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WO2014136806A1 - Organopolysiloxane et procédé de fabrication correspondant - Google Patents

Organopolysiloxane et procédé de fabrication correspondant Download PDF

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Publication number
WO2014136806A1
WO2014136806A1 PCT/JP2014/055531 JP2014055531W WO2014136806A1 WO 2014136806 A1 WO2014136806 A1 WO 2014136806A1 JP 2014055531 W JP2014055531 W JP 2014055531W WO 2014136806 A1 WO2014136806 A1 WO 2014136806A1
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WIPO (PCT)
Prior art keywords
group
organopolysiloxane
carbon atoms
containing organic
general formula
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English (en)
Inventor
Yoshitsugu Morita
Satoshi Onodera
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DuPont Toray Specialty Materials KK
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Dow Corning Toray Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the present invention relates to an organopolysiloxane containing epoxy group-containing organic groups, and condensed polycyclic aromatic groups or condensed polycyclic aromatic group- containing organic groups, and a manufacturing method thereof.
  • Organopolysiloxanes comprising any combination of siloxane units (M units) represented by the general formula: R 3 SiOi 2 , siloxane units (D units) represented by the general formula: R 2 Si0 2/2 , siloxane units (T units) represented by the general formula: PvSi0 3/2 , and siloxane units (Q units) represented by the formula: SiC>4/ 2 (in the formulas, R are the same or different monovalent hydrocarbon groups) are used as optical materials, such as sealing agents for LEDs and lens-molding materials, due to their excellent heat resistance, light resistance, and transparency. In these applications, organopolysiloxanes having high refractive indices are particularly preferred.
  • Patent Document 1 discloses hydrolyzing and condensation reacting di(l -naphthyl)dimethoxysilane or 1 -naphthylmethyl dimethoxysilane, and 3- glycidoxypropyl trimethoxysilane or 3-glycidoxypropyl methyldimethoxysilane.
  • Patent Document 2 discloses hydrolyzing and condensation reacting 9- phenanthrene triethoxysilane, 3-glycidoxypropyl trimethoxysilane, and methyl
  • triethoxysilane and hydrolyzing and condensation reacting 1 ⁇ naphthyl triethoxysilane, 3- glycidoxypropyl trimethoxysilane, and triethoxysilane.
  • the organopolysiloxane prepared in Patent Document 1 contains a condensed polycyclic aromatic group such as a naphthyl group in a D unit, and an epoxy group-containing organic group in another D unit or in a T unit.
  • a condensed polycyclic aromatic group such as a naphthyl group in a D unit
  • an epoxy group-containing organic group in another D unit or in a T unit.
  • Such an organopolysiloxane has a large degree of molecular weight dispersity, and there is a problem that a cured product obtained by curing this organopolysiloxane has significantly low elastic modulus.
  • the organopolysiloxane prepared in Patent Document 2 contains a condensed polycyclic aromatic group such as a naphthyl group in a T unit, and an epoxy group-containing organic group in another T unit. Although such an organopolysiloxane has a small degree of molecular weight dispersity, there is a problem that a cured product obtained by curing this organopolysiloxane has significantly high elastic modulus.
  • a condensed polycyclic aromatic group such as a naphthyl group in a T unit
  • an epoxy group-containing organic group in another T unit.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2010- 007057A
  • Patent Document 2 Japanese Unexamined Patent Application Publication (Translation of PCT Application) No. 201 1-504958A
  • An object of the present invention is to provide an organopolysiloxane that has a high refractive index, and is monodispersed and curable to form a cured product having an adequate elastic modulus, and also to provide a manufacturing method thereof.
  • organopolysiloxane of the present invention is represented by the following average unit formula:
  • R 1 is an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 2 to 12 carbon atoms, or a phenyl group
  • R 2 is an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 2 to 12 carbon atoms, a phenyl group, or an epoxy group-containing organic group, provided that at least one R in a molecule is the epoxy group-containing organic group
  • R is a condensed polycyclic aromatic group or a condensed polycyclic aromatic group-containing organic group
  • X is an alkyl group having from 1 to 3 carbon atoms or a hydrogen atom, a is a number from 0.20 to 0.60, b is a number from 0.40 to 0.80, a sum of a and b is 1.00, and c is a number from 0 to 0.5.
  • the epoxy group-containing organic group for R 2 is preferably a glycidoxyalkyl group, an epoxycyclohexyl alkyl group, or an oxiranylalkyl group, and R 3 is preferably a naphthyl group or a naphthyl ethyl group. Furthermore, at least 10 mol%
  • R' and R in a molecule are preferably epoxy group-containing organic groups.
  • the manufacturing method of the present invention is a manufacturing method of the organopolysiloxane described above.
