WO2012169237A1 - Composite composition of inorganic oxide particles and silicone resin, and transparent composite material - Google Patents

Composite composition of inorganic oxide particles and silicone resin, and transparent composite material Download PDF

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Publication number
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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Prior art keywords
inorganic oxide
oxide particles
silicone resin
silicone
modified
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PCT/JP2012/055066
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French (fr)
Japanese (ja)
Inventor
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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Application filed by 住友大阪セメント株式会社 filed Critical 住友大阪セメント株式会社
Priority to CN201280027849.7A priority Critical patent/CN103597034B/en
Priority to KR1020137032472A priority patent/KR101596378B1/en
Publication of WO2012169237A1 publication Critical patent/WO2012169237A1/en

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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

This composite composition of inorganic oxide particles and a silicone resin is a composite composition containing inorganic oxide particles, which are surface modified by bonding a polydimethylsiloxane backbone polymer having one functional group at one terminal and which have an average dispersed particle diameter of not lower than 1 nm and not higher than 20 nm, a silicone resin, and a reaction catalyst. The silicone resin contains a vinyl-modified silicone and a hydrogen-modified silicone, and the reaction catalyst contains a hydrosilylation reaction catalyst.

Description

無機酸化物粒子とシリコーン樹脂との複合組成物及び透明複合体COMPOSITION COMPOSITION AND TRANSPARENT COMPOSITION OF INORGANIC OXIDE PARTICLES AND SILICONE RESIN
　本発明は、無機酸化物粒子とシリコーン樹脂との複合組成物及び透明複合体に関する。
　本願は、２０１１年６月８日に、日本に出願された特願２０１１－１２８３０２号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a composite composition of inorganic oxide particles and a silicone resin, and a transparent composite.
This application claims priority based on Japanese Patent Application No. 2011-128302 filed in Japan on June 8, 2011, the contents of which are incorporated herein by reference.
　従来、シリカ等無機酸化物をフィラーとして樹脂と複合化することにより、樹脂の機械的特性等を向上させる試みがなされている。このフィラーと樹脂とを複合化する方法としては、無機酸化物を水及び有機溶媒のいずれか一方または双方を含む溶液中に分散させた分散液と、樹脂とを混合する方法が一般的である。分散液と樹脂を種々の方法により混合することにより、無機酸化物粒子が第２相として複合化された無機酸化物粒子複合化プラスチックを作製することができる（例えば、特許文献１参照）。
　また、無機酸化物粒子の表面にポリマーを被覆することにより、機械的特性の他に屈折率や透明性の調整等、光学的特性を趣向したコーティング組成物、塗膜が提案されている（例えば、特許文献２参照）。 In the past, attempts have been made to improve the mechanical properties and the like of a resin by compounding an inorganic oxide such as silica with a resin as a filler. As a method of combining the filler and the resin, a method of mixing a dispersion liquid in which an inorganic oxide is dispersed in a solution containing one or both of water and an organic solvent, and the resin is generally used. . By mixing the dispersion and the resin by various methods, an inorganic oxide particle composite plastic in which the inorganic oxide particles are combined as the second phase can be produced (for example, see Patent Document 1).
In addition, coating compositions and coating films that have optical properties such as refractive index and transparency adjustment in addition to mechanical properties have been proposed by coating the surface of inorganic oxide particles with a polymer (for example, , See Patent Document 2).
　ポリマー材料の中でも、シリコーン樹脂は、耐熱性、耐寒性等の耐候性に優れるとともに、電気的特性、低毒性等にも優れていることから、化粧品材料や医用材料から電気電子材料まで、多岐に亘って使用されている。また、近年では、その透明性にも着目されるようになり、発光ダイオードの透明封止材料等、透明性が求められる部材にも用いられている。
　このような用途において要求される特性としては、透明性、屈折率等の光学的特性、硬度等の機械的特性、耐熱性等の熱的安定性、水蒸気や各種ガスの透過性を抑制するガスバリア性が挙げられる。 Among polymer materials, 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.
　従来より提案されているシリコーン樹脂と無機酸化物等の無機材料とを複合化することで光学的特性や熱的安定性を向上させたものとしては、例えば、酸化ジルコニウム粒子をキレート化剤存在下で水酸基含有ポリシロキサンと複合化した組成物（特許文献３）、酸化ジルコニウム粒子と多官能ポリシロキサンとを複合化した発光素子コーティング用組成物（特許文献４）、無機ナノ粒子を有機化合物で被覆しフェニル基含有シリコーンに混合した発光素子用充填材料（特許文献５）等、多数提案されている。 For example, 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 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.
特開２００５－１６１１１１号公報Japanese Patent Laid-Open No. 2005-161111 特開２００３－２９２８２６号公報JP 2003-292826 A 特開２００６－３１６２６４号公報JP 2006-316264 A 特開２００９－９１３８０号公報JP 2009-91380 A 特開２００７－７０６０３号公報JP 2007-70603 A
　しかしながら、従来では、無機酸化物粒子を疎水性の樹脂と複合化しようとすると、この無機酸化物粒子の表面が親水性であることから、特に疎水性の高いシリコーン樹脂と無機酸化物粒子との間では、シリコーン樹脂と無機酸化物粒子が分離してしまい、複合化することが困難であるという問題点があった。
　そこで、一般的な解決法として、無機酸化物粒子の表面を疎水化するために、有機高分子分散剤等の表面修飾剤を無機酸化物粒子の表面に付与することにより、シリコーン樹脂と無機酸化物粒子との相溶性を高める工夫がなされている。しかしながら、無機酸化物粒子の表面を、シリコーン樹脂と相溶するまで十分に疎水化することが難しいという問題点があった。
　また、無機酸化物粒子の粒径が２０ｎｍ以上と大きく、したがって、透明性が低下し、場合によっては失透してしまうという問題点があった。 However, conventionally, when the inorganic oxide particles are combined with a hydrophobic resin, the surface of the inorganic oxide particles is hydrophilic, and therefore, particularly between the highly hydrophobic silicone resin and the inorganic oxide particles. In the meantime, 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 | formed. However, there is a problem that it is difficult to sufficiently hydrophobize the surface of the inorganic oxide particles until they are compatible with the silicone resin.
