WO2012077529A1 - 付加硬化性メタロシロキサン化合物 - Google Patents
付加硬化性メタロシロキサン化合物 Download PDFInfo
- Publication number
- WO2012077529A1 WO2012077529A1 PCT/JP2011/077496 JP2011077496W WO2012077529A1 WO 2012077529 A1 WO2012077529 A1 WO 2012077529A1 JP 2011077496 W JP2011077496 W JP 2011077496W WO 2012077529 A1 WO2012077529 A1 WO 2012077529A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silane
- compound
- group
- compounds
- vinyl
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- 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
- C08G77/56—Boron-containing linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/04—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing boron
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
Definitions
- the present invention relates to a metallosiloxane compound having addition curability, a curable resin composition having the metallosiloxane compound, and a cured product thereof.
- Patent Document 1 describes an alicyclic epoxy resin containing boric acid ester and alkoxysilane for encapsulation of a solid element device such as a light emitting diode.
- these resins it is described that the deterioration of the resin due to ultraviolet irradiation for a long time has been improved.
- these resins are mainly composed of an epoxy resin, and heat-resistant non-yellowing when exposed to a high temperature of 150 ° C. or longer for a long time is considered to be low.
- a bifunctional silane compound is reacted with a boron compound as an inorganic polymer for insulating film having high heat resistance, moisture resistance and flexibility, and the resulting product is further reacted with a trifunctional silane compound and a boron compound.
- Patent Document 2 a polyborosiloxane obtained by the above process.
- this polyborosiloxane is solid at room temperature and requires the use of a solvent when forming a coating film, and has not been studied as a material for electronic device packaging.
- the present inventor obtained by reacting a bifunctional silane compound, a monofunctional silane compound, a boron compound, and, if necessary, H 2 O at a specific molar ratio.
- the novel metallosiloxane compound produced has no outgassing during curing of the curable resin composition containing the metallosiloxane compound, and the cured product obtained by curing the curable resin composition has excellent heat-resistant non-yellowing And found the present invention.
- R 1 and R 2 are the same or different and each represents a hydrogen atom, a C 1-10 alkyl group, a C 2-10 alkenyl group, a C 6-14 aryl group, or a C 7-15 aralkyl group
- X 1 and X 2 are the same or different and each represents a C 1-10 alkoxy group, a halogen atom, or a hydroxyl group.
- a silane compound (S1) represented by the following formula (2) (Wherein R 3 to R 5 are the same or different and each represents a hydrogen atom, a C 1-10 alkyl group, a C 2-10 alkenyl group, a C 6-14 aryl group, or a C 7-15 aralkyl group, X 3 represents a C 1-10 alkoxy group, a halogen atom, or a hydroxyl group.) Or a silane compound (S2), a boron compound (M), or the silane compound (S1), the silane compound (S2), the boron compound (M), and H 2 O.
- (S1): The silane compound (S2): the boron compound (M): H 2 O n: m: k: a molar ratio, and n, m, k, a are the following relationships (i) A metallosiloxane compound (A) produced by reacting under the conditions satisfying all of (iii) to (iii), and having at least one Si—H bond or C 2-10 alkenyl group in one molecule A metallosiloxane compound is provided.
- the metallosiloxane compound of the present invention is preferably a liquid at any temperature of 0 to 90 ° C.
- the present invention also provides a curable resin composition
- a curable resin composition comprising a compound having a Si—H bond and a compound having a C 2-10 alkenyl group, wherein at least the metallosiloxane compound (A) and the hydrosilylation catalyst (C).
- the curable resin composition characterized by containing these is provided.
- the curable resin composition of the present invention may further contain an inorganic filler (D), and may further contain a silane coupling agent (E).
- the present invention provides a cured product obtained by curing the curable resin composition.
- the curable resin composition containing the metallosiloxane compound has no outgassing during curing, and the cured product obtained by curing the curable resin composition has excellent heat-resistant non-yellowing properties. . Therefore, it is useful as a sealant or sealant for an electronic device such as an LED or a heat resistant hard coat.
- the metallosiloxane compound of the present invention has the following formula (1) Wherein R 1 and R 2 are the same or different and each represents a hydrogen atom, a C 1-10 alkyl group, a C 2-10 alkenyl group, a C 6-14 aryl group, or a C 7-15 aralkyl group, X 1 and X 2 are the same or different and each represents a C 1-10 alkoxy group, a halogen atom, or a hydroxyl group.
- a silane compound (S1) represented by the following formula (2) (Wherein R 3 to R 5 are the same or different and each represents a hydrogen atom, a C 1-10 alkyl group, a C 2-10 alkenyl group, a C 6-14 aryl group, or a C 7-15 aralkyl group, X 3 represents a C 1-10 alkoxy group, a halogen atom, or a hydroxyl group.) Or a silane compound (S1), a boron compound (M), or the silane compound (S1), the silane compound (S2), a boron compound (M), and H 2 O.
- Examples of the C 2-10 alkenyl group contained in at least one molecule of the metallosiloxane compound of the present invention include a vinyl group, an allyl group, a 2-butenyl group, a 2-pentanyl group, and a 2-hexynyl group.
- a vinyl group and an allyl group are preferable.
- n, m, and k are molar ratios of their total amounts when two or more silane compounds (S1), silane compounds (S2), and boron compounds (M) are used as described later. .
- a so-called monofunctional silane compound (S2) having one hydrolyzable group and one hydroxyl group functional group (X 3 ) in one molecule is converted into either a hydrolyzable group or a hydroxyl group.
- These bifunctional and monofunctional silanes are used in a molar ratio of at least 0.5 times the so-called bifunctional silane compound (S1) having two functional groups (X 1 , X 2 ) in one molecule.
- the compound is used in a total of 1.8 times or more (molar ratio) of the boron compound (M).
- the metallosiloxane compound is preferably a liquid at any temperature of 0 to 90 ° C., does not generate outgas when cured, and provides a heat-resistant non-yellowing cured product. Can be obtained.
- the silane compound (S1) represented by the formula (1) is a bifunctional silane compound (S1)
- the silane compound (S2) represented by the formula (2) is a monofunctional silane. It may be called a compound (S2).
- a silane compound containing one or more Si—H bonds is an “H-type” silane compound
- a silane compound containing one or more C 2-10 alkenyl groups such as a vinyl group or an allyl group is a “vinyl-type” silane compound.
- a silane compound containing neither Si—H bonds nor C 2-10 alkenyl groups is referred to as “other” silane compound.
- the use molar ratio m / n of the monofunctional silane compound (S2) and the bifunctional silane compound (S1) is preferably 0.5 or more and 5 or less, more preferably 0.6 or more and 3 or less, particularly Preferably they are 0.6 or more and 1.5 or less.
- the molar ratio (n: m) of the bifunctional silane compound (S1) to the monofunctional silane compound (S2) is 0.7: 1 to 1 7: 1.
- the reaction of the bifunctional silane compound (S1), the monofunctional silane compound (S2), the boron compound (M) and H 2 O used as necessary is performed using a reaction solution in which all of these compounds are mixed.
- the reaction may be performed in stages (one-step reaction), or a reaction (pre-process) in which a bifunctional silane compound (S1), a boron compound (M) and H 2 O are reacted if necessary is performed.
- a step of reacting the liquid with a monofunctional silane compound (S2), a bifunctional silane compound (S1) and a boron compound (M), if necessary, and H 2 O as necessary (rear step) May be carried out (two-stage reaction).
- the above reaction can be performed, for example, at 50 to 150 ° C., preferably 60 to 130 ° C., more preferably 60 to 100 ° C.
- the reaction time varies depending on the reaction temperature and the type of silane compound and boron compound used, but can be, for example, 10 minutes to 10 hours, preferably 1 to 5 hours.
- the reaction temperature is the same as described above.
- the reaction time may be, for example, 1 minute to 5 hours, preferably 10 minutes to 1 hour in the previous step, and 10 minutes to 10 hours, preferably 1 to 5 hours in the subsequent step.
- the metallosiloxane compound (A) produced by the above production method is preferably a liquid at any temperature of 0 to 90 ° C., more preferably any temperature of 0 to 70 ° C., particularly preferably 0 to It is liquid at any temperature of 30 ° C.
- the metallosiloxane compound of the present invention is an oligomer or polymer obtained by cohydrolytic condensation of boron compounds (M) such as boron alkoxides, halides or hydroxides with silicon alkoxides, halides or hydroxides. It is.
- the weight average molecular weight Mw of the metallosiloxane compound (A) of the present invention is preferably 500 to 100,000, and more preferably 500 to 30,000. By setting Mw in such a range, there is a tendency that liquid metallosiloxane is easily obtained.
- the bifunctional silane compound (S1) used in the reaction for producing the metallosiloxane compound (A) of the present invention is represented by the following formula (1).
- R 1 and R 2 are the same or different and each represents a hydrogen atom, a C 1-10 alkyl group, a C 2-10 alkenyl group, a C 6-14 aryl group, or a C 7-15 aralkyl group
- X 1 and X 2 are the same or different and each represents a C 1-10 alkoxy group, a halogen atom, or a hydroxyl group.
- dialkoxysilane compounds, dihalogenated silane compounds, or dihydroxysilane compounds conventionally used for the production of polysiloxanes, polyborosiloxanes, and the like.
- Examples of the C 1-10 alkyl group in R 1 and R 2 in the formula include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, decyl group, etc .; C 2-10 the alkenyl group, a vinyl group, an allyl group, a 2-butenyl group, 2-pentanyl group, 2-hexynyl group; the C 6-14 aryl group, a phenyl group, a naphthyl group; a C 7-15 aralkyl group Examples include benzyl group.
- Examples of the C 1-10 alkoxy group in X 1 and X 2 in the above formula (1) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Can be mentioned.
