WO2012169237A1 - Composition composite de particules d'oxyde inorganiques et de résine de silicone et matière composite transparente - Google Patents

Composition composite de particules d'oxyde inorganiques et de résine de silicone et matière composite transparente Download PDF

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WO2012169237A1
WO2012169237A1 PCT/JP2012/055066 JP2012055066W WO2012169237A1 WO 2012169237 A1 WO2012169237 A1 WO 2012169237A1 JP 2012055066 W JP2012055066 W JP 2012055066W WO 2012169237 A1 WO2012169237 A1 WO 2012169237A1
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inorganic oxide
oxide particles
silicone resin
silicone
modified
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PCT/JP2012/055066
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English (en)
Japanese (ja)
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大塚　剛史
佐藤　洋一
恭行 栗野
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住友大阪セメント株式会社
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Priority to CN201280027849.7A priority Critical patent/CN103597034B/zh
Priority to KR1020137032472A priority patent/KR101596378B1/ko
Publication of WO2012169237A1 publication Critical patent/WO2012169237A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the present invention relates to a composite composition of inorganic oxide particles and a silicone resin, and a transparent composite.
  • silicone resins have excellent weather resistance such as heat resistance and cold resistance, as well as excellent electrical properties and low toxicity, so they range from cosmetic materials and medical materials to electrical and electronic materials. Used throughout. In recent years, attention has been paid to its transparency, and it is also used for a member requiring transparency, such as a transparent sealing material of a light emitting diode. Properties required for such applications include transparency, optical properties such as refractive index, mechanical properties such as hardness, thermal stability such as heat resistance, and gas barrier that suppresses the permeability of water vapor and various gases. Sex.
  • zirconium oxide particles can be produced in the presence of a chelating agent by improving the optical properties and thermal stability by combining a conventionally proposed silicone resin and an inorganic material such as an inorganic oxide.
  • a composition comprising a polysiloxane mixed with a hydroxyl group-containing polysiloxane (Patent Document 3), a composition for coating a light emitting device comprising a composite of zirconium oxide particles and polyfunctional polysiloxane (Patent Document 4), and coating inorganic nanoparticles with an organic compound
  • Patent Document 5 A large number of materials such as a filling material for a light emitting element mixed with phenyl group-containing silicone (Patent Document 5) have been proposed.
  • the surface of the inorganic oxide particles is hydrophilic, and therefore, particularly between the highly hydrophobic silicone resin and the inorganic oxide particles.
  • the silicone resin and the inorganic oxide particles are separated, making it difficult to form a composite. Therefore, as a general solution, in order to hydrophobize the surface of the inorganic oxide particles, a surface modifier such as an organic polymer dispersant is added to the surface of the inorganic oxide particles to thereby form a silicone resin and an inorganic oxide.
  • the device which raises the compatibility with a physical particle is made
  • the particle size of the inorganic oxide particles is as large as 20 nm or more. Therefore, there is a problem that transparency is lowered and devitrification occurs depending on the case.
  • the inorganic oxide particles and the silicone resin are made compatible with each other using a chelating agent, there is a problem that coloring occurs due to a change with time or thermal deterioration.
  • a transparent dispersion in which nanoparticles are dispersed in methylphenyl silicone that easily interacts with various organic molecules has been proposed.
  • the transparent dispersion and the cured product cannot be achieved.
  • addition reaction type dimethyl silicone is used, the silicone before curing is transparently dispersed, but there is a problem that phase separation may occur and whitening may occur in the curing step.
  • the present invention has been made to solve the above problems.
  • inorganic oxide particles that can maintain transparency while improving refractive index, mechanical properties, and gas barrier properties are highly dispersible and prevent phase separation and whitening during curing. It is an object of the present invention to provide a composite composition and a transparent composite of inorganic oxide particles and a silicone resin that can be used.
  • inorganic oxide particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less are surface-modified using a polydimethylsiloxane skeleton polymer having one functional group at one end, and further, a silicone resin and a reaction catalyst are obtained.
  • the inorganic oxide particles are dispersed in the silicone resin, the dispersibility of the inorganic oxide particles is greatly improved and the transparency and the heat resistance of the silicone resin are maintained.
  • the inventors have found that a transparent composite with a controlled refractive index can be obtained while maintaining the properties, and the present invention has been completed.
  • the composite composition of inorganic oxide particles and silicone resin of the present invention is at least inorganic oxide particles, and is surface-modified by bonding with a polydimethylsiloxane skeleton polymer having one functional group at one end.
  • a composite composition comprising inorganic oxide particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less, a silicone resin, and a reaction catalyst, wherein the silicone resin comprises vinyl-modified silicone and hydrogen It contains a modified silicone, and the reaction catalyst contains a hydrosilylation reaction catalyst.
  • the polydimethylsiloxane skeleton polymer is preferably monoglycidyl ether-terminated polydimethylsiloxane and / or monohydroxyether-terminated polydimethylsiloxane.
  • the vinyl-modified silicone includes vinyl dimethyl silicone at both ends, vinyl diphenyl dimethyl silicone at both ends, vinyl phenyl phenyl silicone at both ends, vinyl diethyl ether at both ends, side chain vinyl dimethyl silicone, vinyl methyl silicone, vinyl methoxy silicone. 1 type or 2 types or more selected from the group consisting of vinyl resin dispersions are preferred.
  • the hydrogen-modified silicone is selected from the group consisting of hydrogen-dimethylsilicone at both ends, methylhydrogen-dimethylsilicone, methylhydrogensilicone, ethylhydrogensilicone, methylhydrogen-phenylmethylsilicone, and hydride resin. It is preferable that it is a seed
  • the hydrogen-modified silicone has the following formula (1): (However, R 1 to R 8 are arbitrary organic groups independent of each other (excluding H), m is an integer of 1 or more, and n is a positive integer including 0) It is preferable that the ratio (m / (m + n)) of m to n in the side chain hydrogen-modified silicone is 0.25 or more and 1 or less.
  • the inorganic oxide particles whose surface is modified by bonding a polydimethylsiloxane skeleton polymer having one functional group at one end in a silicone resin has an average dispersed particle diameter of 1 nm or more and 20 nm or less.
  • a hydrosilylation reaction catalyst is contained in the silicone resin.
  • the transparent composite of the present invention is formed by molding and solidifying the composite composition of the inorganic oxide particles of the present invention and the silicone resin into a predetermined shape, or molding the composite composition after solidifying.
  • the surface of the inorganic oxide particles was modified with a polydimethylsiloxane skeleton polymer having one functional group at one end, and the surface was modified.
  • the composite composition of inorganic oxide particles and silicone resin of the present invention is at least inorganic oxide particles, and is surface-modified by bonding with a polydimethylsiloxane skeleton polymer having one functional group at one end. It contains inorganic oxide particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less, a silicone resin, and a reaction catalyst.
  • the silicone resin contains vinyl-modified silicone and hydrogen-modified silicone, and the reaction catalyst is hydrosilyl. Contains a catalyst for the reaction. Thereby, the dispersibility of the inorganic oxide particles in the silicone resin can be greatly improved.
  • this composite composition when the inorganic oxide particles and the silicone resin are combined, the dispersibility is high, and phase separation and whitening at the time of curing can be prevented.