In addition, 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.
　また、例えば高粘性シリコーン樹脂においては、従来の疎水性高分子分散剤を用いても、無機酸化物粒子との相溶がし難く、例え無機酸化物粒子の表面を十分に疎水化することができたとしても、無機酸化物粒子の透明分散液を得ることができないという問題点があった。
　また、水酸基含有ポリシロキサンを用いた場合、架橋の進行に伴い水が発生し、場合によっては、無機酸化物粒子とポリシロキサンとが相分離する虞があり、さらには、得られた複合物にポアやクラックが発生する虞があるという問題点があった。
　一方、多官能ポリシロキサンを用いる場合も無機酸化物粒子とポリシロキサンとの配合に制約があり、特に無機酸化物粒子の量が多い場合にポアやクラックの発生が顕著となるという問題点があった。多官能ポリシロキサンを用いる場合では、未反応の官能基が残留し易く、よって、架橋後の複合体特性に経時変化が生じ易く、更には、耐久性に劣るという問題点があった。 For example, in a high viscosity silicone resin, even if a conventional hydrophobic polymer dispersant is used, it is difficult to be compatible with inorganic oxide particles, and the surface of inorganic oxide particles can be sufficiently hydrophobized. Even if it was possible, there was a problem that a transparent dispersion of inorganic oxide particles could not be obtained.
In addition, when a hydroxyl group-containing polysiloxane is used, water is generated with the progress of crosslinking, and in some cases, there is a possibility that the inorganic oxide particles and the polysiloxane may be phase-separated. There is a problem that pores and cracks may occur.
On the other hand, when polyfunctional polysiloxane is used, there is a limitation in the blending of inorganic oxide particles and polysiloxane, and there is a problem that pores and cracks become prominent particularly when the amount of inorganic oxide particles is large. It was. When the polyfunctional polysiloxane is used, there is a problem that unreacted functional groups are likely to remain, so that the composite characteristics after crosslinking are likely to change with time, and the durability is inferior.
　また、キレート化剤を用いて無機酸化物粒子とシリコーン樹脂とを相溶化させる場合、経時変化や熱劣化が原因で着色を呈するという問題点があった。
　また、高屈折率の発光素子用充填材料においては、各種有機分子と相互作用し易いメチルフェニルシリコーンにナノ粒子を分散させた透明分散液が提案されているが、低極性であるジメチルシリコーン樹脂での透明分散および硬化体については達成できていない。
　また、付加反応型のジメチルシリコーンを用いる場合では、硬化前のシリコーンには透明分散するが、硬化工程で、相分離が発生し白化してしまう場合があるという問題点があった。 Further, when 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.
In addition, as a high refractive index filling material for light-emitting elements, 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.
In addition, when 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.
　一方、従来の金属酸化物粒子の表面を変性シリコーンで処理する方法も提案されているが、一般的に変性シリコーンが多官能であることから、無機酸化物粒子の表面を確実に処理することができず、未反応の変性部位がシリコーン樹脂との相溶に悪影響を及ぼすことがあるという問題点があった。そこで、この問題点を解決するために、二次あるいは三次の表面処理（表面修飾）を施す等の改善が試みられているが、工程が煩雑化する等の問題点があった。 On the other hand, a method of treating the surface of the conventional metal oxide particles with a modified silicone has also been proposed, but since the modified silicone is generally polyfunctional, it is possible to reliably treat the surface of the inorganic oxide particles. However, there is a problem that the unreacted modified site may adversely affect the compatibility with the silicone resin. Therefore, in order to solve this problem, attempts have been made to improve the surface treatment (secondary or tertiary surface treatment), but there have been problems such as complicated processes.
　本発明は、上記の課題を解決するためになされたものである。屈折率、機械的特性およびガスバリア性の向上と共に透明性の維持を可能とする無機酸化物粒子をシリコーン樹脂中に分散した場合に、分散性が高く、しかも、硬化時の相分離・白化を防止することが可能な無機酸化物粒子とシリコーン樹脂との複合組成物及び透明複合体を提供することを目的とする。 The present invention has been made to solve the above problems. When dispersed in silicone resin, 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.
　本発明者等は、上記の課題を解決するために鋭意検討を重ねた。その結果、平均分散粒子径が１ｎｍ以上かつ２０ｎｍ以下の無機酸化物粒子を、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーを用いて表面修飾し、さらに、シリコーン樹脂と、反応触媒とを用いて複合化することにより、無機酸化物粒子をシリコーン樹脂中に分散した場合に、無機酸化物粒子の分散性が大幅に向上すると共に、透明性を維持しつつ、シリコーン樹脂の耐熱性及び耐光性を維持するともに、屈折率が制御された透明複合体を得ることができることを見出し、本発明を完成するに至った。 The inventors of the present invention made extensive studies to solve the above problems. As a result, 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. When 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.
　すなわち、本発明の無機酸化物粒子とシリコーン樹脂との複合組成物は、少なくとも、無機酸化物粒子であって、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーが結合することにより表面修飾されるとともに平均分散粒子径が１ｎｍ以上かつ２０ｎｍ以下である無機酸化物粒子と、シリコーン樹脂と、反応触媒とを含有してなる複合組成物であって、前記シリコーン樹脂は、ビニル変性シリコーン及びハイドロジェン変性シリコーンを含有し、前記反応触媒は、ヒドロシリル化反応触媒を含有してなることを特徴とする。 That is, 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. And 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.
　前記ポリジメチルシロキサン骨格ポリマーは、モノグリシジルエーテル末端ポリジメチルシロキサンおよび／またはモノヒドロキシエーテル末端ポリジメチルシロキサンであることが好ましい。
　前記ビニル変性シリコーンは、両末端ビニル－ジメチルシリコーン、両末端ビニルジフェニル－ジメチルシリコーン、両末端ビニル－フェニルメチルシリコーン、両末端ビニル－ジエチルシリコーン、側鎖ビニル－ジメチルシリコーン、ビニルメチルシリコーン、ビニルメトキシシリコーン、ビニルレジン分散体からなる群から選択された１種または２種以上であることが好ましい。 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.