  • the manufacturing method comprises a step of, in the presence of an acid or an alkali, hydrolyzing and condensation reacting:
  • R 1 is an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 2 to 12 carbon atoms, or a phenyl group
  • R 4 is an epoxy group-containing organic group
  • Y is a hydrolysable group
  • R 1 and R 4 are synonymous with those described above, and m is an integer from 1 to 100;
  • R 1 and Y are synonymous with those described above;
  • R 3 is a condensed polycyclic aromatic group or a condensed polycyclic aromatic group-containing organic group, and Y is synonymous with those described above.
  • R 4 is preferably a glycidoxyalkyl group, an epoxycyclohexyl alkyl group, or an oxiranylalkyl group.
  • R 3 is preferably a naphthyl group or a naphthyl ethyl group.
  • the organopolysiloxane of the present invention is characterized by having a high refractive index, and being monodispersed and curable to form a cured product having an adequate elastic modulus.
  • the manufacturing method of the present invention is characterized by being able to efficiently manufacture such an
  • organopolysiloxane of the present invention is represented by the following average unit formula:
  • R 1 is an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 2 to 12 carbon atoms, or a phenyl group.
  • the alkyl group for R 1 include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a cyclopentyl group, and a cyclooctyl group. Of these, a methyl group is preferable.
  • Examples of the alkenyl group for R 1 include a vinyl group, an allyl group, and a butenyl group. Of these, a vinyl group is preferable.
  • R 2 is an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 2 to 12 carbon atoms, a phenyl group, or an epoxy group- containing organic group.
  • alkyl group for R include the same groups described for R 1 . Of these, a methyl group is preferable.
  • alkenyl group for R 2 include the same groups described for R 1 . Of these, a vinyl group is preferable.
  • Examples of the epoxy group-containing organic group for R 2 include glycidoxyalkyl groups such as a 2-glycidoxyethyl group, a 3-glycidoxypropyl group, and a 4- glycidoxybutyl group; epoxycycloalkylalkyl groups such as a 2-(3,4-epoxycyclohexyl) ethyl group, a 3-(3,4-epoxycyclohexyl)propyl group, a 2-(3,4-epoxynorbornyl)ethyl group, and a 2-(3,4-epoxy-3-methylcyclohexyl)-2-methylethyl group; and oxiranylalkyl groups such as a 4-oxiranylbutyl group and an 8-oxiranyloctyl group.
  • a glycidoxyalkyl group is preferable, and a 3-glycidoxypropyl group is particularly preferable.
  • R 2 are epoxy group-containing organic groups.
  • the proportion of the epoxy group-containing organic groups relative to all of R and R in a molecule is preferably at least 10 mol%, and more preferably at least 15 mol%.
  • R 3 is a condensed polycyclic aromatic group or a condensed polycyclic aromatic group-containing organic group.
  • the condensed polycyclic aromatic group for R include a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, and such condensed polycyclic aromatic groups where a hydrogen atom is replaced by an alkyl group such as a methyl group or an ethyl group; by an alkoxy group such as a methoxy group or an ethoxy group; or by a halogen atom such as a chlorine atom or a bromine atom.
  • a naphthyl group is preferable.
  • Examples of the condensed polycyclic aromatic group-containing organic group for R 3 include condensed polycyclic aromatic group-containing alkyl groups such as a naphthyl ethyl group, a naphthyl propyl group, an anthracenyl ethyl group, a phenanthryl ethyl group, and a pyrenyl ethyl group; and such condensed polycyclic aromatic groups where a hydrogen atom is replaced by an alkyl group such as a methyl group or an ethyl group; by an alkoxy group such as a methoxy group or an ethoxy group; or by a halogen atom such as a chlorine atom or a bromine atom.
  • condensed polycyclic aromatic group-containing alkyl groups such as a naphthyl ethyl group, a naphthyl propyl group, an anthracenyl ethyl group, a phenanth
  • the condensed polycyclic aromatic group- containing organic group for R 3 is preferably the condensed polycyclic aromatic group- containing alkyl groups, and particularly preferably a naphthyl ethyl group.
  • An organopolysiloxane containing a condensed polycyclic aromatic group-containing alkyl group as R 3 has relatively low viscosity, and thus the viscosity of the curable silicone composition containing the organopolysiloxane as a main component can be lowered.
  • X is an alkyl group having from 1 to 3 carbon atoms or a hydrogen atom.
  • alkyl group for X include a methyl group, an ethyl group, and a propyl group. Of these, a methyl group is preferable.