  • a transparent composite with a controlled refractive index can be obtained while maintaining heat resistance and light resistance.
  • inorganic oxide particles whose surface is modified by bonding a polydimethylsiloxane skeleton polymer having one functional group at one end in a silicone resin has an average dispersed particle diameter of 1 nm or more and 20 nm.
  • the silicone resin contained a hydrosilylation reaction catalyst.
  • the composite composition of the inorganic oxide particles of the present invention and the silicone resin is formed into a predetermined shape and solidified, or is formed after the composite composition is solidified.
  • the present invention relates to a composite composition of inorganic oxide particles and a silicone resin, and a transparent composite. More specifically, inorganic oxide particles that are suitably used as a filler material for silicone resin and that can maintain transparency while improving refractive index, mechanical properties and gas barrier properties are dispersed when dispersed in silicone resin.
  • the present invention relates to a composite composition of inorganic oxide particles and silicone resin capable of preventing phase separation and whitening during curing and curing, and a transparent composite obtained by molding and solidifying the composite composition.
  • grains and silicone resin of this invention is demonstrated. This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified. Additions, omissions, substitutions, and other modifications can be made without departing from the spirit of the present invention.
  • composite composition of inorganic oxide particles and silicone resin is a composite composition in which inorganic oxide particles are dispersed in a silicone resin. At least inorganic oxide particles that are surface-modified by bonding with a polydimethylsiloxane skeleton polymer having one functional group at one end and have an average dispersed particle diameter of 1 nm or more and 20 nm or less It is a composite composition comprising product particles, a silicone resin, and a reaction catalyst.
  • the “composite composition” does not have a specific shape, has an irreversible deformability that does not return to the original shape once deformed, and becomes a raw material of a transparent composite described later.
  • a state of this composite composition for example, a state in a liquid state or a gel state having thixotropy shall be shown.
  • the inorganic oxide that is a component of the inorganic oxide particles is not particularly limited, but is an oxide of a nonmetallic element such as silicon (Si), zirconium (Zr), titanium (Ti), aluminum (Al), iron (Fe ), Copper (Cu), zinc (Zn), yttrium (Y), niobium (Nb), molybdenum (Mo), indium (In), tin (Sn), tantalum (Ta), tungsten (W), lead (Pb) ), Bismuth (Bi), cerium (Ce), antimony (Sb), germanium (Ge) and other metal element oxides.
  • a nonmetallic element such as silicon (Si), zirconium (Zr), titanium (Ti), aluminum (Al), iron (Fe ), Copper (Cu), zinc (Zn), yttrium (Y), niobium (Nb), molybdenum (Mo), indium (In), tin (Sn), tantalum (T
  • inorganic oxides examples include zirconium oxide (ZrO 2 ), titanium oxide (TiO 2 ), silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), iron oxide (Fe 2 O 3 , FeO). , Fe 3 O 4), copper oxide (CuO, Cu 2 O), zinc oxide (ZnO), yttrium oxide (Y 2 O 3), niobium oxide (Nb 2 O 5), molybdenum oxide (MoO 3), indium oxide (In 2 O 3 , In 2 O), tin oxide (SnO 2 ), tantalum oxide (Ta 2 O 5 ), tungsten oxide (WO 3 , W 2 O 5 ), lead oxide (PbO, PbO 2 ), bismuth oxide (Bi 2 O 3 ), cerium oxide (CeO 2 , Ce 2 O 3 ), antimony oxide (Sb 2 O 3 , Sb 2 O 5 ) germanium oxide (GeO 2 , GeO) Etc.
  • ZrO 2
  • Such inorganic oxides also include composite oxides such as tin-added indium tin oxide (ITO) and yttria stabilized zirconia (YSZ). Such inorganic oxides may be used alone or in combination of two or more. In particular, when increasing the refractive index of a composite composition with a silicone resin, zirconium oxide (ZrO 2 ) or titanium oxide (TiO 2 ) having a high refractive index, being colorless and transparent to visible light, and having high hardness. 2 ) is preferred.
  • an inorganic oxide that has a low refractive index as a whole particle by having voids in the particles such as hollow silica particles and porous silica particles. It is preferable to use physical particles.
  • the average dispersed particle size in the composite composition of the inorganic oxide particles is preferably 1 nm or more and 20 nm or less.
  • the average dispersed particle size is more preferably 3 nm or more and 10 nm or less.
  • the reason why the average dispersed particle diameter of the inorganic oxide particles is limited to 1 nm or more and 20 nm or less is as follows.
  • the average dispersed particle size is less than 1 nm, the primary particle size of the particles constituting the particles is extremely small, less than 1 nm. For this reason, the crystallinity of inorganic oxide particles becomes poor, and it becomes difficult to express particle characteristics such as refractive index.
  • the average dispersed particle diameter exceeds 20 nm, the influence of Rayleigh scattering by the inorganic oxide particles is increased, and the transparency of the composite composition is reduced, or the composite composition is obtained by molding and solidifying. The transparency of the transparent composite decreases.
  • the inorganic oxide particles are nanometer-sized particles, a composite composition in which the inorganic oxide particles are dispersed in a silicone resin, or a transparent product formed by molding and solidifying the composite composition. Even in the composite, light scattering is small, and the transparency of the composite composition and the transparent composite can be maintained.
  • the content of the inorganic oxide particles in the composite composition is preferably 1% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 90% by mass or less, and further preferably 10% by mass or more. And it is 85 mass% or less.
  • the reason for limiting the content of the inorganic oxide particles to 1% by mass or more and 90% by mass or less is as follows. When the content is less than 1% by mass, the amount of inorganic oxide particles is too small, and when inorganic oxide particles are combined with a silicone resin, changes in the optical properties and mechanical properties of the silicone resin are manifested. As a result, the effect of combining inorganic oxide particles cannot be obtained, which is not preferable. On the other hand, when the content exceeds 90% by mass, the dispersibility of the inorganic oxide particles cannot be ensured sufficiently, the fluidity in the composite composition is lowered, and the moldability is deteriorated.
  • the surface of the inorganic oxide particles is modified with a surface modifier made of a polydimethylsiloxane skeleton polymer having one functional group at one end.
  • This surface modifier has a polydimethylsiloxane skeleton, in particular, a linear polydimethylsiloxane skeleton in the main chain, and has only one polar group as a functional group at one end (one end side) of the main chain. ing.
  • this functional group (polar group) is selectively bonded to the surface of the inorganic oxide particle, the other end, that is, the siloxane skeleton part is aligned and faces the outside of the particle (the direction away from the surface of the inorganic oxide particle). It becomes.
  • the siloxane skeleton portion and the silicone resin are highly compatible and have good affinity
  • the inorganic oxide particles surface-modified with the surface modifier made of the polydimethylsiloxane skeleton polymer are contained in the silicone resin. Can be uniformly dispersed, and a good composite composition can be formed.
  • the “linear polydimethylsiloxane skeleton” means that the polydimethylsiloxane skeleton has no branches (branches).
  • the polydimethylsiloxane skeleton is branched (branched), or the polar group which is a functional group is located in the middle of the siloxane skeleton (the silicon in which the functional group is located in the middle of the siloxane skeleton).
