formula (3); To obtain organopolysiloxane.
  • Organopolysiloxane obtained by reacting the obtained organopolysiloxane with methyltrimethoxysilane which is a silicon compound examples include “XR31-B2733” manufactured by Momentive Performance Materials Japan GK.
  • MQ resin “SR1000” manufactured by Momentive Performance Materials Japan GK which is a combination of the M unit and the Q unit, may be used.
  • organopolysiloxane represented by the above formula (2) “XR31-B2733” manufactured by Momentive Performance Materials Japan GK, and “SR1000” manufactured by Momentive Performance Materials Japan GK
  • organopolysiloxanes obtained by reacting ⁇ -glycidoxypropyltrimethoxysilane may be used.
  • Component B is an In compound.
  • the In compound is contained in the curable organopolysiloxane composition as a catalyst for the condensation reaction.
  • Component B has catalytic performance with the In compound itself even if there is no acid acting as a catalyst in the system.
  • the condensation reaction here means dehydration condensation reaction between silanol groups (Si—OH), condensation reaction between silanol groups and hydrolyzable groups, dehydration between silanol groups and hydrosilyl groups (Si—H).
  • An elementary condensation reaction When the hydrolyzable group is an alkoxy group (Si—OR), the condensation reaction with the silanol group becomes a dealcoholization reaction accompanied by generation of R—OH.
  • an organic indium compound selected from an indium chelate complex, an alkoxide, and a fatty acid salt can be used. That is, an embodiment of the present invention includes an organopolysiloxane condensation catalyst containing at least one organic indium compound selected from an indium chelate complex, an alkoxide, and a fatty acid salt.
  • the In compound is preferably soluble in the organopolysiloxane because it easily acts effectively as a catalyst for the condensation reaction.
  • the curable organopolysiloxane composition according to the embodiment of the present invention includes a hydroxyl group or a hydrolyzable group in which at least one organic indium compound selected from an indium chelate complex, an alkoxide, and a fatty acid salt is bonded to a silicon atom.
  • at least one of them is dissolved in an organopolysiloxane having two or more in one molecule.
  • dissolution may be performed when heated to condense the organopolysiloxane, but it is preferably dissolved in the organopolysiloxane at room temperature (about 25 ° C.).
  • Examples of the ligand of the chelate complex include ⁇ -diketone type compounds and multidentate ligands such as O-ketophenol type compounds.
  • Examples of ⁇ -diketone type compounds include those having structures represented by the following formulas (8) to (10).
  • each R 1 independently represents an alkyl group, a phenyl group, or a halogen-substituted alkyl group.
  • R 2 represents a hydrogen atom, an alkyl group, a phenyl group, or a halogen-substituted alkyl group.
  • Specific examples of the compound of formula (8) include acetylacetone, trifluoroacetylacetone, pentafluoroacetylacetone, hexafluoroacetylacetone, 3-phenylacetylacetone and the like, and specific examples of the compound of formula (9) include ethylacetoacetate and the like.
  • Specific examples of the compound of formula (10) include diethyl malonate.
  • O-ketophenol type compound examples include a compound represented by the following formula (11).
  • R ′ independently represents a hydrogen atom, an alkyl group, a halogen-substituted alkyl group or an alkoxy group.
  • Specific examples of the compound of formula (11) include salicylaldehyde, ethyl-O-hydroxyphenyl ketone and the like.
  • indium alkoxides examples include trimethoxy indium, triethoxy indium, tri-i-propoxy indium (also called indium triisopropoxide, etc.), tri-n-propoxy indium, tri-n-butoxy indium, tri-t-butoxy. Examples include indium and tris-1-methoxy-2-methyl-2-propoxyindium.
  • the alkoxy groups bonded to indium may be the same as or different from each other.
  • the indium alkoxide may be an oligomer such as a dimer or a trimer as long as it is dissolved in the curable organopolysiloxane composition of the present invention.
  • indium fatty acid salts include indium acetate, indium oxalate, indium 2-ethylhexanoate, indium n-octylate, and indium naphthenate.
  • in compounds preferable in terms of good catalytic activity include indium acetylacetonate [also called tris (acetylacetonato) indium (III)], indium 2-ethylhexanoate, indium n-octylate, indium naphthenate, and the like. It is. In the selection of the In compound, those having good solubility or dispersibility in Component A are preferable.
  • the indium chelate complex those in which the ligand is a ⁇ -diketone type compound are preferred, those having the structure represented by the above formula (8) are more preferred, and indium acetylacetonate is particularly preferred.
  • indium alkoxide indium triisopropoxide is preferable.
  • the indium fatty acid salt is preferably indium 2-ethylhexanoate. Note that In compounds having different ligands may be used. Two or more types of In compounds can also be used in any combination.
  • the In compound may be used after being dissolved in a solvent so as to be easily dissolved in the organopolysiloxane according to the present invention.
  • Solvents include mineral spirits, hydrocarbons having 6 to 15 carbon atoms, kerosene, aromatic hydrocarbons such as benzene, toluene, xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, ethyl acetate, butyl acetate And esters such as methyl acetoacetate and alcohols having 1 to 5 carbon atoms.
  • the solvent can be arbitrarily selected as long as it does not affect the catalytic activity of the In compound. However, a hydrocarbon solvent that is difficult to chemically modify and excellent in solubility in organopolysiloxane is preferable.
  • the solvent mineral spirits and hydrocarbons having 10 to 15 carbon atoms are preferable.
  • the amount of the solvent is preferably small as long as the In compound according to the present invention can be dissolved.
  • the solvent is usually removed by volatilization by reducing pressure or heating before and / or when the organopolysiloxane is cured.
  • the amount of the In compound used may be appropriately determined according to its catalytic activity. In other words, any amount that effectively acts as a catalyst may be used.