- H-type dialkoxysilane compounds include di-C 1-10 alkoxysilane compounds containing two hydrogen atoms such as dimethoxysilane, diethoxysilane, dipropoxysilane, dibutoxysilane; methyldimethoxysilane, methyldiethoxysilane , Methyldipropoxysilane, methyldibutoxysilane, ethyldimethoxysilane, ethyldiethoxysilane, ethyldipropoxysilane, ethyldibutoxysilane, propyldimethoxysilane, propyldiethoxysilane, propyldipropoxysilane, propyldibutoxysilane, butyl Dimethoxysilane, Butyldiethoxysilane, Butyldipropoxysilane, Butyldibutoxysilane, Phenyldimethoxysilane, Phen
- vinyl type dialkoxysilane compounds include divinyldimethoxysilane, diallyldimethoxysilane, di (2-butenyl) propyldimethoxysilane, di (2-pentanyl) dimethoxysilane, divinyldiethoxysilane, diallyldiethoxysilane, di ( 2-butenyl) propyldiethoxysilane, di (2-pentanyl) diethoxysilane, divinyldipropoxysilane, diallyldipropoxysilane, di (2-butenyl) propyldipropoxysilane, di (2-pentanyl) dipropoxysilane, DiC 2-10 alkenyl di C 1-10 alkoxysilane compounds such as divinyldibutoxysilane, diallyldibutoxysilane, di (2-butenyl) propyldibutoxysilane, di (2-pentanyl) dibutoxysilane;
- dialkoxysilane compounds include, for example, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, dibutyldiethoxysilane, dimethyl Di-C 1-10 alkyl di-C 1 such as dipropoxy silane, diethyl dipropoxy silane, dipropyl dipropoxy silane, dibutyl dipropoxy silane, dimethyl dibutoxy silane, diethyl dibutoxy silane, dipropyl dibutoxy silane, dibutyl dibutoxy silane -10 alkoxysilane compounds; diphenyldimethoxysilane, dinaphthyldimethoxysilane, diphenyldiethoxysilane, dinaphthyldiethoxysilane, dipheny
- H-type dihalogenated silane compound examples include dihalogenated silane compounds containing two hydrogen atoms such as difluorosilane, dichlorosilane, and dibromosilane; difluoromethylsilane, dichloromethylsilane, dibromomethylsilane, difluoroethylsilane, and dichloroethyl.
- Silane dibromoethylsilane, difluoropropylsilane, dichloropropylsilane, dibromopropylsilane, difluorobutylsilane, dichlorobutylsilane, dibromobutylsilane, difluorophenylsilane, dichlorophenylsilane, dibromophenylsilane, difluoronaphthylsilane, dichloronaphthylsilane, dibromo Contains one hydrogen atom such as naphthylsilane, fluorobenzylsilane, dichlorobenzylsilane, dibromobenzylsilane Halogenated silane compounds, and the like.
- vinyl-type dihalogenated silane compounds include difluorodivinylsilane, dichlorodivinylsilane, dibromodivinylsilane, difluorodiallylsilane, dichlorodiallylsilane, dibromodiallylsilane, difluorodi (2-butenyl) silane, and dichlorodi (2-butenyl) silane.
- Dihalogenated diC 2-10 alkenylsilane compounds such as dibromodi (2-butenyl) silane, difluorodi (2-pentanyl) silane, dichlorodi (2-pentanyl) silane, dibromodi (2-pentanyl) silane; difluoromethylvinylsilane, difluoro Ethyl vinyl silane, difluoropropyl vinyl silane, difluorobutyl vinyl silane, dichloromethyl vinyl silane, dichloroethyl vinyl silane, dichloropropyl vinyl silane Dichlorobutylvinylsilane, dibromomethylvinylsilane, dibromoethylvinylsilane, dibromopropylvinylsilane, dibromobutylvinylsilane, difluoromethylallylsilane, difluoroethylallylsilane, difluoropropylallylsi
- dihalogenated silane compounds include difluorodimethylsilane, dichlorodimethylsilane, dibromodimethylsilane, difluorodiethylsilane, dichlorodiethylsilane, dibromodiethylsilane, difluorodipropylsilane, dichlorodipropylsilane, dibromodipropylsilane, Dihalogenated diC 1-10 alkylsilane compounds such as difluorodibutylsilane, dichlorodibutylsilane, dibromodibutylsilane; difluorodiphenylsilane, dichlorodiphenylsilane, dibromodiphenylsilane, difluorodinaphthylsilane, dichlorodinaphthylsilane, dibromodinaphthylsilane Dihalogenated di C 6-14 arylsilane compounds such as
- H-type dihydroxysilane compound examples include dihydroxysilane (containing two hydrogen atoms); methyldihydroxysilane, ethyldihydroxysilane, propyldihydroxysilane, butyldihydroxysilane, phenyldihydroxysilane, naphthyldihydroxysilane, benzyldihydroxysilane, and the like.
- a dihydroxysilane compound containing one hydrogen atom is exemplified.
- vinyl-type dihydroxysilane compounds include diC 2-10 alkenyldihydroxysilane compounds such as divinyldihydroxysilane, diallyldihydroxysilane, di (2-butenyl) dihydroxysilane, and di (2-pentanyl) dihydroxysilane; C 1-10 alkyl C 2-10 alkenyl dihydroxy silane such as silane, ethyl vinyl dihydroxy silane, propyl vinyl dihydroxy silane, butyl vinyl dihydroxy silane, methyl allyl dihydroxy silane, ethyl allyl dihydroxy silane, propyl allyl dihydroxy silane, butyl allyl dihydroxy silane Compound; phenyl vinyl dihydroxy silane, naphthyl vinyl dihydroxy silane, phenyl allyl dihydroxy silane, naphthyl allyl C 6-14 aryl C 2-10 alkenyl dihydroxy silane compounds such as hydroxy silane; benzyl vinyl dihydroxysilane, C 7
- dihydroxysilane compounds examples include di-C 1-10 alkyl dihydroxysilane compounds such as dimethyldihydroxysilane, diethyldihydroxysilane, dipropyldihydroxysilane, and dibutyldihydroxysilane; di-C such as diphenyldihydroxysilane and dinaphthyldihydroxysilane.
- the C 1-10 alkyl group as R 1 and R 2 in the above formula (1) is particularly preferably a C 1-5 alkyl group, and the C 2-10 alkenyl group is particularly preferably C 2 ⁇ 5- Alkenyl groups are preferred.
- R 1 and R 2 are preferably a methyl group, an ethyl group, a phenyl group, a vinyl group, or an allyl group from the viewpoint of heat-resistant non-yellowing. Further, a phenyl group is more preferable from the viewpoint of hydrolysis resistance.
- X 1 and X 2 are particularly preferable.
- X 1 and X 2 are preferably a methoxy group, an ethoxy group, a chlorine atom, a bromine atom and a hydroxyl group from the viewpoint of availability, and more preferably a methoxy group and an ethoxy group from the viewpoint of stability before the reaction.
- silane compound (S1) examples include di-C 1-10 alkyl di-C 1-12 alkoxy silane (and di-C 1-5 alkyl di-C 1-6 alkoxy silane) and di-C 6- 14 aryldi C 1-10 alkoxysilanes (more preferably diphenyldiC 1-6 alkoxysilanes) are preferred, especially dimethyldimethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, divinyldimethoxysilane, diallyldimethoxysilane, dimethyldiethoxysilane, Diethyldiethoxysilane, diphenyldiethoxysilane, divinyldiethoxysilane, or diallyldiethoxysilane can be preferably used.
- the monofunctional silane compound (S2) used in the reaction for producing the metallosiloxane compound (A) of the present invention is represented by the following formula (2).
- R 3 to R 5 are the same or different and each represents a hydrogen atom, a C 1-10 alkyl group, a C 2-10 alkenyl group, a C 6-14 aryl group, or a C 7-15 aralkyl group
- X 3 represents a C 1-10 alkoxy group, a halogen atom, or a hydroxyl group.
- known monoalkoxysilane compounds, monohalogenated silane compounds, or monohydroxysilane compounds conventionally used for the production of polysiloxane, polyborosiloxane and the like.
- the above bifunctional silane compound (S1) examples of R 1 and R 2 can be used.
- R 1 and R 2 examples of R 1 and R 2 can be used.
- the C 1-10 alkoxy group and halogen atom in X 3 those exemplified as X 1 and X 2 in the silane compound (S1) can be used.
- H-type monoalkoxysilane compound examples include C 1-10 alkoxysilane compounds containing three hydrogen atoms such as methoxysilane, ethoxysilane, propoxysilane, and butoxysilane; methylmethoxysilane, methylethoxysilane, methylpropoxysilane, Methylbutoxysilane, ethylmethoxysilane, ethylethoxysilane, ethylpropoxysilane, ethylbutoxysilane, propylmethoxysilane, propylethoxysilane, propylpropoxysilane, propylbutoxysilane, butylmethoxysilane, butylethoxysilane, butylpropoxysilane, butylbutoxy Silane, phenylmethoxysilane, phenylethoxysilane, phenylpropoxysilane, phenylbutoxysilane
- vinyl monoalkoxysilane compounds include trivinylmethoxysilane, trivinylethoxysilane, trivinylpropoxysilane, trivinylbutoxysilane, triallylmethoxysilane, triallylethoxysilane, triallylpropoxysilane, triallylbutoxysilane.
- Tri C 2-10 alkenyl C 1-10 alkoxy silane compounds such as: methyldivinylmethoxysilane, methyldivinylethoxysilane, methyldivinylpropoxysilane, methyldivinylbutoxysilane, ethyldivinylmethoxysilane, ethyldivinylethoxysilane, ethyldivinylpropoxysilane , Ethyldivinylbutoxysilane, propyldivinylmethoxysilane, propyldivinylethoxysilane, propyldivinylpropoxysilane, propyl Divinylbutoxysilane, butyldivinylmethoxysilane, butyldivinylethoxysilane, butyldivinylpropoxysilane, butyldivinylbutoxysilane, methyldiallylmethoxysilane, methyldiallyleth
- vinyl-type monoalkoxysilane compound examples include, for example, dimethylvinylmethoxysilane, diethylvinylmethoxysilane, dipropylvinylmethoxysilane, dibutylvinylmethoxysilane, dimethylvinylethoxysilane, diethylvinylethoxysilane, dipropylvinylethoxysilane, Dibutylvinylethoxysilane, dimethylvinylpropoxysilane, diethylvinylpropoxysilane, dipropylvinylpropoxysilane, dibutylvinylpropoxysilane, dimethylvinylbutoxysilane, diethylvinylbutoxysilane, dipropylvinylbutoxysilane, dibutylvinylbutoxysilane, dimethylallylmethoxy Silane, diethylallylmethoxysilane, dipropylallylmethoxys
- Examples of other monoalkoxysilane compounds include trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldiethylmethoxysilane, phenyldiethylethoxysilane, and diphenyl. Examples include methylmethoxysilane, diphenylmethylethoxysilane, diphenylethylmethoxysilane, and diphenylethylethoxysilane.