  • the siloxane skeleton is likely to face the surface direction of the inorganic oxide particles or the direction parallel to the particle surface.
  • the amount of the siloxane skeleton directed to the outside of the inorganic oxide particles is reduced, and the compatibility and affinity between the inorganic oxide particles and the silicone resin may be reduced. Furthermore, since the uniformity of the direction of the siloxane skeleton is lost, entanglement and steric hindrance between the siloxane skeletons may occur, and the compatibility and affinity between the inorganic oxide particles and the silicone resin may also decrease.
  • this surface modifier is a monofunctional group having only one polar group, and since this functional group is used for bonding with the inorganic oxide particles, the surface bonded to the inorganic oxide particles. There are no functional groups in the modifier. Therefore, when using a conventional polyfunctional polysiloxane, there is no risk of deterioration of compatibility with the silicone resin generated due to unreacted functional groups, such as white turbidity, A stable composite composition can be obtained.
  • Such a surface modifier preferably has monoglycidyl ether-terminated polydimethylsiloxane and / or monohydroxyether-terminated polydimethylsiloxane.
  • the monoglycidyl ether-terminated polydimethylsiloxane used in the present invention preferably has a molecular weight of 500 to 10,000.
  • the monohydroxy ether-terminated polydimethylsiloxane used in the present invention preferably has a molecular weight of 500 to 10,000.
  • the monoglycidyl ether terminal is bonded to the hydroxyl group on the surface of the inorganic oxide particle by opening the epoxy group part which is a part of the glycidyl group.
  • the ether terminal is bonded by dehydration condensation between the terminal hydroxyl group and the hydroxyl group on the surface of the inorganic oxide particle.
  • monoglycidyl ether-terminated polydimethylsiloxane does not naturally contain hydroxyl groups, and monohydroxyether-terminated polydimethylsiloxane has hydroxyl groups only on functional groups that bind to inorganic oxide particles.
  • any surface modifier after bonding to the surface of the inorganic oxide particle, it does not have a hydroxyl group, or the hydroxyl group exists in the vicinity of the surface of the inorganic oxide particle, and is compatible with the silicone resin. It is in a state that does not interfere.
  • the transparent composite obtained from the composite composition of the inorganic oxide particles surface-modified with these surface modifiers and the silicone resin has a small shrinkage rate. As a result, there is no generation of pores or cracks in the transparent composite, and the dispersibility of the inorganic oxide particles in the cured silicone resin is maintained well, and a transparent composite free from defects is obtained.
  • the inorganic oxide particles of this embodiment are surface-modified with a polydimethylsiloxane skeleton polymer having one functional group at one end, they are excellent in compatibility and dispersibility with respect to silicone resins.
  • the silicone resin itself is not particularly limited, and any ordinary silicone resin can be used without any problem.
  • silicone resins particularly preferred are silicone resins using a hydrosilylation reaction in which a cured product is obtained at room temperature (25 ° C.) or more and about 150 ° C. or less. Examples of such silicone resins include vinyl-modified silicones and Hydrogen-modified silicone is preferred.
  • both ends vinyl-dimethyl silicone both ends vinyl diphenyl-dimethyl silicone, both ends vinyl-phenyl methyl silicone, both ends vinyl-diethyl silicone, side chain vinyl-dimethyl silicone, vinyl methyl silicone, vinyl methoxy silicone And vinyl resin dispersion.
  • One kind of these vinyl-modified silicones may be selected and used, or two or more kinds may be used in combination.
  • Examples of the hydrogen-modified silicone include double-end hydrogen-dimethylsilicone, methylhydrogen-dimethylsilicone, methylhydrogensilicone, ethylhydrogensilicone, methylhydrogen-phenylmethylsilicone, and hydride resin.
  • One type of these hydrogen-modified silicones may be selected and used, or two or more types may be used in combination.
  • the side chain hydrogen-modified silicone is preferable to contain the side chain hydrogen-modified silicone shown in FIG.
  • the reason why the side chain hydrogen-modified silicone is preferable is that, when a silicone resin polymer is formed by polymerization and curing with a vinyl-modified silicone and a hydrosilylation reaction, the reactivity is higher than the terminal hydrogen-modified silicone, Furthermore, since the amount of the hydrogen-modified silicone as a reactive group can be increased, the crosslinking density is increased, and the characteristics of the resulting silicone resin polymer can be improved.
  • the ratio (m / (m + n)) of m to n in the side chain hydrogen-modified silicone represented by the above formula (1) is preferably 0.25 or more and 1 or less.
  • the ratio (m / (m + n)) is more preferably 0.30 or more and 0.70 or less.
  • the reason why the ratio of m to n (m / (m + n)) is limited to 0.25 or more and 1 or less is as follows. First, if the ratio of m to n (m / (m + n)) is less than 0.25, the crosslinking density at the time of curing is too small, and the aggregation / phase separation rate of the inorganic oxide particles is thus set to cure the silicone resin. This is because it becomes faster than the speed, and as a result, the transparency is lost upon curing with the silicone resin.
  • the upper limit of the ratio of m to n (m / (m + n)) is 1.
  • the ratio of m to n (m / (m + n)) increases, the following formula (2) It is considered that the content ratio of the hydrogen-containing units shown in (2) increases, and the ratio of vinyl-modified silicone and unreacted units increases even after the formation of the transparent composite. However, this unreacted hydrogen-containing unit has little influence on the properties of the transparent composite. Therefore, the maximum value of the ratio of m to n (m / (m + n)) in the side chain hydrogen-modified silicone may be 1.
  • R 1 to R 8 are arbitrary organic groups (excluding H) which are mutually independent, part or all of which may be the same.
  • “partially the same” means, for example, that R 1 , R 3 , R 4 and R 6 are the same, and R 1 , R 2 , R 5 , R 7 and R 8 are different from each other. , so that, not only when only part of the same species, example, R 1 and R 3 and R 4 are the same and R 2 and R 5 R 7 and R 8 are the same, and R The same combination may be used such that 1 and R 2 and R 6 are different from each other.
  • the “organic group” represents all groups composed of organic substances such as a characteristic group, a functional group, and a substituent, and includes, for example, an alkyl group and an alkoxy group.
  • This silicone resin does not have a specific shape as a characteristic of the composite composition after mixing with inorganic oxide particles or the like, and has an irreversible deformability that does not return to the original shape once deformed.
  • Any material can be used as long as it is a raw material for the transparent composite, for example, in a liquid state or a gel-like state having thixotropy, and the degree of polymerization is not particularly limited.
  • the composite composition may be any of a monomer (monomer), an oligomer (a polymer of about 2 to several hundreds), and a polymer (a polymer of several hundreds or more). You may use what gave the width
  • the composite composition of this embodiment contains a reaction catalyst.
  • the reaction catalyst preferably contains a hydrosilylation reaction catalyst.
  • the hydrosilylation reaction catalyst include a noble metal catalyst, and a noble metal powder, a noble metal salt, a noble metal complex, and the like can be appropriately selected.
  • the noble metal catalysts platinum group catalysts are preferable, and examples thereof include platinum catalysts, rhodium catalysts, palladium catalysts, and the like, and platinum catalysts are particularly preferable.
