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WO2007119627A1 - Formule durcissable, silsesquioxanes durcis, et leurs procédés de production - Google Patents

Formule durcissable, silsesquioxanes durcis, et leurs procédés de production Download PDF

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Publication number
WO2007119627A1
WO2007119627A1 PCT/JP2007/057285 JP2007057285W WO2007119627A1 WO 2007119627 A1 WO2007119627 A1 WO 2007119627A1 JP 2007057285 W JP2007057285 W JP 2007057285W WO 2007119627 A1 WO2007119627 A1 WO 2007119627A1
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Prior art keywords
component
carbon
silsesquioxane
group
force
Prior art date
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PCT/JP2007/057285
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English (en)
Japanese (ja)
Inventor
Yasuhiro Tanaka
Harunori Fujita
Hiroko Kaise
Shigeru Yao
Kuninori Obata
Kazuko Suzuki
Koji Fujimoto
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Ube Corp
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Ube Industries Ltd
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Priority to JP2008510906A priority Critical patent/JPWO2007119627A1/ja
Publication of WO2007119627A1 publication Critical patent/WO2007119627A1/fr
Anticipated expiration legal-status Critical
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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
    • 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
    • C08G77/045—Polysiloxanes containing less than 25 silicon 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

Definitions

  • Curable composition silsesquioxane cured product, and production method thereof
  • the present invention relates to a silsesquioxane having, as a main component, a force-type silsesquioxane having a substituent containing a carbon-carbon double bond, a partial cleavage structure of these force-form silsesquioxanes, and the like. It is possible to obtain a cured product excellent in heat resistance and transparency obtained by reacting an oligomer of oxan, a compound having a SiH group and a compound having a substituent containing a carbon-carbon double bond, and a cured product thereof.
  • the present invention relates to a curable composition that can be produced and a method for producing these cured products.
  • glass plates are widely used as display element circuit boards (particularly active matrix type) for liquid crystal display elements and organic EL display elements, color filter substrates, solar cell substrates, and the like.
  • transparent plastic substrates have recently been investigated as an alternative to glass plates because they are easily broken, cannot be bent, have large specific gravity, and are not suitable for light weight.
  • transparent thermoplastics such as PMMA (polymethyl methacrylate), PC (polycarbonate), epoxy resin, curable (meth) acrylate resin, silicone resin, silsesquioxanes
  • Transparent thermosetting plastics such as cured products obtained by reaction as the main component are being studied. Of these, cured products obtained by reacting silsesquioxanes as the main component are excellent in heat resistance.
  • Patent Document 1 discloses a silicone resin that is further condensed with an oligomer obtained by cohydrolyzing a trialkoxysilane having an organic group that can be polymerized with a phenyltrialkoxysilane, using a base catalyst. A manufacturing method is disclosed.
  • Patent Document 2 discloses that a substituent containing at least 1 to 2 polymerizable unsaturated double bonds per molecule and a side chain organic group.
  • Contamination resistance characterized by providing a layer on the coating surface A coating with improved properties is disclosed.
  • Patent Document 3 discloses (A) a silsesquioxane ladder polymer having a number average molecular weight of 500 or more as a cured product having an interpenetrating structure between a reaction product of a bur compound and a SiH compound and a silsesquioxane oligomer. (B) a key compound having at least two SiH groups in the molecule and having a molecular weight of 1000 or less, (C) a key compound having at least two butylsilyl groups in the molecule and having a molecular weight of 1000 or less, (D ) A curable composition containing a neutral platinum catalyst.
  • R is an optionally substituted alkyl group having 1 to 20 carbon atoms or aryl group.
  • Patent Document 5 includes (A) a ladder-type silsesquioxane polymer, (B) a silanol condensation catalyst, (C) a silicon compound having at least two SiH groups in the molecule, (D) Disclosed are compounds having at least two carbon-carbon double bonds in the molecule, (E) hydrosilylation soot catalyst, (F) hydrosilylation soot inhibitor, and (A) to (F) components and a pre-preda that has reinforcing fiber strength. Has been.
  • Patent Document 6 discloses a forceful silsesquioxane having a methacryl group or a bur group, and a transparent resin composition having an unsaturated compound power copolymerizable therewith. It is desirable to further improve the heat resistance, mechanical strength and total light transmittance of the fat composition.
  • Patent Document 1 Japanese Patent Laid-Open No. 56-151731
  • Patent Document 2 JP-A-8-48734
  • Patent Document 3 JP-A-8-225647
  • Patent Document 4 Japanese Patent Laid-Open No. 2001-89662
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2002-194122
  • Patent Document 6 Japanese Unexamined Patent Application Publication No. 2004-123936
  • the present invention relates to a silsesquioxane having as a main component a force-type silsesquioxane having a substituent containing a carbon-carbon double bond, a partial cleavage structure of these force-form silsesquioxanes, and the like.
  • Silsesquioxane cured products having both heat resistance and transparency using oligomers of oxane as raw materials, curable compositions from which these cured products are obtained, and cured silsesquioxane excellent in workability and production efficiency Means for Solving the Problems with the Purpose of Providing a Manufacturing Method
  • At least one structure force selected from force-type silsesquioxanes having substituents containing carbon double bonds and partial cleavage structures of these force-type silsesquioxanes Silsesquioxane oligomers (component a),
  • radical generator (e component) Is a curable composition containing.
  • At least one structure force selected from force-type silsesquioxanes having substituents containing carbon double bonds and partial cleavage structures of these force-type silsesquioxanes Silsesquioxane oligomers (component a),
  • At least one type of structural force selected from force-type silsesquioxanes having substituents containing carbon-carbon double bonds and partial cleavage structures of these force-type silsesquioxanes is also obtained. Oligomers of silsesquioxanes,
  • the present invention relates to a cured silsesquioxane obtained by bonding.
  • the present invention relates to a cured silsesquioxane obtained by bonding.
  • the seventh of the present invention is
  • At least one structure force selected from force-type silsesquioxanes having substituents containing carbon double bonds and partial cleavage structures of these force-type silsesquioxanes Silsesquioxane oligomers (component a),
  • component c a compound (component c) having at least two carbon-carbon double bonds in the same molecule excluding the silsesquioxane oligomer which is component a,
  • the present invention relates to a cured product of silsesquioxane obtained by forming a chemical bond.
  • component b a compound having at least two SiH groups in the same molecule (component b), and c) a compound (component c) having at least two carbon-carbon double bonds in the same molecule excluding the silsesquioxane oligomer which is component a,
  • the present invention relates to a cured product of silsesquioxane obtained by forming a chemical bond.
  • At least one type of structural force selected from force-type silsesquioxanes having substituents containing carbon-carbon double bonds and partial cleavage structures of these force-type silsesquioxanes is also obtained. Oligomers of silsesquioxanes,
  • the present invention relates to a process for producing a cured silsesquioxane, characterized in that a cured product is obtained by raising the temperature stepwise or continuously within a range of 20 ° C force and 400 ° C.
  • the tenth aspect of the present invention is a method for producing a cured product of silsesquioxane and a cured product of Z or a sixth cured product of silsesquioxane of the present invention.
  • the resulting silsesquioxane oligomers
  • the present invention relates to a process for producing a silsesquioxane cured product, which is characterized by obtaining a cured product by the following reaction A or reaction B.
  • a cured product is obtained by performing hydrosilylation reaction and radical reaction in the range of 80 ° C force and 400 ° C.
  • a cured product is obtained by performing hydrosilylation reaction and radical reaction in the range of 80 ° C force and 400 ° C.
  • the eleventh aspect of the present invention is a process for producing a cured product of silsesquioxane according to the third curable composition of the present invention and a process for producing a cured product of Z or seventh silsesquioxane according to the present invention.
  • the present invention relates to a process for producing a cured silsesquioxane, characterized in that a cured product is obtained by raising the temperature stepwise or continuously within a range of 20 ° C force and 400 ° C.
  • the twelfth aspect of the present invention is the fourth curable composition strength of the present invention, a process for producing a silsesquioxane cured product, and a method for producing Z or the eighth silsesquioxane cured product of the present invention.
  • the present invention relates to a method for producing a cured product of a silsesquioxane-containing composite, wherein a cured product is obtained by the following reaction A or reaction B.
  • a cured product is obtained by performing hydrosilylation reaction and radical reaction in the range of 80 ° C force and 400 ° C.
  • a cured product is obtained by performing hydrosilylation reaction and radical reaction in the range of 80 ° C force and 400 ° C.
  • the fifth and eighth silsesquioxane cured product of the present invention is used for an optical film, an optical sheet, a display element circuit substrate, or a transparent substrate. Furthermore, the fifth power of the present invention, the eighth silsesquioxane cured product, is used as an optical element sealant, a light emitting element sealant, particularly a white LED sealant, or a semiconductor sealant. .
  • the e component is a radical generator that generates radicals by light irradiation (second, fourth, sixth, and eighth of the present invention).
  • the e-component radical generator has a 10-hour half-life temperature of not lower than 100 ° C and not higher than 400 ° C (second, fourth, sixth and eighth of the present invention).
  • the refractive index of the f component is 1.48 to: L 60 (third, fourth, seventh and eighth of the present invention)
  • the f component is a sheet-like material having a thickness of 10 to 2000 / ⁇ ⁇ (third, fourth, seventh and eighth of the present invention).
  • component a 1 to 60 parts by mass of component a is contained in 100 parts by mass of the total weight of component a, component b and component c (first to eighth of the present invention).
  • composition ratio of component a, component b, and component c is the molar ratio between the component SiH group of component b and the sum of carbon and carbon double bonds of component a and component c (SiH group Z carbon carbon (Double bond) is 0.4 to 3 (first to eighth of the present invention).
  • the functional group molar ratio of carbon carbon double bond between component c and component a is 2 to 200 (of the present invention 1st to 8th).
  • n is an integer from 6 to 20.