  • a indicates a proportion of D units and is a number from 0.20 to 0.60
  • b indicates a proportion of T units and is a number from 0.40 to 0.80. Note that the sum of a and b is 1.00. This is because, when the value of a is greater than or equal to the lower limit of the range described above, the cured product of the organopolysiloxane will exhibit a good elastic modulus, and when the value of a is less than or equal to the upper limit of the range described above, the organopolysiloxane will exhibit a high refractive index and become monodispersed.
  • c indicates a proportion of a unit represented by the formula: XOi 2 that is formed in the course of manufacturing the organopolysiloxane of the present invention, and is a number from 0 to 0.5. This is because when the value of c is less than or equal to the upper limit of the range described above, stability of the organopolysiloxane itself will be enhanced.
  • the above units are preferably contained in the
  • organopolysiloxane because the adhesive properties of a curable silicone composition containing, as a main component, the organopolysiloxane of the present invention can be enhanced, and/or the bonding properties toward substrates of the cured product of the curable silicone composition can be enhanced.
  • the molecular weight of this type of organopolysiloxane of the present invention is not particularly limited, but from the perspectives of excellent
  • the weight average molecular weight in terms of standard polystyrene, as measured by gel permeation chromatography, is preferably in a range of 400 to 5,000, more preferably in a range of 500 to 3,000, and particularly preferably in a range of 1 ,000 to 2,000.
  • a form of such an organopolysiloxane of the present invention at 25°C is not particularly limited, and examples of the form include oillike, paste-like, resin-like, gum-like, and solid (powder).
  • the refractive index at 25°C and at a wavelength of 632.8 nm of the organopolysiloxane of the present invention is preferably greater than or equal to 1.50, and particularly preferably greater than or equal to 1.53.
  • a curable silicone composition can be formed by compounding a curing agent and a curing accelerator in the organopolysiloxane of the present invention.
  • the curing agent is not particularly limited as long as the curing agent reacts with an epoxy group in the organopolysiloxane of the present invention to cure.
  • the curing agent examples include phenol resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromo bisphenol A, tetrachloro bisphenol A, tetrafluoro bisphenol A, biphenol, dihydroxynaphthalene, l ,l ,l-tris(4- hydroxyphenyl)methane, 4,4-( 1 -(4-( 1 -(4-hydroxyphenyl)- 1 - methylethyl)phenyl)ethylidene)bisphenol, phenolnovolac, cresolnovolac, bisphenol A novolac, bromophenol novolac, and bromo bisphenol A novolac; polyols that have hydrogenated aromatic rings of these phenol resins; alicyclic acid anhydrides such as polyazelaic anhydride,
  • 3-methyl glutaric acid anhydride 2,3-dialkyl glutaric acid anhydride that may be branched and contains an alkyl group having from 1 to 8 carbon atoms (e.g. 2- ethyl-3 -propyl glutaric acid anhydride), and 2,4-dialkyl glutaric acid anhydride that may be branched and contains an alkyl group having from 1 to 8 carbon atoms (e.g. 2,4-diethyl glutaric acid anhydride and 2,4-dimethyl glutaric acid anhydride); and aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride.
  • aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride.
  • the compounded amount of the curing agent is not particularly limited, the compounded amount is preferably in a range of 1 to 200 parts by weight, and particularly preferably in a range of 20 to 160 parts by weight, per 100 parts by weight of the organopolysiloxane of the present invention because the organopolysiloxane of the present invention can be sufficiently cured and the resulting cured product exhibits good heat resistance and weather resistance.
  • the curing accelerator is not particularly limited as long as the curing accelerator accelerates the curing reaction between the curing agent and the
  • the curing accelerators include aliphatic amines such as ethylene diamine, Methylene pentamine, hexamethylene diamine, dimer acid-modified ethylenediamine, N-ethylamino piperazine, and isophoronediamine; aromatic amines such as m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylmethane, and 4,4'- diaminodiphenylether; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole; tertiary amines such as dimethyl benzylamine l ,8-diazabicyclo
  • the compounded amount of the curing accelerator is not particularly limited, the compounded amount is preferably in a range of 0.01 to 5 parts by weight, and particularly preferably in a range of 0.1 to 5 parts by weight, per 100 parts by weight of the organopolysiloxane of the present invention because the curing of the organopolysiloxane of the present invention can be sufficiently accelerated and the resulting cured product exhibits good heat resistance and weather resistance.
  • epoxy compounds such as 3',4'- epoxycyclohexylmethyl-3 ,4-epoxycyclohexane carboxylate, bis(3 ,4- epoxycyclohexylmethyl)adipate, vinylcyclohexene dioxide, and hydrogenated bisphenol A diglycidylether may be compounded in the curable silicone composition containing as a main component the organopolysiloxane of the present invention.