  • the platinum catalyst include platinum fine powder, chloroplatinic acid, platinum-olefin complex, platinum-carbonyl complex, and the like, and these can be used alone or in combination of two or more.
  • the composite composition of this embodiment can contain an organic solvent.
  • the first advantage is viscosity control of the composite composition.
  • the viscosity of the mixture of inorganic oxide particles and silicone resin is preferably 0.05 Pa ⁇ s to 10,000 Pa ⁇ s, more preferably 0.1 Pa ⁇ s to 100 Pa ⁇ s.
  • the second advantage is easy mixing and dispersion.
  • inorganic oxide particles modified with a surface modifier are first dispersed in an organic solvent highly compatible with the silicone resin to be used to form an inorganic oxide particle dispersion, and this inorganic oxide particle dispersion and silicone It is preferable to mix and stir the resin since the dispersibility of the inorganic oxide particles in the silicone resin becomes very high.
  • a hydrophobic solvent is preferably used as the organic solvent.
  • a hydrophobic solvent is suitable as a solvent having high dispersibility of the surface-modified inorganic oxide and high compatibility with the silicone resin.
  • aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and chlorine-containing solvents such as dichloromethane, chloroform, and carbon tetrachloride are preferably used.
  • aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene
  • chlorine-containing solvents such as dichloromethane, chloroform, and carbon tetrachloride are preferably used.
  • One of these solvents is used. Can be used alone or in admixture of two or more.
  • the content of the organic solvent is not particularly limited as long as the above-mentioned solvent addition effect can be obtained, but is usually 400% by mass with respect to the total amount of the surface-modified inorganic oxide particles and the silicone resin. The following is preferable.
  • the content of the organic solvent is more preferably 100% by mass or less. The reason for this is that if an organic solvent is present in excess, when forming a transparent composite described later using this composite composition, the viscosity is too low, resulting in difficulty in moldability, or removal of the organic solvent. This is because it takes time and is not preferable.
  • the surface of the inorganic oxide particles is modified with a polydimethylsiloxane skeleton polymer having one functional group at one end, and the average dispersed particle diameter with the surface modified is 1 nm.
  • This is a method of forming inorganic oxide particles of 20 nm or less and then mixing the surface-modified inorganic oxide particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less, a silicone resin, and a reaction catalyst. .
  • a specific dispersant is bonded to the surface of the inorganic oxide particles in advance so as to have dispersibility in a hydrophobic solvent (organic solvent).
  • the inorganic oxide particles are dispersed in a hydrophobic solvent to obtain a dispersion.
  • a surface modifier composed of a polydimethylsiloxane skeleton polymer having one functional group at one end is added to the obtained dispersion, and the surface is specifically bonded to the surface of the inorganic oxide particles in this hydrophobic solvent.
  • a method of substituting the surface modifier made of a polydimethylsiloxane skeleton polymer having one functional group at one end is
  • a specific dispersant is bonded to the surface of the inorganic oxide particles so as to have dispersibility in a hydrophobic solvent.
  • the inorganic oxide particles to which this specific dispersant is bonded are easily dispersed in a hydrophobic solvent.
  • the inorganic oxide particles to which the specific dispersant is bonded are already bonded on the surface of the inorganic oxide particles when a surface modifier composed of a polydimethylsiloxane skeleton polymer having one functional group at one end coexists.
  • the specific dispersing agent and the surface modifier can easily undergo substitution.
  • the dispersant include organic acid compounds and organic base compounds.
  • the organic acid compound include carboxylic acid, phosphoric acid, and sulfonic acid
  • examples of the organic base compound include amine and phosphazene base.
  • carboxylic acids and amines are preferably used because they function as a dispersant for dispersing the inorganic oxide particles and can be favorably eliminated during the reaction with the surface modifier. .
  • carboxylic acid examples include 1 selected from saturated fatty acids such as formic acid, acetic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, stearic acid, and unsaturated fatty acids such as oleic acid.
  • saturated fatty acids such as formic acid, acetic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, stearic acid, and unsaturated fatty acids such as oleic acid.
  • a species or two or more species may be selected and used.
  • the amine for example, one or more selected from aromatic amines such as pyridine and bipyridine and aliphatic amines such as triethylamine, diethylamine, monoethylamine, and butylamine may be selected and used.
  • the inorganic oxide particles having a specific dispersant bonded to the surface are dispersed in a hydrophobic solvent.
  • the hydrophobic solvent is not particularly limited as long as the inorganic oxide particles having a specific dispersant bonded to the surface thereof are stably dispersed.
  • aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, dichloromethane Chlorine-containing solvents such as chloroform and carbon tetrachloride are preferably used, and one or more of these solvents can be used.
  • a surface modifier composed of a polydimethylsiloxane skeleton polymer having one functional group at one end is added to the hydrophobic solvent in which inorganic oxide particles having a specific dispersant bonded to the surface are dispersed, This surface modifier is replaced with a specific dispersant already bonded to the inorganic oxide surface. Thereby, the surface of the inorganic oxide particles is modified with a surface modifier composed of a polydimethylsiloxane skeleton polymer having one functional group at one end.
  • the mass ratio of the surface modifier comprising the polydimethylsiloxane skeleton polymer having one functional group at one end to the inorganic oxide particles is 5% by mass or more and 200% by mass or less with respect to the total mass of the inorganic oxide particles. More preferably, it is 10 mass% or more and 100 mass% or less, More preferably, it is 20 mass% or more and 100 mass% or less.
  • the reason why the mass ratio of the surface modifier is limited to 5% by mass or more and 200% by mass or less is that when the mass ratio of the surface modifier is less than 5% by mass, the amount of the surface modifier is too small and inorganic. The surface of the oxide particles cannot be sufficiently modified. Therefore, it becomes difficult for the inorganic oxide particles having insufficient surface modification to be compatible with the silicone resin. Because it is lost.
  • the mass ratio of the surface modifier exceeds 200% by mass, the ratio of the surface modifier in the composite composition increases so as not to be negligible, and thus greatly affects the characteristics of the composite composition. This is because it may cause a decrease.
  • a surface modifier composed of a polydimethylsiloxane skeleton polymer having one functional group at one end and reacting the surface modifier with inorganic oxide particles in a hydrophobic solvent
  • the groups (polar groups) are selectively oriented and bonded to the inorganic oxide particles, while the other end side is directed to the outside of the inorganic oxide particles so as to be dispersed in the hydrophobic solvent. Therefore, these surface treatment agents have a shape in which the functional group portion is bonded to the inorganic oxide particles, and the other end side is radially separated from the inorganic oxide particles.
  • inorganic oxide particles whose surface is modified with the polydimethylsiloxane skeleton polymer having one functional group at one end and whose average dispersed particle diameter is 1 nm or more and 20 nm or less are obtained.
  • the inorganic oxide particles having a surface-modified average dispersed particle diameter of 1 nm or more and 20 nm or less, a silicone resin, and a reaction catalyst are mixed.
  • an organic solvent may be added as necessary.
  • the silicone resin itself is not particularly limited, and any combination of vinyl-modified silicone and hydrogen-modified silicone that can be cured by the hydrosilylation reaction described above can be used without any problem.