  • silsesquioxane oligomer is a mixture having a number average molecular weight of 500 to 4000 (first to eighth of the present invention).
  • At least one kind of compound force selected from force-type silsesquioxanes having a substituent containing a carbon-carbon double bond and a partial cleavage structure of these force-type silsesquioxanes is obtained.
  • the oligomer of silsesquioxane is a mixture having a value of (weight average molecular weight) / (number average molecular weight) of 1 to 1.5 (first to eighth of the present invention).
  • the cured silsesquioxane is a sheet having a thickness of 10 to 2000 ⁇ m (first to eighth of the present invention).
  • the average coefficient of linear expansion of the cured silsesquioxane from 20 ° C to 200 ° C is 5 ppmZK or more and 60 ppm or less ZK (the seventh and eighth aspects of the present invention).
  • the total light transmittance of the cured silsesquioxane at a wavelength of 400 nm to 800 nm is 85% or more and 100% or less (the first power of the present invention is also eighth).
  • the 5% weight reduction temperature of the cured silsesquioxane is 400 ° C or higher and 800 ° C or lower (first to eighth of the present invention).
  • the maximum point elongation in the tensile property evaluation of the cured silsesquioxane is 10% or more and 40% or less (the fifth and sixth aspects of the present invention).
  • the first, fifth and ninth of the present invention include
  • At least one type of structural force selected from force-type silsesquioxanes having substituents containing carbon-carbon double bonds and partial cleavage structures of these force-type silsesquioxanes is also obtained. Oligomers of silsesquioxanes,
  • At least one type of structural force selected from force-type silsesquioxanes having substituents containing carbon-carbon double bonds and partial cleavage structures of these force-type silsesquioxanes is also obtained. Oligomers of silsesquioxanes,
  • the reaction occurs uniformly and a cured product having excellent transparency can be obtained. More preferably, the a component, b component, c component and d component are uniformly compatible. In the case of a composition containing the e component, it is particularly preferred that the a component, b component, c component, d component and e component are uniformly compatible.
  • the present invention is a long-term storage-stable curable composition capable of obtaining a cured product excellent in heat resistance and transparency using a silsesquioxane composition excellent in moldability.
  • the present invention is manufactured from a silsesquioxane composition having excellent moldability, and has excellent heat resistance and transparency, including a liquid crystal element display substrate including an active matrix type, a display element substrate for organic EL, and a color filter.
  • a liquid crystal element display substrate including an active matrix type, a display element substrate for organic EL, and a color filter.
  • a cured product obtained by molding a silsesquioxane cured product having both heat resistance and transparency by a simple method can be produced.
  • the component a is at least one kind selected from force-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these force-type silsesquioxanes. It means an oligomer of silsesquioxanes that can also provide structural strength.
  • Component b means a compound having at least 2 SiH groups in the same molecule.
  • the component c means a compound having at least two carbon-carbon double bonds in the same molecule excluding the silsesquioxane oligomer which is the component a.
  • Component d means a hydrosilylation catalyst.
  • the e component means a radical generator.
  • the f component means a reinforcing filler.
  • the curable composition means a composition containing a component to d component, or a composition containing a component to d component, e component and Z or f component.
  • cured material means the hardened
  • the a component, the b component, and the c component are uniformly compatible since a cured product having excellent transparency can be easily obtained.
  • the component a, the component b, the component c, and the component d are uniformly compatible.
  • it further contains e component it is particularly preferable that the component a, component b, component c, component d, and component e are uniformly compatible.
  • curable composition C, D a composition (curable composition C, D) containing a radical generator (e component) and a soot composition (curable composition A, B) are obtained.
  • the curable composition A is:
  • At least one structure force selected from force-type silsesquioxanes having substituents containing carbon double bonds and partial cleavage structures of these force-type silsesquioxanes Silsesquioxane oligomers (component a),
  • a cured product can be obtained by bonding (polymerizing) the c component from the a component with the d component.
  • the curable composition B is:
  • At least one structure force selected from force-type silsesquioxanes having substituents containing carbon double bonds and partial cleavage structures of these force-type silsesquioxanes Silsesquioxane oligomers (component a),
  • a cured product can be obtained by bonding (polymerizing) the c component from the a component with the d component.
  • a cured product is obtained by combining (polymerizing) component c and component f from component a with component d. Can do.
  • the curable composition C is: a) Obtained from at least one compound selected from a force-type silsesquioxane having a substituent containing a carbon-carbon double bond and a partial cleavage structure of these force-type silsesquioxanes.
  • Silsesquioxane oligomers component a
  • component c) a compound having at least two carbon-carbon double bonds (component c) excluding the silsesquioxane oligomer which is component a,
  • a cured product can be obtained by forming (polymerizing) the c component from the a component with the d component and the e component.
  • the curable composition D is:
  • component c) a compound having at least two carbon-carbon double bonds (component c) excluding the silsesquioxane oligomer which is component a,
  • a cured product can be obtained by forming (polymerizing) the c component from the a component with the d component and the e component.
  • d component and e component are used to bond and form (polymerize) c component and f component to cure. You can get things.
  • Silsesquioxane oligomers component a
  • b) A compound having at least two SiH groups in the same molecule (component b), and c) A compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of the silsesquioxane of component a A composition comprising a compound (component c), or further f) a composition comprising an enhanced filler (component f),
  • the mixing ratios of the raw materials a, b and c can be selected as appropriate.
  • component a is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, more preferably 5 to 45 parts by mass,
  • composition ratio of the a component, the b component, and the c component is preferably a molar ratio between the SiH group of the b component and the sum of the carbon-carbon double bond groups of the a component and the c component (SiH group Z Carbon-carbon double bond group) is 0.4 to 3, more preferably 1 to 2, still more preferably 1 to 1.6, and particularly preferably 1.2 to 1.4.
  • the heat resistance may be lowered.
  • the crosslinking density is lowered, the heat resistance is lowered, and the material may become brittle.
  • the molar ratio of the Si component of b component to the sum of the carbon and carbon double bond groups of component a and c is smaller than the above range, crosslinking is sufficient.
  • the heat resistance may be low and it may become brittle.
  • a silsesquioxane is obtained from a composition containing a component, b component and c component by using a hydrosilylation catalyst (d component) without containing a radical generator (e component) and a reinforcing filler (f component).
  • a hydrosilylation catalyst d component
  • e component radical generator
  • f component reinforcing filler
  • component a is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, more preferably 5 to 45 parts by mass,
  • composition ratio of the a component, the b component, and the c component is preferably a molar ratio between the SiH group of the b component and the sum of the carbon-carbon double bond groups of the a component and the c component (SiH group Z Carbon Carbon double bond group
  • the carbon-carbon double bond functional group molar ratio of component c and component a is preferably 8-200, more preferably 8 to 120, more preferably 8 to 30, particularly preferably 8 to 20,
  • a cured product of silsesquioxane When a cured product of silsesquioxane is used, it is easy to obtain a cured product having a maximum point elongation of 10% or more and 40% or less, preferably 10 to 30%, and excellent extensibility, when evaluating tensile properties. It can be used as a cured silsesquioxane.
  • the composition ratio of the component a, the component b, and the component c is such that if the content of the component a is smaller than the above range, the heat resistance is lowered and the composition may become brittle.
  • the content of the component a is larger than the above range, the crosslinking density is lowered, the heat resistance is lowered, and the brittleness or transparency may be lost.
  • the molar ratio (SiH group Z carbon carbon double bond group) of the Si component of component b to the sum of the carbon and carbon double bond groups of component a and component c is smaller than the above range, crosslinking is insufficient. Heat resistance may be low and become brittle.
  • the molar ratio is larger than the above range, the number of SiH groups that are not cross-linked increases, and the cross-linking density is lowered, resulting in low heat resistance and brittleness.
  • the functional group molar ratio of the carbon-carbon double bond between component c and component a is smaller than the above range, it becomes brittle or transparent. May be lost or the tensile elongation may decrease.
  • the mole ratio is larger than the above range, the heat resistance may be lowered and the material may become brittle.
  • component a is preferably 30-6 0 part by mass, more preferably 35 to 55 parts by mass, more preferably 40 to 50 parts by mass.
  • the composition ratio of component a, component b and component c is preferably the Si component of component b and a
  • the molar ratio (SiH group Z carbon carbon double bond group) of the component and the sum of carbon and carbon double bond groups of the component c is 0.3 to 1, more preferably 0.5 to 1. More preferably, it is 0.8-1.
  • the composition ratio of component a, component b, and component c may be lower than the above range, and heat resistance may be reduced.
  • the component a is larger than the above range, the crosslinking density is lowered, the heat resistance is lowered, and the material may become brittle.
  • the molar ratio of the Si component of b component to the sum of the carbon-carbon double bond groups of component a and c SiH group Z carbon carbon double bond group
  • crosslinking is sufficient.
  • the heat resistance may be low and it may become brittle.
  • the mole ratio is larger than the above range, the number of SiH groups that are not cross-linked increases, and the cross-linking density is lowered, resulting in low heat resistance and brittleness.
  • the component a a carbonic silsesquioxane having a substituent containing a carbon-carbon double bond, is a compound represented by the following general formula (1).
  • R is a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms or an aryloxy group, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing functional group having 1 to 20 carbon atoms) Hydrocarbon group, a nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functional group having 1 to 20 carbon atoms, a hydrocarbon group, or a key atom having 1 to 10 carbon atoms
  • a plurality of R on the same silsesquioxane molecule may be the same or different, and at least two are substituents containing a carbon-carbon double bond.
  • ⁇ is an integer from 6 to 20.
  • ⁇ is an integer of 6 to 20, or a combination of these, and is particularly suitable for reducing the average molecular weight and increasing the compatibility of the cured composition, 6, 8, 10, 12, and ⁇ or 14, or A combination of these is preferred, especially 8, 10, and ⁇ or 12, or a combination of these is preferred.