- H-type monohalogenated silane compound examples include monohalogenated silane compounds containing three hydrogen atoms such as monofluorosilane, monochlorosilane, and monobromosilane; fluoromethylsilane, chloromethylsilane, bromomethylsilane, and fluoroethyl Silane, chloroethylsilane, bromoethylsilane, fluoropropylsilane, chloropropylsilane, bromopropylsilane, fluorobutylsilane, chlorobutylsilane, bromobutylsilane, fluorophenylsilane, chlorophenylsilane, bromophenylsilane, fluoronaphthylsilane, chloro Monohalogenated silane compounds containing two hydrogen atoms such as naphthylsilane, bromonaphthylsilane, fluorobenzylsilane,
- Aralkylsilane compounds fluoromethylphenylsilane, fluoroethylphenylsilane, fluoropropylphenylsilane, fluorobutylphenylsilane, chloromethylphenylsilane, chloroethylphenylsilane, chloropropylphenylsilane, chlorobutylphenylsilane, bromomethylnaphthyl Monohalogenated C 1-10 alkyl C 6-14 arylsilane compounds containing one hydrogen atom, such as silane, bromoethylnaphthylsilane, bromopropylnaphthylsilane, bromobutylnaphthylsilane; fluoromethylbenzylsilane, fluoroethylbenzylsilane, Fluoropropylbenzylsilane, fluorobutylbenzylsilane,
- vinyl monohalogenated silane compound examples include monohalogenated tri-C 2-10 alkenylsilane compounds such as fluorotrivinylsilane, chlorotrivinylsilane, bromotrivinylsilane, fluorotriallylsilane, chlorotriallylsilane, and bromotriallylsilane; Methyldivinylsilane, chloromethyldivinylsilane, bromomethyldivinylsilane, fluoroethyldivinylsilane, chloroethyldivinylsilane, bromoethyldivinylsilane, fluoropropyldivinylsilane, chloropropyldivinylsilane, bromopropyldivinylsilane, fluorobutyldivinylsilane, chloro Butyldivinylsilane, bromobutyldivinylsilane, fluoro
- Monohalogenated C 1-10 alkyldiC 2-10 alkenylsilane compounds fluorophenyldivinylsilane, chlorophenyldivinylsilane, bromophenyldivinylsilane, fluoronaphthyldivinylsilane, chloronaphthyldivinylsilane, bromonaphthyldivinylsilane, fluorophenyldiallylsilane, Chlorophenyldiallylsilane, bromophenyldiallylsilane, fluoronaphthyldiallylsilane, chloronaphth Rujiarirushiran, monohalogenated C 6-14 aryldi C 2-10 alkenyl silane compound such as bromo naphthyl diallyl silane; fluorobenzyl divinyl silane, chlorobenzyl divinyl silane, bromobenzyl divinyl silane
- vinyl type monohalogenated silane compound examples include, for example, fluorodimethylvinylsilane, chlorodimethylvinylsilane, bromodimethylvinylsilane, fluorodiethylvinylsilane, chlorodiethylvinylsilane, bromodiethylvinylsilane, fluorodipropylvinylsilane, chlorodipropylvinylsilane, bromodi Propyl vinyl silane, fluorodibutyl vinyl silane, chloro dibutyl vinyl silane, bromo dibutyl vinyl silane, fluoro dimethyl allyl silane, bromo dimethyl allyl silane, fluoro diethyl allyl silane, chloro diethyl allyl silane, bromo diethyl allyl silane, fluoro dipropyl allyl silane, chloro dipropyl allyl silane, bromo Dipropyl
- Examples of other monohalogenated silane compounds include fluorotrimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, fluorotriphenylsilane, chlorotriphenylsilane, bromotriphenylsilane, fluorophenyldimethylsilane, chlorophenyldimethylsilane, and bromophenyl.
- Examples include dimethylsilane, fluorophenyldiethylsilane, chlorophenyldiethylsilane, bromophenyldiethylsilane, fluorodiphenylmethylsilane, chlorodiphenylmethylsilane, bromodiphenylmethylsilane, fluorodiphenylethylsilane, chlorodiphenylethylsilane, and bromodiphenylethylsilane.
- H-type monohydroxysilane compound examples include monohydroxysilane (including 3 hydrogen atoms); methylhydroxysilane, ethylhydroxysilane, propylhydroxysilane, butylhydroxysilane, phenylhydroxysilane, naphthylhydroxysilane, and benzylhydroxysilane.
- a hydroxysilane compound containing two hydrogen atoms such as dimethylhydroxysilane, diethylhydroxysilane, dipropylhydroxysilane, dibutylhydroxysilane, and the like; a diC 1-10 alkylhydroxysilane compound containing one hydrogen atom; dinaphthyl hydroxydicarboxylic C 6-14 aryl hydroxy silane compound containing one hydrogen atom such as silane; dibenzyl hydroxydicarboxylic C 7-15 aralkyl containing one hydrogen atom such as a silane Droxysilane compound; contains one hydrogen atom such as methylphenylhydroxysilane, ethylphenylhydroxysilane, propylphenylhydroxysilane, butylphenylhydroxysilane, methylnaphthylhydroxysilane, ethylnaphthylhydroxysilane, propylnaphthylhydroxysilane, butylnaph
- C 1-10 alkyl C 6-14 arylhydroxysilane compound C 1-10 alkyl C 7-15 containing one hydrogen atom such as methylbenzylhydroxysilane, ethylbenzylhydroxysilane, propylbenzylhydroxysilane, butylbenzylhydroxysilane, etc. Examples thereof include aralkylhydroxysilane compounds.
- vinyl-type monohydroxysilane compound examples include tri-C 2-10 alkenylhydroxysilane compounds such as trivinylhydroxysilane and triallylhydroxysilane; methyldivinylhydroxysilane, ethyldivinylhydroxysilane, propyldivinylhydroxysilane, butyldivinylhydroxy C 1-10 alkyldi-C 2-10 alkenylhydroxysilane compounds such as silane, methyldiallylhydroxysilane, ethyldiallylhydroxysilane, propyldiallylhydroxysilane, butyldiallylhydroxysilane; phenyldivinylhydroxysilane, naphthyldivinylhydroxysilane, phenyldiallylhydroxy C 6-14 aryldi-C 2-10 alkenyl hydroxysilane compounds such as silane and naphthyl diallylhydroxysilane C 7-15 aralkyl C 1-10 alkyl diC 2-10 al
- vinyl type monohydroxysilane compound for example, dimethylvinylhydroxysilane, diethylvinylhydroxysilane, dipropylvinylhydroxysilane, dibutylvinylhydroxysilane, dimethylallylhydroxysilane, diethylallylhydroxysilane, dipropylallylhydroxysilane, DiC 1-10 alkyl C 2-10 alkenyl hydroxysilane compounds such as dibutylallylhydroxysilane; diC 6-14 aryl such as diphenylvinylhydroxysilane, dinaphthylvinylhydroxysilane, diphenylallylhydroxysilane, dinaphthylallylhydroxysilane C 2-10 alkenyl hydroxysilane compounds; di-C 7-15 aralkyl C 2- such as dibenzylvinylhydroxysilane and dibenzylallylhydroxysilane 10 alkenyl hydroxysilane compounds; methyl phenyl vinyl hydroxy
- Examples of other monohydroxysilane compounds include trimethylhydroxysilane, triphenylhydroxysilane, phenyldimethylhydroxysilane, phenyldiethylhydroxysilane, diphenylmethylhydroxysilane, diphenylethylhydroxysilane, and the like.
- silane compound (S2) the above-exemplified compounds can be used alone or in admixture of two or more.
- the C 1-10 alkyl group as R 3 to R 5 is particularly preferably a C 1-5 alkyl group
- the C 2-10 alkenyl group is particularly preferably a C 2-5 alkenyl group.
- R 3 to R 5 are preferably a methyl group, an ethyl group, a phenyl group, a vinyl group, or an allyl group from the viewpoint of heat-resistant non-yellowing. From the viewpoint of hydrolysis resistance, a phenyl group is more preferable.
- X 3 is preferably a methoxy group, an ethoxy group, a chlorine atom, a bromine atom or a hydroxyl group from the viewpoint of availability, and more preferably a methoxy group or an ethoxy group from the viewpoint of stability before the reaction.
- Examples of the monofunctional silane compound (S2) include di-C 1-10 alkyl C 1-10 alkoxysilane (and di-C 1-5 alkyl C 1-6 alkoxysilane), di-C 6-14 aryl C 1-10 Alkoxysilanes (more preferably diphenyl C 1-6 alkoxysilanes) are preferred, and more specifically, dimethylmethoxysilane, diethylmethoxysilane, diphenylmethoxysilane, dimethylethoxysilane, diethylethoxysilane, diphenylethoxysilane, dimethylvinylmethoxysilane, Diethyl vinyl methoxy silane, diphenyl vinyl methoxy silane, dimethyl vinyl ethoxy silane, diethyl vinyl ethoxy silane, diphenyl vinyl ethoxy silane, dimethyl allyl methoxy silane, diethyl allyl methoxy silane, diphenyl allyl meth
- the metallosiloxane compound of the present invention has at least one Si—H bond or C 2-10 alkenyl group capable of hydrosilylation in one molecule
- silane used for the production of the metallosiloxane compound At least one of the compounds is an H-type silane compound having at least one Si—H bond in one molecule, or a vinyl-type silane compound having at least one C 2-10 alkenyl group in one molecule.
- boron compound (M) a boric acid compound conventionally used for producing polyborosiloxane can be used.
- boron hydride eg, borane, diborane, tetraborane, pentaborane, decaborane
- boric acid Orthoboric acid, metaboric acid, tetraboric acid, etc.
- borates eg, nickel borate, magnesium borate, manganese borate, etc.
- boron oxides such as B 2 O 3 , borazane, borazene, borazine, boron
- Nitrogen compounds such as amide and boron imide, BF 3 , BCl 3 , halides such as tetrafluoroborate, boric acid esters (eg, alkyl borate such as methyl borate and ethyl borate; dimethyl borate, boric acid Dialkyl borates such as diethyl;
- Y 1 to Y 3 are the same or different and each represents a C 1-12 alkoxy group, a halogen atom, or a hydroxyl group.
- the boron compound represented by these is preferable.
- the C 1-12 alkoxy group in Y 1 to Y 3 include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a C 1-6 alkoxy group is preferable.