  • the compounded amount of the epoxy compound is not particularly limited, the compounded amount is preferably not greater than 200 parts by weight, and particularly preferably not greater than 100 parts by weight, per 100 parts by weight of the organopolysiloxane of the present invention.
  • the organopolysiloxane of the present invention can be cured to form a cured product that is transparent and has a high refractive index and an adequate elastic modulus.
  • the elastic modulus of the cured product is not particularly limited, for example, the storage elastic modulus is preferably in a range of 1 to 50 MPa.
  • R 1 is an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 2 to 12 carbon atoms, or a phenyl group, and examples thereof are synonymous with the groups described above. Of these, a methyl group is preferable.
  • examples of the epoxy group-containing organic group for R 4 include glycidoxyalkyl groups such as a 2-glycidoxyethyl group, a 3-glycidoxypropyl group, and a 4-glycidoxybutyl group; epoxycycloalkylalkyl groups such as a 2-(3,4- epoxycyclohexyl) ethyl group, a 3-(3,4-epoxycyclohexyl)propyl group, a 2-(3,4- epoxynorbornyl)ethyl group, and a 2-(3,4-epoxy-3-methylcyclohexyl)-2-methylethyl group; and oxiranylalkyl groups such as a 4-oxiranylbutyl group and an 8-oxiranyloctyl group.
  • a glycidoxyalkyl group is preferable, and a 3-glycidoxypropyl group is particularly preferable.
  • Y is a hydrolysable group, and examples thereof include an alkoxy group, an acyloxy group, and a halogen atom.
  • alkoxy group for Y include a methoxy group, an ethoxy group, and a propoxy group.
  • examples of the acyloxy group for Y include an acetoxy group.
  • examples of the halogen atom for Y include a chlorine atom and a bromine atom.
  • Examples of such a silane compound include 3-glycidoxypropyl
  • methyldiacetoxysilane 3-glycidoxypropyl methyldichlorosilane, 3-glycidoxypropyl ethyldichlorosilane, and 2-(3,4-epoxycyclohexyl)ethyl methyldichlorosilane.
  • R 1 is an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 2 to 12 carbon atoms, or a phenyl group, and examples thereof are synonymous with the groups described above. Of these, a methyl group is preferable.
  • R 4 is an epoxy group-containing organic group, and examples thereof are synonymous with the groups described above. Of these, a glycidoxyalkyl group is preferable, and particularly a 3-glycidoxypropyl group is preferable.
  • m is an integer from 1 to 100, preferably an integer from 1 to 50, and particularly preferably an integer from 1 to 20.
  • R 1 is an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 2 to 12 carbon atoms, or a phenyl group, and examples thereof are synonymous with the groups described above. Of these, a methyl group is preferable. Also, Y is a hydrolysable group, and examples thereof are synonymous with the groups described above.
  • Examples of such a silane compound include dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylethyldimethoxysilane, ethylphenyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethyldiacetoxysilane, methylphenyldiacetoxysilane, ethylphenyldiacetoxysilane, diphenyldiacetoxysilane, dimethyldichlorosilane,
  • R 1 is an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 2 to 12 carbon atoms, or a phenyl group, and examples thereof are synonymous with the groups described above. Of these, a methyl group is preferable. Also, in the formula, n is an integer from 1 to 100, preferably an integer from 1 to 50, and particularly preferably an integer from 1 to 20.
  • R 3 is a condensed polycyclic aromatic group or a condensed polycyclic aromatic group-containing organic group, and examples thereof are
  • Y is a hydrolysable group, and examples thereof are synonymous with the groups described above.
  • Examples of such a silane compound include naphthyl trimethoxy silane, anthracenyl trimethoxysilane, phenanthryl trimethoxysilane, pyrenyl trimethoxysilane, naphthyl triethoxysilane, anthracenyl triethoxysilane, phenanthryl triethoxysilane, pyrenyl triethoxysilane, naphthyl ethyl trimethoxysilane, naphthyl propyl trimethoxysilane, anthracenyl ethyl trimethoxysilane, naphthyl triacetoxysilane, anthracenyl triacetoxysilane, phenanthryl triacetoxysilane, pyrenyl triacetoxysilane, naphthyl trichlorosilane, anthracenyl trichlorosilane, phen
  • the manufacturing method of the present invention is characterized by, in the presence of an acid or an alkali, hydrolyzing and condensation reacting the silane compound represented by the general formula (I) and/or the siloxane compound
  • silane compound represented by the general formula (II) and optionally, the silane compound represented by the general formula (III) and/or the siloxane compound represented by the general formula (IV), with the silane compound represented by the general formula (V).