  • the alkoxy group or aryloxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 4 carbon atoms or an aryloxy group having 6 carbon atoms.
  • Preferable examples include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group and the like.
  • the hydrocarbon group having 1 to 20 carbon atoms is preferably a hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrocarbon group having 1 to 6 carbon atoms.
  • Preferred examples include aromatic hydrocarbons such as saturated hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclopentyl group, and cyclohexyl group, phenol group, and methylphenol group.
  • hydrocarbon groups containing carbon-carbon double bonds such as hydrogen groups, vinyl groups, propenyl groups, butenyl groups, and styryl groups.
  • oxygen-containing functional group 20 hydrocarbon group having 1 to 20 carbon atoms, preferably an oxygen-containing functional group ⁇ hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
  • This is an oxygen-containing functionalized hydrocarbon group.
  • Preferred examples include methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2 ethoxyethyl group, 2- (3,4 epoxy cyclohexyl) ethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3- Examples thereof include a glycidoxypropyl group, a 3-methacryloxypropyl group, and a 3-aryloxypropyl group.
  • the nitrogen-containing functional group ⁇ hydrocarbon group having 1 to 20 carbon atoms is preferably a nitrogen-containing functional group ⁇ hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. This is a nitrogen-containing functionalized hydrocarbon group.
  • Preferable examples include aminomethyl group, 2-aminoethyl group, 3-aminopropyl group, N-2 aminomethyl-3 aminopropyl group, N-phenyl-3-aminopropyl group and the like.
  • halogen-containing functional group ⁇ hydrocarbon group having 1 to 20 carbon atoms preferably a halogen-containing functional group ⁇ hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to
  • the halogen-containing functional group 6 is a hydrocarbon group.
  • Preferred examples include a chloromethyl group, a 2-chloroethyl group, a 3-chloropropyl group, a bromomethyl group, a 2-bromomethyl group, a 3-bromomethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, 3-Fluoropropyl group, 3, 3, 3-Trifluoropropyl group, etc. can give.
  • the C 1 -C 10 -containing group is preferably a C 1 -C 6 -containing group.
  • Preferred examples include a dimethylsiloxy group and a 3- (dimethylsilyl) propyl group.
  • Examples of the partially cleaved structure of force-type silsesquioxane having a substituent containing a carbon-carbon double bond as component a include the following (al) to (a3).
  • the remaining part of the defect in the cage shape is a force-type silsesquioxane containing at least one Si—OH part.
  • the cleavage structure will be described using a force-silk silsesquioxane of the general formula (2).
  • a force-silk silsesquioxane of the general formula (2) As shown in the general formula (3), one Si—O—Si bond part constituting the force-silk silsesquioxane is converted to two Si—OH.
  • the cleavage structure of the above (a2) is apparently missing one RSiO unit constituting the force-silksilsesquioxane, and the cage at the defect site is Remaining in shape
  • the site is a force-type silsesquioxane containing one Si-OH part.
  • the component a uses a number average molecular weight (Mn) force S, preferably a mixture of 500 to 4000, more preferably a mixture of ⁇ or 500 to 3000, more preferably a mixture of ⁇ or 500 to 1800. This is preferable because the compatibility with the b, c, d, and e components is improved. Number average numerator If the amount is less than 500, it is difficult to selectively synthesize the cage structure. Also, if the number average molecular weight exceeds 4000, the compatibility may be lowered.
  • Mn number average molecular weight
  • the component a is preferably a mixture having a value of (weight average molecular weight Mw) Z (number average molecular weight Mn) of 1 to 1.5, more preferably a mixture of 1 to 1.3, more preferably 1 to 1.
  • compatibility with b component, c component, d component, and e component improves, it is preferable. If the above value exceeds 1.5, the compatibility with these components may be lowered.
  • the component a it is preferable to use a product of hydrolysis of trialkoxysilane and subsequent condensation reaction.
  • a co-hydrolysis-condensation reaction product of methyltrialkoxysilane and butyltrialkoxysilane or a cohydrolysis monocondensation reaction product of phenyltrialkoxysilane and butyltrialkoxysilane is preferably used. That's right.
  • the compound having at least two SiH groups in the molecule of component b a known compound having two SiH groups can be used.
  • the compounds (bl) to (b4) shown below can be used alone or in combination of two or more (for example, a combination of bl and bl, bl and b2, etc.).
  • z is an integer of 1 to 50, preferably an integer of 1 to 12.
  • the substituent R 1 includes a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms or an aryloxy group, a hydrocarbon group having 1 to 20 carbon atoms, and an oxygen-containing functional hydrocarbon having 1 to 20 carbon atoms.
  • R 1 in one molecule may be the same or different.
  • the alkoxy group or aryloxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 4 carbon atoms or an aryloxy group having 6 carbon atoms.
  • Preferable examples include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group and the like.
  • the hydrocarbon group having 1 to 20 carbon atoms is preferably a hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrocarbon group having 1 to 6 carbon atoms.
  • Preferred examples include aromatic hydrocarbons such as saturated hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclopentyl group, and cyclohexyl group, phenol group, and methylphenol group.
  • hydrocarbon groups containing carbon-carbon double bonds such as hydrogen groups, vinyl groups, propenyl groups, butenyl groups, and styryl groups.
  • oxygen-containing functional group 20 hydrocarbon group having 1 to 20 carbon atoms, preferably an oxygen-containing functional group ⁇ hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
  • This is an oxygen-containing functionalized hydrocarbon group.
  • Preferred examples include methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2 ethoxyethyl group, 2- (3,4 epoxy cyclohexyl) ethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3- Examples thereof include a glycidoxypropyl group, a 3-methacryloxypropyl group, and a 3-aryloxypropyl group.
  • the nitrogen-containing functional group ⁇ hydrocarbon group having 1 to 20 carbon atoms is preferably a nitrogen-containing functional group ⁇ hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. This is a nitrogen-containing functionalized hydrocarbon group.
  • Preferable examples include aminomethyl group, 2-aminoethyl group, 3-aminopropyl group, N-2 aminomethyl-3 aminopropyl group, N-phenyl-3-aminopropyl group and the like.
  • halogen-containing functional group ⁇ hydrocarbon group having 1 to 20 carbon atoms preferably a halogen-containing functional group ⁇ hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to
  • the halogen-containing functional group 6 is a hydrocarbon group.
  • Preferred examples include a chloromethyl group, a 2-chloroethyl group, a 3-chloropropyl group, a bromomethyl group, a 2-bromomethyl group, a 3-bromomethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, 3-Fluoropropyl group, 3, 3, 3-Trifluoropropyl group, etc. can give.
  • the C 1 -C 10 -containing group is preferably a C 1 -C 6 -containing group.
  • Preferred examples include a dimethylsiloxy group and a 3- (dimethylsilyl) propyl group.
  • polar group examples include cyan group, carbo group and carboxyl group. These may constitute a substituent by themselves, or may be a single substituent in a saturated hydrocarbon group, a alkenyl group, an aryl group, or a skeleton substituent.
  • the divalent substituent represented by Q includes at least one selected from the group consisting of a saturated hydrocarbon group, an aryl group, and an oxygen-containing group.
  • the saturated hydrocarbon group preferably has 1 to 6 carbon atoms, preferably 1 to 10 carbon atoms.
  • Preferable examples include methylene, ethylene, propylene, butylene and the like, which may have a substituent such as a saturated hydrocarbon group, a alkenyl group, an aryl group, or a polar group on the carbon.
  • the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 18 carbon atoms.
  • Preferable examples include a phenyl group, a tolyl group, a naphthyl group, and the like, and the carbon may have a substituent such as a saturated hydrocarbon group, an alkaryl group, an aryl group, or a polar group.
  • Preferred examples of the oxygen-containing group include a carbon group in addition to the oxygen atom itself.
  • Examples of (bl) include cyclosiloxane compounds such as trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, and pentamethylcyclopentasiloxane.
  • (b2) includes linear siloxane compounds such as polymethylhydrosiloxane, polyphenylhydrosiloxane, methylhydrosiloxane-dimethylsiloxane copolymer, and methylhydrosiloxane phenylmethylsiloxane copolymer.
  • Examples of (b3) include silane compounds such as dimethylsilane, diphenylsilane, and methylphenolsilane.
  • the component c is a compound having at least two carbon-carbon double bonds in the molecule, and the following compounds (cl) to (c7) can be used.
  • (cl) -CH CH or more substituted benzene or diphenyl.
  • (cl) -CH CH or more substituted benzene or diphenyl.
  • Preferable examples include 1,5-hexagen, 1,2-polybutadiene oligomer and the like.
  • (c3) CH CH substituted with 2 or more main chain carbon atoms 5-12, preferably main chain carbon atoms
  • Preferable examples include a 1,2-vinyl structure-containing compound of a polybutadiene oligomer.
  • (c5) Al force polyene having 6 to 500 main chain carbon atoms, preferably 6 to 200 main chain carbon atoms, containing two or more CH ⁇ CH— in the molecular chain.
  • Preferable examples include 2,4-hexagen and polybutaene oligomer.
  • a cycloalkaline having 5 to 18 main chain carbon atoms, preferably 5 to 10 main chain carbon atoms, containing two or more CH CH in the molecular chain.
  • Preferred examples include norbornagen and cyclootatriene.
  • (c7) An ester of bur alcohol or allylic alcohol and polycarboxylic acid.
  • Preferable examples include dibule phthalate and diaryl phthalate.
  • d component hydrosilylation catalyst a commonly known catalyst can be used without any particular limitation, and a platinum catalyst is particularly preferable in order to allow the hydrosilylation reaction to proceed with good yield.