- the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
- the C 1-12 alkoxy group in Y 1 to Y 3 is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a chlorine atom, a bromine atom or a hydroxyl group from the viewpoint of availability.
- a propoxy group, a butoxy group, and a hydroxyl group are more preferable, and a hydroxyl group is particularly preferable from the viewpoint of easy reaction.
- Preferred boron compounds (M) include boric acid such as borohydride and orthoboric acid or salts thereof, and boric acid in particular.
- the boron compound (M) has a hydrolyzable substituent such as an alkoxy group or a halogen atom
- the molar ratio (a) of H 2 O to be added is 1 with respect to the total mole of the substituent. / 2 or more.
- the silane compound (S1), the silane compound (S2), and the boron compound (M) have a hydroxyl group
- the amount of H 2 O to be added is reduced depending on the total number of moles or H 2 O is not used. Also good.
- Bases include inorganic and organic bases.
- the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, and barium hydroxide.
- Alkaline metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; alkaline earth metal carbonates such as magnesium carbonate; alkali metal carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and cesium hydrogen carbonate Examples thereof include hydrogen salt.
- the organic base examples include alkali metal organic acid salts (particularly alkali metal acetate) such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate; alkaline earth metal organic acid salts such as magnesium acetate; methyllithium, butyl Alkyllithium such as lithium (n-butyllithium, s-butyllithium, t-butyllithium, etc.); alkali metal alkoxide such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide; sodium Alkali metal phenoxides such as phenoxide; triethylamine, N-methylpiperidine, 4-dimethylaminopyridine (DMAP), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), triethylenediamine (1,4-diazabicyclo [2.2.2] octane; DABCO), 1,5-d
- bases can be used alone or in combination of two or more.
- tertiary amines such as triethylamine and 4-dimethylaminopyridine; nitrogen-containing aromatic heterocyclic compounds such as pyridine, lutidine and picoline are preferable.
- the acid catalyst examples include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, carboxylic acids (such as C 1-10 saturated or unsaturated mono- or polycarboxylic acids such as acetic acid and propionic acid), and sulfonic acids (methanesulfone).
- inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid
- carboxylic acids such as C 1-10 saturated or unsaturated mono- or polycarboxylic acids such as acetic acid and propionic acid
- sulfonic acids methanesulfone
- C 1-6 alkane sulfonic acids such as acid and ethane sulfonic acid; aromatic sulfonic acids such as benzene sulfonic acid and p-toluene sulfonic acid), halogenated organic acids (halogenated carboxylic acids such as trifluoroacetic acid; trifluoromethane Organic acids such as halogenated alkane sulfonic acids such as sulfonic acids, etc .; sulfates (calcium sulfate etc.), metal oxides (SiO 2 , Al 2 O 3 etc.), zeolites (Y type, X type having acidic OH, And solid acids such as ion exchange resins (cation exchange resins such as H type) and the like.
- halogenated organic acids halogenated carboxylic acids such as trifluoroacetic acid
- trifluoromethane Organic acids such as halogenated alkane sulfonic acids such as sulf
- the amount of the acid catalyst or base catalyst used is not particularly limited, and is, for example, 0.01 to 5 mol, preferably 0.1 to 2 mol, and more preferably 0.8 to 1 mol of hydroxyl group in the reaction system. About 1.2 mol. When no acid catalyst or base catalyst is used, the reaction can be accelerated by heating or the like.
- the reaction may be performed in the presence of a polymerization inhibitor.
- the reaction temperature can be appropriately selected depending on the reaction components and the type of catalyst. For example, when vinyl silane is used, it is about 20 to 200 ° C., preferably about 20 to 100 ° C., and more preferably about 40 to 60 ° C.
- the reaction temperature can be appropriately selected depending on the reaction components and the type of catalyst, and is, for example, ⁇ 78 to 110 ° C., preferably ⁇ 30 to 40 ° C., more preferably about ⁇ 10 to 10 ° C. It is.
- the reaction may be carried out at normal pressure or under reduced pressure or pressure.
- the reaction atmosphere is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.
- the reaction can be carried out by any method such as batch, semi-batch, and continuous methods.
- the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.
- separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.
- the mixture after the reaction may be washed by adding an aqueous solvent such as water, 1 to 7% dilute hydrochloric acid, and 1 to 7% sodium bicarbonate water.
- the curable resin composition of the present invention is a curable resin composition comprising a compound having a Si—H bond and a compound having a C 2-10 alkenyl group, and is hydrosilylated with at least the metallosiloxane compound (A). It contains a catalyst (C).
- the content of the metallosiloxane compound (A) in the curable resin composition is, for example, 30 to 99% by weight, preferably 40 to 60% by weight.
- the curable resin composition of the present invention may contain a compound (B) having at least one Si—H bond or C 2-10 alkenyl group in one molecule other than the metallosiloxane compound (A). Good.
- the metallosiloxane compound (A) is an H-type compound
- the curable resin composition has a compound (B) [vinyl type compound (B)] having at least one C 2-10 alkenyl group in one molecule. Containing.
- the metallosiloxane compound (A) is a vinyl type compound
- the curable resin composition has a compound (B) having at least one Si—H bond in one molecule [H type compound (B)]. Containing.
- the H-type or vinyl-type compound (B) includes a main chain composed of a siloxane bond (Si—O—Si) having at least one Si—H bond or C 2-10 alkenyl group in one molecule.
- H-type or vinyl-type polysiloxanes having the following can be used.
- the C 2-10 alkenyl group examples are mentioned as a good C 2-10 alkenyl group which may be included in the silane compound.
- Specific examples of the polysiloxane include linear, branched or cyclic siloxane, and a crosslinked silicone resin having a three-dimensional structure.
- the compound (B) include tetramethylsiloxane, tetramethyldivinylsiloxane, hexamethyltrisiloxane, hexamethyldivinyltrisiloxane, heptamethyltrisiloxane, heptamethylvinyltrisiloxane, octamethyltetrasiloxane, octamethyldivinyl.
- Tetrasiloxane nonamethyltetrasiloxane, nonamethylvinyltetrasiloxane, nonamethyldivinyltetrasiloxane, decamethylpentasiloxane, decamethyldivinylpentasiloxane, undecamethylpentasiloxane, undecamethylvinylpentasiloxane, decamethyldivinylpentasiloxane, etc.
- polysiloxane further include compounds in which all or part of alkyl groups such as methyl groups in the above exemplified compounds are substituted with aryl groups such as phenyl groups (preferably C 6-20 aryl groups), such as 1
- aryl groups such as phenyl groups (preferably C 6-20 aryl groups), such as 1
- a linear or cyclic polydiarylsiloxane such as polydiphenylsiloxane (preferably polydiC6-20 arylsiloxane ) having at least two Si—H bonds or C 2-10 alkenyl groups in the molecule
- a linear or cyclic polyalkylaryl siloxane such as polyphenylmethylsiloxane (preferably a poly C 1-10 alkyl C 6-20 aryl siloxane) having at least two Si—H bonds or C 2-10 alkenyl groups );
- the polysiloxane exemplified above may have a branched chain. Also, p-bis (dimethylsilyl) benzene, p-bis (dimethylvinylsilyl) benzene, and the like can be used.
- the molecular weight of the polysiloxane can be, for example, 1,000,000 to 1,000, and preferably 100,000 to 5,000. When the molecular weight of the polysiloxane is within this range, it is preferable that the polysiloxane easily dissolves with the metallosiloxane.
- the polysiloxane can be used alone or in combination of two or more. Among them, tetramethyldisiloxane, hexamethyltrisiloxane, tetramethylcyclotetrasiloxane, hydrosilyl group-containing silicone, p-bis (dimethylsilyl) benzene as the H type compound (B), and tetra as the vinyl type compound (B). Methyldivinylsiloxane, hexamethyltrisiloxane, tetramethyltetravinylcyclotetrasiloxane, vinyl group-containing silicone, and p-bis (dimethylvinylsilyl) benzene are preferred.
- compounds having a B-0-Si bond such as boron dimethyl vinyl siloxane and boron diethyl vinyl siloxane can also be used.
- Examples of the compound having a Si—H bond and the compound having a C 2-10 alkenyl group contained in the curable resin composition of the present invention include an H-type metallosiloxane compound (A) and a corresponding vinyl-type metallosiloxane compound ( A) can also be used.
- the content of the compound (B) can be, for example, 0 to 100 parts by weight, preferably 5 to 60 parts by weight with respect to 100 parts by weight of the metallosiloxane compound (A).
- the content of the compound (B) is within this range, it is preferable because a hardened body that is easily dissolved in metallosiloxane and easily obtained can be obtained.
- the compound (B) may not be used.
- the curable resin composition of the present invention contains other silane compounds that do not contain both Si—H bonds and alkenyl groups, corresponding to the H-type and vinyl-type compounds (B) exemplified above. Also good.
- the silicon atom content in the curable resin composition is, for example, 10 to 30% by weight, preferably 10 to 20% by weight.
- the boron atom content in the curable resin composition can be, for example, 1 to 10% by weight, preferably 1 to 5% by weight.
- hydrosilylation catalyst (C) examples include known hydrosilylation reaction catalysts such as platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts.
- the content of the hydrosilylation catalyst (C) in the curable resin composition of the present invention is an amount such that platinum, palladium, or rhodium in the catalyst is in the range of 0.01 to 1,000 ppm by weight. Preferably, it is in the range of 0.1 to 500 ppm.
- the content of the hydrosilylation catalyst (C) is the total content of two or more when used in combination. When the content of the hydrosilylation catalyst (C) is in such a range, the crosslinking rate is not significantly slowed, and there is less possibility of causing problems such as coloring in the crosslinked product, which is preferable.
- the curable resin composition of the present invention may contain a hydrosilylation reaction inhibitor to adjust the speed of the hydrosilylation reaction.
- the hydrosilylation inhibitor include alkyne alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and phenylbutynol; 3-methyl-3-pentene Ene-in compounds such as 1-yne, 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1, Examples include 3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane and benzotriazole.
- the content of the hydrosilylation reaction inhibitor varies depending on the crosslinking conditions of the composition, but is practically within the range of 0.00001 to 5 parts by weight with respect to 100 parts by weight of the curable resin composition
- solvent A conventionally known solvent such as toluene, hexane, isopropanol, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate may be used during the hydrosilylation reaction.