  • the compounding amount of each of the raw materials is such that the proportion of the D unit introduced to the resulting organopolysiloxane (by using the silane compound represented by the general formula (I) and/or the siloxane compound represented by the general formula (II), and optionally, the silane compound represented by the general formula (III) and/or the siloxane compound represented by the general formula (IV) as raw materials) will be a number from 0.20 to 0.60, and that the proportion of the T unit introduced to the resulting organopolysiloxane (by using the silane compound represented by the general formula (V) as a raw material) will be a number from 0.40 to 0.80.
  • the proportion of the silane compound represented by the general formula (I) or the siloxane compound represented by the general formula (II), and the optionally used silane compound represented by the general formula (III) or siloxane compound represented by the general formula (IV), for introducing the D unit is not particularly limited.
  • the proportion of these compounds are at an amount where the proportion of R 4 to all of R 1 and R 4 will be preferably at least 10 mol%, and more preferably will be at least 15 mol%.
  • Examples of the acid that can be used in the manufacturing method of the present invention include hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acid,
  • examples of the alkali that can be used in the manufacturing method of the present invention include inorganic alkalis such as potassium hydroxide, sodium hydroxide, and cesium hydroxide; and organic base compounds such as triethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, ammonia water, tetramethylammonium hydroxide, alkoxysilanes having an amino group, and aminopropyltrimethoxysilane.
  • inorganic alkalis such as potassium hydroxide, sodium hydroxide, and cesium hydroxide
  • organic base compounds such as triethylamine, diethylamine, monoethanolamine, diethanolamine, triethanolamine, ammonia water, tetramethylammonium hydroxide, alkoxysilanes having an amino group, and aminopropyltrimethoxysilane.
  • an organic solvent may be used.
  • the organic solvent include ethers, ketones, acetates, aromatic or aliphatic hydrocarbons, and 3-butyrolactone; and mixtures of two or more types of such solvents.
  • the organic solvents are exemplified by propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, 3-butyrolactone, toluene, and xylene.
  • water or a mixed solution of water and an alcohol is preferably added.
  • Preferred examples of the alcohol include methanol and ethanol. If an organic solvent is used and this reaction is accelerated by heating, the reaction is preferably performed at the reflux temperature of the organic solvent.
  • organopolysiloxane and the manufacturing method thereof of the present invention will now be described in greater detail using Examples.
  • Me in the formulas is a methyl group
  • Ph in the formulas is a phenyl group
  • Naph in the formulas is a 1-naphthyl group
  • Ep in the formulas is a 3-glycidoxypropyl group.
  • the characteristics of the organopolysiloxane were evaluated as follows.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene of the organopolysiloxane were determined by gel permeation chromatography using an RI detector.
  • the dispersity (Mw/Mn) was determined from these values.
  • the refractive index of the organopolysiloxane at 25°C was measured using an
  • the viscosity at 25°C of the organopolysiloxane was measured using a rotational viscometer VG-DA (manufactured by Shibaura System Co., Ltd.).
  • the methoxy group content (% by weight) in the organopolysiloxane was determined.
  • the characteristics of the curable silicone composition containing the organopolysiloxane as a main component, and a curing agent and a curing accelerator compounded thereto, and the characteristics of the cured product thereof were evaluated as follows.
  • the viscosity at 25 °C of the curable silicone composition was measured using an AR 500 (manufactured by TA Instruments). Note that the viscosity was measured using a cone having a cone diameter of 20 mm, and a cone angle of 2° at 20 s "1 .
  • the curable silicone composition was heated for one hour at 150°C to produce a film-like cured product having a 0.5 mm thickness.
  • an MCR 301 Rheometer manufactured by Anton Paar GmbH
  • the 0.5 mm thick film sample was sandwiched between parallel plates having diameters of 8 mm, and the storage elastic modulus value at 25°C was measured by applying the following conditions: strain: 0.1%; frequency: 1 Hz; normal force: constant pressure of 5 N; and the temperature was raised at a rate of 3°C/min from -10°C up to 50°C.
  • the refractive index at 25°C of the cured product prepared by the method described above was measured using a prism coupler method. A 632.8 nm laser light source was used for the measurement.
  • methyldimethoxysilane, and 47.49 g of toluene were placed in a reaction vessel provided with an agitator, a thermometer, a reflux tube, and a dropping funnel, and agitated.
  • a mixture of 0.07 g of 50% potassium hydroxide aqueous solution, 9.90 g of water, and 9.90 g of methanol was gradually added to the reaction vessel using the dropping funnel. After the addition was completed, the mixture was refluxed for one hour. Produced methanol and excess water were removed via azeotropic dehydration, and then the resulting product was reacted for eight hours in toluene at reflux. After cooling, the resulting product was neutralized using acetic acid. After the neutralized salt was filtered, toluene and low- boiling components were heated under reduced pressure to remove them by distillation. Thus, 47.00 g of transparent brown solid (at room temperature) was obtained.