  • both terminal vinyl-dimethyl silicone both terminal vinyl diphenyl-dimethyl silicone, both terminal vinyl-phenylmethyl silicone, both terminal vinyl-diethyl silicone, side chain vinyl-dimethyl silicone, vinyl methyl silicone, vinyl From methoxysilicone, vinyl resin dispersion, etc.
  • one kind can be selected and used alone or in combination of two or more kinds.
  • Examples of the hydrogen-modified silicone include hydrogen dimethyl silicone at both ends, methyl hydrogen-dimethyl silicone, methyl hydrogen silicone, ethyl hydrogen silicone, methyl hydrogen-phenyl methyl silicone, hydride resin, and the like.
  • the types can be selected and used alone or in combination of two or more.
  • the hydrogen-modified silicone preferably contains a side chain hydrogen-modified silicone represented by the above formula (1).
  • the reason why the side chain hydrogen-modified silicone is preferable is that, when a silicone resin polymer is formed by polymerization and curing with a vinyl-modified silicone and a hydrosilylation reaction, the reactivity is higher than the terminal hydrogen-modified silicone, Furthermore, since the amount of the hydrogen-modified silicone as a reactive group can be increased, the crosslinking density is increased, and the characteristics of the resulting silicone resin polymer can be improved.
  • the ratio (m / (m + n)) of m to n in the side chain hydrogen-modified silicone represented by the above formula (2) is preferably 0.25 or more and 1 or less.
  • the ratio (m / (m + n)) is more preferably 0.30 or more and 0.70 or less.
  • the reason why the ratio of m to n (m / (m + n)) is limited to 0.25 or more is as follows. First, if the ratio of m to n (m / (m + n)) is less than 0.25, the crosslinking density at the time of curing is too small, and the aggregation / phase separation rate of the inorganic oxide particles is thus set to cure the silicone resin. This is because it becomes faster than the speed, and as a result, the transparency is lost upon curing with the silicone resin.
  • the upper limit of the ratio of m to n (m / (m + n)) is 1.
  • the hydrodynamic ratio shown in the above formula (2) is increased. It is considered that the ratio of the vinyl-modified silicone and the unreacted unit is increased even after the formation of the transparent composite by increasing the content of the gen-containing unit. However, this unreacted hydrogen-containing unit has little influence on the properties of the transparent composite. Therefore, the maximum value of the ratio of m to n (m / (m + n)) in the side chain hydrogen-modified silicone may be 1.
  • the method of mixing the surface-modified inorganic oxide particles and the silicone resin is not particularly limited, and a conventionally known method such as a mixer, various mills, or application of ultrasonic waves may be used.
  • the inorganic oxide particles whose surface is modified by the surface modifier can be mixed with the silicone resin in the state of the particles.
  • it is compatible with the silicone resin using the surface-modified inorganic oxide particles in advance. It is preferable to re-disperse in a high organic solvent (hydrophobic solvent) and to mix and stir the resulting inorganic oxide particle dispersion and the silicone resin.
  • the organic solvent itself has a low viscosity.
  • the dispersion liquid in which the inorganic oxide particles are uniformly dispersed and the silicone resin are mixed, the liquids are mixed together. Therefore, even if the silicone resin has a certain degree of viscosity, the low-viscosity dispersion liquid As a result, the inorganic oxide particles are easily and uniformly dispersed in the silicone resin. Furthermore, since the process itself is a process of mixing the low-viscosity inorganic oxide particle dispersion and the viscous silicone resin, and a process of mixing the solutions, a great deal of labor is not required.
  • the mixture of the surface-modified inorganic oxide particles and the silicone resin has a high viscosity
  • the fluidity of the mixture deteriorates, and as a result, the moldability of the transparent composite described later and ease of handling are reduced.
  • an organic solvent having a high dispersibility of the surface-modified inorganic oxide particles and a high compatibility with the silicone resin is used. It is preferable to add a solvent to reduce the viscosity of the resulting mixture.
  • a hydrophobic solvent is preferably used.
  • aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and chlorine-containing solvents such as dichloromethane, chloroform, and carbon tetrachloride are suitably used.
  • the content of the organic solvent is not particularly limited as long as the above-mentioned solvent addition effect can be obtained, but usually 400 mass with respect to the total amount of the surface-modified inorganic oxide particles and the silicone resin. % Or less is preferable.
  • the content of the organic solvent is more preferably 100% by mass or less. The reason for this is that if an organic solvent is present in excess, when forming a transparent composite described later using this composite composition, the viscosity is too low, resulting in difficulty in moldability, or removal of the organic solvent. It takes time.
  • the silicone resin is added to the dispersion
  • an organic solvent is appropriately added to the mixture, and the viscosity is adjusted by stirring and mixing using a mixer or the like. And the like, and the like.
  • the viscosity of the mixture obtained by the addition of the organic solvent is low, the viscosity may be adjusted (high viscosity) by removing part or all of the organic solvent by volatilization or the like.
  • the composite composition of the present embodiment can be obtained.
  • the inorganic oxide particles whose surface is modified by bonding a polydimethylsiloxane skeleton polymer having one functional group at one end in a silicone resin have an average dispersed particle diameter of 1 nm or more and 20 nm or less.
  • a transparent composite containing a hydrosilylation reaction catalyst in the silicone resin In this transparent composite, an organic solvent, especially a hydrophobic solvent, is not basically contained, and even if it is contained, the amount is very small.
  • the “transparent composite” has a specific shape, but this “having a predetermined shape” means that the transparent composite does not have irreversible deformability such as liquid or gel. This means that a certain shape can be maintained according to the purpose and method. That is, it does not indicate that the shape itself is a specific shape, including a normal solid state that hardly deforms, or a rubber-like one having elastic deformability (shape restoring property).
  • This transparent composite has a predetermined shape by increasing the degree of polymerization and crosslinking of the silicone resin in the above composite composition, or the number of polymerizations and crosslinking between the silicone resin and the siloxane skeleton of the surface modifier. Can be obtained. Therefore, each component of the transparent composite, that is, the inorganic oxide particles, the silicone resin, and the reaction catalyst, the surface of which is modified with a surface modifier made of a polydimethylsiloxane skeleton polymer having one functional group at one end. About 3 components, it is the same as the above-mentioned composite composition.
  • the surface-modified inorganic oxide particles constituting the composite itself have high compatibility and affinity with the silicone resin and good dispersibility in the silicone resin. Therefore, there is no occurrence of phase separation between inorganic oxide particles and silicone resin, or aggregation of inorganic oxide particles. Therefore, there is no possibility of causing deterioration of optical characteristics, mechanical characteristics, thermal stability and the like due to these, and good characteristics can be maintained.
  • the curing rate of the silicone resin is faster than the aggregation / phase separation rate of the inorganic oxide particles. Therefore, the transparency is high without the inorganic oxide particles aggregating in the obtained transparent composite.
  • the composite composition which is a material for forming the transparent composite does not use a chelating agent, there is no possibility of coloring the transparent composite.
  • the average dispersed particle size of the inorganic oxide particles contained in the transparent composite is set to 20 nm or less. Therefore, the occurrence of Rayleigh scattering, which has a large influence when the average dispersed particle diameter exceeds 20 nm, is suppressed to a low level, and the transparency of the transparent composite is not lowered.