  • Hidoroshirirui is not particularly limited as usage spoon catalyst, preferably a gesture et preferable to use a ratio of 10- 1 ⁇ 10 _8 mol relative to SiH groups 1 mol in the cured composition 10
  • a gesture et preferable to use a ratio of 10- 1 ⁇ 10 _8 mol relative to SiH groups 1 mol in the cured composition 10
  • Examples of the d component hydrosilylation catalyst include, for example, chloroplatinic acid, platinum (0) 1, 2 dibiruo 1, 1, 3, 3-tetramethylsiloxane complex, platinum (0) -acetylene Examples thereof include a platinum catalyst such as a setnerate complex and a platinum (0) -decadiene complex.
  • e-component radical generator generally known ones can be used without any particular limitation.
  • a combination of a hydrosilylation catalyst and a radical generator can combine carbon-carbon double bonds contained in the c component that does not react with the SiH group. And has the effect of increasing the crosslinking density.
  • a compound in which radical generation is initiated by light can be used as the component e.
  • a compound initiated by heat thermal decomposable radical generator
  • thermal decomposable radical generator a compound initiated by heat
  • photodegradable radical generator 10-hour half-life, because bond formation by radical reaction can be controlled in stages, and heat resistance and strength are easily improved without impairing the transparency of the cured product.
  • a radical generator having a temperature of 100 ° C. or more and 400 ° C. or less, preferably 100 to 180 ° C. can be used particularly preferably.
  • the gesture et preferred to use a ratio of 10- 1 ⁇ 10 _8 mol to the carbon-carbon double bonds lmol in cured composition 1 Used at a ratio of O_3 to 10_6 mol.
  • the e component for example, as a photodegradable radical generator, 2, 2 dimethoxy-1, 2 dipheluetane 1 on (trade name Irgacure 651: Ciba 'Specialty' Chemicals), 1 —Hydroxy monocyclohexyl monophenol monoketone (trade name Yirga Cure 184: Chinoku 'Specialty Chemicals), 2 Hydroxy-2-methyl 1-phenol Propanone 1-on (trade name Darocur 1173: Chinoku' Specialty Chemicals), 1— [4— (2 Hydroxyethoxy) -Phenol] 2 Hydroxy-2 Methyl 1—Propane-1-one (trade name Irgacure 2959: Chinoku Specialty Chemicals) it can.
  • Irgacure 651 Ciba 'Specialty' Chemicals
  • 1 Hydroxy monocyclohexyl monophenol monoketone
  • Yirga Cure 184 Chinoku 'Speci
  • Thermally decomposable radical generators include azobisisobuty-titolyl-tolyl, dibenzoyl peroxide (trade name Nyper BW: Nippon Oil & Fats), t-butyl peroxybenzoate (trade name Perbutyl Z: Nippon Oil & Fats), dicumyl pero Examples include Koxide (trade name Park Milta D: Nippon Oil & Fats).
  • radical generators having a 10-hour half-life temperature of 100 ° C or higher include di-t-butyl peroxide (trade name Barocta D: Nippon Oil & Fats), p-menthane hydroperoxide (trade name Permenta H: Nippon Oil & Fats, Diisopropylbenzene Hydroperoxide (trade name Park Mill P: Nippon Oil & Fats), 1, 1, 3, 3-tetramethylbutyl hydroperoxide (trade name Barocta H: Nippon Oil & Fats), Tamen Hydro Examples thereof include peroxide (trade name Parkmill H: Nippon Oil & Fats) and t-butyl hydroperoxide (trade name Perbutyl H: Japanese fats and oils).
  • Sheets made of glass fibers such as glass cloth and glass nonwoven fabric, and fibers made from glass materials such as glass fibers, glass beads, glass flakes, glass powder, milled glass, and glass wool , Particulates or sheets (nonwoven fabrics, woven fabrics, fiber sheets and multiple layers of these), etc.
  • cellulose fiber sheet For example, cellulose fiber sheet, bacterial cellulose fiber sheet, polyimide porous membrane, cellulose fiber, polyimide fiber, aramid fiber, polyimide fiber, polyketone fiber, silica unole, fumed silica and other porous materials such as zeolite and mesoporous silica
  • examples include inorganic materials, mica, vermiculite, montmorillonite, iron montmorillonite, neiderite, savonite, hectorite, stevensite, nontronite and other clay materials.
  • the strengthening filler is used as a sheet-like material because the deaeration treatment is relatively simple when mixed with the a component to the d component. It is more preferable to use it as a sheet-like material having a thickness of 10 to 2000 ⁇ m, preferably 50 to: LOOO ⁇ m.
  • the linear expansion coefficient of the obtained cured product is reduced, and thus the cured product can be easily used as a substrate material.
  • the component f is preferably composed of glass fiber such as glass fiber, glass cloth, glass nonwoven fabric, etc., and glass cloth is most preferred since it has a high effect of reducing the linear expansion coefficient.
  • the types of glass materials used are E glass, C glass, A glass, S glass, D glass, NE glass, T glass, AR glass, quartz, low dielectric constant glass E glass, S glass, T glass, and NE glass are preferred because they are free of ionic impurities such as alkali metals and easily available.
  • the cured silsesquioxane obtained from the curable composition containing the a component, the b component, the c component, and the d component, or the a component, the b component of the present invention the adhesion between the silsesquioxane cured product obtained from the curable composition containing the c component, the d component and the e component and the f component is preferably higher from the viewpoint of the transparency and material strength of the obtained cured product. .
  • the surface of the f component is appropriately treated.
  • the glass material used as the f component is commonly referred to as a silane coupling agent in addition to the heat cleaning treatment in which it is preferable that the surface of the glass is subjected to heat cleaning to be free of unnecessary organic substances on the surface. It is more preferable that the surface is appropriately modified with a commercially available silane compound.
  • silanol groups are used in post-heat-cleaning treatment, epoxy groups are treated in 3-glycidoxypropyltrialkoxysilane treatment, amino groups are treated in 3-aminopropyltrialkoxysilane treatment, and bull groups are treated in butylreal alkoxysilane treatment.
  • an allyloyl group can be present on the glass surface with a chemical bond.
  • the functional group present on the surface of the glass is suitable for the purpose of enhancing adhesion, as the functional group that forms a bond with the curable composition under curing conditions.
  • Suitable surface functional groups include a silanol group, a vinyl group, and the like, more preferably a force such as an epoxy group or an attalyloyl group.
  • glass materials subjected to silane coupling treatment are commercially available, and commercially available products may be used.
  • the f component is not a glass material, if functional groups such as surface hydroxyl groups are introduced by partial oxidation treatment, partial hydrolysis treatment, electron beam irradiation, plasma irradiation, radiation irradiation, etc., the f component surface functional group And the curable composition can be bonded to each other, and the adhesion is improved.
  • functional groups such as surface hydroxyl groups are introduced by partial oxidation treatment, partial hydrolysis treatment, electron beam irradiation, plasma irradiation, radiation irradiation, etc.
  • the refractive index of the f-component reinforcing filler used in the present invention is 1.4 to obtain excellent transparency. It is preferably 8 to 1.60.
  • a refractive index of 1.51 to L57 is particularly preferable because a transparent resin close to the Abbe number of the glass can be selected. The closer the Abbe number between the transparent resin and the glass, the higher the light transmittance in a wide range because the refractive index matches in a wider wavelength range.
  • the precise refractive index of the filler is a solvent that does not cause a chemical change in the filler, which has a higher refractive index than the filler, and a solvent that has a lower refractive index than the filler, and that does not cause a chemical change in the filler.
  • the filler is immersed in a solvent having a refractive index higher than that of the filler, a solvent having a refractive index lower than that of the filler is dropped, and the refractive index of the mixed solution is measured when the visually immersed filler becomes invisible.
  • the refractive index of the filler can be known.
  • an S-based glass cloth reffractive index of about 1.52
  • the refractive index of the glass cloth can be determined.
  • the refractive index of this S-based glass cloth can be determined to be 1.5203 to 1.5206.
  • the difference between the refractive index of the cured silsesquioxane obtained from the curable composition containing it and the refractive index of the reinforcing filler as the f component should be 0.01 or less in order to maintain excellent transparency. More preferably, 0.005 or less is more preferable. When the refractive index difference is greater than 0.01, the transparency of the obtained transparent material tends to be inferior.
  • the f component does not impair the characteristics of the present invention!
  • the curable composition containing the a component, b component, c component and d component, or the a component, b component, c component, d component can be used in a curable composition containing the e component.
  • the amount of component f is 1 to 90% by weight, more preferably 10 to 80% by weight, and still more preferably 20 to 70% by weight, based on the total amount (100% by weight) of the curable composition. And particularly preferably 30 to 60% by mass.
  • the blending amount of the glass material is preferably 1 to 90% by mass, more preferably 10 to 80% by mass with respect to the total amount of the curable composition (100% by mass). More preferably 30 to 70% by mass. If the amount of component f is within this range, molding is easy and effective in reducing the linear expansion coefficient.
  • the curable composition and the cured silsesquioxane of the present invention can be used in a range that does not impair characteristics such as transparency, solvent resistance, heat resistance, dimensional stability, and mechanical strength, if necessary.
  • thermoplastic or thermosetting oligomers and polymers By using these thermoplastic or thermosetting oligomers and polymers in combination, for example, when a reinforcing filler is further included, the composition is adjusted so that the overall refractive index matches the refractive index of the reinforcing filler (f component). It becomes easy to adjust the ratio.
  • the cured silsesquioxane of the present invention is produced by mixing [a component, b component, c component and d component] or [a component, b component, c component, d component and e component] with stirring. After uniform mutual dissolution, a curable composition is obtained through a normal degassing operation, and the curable composition is poured into an appropriate mold, and then the bond-forming reaction proceeds by heating and irradiation with Z or light. This can be done.
  • the silsesquioxane cured product containing the f component is produced by [a component, b component, c component and d component] or [a component, b component, c component, d component and e component].
  • the mixture is permeated and impregnated into a reinforcing filler of a sheet-like material such as glass cloth or glass nonwoven cloth through a normal deaeration operation, and then as necessary.
  • a curable composition can be obtained through a deaeration operation or the like.