  • the amount of In compound used is preferably large in that it easily acts effectively as a catalyst in the condensation reaction, but is small in that the cured organopolysiloxane according to the present invention tends to be excellent in physical properties such as strength. It is preferable. Therefore, specifically, the minimum amount is preferably the amount that acts as a catalyst.
  • the amount of the In compound is preferably 0.001 part by weight or more, more preferably 0.1 part by weight or more, based on 100 parts by weight of the organopolysiloxane of component A.
  • the condensation reaction catalyst made of an organometallic compound that has been conventionally used promotes hydrolysis of the siloxane chain when added to organopolysiloxane at a high concentration. Even at the expense of its properties, it had to be used at a low concentration.
  • the In compound according to the present invention hardly causes hydrolysis of the siloxane chain of the organopolysiloxane and has little dependence on heat-resistant catalyst concentration, so the concentration can be freely set from low to high depending on the purpose. There are advantages you can do.
  • Component C is a compound having three or more hydroxyl groups or hydrolyzable groups bonded to silicon atoms in one molecule.
  • the hydrolyzable group is the same as that exemplified in the description of Component A.
  • the curable organopolysiloxane composition of the present invention preferably contains the silicon compound in that the cured product of the organopolysiloxane of the present invention is likely to be a coating film excellent in physical and mechanical strength.
  • the silicon compound is preferably included.
  • the silicon compound according to the present invention is preferably polysiloxane or silane.
  • the total number of hydroxyl groups and / or hydrolyzable groups bonded to silicon atoms in the silicon compound according to the present invention is such that the cured product of the organopolysiloxane of the present invention is likely to be a coating film having excellent physical and mechanical strength. In terms of the point, it is preferable to be large, but it is preferable that the curable organopolysiloxane composition of the present invention has a low viscosity and is excellent in workability. Specifically, the total number is preferably 4 or more. On the other hand, when the silicon compound according to the present invention is silane, the total number is 4 or less than the valence of silicon.
  • Examples of the silicon compound according to the present invention include a silane compound represented by the above formula (13).
  • Examples of commercially available silane compounds represented by the above formula (13) include “KBM-13” (methyltrimethoxysilane) and “KBM403” ( ⁇ -glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.
  • Examples thereof include silane coupling agents having 3 hydrolyzable groups in one molecule and tetraalkoxysilanes having 4 hydrolyzable groups, which are commercially available from companies selling silicones.
  • Another example of the silicon compound according to the present invention is an oligomer of a silane compound represented by the above formula (13). The oligomer may further contain silicon of D unit or M unit.
  • the silicon compound according to the present invention preferably has a lower molecular weight than the organopolysiloxane of Component A.
  • the molecular weight of the silicon compound according to the present invention is preferably 100 to 2500 because it has high reactivity and easily contributes to crosslinking.
  • the weight average molecular weight when converted to polystyrene by GPC gel permeation chromatography
  • the weight average molecular weight when converted to polystyrene by GPC (gel permeation chromatography) of the silicon compound according to the present invention is preferably 100 or more, more preferably 200 or more, and on the other hand, 2500 or less. Preferably less than 500, more preferably less than 400.
  • Component D is a polysiloxane having at least three hydrosilyl groups per molecule.
  • Specific examples of component D include side chain Si—H modified dimethyl silicone resin and side chain Si—H modified dimethyl diphenyl silicone resin.
  • Examples of commercially available polysiloxane materials that can be used as Component D include methyl hydrogen silicone oils “KF-99” and “KF-9901”, which are products of Shin-Etsu Chemical Co., Ltd.
  • the component A may be a polysiloxane having at least three hydrosilyl groups in one molecule as in the above component C. Alternatively, it may contain component D polysiloxane.
  • component A is a polysiloxane having at least three hydrosilyl groups in one molecule
  • the polysiloxane has, for example, at least two silicon atoms bonded to a hydroxyl group and / or a hydrolyzable group in one molecule. It can be obtained by reacting an organopolysiloxane having at least three hydrosilyl groups in one molecule with each other. Specific examples of such components include the following compounds.
  • organopolysiloxane is obtained by reacting a silanol-modified dimethylsiloxane oligomer having both ends, which is an organopolysiloxane represented by the above formula (2), with methyltrimethoxysilane, which is a silicon compound according to the present invention.
  • Organopolysiloxane obtained by reacting the obtained organopolysiloxane with a side-chain Si—H-modified dimethyl silicone resin (see Example 4 described later)
  • An organopolysiloxane is obtained by reacting a silanol-modified dimethylsiloxane oligomer having both ends, which is an organopolysiloxane represented by the above formula (2), with methyltrimethoxysilane, which is a silicon compound according to the present invention.
  • Organopolysiloxane obtained by reacting the obtained organopolysiloxane, side-chain Si—H-modified dimethylsilicone resin, and both-end silanol-modified polydimethylsiloxane (see Example 6 described later)
  • the curable organopolysiloxane composition according to the embodiment of the present invention can contain any component other than the components A to D as long as the object and effect of the invention are not impaired.
  • the curable organopolysiloxane composition of the present invention may contain one or more other condensation reaction catalysts in addition to the component B (In compound).
  • condensation reaction catalysts include metal compounds.
  • the metal compound include zirconium, hafnium, yttrium, tin, zinc, titanium or gallium chelate complex, organic acid salt, inorganic salt or alkoxide.
  • the total amount of component A and component B is preferably 50% by weight or more, and 60% by weight or more. More preferably, it is more preferably 70% by weight or more.
  • the upper limit is 100% by weight.
  • the total amount of components A to D in the curable organopolysiloxane composition of the present invention is preferably 60% by weight or more, and more preferably 70% by weight or more.
  • the upper limit is 100% by weight.
  • the In compound of Component B acts as a catalyst for the condensation reaction, it is necessary to further contain an acid in order to cause the In compound of Component B to act as a catalyst. No.