  • the inorganic oxide particles are nanometer-sized particles, light scattering is small even in a composite composition or a transparent composite in which the inorganic oxide particles are dispersed in a silicone resin. And the transparency of the transparent composite can be maintained.
  • the average dispersed particle diameter of the inorganic oxide particles contained in the transparent composite is 1 nm or more, the average primary particle diameter of the inorganic oxide particles does not become less than 1 nm at which the maintenance of crystallinity is lowered. . Therefore, the inorganic oxide particles are maintained in good crystallinity.
  • the characteristics of the inorganic oxide particles themselves that is, characteristics such as refractive index, hardness, and heat resistance do not deteriorate. Therefore, the effect as a transparent composite obtained by combining inorganic oxide particles with a silicone resin can be sufficiently obtained.
  • the optical properties of the transparent composite include refractive index control. Since the refractive index of the silicone resin is about 1.4, the refractive index of the transparent composite can be reduced by combining the silicone resin and high refractive index oxide particles having a higher refractive index than that of the silicone resin. It can be increased compared to the case of. In particular, it is effective to form a composite with high refractive index inorganic oxide particles having a refractive index of 2 or more, such as tetragonal zirconium oxide (refractive index: 2.15) or titanium oxide (refractive index: about 2.6). By using these high refractive index inorganic oxide particles, the refractive index of the transparent composite can be increased from about 1.5 to about 1.65, which is about 0.1 to 0.2 higher than that of the silicone resin alone. Is possible.
  • the light scattering can be suppressed sufficiently low by setting the average dispersed particle size of the inorganic oxide particles to 20 nm or less. Therefore, the transparency is sufficiently maintained in this transparent composite.
  • the inorganic oxide particles such as hollow silica particles and porous silica particles having voids in the particles and having a lower refractive index than the silicone resin as a whole are combined with the silicone resin, a transparent composite It is also possible to lower the refractive index of the resin as compared with the case of a silicone resin alone.
  • the mechanical properties of the transparent composite include an improvement in hardness as compared with the resin alone.
  • Ordinary inorganic oxide particles have higher hardness than silicone resin, and by compounding inorganic oxide particles with silicone resin, the surface hardness of the transparent composite can be increased compared to the case of silicone resin alone. it can. Thereby, the scratch resistance of the transparent composite can be improved, and the dimensional accuracy of the transparent composite itself can be improved.
  • zirconium oxide has a high hardness among oxide-based ceramics, it can exhibit a high effect in improving the surface hardness by combining.
  • the silicone resin itself contains silicon (Si) in the skeleton it is superior in thermal stability and chemical stability such as heat resistance and chemical resistance as compared with a normal resin.
  • inorganic oxide particles are superior to silicone resins in terms of heat resistance. Therefore, if inorganic oxide particles with high chemical stability are selected and the inorganic oxide particles with high chemical stability are combined with a silicone resin, the thermal stability and chemical properties of the resulting transparent composite are obtained. As compared with the case of the silicone resin alone, the mechanical stability can be further enhanced.
  • the silicone resin is hydrophobic (water repellency), but has high flexibility and low gas barrier property against water vapor compared to other resins.
  • the inorganic oxide particles having excellent gas barrier properties are uniformly dispersed inside the transparent composite, and the bondability between the inorganic oxide particles and the silicone resin is high.
  • the gas barrier property against water vapor in can be improved to a higher state than in the case of a silicone resin alone.
  • This transparent composite can be suitably used for an optical lens.
  • the refractive index of the transparent composite obtained by combining a high refractive index inorganic oxide particle, particularly zirconium oxide, with a silicone resin can be obtained in the case of a silicone resin alone, for example. It can be increased from about 1.4 to about 1.65.
  • the dimensional accuracy can be improved by improving the hardness as compared with the case of the silicone resin alone. Therefore, the design freedom in the optical element can be improved.
  • a single silicone resin is used for the optical lens, it becomes possible to reduce the size, the thickness, the integration, the light collection efficiency, the refractive index wavelength dependency, and the like. . Therefore, improvement in characteristics of a CCD or CMOS camera, which is a device using such an optical element, such as higher resolution and higher sensitivity can be expected.
  • this transparent composite can be suitably used as a sealing material for LEDs that are light emitting elements. For this reason, since this transparent composite has a higher refractive index than a single silicone resin, when used as a sealing material for an LED, which is a light emitting element, a light emitting body covered with a sealing material, A member having a high refractive index, such as a substrate for forming a light emitter (the refractive index of a semiconductor material that is a light emitter of an LED is about 2.5; And the refractive index matching with about 76) can be improved. Therefore, it is possible to reduce internal reflection in the process of extracting light emitted from the LED light emitter.
  • the transparent composite of the present embodiment as an LED sealing material, the light extraction efficiency from the LED can be improved by about 10% to 15%. As a result, the luminance of the LED can be improved. Furthermore, since this transparent composite has a high gas barrier property against water vapor, it is possible to suppress the intrusion of moisture from the outside and suppress the deterioration of the light emitting region. Therefore, the lifetime of the light emitting element can be extended.
  • this transparent composite can be suitably used as a sealing material for organic EL elements.
  • the gas barrier property against water vapor is high, so that moisture penetration from the outside can be suppressed and deterioration of the light emitting region can be suppressed.
  • the inorganic oxide particles in the transparent composite can effectively suppress the permeation of oxygen gas, the deterioration of the light emitting region can be similarly suppressed. Therefore, the lifetime of the light emitting element in the organic EL element can be extended by using the transparent composite of the present embodiment as a sealing material for the organic EL element.
  • the transparent composite of the present embodiment can be obtained by molding and solidifying the composite composition of the present embodiment into a predetermined shape, or molding the composite composition into a predetermined shape after solidifying the composite composition. .
  • the “method of forming into a predetermined shape and solidifying” is as follows. First, the composite composition of the present embodiment is molded using a mold or a mold, or filled into a mold or a mold-shaped container, thereby forming a molded body or a filling molded into a target shape. Get things. At this time, if the composite composition to be used has a high viscosity, an organic solvent or the like is added in advance and stirred and mixed so as to reduce the viscosity, so that the viscosity is suitable for molding and filling. Is preferred.
  • the silicone resins or a part of the silicone resin and the surface modifier are polymerized or crosslinked in advance as described below, or the composite composition contains an organic solvent.
  • the molded body or the filling is left at room temperature (about 25 ° C.) or heated to a predetermined temperature (room temperature to 150 ° C., preferably 80 ° C. to 150 ° C.) and left to stand for a predetermined time.
  • a predetermined temperature room temperature to 150 ° C., preferably 80 ° C. to 150 ° C.
  • Reactions such as polymerization and crosslinking are caused to occur in the silicone resin and the surface modifier in the composition via a reaction catalyst, and the degree of bonding (degree of polymerization) between the silicone resins and between the silicone resin and the surface modifier is increased.
  • an organic solvent remains in the molded body or the filling, the organic solvent is removed by volatilization.
  • the transparent composite of the present embodiment having no defects, excellent optical characteristics and mechanical characteristics, and having high thermal stability and chemical stability.
  • molding in a predetermined shape after solidifying a composite composition is as follows.
  • the composite composition of this embodiment is solidified to obtain a solidified product (unformed transparent composite) of the composite composition.