  • the epoxy equivalent weight of the organopolysiloxane was 740 g/mol.
  • the methoxy group content of the organopolysiloxane was 0.8 % by weight.
  • the weight average molecular weight (Mw) was 1 ,400.
  • the dispersity (Mw/Mn) was 1.12.
  • the refractive index was 1 .615.
  • methyldimethoxysilane, and 53.03 g of toluene were placed in a reaction vessel provided with an agitator, a thermometer, a reflux tube, and a dropping funnel, and agitated.
  • a mixture of 0.07 g of 50% potassium hydroxide aqueous solution, 10.12 g of water, and 10.12 g of methanol was gradually added to the reaction vessel using the dropping funnel. After the addition was completed, the mixture was refluxed for one hour. Produced methanol and excess water were removed via azeotropic dehydration, and then the resulting product was reacted for eight hours in toluene at reflux. After cooling, the resulting product was neutralized using acetic acid. After the neutralized salt was filtered, toluene and low-boiling components were heated under reduced pressure to remove them by distillation. Thus, 53.70 g of transparent brown gum-like substance (at room temperature) was obtained.
  • the epoxy equivalent weight of the organopolysiloxane was 350 g/mol. Almost no methoxy group was observed, and the methoxy group content was less than 0.1 % by weight.
  • the weight average molecular weight (Mw) was 1,800.
  • methyldimethoxysilane, and 58.22 g of toluene were placed in a reaction vessel provided with an agitator, a thermometer, a reflux tube, and a dropping funnel, and agitated.
  • a mixture of 0.07 g of 50% potassium hydroxide aqueous solution, 4.73 g of water, and 4.73 g of methanol was gradually added to the reaction vessel using the dropping funnel. After the addition was completed, the mixture was refluxed for one hour. Produced methanol and excess water were removed via azeotropic dehydration, and then the resulting product was reacted for eight hours in toluene at reflux. After cooling, the resulting product was neutralized using acetic acid. After the neutralized salt was filtered, toluene and low- boiling components were heated under reduced pressure to remove them by distillation. Thus, 56.95 g of transparent yellow liquid with a viscosity of 1 ,600 mPa*s was obtained.
  • the epoxy equivalent weight of the organopolysiloxane was 370 g/mol.
  • the methoxy group content of the organopolysiloxane was 3.4 % by weight.
  • the weight average molecular weight (Mw) was 1 ,200.
  • the dispersity (Mw/Mn) was 1.26.
  • the refractive index was 1.543.
  • methyldimethoxysilane, and 47.49 g of toluene were placed in a reaction vessel provided with an agitator, a thermometer, a reflux tube, and a dropping funnel, and agitated.
  • a mixture of 0.10 g of cesium hydroxide monohydrate, 9.90 g of water, and 9.90 g of methanol was gradually added to the reaction vessel using the dropping funnel. After the addition was completed, the mixture was refluxed for one hour. Produced methanol and excess water were removed via azeotropic dehydration, and then the resulting product was reacted for eight hours in toluene at reflux. After cooling, the resulting product was neutralized using acetic acid. After the neutralized salt was filtered, toluene and low- boiling components were heated under reduced pressure to remove them by distillation. Thus, 48.77 g of transparent pale yellow liquid (at room temperature) was obtained.
  • the epoxy equivalent weight of the organopolysiloxane was 740 g/mol.
  • the methoxy group content of the organopolysiloxane was 0.1 % by weight.
  • the weight average molecular weight (Mw) was 1 ,300.
  • the dispersity (Mw/Mn) was 1.07.
  • the refractive index was 1.600.
  • methyldimethoxysilane, and 58.22 g of toluene were placed in a reaction vessel provided with an agitator, a thermometer, a reflux tube, and a dropping funnel, and agitated.
  • a mixture of 0.12 g of cesium hydroxide monohydrate, 4.73 g of water, and 4.73 g of methanol was gradually added to the reaction vessel using the dropping funnel. After the addition was completed, the mixture was refluxed for one hour. Produced methanol and excess water were removed via azeotropic dehydration, and then the resulting product was reacted for eight hours in toluene at reflux. After cooling, the resulting product was neutralized using acetic acid. After the neutralized salt was filtered, toluene and low- boiling components were heated under reduced pressure to remove them by distillation. Thus, 58.63 g of transparent yellow liquid with a viscosity of 800 mPa » s was obtained.
  • the epoxy equivalent weight of the organopolysiloxane was 360 g/mol.
  • the methoxy group content of the organopolysiloxane was 3.9 % by weight.