  • a method for producing a curable organopolysiloxane composition according to an embodiment of the present invention comprises component A described in 1.1 above and component B described in 1.2 above. Preparing a mixture comprising. This mixture may further contain component C described in 1.3, component D described in 1.4, or other components.
  • the method for producing a curable organopolysiloxane composition according to the embodiment may further include a step of thickening the prepared mixture by heating.
  • Thickening is a phenomenon that occurs when the degree of polymerization of the polysiloxane compound contained in the mixture increases as a result of the occurrence of a polycondensation reaction in the mixture.
  • the heating temperature for thickening is preferably 100 ° C. or higher and 130 ° C. or lower, and the heating time is preferably in the range of 1 hour or longer and 5 hours or shorter.
  • a solvent may be used.
  • the solvent for example, lower alcohols having 1 to 3 carbon atoms, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl ethyl ketone, toluene, water and the like can be arbitrarily used.
  • one that does not show strong acidity or basicity is selected.
  • the minimum amount of solvent it is preferable to use the minimum amount of solvent.
  • the step of removing foreign matters, coloring components, metal impurities, halogens (chlorine compounds, etc.) and the like from the mixture after thickening can be optionally performed. Removal of low boiling point components can be accomplished by distillation. The water-soluble component can be removed by washing the composition with water. As a preferable method for removing unnecessary components, there is a method using an adsorbent. As the adsorbent, cation exchange resin, anion exchange resin, synthetic adsorbent, silica gel, alumina, activated carbon, activated clay, clay compound and the like can be used.
  • the step of mixing the other components exemplified in 1.5 with the components A and B is preferably performed after the step of removing the unnecessary components.
  • a condensation catalyst may be added after the step of removing unnecessary components.
  • the condensation catalyst to be added may be an In compound according to the present invention, or may be a condensation catalyst other than the In compound according to the present invention, which can be selected from an Sn compound, a Zn compound, a Zr compound, a Ga compound, and the like. .
  • a condensation catalyst other than the In compound is used in the step of thickening by heating, and the In compound of component B is added as a condensation catalyst for the curing reaction after the step of thickening by heating.
  • the In compound of component B may be added after removing the condensation catalyst used for thickening.
  • the material thickened by heating corresponds to the organopolysiloxane (component A) according to the present invention.
  • the curable organopolysiloxane composition of the present invention may be a one-component composition in which an In compound is added to Component A, or Component A (first solution) and In Compound of Component B It may be a two-component composition in which a solution (second solution) in which is dissolved in a volatile or reactive solvent is mixed at the time of use.
  • Method for producing cured organopolysiloxane condenses organopolysiloxanes having a hydroxyl group and / or a hydrolyzable group using an In compound as a catalyst. Having steps.
  • an organopolysiloxane composition obtained by thickening a mixture containing Component A described in 1.1, Component B described in 1.2, and Component C described in 1.3 is The thermosetting property can be exhibited by leaving at least a part of component B (In compound) after thickening.
  • the organopolysiloxane composition obtained by thickening a mixture containing the component A, the component B, and the component C has a crosslinked structure formed by a condensation reaction catalyzed by the In compound of the component B.
  • a curable organopolysiloxane composition of the condensation curing type is obtained.
  • the ligand of the In compound may be altered.
  • Examples of the alteration include generation of a silanol adduct in which a silanol having an organopolysiloxane is bonded, oligomerization of an In compound, or the like, in which a ligand of the In compound is lost.
  • the In compound is contained in the reaction system in the condensation reaction of the organopolysiloxane. As long as it is dissolved and at least a part of the ligand before the alteration remains and has a condensation catalyst activity, it is included in the component B according to the present invention.
  • the embodiment of the present invention also includes a case where the mixture containing the component A and the component B is not thickened in advance, and the component B is used as a catalyst to crosslink and cure the components A by polycondensation reaction. It corresponds to the manufacturing method of the cured organopolysiloxane.
  • the curing temperature is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and the curing time is usually 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1 hour or longer.
  • the organopolysiloxane cured product obtained by the method for producing a cured organopolysiloxane of the present invention is easily suitable for an optical semiconductor encapsulant and the like, it is colorless and transparent, and bubbles generated when the cured product is produced. It is preferable that the surface is smooth and the leveling property is excellent. Moreover, the hardness of the cured organopolysiloxane obtained by the method for producing a cured organopolysiloxane of the present invention can be appropriately selected according to the application.
  • the hardness of the cured organopolysiloxane obtained by the method for producing a cured organopolysiloxane of the present invention is preferably 5 or more in Shore A (or JIS Type A), more preferably 10 or more, particularly preferably 20 or more, On the other hand, 90 or less is preferable, 80 or less is more preferable, and 70 or less is particularly preferable.
  • the hardness is preferably high in terms of protection of the semiconductor light emitting device 1, but has a high function of relieving thermal stress, and the bonding wire 3 is cut and the resin molded body 2 and the sealing material 4 are peeled off. In terms of difficulty, it is preferably low.
  • the cured organopolysiloxane obtained by the method for producing a cured organopolysiloxane of the present invention is likely to be excellent in heat resistance as supported in the examples described later.
  • the organopolysiloxane cured product obtained by the method for producing a cured organopolysiloxane of the present invention has a high barrier property against the sulfur component and the like because the In compound captures the sulfur component as supported in the examples described later. It is easy to become a thing. Therefore, when the cured product is used for an optical semiconductor encapsulant or the like, it is difficult for the silver-plated electrode to be colored due to sulfur components such as hydrogen sulfide in the atmosphere, and the high reflectance by the silver-plated electrode is maintained. Seem.