  • the composite composition is allowed to stand at room temperature (about 25 ° C.) or at a predetermined temperature (room temperature to 150 ° C., preferably 80 ° C. to 150 ° C.) and allowed to stand for a predetermined time.
  • this solidified product is formed into a necessary shape by a machining method such as cutting or die cutting.
  • the silicone resin of the present embodiment has flexibility even after curing and can be easily processed.
  • the molded body after processing may be further solidified by increasing the degree of bonding (degree of polymerization) between the silicone resins or between the silicone resin and the surface modifier, or by removing the remaining organic solvent. .
  • degree of bonding degree of polymerization
  • the purpose is to improve only the surface hardness of a composite containing inorganic oxide particles and a silicone resin
  • particles having an average dispersed particle size larger than 20 nm, for example, 100 nm inorganic oxide particles should be used. You can also. Even in such a case, by applying the manufacturing method of the composite composition of the present embodiment, the dispersibility of the inorganic oxide particles in the composite composition is increased, and a molded body or filling having good physical properties. It can be set as the composite composition which can produce a thing.
  • this mixture was dried at 130 ° C. for 24 hours in the air using a drier to obtain a solid.
  • the solid was pulverized using an automatic mortar, and then baked at 500 ° C. for 1 hour in the air using an electric furnace.
  • the fired product is put into pure water, stirred to form a slurry, washed using a centrifuge, and after sufficiently removing the added sodium sulfate, dried in a dryer, Zirconia particles were obtained.
  • the recovered surface-modified zirconia particles were 15 g.
  • this surface-modified zirconia particle-silicone resin composite composition was stirred and dissolved, then poured into a mold assembled with a glass plate, and a curing reaction was performed while removing the organic solvent under a vacuum of 40 ° C. A transparent composite having a thickness of 1 of 1 mm was obtained. The content of zirconia particles in this transparent composite was 25% by mass.
  • the cross section of the obtained transparent composite of Example 1 was observed using a field emission transmission electron microscope JEM-2100F (manufactured by JEOL Ltd.), and the particle size of 100 particles randomly selected was measured.
  • the average value was defined as the average dispersed particle size of the zirconia particles in the transparent composite.
  • the average dispersed particle size was 7 nm. From this measurement result, it was concluded that the average dispersed particle size of the zirconia particles in the composite composition of Example 1 was 7 nm or less.
  • Example 2 Zirconia particles from 10 g (25 wt%) to 14 g (35 wt%), and side chain vinyl-dimethylsilicone VDT-131 as vinyl-modified silicone from 14.1 g (47 wt%) to 8.4 g (28 wt%)
  • Example 2 was performed in the same manner as in Example 1 except that methylhydrogen-dimethylsilicone HMS-151 was changed from 0.9 g (3% by mass) to 0.6 g (2% by mass) as the hydrogen-modified silicone.
  • the surface-modified zirconia particle-silicone resin composite composition and a transparent composite having a thickness of 1 mm were obtained. The content of zirconia particles in this transparent composite was 35% by mass.
  • Example 3 As a result of measuring the particle diameter of the zirconia particles in the obtained transparent composite of Example 2 in the same manner as in Example 1, the average dispersed particle diameter was 8 nm. From this result, it was concluded that the average dispersed particle size of the zirconia particles in the composite composition of Example 2 was 8 nm or less.
  • the obtained transparent composite of Example 2 was subjected to elemental analysis. As a result, an amount of platinum component equivalent to the amount added as a reaction catalyst could be detected, and thus the transparent composite of the present invention was obtained. It was confirmed. [Example 3]
  • Zirconia particles from 10 g (25 wt%) to 16 g (40 wt%), and side chain vinyl-dimethylsilicone VDT-131 as vinyl-modified silicone from 14.1 g (47 wt%) to 5.7 g (19 wt%) From 0.9 g (3% by mass) to 0.3 g (1% by mass) of methylhydrogen-dimethylsilicone HMS-151 as the hydrogen-modified silicone, and 6 mg of platinum divinyltetramethyldisiloxane SIP6830.3 as the reaction catalyst (
  • the surface-modified zirconia particle-silicone resin composite composition of Example 3 and a transparent composite having a thickness of 1 mm are the same as in Example 1 except that the content is changed from 0.02% by mass to 3 mg (0.01% by mass). Got the body.
  • the content of zirconia particles in this transparent composite was 40% by mass.
  • Example 4 As a result of measuring the particle diameter of the zirconia particles in the obtained transparent composite of Example 3 in the same manner as in Example 1, the average dispersed particle diameter was 10 nm. From this result, it was concluded that the average dispersed particle size of the zirconia particles in the composite composition of Example 3 was 10 nm or less.
  • the obtained transparent composite of Example 3 was subjected to elemental analysis. As a result, an amount of platinum component equivalent to the amount added as a reaction catalyst could be detected, and thus the transparent composite of the present invention was obtained. It was confirmed. [Example 4]
  • Example 5 As a result of measuring the particle diameter of the zirconia particles in the obtained transparent composite of Example 4 in the same manner as in Example 1, the average dispersed particle diameter was 7 nm. From this result, it was concluded that the average dispersed particle size of the zirconia particles in the composite composition of Example 4 was 7 nm or less.
  • the obtained transparent composite of Example 4 was subjected to elemental analysis. As a result, an amount of platinum component equivalent to the amount added as a reaction catalyst could be detected, and thus the transparent composite of the present invention was obtained. It was confirmed. [Example 5]
  • Example 6 As a result of measuring the particle diameter of the zirconia particles in the obtained transparent composite of Example 5 in the same manner as in Example 1, the average dispersed particle diameter was 7 nm. From this result, it was concluded that the average dispersed particle size of the zirconia particles in the composite composition of Example 5 was 7 nm or less. Further, as a result of conducting elemental analysis on the obtained transparent composite of Example 5, it was possible to detect an amount of platinum component equivalent to the amount added as a reaction catalyst, and thus the transparent composite of the present invention was obtained. It was confirmed. [Example 6]
  • Example 7 As a result of measuring the particle diameter of zirconia particles in the obtained transparent composite of Example 6 in the same manner as in Example 1, the average dispersed particle diameter was 10 nm. From this result, it was concluded that the average dispersed particle size of zirconia particles in the composite composition of Example 6 was 10 nm or less.
  • the obtained transparent composite of Example 6 was subjected to elemental analysis. As a result, an amount of platinum component equivalent to the amount added as a reaction catalyst could be detected, and thus the transparent composite of the present invention was obtained. It was confirmed. [Example 7]
  • the particle diameter of the zirconia particles in the obtained transparent composite of Example 7 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 10 nm. From this result, it was concluded that the average dispersed particle size of zirconia particles in the composite composition of Example 7 was 10 nm or less.
  • the obtained transparent composite of Example 7 was subjected to elemental analysis. As a result, an amount of platinum component equivalent to the amount added as a reaction catalyst could be detected, and thus the transparent composite of the present invention was obtained. It was confirmed. [Example 8]
  • the side chain vinyl-dimethylsilicone VDT-131 was changed from 14.1 g (47% by mass) to 14.4 g (48% by mass) as the vinyl-modified silicone, and 0.1% of methylhydrogen-dimethylsilicone HMS-151 as the hydrogen-modified silicone.