  • the weight average molecular weight (Mw) was 1 ,200.
  • the dispersity (Mw/Mn) was 1.27.
  • the refractive index was 1.539.
  • the epoxy equivalent weight of the organopolysiloxane was 2,100 g/mol. Almost no methoxy group was observed, and the methoxy group content was less than 0.1 % by weight.
  • the weight average molecular weight (Mw) was 1 ,300. The dispersity
  • the epoxy equivalent weight of the organopolysiloxane was 370 g/mol. Almost no methoxy group was observed, and the methoxy group content was less than 0.1 % by weight.
  • the weight average molecular weight (Mw) was 1 ,700.
  • methyldimethoxysilane, and 91.00 g of toluene were placed in a reaction vessel provided with an agitator, a thermometer, a reflux tube, and a dropping funnel, and agitated.
  • a mixture of 0.13 g of 50% potassium hydroxide aqueous solution, 20.25 g of water, and 20.25 g of methanol was gradually added to the reaction vessel using the dropping funnel. After the addition was completed, the mixture was refluxed for one hour. Produced methanol and excess water were removed via azeotropic dehydration, and then the resulting product was reacted for eight hours in toluene at reflux. After cooling, the resulting product was neutralized using acetic acid.
  • the epoxy equivalent weight of the organopolysiloxane was 300 g/mol. Almost no methoxy group was observed, and the methoxy group content was less than 0.1 % by weight.
  • the weight average molecular weight (Mw) was 2,600.
  • methyldimethoxysilane, and 101.35 g of toluene were placed in a reaction vessel provided with an agitator, a thermometer, a reflux tube, and a dropping funnel, and agitated.
  • a mixture of 0.13 g of 50% potassium hydroxide aqueous solution, 9.45 g of water, and 9.45 g of methanol was gradually added to the reaction vessel using the dropping funnel. After the addition was completed, the mixture was refluxed for one hour. Produced methanol and excess water were removed via azeotropic dehydration, and then the resulting product was reacted for eight hours in toluene at reflux. After cooling, the resulting product was neutralized using acetic acid.
  • the epoxy equivalent weight of the organopolysiloxane was 310 g/mol.
  • the methoxy group content of the organopolysiloxane was 4.1 % by weight.
  • the weight average molecular weight (Mw) was 1 ,400.
  • the dispersity (Mw/Mn) was 1.28.
  • the refractive index was 1.491.
  • trimethoxysilane, and 47.03 g of toluene were placed in a reaction vessel provided with an agitator, a thermometer, a reflux tube, and a dropping funnel, and agitated.
  • a mixture of 0.07 g of 50% potassium hydroxide aqueous solution, 10.80 g of water, and 10.80 g of methanol was gradually added to the reaction vessel using the dropping funnel. After the addition was completed, the mixture was refluxed for one hour. Produced methanol and excess water were removed via azeotropic dehydration, and then the resulting product was reacted for eight hours in toluene at reflux. After cooling, the resulting product was neutralized using acetic acid. After the neutralized salt was filtered, toluene and low- boiling components were heated under reduced pressure to remove them by distillation. Thus, 56.95 g of transparent pale yellow powder (at room temperature) was obtained.
  • the epoxy equivalent weight of the organopolysiloxane was 720 g/mol. Almost no methoxy group was observed, and the methoxy group content was less than 0.1 % by weight.
  • the weight average molecular weight (Mw) was 2,200.
  • the dispersity (Mw/Mn) was 1.37.
  • the refractive index was 1.623.
  • This curable silicone composition was coated on a quartz glass plate and cured by being heated for one hour at 150°C.
  • the obtained cured product was clear and colorless, and had a storage elastic modulus of 1.84 MPa and a refractive index of 1.5284.
  • This curable silicone composition was coated on a quartz glass plate. After the toluene was volatilized by air-drying for one day, the curable silicone composition was cured by being heated for one hour at 150°C. The obtained cured product was clear and colorless, and had a storage elastic modulus of 30.3 MPa and a refractive index of 1.5524.
  • This curable silicone composition was coated on a quartz glass plate. After the toluene was volatilized by air-drying for one day, the curable silicone composition was cured by being heated for one hour at 150°C. The obtained cured product was clear and colorless, and had a storage elastic modulus of 12.9 MPa and a refractive index of 1.5484.
  • This curable silicone composition was coated on a quartz glass plate. After the toluene was volatilized by air-drying for one day, the curable silicone composition was cured by being heated for one hour at 150°C. The obtained cured product was clear and colorless, and had a storage elastic modulus of 0.89 MPa and a refractive index of 1.5481.
  • This curable silicone composition was coated on a quartz glass plate and cured by being heated for one hour at 150°C.