  • the indium sulfide produced by the reaction of the indium compound and the sulfur component according to the present invention is yellow, and it is not a dark color that absorbs light in a wide wavelength range, so that the transparency of the encapsulant is greatly impaired. There is no. Therefore, when the cured product of the present invention is used for a sealed optical semiconductor, high brightness can be maintained.
  • a condensation catalyst or a decomposition product thereof remains in the cured organopolysiloxane obtained by the method for producing a cured organopolysiloxane of the present invention.
  • the organopolysiloxane cured product is obtained by the method for producing a cured organopolysiloxane of the present invention.
  • the analysis of In can be performed by an ICP (inductively coupled plasma) analysis method or the like.
  • the curable organopolysiloxane composition and the method for producing the same, and the method for producing a cured organopolysiloxane according to the embodiment of the present invention can be used for sealing various inorganic semiconductor devices and organic semiconductor devices.
  • Specific devices include semiconductor light emitting devices such as light emitting diodes (LEDs) and semiconductor lasers, photodetectors, electro-optical displays, organic light emitting diodes (OLEDs), electroluminescent displays, organic solar cell (OPV) devices, and lighting devices. Etc.
  • the curable organopolysiloxane composition according to the embodiment of the present invention can also be used for the production of optical element materials such as lenses, light guide plates, and light diffusion plates, and the production of adhesives for optical elements.
  • optical element materials such as lenses, light guide plates, and light diffusion plates
  • adhesives for optical elements such as lenses, light guide plates, and light diffusion plates.
  • the curable organopolysiloxane composition according to the embodiment of the present invention for a light emitting diode (LED), for example, after embedding the optical semiconductor chip with the curable organopolysiloxane composition according to the embodiment of the present invention, An optical semiconductor encapsulant obtained by curing the curable organopolysiloxane composition by heating is preferred.
  • FIG. 1 is a cross-sectional view of a semiconductor light emitting device using a curable organopolysiloxane composition according to an embodiment.
  • the semiconductor light emitting device shown in FIG. 1 includes a semiconductor light emitting element 1, a resin molded body 2, a bonding wire 3, a sealing material 4, and a lead frame 5.
  • the semiconductor light emitting element 1 is any one of a near ultraviolet LED, a purple LED, and a blue LED.
  • the resin molded body 2 is molded together with the lead frame 5.
  • the lead frame 5 is made of a conductive metal and plays a role of supplying a current to the semiconductor light emitting element 1.
  • the bonding wire 3 electrically connects the semiconductor light emitting element 1 and the lead frame 5.
  • the semiconductor light emitting element 1 is installed in a recess provided in the resin molded body 2 and sealed with a sealing material 4.
  • the sealing material 4 is obtained by curing the curable organopolysiloxane composition according to the embodiment of the present invention.
  • a particulate phosphor is usually disposed.
  • a blue phosphor such as (Ca, Sr, Ba) MgAl 10 O 17 : Eu, (Sr, Ca, Ba, Mg) 10 (PO 4 ) 6 (Cl, F) 2 : Eu, Y 3 (Al , Ga) 5 O 12 : Ce, (Sr, Ba) 2 SiO 4 : Eu, ⁇ -type sialon: Green phosphor such as Eu, Y 3 Al 5 O 12 : Ce, (Y, Gd) 3 Al 5 O 12 : Ce, (Sr, Ca, Ba, Mg) 2 SiO 4 : Yellow phosphor such as Eu, (Ca, Sr, Ba) 2 Si 5 (N, O) 8 : Eu, (Ca, Sr, Ba) ) AlSi (N, O) 3 : Eu, (La, Y) 2 O 2 S: Eu, K 2 SiF 6 : Mn is a red phosphor such as (Ca, Sr,
  • the sealing material 4 may further contain inorganic oxide fine particles such as silica, barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, yttrium oxide, and diamond fine particles. These fine particles are added to the sealing material 4 for the purpose of a light scattering material, an aggregate, a thickener (thixotropic agent), a refractive index adjusting agent and the like.
  • inorganic oxide fine particles such as silica, barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, yttrium oxide, and diamond fine particles.
  • the hardness of the sealing material 4 is preferably 10 or more and 80 or less in Shore A (or JIS Type A). More preferably, it is 20 or more and 80 or less, More preferably, it is 30 or more and 70 or less.
  • the hardness is preferably high in terms of protection of the semiconductor light emitting device 1, but has a high function of relieving thermal stress, and the bonding wire 3 is cut and the resin molded body 2 and the sealing material 4 are peeled off. In terms of difficulty, it is preferably low.
  • the curable organopolysiloxane composition according to the embodiment of the present invention can also be used as a die bond agent for bonding the semiconductor light emitting element 1 to the resin molded body 2 or the lead frame 5.
  • Organopolysiloxane Condensation Catalyst An organopolysiloxane condensation catalyst according to an embodiment of the present invention is an organopolysiloxane having at least one of a hydroxyl group bonded to a silicon atom or a hydrolyzable group in one molecule. Contains soluble organic indium compounds. Preferable examples of the organic indium compound are indium chelate complexes, alkoxides and fatty acid salts.
  • Example 1 100 g of both-end silanol-modified dimethylsiloxane oligomer (component 1), 2.6 g of methyltrimethoxysilane (component 10) and 0.1 g of zirconium acetylacetonate (component 5) are mixed and heated at 130 ° C. The viscosity was increased to 200 mPa ⁇ s. Next, zirconium was removed using activated carbon. Specifically, activated carbon was added to the thickened mixture and stirred with a stirring rod made of PTFE (polytetrafluoroethylene), and then the activated carbon was removed by filtration to obtain a mixture A1.