  • a fibrous or particulate reinforcing filler can be uniformly dispersed in the mixture by stirring and mixing and degassing operations to obtain a curable composition.
  • the fibrous material or the particulate material should be removed by stirring and mixing the above mixture. In addition, the number of steps may be reduced.
  • the curable composition after the curable composition has a desired shape according to the application, it can be cured by heating and by causing a bond formation reaction to proceed by irradiation with Z or light.
  • the target shape is a sheet or film
  • the curable composition obtained by impregnating or impregnating the sheet-like reinforcing filler is fixed on one or both sides with a glass flat plate or stainless steel flat plate. Then, a method of curing by heating, Z or light irradiation to advance the bond formation reaction is preferable.
  • a curable composition obtained by dispersing a fibrous or particulate reinforcing filler is cast into a glass flat plate, a stainless steel flat plate, etc., heated and z
  • it may be a method of curing by curing the bond formation reaction by irradiation with light.
  • Silsesquioxane obtained from at least one compound selected from force-silksilsesquioxanes having a substituent containing a carbon-carbon double bond and a partial cleavage structure of these force-silksilsesquioxanes Except for the oligomers of xanes (component a), the compounds having at least two SiH groups in the same molecule (component b), and the oligomers of silsesquioxanes, which are components a, at least in the same molecule Add a compound having two carbon-carbon double bonds (component c) and, if necessary, a solvent and mix, preferably mix uniformly, and then add a hydrosilylation catalyst (component d) and mix. Preferably, after mixing uniformly, a transparent liquid composition (curable composition) is obtained by performing a de-treatment under reduced pressure.
  • This curable composition is poured into a mold, heated in a stepwise or continuous manner within a range of 20 ° C to 400 ° C, and reacted for 0.5 to 72 hours to produce a cured product. be able to
  • the resulting curable composition can be stored for a long time without impairing the curability when stored in a cool, dark place without contact with air.
  • a commercially available plastic syringe sealing the tip of the syringe and storing it in a cool temperature of 5 ° C to 10 ° C
  • the same procedure is followed.
  • a cured product having physical properties equivalent to those of the sample cured immediately after preparation of the composition is obtained.
  • the silsesquioxane cured product further containing a reinforcing filler (component f) is obtained by The composition is impregnated with a sheet-like reinforcing filler (component f) and then deaerated as necessary to obtain a curable composition.
  • a fibrous or particulate reinforcing filler (component f) is dispersed in this composition by stirring and mixing, and then degassed as necessary to obtain a curable composition.
  • a cured product can be produced by raising the temperature of the curable composition stepwise or continuously within a range of 20 ° C force to 400 ° C and reacting for 0.5 to 72 hours.
  • component c a compound (component c) having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane, which is component a,
  • the solvent is added and mixed, preferably mixed uniformly, and further, the hydrosilylation catalyst (component d) and the radical generator (component e) are added and mixed, preferably mixed uniformly.
  • a transparent liquid composition (curable composition) can be obtained by performing a degassing treatment under reduced pressure.
  • the reinforcing filler (f component) is added to the above composition, or the composition is added to the reinforcing filler (f component). If necessary, deaeration to obtain a curable composition.
  • this curable composition was subjected to a hydrosilylation reaction in the range of 20 ° C to 120 ° C, preferably in the range of 20 ° C to 80 ° C, for 0.5 to 24 hours. After finishing the reaction or after hydrosilylation reaction,
  • Radiation is generated from the radical generator by performing UV irradiation (e.g. UV irradiation amount should be such that the radical amount necessary for initiation of radical reaction is generated from the radical generator, e.g. UV irradiation time is 0 1 ⁇ : The range of LO minutes.),
  • the reinforcing filler (f component) is included and the reinforcing filler (f component) is a fibrous material or a particulate material
  • the reinforcing filler (f component) is added to the curable composition.
  • the reinforcing filler (component f) is a sheet, it can be used by impregnating the curable composition into one or a plurality of sheets of reinforcing filler (component f).
  • a reinforcing filler (f component) when included and a fibrous or particulate material is used in combination with a sheet-like material as the reinforcing filler (f component), the fibrous material is used.
  • the particulate matter can be dispersed in the curable composition and then impregnated with the curable composition in a sheet-like reinforcing filler (component f).
  • Silcerxoxane cured product is molded by injecting or casting a curable composition (curable mixture) into a mold that matches the desired cured product shape, and then proceeding with the curing reaction. A cured product having a specific shape can be produced.
  • a curable composition with a component, b component, c component and d component, and a curable composition with a component, b component, c component, d component and e component are handled as a solution.
  • a curable composition with a component, b component, c component, d component and e component are handled as a solution.
  • the viscosity is relatively low, a thin tube can be flowed, and a fine molding process can be performed.
  • the curable composition contains a solvent component, it is poured into a mold or cast.
  • the curing reaction can proceed after removing the solvent component by general heating and Z or reduced pressure treatment, or the removal of the solvent component and the curing reaction can proceed in parallel.
  • the curable composition contains a reinforcing filler (component f), the reinforcing filler
  • composition containing the component (f) is cast into a mold having a desired shape and then cured, or the composition containing components other than the reinforcing filler is impregnated into a glass cloth or a glass nonwoven fabric and cured. Examples thereof include a method of forming a composition and then curing it to form a sheet.
  • the material of the mold can be appropriately selected from those commonly used on the condition that the material does not change in the heating process during curing. Glass, stainless steel, aluminum, Teflon (registered) Trademark). In order to facilitate release of the cured product from the mold, it is generally used and a release agent may be used.
  • the curable composition (curable mixture) is injected into a mold having a spacer for controlling the thickness between two glass plates, It can be produced satisfactorily by heating at 120 ° C for 2 hours and further at 200 ° C for 30 minutes.
  • cured products of various shapes such as a film, a sheet, a plate, a column, and a cylinder can be obtained.
  • a cured product having an arbitrary shape such as a lens shape or a prism shape can be obtained by using a corresponding mold.
  • the material can be cured in a state of being coated or sealed. In the case of use for coating or sealing, the viscosity of the curable composition is relatively low, so that it is possible to easily cover or seal even a material having a complicated shape.
  • the cured product of silsesquioxane of the present invention is excellent in heat resistance, transparency, and molding processability.
  • a transparent coating material for electronic circuits, etc. Can be used for applications.
  • it is suitable for use as an electronic circuit transparent substrate for display that requires heat resistance and transparency.
  • a sealing material that requires heat resistance and transparency as well as molding processability, particularly as a sealing material for a high-power light emitting element, for example, a sealing material for a high-power white LED.
  • a cured silsesquioxane further containing a reinforcing filler (component f) is excellent in heat resistance, dimensional stability, mechanical strength, transparency, and molding processability. It can be particularly suitably used for applications such as active matrix type liquid crystal element display substrates, organic EL display element substrates, color filter substrates, touch panel substrates, electronic paper substrates, solar cell substrates, and the like. Further, it can be formed into an arbitrary shape, and can be suitably used for an optical lens, an optical waveguide, an optical element sealing material, and the like.
  • This cured silsesquioxane is used for transparent circuit boards such as plastic substrates for liquid crystal displays, substrates for color filters, plastic substrates for organic EL display elements, substrates for electronic paper, solar cell substrates, touch panels, etc.
  • the thickness of the substrate is preferably 50 to 2000 ⁇ m, more preferably 50 to: LOOO ⁇ m. If the thickness of the substrate is within this range, the flatness will be excellent and the substrate will be lighter than the glass substrate.
  • the average linear expansion coefficient at 20 to 200 ° C is preferably 5 ppmZK or more and 60 ppmZK or less, more preferably 40 ppmZK or less, and most preferably 20 ppmZK or less.
  • the wavelength is 400 ⁇ !
  • the total light transmittance at ⁇ 800 nm is required to be 85% or more, more preferably 87% or more, and most preferably 90% or more.
  • Wavelength 400 ⁇ ! Display performance is sufficient, with total light transmittance below 85% at ⁇ 800nm!
  • the peak appearing at ⁇ -80ppm was attributed to the peak derived from trisyloxysilyl (hereinafter referred to as ⁇ 3), and the peak appearing near ⁇ -70ppm was attributed to the peak derived from disiloxysilyl (hereinafter referred to as T2).
  • the number average molecular weight Mn and dispersity MwZMn were determined using polystyrene as a standard substance.
  • the number average molecular weight Mn and the degree of dispersion MwZMn were calculated using the software attached to the apparatus.
  • Td5 5% weight loss temperature
  • the 5% weight loss temperature (hereinafter referred to as Td5) was measured at 20 ° CZmin from room temperature to 550 ° C using about 10 mg of sample and passing through 200 mlZmin of air. The temperature was reduced by 5% from the initial weight when the temperature was raised.
  • Tg glass transition temperature
  • an acetone immersion test was performed according to the following procedure.
  • the cured product was dried at 110 ° C. for 30 minutes and then weighed.
  • the cured product was immersed in acetone (20 to 25 ° C.) for 20 to 24 hours in a stationary state.
  • the cured product was taken out from acetone, dried at 110 ° C for 30 minutes, weighed, and compared the weight before and after the test.
  • the presence or absence of cracks and devitrification of the cured product before and after the test was visually observed.
  • the product lg contains 2.61 mmol equivalent as a bur group.
  • the synthesized force-silsesquioxane oligomers consisted of 8 to 20 key units per molecule from the results of GPC measurement, and from the results of 29 Si-NMR. It can be estimated that a part of the cage structure has a ring-opened structure.
  • the partial ring-opening cage structure will be described. From the GPC measurement results of the synthesized silsesquioxane oligomers, it can be estimated that the structure consists of 8 to 20 key units. Assuming that the polysilsesquioxane synthesized in this study has 10 key units per molecule and the measurement power of the key NMR is 1Z9, the number of T2 and T3 units is 1 and 9, respectively. It becomes.
  • both structures are structures in which a part of the cage structure is opened.