- the curable resin composition of the present invention may further contain an inorganic filler (D).
- the inorganic filler (D) is not particularly limited, but nano silica, nano titania, nano zirconia, carbon nanotubes, silica, alumina, mica, synthetic mica, talc, calcium oxide, calcium carbonate, zirconium oxide, titanium oxide, Barium titanate, kaolin, bentonite, diatomaceous earth, boron nitride, aluminum nitride, silicon carbide, zinc oxide, cerium oxide, cesium oxide, magnesium oxide, glass beads, glass fiber, graphite, calcium hydroxide, magnesium hydroxide, aluminum hydroxide
- These inorganic fillers (D) can be produced by a known method such as a flame hydrolysis method, a flame pyrolysis method, or a plasma method described in, for example, International Publication No. 96/31572.
- nano-dispersed sols of stabilized colloidal inorganic particles such as nano silica, nano titania, nano zirconia, and carbon nanotube can be used, and commercially available products include silica sol manufactured by BAYER. SnO 2 sols from Goldschmidt, TiO 2 sols from MERCK, SiO 2 , ZrO 2 , A1 2 O 3 and Sb 2 O 3 sols from Nissan Chemicals, Aerosil dispersions from DEGUSSA, etc. Are commercially available.
- the inorganic filler (D) needs not to block visible light.
- the inorganic filler (D) can change the viscosity behavior by surface modification.
- the surface modification of the particles can be performed using a known surface modifier.
- a surface modifier for example, a compound capable of interacting with a functional group present on the surface of the inorganic filler (D) such as a covalent bond or complex formation, or a compound capable of interacting with a polymer matrix.
- Examples of such surface modifiers include carboxyl groups, (primary, secondary, and tertiary) amino groups, quaternary ammonium groups, carbonyl groups, glycidyl groups, vinyl groups, )
- a compound having a functional group such as acryloxy group or mercapto group can be used.
- Such a surface modifier is usually a liquid under standard temperature and pressure conditions, and is composed of a low molecular organic compound having a carbon number in the molecule of, for example, 15 or less, preferably 10 or less, particularly preferably 8 or less. Is done.
- the molecular weight of the low molecular weight organic compound is, for example, 500 or less, preferably 350 or less, particularly 200 or less.
- Preferred surface modifiers include, for example, formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid, adipic acid, succinic acid, glutaric acid, oxalic acid, malein C1-C12 saturated or unsaturated mono- and polycarboxylic acids (preferably monocarboxylic acids) such as acids and fumaric acids; and esters thereof (preferably C 1-4 alkyl esters such as methyl methacrylate) ); Amides; ⁇ -dicarbonyl compounds such as acetylacetone, 2,4-hexanedione, 3,5-heptanedione, acetoacetic acid and C 1-4 alkylacetoacetic acids.
- a well-known and usual silane coupling agent can also be used as a surface modifier.
- the particle size of the inorganic filler (D) is usually about 0.01 nm to 200 ⁇ m, preferably 0.1 nm to 100 ⁇ m, particularly about 0.1 nm to 50 ⁇ m.
- the content of the inorganic filler (D) is preferably 1 to 2000 parts by weight, more preferably 10 to 1000 parts by weight, where the total content of the compound (A) and the compound (B) is 100 parts by weight. is there.
- the content of the inorganic filler (D) with respect to the total amount of the curable resin composition is, for example, 5 to 95% by weight, preferably 10 to 90% by weight.
- the curable resin composition of the present invention may further contain a silane coupling agent (E) in order to improve adhesion to an adherend such as a substrate.
- a silane coupling agent (E) is not specifically limited, A well-known and usual silane coupling agent can be used. Examples of the silane coupling agent (E) include tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (methoxyethoxysilane).
- the amount of the silane coupling agent (E) used is preferably about 0.1 to 20% by weight in the curable resin composition, more preferably 0.3 to 8% by weight, and still more preferably 0. The range is from 5 to 5% by weight. If it is less than 0.1% by weight, the crosslinking effect of the resin by the silane coupling agent (E) is poor, so a dense film cannot be obtained, and the coupling effect to the metal substrate is poor and the adhesion is poor, which is desirable. Alkali resistance and rust resistance are difficult to obtain. When the content is more than 20% by weight, various performances such as water resistance and alkali resistance due to hydrolysis are remarkably deteriorated, resulting in a problem of film-forming property and easily disadvantageous in terms of economy.
- organic resin fine powders such as silicone resin, epoxy resin and fluororesin
- filler such as conductive metal powder such as silver and copper, solvent, Stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers, etc.), flame retardants (phosphorous flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, crosslinking agents , Reinforcing materials (other fillers, etc.), nucleating agents, coupling agents, agents, waxes, plasticizers, mold release agents, impact resistance improvers, hue improvers, fluidity improvers, colorants (dyes, pigments, etc.) ), Dispersants, antifoaming agents, defoaming agents, antibacterial agents, preservatives, viscosity modifiers, thickeners, leveling agents, ion adsorbers, phosphors and the like may be included.
- the curable resin composition of the present invention is preferably a liquid at any temperature of 0 to 90 ° C., more preferably 0 to 40 ° C., particularly preferably around room temperature (about 0 to 30 ° C.). Excellent workability during sealing, sealing and coating. Therefore, it can be used as a sealant, a sealant, and the like for an electronic component that requires a high refractive index and low moisture permeability, such as an organic electroluminescence device and an LED. It can also be used as a coating agent or an adhesive for an antireflection film of a display.
- the curable resin composition of the present invention can be obtained by uniformly mixing the above components.
- each component is preferably used by using generally known mixing equipment such as a revolving type stirring and defoaming device, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill. It is desirable to perform stirring, dissolution, mixing, dispersion, etc. so as to be uniform.
- the curable resin composition of the present invention can be cured by light or heat.
- light irradiation of 1000 mJ / cm 2 or more can be performed with a mercury lamp or the like.
- the temperature is 50 to 200 ° C., preferably 50 to 190 ° C., more preferably 50 to 180 ° C.
- the curing time is 10 to 600 minutes, preferably 10 to 480 minutes, more preferably. Can be cured in 15 to 360 minutes. If the curing temperature and the curing time are lower than the lower limit of the range, curing is insufficient.
- the resin component may be decomposed.
- the curing conditions depend on various conditions, the curing time is short when the curing temperature is high, and the curing time is long when the curing temperature is low, and can be adjusted as appropriate.
- the curable resin composition of the present invention can be used as a sealant, a sealant, or a coating agent for an organic electroluminescence device, LED, or display.
- Example 1 A glass flask equipped with a stirrer, thermometer, and Jimroth cooling bowl was charged with 3.09 g (50 mmol) of boric acid and 18.03 g (150 mmol) of dimethyldimethoxysilane (D1052 manufactured by Tokyo Chemical Industry Co., Ltd.) and stirred at 80 ° C. did.
- D1052 dimethyldimethoxysilane
- Example 2 26.05 g (200 mmol) of dimethylvinylethoxysilane in Example 1 was changed to 20.85 g (200 mmol) of dimethylethoxysilane (SIV9072.0 manufactured by Gelest), and a hydrosilyl group-containing boromethylphenylsiloxane was obtained through the same operation. It was.
- Example 3 0.4 ⁇ L of platinum catalyst (326-49351 manufactured by Wako Pure Chemical Industries, Ltd.) was added to 0.20 g of the liquid vinyl group-containing boromethylphenylsiloxane obtained in Example 1, and then hydrosilyl group-containing silicone (HMS-manufactured by Gelest) 64, molecular weight 55000-65000) was added and mixed. The mixture was applied onto a glass plate and cured in an oven at 60 ° C. for 1 hour and then at 120 ° C. for 3 hours. No bubbles were observed in the cured product, and it remained colorless and transparent even when left in an oven at 180 ° C. for 500 hours or longer.
- platinum catalyst 326-49351 manufactured by Wako Pure Chemical Industries, Ltd.
- Example 4 Boron dimethyl vinyl siloxane (AKB159. Manufactured by Gelest Co., Ltd.) obtained by adding 0.4 ⁇ L of a platinum catalyst (326-49351 manufactured by Wako Pure Chemical Industries, Ltd.) to 0.10 g of the liquid hydrosilyl group-containing boromethylphenylsiloxane obtained in Example 2. 9, 0.059 g of molecular weight 314) and 0.078 g of vinyl group-containing silicone (DMS-V21 made by Gelest, molecular weight 6000) were added and mixed. The mixture was applied onto a glass plate and cured in an oven at 60 ° C. for 1 hour and then at 120 ° C. for 3 hours. No bubbles were observed in the cured product, and it remained colorless and transparent even when left in an oven at 180 ° C. for 500 hours or longer.
- a platinum catalyst 326-49351 manufactured by Wako Pure Chemical Industries, Ltd.