  • PTFE polytetrafluoroethylene
  • This mixture A1 was a condensation reaction product of component 1 and component 10, and component 1 and component 10 were consumed in the condensation reaction and did not remain. Moreover, as a result of further increasing the viscosity by heating the mixture A1 at 150 ° C. for 3 hours, the rate of increase in viscosity was less than 10%, and the component 5 was removed to an amount that was not sufficient to cure. 3 mg of indium acetylacetonate (component 6) was added to 3 g of the mixture A1, and the mixture was heated in an oil bath at 120 ° C. while stirring with a stirring rod made of PTFE (polytetrafluoroethylene), and cured in 20 minutes. In addition, indium acetylacetonate (component 6) added to the mixture A1 was visually dissolved uniformly.
  • the low boiling point component was removed by heating at 80 ° C. under reduced pressure.
  • activated carbon is added to the thickened mixture, and the mixture is stirred with a stirring rod made of PTFE (polytetrafluoroethylene) while being heated to 80 ° C.
  • the activated carbon is removed by filtration, and the mixture A2 Got.
  • This mixture A2 was a condensation reaction product of component 1, component 2 and component 10, and component 1, component 2 and component 10 were consumed by the reaction and did not remain. Further, the mixture A2 was heated at 150 ° C. for 3 hours to further increase the viscosity.
  • the increase in viscosity was less than 10%, and the component 8 was removed to an amount that was not sufficient to cure.
  • 3 mg of indium acetylacetonate (component 6) was added to 3 g of the mixture A2, and the mixture was heated in an oil bath at 120 ° C. while stirring with a stirring rod made of PTFE (polytetrafluoroethylene), and cured in 20 minutes.
  • indium acetylacetonate (component 6) added to the mixture A2 was visually dissolved uniformly.
  • Example 4 3 g of the mixture A1 obtained in Example 1, 3 g of a side chain Si—H-modified dimethyl silicone resin (component 11), and 24 mg of indium acetylacetonate (component 6) were mixed to produce PTFE (polytetrafluoroethylene). The mixture was heated at 120 ° C. while stirring with a stir bar to increase the viscosity to about 2000 mPa ⁇ s to obtain a mixture A3. The mixture A3 was put into a PTFE (polytetrafluoroethylene) petri dish having a diameter of 5 cm, and cured at 150 ° C. for 1 hour in a dryer. In addition, in the said mixture A3, indium acetylacetonate (component 6) was melt
  • PTFE polytetrafluoroethylene
  • Example 5 A mixture A2 was obtained in the same manner as in Example 2. 3 g of the above mixture A2, 3 g of side chain Si—H-modified dimethyldiphenyl silicone resin (component 12), and 24 mg of indium acetylacetonate (component 6) were mixed and mixed with a stirring rod made of PTFE (polytetrafluoroethylene). It heated with the oil bath of 120 degreeC, stirring, and was made to thicken to about 20000 mPa * s, and mixture A4 was obtained. The mixture A4 was put into a PTFE (polytetrafluoroethylene) petri dish having a diameter of 5 cm, and cured at 150 ° C. for 1 hour in a dryer. In the above mixture A4, indium acetylacetonate (component 6) was uniformly dissolved visually.
  • PTFE polytetrafluoroethylene
  • Example 6 A mixture A1 was obtained in the same manner as in Example 1. 5 g of the above mixture A1, 3 g of side chain Si—H modified dimethyl silicone resin (component 11), 4 g of both-end silanol modified polydimethylsiloxane (component 3) and 3 mg of indium acetylacetonate (component 6) were mixed. The mixture was heated at 120 ° C. with stirring in an eggplant type flask, and the pressure was reduced until foaming disappeared when the viscosity reached about 2000 mPa ⁇ s. To 3 g of the above mixture, 0.3 g of zirconium 2-ethylhexanoate (component 9) was added and stirred until uniform.
  • Example 7 Mixture A5 composed of mixture A1 and the following three components (mixture of 100 parts by weight of mixture A1, 200 parts by weight of component 13, 200 parts by weight of component 14, and 0.15 parts by weight of component 15) 100 2 g of a mixture obtained by adding 0.3 part by weight of component 6 as a metal amount with respect to parts by weight was placed in a petri dish made of PTFE (polytetrafluoroethylene) having a diameter of 5 cm. This was heated in a dryer at 110 ° C. for 3 hours and then heated at 150 ° C. for 3 hours to be cured.
  • PTFE polytetrafluoroethylene
  • Example 8 In Example 7, except that indium 2-ethylhexanoate (manufactured by Shinsei Chemical Industry Co., Ltd.) was used instead of Component 6, the experiment was performed in the same manner as in Example 7, and the mixture A5 was cured by heating. I let you. The indium 2-ethylhexanoate was uniformly dissolved visually in the mixture A5 at room temperature (about 25 ° C.). Further, the result of visual observation of the cured composition was colorless and transparent, free from foaming and surface wrinkles, formed into a uniform thickness film, and had good leveling properties. The Shore A hardness of the composition after curing was 57, which was an appropriate hardness.
  • Example 9 In Example 7, except that indium triisopropoxide (Alfa Aesar) was used instead of Component 6, the experiment was performed in the same manner as in Example 7, and the mixture A5 was cured by heating. Indium triisopropoxide was uniformly dissolved visually in the mixture A5 at room temperature (about 25 ° C.). Further, the result of visual observation of the cured composition was colorless and transparent, free from foaming and surface wrinkles, formed into a uniform thickness film, and had good leveling properties. The Shore A hardness of the composition after curing was 47, which was an appropriate hardness.
  • Example 7 Comparative Example 1
  • indium trifluoromethanesulfonate manufactured by Aldrich
  • the experiment was performed in the same manner as in Example 7, and the mixture A5 was cured by heating.
  • indium trifluoromethanesulfonate was visually dissolved at room temperature (about 25 ° C.) with respect to the mixture A5. Further, the result of visual observation of the cured composition was yellow, had many foams, and the surface was not smooth.
  • the composition before curing thickened in a gel-like state when mixed with indium trifluoromethanesulfonate at room temperature (about 25 ° C.), and the viscosity of the liquid was high, so that it could not be poured into a petri dish flatly.