  • the concentrated solution was transferred to a separatory funnel, and 500 ml of ethyl acetate and 300 ml of saturated saline were added to carry out a liquid separation operation.
  • the organic layer was washed 3 times with saturated brine and then dehydrated with anhydrous magnesium sulfate for one day. This was filtered and concentrated, and the concentrated solution was dropped into 8000 ml of n-heptane to form a precipitate.
  • the product was white powder, yield 222g, yield 78%.
  • the product lg contains 2.50 mmol equivalent as a bur group.
  • the low boiling point was distilled off using a rotary evaporator.
  • 200 ml of jetyl ether was added for extraction, and the organic phase was washed with distilled water followed by saturated brine and dehydrated over anhydrous magnesium sulfate for 3 hours or more.
  • Insoluble matter such as salt was removed by filtration, concentrated by drying under reduced pressure, added to 200 ml of hexane with stirring, and purified by reprecipitation.
  • the product was a white powder, and the yield was 47.5 g and the yield was 95.1%.
  • the product lg contains 4.67 mmol equivalent as a bur group.
  • Reactive polysilsesquioxane was synthesized according to the following procedure. In a three-necked flask with a 2000 ml thread equipped with a reflux condenser, 45 ml of 1N sodium hydroxide aqueous solution, 1,200 ml of tetrahydrofuran with tetrahydride, 28.5 g (144 mmol) of phenol trimethoxysilane, 49.7 g (336 mmol) of butyltrimethoxysilane And heated to 60 ° C with mechanical stirring and allowed to react for 20 hours. After the reaction, return to room temperature, neutralize with 45 ml of 1N hydrochloric acid, and then add saturated sodium bicarbonate.
  • the product lg contains 7.35 mmol equivalent as a bur group.
  • the concentrated liquid was transferred to a separatory funnel, and 150 ml of jetyl ether and 30 ml of saturated saline were added to carry out a liquid separation operation.
  • the organic layer was washed 3 times with saturated brine, and dehydrated with anhydrous magnesium sulfate overnight. This was filtered and concentrated, and the concentrated solution was dropped into 2000 ml of n-hexane to remove the precipitate. The supernatant was collected and dried under reduced pressure to obtain a white solid product (yield 23.20 g, yield 66%).
  • the product lg contains 6.70 mmol equivalent as a bur group.
  • the organic layer was washed 3 times with saturated brine, and then dehydrated with anhydrous magnesium sulfate for one day. This was filtered and concentrated, and the concentrated solution was dropped into 2000 ml of n-hexane to form a precipitate. The supernatant was collected and dried under reduced pressure. The product was a white powder, yield 33.2 g, yield 72%.
  • NMR ⁇ (ppm) 5.3-6.2 (m, 9H), 6.8 — 8.0 (m, 35H); 29 Si— NMR ⁇ (ppm): —83 —75 (T3), 81 mol%, —72 — —66 (T2), 19 mol%.
  • the product lg contains 7.30 mmol equivalent as a bur group.
  • Teflon spacer thickness 0.3 mm
  • Araji-jime sales release agent a curable composition was injected into the mold. Hold for 2 hours in a constant temperature bath at 120 ° C, and then hold at 200 ° C for 30 minutes. The composition was cured.
  • the obtained cured product was a colorless and transparent film (thickness 0.3 mm).
  • Tg of the cured product was not observed between room temperature forces of 400 ° C, Td5 was 447 ° C, tensile properties were 1.30 GPa, maximum point stress 33.6 MPa, elongation at break 8.3% .
  • the total light transmittance is 92. / 0 .
  • the curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump and defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
  • the obtained cured product was a colorless and transparent sheet.
  • the Tg of the cured product was not observed between room temperature forces of 400 ° C, and Td5 was 386 ° C.
  • the rugged silsesquioxane oligomer synthesized in Synthesis Example 1 2.00 g (5.21 mmol as a bull group) and 1.00 g dibutylbenzene (15.4 mmol as a bull group) were added to 1, 3, 5, 7— Tetramethylcyclotetrasiloxane 1.05 g (17.5 mmol as SiH group) was mixed to obtain a homogeneous solution. To this was added 20 1 of a 2% xylene solution of platinum (0) 1,2-dibulol 1,1,3,3-tetramethylsiloxane complex. It was sucked with a vacuum pump and defoamed to obtain a curable composition which was colorless and transparent and was compatible with each other.
  • the curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump, defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
  • the obtained cured product was a colorless and transparent sheet.
  • the Tg of the cured product was not observed between room temperature forces of 400 ° C, and Td5 was 405 ° C.
  • the curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump, defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
  • the obtained cured product was a colorless and transparent sheet.
  • Tg of the cured product was not observed between room temperature forces of 400 ° C, Td5 was 419 ° C, tensile properties were elastic modulus 0.996 GPa, maximum point stress 27.8 MPa, elongation at break 4.5%. .
  • a glass plate coated with Teflon spacer on two glass plates coated with a brute force release agent is poured into the mold, and the above curable composition is injected into it in a 120 ° C constant temperature bath for 2 hours. Thereafter, the curable composition was cured by holding at 200 ° C. for 30 minutes.
  • the obtained cured product was a colorless and transparent sheet.
  • Tg of the cured product was not observed between room temperature forces of 400 ° C, Td5 was 449 ° C, tensile properties were elastic modulus 1.29 GPa, maximum point stress 30.8 MPa, elongation at break 7.6%. .
  • the total light transmittance was 92%.
  • Example 6 The rugged silsesquioxane oligomer synthesized in Synthesis Example 1 2.00 g (5.21 mmol as a bull group) and 1.00 g dibutylbenzene (15.4 mmol as a bull group) were added to 1, 3, 5, 7— Tetramethylcyclotetrasiloxane 2.18 g (36.3 mmol as SiH group) was mixed to obtain a homogeneous solution. To this was added 20 1 of a 2% xylene solution of platinum (0) 1,2-dibi-luro 1,1,3,3-tetramethylsiloxane complex.
  • curable composition which was colorless and transparent and was compatible with each other.
  • the curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump, defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
  • the obtained cured product was a colorless and transparent sheet.
  • the Tg of the cured product was not observed between room temperature forces of 400 ° C, and Td5 was 418 ° C.
  • the curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump, defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
  • the obtained cured product was a colorless and transparent sheet.
  • Tg of the cured product was not recognized between room temperature forces of 400 ° C, Td5 was 393 ° C, tensile properties were elastic modulus 0.887 GPa, maximum point stress 25.7 MPa, elongation at break 5.8%. .
  • the rugged silsesquioxane oligomer synthesized in Synthesis Example 1 2.00 g (5.21 mmol as a bull group) and 0.50 g (7.68 mmol as a bull group) of 1, 3, 5, 7— Tetramethylcyclotetrasiloxane was mixed with 0.89 g (14.8 mmol as SiH group) to obtain a homogeneous solution.
  • Platinum (0) 1, 2—Dibiru 1, 1, 3, 3—Tetramethyl 20 1 of a 2% xylene solution of a siloxane complex was added. It was sucked with a vacuum pump and defoamed to obtain a curable composition which was colorless and transparent and was compatible with each other.
  • the curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump, defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
  • the obtained cured product was a colorless and transparent sheet.
  • Tg of the cured product was not observed between room temperature forces of 400 ° C, Td5 was 403 ° C, tensile properties were elastic modulus 1.10 GPa, maximum point stress 28.6 MPa, elongation at break 3.4% .
  • Divinylinolebenzene 1.00 g (15.4 mmol as a vinylol group) and 1, 3, 5, 7-tetramethylole cyclotetrasiloxane 0.92 g (15.4 mmol as a SiH group) were mixed with each other to obtain a homogeneous solution. .
  • 20 1 parts of a 2% xylene solution of platinum (0) 1,2-dibule 1,1,3,3-tetramethylsiloxane complex was added. After sucking with a vacuum pump and degassing, pour into a Teflon sheet mold and sucking with a vacuum pump to degas, first heat at 110 ° C for 12 hours, then heat at 200 ° C for 30 minutes to obtain a molded body It was.
  • the molded body was brittle and could not carry out the acetone immersion test.
  • Td5 was 327 ° C.
  • curable composition which was colorless and transparent and was compatible with each other.
  • the curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump, defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
  • the obtained cured product was a colorless and transparent sheet. No change in weight was observed in the acetone immersion test.
  • the Tg of the cured product was not observed between room temperature forces of 400 ° C, Td5 was 407 ° C, tensile properties were elastic modulus 1.03 GPa, maximum point stress 10.5 MPa, elongation at break 1.4%. .
  • 5,82-tetramethylcyclotetrasiloxane was mixed with 1.82 g (30.3 mmol as SiH group) to obtain a homogeneous solution.
  • 20 1 of a 2% xylene solution of platinum (0) 1,2-dibi-luro 1,1,3,3-tetramethylsiloxane complex was added 20 1 of a 2% xylene solution of platinum (0) 1,2-dibi-luro 1,1,3,3-tetramethylsiloxane complex.
  • a curable composition which was sucked with a vacuum pump and defoamed was colorless and transparent, and was uniformly compatible.
  • the curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump and defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
  • the obtained cured product was a colorless and transparent sheet. No change in weight was observed in the acetone immersion test.
  • the Tg of the cured product was not observed between room temperature forces of 400 ° C, Td5 was 415 ° C, tensile properties were elastic modulus 1. OlGPa, maximum point stress 12.3 MPa, elongation at break 1.1% .
  • a curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible.
  • This curable composition is poured into a Teflon sheet mold, sucked with a vacuum pump, defoamed, and initially held at 80 ° C for 5 hours, then UV irradiation [metal halide lamp 120 W / cm] for 1 minute, then 200 ° Holding at C for 30 minutes, the curable composition was cured.