　前記ハイドロジェン変性シリコーンは、両末端ハイドロジェン－ジメチルシリコーン、メチルハイドロジェン－ジメチルシリコーン、メチルハイドロジェンシリコーン、エチルハイドロジェンシリコーン、メチルハイドロジェン－フェニルメチルシリコーン、ハイドライドレジンからなる群から選択された１種または２種以上であることが好ましい。 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 | species or 2 or more types.
　前記ハイドロジェン変性シリコーンは、下記の式（１）
Figure JPOXMLDOC01-appb-C000002
 　（但し、Ｒ１～Ｒ８は相互に独立な任意の有機基（Ｈを除く）、ｍは１以上の整数、ｎは０を含む正の整数である）
に示す側鎖ハイドロジェン変性シリコーンを含有してなり、前記側鎖ハイドロジェン変性シリコーンにおけるｍとｎとの比（ｍ／（ｍ＋ｎ））は０．２５以上かつ１以下であることが好ましい。 The hydrogen-modified silicone has the following formula (1):
Figure JPOXMLDOC01-appb-C000002
 (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.
　本発明の透明複合体は、シリコーン樹脂中に、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーが結合することにより表面修飾された無機酸化物粒子が平均分散粒子径１ｎｍ以上かつ２０ｎｍ以下にて分散するとともに、前記シリコーン樹脂中にヒドロシリル化反応触媒を含有してなることを特徴とする。 In the transparent composite of the present invention, 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. And a hydrosilylation reaction catalyst is contained in the silicone resin.
　本発明の透明複合体は、本発明の無機酸化物粒子とシリコーン樹脂との複合組成物を、所定の形状に成形し固化するか、または前記複合組成物を固化した後に成形してなることを特徴とする。 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. Features.
　本発明の無機酸化物粒子とシリコーン樹脂との複合組成物の製造方法は、無機酸化物粒子の表面を、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーにより修飾し、表面が修飾された平均分散粒子径が１ｎｍ以上かつ２０ｎｍ以下の無機酸化物粒子を得る工程と、前記表面が修飾された平均分散粒子径が１ｎｍ以上かつ２０ｎｍ以下の無機酸化物粒子と、シリコーン樹脂と、反応触媒とを混合する工程とを含むことを特徴とする。 In the method for producing a composite composition of inorganic oxide particles and silicone resin according to the present invention, 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. A step of obtaining inorganic oxide particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less, an inorganic oxide particle having an average dispersed particle diameter of 1 nm or more and 20 nm or less whose surface has been modified, a silicone resin, a reaction catalyst, And a step of mixing.
　本発明の無機酸化物粒子とシリコーン樹脂との複合組成物は、少なくとも、無機酸化物粒子であって、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーが結合することにより表面修飾されるとともに平均分散粒子径が１ｎｍ以上かつ２０ｎｍ以下である無機酸化物粒子と、シリコーン樹脂と、反応触媒とを含有し、シリコーン樹脂は、ビニル変性シリコーン及びハイドロジェン変性シリコーンを含有し、反応触媒は、ヒドロシリル化反応触媒を含有する。これにより、シリコーン樹脂中における無機酸化物粒子の分散性を大幅に向上させることができる。
　したがって、この複合組成物を用いれば、無機酸化物粒子とシリコーン樹脂とを複合化した場合に、分散性が高く、しかも、硬化時の相分離・白化を防止することができ、よって、透明性、耐熱性及び耐光性を維持しつつ、屈折率が制御された透明複合体を得ることができる。 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.
Therefore, when this composite composition is used, 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.
　本発明の透明複合体によれば、シリコーン樹脂中に、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーが結合することにより表面修飾された無機酸化物粒子が平均分散粒子径１ｎｍ以上かつ２０ｎｍ以下にて分散するとともに、前記シリコーン樹脂中にヒドロシリル化反応触媒を含有することとした。これにより、透明性、耐熱性及び耐光性を維持しつつ、屈折率が制御された無機酸化物粒子とシリコーン樹脂との透明複合体を容易に得ることができる。 According to the transparent composite of the present invention, 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. In addition to being dispersed below, the silicone resin contained a hydrosilylation reaction catalyst. Thereby, it is possible to easily obtain a transparent composite of inorganic oxide particles having a controlled refractive index and a silicone resin while maintaining transparency, heat resistance, and light resistance.
　本発明の透明複合体によれば、本発明の無機酸化物粒子とシリコーン樹脂との複合組成物を、所定の形状に成形し固化するか、または複合組成物を固化した後に成形する。これにより、透明性、耐熱性及び耐光性を維持しつつ、屈折率が制御された無機酸化物粒子とシリコーン樹脂との透明複合体を容易に得ることができる。 According to the transparent composite of the present invention, 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. Thereby, it is possible to easily obtain a transparent composite of inorganic oxide particles having a controlled refractive index and a silicone resin while maintaining transparency, heat resistance, and light resistance.
　本発明は、無機酸化物粒子とシリコーン樹脂との複合組成物及び透明複合体に関する。さらに詳しくは、シリコーン樹脂のフィラー材として好適に用いられ、屈折率、機械的特性およびガスバリア性の向上と共に透明性の維持を可能とする無機酸化物粒子について、シリコーン樹脂中に分散した場合の分散性および硬化時の相分離・白化を防止することが可能な無機酸化物粒子とシリコーン樹脂との複合組成物、及び、この複合組成物を成形固化した透明複合体に関するものである。
　本発明の無機酸化物粒子とシリコーン樹脂との複合組成物及び透明複合体を実施するための好ましい形態について説明する。
　この形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。本発明の趣旨を逸脱しない範囲で、構成の付加、省略、置換、およびその他の変更が可能である。 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.
The preferable form for implementing the composite composition and transparent composite_body | complex of the inorganic oxide particle | 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.