  • the obtained cured product was clear and colorless, and had a storage elastic modulus of 8.0 MPa and a refractive index of 1.5073.
  • This curable silicone composition was coated on a quartz glass plate and cured by being heated for one hour at 150°C.
  • the obtained cured product was clear and colorless, and had a storage elastic modulus of 1 1.8 MPa and a refractive index of 1.5098.
  • This curable silicone composition was coated on a quartz glass plate. After the toluene was volatilized by air-drying for one day, the curable silicone composition was cured by being heated for one hour at 150°C. The obtained cured product was clear and colorless, and had a storage elastic modulus of 68.7 MPa and a refractive index of 1.6029.
  • the organopolysiloxane of the present invention is curable via the reaction of the epoxy group, and forms a cured product that is transparent and has a high refractive index and an adequate elastic modulus
  • the organopolysiloxane of the present invention is preferably used in optical materials such as resists, coatings, films, sheets, adhesives, coating materials, sealing materials, lenses, light guide plates, and optical waveguides, and particularly preferably used in sealing materials, coating agents, or adhesives for LED elements; coatings for electrodes or the like around an element; or lens forming materials.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne un organopolysiloxane représenté par la formule d'unité moyenne : (R1R2SiO2/2)a(R3SiO3/2)b(XO1/2)c,, dans laquelle R1 est un groupe alkyle ayant 1 à 12 atomes de carbone, un groupe alcényle ayant 2 à 12 atomes de carbone, ou un groupe phényle; R2 est un groupe alkyle ayant 1 à 12 atomes de carbone, un groupe alcényle ayant 2 à 12 atomes de carbone, un groupe phényle, ou un groupe organique contenant un groupe époxy, à condition qu'au moins un R2 dans une molécule est le groupe organique contenant un groupe époxy; R3 est un groupe aromatique polycyclique condensé ou un groupe organique contenant un groupe aromatique polycyclique condensé; X est un groupe alkyle ayant 1 à 3 atomes de carbone ou un atome d'hydrogène; a est un nombre compris entre 0,20 à 0,60, b est un nombre allant de 0,40 à 0,80, une somme de a et de b est égale à 1,00, et c est un nombre de 0 à 0,5. L'organopolysiloxane présente un indice de réfraction élevé, et est monodispersé et durcissable pour former un produit durci ayant un module d'élasticité adéquate.
PCT/JP2014/055531 2013-03-05 2014-02-26 Organopolysiloxane et procédé de fabrication correspondant Ceased WO2014136806A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110998445A (zh) * 2017-08-24 2020-04-10 陶氏环球技术有限责任公司 光波导制造方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6722129B2 (ja) * 2017-03-09 2020-07-15 信越化学工業株式会社 光半導体素子封止用エポキシ・シリコーンハイブリッド樹脂組成物及びこれを用いた光半導体装置
JP7401977B2 (ja) * 2019-03-28 2023-12-20 株式会社カネカ ポリオルガノシロキサン及びその製造方法、並びに塗料用組成物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010007057A (ja) 2008-05-30 2010-01-14 Toray Ind Inc シロキサン系樹脂組成物およびこれを用いた光学デバイス
JP2011504958A (ja) 2007-11-30 2011-02-17 ブラゴーン オサケ ユキチュア シロキサンポリマー組成物及びその使用方法
US20110160410A1 (en) * 2008-06-18 2011-06-30 Takashi Sagawa Curable Organopolysiloxane Composition and Semiconductor Device
US20120178022A1 (en) * 2009-09-29 2012-07-12 Masao Kamogawa Positive photosensitive resin composition, cured film obtained using same, and optical device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011504958A (ja) 2007-11-30 2011-02-17 ブラゴーン オサケ ユキチュア シロキサンポリマー組成物及びその使用方法
JP2010007057A (ja) 2008-05-30 2010-01-14 Toray Ind Inc シロキサン系樹脂組成物およびこれを用いた光学デバイス
US20110160410A1 (en) * 2008-06-18 2011-06-30 Takashi Sagawa Curable Organopolysiloxane Composition and Semiconductor Device
US20120178022A1 (en) * 2009-09-29 2012-07-12 Masao Kamogawa Positive photosensitive resin composition, cured film obtained using same, and optical device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Silicones", 15 April 2003, ENCYCLOPEDIA OF POLYMER SCIENCE AND TECHNOLOGY, WILEY, US, PAGE(S) 765 - 841, XP007918236 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110998445A (zh) * 2017-08-24 2020-04-10 陶氏环球技术有限责任公司 光波导制造方法
CN110998445B (zh) * 2017-08-24 2023-07-07 陶氏环球技术有限责任公司 光波导制造方法

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