- the curable resin composition containing the metallosiloxane compound does not generate outgas at the time of curing, and the cured product obtained by curing the curable resin composition exhibits excellent heat resistance and no yellowing. Have. Therefore, it is useful as a sealant or sealant for an electronic device such as an LED or a heat resistant hard coat.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
また、本発明の他の目的は、上記メタロシロキサン化合物を含み、アウトガスが発生せず、それを硬化させることで耐熱無黄変の無機系硬化樹脂が得られる硬化性樹脂組成物を提供することにある。
また、本発明の他の目的は、上記硬化性樹脂組成物を硬化して得られる、耐熱無黄変の硬化物を提供することにある。
で表されるシラン化合物(S1)と下記式(2)
で表されるシラン化合物(S2)とホウ素化合物(M)とを、又は、該シラン化合物(S1)と該シラン化合物(S2)と該ホウ素化合物(M)とH2Oとを、該シラン化合物(S1):該シラン化合物(S2):該ホウ素化合物(M):H2O=n:m:k:aのモル比で、且つ、n,m,k,aが以下の関係(i)~(iii)を全て満たす条件で反応させて製造されるメタロシロキサン化合物(A)であって、1分子中にSi-H結合又はC2-10アルケニル基を少なくとも1つ有することを特徴とするメタロシロキサン化合物を提供する。
(i) n>0,m>0,k>0,a≧0
(ii) m/n≧0.5
(iii) (n+m)/k≧1.8
本発明のメタロシロキサン化合物は、好ましくは、0~90℃のいずれかの温度において液体である。
本発明の硬化性樹脂組成物は、さらに無機フィラー(D)を含有していてもよく、また、さらにシランカップリング剤(E)を含有していてもよい。
本発明のメタロシロキサン化合物は、下記式(1)
で表されるシラン化合物(S1)と下記式(2)
で表されるシラン化合物(S2)とホウ素化合物(M)とを、又は、上記シラン化合物(S1)と上記シラン化合物(S2)とホウ素化合物(M)とH2Oとを、シラン化合物(S1):シラン化合物(S2):ホウ素化合物(M):H2O=n:m:k:aのモル比で、且つ、n,m,k,aが以下の関係(i)~(iii)を全て満たす条件で反応させて得られるメタロシロキサン化合物(A)であって、1分子中にSi-H結合又はC2-10アルケニル基を少なくとも1つ有することを特徴とする。
(i) n>0,m>0,k>0,a≧0
(ii) m/n≧0.5
(iii) (n+m)/k≧1.8
本発明のメタロシロキサン化合物(A)を製造する反応に使用する2官能のシラン化合物(S1)は、下記式(1)
で表され、ポリシロキサン、ポリボロシロキサン等の製造に従来から使用されている公知のジアルコキシシラン化合物、ジハロゲン化シラン化合物、又はジヒドロキシシラン化合物を使用できる。
本発明のメタロシロキサン化合物(A)を製造する反応に使用する単官能のシラン化合物(S2)は、下記式(2)
で表され、ポリシロキサン、ポリボロシロキサン等の製造に従来から使用されている公知モノアルコキシシラン化合物、モノハロゲン化シラン化合物、又はモノヒドロキシシラン化合物を使用できる。
ホウ素化合物(M)としては、従来ポリボロシロキサンを製造するのに使用されていたホウ酸化合物を使用でき、例えば、水素化ホウ素(例えば、ボラン、ジボラン、テトラボラン、ペンタボラン、デカボランなど)、ホウ酸(オルトホウ酸、メタホウ酸、四ホウ酸など)、ホウ酸塩(例えば、ホウ酸ニッケル、ホウ酸マグネシウム、ホウ酸マンガンなど)、B2O3などのホウ素酸化物、ボラザン、ボラゼン、ボラジン、ホウ素アミド、ホウ素イミドなどの窒素化合物、BF3、BCl3、テトラフルオロホウ酸塩などのハロゲン化物、ホウ酸エステル(例えば、ホウ酸メチル、ホウ酸エチルなどのホウ酸アルキル;ホウ酸ジメチル、ホウ酸ジエチルなどのホウ酸ジアルキル;ホウ酸トリメチル、ホウ酸トリエチルなどのホウ酸トリアルキル;ホウ酸フェニルなどのホウ酸アリール等)などが挙げられる。ホウ素化合物(M)としては、上記例示の化合物を単独でまたは2種以上を混合して使用できる。
で表されるホウ素化合物が好ましい。Y1~Y3におけるC1-12アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基などが挙げられ、好ましくはC1-6アルコキシ基である。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子などが挙げられる。
添加するH2Oのモル比(a)は上記ホウ素化合物(M)がアルコキシ基、ハロゲン原子等の加水分解性の置換基を有している場合に、その置換基の合計モルに対して1/2以上とすることができる。上記シラン化合物(S1)と上記シラン化合物(S2)とホウ素化合物(M)がヒドロキシル基を有する場合、その合計モル数に応じて添加するH2Oの量を減ずるもしくはH2Oを用いなくてもよい。例えば、ホウ素化合物(M)としてヒドロキシル基を3つ有するホウ酸を使用した場合には、H2Oを用いなくてもよい(この場合、a=0である)。
上記反応は触媒なしでも進行する場合もあるが、必要に応じて酸触媒、塩基触媒を添加してもよい。反応系に酸触媒、又は塩基触媒を存在させることにより一般に反応速度が著しく増大する。塩基には無機塩基及び有機塩基が含まれる。無機塩基としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化セシウムなどのアルカリ金属水酸化物;水酸化マグネシウム、水酸化カルシウム、水酸化バリウムなどのアルカリ土類金属水酸化物;炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸セシウムなどのアルカリ金属炭酸塩;炭酸マグネシウムなどのアルカリ土類金属炭酸塩;炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素セシウムなどのアルカリ金属炭酸水素塩などが挙げられる。
本発明の硬化性樹脂組成物は、Si-H結合を有する化合物とC2-10アルケニル基を有する化合物とを含む硬化性樹脂組成物であって、少なくとも上記メタロシロキサン化合物(A)とヒドロシリル化触媒(C)とを含有することを特徴とする。メタロシロキサン化合物(A)の硬化性樹脂組成物中における含有量は、例えば30~99重量%、好ましくは40~60重量%である。
上記H型又はビニル型の化合物(B)としては、1分子中にSi-H結合又はC2-10アルケニル基を少なくとも1つ有する、シロキサン結合(Si-O-Si)で構成された主鎖を有するH型又はビニル型のポリシロキサンが使用できる。C2-10アルケニル基としては、上記シラン化合物に含まれてもよいC2-10アルケニル基として例示のものが挙げられる。ポリシロキサンとしては、具体的には、直鎖状、分岐鎖状又は環状のシロキサン、架橋された三次元構造を有するシリコーン樹脂などが挙げられる。
本発明の硬化性樹脂組成物に含まれるヒドロシリル化触媒(C)としては、白金系触媒、ロジウム系触媒、パラジウム系触媒等の周知のヒドロシリル化反応用触媒が例示され、具体的には、白金微粉末、白金黒、白金担持シリカ微粉末、白金担持活性炭、塩化白金酸、塩化白金酸とアルコール、アルデヒド、ケトン等との錯体、白金のオレフィン錯体、白金-カルボニルビニルメチル錯体などの白金のカルボニル錯体、白金-ジビニルテトラメチルジシロキサン錯体や白金-シクロビニルメチルシロキサン錯体などの白金ビニルメチルシロキサン錯体、白金-ホスフィン錯体、白金-ホスファイト錯体等の白金系触媒、ならびに上記白金系触媒において白金原子の代わりにパラジウム原子又はロジウム原子を含有するパラジウム系触媒又はロジウム系触媒が挙げられる。これらは1種で用いてもよく、2種以上を併用してもよい。なかでも、白金ビニルメチルシロキサン錯体が、反応速度が良好であることから好ましい。
本発明の硬化性樹脂組成物には、ヒドロシリル化反応の速度を調整するために、ヒドロシリル化反応抑制剤を含有していてもよい。このヒドロシリル化反応抑制剤としては、3-メチル-1-ブチン-3-オール、3,5-ジメチル-1-ヘキシン-3-オール、フェニルブチノール等のアルキンアルコール;3-メチル-3-ペンテン-1-イン、3,5-ジメチル-3-ヘキセン-1-イン等のエンイン化合物;1,3,5,7-テトラメチル-1,3,5,7-テトラビニルシクロテトラシロキサン、1,3,5,7-テトラメチル-1,3,5,7-テトラヘキセニルシクロテトラシロキサン、ベンゾトリアゾールが例示される。このヒドロシリル化反応抑制剤の含有量としては、上記組成物の架橋条件により異なるが、実用上、硬化性樹脂組成物100重量部に対して、0.00001~5重量部の範囲内であることが好ましい。
ヒドロシリル化反応時にトルエン、ヘキサン、イソプロパノール、メチルイソブチルケトン、シクロペンタノン、プロピレングリコールモノメチルエーテルアセテート等の従来公知の溶媒を使用してもよい。
本発明の硬化性樹脂組成物は、さらに、無機フィラー(D)を含んでいてもよい。無機フィラー(D)としては、特に限定するものではないが、ナノシリカ、ナノチタニア、ナノジルコニア、カーボンナノチューブ等、シリカ、アルミナ、マイカ、合成マイカ、タルク、酸化カルシウム、炭酸カルシウム、酸化ジルコニウム、酸化チタン、チタン酸バリウム、カオリン、ベントナイト、珪藻土、窒化ホウ素、窒化アルミ、炭化ケイ素、酸化亜鉛、酸化セリウム、酸化セシウム、酸化マグネシウム、ガラスビーズ、ガラス繊維、グラファイト、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、セルロースなどを1種類以上使用することができる。これらの無機フィラー(D)は、例えば国際公開第96/31572号に記載されている火炎加水分解法や、火炎熱分解法、プラズマ法等の公知の方法で製造することができる。
本発明の硬化性樹脂組成物は、基板等の被接着体との接着性などを向上させるために、さらに、シランカップリング剤(E)を含んでいてもよい。シランカップリング剤(E)は特に限定されず、公知慣用のシランカップリング剤を使用できる。シランカップリング剤(E)としては、例えば、テトラメトキシシラン、テトラエトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、メチルトリエトキシシラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリス(メトキシエトキシシラン)、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、ビニルトリアセトキシシラン、γ-(メタ)アクリロキシプロピルトリエトキシシラン、γ-(メタ)アクリロキシプロピルトリメトキシシラン、γ-(メタ)アクリロキシプロピルメチルジメトキシシラン、γ-(メタ)アクリロキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、p-スチリルトリメトキシシラン、3-アクリロキシプロピルトリメトキシシラン、N-(β-アミノエチル)-γ-アミノプロピルメチルジメトキシシラン、N-(β-アミノエチル)-γ-アミノプロピルメチルジエトキシシラン、N-(β-アミノエチル)-γ-アミノプロピルトリメトキシシラン、N-(β-アミノエチル)-γ-アミノプロピルトリエトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-メルカプトプロピルトリエトキシシラン、3-メルカプトプロピルメチルジメトキシシラン、ビス(トリエトキシシリルプロピル)テトラスルフィド、3-イソシアネートプロピルトリエトキシシラン等の水溶液中で比較的安定なものの中から選ばれる。
さらに、本発明の硬化性樹脂組成物には、その他任意の成分として、シリコーン樹脂、エポキシ樹脂、フッ素樹脂等の有機樹脂微粉末;銀、銅等の導電性金属粉末等の充填剤、溶剤、安定化剤(酸化防止剤、紫外線吸収剤、耐光安定剤、熱安定化剤など)、難燃剤(リン系難燃剤、ハロゲン系難燃剤、無機系難燃剤など)、難燃助剤、架橋剤、補強材(他の充填剤など)、核剤、カップリング剤、剤、ワックス、可塑剤、離型剤、耐衝撃改良剤、色相改良剤、流動性改良剤、着色剤(染料、顔料など)、分散剤、消泡剤、脱泡剤、抗菌剤、防腐剤、粘度調整剤、増粘剤、レベリング剤、イオン吸着体、蛍光体などの慣用の添加剤が含まれていてもよい。これらの添加剤は、単独で又は二種以上組み合わせて使用できる。
本発明の硬化性樹脂組成物は上記各成分を均一に混合することにより得られる。本発明の硬化性樹脂組成物を得るには、各成分を自公転式攪拌脱泡装置、ホモジナイザー、プラネタリーミキサー、3本ロールミル、ビーズミル等の一般的に知られる混合用機器を使用してなるべく均一になるように、攪拌、溶解、混合、分散等を行うことが望ましい。
本発明の硬化性樹脂組成物は、光若しくは熱により硬化させることができる。光により硬化させる場合、水銀ランプ等で1000mJ/cm2以上の光照射を行うことができる。また、熱により硬化させる場合、温度50~200℃、好ましくは、50~190℃、さらに好ましくは、50~180℃で、硬化時間10~600分、好ましくは、10~480分、さらに好ましくは、15~360分で硬化させることができる。硬化温度と硬化時間が上記範囲下限値より低い場合は、硬化が不十分となり、逆に上記範囲上限値より高い場合、樹脂成分の分解が起きる場合があるので、何れも好ましくない場合がある。硬化条件は種々の条件に依存するが、硬化温度が高い場合には硬化時間は短く、硬化温度が低い場合には硬化時間は長く、適宜調整することができる。本発明の硬化性樹脂組成物を硬化させることにより、気泡が少なく透明性に優れ、さらに耐熱黄変性に優れた硬化物が得られる。本発明の硬化性樹脂組成物は、有機エレクトロルミネッセンスデバイス、LED、又はディスプレイなどの封止剤、シール剤、又はコーティング剤として使用できる。