［無機酸化物粒子とシリコーン樹脂との複合組成物］
　本実施形態の無機酸化物粒子とシリコーン樹脂との複合組成物（以下、単に「複合組成物」と称することもある。）は、無機酸化物粒子をシリコーン樹脂中に分散してなる複合組成物であり、少なくとも、無機酸化物粒子であって、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーが結合することにより表面修飾されるとともに平均分散粒子径が１ｎｍ以上かつ２０ｎｍ以下である無機酸化物粒子と、シリコーン樹脂と、反応触媒とを含有してなる複合組成物である。 [Composite composition of inorganic oxide particles and silicone resin]
The composite composition of inorganic oxide particles and silicone resin of the present embodiment (hereinafter sometimes simply referred to as “composite composition”) 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.
　ここで「複合組成物」は、特定の形状を有さず、一度変形すると元の形状には戻らない不可逆的な変形性を有し、後述の透明複合体の原料となる。
　この複合組成物の状態としては、例えば、液状やチクソトロピー性を有するゲル状の状態にあるものを示すものとする。 Here, 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.
As a state of this composite composition, for example, a state in a liquid state or a gel state having thixotropy shall be shown.
　無機酸化物粒子の成分である無機酸化物としては、特に限定されないが、ケイ素（Ｓｉ）等の非金属元素の酸化物、ジルコニウム（Ｚｒ）、チタン（Ｔｉ）、アルミニウム（Ａｌ）、鉄（Ｆｅ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、イットリウム（Ｙ）、ニオブ（Ｎｂ）、モリブデン（Ｍｏ）、インジウム（Ｉｎ）、スズ（Ｓｎ）、タンタル（Ｔａ）、タングステン（Ｗ）、鉛（Ｐｂ）、ビスマス（Ｂｉ）、セリウム（Ｃｅ）、アンチモン（Ｓｂ）、ゲルマニウム（Ｇｅ）等の金属元素の酸化物が挙げられる。 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.
　このような無機酸化物としては、例えば、酸化ジルコニウム（ＺｒＯ２）、酸化チタン（ＴｉＯ２）、酸化ケイ素（ＳｉＯ２）、酸化アルミニウム（Ａｌ２Ｏ３）、酸化鉄（Ｆｅ２Ｏ３、ＦｅＯ、Ｆｅ３Ｏ４）、酸化銅（ＣｕＯ、Ｃｕ２Ｏ）、酸化亜鉛（ＺｎＯ）、酸化イットリウム（Ｙ２Ｏ３）、酸化ニオブ（Ｎｂ２Ｏ５）、酸化モリブデン（ＭｏＯ３）、酸化インジウム（Ｉｎ２Ｏ３、Ｉｎ２Ｏ）、酸化スズ（ＳｎＯ２）、酸化タンタル（Ｔａ２Ｏ５）、酸化タングステン（ＷＯ３、Ｗ２Ｏ５）、酸化鉛（ＰｂＯ、ＰｂＯ２）、酸化ビスマス（Ｂｉ２Ｏ３）、酸化セリウム（ＣｅＯ２、Ｃｅ２Ｏ３）、酸化アンチモン（Ｓｂ２Ｏ３、Ｓｂ２Ｏ５）酸化ゲルマニウム（ＧｅＯ２、ＧｅＯ）等が挙げられる。 Examples of such inorganic oxides 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.
　このような無機酸化物には、スズ添加酸化インジウム（ＩＴＯ：Indium Tin Oxide）、イットリア安定化ジルコニア（ＹＳＺ：Yttria Stabilized Zirconia）等の複合酸化物も含まれる。
　このような無機酸化物は、１種のみを単独で用いてもよく、２種以上を混合して用いてもよい。
　特に、シリコーン樹脂との複合組成物を高屈折率化する場合には、高い屈折率を有し、可視光線に対して無色透明であり、硬度も高い酸化ジルコニウム（ＺｒＯ２）や酸化チタン（ＴｉＯ２）が好適である。 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.
　また、シリコーン樹脂との複合組成物を低屈折率化する場合には、例えば、中空シリカ粒子や多孔質シリカ粒子のような粒子内に空隙を有することで粒子全体として低屈折率となる無機酸化物粒子を用いることが好ましい。 Further, when reducing the refractive index of a composite composition with a silicone resin, for example, 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.
　この無機酸化物粒子の複合組成物中における平均分散粒子径は、１ｎｍ以上かつ２０ｎｍ以下であることが好ましい。平均分散粒子径は、より好ましくは３ｎｍ以上かつ１０ｎｍ以下である。
　ここで、無機酸化物粒子の平均分散粒子径を１ｎｍ以上かつ２０ｎｍ以下と限定した理由は以下の通りである。平均分散粒子径が１ｎｍ未満であると、この粒子を構成する粒子の一次粒子径も１ｎｍ未満と極めて小さくなる。このため、無機酸化物粒子の結晶性が乏しくなり、屈折率等の粒子特性を発現することが難しくなる。一方、平均分散粒子径が２０ｎｍを超えると、無機酸化物粒子によるレイリー散乱の影響が大きくなり、複合組成物の透明性が低下したり、あるいは、この複合組成物を成形・固化して得られる透明複合体の透明性が低下する。 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.
Here, 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. When 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. On the other hand, if 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.
　このように、無機酸化物粒子は、ナノメートルサイズの粒子であるから、この無機酸化物粒子をシリコーン樹脂中に分散させた複合組成物、あるいは、この複合組成物を成形・固化してなる透明複合体においても、光散乱が小さく、複合組成物や透明複合体の透明性を維持することが可能である。 Thus, since 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.
　この無機酸化物粒子の複合組成物中の含有率は、１質量％以上かつ９０質量％以下であることが好ましく、より好ましくは５質量％以上かつ９０質量％以下、さらに好ましくは１０質量％以上かつ８５質量％以下である。
　ここで、無機酸化物粒子の含有率を１質量％以上かつ９０質量％以下と限定した理由は以下の通りである。含有率が１質量％未満であると、無機酸化物粒子の量が少なすぎてしまい、無機酸化物粒子をシリコーン樹脂と複合化した場合にシリコーン樹脂の光学特性や機械的特性の変化が発現し難くなり、結果として無機酸化物粒子を複合化させる効果が得られなくなるので好ましくない。一方、含有率が９０質量％を越えると、無機酸化物粒子の分散性が十分に確保できなくなったり、複合組成物中における流動性が低下し、成形性が悪化したりするので好ましくない。 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.