  • a resin composite composition and a transparent composite having a thickness of 1 mm were obtained. The content of zirconia particles in this transparent composite was 25% by mass.
  • Example 9 As a result of measuring the particle diameter of the zirconia particles in the obtained transparent composite of Example 8 in the same manner as in Example 1, the average dispersed particle diameter was 7 nm. From this result, it was concluded that the average dispersed particle size of zirconia particles in the composite composition of Example 8 was 7 nm or less.
  • the obtained transparent composite of Example 8 was subjected to elemental analysis. As a result, an amount of platinum component equivalent to the amount added as a reaction catalyst could be detected, and thus the transparent composite of the present invention was obtained. It was confirmed. [Example 9]
  • the particle diameter of the zirconia particles in the obtained transparent composite of Example 9 was measured in the same manner as in Example 1. As a result, the average dispersed particle diameter was 7 nm. From this result, it was concluded that the average dispersed particle size of zirconia particles in the composite composition of Example 9 was 7 nm or less. Further, as a result of conducting elemental analysis on the obtained transparent composite of Example 9, it was possible to detect an amount of platinum component equivalent to the amount added as a reaction catalyst, and thus the transparent composite of the present invention was obtained. It was confirmed. [Example 10]
  • Example 3 was changed to platinum cyclovinylmethylsiloxane SIP 6832.2 (manufactured by Gelest), respectively, and the surface-modified zirconia particle-silicone resin composite composition of Example 10 and a transparent film having a thickness of 1 mm were prepared in the same manner as in Example 1. A complex was obtained. The content of zirconia particles in this transparent composite was 25% by mass.
  • the average dispersed particle diameter of the zirconia particles in the obtained transparent composite of Example 10 was 9 nm. From this result, it was concluded that the average dispersed particle size of the zirconia particles in the composite composition of Example 10 was 9 nm or less. Further, as a result of conducting elemental analysis on the obtained transparent composite of Example 10, it was possible to detect an amount of platinum component equivalent to the amount added as a reaction catalyst, and thus the transparent composite of the present invention was obtained. It was confirmed.
  • “Comparative Example 1” 14.1 g (47% by mass) of side chain vinyl-dimethylsilicone VDT-131 as vinyl-modified silicone, 8.7 g (29% by mass) of vinyl-dimethylsilicone DMS-V21 at both ends, and methyl as hydrogen-modified silicone According to Example 1, except that 0.9 g (3% by mass) of hydrogen-dimethylsilicone HMS-151 was changed to 6.3 g (21% by mass) of methylhydrogen-dimethylsilicone HMS-031.
  • the surface-modified zirconia particle-silicone resin composite composition of Comparative Example 1 and a composite having a thickness of 1 mm were obtained. The content of zirconia particles in this composite was 25% by mass.
  • the average dispersed particle diameter was 35 nm.
  • Comparative Example 2 14.1 g (47% by mass) of side chain vinyl-dimethylsilicone VDT-131 as vinyl-modified silicone, 13.2 g (44% by mass) of vinyl-dimethylsilicone DMS-V22 at both ends, and methyl as hydrogen-modified silicone According to Example 1, except that 0.9 g (3% by mass) of hydrogen-dimethylsilicone HMS-151 was changed to 1.8 g (6% by mass) of methylhydrogen-dimethylsilicone HMS-031.
  • the surface-modified zirconia particle-silicone resin composite composition of Comparative Example 2 and a composite having a thickness of 1 mm were obtained. The content of zirconia particles in this composite was 25% by mass.
  • the average dispersed particle diameter was 42 nm.
  • “Comparative Example 3” To 10 g of zirconia particles produced in the same manner as in Example 1, 85 g of toluene and 5 g of caproic acid were added and mixed, and the surface of the zirconia particles was modified with caproic acid as a ligand. Then, the dispersion process was performed and the zirconia transparent dispersion liquid was prepared. After completion of the reaction, the solvent was removed with an evaporator, and acetone washing and centrifugation were repeated to remove zirconia particles and unreacted caproic acid. The recovered zirconia particles modified with caproic acid whose surface was a ligand was 11 g.
  • the caproic acid-modified zirconia particles 10 g (25% by mass) are used as zirconia particles, and the side chain vinyl-dimethylsilicone VDT-131 is changed from 14.1 g (47% by mass) to 18.8 g (63% by mass) as vinyl-modified silicone.
  • each of the transparent composites of Examples 1 to 10 was excellent in all of transparency, refractive index, and durability.
  • the composites of Comparative Examples 1 and 2 had an extremely low visible light transmittance of 0% to 20%, and the refractive index could not be measured.
  • both hydrogen-modified silicone and vinyl-modified silicone have low crosslink density, so the aggregation / phase separation rate of the inorganic oxide particles is faster than the curing rate of the silicone resin.
  • the inorganic oxide particles and the silicone resin This is thought to be due to the loss of transparency during curing.
  • the composite of Comparative Example 3 had a very low visible light transmittance of 10% or less, and the refractive index could not be measured.
  • the present invention is highly dispersible when inorganic oxide particles capable of improving the refractive index, mechanical properties and gas barrier properties are dispersed in the silicone resin, and prevents phase separation and whitening during curing. It is possible to provide a composite composition and a transparent composite of inorganic oxide particles and a silicone resin that can ensure transparency.
  • the composite composition of inorganic oxide particles and silicone resin of the present invention is a composite composition in which inorganic oxide particles are dispersed in a silicone resin, and is at least inorganic oxide particles having 1 at one end.
  • the surface is modified by bonding with a polydimethylsiloxane skeleton polymer having a functional group, and contains inorganic oxide particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less, a silicone resin, and a reaction catalyst.
  • a semiconductor light-emitting element (LED) sealing material a substrate for liquid crystal display device, a substrate for organic EL display device, a substrate for color filter, a substrate for touch panel, a substrate for solar cell, a transparent plate, an optical lens,
  • LED semiconductor light-emitting element

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Abstract

Cette composition composite de particules d'oxyde inorganiques et d'une résine de silicone est une composition composite contenant des particules d'oxyde inorganiques, qui sont modifiées en surface par liaison d'un polymère à squelette polydiméthylsiloxane ayant un groupe fonctionnel à une extrémité terminale et qui ont un diamètre moyen de particule dispersée non inférieur à 1 nm et non supérieur à 20 nm, une résine de silicone et un catalyseur de réaction. La résine de silicone contient une silicone modifiée par vinyle et une silicone modifiée par hydrogène et le catalyseur de réaction contient un catalyseur de réaction d'hydrosilylation.
PCT/JP2012/055066 2011-06-08 2012-02-29 Composition composite de particules d'oxyde inorganiques et de résine de silicone et matière composite transparente WO2012169237A1 (fr)

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EP3134462A4 (fr) * 2014-04-24 2017-12-13 Rensselaer Polytechnic Institute Nanocomposites polymères sans matrice et produits et procédés associés

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WO2015061075A1 (fr) * 2013-10-24 2015-04-30 Dow Corning Corporation Silicone durcie ayant une transmittance de la lumière élevée, silicone durcissable utilisée pour la préparer, dispositifs et procédés associés
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