  • the composition after curing was not a film having a uniform thickness but a dumpling state, and the leveling properties were better in Examples 7 to 9 than in Comparative Example 1.
  • the cured composition had a Shore A hardness of 47 and an appropriate hardness.
  • indium trifluoromethanesulfonate which is a salt of a strong acid
  • indium trifluoromethanesulfonate which is a salt of a strong acid
  • the catalytic activity of trifluoromethanesulfonic acid released from indium trifluoromethanesulfonate was not controlled, the viscosity of the reaction solution was increased at room temperature, which is considered to be a cause of uneven curing.
  • indium strong acid salts that are water-soluble such as indium nitrate and are not soluble in organic solvents such as diethyl ether and acetone, and silicone (organopolysiloxane) are also similar to the indium trifluoromethanesulfonate. It is expected that it is not suitable as a condensation catalyst for siloxane.
  • Example 7 except that indium hydroxide was used in place of Component 6, an experiment was conducted in the same manner as in Example 7 to try to cure the mixture A5 by heating. However, indium hydroxide was visually insoluble in the mixture A5 at room temperature (about 25 ° C.), and the mixture A was not cured.
  • Table 2 The results of Examples 7 to 9 and Comparative Examples 1 and 2 are summarized in Table 2.
  • Example 10 2 g of a mixture obtained by adding 0.06 part by weight of indium 2-ethylhexanoate (manufactured by Shinsei Chemical Industry Co., Ltd.) as a metal amount to 100 parts by weight of the mixture A1 obtained in Example 1 was added to PTFE (diameter 5 cm). It was placed in a petri dish made of polytetrafluoroethylene. This was heated in a dryer at 110 ° C. for 3 hours and then heated at 150 ° C. for 3 hours to be cured. The indium 2-ethylhexanoate was visually dissolved in the mixture A1 at room temperature (about 25 ° C.).
  • indium 2-ethylhexanoate manufactured by Shinsei Chemical Industry Co., Ltd.
  • the composition As a result of visually observing the cured composition, the composition was colorless and transparent, had no foam or surface wrinkles, had a uniform thickness, and had good leveling properties.
  • the composition after curing was self-supporting and had an appropriate hardness.
  • the weight maintenance factor after a heating is 90.1%, and the composition after hardening becomes heat resistance. I found it excellent.
  • the ability of the cured composition to prevent sulfidation of the silver-plated electrode was evaluated according to the following method.
  • indium 2-ethylhexanoate manufactured by Shinsei Chemical Industry Co., Ltd.
  • 10 microliters of this mixture was applied to a 50 ⁇ 50 mm package made of polyphthalamide resin having a silver plated copper electrode on the bottom of the recess. After heating this at 110 degreeC for 3 hours, the composition was hardened by heating at 150 degreeC for 3 hours, and the silver plating electrode in a recessed part was sealed.
  • This package is fixed with double-sided tape inside the upper lid of a petri dish with a glass lid with a diameter of 6 cm, 1 g of sulfur powder is laid flat on the lower lid, the upper and lower lids are combined, and the lid is covered with piping tape manufactured by ThreeBond Co., Ltd. The joint was sealed.
  • This sealed petri dish is further put into a petri dish with a glass lid having a diameter of 15 cm, and the joint part of the lid is sealed with piping tape manufactured by ThreeBond Co., Ltd., and then put into a dryer at 80 ° C. and heated for 6 hours, whereby the package is obtained. Exposed to sulfur atmosphere.
  • the reflectance at a wavelength of 450 nm of the package sealing portion before and after exposure to a sulfur atmosphere was measured using “CM-2600d” manufactured by Konica Minolta.
  • the maintenance ratio of the light reflectance (the value obtained by dividing the reflectance after exposure to the sulfur atmosphere by the reflectance before exposure to the sulfur atmosphere) is as high as 93%, and the silver electrode is not easily discolored by sulfur, and the composition after curing was confirmed to be excellent in the ability to prevent sulfidation.
  • Example 11 In Example 10 described above, the amount of indium 2-ethylhexanoate (manufactured by Shinsei Chemical Industry Co., Ltd.) was changed from 0.06 parts by weight to 0.3 parts by weight as the metal amount with respect to 100 parts by weight of the mixture A1. Except having increased, it experimented similarly to the said Example 10, and hardened
  • the composition after curing had a Shore A hardness of 21 and an appropriate hardness. Moreover, about the heat resistance of the composition after hardening, as a result of heating the composition after hardening for 1032 hours at 200 degreeC, the weight maintenance factor after a heating is 87.5%, and the composition after hardening becomes heat resistance. I found it excellent. Further, the ability to prevent sulfidation of the cured composition was also evaluated in the same manner as in Example 9. As a result, the light reflectance maintenance factor was as high as 92%, and it was confirmed that the cured composition was excellent in sulfur prevention ability.
  • Example 12 In Example 11, instead of only the mixture A1, an experiment was performed in the same manner as in Example 11 except that the mixture A6, which is an equal weight mixture of the mixture A1 and the component 13, was used to obtain a cured product. . Also in Example 12, indium 2-ethylhexanoate was visually dissolved in the mixture A6 at room temperature (about 25 ° C.). Further, the result of visual observation of the cured composition was colorless and transparent, free from foaming and surface wrinkles, formed into a uniform thickness film, and had good leveling properties. The composition after curing had a Shore A hardness of 21 and an appropriate hardness.
  • the weight maintenance factor after a heating is 83.4%, and the composition after hardening becomes heat resistance. I found it excellent.
  • Example 10 except that 0.02 part by weight of zirconyl 2-ethylhexanoate (Nippon Chemical Industry Co., Ltd.) was used instead of 0.06 part by weight of indium 2-ethylhexanoate in Example 10 above.