Here, 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.
　次に、この無機酸化物粒子の表面修飾について説明する。
　この無機酸化物粒子の表面は、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーからなる表面修飾剤により修飾されている。
　この表面修飾剤は、ポリジメチルシロキサン骨格、特に直鎖状のポリジメチルシロキサン骨格を主鎖に有し、この主鎖の片末端（一端側）に官能基である極性基を１基のみ有している。そのため、この官能基（極性基）が無機酸化物粒子の表面へ選択的に結合すると、他端側、すなわちシロキサン骨格部分は揃って粒子外側（無機酸化物粒子の表面から遠ざかる方向）を向く形となる。 Next, the surface modification of the inorganic oxide particles will be described.
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. Therefore, when 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.
　しかも、このシロキサン骨格部分とシリコーン樹脂とは相溶性が高く、かつ親和性も良好であるから、このポリジメチルシロキサン骨格ポリマーからなる表面修飾剤により表面修飾された無機酸化物粒子は、シリコーン樹脂中に均一に分散することができ、良好な複合組成物を形成することができる。 Moreover, since 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.
　ここで、「直鎖状のポリジメチルシロキサン骨格」とは、ポリジメチルシロキサン骨格に枝分れ（分岐）がないことを示している。
　ここで、このポリジメチルシロキサン骨格に枝分れ（分岐）があったり、あるいは、官能基である極性基がシロキサン骨格の中間に位置している（官能基がシロキサン骨格の中間に位置するケイ素に結合している）場合には、シロキサン骨格の少なくとも一部は、無機酸化物粒子の表面方向を向いたり、粒子表面に平行な方向を向いたりし易い。この場合、無機酸化物粒子の外側に向いたシロキサン骨格の量が減少することになり、無機酸化物粒子とシリコーン樹脂との間の相溶性や親和性が低下する虞が生じる。さらに、シロキサン骨格の方向に統一性が無くなるために、シロキサン骨格同士の絡み合いや立体障害が生じ、やはり無機酸化物粒子とシリコーン樹脂との間の相溶性や親和性が低下する虞がある。 Here, the “linear polydimethylsiloxane skeleton” means that the polydimethylsiloxane skeleton has no branches (branches).
Here, 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). In the case of bonding, at least a part of the siloxane skeleton is likely to face the surface direction of the inorganic oxide particles or the direction parallel to the particle surface. In this case, 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.
　また、この表面修飾剤は極性基を１基のみ有している１官能基であり、しかも、この官能基が無機酸化物粒子との結合に使用されるので、無機酸化物粒子に結合した表面修飾剤には官能基が存在しない。したがって、従来の多官能ポリシロキサンを用いた場合に、未反応で残留している官能基が原因となって発生するシリコーン樹脂との相溶性の悪化、例えば白濁化等が発生する虞が無く、安定した複合組成物を得ることができる。 Further, 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.
　このような表面修飾剤としては、モノグリシジルエーテル末端ポリジメチルシロキサンおよび／またはモノヒドロキシエーテル末端ポリジメチルシロキサンを有することが好ましい。本発明に使用されるモノグリシジルエーテル末端ポリジメチルシロキサンは、分子量が５００～１００００であることが好ましい。また、本発明に使用されるモノヒドロキシエーテル末端ポリジメチルシロキサンは、分子量が５００～１００００であることが好ましい。
　これらの表面修飾剤が有する末端基のうち、モノグリシジルエーテル末端は、グリシジル基の一部であるエポキシ基の部分が開環して無機酸化物粒子の表面の水酸基と結合し、また、モノヒドロキシエーテル末端は、末端の水酸基と無機酸化物粒子の表面の水酸基とが脱水縮合することで結合する。 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.
Among the terminal groups possessed by these surface modifiers, 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.
　これらの表面修飾剤のうち、モノグリシジルエーテル末端ポリジメチルシロキサンは、もとより水酸基を含有しておらず、また、モノヒドロキシエーテル末端ポリジメチルシロキサンは、無機酸化物粒子と結合する官能基のみに水酸基を有している。したがって、いずれの表面修飾剤においても、無機酸化物粒子の表面に結合した後は、水酸基を有さないか、もしくは水酸基が無機酸化物粒子の表面近傍に存在し、シリコーン樹脂との相溶を妨げない状態となっている。 Of these surface modifiers, 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. Have. Therefore, in 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.
　また、これらの表面修飾剤により表面修飾された無機酸化物粒子とシリコーン樹脂との複合組成物から得られた透明複合体は、収縮率が小さい。これにより、透明複合体におけるポアやクラックの発生が無く、また硬化したシリコーン樹脂中における無機酸化物粒子の分散性も良好に保たれ、欠陥のない透明複合体が得られることとなる。 Further, 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.
　本実施形態の無機酸化物粒子は、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーにより表面修飾されているので、シリコーン樹脂に対して、相溶性や分散性が優れている。したがって、シリコーン樹脂自体には特段の制限は無く、通常のシリコーン樹脂であれば問題なく使用することができる。
　これらのシリコーン樹脂の中でも、特に、室温（２５℃）以上かつ１５０℃程度以下で硬化物が得られるヒドロシリル化反応を用いたシリコーン樹脂が特に好ましく、このようなシリコーン樹脂としては、ビニル変性シリコーンおよびハイドロジェン変性シリコーンが好適である。 Since 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. Accordingly, the silicone resin itself is not particularly limited, and any ordinary silicone resin can be used without any problem.
Among these 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.
　ビニル変性シリコーンとしては、両末端ビニル－ジメチルシリコーン、両末端ビニルジフェニル－ジメチルシリコーン、両末端ビニル－フェニルメチルシリコーン、両末端ビニル－ジエチルシリコーン、側鎖ビニル－ジメチルシリコーン、ビニルメチルシリコーン、ビニルメトキシシリコーン、ビニルレジン分散体等が挙げられる。これらのビニル変性シリコーンは、１種類を選択使用してもよく、２種類以上を組み合わせて使用してもよい。 As vinyl-modified silicones, 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.