  • the obtained cured product was a colorless and transparent sheet. No change in weight was observed in the acetone immersion test. The Tg of the cured product was not observed between room temperature forces of 400 ° C, and Td5 was 410 ° C.
  • a curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible.
  • This curable composition is poured into a Teflon sheet mold, sucked with a vacuum pump, defoamed, and initially held at 80 ° C for 5 hours, then UV irradiation [metal halide lamp 120 W / cm] for 1 minute, then 200 ° Holding at C for 30 minutes, the curable composition was cured.
  • the obtained cured product was a colorless and transparent sheet. No change in weight was observed in the acetone immersion test. The Tg of the cured product was not observed between room temperature forces of 400 ° C, and Td5 was 415 ° C.
  • This curable composition is poured into a Teflon sheet mold, sucked with a vacuum pump, defoamed, and initially held at 80 ° C for 5 hours, then UV irradiation [metal halide lamp 120 W / cm] for 1 minute, then 200 ° Holding at C for 30 minutes, the curable composition was cured.
  • the obtained cured product was a colorless and transparent sheet.
  • the Tg of the cured product was not observed between room temperature forces of 400 ° C, and Td5 was 407 ° C.
  • This curable composition is poured into a Teflon sheet mold, sucked with a vacuum pump, defoamed, and initially held at 80 ° C for 5 hours, then UV irradiation [metal halide lamp 120 W / cm] for 1 minute, then 200 ° Holding at C for 30 minutes, the curable composition was cured.
  • the obtained cured product was a colorless and transparent sheet. No change in weight was observed in the acetone immersion test. The Tg of the cured product was not observed between room temperature forces of 400 ° C, and Td5 was 409 ° C.
  • Example 5 0172 g was added thereto, and the mixture was poured into a mold produced in the same manner as in Example 5. Next, the same heating as in Example 16 was performed to cure the curable composition. The obtained cured product was a colorless transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction by crosslinking was sufficiently advanced. Td5 was 461 ° C, tensile properties were elastic modulus 1.01 GPa, maximum point stress 21. OMPa, elongation at break 1.9%. The total light transmittance was 91%.
  • Example 5 0159 g was added thereto, and the mixture was poured into a mold produced in the same manner as in Example 5. Next, the same heating as in Example 16 was performed to cure the curable composition. The obtained cured product was a colorless transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction by crosslinking was sufficiently advanced. Td5 was 459 ° C and the total light transmittance was 91%.
  • Example 5 0151 g was added thereto, and the mixture was poured into a mold produced in the same manner as in Example 5. Next, the same heating as in Example 16 was performed to cure the curable composition. The obtained cured product was a colorless transparent sheet. In the acetone immersion test, both weight change and appearance change were recognized. In other words, it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. Td5 was 455 ° C, tensile properties were elastic modulus 1.53 GPa, maximum point stress 14. OMPa, elongation at break 1.01%. The total light transmittance was 92%.
  • Teflon 0.5 mm thick Teflon was sandwiched between two glass plates with a side of 15 cm, fixed with a fixture, and the mixture was poured into the gap. After heating at 80 ° C for 3 hours, the fixture was removed, and the curable composition was cured by heating at 120 ° C for 1 hour. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction by crosslinking was sufficiently advanced. Td 5 was 451 ° C. and the total light transmittance was 93%.
  • the Td5 of the cured product was 459.6 ° C
  • the tensile properties were an elastic modulus of 6.80 GPa
  • the maximum point stress was 214.5 MPa
  • the elongation at break was 4.8%.
  • the linear expansion coefficient of the cured product was 12.2ppmZK
  • the total light transmittance was 87.1%.
  • the curable composition was impregnated with an S glass-based glass cloth (refractive index: 1.52, treated with a bull silane coupling agent, manufactured by Utica) having a thickness of 0.050 mm and a density of 60 ⁇ 58 Z inches. Defoamed.
  • This curable composition is sandwiched between release-molded glass plates, heated in a dryer at 120 ° C for 90 minutes, and then heated at 200 ° C for 30 minutes to obtain a transparent film having a thickness of 0.09 lmm. It was. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction by crosslinking was sufficiently advanced.
  • the Td5 of the hard material was 425.5 ° C, the tensile properties were the elastic modulus 5.49GPa, the maximum point stress 210.lMPa, and the elongation at break 5.0%.
  • the linear expansion coefficient of the cured product was 10.9 ppmZK, and the total light transmittance was 90.3%.
  • the refractive index of only the resin portion of the cured composition was 1.519.
  • the force-type silsesquioxane oligomer prepared in Synthesis Example 2 is 3. OOg (7.47 mmol as the bull group), dibulene 3. OOg (46. lmmol as the bull group), and 1, 3, 5, 7 — Tetramethylcyclotetrasiloxane (4.35 g, 72.4 mmol as SiH group) was mixed and stirred for 10 minutes with ultrasonic mixing to be compatible. A drop of lwt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to give a curable composition that was colorless and transparent and was compatible with the mixture.
  • the curable composition was cured by holding in a thermostatic bath for 1.5 hours and then holding at 200 ° C for 30 minutes.
  • the obtained cured product was a colorless and transparent sheet. Weight change in acetone immersion test, outside No change in view was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced.
  • Td5 was 467.9 ° C
  • tensile properties were 0.995 GPa
  • maximum point stress was 30.5 MPa
  • elongation at break was 8.99%.
  • the linear expansion coefficient of the cured product was 200 ppmZK, and the total light transmittance was 91.8%.
  • Divininolebenzene 2.OOg (30.7 mmol as a vinylene group) and 2.46 g (40.9 mmol as a SiH group) 1,3,5,7-tetramethylolcyclotetrasiloxane were mixed with each other to obtain a homogeneous solution.
  • the curable composition was impregnated with a thickness of 100 / zm, a refractive index of 1.558, manufactured by Nittobo, and defoamed.
  • This curable composition is sandwiched between release-molded glass plates, heated in a dryer at 120 ° C for 90 minutes, and then heated at 200 ° C for 30 minutes to form a transparent film with a thickness of 0.11 mm. Obtained .
  • the Td5 of the cured product was 40.2 ° C, the tensile properties were elastic modulus 4.38 GPa, maximum point stress 217.5 MPa, elongation at break 4.84. 87%.
  • the linear expansion coefficient of the cured product was 11.8 ppmZK, and the total light transmittance was 84.3%.
  • the curable composition was cured by holding in a constant temperature bath at 120 ° C for 90 minutes and then holding at 200 ° C for 30 minutes.
  • the obtained cured product was a colorless and transparent sheet.
  • Td5 was 462 ° C
  • tensile properties were elastic modulus 1.03 GPa
  • maximum point stress 26.2 MPa maximum point stress 26.2 MPa
  • the total light transmittance was 92%.
  • the curable composition was cured by holding for 90 minutes in a 120 ° C constant temperature bath and then holding for 30 minutes at 200 ° C.
  • the obtained cured product was a colorless and transparent sheet.
  • Td5 was 461 ° C
  • tensile properties were a tensile strength of 1.14 GPa, a maximum point stress of 25.7 MPa, and an elongation at break of 11.2%.
  • the total light transmittance was 92%.
  • This curable composition was poured into a mold produced in the same manner as in Example 1. Next, hold it in a 120 ° C constant temperature bath for 90 minutes, and then hold it at 200 ° C for 30 minutes. Thus, the curable composition was cured. The obtained cured product was a colorless and transparent sheet. In the caseon immersion test, there was almost no change in weight and no change in appearance, confirming that the curing reaction by cross-linking had progressed sufficiently. Td5 was 466 ° C, tensile properties were elastic modulus 1.03 GPa, maximum point stress 25.7 MPa, elongation at break 10.2%. The total light transmittance was 92%.
  • This curable composition was poured into a mold produced in the same manner as in Example 1. Next, the curable composition was cured by holding in a constant temperature bath at 120 ° C for 90 minutes and then holding at 200 ° C for 30 minutes. The obtained cured product was a colorless and transparent sheet. In the caseon immersion test, there was almost no change in weight and no change in appearance, confirming that the curing reaction by cross-linking had progressed sufficiently. Td5 was 457 ° C, tensile properties were elastic modulus 1.26 GPa, maximum point stress 24. OMPa, elongation at break 12.5%. The total light transmittance was 92%.
  • the curable composition was cured by holding in a constant temperature bath at 120 ° C for 90 minutes and then holding at 200 ° C for 30 minutes.
  • the obtained cured product was a colorless and transparent sheet.
  • Td5 was 467 ° C
  • tensile properties were elastic modulus 1.08 GPa, maximum point stress 24.
  • OMPa elongation at break 3.1%.
  • the total light transmittance was 93%.

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Abstract

La présente invention concerne des silsesquioxanes durcis dont les caractéristiques de résistance à la chaleur et de transparence sont excellentes. Les silsesquioxanes durcis sont obtenus par soumission d'une préparation qui comprend (a) un oligomère de silsesquioxane synthétisé à partir d'au moins un élément sélectionné parmi les silsesquioxanes cages portant des substituants contenant des doubles liaisons carbone-carbone et des structures dérivées des silsesquioxanes cages par clivage partiel, (b) un composé comportant au moins deux groupements SiH par molécule, et (c) un composé comportant au moins deux doubles liaisons carbone-carbone par molécule à l'exception du composant (a) à une réaction en présence de (d) un catalyseur d'hydrosilylation.