攪拌機、温度計、ジムロート冷却菅を備えたガラス製のフラスコにホウ酸3.09g(50mmol)、ジメチルジメトキシシラン(東京化成工業社製D1052)18.03g(150mmol)を投入し、80℃で攪拌した。その後、フラスコを室温まで放冷し、次にホウ酸6.18g(100mmol)、ジメトキシジフェニルシラン(東京化成工業社製D1731)12.22g(50mmol)、ジメチルビニルエトキシシラン(東京化成工業社製V0046)26.05g(200mmol)を添加し、80℃で3時間攪拌した。反応終了後、室温まで放冷し、エバポレータにより未反応分、揮発分を留去して液状のビニル基含有ボロメチルフェニルシロキサンを得た。
実施例1のジメチルビニルエトキシシラン26.05g(200mmol)をジメチルエトキシシラン(Gelest社製SIV9072.0)20.85g(200mmol)に変更し、同様の操作を経てヒドロシリル基含有ボロメチルフェニルシロキサンを得た。
実施例1で得た液状のビニル基含有ボロメチルフェニルシロキサン0.20gに白金触媒(和光純薬工業社製326-49351)0.4μLを添加し、その後ヒドロシリル基含有シリコーン(Gelest社製HMS-64、分子量55000~65000)0.037gを添加、混合した。その混合液をガラスプレート上に塗布し、オーブンにて60℃1時間、次いで120℃3時間で硬化させた。硬化物に気泡は見受けられず、また180℃のオーブンに500時間以上静置しても無色透明のままであった。
実施例2で得た液状のヒドロシリル基含有ボロメチルフェニルシロキサン0.10gに、白金触媒(和光純薬工業社製326-49351)0.4μLを添加したボロンジメチルビニルシロキサイド(Gelest社製AKB159.9、分子量314)0.059gとビニル基含有シリコーン(Gelest社製DMS-V21、分子量6000)0.078gの混合液を添加、混合した。その混合液をガラスプレート上に塗布し、オーブンにて60℃1時間、次いで120℃3時間で硬化させた。硬化物に気泡は見受けられず、また180℃のオーブンに500時間以上静置しても無色透明のままであった。
Claims (6)
- 下記式(1)
で表されるシラン化合物(S1)と下記式(2)
で表されるシラン化合物(S2)とホウ素化合物(M)とを、又は、該シラン化合物(S1)と該シラン化合物(S2)と該ホウ素化合物(M)とH2Oとを、該シラン化合物(S1):該シラン化合物(S2):該ホウ素化合物(M):H2O=n:m:k:aのモル比で、且つ、n,m,k,aが以下の関係(i)~(iii)を全て満たす条件で反応させて製造されるメタロシロキサン化合物(A)であって、1分子中にSi-H結合又はC2-10アルケニル基を少なくとも1つ有することを特徴とするメタロシロキサン化合物。
(i) n>0,m>0,k>0,a≧0
(ii) m/n≧0.5
(iii) (n+m)/k≧1.8 - 0~90℃のいずれかの温度において液体である、請求項1記載のメタロシロキサン化合物。
- Si-H結合を有する化合物とC2-10アルケニル基を有する化合物とを含む硬化性樹脂組成物であって、少なくとも請求項1又は2記載のメタロシロキサン化合物(A)とヒドロシリル化触媒(C)とを含有することを特徴とする硬化性樹脂組成物。
- さらに無機フィラー(D)を含有する、請求項3記載の硬化性樹脂組成物。
- さらにシランカップリング剤(E)を含有する、請求項3又は4記載の硬化性樹脂組成物。
- 請求項3~5の何れか1項に記載の硬化性樹脂組成物を硬化して得られる硬化物。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020137017778A KR20130126663A (ko) | 2010-12-09 | 2011-11-29 | 부가 경화성 금속 실록산 화합물 |
EP11846305.8A EP2650319A4 (en) | 2010-12-09 | 2011-11-29 | ADDITION-CURABLE METALLOSILOXANE COMPOUND |
US13/992,665 US8791221B2 (en) | 2010-12-09 | 2011-11-29 | Addition-curable metallosiloxane compound |
CN2011800585202A CN103249762A (zh) | 2010-12-09 | 2011-11-29 | 加成固化性金属硅氧烷化合物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010274245A JP2012122002A (ja) | 2010-12-09 | 2010-12-09 | 付加硬化性メタロシロキサン化合物 |
JP2010-274245 | 2010-12-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012077529A1 true WO2012077529A1 (ja) | 2012-06-14 |
Family
ID=46207020
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/077496 WO2012077529A1 (ja) | 2010-12-09 | 2011-11-29 | 付加硬化性メタロシロキサン化合物 |
Country Status (7)
Country | Link |
---|---|
US (1) | US8791221B2 (ja) |
EP (1) | EP2650319A4 (ja) |
JP (1) | JP2012122002A (ja) |
KR (1) | KR20130126663A (ja) |
CN (1) | CN103249762A (ja) |
TW (1) | TW201231472A (ja) |
WO (1) | WO2012077529A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140142242A1 (en) * | 2012-11-16 | 2014-05-22 | Mitsubishi Chemical Corporation | Process for synthesis of hybrid siloxy derived resins and crosslinked networks therefrom |
WO2017010327A1 (ja) * | 2015-07-10 | 2017-01-19 | セントラル硝子株式会社 | 硬化性ポリボロシロキサン樹脂組成物およびその硬化物、並びにこれらを用いた光半導体装置 |
JP2020527645A (ja) * | 2017-07-19 | 2020-09-10 | アヴァンター・パフォーマンス・マテリアルズ・エルエルシー | 動的共有結合ポリシロキサンを含む硬化性オルガノポリシロキサン組成物 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8703625B2 (en) * | 2010-02-04 | 2014-04-22 | Air Products And Chemicals, Inc. | Methods to prepare silicon-containing films |
JP6206079B2 (ja) * | 2012-10-30 | 2017-10-04 | 東ソー株式会社 | ポリメタロキサン組成物、その製造方法、及びその用途 |
CN105051113B (zh) * | 2013-03-15 | 2018-08-10 | 美国陶氏有机硅公司 | 包含碱土金属的含有芳基基团的硅氧烷组合物 |
CN103739848B (zh) * | 2013-12-25 | 2016-06-01 | 北京化工大学 | 加成型有机硅封装胶用增粘剂及其制备方法 |
CN103951983B (zh) * | 2014-04-17 | 2016-09-07 | 中科院广州化学有限公司 | 一种高导热耐高温聚硅氧烷陶瓷复合材料及其制法和应用 |
CN104031603B (zh) * | 2014-05-26 | 2015-09-23 | 中科院广州化学有限公司 | 一种高导热硼杂聚硅氧烷灌封胶及其制备方法 |
CN108047449A (zh) * | 2017-12-30 | 2018-05-18 | 汕头市骏码凯撒有限公司 | 一种含硼增粘剂的合成方法 |
CN111154453B (zh) * | 2020-01-19 | 2022-01-28 | 厦门艾贝森电子有限公司 | 一种耐热单组份加成型有机硅胶黏剂及其制备方法 |
CN111394054A (zh) * | 2020-03-24 | 2020-07-10 | 新安天玉有机硅有限公司 | 一种自粘胶带用硅橡胶及其制备方法 |
CN116396681B (zh) * | 2023-03-29 | 2024-03-22 | 中科融志国际科技(北京)有限公司 | 防凝露防冰涂层以及风机叶片 |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5222051A (en) * | 1975-08-13 | 1977-02-19 | Shin Etsu Chem Co Ltd | Autohesive silicone rubber composition |
JPS5342300A (en) * | 1976-09-30 | 1978-04-17 | Tokushiyu Muki Zairiyou Kenkiy | Polysiloxane with threeedimensional nettwork structure which excels in hydrolysiss and heattresistance |
JPS5350299A (en) * | 1976-10-18 | 1978-05-08 | Tokushiyu Muki Zairiyou Kenkiy | Process for preparing inorganic polymer whose main chain contains si b and o as elemental component |
JPS5488247A (en) * | 1977-12-20 | 1979-07-13 | Asahi Chem Ind Co Ltd | Borosiloxane compound and its peparation |
JPS6438473A (en) * | 1987-08-04 | 1989-02-08 | Toshiba Silicone | Release composition |
JPH07207161A (ja) * | 1994-01-11 | 1995-08-08 | Toshiba Silicone Co Ltd | 自己融着性シリコーンゴム組成物 |
WO1996031572A1 (de) | 1995-04-03 | 1996-10-10 | Institut für Neue Materialien Gemeinnützige GmbH | Kompositklebstoff für optische und optoelektronische anwendungen |
JPH10152561A (ja) | 1996-11-26 | 1998-06-09 | Showa Electric Wire & Cable Co Ltd | ポリボロシロキサンの製造方法、ポリボロシロキサン塗膜及び該塗膜を有する無機絶縁電線 |
JP2002265609A (ja) * | 2001-03-14 | 2002-09-18 | Lintec Corp | ホウ素含有ポリオルガノシルセスキオキサン及び接着剤組成物 |
JP2003176333A (ja) | 2001-08-23 | 2003-06-24 | General Electric Co <Ge> | エポキシ樹脂組成物、該組成物で封入された固体素子デバイス及び封入方法 |
JP2005298796A (ja) * | 2003-09-29 | 2005-10-27 | Sanyo Electric Co Ltd | 有機金属ポリマー材料及びその製造方法 |
JP2009019104A (ja) * | 2007-07-11 | 2009-01-29 | Nitto Denko Corp | ポリボロシロキサンからなる光半導体素子封止用樹脂 |
WO2009111193A1 (en) * | 2008-03-04 | 2009-09-11 | Dow Corning Corporation | Borosiloxane composition, borosiloxane adhesive, coated and laminated substrates |
WO2009111191A1 (en) * | 2008-03-04 | 2009-09-11 | Dow Corning Corporation | Polyborosiloxane and method of preparing same |
JP2010518234A (ja) * | 2007-02-08 | 2010-05-27 | ダウ・コーニング・コーポレイション | ヘテロ元素を含むシロキサン化合物およびポリマー |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5322051A (en) | 1976-08-09 | 1978-03-01 | Taiyo Kogyo Co Ltd | Cultivation of straighttshaped cucumber and welllregulating and packaging case therefor |