　ハイドロジェン変性シリコーンとしては、両末端ハイドロジェン－ジメチルシリコーン、メチルハイドロジェン－ジメチルシリコーン、メチルハイドロジェンシリコーン、エチルハイドロジェンシリコーン、メチルハイドロジェン－フェニルメチルシリコーン、ハイドライドレジン等が挙げられる。これらのハイドロジェン変性シリコーンは、１種類を選択使用してもよく、２種類以上を組み合わせて使用してもよい。 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.
　このハイドロジェン変性シリコーンにおいては、下記の式（１）
　（但し、Ｒ１～Ｒ８は相互に独立な任意の有機基（Ｈを除く）、ｍは１以上の整数、ｎは０を含む正の整数である）
に示す側鎖ハイドロジェン変性シリコーンを含有していることが好ましい。
　ここで、側鎖ハイドロジェン変性シリコーンが好ましい理由は、ビニル変性シリコーンとヒドロシリル化反応等により重合硬化してシリコーン樹脂重合体を形成する際に、末端ハイドロジェン変性シリコーンに比べて反応性が高く、さらに反応基であるハイドロジェン変性シリコーンの量が多くできることから架橋密度が高くなり、結果として得られたシリコーン樹脂重合体の特性を向上させることができるからである。 In this hydrogen-modified silicone, 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 to contain the side chain hydrogen-modified silicone shown in FIG.
Here, 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.
　さらにまた、上記の式（１）に示す側鎖ハイドロジェン変性シリコーンにおけるｍとｎとの比（ｍ／（ｍ＋ｎ））は、０．２５以上かつ１以下であることが好ましい。比（ｍ／（ｍ＋ｎ））は、より好ましくは０．３０以上かつ０．７０以下である。
　ここで、ｍとｎとの比（ｍ／（ｍ＋ｎ））を０．２５以上かつ１以下に限定した理由は、次のとおりである。まず、ｍとｎとの比（ｍ／（ｍ＋ｎ））が０．２５未満であると、硬化時の架橋密度が少なすぎるために、無機酸化物粒子の凝集・相分離速度がシリコーン樹脂の硬化速度よりも速くなり、その結果、シリコーン樹脂との硬化の際に透明性が失われるからである。 Furthermore, 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.
Here, 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.
　次に、ｍとｎとの比（ｍ／（ｍ＋ｎ））は１が上限であるが、ｍとｎの比（ｍ／（ｍ＋ｎ））が大きくなるほど、下記の式（２）
Figure JPOXMLDOC01-appb-C000004
 に示すハイドロジェン含有ユニットの含有率が高くなり、透明複合体を形成した後もビニル変性シリコーンと未反応のユニットの割合が増加すると考えられる。しかしながら、この未反応ハイドロジェン含有ユニットが透明複合体の特性に及ぼす影響はほとんど無い。したがって、側鎖ハイドロジェン変性シリコーンにおけるｍとｎの比（ｍ／（ｍ＋ｎ））の最大値は１であってよい。 Next, the upper limit of the ratio of m to n (m / (m + n)) is 1. However, as the ratio of m to n (m / (m + n)) increases, the following formula (2)
Figure JPOXMLDOC01-appb-C000004
 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.
　上記の式（１）においては、Ｒ１～Ｒ８は相互に独立な任意の有機基（Ｈを除く）であり、その一部または全てが同一であってもよい。ここで「一部が同一」とは、例えば、Ｒ１とＲ３とＲ４とＲ６とが同一であり、かつＲ１とＲ２とＲ５とＲ７とＲ８とは相互に異なる、というように、一部のみが同一種である場合だけでなく、例えば、Ｒ１とＲ３とＲ４とが同一かつＲ２とＲ５とＲ７とＲ８が同一であり、かつＲ１とＲ２とＲ６とは相互に異なる、というような、その一部同士が同一の組み合わせであってもよい。
　また、「有機基」とは、特性基、官能基、置換基等の有機物からなる基全般を表すものであって、例えば、アルキル基、アルコキシ基等が含まれる。 In the above formula (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. Here, “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.
Further, 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.
　このシリコーン樹脂は、無機酸化物粒子等と混合後の複合組成物の特性として、特定の形状を有さず、一度変形すると元の形状には戻らない不可逆的な変形性を有し、後述の透明複合体の原料となり、例えば液状やチクソトロピー性を有するゲル状の状態にあるものであればよく、その重合度は特に限定されない。 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.
　すなわち、複合組成物が上記特性を有するものであれば、モノマー（単量体）、オリゴマー（２～数百程度の重合体）、ポリマー（数百以上の重合体）のいずれでもよく、またこれらを組み合わせることで重合度に幅を持たせたものを用いてもかまわない。
　また、このシリコーン樹脂においては、その特性を損なわない範囲で酸化防止剤、離型剤、カップリング剤、無機充填剤等を添加してもよい。 That is, as long as the composite composition has the above properties, it 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 | variety of polymerization degree by combining.
Moreover, in this silicone resin, you may add antioxidant, a mold release agent, a coupling agent, an inorganic filler, etc. in the range which does not impair the characteristic.
　本実施形態の複合組成物は、反応触媒を含有している。
　この反応触媒としては、ヒドロシリル化反応触媒を含有していることが好ましい。このヒドロシリル化反応触媒としては貴金属系触媒が挙げられ、貴金属の粉体、貴金属塩、貴金属錯体等を適宜選択することができる。貴金属系触媒の中では白金族系触媒が好ましく、例えば、白金系触媒、ロジウム系触媒、パラジウム系触媒等を挙げることができ、特に、白金系触媒が好ましい。この白金系触媒としては、白金微粉体、塩化白金酸、白金－オレフィン錯体、白金－カルボニル錯体等が挙げられ、これらを単独で、あるいは２種以上を組み合わせて用いることができる。 The composite composition of this embodiment contains a reaction catalyst.
The reaction catalyst preferably contains a hydrosilylation reaction catalyst. Examples of 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. Among 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. Examples of 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.