  • An experiment was conducted in the same manner as above to obtain a cured product.
  • the composition after curing had a Shore A hardness of 21.
  • the weight maintenance factor after a heating was 86.1%.
  • Example 10 except that 0.3 part by weight of zirconyl 2-ethylhexanoate (Nippon Chemical Industry Co., Ltd.) was used instead of 0.06 part by weight of indium 2-ethylhexanoate.
  • An experiment was conducted in the same manner as above to obtain a cured product.
  • As a result of visual observation of the cured composition there was no foaming, the film had a uniform thickness, and the leveling property was good. However, wrinkles were generated on the surface when the air volume in the oven was large during heating.
  • the composition after curing had a Shore A hardness of 27.
  • Example 10 About the heat resistance of the composition after hardening, as a result of heating the composition after hardening for 1032 hours at 200 degreeC, the weight maintenance factor after a heating was 34.3% and was low compared with Example 10. FIG. Further, the ability to prevent sulfidation of the composition after curing was also evaluated in the same manner as in Example 10. As a result, the light reflectance maintenance factor was 75%, which was lower than that of Example 10.
  • Example 10 Comparative Example 5 In Example 10, an experiment was performed in the same manner as in Example 10 except that zinc 2-ethylhexanoate (Wako Pure Chemical Industries, Ltd.) was used instead of indium 2-ethylhexanoate. However, the mixture A1 remained liquid.
  • Example 10 except that 0.3% by weight of zinc 2-ethylhexanoate (Wako Pure Chemical Industries, Ltd.) was used instead of 0.06% by weight of indium 2-ethylhexanoate in Example 10 above.
  • the mixture A1 was tried to be cured by heating, but the viscosity of the mixture A1 increased but remained liquid.
  • Example 12 except that zinc 2-ethylhexanoate (Wako Pure Chemical Industries, Ltd.) was used instead of indium 2-ethylhexanoate, an experiment was conducted in the same manner as in Example 12 to obtain a cured product. Obtained. As a result of visual observation of the cured composition, there was no foaming or surface wrinkling, and the film had a uniform thickness, and the leveling property was also good. The composition after curing was self-supporting and had an appropriate hardness. However, regarding the heat resistance of the cured composition, the cured composition was heated at 200 ° C. for 1032 hours, and as a result, the weight retention after heating was 72.8%, which was lower than Example 12. The results of Examples 10 to 12 and Comparative Examples 3 to 7 are summarized in Table 3.
  • Example 13 In Example 10 above, instead of the mixture A1, using the mixture A2 obtained in Example 2 above, indium 2-ethylhexanoate was increased from 0.06 wt% to 0.3 wt% as a metal amount, An experiment was performed in the same manner as in Example 10 except that the weight of the pre-curing composition placed in a PTFE (polytetrafluoroethylene) petri dish was increased from 2 g to 2.3 g to obtain a cured product. As a result of visual observation of the cured composition, there was no foaming or surface wrinkling, and the film had a uniform thickness, and the leveling property was also good. The composition after curing had a Shore A hardness of 24 and an appropriate hardness.
  • PTFE polytetrafluoroethylene
  • the weight maintenance factor after a heating is 92.1%, and the composition after hardening is heat resistant. I found it excellent.
  • the light reflectance maintenance rate was as high as 93%, and the cured composition was excellent in sulfidation preventing ability. confirmed.
  • Example 13 except that zirconyl 2-ethylhexanoate (Nippon Chemical Industry Co., Ltd.) was used instead of indium 2-ethylhexanoate, an experiment was performed in the same manner as in Example 13 to obtain a cured product. It was. As a result of visual observation of the cured composition, there was no foaming or surface wrinkling, and the film had a uniform thickness, and the leveling property was also good. The composition after curing had a Shore A hardness of 36 and an appropriate hardness. However, as for the heat resistance of the cured composition, the cured composition was heated at 200 ° C. for 1032 hours.
  • Example 13 the weight retention after heating was 89.7%, which was lower than Example 13. Moreover, as a result of evaluating the sulfidation preventing ability of the cured composition in the same manner as in Example 13, the retention rate of light reflectance was 86%, which was lower than that in Example 13.
  • Example 9 A cured product was obtained in the same manner as in Example 13 except that gallium triacetylacetonate (manufactured by STREM CHEMICALS) was used in place of indium 2-ethylhexanoate in Example 13.
  • gallium triacetylacetonate manufactured by STREM CHEMICALS
  • the Shore A hardness of the composition after curing was 37, which was an appropriate hardness.
  • the heat resistance of the cured composition the cured composition was heated at 200 ° C. for 1032 hours.
  • the weight retention after heating was 90.0%, which was lower than Example 13.
  • the retention rate of the light reflectance was 90%, which was lower than that in Example 13.
  • Example 13 Comparative Example 10 In Example 13, an experiment was performed in the same manner as in Example 13 except that zinc 2-ethylhexanoate (Wako Pure Chemical Industries, Ltd.) was used instead of indium 2-ethylhexanoate. Got. As a result of visual observation of the cured composition, there was no foaming or surface wrinkling, and the film had a uniform thickness, and the leveling property was also good. The composition after curing had a Shore A hardness of 28 and an appropriate hardness. However, as for the heat resistance of the cured composition, the cured composition was heated at 200 ° C. for 1032 hours. As a result, the weight retention after heating was 79.8%, which was lower than that of Example 13.
  • Example 13 the antisulfurization ability of the composition after thickening was evaluated in the same manner as in Example 13. As a result, the light reflectance maintenance factor was 95%, and it was found that Example 13 had the same level of sulfidation prevention capability as when zinc 2-ethylhexanoate was used.