US4152509A (en) | 1976-09-30 | 1979-05-01 | The Foundation: The Research Institute For Special Inorganic Materials | Borosiloxane polymers and a method for producing the same |
US4228270A (en) | 1977-12-14 | 1980-10-14 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyborodiphenylsiloxanes |
DE4339478A1 (de) * | 1993-11-19 | 1995-05-24 | Wacker Chemie Gmbh | Organopolysilan/Alkenylsiloxan-Copolymere |
FR2745563B1 (fr) * | 1996-02-29 | 1998-04-10 | France Etat | Procede pour la preparation d'oxynitrures de silicium et de bore, les oxynitrures obtenus, les polybrorsiloxanes obtenus comme intermediaire de synthese |
JP4343475B2 (ja) * | 1999-08-24 | 2009-10-14 | 株式会社カネカ | 難燃剤及びこれを用いた難燃性樹脂組成物 |
CN1616523B (zh) | 2003-09-29 | 2010-12-08 | 三洋电机株式会社 | 有机金属聚合物材料及其制造方法 |
-
2010
- 2010-12-09 JP JP2010274245A patent/JP2012122002A/ja not_active Withdrawn
-
2011
- 2011-11-29 WO PCT/JP2011/077496 patent/WO2012077529A1/ja active Application Filing
- 2011-11-29 KR KR1020137017778A patent/KR20130126663A/ko not_active Application Discontinuation
- 2011-11-29 EP EP11846305.8A patent/EP2650319A4/en not_active Withdrawn
- 2011-11-29 US US13/992,665 patent/US8791221B2/en not_active Expired - Fee Related
- 2011-11-29 CN CN2011800585202A patent/CN103249762A/zh active Pending
- 2011-12-08 TW TW100145210A patent/TW201231472A/zh unknown
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5222051A (en) * | 1975-08-13 | 1977-02-19 | Shin Etsu Chem Co Ltd | Autohesive silicone rubber composition |
JPS5342300A (en) * | 1976-09-30 | 1978-04-17 | Tokushiyu Muki Zairiyou Kenkiy | Polysiloxane with threeedimensional nettwork structure which excels in hydrolysiss and heattresistance |
JPS5350299A (en) * | 1976-10-18 | 1978-05-08 | Tokushiyu Muki Zairiyou Kenkiy | Process for preparing inorganic polymer whose main chain contains si b and o as elemental component |
JPS5488247A (en) * | 1977-12-20 | 1979-07-13 | Asahi Chem Ind Co Ltd | Borosiloxane compound and its peparation |
JPS6438473A (en) * | 1987-08-04 | 1989-02-08 | Toshiba Silicone | Release composition |
JPH07207161A (ja) * | 1994-01-11 | 1995-08-08 | Toshiba Silicone Co Ltd | 自己融着性シリコーンゴム組成物 |
WO1996031572A1 (de) | 1995-04-03 | 1996-10-10 | Institut für Neue Materialien Gemeinnützige GmbH | Kompositklebstoff für optische und optoelektronische anwendungen |
JPH10152561A (ja) | 1996-11-26 | 1998-06-09 | Showa Electric Wire & Cable Co Ltd | ポリボロシロキサンの製造方法、ポリボロシロキサン塗膜及び該塗膜を有する無機絶縁電線 |
JP2002265609A (ja) * | 2001-03-14 | 2002-09-18 | Lintec Corp | ホウ素含有ポリオルガノシルセスキオキサン及び接着剤組成物 |
JP2003176333A (ja) | 2001-08-23 | 2003-06-24 | General Electric Co <Ge> | エポキシ樹脂組成物、該組成物で封入された固体素子デバイス及び封入方法 |
JP2005298796A (ja) * | 2003-09-29 | 2005-10-27 | Sanyo Electric Co Ltd | 有機金属ポリマー材料及びその製造方法 |
JP2010518234A (ja) * | 2007-02-08 | 2010-05-27 | ダウ・コーニング・コーポレイション | ヘテロ元素を含むシロキサン化合物およびポリマー |
JP2009019104A (ja) * | 2007-07-11 | 2009-01-29 | Nitto Denko Corp | ポリボロシロキサンからなる光半導体素子封止用樹脂 |
WO2009111193A1 (en) * | 2008-03-04 | 2009-09-11 | Dow Corning Corporation | Borosiloxane composition, borosiloxane adhesive, coated and laminated substrates |
WO2009111191A1 (en) * | 2008-03-04 | 2009-09-11 | Dow Corning Corporation | Polyborosiloxane and method of preparing same |
Non-Patent Citations (1)
Title |
---|
See also references of EP2650319A4 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140142242A1 (en) * | 2012-11-16 | 2014-05-22 | Mitsubishi Chemical Corporation | Process for synthesis of hybrid siloxy derived resins and crosslinked networks therefrom |
US9246173B2 (en) * | 2012-11-16 | 2016-01-26 | Mitsubishi Chemical Corporation | Process for synthesis of hybrid siloxy derived resins and crosslinked networks therefrom |
WO2017010327A1 (ja) * | 2015-07-10 | 2017-01-19 | セントラル硝子株式会社 | 硬化性ポリボロシロキサン樹脂組成物およびその硬化物、並びにこれらを用いた光半導体装置 |
JP2020527645A (ja) * | 2017-07-19 | 2020-09-10 | アヴァンター・パフォーマンス・マテリアルズ・エルエルシー | 動的共有結合ポリシロキサンを含む硬化性オルガノポリシロキサン組成物 |
Also Published As
Publication number | Publication date |
---|---|
US8791221B2 (en) | 2014-07-29 |
EP2650319A1 (en) | 2013-10-16 |
US20130267653A1 (en) | 2013-10-10 |
EP2650319A4 (en) | 2014-05-07 |
JP2012122002A (ja) | 2012-06-28 |
CN103249762A (zh) | 2013-08-14 |
TW201231472A (en) | 2012-08-01 |
KR20130126663A (ko) | 2013-11-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2012077529A1 (ja) | 付加硬化性メタロシロキサン化合物 | |
US9688851B2 (en) | Polysiloxane composition, hardened material and optical device | |
US20070225465A1 (en) | Composition for Sealing Optical Semiconductor, Optical Semiconductor Sealing Material, and Method for Producing Composition for Sealing Optical Semiconductor | |
JP6213257B2 (ja) | シリコーンを含む硬化性組成物およびその硬化物 | |
JPWO2017122762A1 (ja) | 縮合反応型シリコーン組成物及び硬化物 | |
US20130192491A1 (en) | Modified polyhedral polysiloxane, composition containing the modified polyhedral polysiloxane, and cured product obtained by curing the composition | |
JP5491159B2 (ja) | シリカ粒子含有縮合反応物、樹脂組成物、封止樹脂、レンズ及びアンダーフィル材 | |
JP6338327B2 (ja) | 硬化性樹脂組成物、該組成物を硬化させてなる硬化物 | |
JP5661429B2 (ja) | 液状付加硬化性メタロシロキサン | |
EP0982349A2 (en) | Adhesion promoting organosiloxane compositions | |
JP2014077092A (ja) | 表面修飾複合金属酸化物を含有する樹脂組成物 | |
JP5715828B2 (ja) | オルガノポリシロキサン系組成物および硬化物 | |
JP2011246652A (ja) | ポリシロキサン系組成物 | |
JP5972544B2 (ja) | オルガノポリシロキサン系組成物および硬化物 | |
JP2017183506A (ja) | 樹脂成形体用材料 | |
JP5607522B2 (ja) | オルガノポリシロキサン系組成物および硬化物 | |
JP6239948B2 (ja) | 多面体構造ポリシロキサンを添加した硬化性組成物、硬化物および半導体発光装置、半導体発光装置の製造方法 | |
JP5919361B2 (ja) | オルガノポリシロキサン系組成物および硬化物 | |
JP2020094093A (ja) | 透明熱硬化性樹脂組成物、その硬化物、それを用いた光学素子用封止剤、及び光半導体装置 | |
JP6335036B2 (ja) | 硬化性組成物および半導体発光装置、半導体発光装置の製造方法 | |
JP5695372B2 (ja) | オルガノポリシロキサン系組成物および硬化物 | |
JP2012077142A (ja) | 多面体構造ポリシロキサン系組成物、およびこれを封止剤として用いてなる光半導体 | |
JP6726517B2 (ja) | Led封止剤用樹脂組成物およびled封止剤 | |
JP6075939B2 (ja) | ポリシロキサン系組成物 | |
JP2012188655A (ja) | ポリシロキサン系組成物、該組成物を用いてなる封止剤、および光学デバイス |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11846305 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13992665 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20137017778 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011846305 Country of ref document: EP |