　また、本実施形態の複合組成物は、有機溶媒を含有することができる。
　ここで、複合組成物が有機溶媒を含有する利点としては、次のような点が上げられる。
　第１の利点としては、複合組成物の粘度制御が挙げられる。例えば、無機酸化物粒子とシリコーン樹脂との混合物が高粘度の場合、流動性が悪化し、後述の透明複合体の成形性の低下や取り扱いの容易性が低下するという問題が生じる場合がある。そこで、これらの問題を解消するために、有機溶媒を混合物に添加することにより、この混合物の粘度を所望の粘度にまで低下させることが可能になる。無機酸化物粒子とシリコーン樹脂との混合物の粘度は、好ましくは０．０５Ｐａ・ｓ～１００００Ｐａ・ｓであり、より好ましくは０．１Ｐａ・ｓ～１００Ｐａ・ｓである。 Moreover, the composite composition of this embodiment can contain an organic solvent.
Here, the following points can be raised as advantages of the composite composition containing an organic solvent.
The first advantage is viscosity control of the composite composition. For example, when the mixture of the inorganic oxide particles and the silicone resin has a high viscosity, the fluidity is deteriorated, and there may be a problem that the moldability and ease of handling of the transparent composite described later are lowered. Therefore, in order to solve these problems, it is possible to reduce the viscosity of the mixture to a desired viscosity by adding an organic solvent to the mixture. 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.
　第２の利点としては、混合・分散の容易化が挙げられる。例えば、表面修飾剤により修飾された無機酸化物粒子を、まず、使用するシリコーン樹脂と相溶性の高い有機溶媒中に分散させて無機酸化物粒子分散液とし、この無機酸化物粒子分散液とシリコーン樹脂とを混合・攪拌すれば、無機酸化物粒子のシリコーン樹脂に対する分散性が非常に高くなるので好ましい。 The second advantage is easy mixing and dispersion. For example, 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.
　この有機溶媒としては、疎水性溶媒を用いることが好ましい。その理由は、表面修飾された無機酸化物の分散性が高く、シリコーン樹脂との相溶性が高い溶媒として、疎水性溶媒が適しているからである。
　このような疎水性溶媒としては、例えば、ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素、ジクロロメタン、クロロホルム、四塩化炭素等の塩素含有溶媒が好適に用いられ、これらの溶媒のうち１種を単独で、または２種以上を混合して用いることができる。 As the organic solvent, a hydrophobic solvent is preferably used. The reason is that a hydrophobic solvent is suitable as a solvent having high dispersibility of the surface-modified inorganic oxide and high compatibility with the silicone resin.
As such a hydrophobic solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and 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.
　この有機溶媒の含有率は、上記等の溶媒添加効果が得られるものであれば特に限定はされないが、通常、表面修飾された無機酸化物粒子とシリコーン樹脂との合計量に対して４００質量％以下であることが好ましい。有機溶媒の含有率は、より好ましくは１００質量％以下である。その理由としては、有機溶媒が過剰に存在すると、この複合組成物を用いて後述の透明複合体を形成する際に、粘度が低すぎて成形性に難が生じたり、あるいは有機溶媒の除去に時間を要したりするので、好ましくないからである。 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.
［複合組成物の製造方法］
　本実施形態の複合組成物の製造方法は、まず、無機酸化物粒子の表面を、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーにより修飾し、表面が修飾された平均分散粒子径が１ｎｍ以上かつ２０ｎｍ以下の無機酸化物粒子を形成し、次いで、この表面修飾された平均分散粒子径が１ｎｍ以上かつ２０ｎｍ以下の無機酸化物粒子と、シリコーン樹脂と、反応触媒とを混合する方法である。 [Method for producing composite composition]
In the manufacturing method of the composite composition of this embodiment, first, 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. .
　ここで、無機酸化物粒子の表面を、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーにより修飾する方法としては、次に示す方法を挙げることができる。すなわち、始めに無機酸化物粒子の表面に予め特定の分散剤を結合させて疎水性溶媒（有機溶媒）への分散性を持たせる。次に、この無機酸化物粒子を疎水性溶媒中に分散させ、分散液を得る。次に、得られた分散液に片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーからなる表面修飾剤を加え、この疎水性溶媒中にて無機酸化物粒子の表面に予め結合している特定の分散剤と、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーからなる表面修飾剤とを置換させる、という方法を挙げることができる。 Here, as a method of modifying the surface of the inorganic oxide particles with a polydimethylsiloxane skeleton polymer having one functional group at one end, the following method can be exemplified. That is, first, 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). Next, the inorganic oxide particles are dispersed in a hydrophobic solvent to obtain a dispersion. Next, 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. And a method of substituting the surface modifier made of a polydimethylsiloxane skeleton polymer having one functional group at one end.
　上記の方法を、より詳細に説明する。
　始めに、無機酸化物粒子の表面に特定の分散剤を結合させて、疎水性溶媒への分散性を持たせる。
　この特定の分散剤が結合した無機酸化物粒子は疎水性溶媒に容易に分散する。また、この特定の分散剤が結合した無機酸化物粒子は、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーよりなる表面修飾剤が共存する場合に、前記無機酸化物粒子表面において、既に結合している特定の分散剤と前記表面修飾剤とが、容易に置換を起こすことができる。 The above method will be described in more detail.
First, 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. In addition, 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.
　特定の分散剤としては、有機酸化合物または有機塩基化合物を挙げることができる。有機酸化合物としてはカルボン酸、リン酸、スルホン酸等が、有機塩基化合物としてはアミン、フォスファゼン塩基等が挙げられる。
　これらの分散剤の中でも、無機酸化物粒子を分散させる分散剤として機能し、かつ表面修飾剤との反応時には良好に脱離させることが可能であることから、カルボン酸やアミンが好適に用いられる。 Specific examples of the dispersant include organic acid compounds and organic base compounds. Examples of the organic acid compound include carboxylic acid, phosphoric acid, and sulfonic acid, and examples of the organic base compound include amine and phosphazene base.
Among these dispersants, 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. .