  • Example 14 In Example 13, the amount of indium 2-ethylhexanoate (manufactured by Shinsei Chemical Industry Co., Ltd.) was changed from 0.3 parts by weight to 1.0 parts by weight as the amount of metal with respect to 100 parts by weight of the mixture A2. Except having increased, it experimented similarly to the said Example 13 and obtained hardened
  • Example 15 In Example 13, instead of indium 2-ethylhexanoate, 100 parts by weight of the mixture A2, 0.3 parts by weight of indium 2-ethylhexanoate as a metal amount and gallium triacetylacetonate (STREM CHEMICALS Except for adding 0.1 part by weight of the product as a metal amount, an experiment was conducted in the same manner as in Example 13 to obtain a cured product. As a result of visual observation of the cured composition, there was no foaming or surface wrinkling, and the film had a uniform thickness, and the leveling property was also good. The composition after curing had a Shore A hardness of 45 and an appropriate hardness.
  • the In compound according to the present invention is superior in the heat resistance of the composition after curing compared to the zirconium-based catalyst and the zinc-based catalyst, and the change depending on the concentration of the heat-resistant catalyst is low. It has been found. That is, it was found that heat resistance and curability can be ensured by increasing the catalyst concentration from the zirconium-based catalyst.
  • the In compound according to the present invention is also useful in the production of phenyl-based condensation-type silicones, and is superior in heat resistance of the cured composition compared to zirconium-based catalysts and gallium-based catalysts. It was found that wrinkles and foaming were less likely to occur on the catalyst.
  • the In compound catalyst according to the present invention is also excellent in sulfidation prevention ability, and since the change depending on the catalyst concentration of this sulfidation prevention ability is small, it is expected to be suitable for a sealed optical semiconductor.
  • the composition according to the present invention has an excellent balance of properties such as curability, heat resistance, and antisulfurization properties by supplementing curability with a small amount of zirconium-based catalyst or gallium-based catalyst as appropriate. It can be considered as a product.
  • curable organopolysiloxane composition of the present invention may be used for any application, it can be suitably used particularly for sealing semiconductor devices.

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Abstract

La présente invention concerne une composition d'organopolysiloxane durcissable obtenue au moyen d'un nouveau catalyseur de condensation et concerne une composition d'organopolysiloxane durcissable, contenant un organopolysiloxane qui contient deux groupes hydroxyle, ou plus, et/ou deux groupes hydrolysables, ou plus, dans chaque molécule, lesdits groupes étant respectivement liés à des atomes de silicium, et au moins un composé organique d'indium sélectionné parmi les complexes chélatés, les alcoxydes et les sels d'acide gras d'indium. On préfère que l'organopolysiloxane contienne une structure de polydiorganosiloxane. Cet organopolysiloxane peut contenir trois groupes hydroxyle, ou plus, et/ou trois groupes hydrolysables, ou plus, dans chaque molécule, lesdits groupes étant respectivement liés à des atomes de silicium. De plus, cette composition d'organopolysiloxane durcissable peut contenir l'organopolysiloxane décrit ci-dessus, le composé organique d'indium décrit ci-dessus et un composé de silicium qui contient trois groupes hydroxyle, ou plus, et/ou trois groupes hydrolysables, ou plus, dans chaque molécule, lesdits groupes étant respectivement liés à des atomes de silicium.
PCT/JP2013/070218 2012-07-27 2013-07-25 Composition d'organopolysiloxane durcissable, son procédé de préparation, procédé de préparation d'organopolysiloxane durci, procédé de condensation d'organopolysiloxane, emballage semi-conducteur optique et catalyseur de condensation destiné à des organopolysiloxanes WO2014017598A1 (fr)

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CN201380038094.5A CN104487520B (zh) 2012-07-27 2013-07-25 固化性有机聚硅氧烷组合物、其制造方法、有机聚硅氧烷固化物的制造方法、有机聚硅氧烷的缩合方法、光半导体密封体以及有机聚硅氧烷的缩合催化剂
JP2014527007A JP6277956B2 (ja) 2012-07-27 2013-07-25 硬化性オルガノポリシロキサン組成物、その製造方法、オルガノポリシロキサン硬化物の製造方法、オルガノポリシロキサンの縮合方法、光半導体封止体、及びオルガノポリシロキサンの縮合触媒
KR1020157001008A KR20150037830A (ko) 2012-07-27 2013-07-25 경화성 오르가노폴리실록산 조성물, 그 제조 방법, 오르가노폴리실록산 경화물의 제조 방법, 오르가노폴리실록산의 축합 방법, 광 반도체 밀봉체, 및 오르가노폴리실록산의 축합 촉매

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WO2019188831A1 (fr) * 2018-03-29 2019-10-03 Ａｇｃ株式会社 Élément de conversion de longueur d'onde et procédé de fabrication associé
JP2021534264A (ja) * 2018-08-24 2021-12-09 ダウ シリコーンズ コーポレーション ヒドロキシル末端ポリジオルガノシロキサンの縮合重合のため方法
TWI805569B (zh) * 2017-02-02 2023-06-21 日商力森諾科股份有限公司 撥水結構體及其製造方法

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CN104576901B (zh) * 2015-01-16 2017-12-12 中国科学院化学研究所 一种具有提高的防硫化性能的led元件及其制备方法
CN106008979A (zh) * 2015-03-27 2016-10-12 豪雅冠得股份有限公司 固化性树脂组合物及光半导体装置
KR20180100561A (ko) * 2016-01-08 2018-09-11 주식회사 다이셀 경화성 실리콘 수지 조성물 및 그의 경화물, 및 광 반도체 장치
TWI648878B (zh) * 2018-05-15 2019-01-21 東貝光電科技股份有限公司 Led發光源、led發光源之製造方法及其直下式顯示器
CN111234229B (zh) * 2020-02-26 2021-12-21 华南理工大学 一种led封装胶用乙烯基苯基硅树脂及其制备方法与应用

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