PCT/JP2007/057285 2006-04-10 2007-03-30 Formule durcissable, silsesquioxanes durcis, et leurs procédés de production Ceased WO2007119627A1 (fr)

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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08225647A (ja) * 1994-12-01 1996-09-03 Kanegafuchi Chem Ind Co Ltd 硬化性組成物及びそれを用いた成形体の作製方法
JPH1171462A (ja) * 1997-08-29 1999-03-16 Toshiba Silicone Co Ltd 新規な含ケイ素重合体
JP2000154252A (ja) * 1998-11-18 2000-06-06 Agency Of Ind Science & Technol 新型含シルセスキオキサンポリマー及びその製造方法
JP2000265066A (ja) * 1999-03-17 2000-09-26 Dow Corning Asia Ltd 有機溶剤可溶性の水素化オクタシルセスキオキサン−ビニル基含有化合物共重合体及び同共重合体からなる絶縁材料
JP2002194122A (ja) * 2000-12-25 2002-07-10 Kanegafuchi Chem Ind Co Ltd シルセスキオキサンポリマーおよびポリカルボシラン複合系プリプレグ及びそれを用いた積層板
JP2002363414A (ja) * 2001-06-12 2002-12-18 Asahi Kasei Corp 籠状シルセスキオキサン含有組成物
JP2003137944A (ja) * 2001-11-05 2003-05-14 Nippon Steel Chem Co Ltd シリコーン樹脂組成物及びシリコーン樹脂成形体
JP2004123936A (ja) * 2002-10-03 2004-04-22 Nippon Steel Chem Co Ltd シリコーン樹脂組成物及びシリコーン樹脂成形体
JP2005290352A (ja) * 2004-03-12 2005-10-20 Asahi Kasei Corp カゴ状シルセスキオキサン構造を有する化合物
JP2005343984A (ja) * 2004-06-02 2005-12-15 Kaneka Corp 硬化性組成物及び該硬化性組成物により封止された半導体装置
JP2006022207A (ja) * 2004-07-08 2006-01-26 Chisso Corp ケイ素化合物
JP2007031619A (ja) * 2005-07-28 2007-02-08 Nagase Chemtex Corp 光素子封止用樹脂組成物

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006299150A (ja) * 2005-04-22 2006-11-02 Asahi Kasei Corp 封止材用組成物及び光学デバイス
JP2006299149A (ja) * 2005-04-22 2006-11-02 Asahi Kasei Corp 封止材用組成物及び光学デバイス

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08225647A (ja) * 1994-12-01 1996-09-03 Kanegafuchi Chem Ind Co Ltd 硬化性組成物及びそれを用いた成形体の作製方法
JPH1171462A (ja) * 1997-08-29 1999-03-16 Toshiba Silicone Co Ltd 新規な含ケイ素重合体
JP2000154252A (ja) * 1998-11-18 2000-06-06 Agency Of Ind Science & Technol 新型含シルセスキオキサンポリマー及びその製造方法
JP2000265066A (ja) * 1999-03-17 2000-09-26 Dow Corning Asia Ltd 有機溶剤可溶性の水素化オクタシルセスキオキサン−ビニル基含有化合物共重合体及び同共重合体からなる絶縁材料
JP2002194122A (ja) * 2000-12-25 2002-07-10 Kanegafuchi Chem Ind Co Ltd シルセスキオキサンポリマーおよびポリカルボシラン複合系プリプレグ及びそれを用いた積層板
JP2002363414A (ja) * 2001-06-12 2002-12-18 Asahi Kasei Corp 籠状シルセスキオキサン含有組成物
JP2003137944A (ja) * 2001-11-05 2003-05-14 Nippon Steel Chem Co Ltd シリコーン樹脂組成物及びシリコーン樹脂成形体
JP2004123936A (ja) * 2002-10-03 2004-04-22 Nippon Steel Chem Co Ltd シリコーン樹脂組成物及びシリコーン樹脂成形体
JP2005290352A (ja) * 2004-03-12 2005-10-20 Asahi Kasei Corp カゴ状シルセスキオキサン構造を有する化合物
JP2005343984A (ja) * 2004-06-02 2005-12-15 Kaneka Corp 硬化性組成物及び該硬化性組成物により封止された半導体装置
JP2006022207A (ja) * 2004-07-08 2006-01-26 Chisso Corp ケイ素化合物
JP2007031619A (ja) * 2005-07-28 2007-02-08 Nagase Chemtex Corp 光素子封止用樹脂組成物

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008065967A1 (fr) * 2006-11-27 2008-06-05 Panasonic Electric Works Co., Ltd. Dispositif optique semi-conducteur et élément optique transparent
JPWO2008065966A1 (ja) * 2006-11-27 2010-03-04 パナソニック電工株式会社 半導体光装置及び透明光学部材
WO2008065966A1 (fr) * 2006-11-27 2008-06-05 Panasonic Electric Works Co., Ltd. Dispositif optique semi-conducteur et élément optique transparent
JP2009109579A (ja) * 2007-10-26 2009-05-21 Nippon Steel Chem Co Ltd 耐熱性複合型レンズ
TWI459020B (zh) * 2007-10-26 2014-11-01 Nippon Steel & Sumikin Chem Co A method for manufacturing a heat resistant composite lens
WO2009119253A1 (fr) * 2008-03-28 2009-10-01 新日鐵化学株式会社 Composé silsesquioxane de type cage, durcissable, contenant un groupe silanol, copolymère de silicone durcissable, contenant une structure en cage, leurs procédés de production, et composition de résine durcissable
JP2009270067A (ja) * 2008-05-09 2009-11-19 Tohoku Univ 光硬化型組成物、硬化物および光硬化型樹脂フィルム
CN102449034B (zh) * 2009-06-02 2013-06-19 Jnc株式会社 有机硅化合物、含有该有机硅化合物的热硬化性组成物及光半导体用密封材料
WO2010140635A1 (fr) * 2009-06-02 2010-12-09 チッソ株式会社 Composé organopolysiloxane, composition thermodurcissable contenant ledit composé organopolysiloxane et matériau d'étanchéité pour semi-conducteur optique
JP2010280766A (ja) * 2009-06-02 2010-12-16 Chisso Corp 有機ケイ素化合物、該有機ケイ素化合物を含む熱硬化性組成物、および光半導体用封止材料
CN102449034A (zh) * 2009-06-02 2012-05-09 Jnc株式会社 有机硅化合物、含有该有机硅化合物的热硬化性组成物及光半导体用密封材料
JP2011068753A (ja) * 2009-09-25 2011-04-07 Kaneka Corp 多面体構造ポリシロキサン系変性体及び組成物
JP5844252B2 (ja) * 2010-04-02 2016-01-13 株式会社カネカ 硬化性樹脂組成物、硬化性樹脂組成物タブレット、成形体、半導体のパッケージ、半導体部品及び発光ダイオード
US9178120B2 (en) 2010-04-02 2015-11-03 Kaneka Corporation Curable resin composition, curable resin composition tablet, molded body, semiconductor package, semiconductor component and light emitting diode
US9496468B2 (en) 2010-04-02 2016-11-15 Kaneka Corporation Curable resin composition, curable resin composition tablet, molded body, semiconductor package, semiconductor component and light emitting diode
JPWO2011145638A1 (ja) * 2010-05-18 2013-07-22 Jnc株式会社 新規有機ケイ素化合物、該有機ケイ素化合物を含む熱硬化性樹脂組成物、硬化樹脂および光半導体用封止材料
WO2011145638A1 (fr) * 2010-05-18 2011-11-24 Jnc株式会社 Nouveau composé organique du silicium et composition de résine thermodurcissable, résine durcie et matériau d'étanchéité pour semi-conducteur contenant ledit composé organique du silicium
JP2012131935A (ja) * 2010-12-22 2012-07-12 Kaneka Corp オルガノポリシロキサン系組成物および硬化物
JP2012144607A (ja) * 2011-01-11 2012-08-02 Kaneka Corp オルガノポリシロキサン系組成物および硬化物。
JP2013057031A (ja) * 2011-09-09 2013-03-28 Kaneka Corp オルガノポリシロキサン系組成物および硬化物
WO2013094585A1 (fr) * 2011-12-22 2013-06-27 新日鐵住金化学株式会社 Substrat de résine composite avec fibres de verre
WO2014061517A1 (fr) * 2012-10-18 2014-04-24 セントラル硝子株式会社 Composition durcissable contenant des particules de silice, son produit durci et matière de scellement étanche de semi-conducteur l'utilisant
KR20140056029A (ko) * 2012-10-29 2014-05-09 신에쓰 가가꾸 고교 가부시끼가이샤 실리콘 수지 조성물, 및 이것을 이용한 실리콘 적층 기판과 그의 제조 방법 및 ｌｅｄ 장치
US9163144B2 (en) 2012-10-29 2015-10-20 Shin-Etsu Chemical Co., Ltd. Silicone resin composition, silicone laminated substrate using the same, method for producing the same, and LED device
JP2014088459A (ja) * 2012-10-29 2014-05-15 Shin Etsu Chem Co Ltd シリコーン樹脂組成物、並びにこれを用いたシリコーン積層基板とその製造方法、及びｌｅｄ装置
KR102082014B1 (ko) * 2012-10-29 2020-02-26 신에쓰 가가꾸 고교 가부시끼가이샤 실리콘 수지 조성물, 및 이것을 이용한 실리콘 적층 기판과 그의 제조 방법 및 ｌｅｄ 장치
JP2015034303A (ja) * 2014-11-18 2015-02-19 株式会社カネカ オルガノポリシロキサン系組成物および硬化物
WO2016170771A1 (fr) * 2015-04-24 2016-10-27 日本曹達株式会社 Composition pour la formation d'un composite organique-inorganique
CN111093963A (zh) * 2015-06-17 2020-05-01 株式会社大赛璐 成形体
CN111093963B (zh) * 2015-06-17 2022-02-25 株式会社大赛璐 成形体
JP2021504507A (ja) * 2017-12-01 2021-02-15 メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ ポリシロキサン、これを含んでなる組成物、およびこれを用いた硬化膜
JP7500423B2 (ja) 2017-12-01 2024-06-17 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング ポリシロキサン、これを含んでなる組成物、およびこれを用いた硬化膜
CN111788254A (zh) * 2018-02-20 2020-10-16 捷恩智株式会社 液状有机硅化合物及掺合所述化合物的热硬化性树脂组合物

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