　カルボン酸としては、例えば、ギ酸、酢酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、カプリン酸、ラウリン酸、ステアリン酸などの飽和脂肪酸、オレイン酸などの不飽和脂肪酸から選択された１種または２種以上を選択して用いればよい。また、アミンとしては、例えば、ピリジン、ビピリジンなどの芳香族アミンや、トリエチルアミン、ジエチルアミン、モノエチルアミン、ブチルアミンなどの脂肪族アミンから選択された１種または２種以上を選択して用いればよい。 Examples of the carboxylic acid 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. A species or two or more species may be selected and used. As 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.
　次いで、表面に特定の分散剤を結合させた無機酸化物粒子を、疎水性溶媒中へ分散させる。
　疎水性溶媒としては、前記表面に特定の分散剤を結合させた無機酸化物粒子が安定に分散するものであればよいが、例えば、ベンゼン、トルエン、キシレン、エチルベンゼンなどの芳香族炭化水素、ジクロロメタン、クロロホルム、四塩化炭素などの含塩素溶媒が好適に用いられ、これらの溶媒のうち１種または２種以上を用いることができる。 Next, 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. For example, 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.
　次いで、前記表面に特定の分散剤を結合させた無機酸化物粒子を分散させた疎水性溶媒に、既に述べた片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーからなる表面修飾剤を加え、この表面修飾剤を無機酸化物表面に既に結合している特定の分散剤と置換させる。これにより、無機酸化物粒子の表面を、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーからなる表面修飾剤にて修飾する。
　この片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーからなる表面修飾剤の無機酸化物粒子に対する質量比は、無機酸化物粒子の全質量に対して５質量％以上かつ２００質量％以下であることが好ましく、より好ましくは１０質量％以上かつ１００質量％以下、さらに好ましくは２０質量％以上かつ１００質量％以下である。 Next, 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.
　ここで、表面修飾剤の質量比を５質量％以上かつ２００質量％以下と限定した理由は、表面修飾剤の質量比が５質量％未満であると、表面修飾剤の量が少なすぎて無機酸化物粒子の表面を十分に修飾することができず、したがって、この表面修飾が不十分な無機酸化物粒子のシリコーン樹脂への相溶が困難となり、シリコーン樹脂との複合化の際に透明性が失われるからである。一方、表面修飾剤の質量比が２００質量％を超えると、複合組成物における表面修飾剤の割合が無視できなくなる程増大し、したがって、複合組成物の特性に大きく影響を及ぼすこととなり、特性の低下を引き起こす虞があるからである。 Here, 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. On the other hand, when 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.
　このように、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーからなる表面修飾剤を用い、この表面修飾剤を疎水性溶媒中で無機酸化物粒子と反応させることにより、表面修飾剤の官能基（極性基）は無機酸化物粒子へ選択的に配向・結合し、一方他端側は疎水性溶媒中に分散しようとして、無機酸化物粒子の外側を向く形となる。したがって、これらの表面処理剤は、官能基部分を無機酸化物粒子と結合し、他端側は無機酸化物粒子に対して放射状に離れるような形となる。
　以上により、表面が片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーにより修飾されるとともに平均分散粒子径が１ｎｍ以上かつ２０ｎｍ以下である無機酸化物粒子が得られる。 Thus, by using 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.
As described above, 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.
　次いで、この表面修飾された平均分散粒子径が１ｎｍ以上かつ２０ｎｍ以下の無機酸化物粒子と、シリコーン樹脂と、反応触媒とを混合する。この際、必要に応じて有機溶媒を加えてもよい。
　ここで、シリコーン樹脂自体には特段の限定は無く、上述したヒドロシリル化反応により硬化可能なビニル変性シリコーンおよびハイドロジェン変性シリコーンの組み合わせであれば問題なく使用することができる。 Next, 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. At this time, an organic solvent may be added as necessary.
Here, 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.
　すなわち、ビニル変性シリコーンとしては、両末端ビニル－ジメチルシリコーン、両末端ビニルジフェニル－ジメチルシリコーン、両末端ビニル－フェニルメチルシリコーン、両末端ビニル－ジエチルシリコーン、側鎖ビニル－ジメチルシリコーン、ビニルメチルシリコーン、ビニルメトキシシリコーン、ビニルレジン分散体等の中から、１種類を単独で、または２種類以上を組み合わせて選択使用することができる。 That is, as vinyl-modified silicone, 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.
　また、ハイドロジェン変性シリコーンとしては、両末端ハイドロジェン－ジメチルシリコーン、メチルハイドロジェン－ジメチルシリコーン、メチルハイドロジェンシリコーン、エチルハイドロジェンシリコーン、メチルハイドロジェン－フェニルメチルシリコーン、ハイドライドレジン等の中から、１種類を単独で、または２種類以上を組み合わせて選択使用することができる。 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.
　また、ハイドロジェン変性シリコーンにおいては、上記の式（１）に示す側鎖ハイドロジェン変性シリコーンを含有していることが好ましい。
　ここで、側鎖ハイドロジェン変性シリコーンが好ましい理由は、ビニル変性シリコーンとヒドロシリル化反応等により重合硬化してシリコーン樹脂重合体を形成する際に、末端ハイドロジェン変性シリコーンに比べて反応性が高く、さらに反応基であるハイドロジェン変性シリコーンの量が多くできることから架橋密度が高くなり、結果として得られたシリコーン樹脂重合体の特性を向上させることができるからである。 The hydrogen-modified silicone preferably contains a side chain hydrogen-modified silicone represented by the above formula (1).
Here, 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.
　さらにまた、上記の式（２）に示す側鎖ハイドロジェン変性シリコーンにおけるｍとｎとの比（ｍ／（ｍ＋ｎ））は０．２５以上かつ１以下であることが好ましい。比（ｍ／（ｍ＋ｎ））は、より好ましくは０．３０以上かつ０．７０以下である。
　ここで、ｍとｎとの比（ｍ／（ｍ＋ｎ））を０．２５以上に限定した理由は、次のとおりである。まず、ｍとｎとの比（ｍ／（ｍ＋ｎ））が０．２５未満であると、硬化時の架橋密度が少なすぎるために、無機酸化物粒子の凝集・相分離速度がシリコーン樹脂の硬化速度よりも速くなり、その結果、シリコーン樹脂との硬化の際に透明性が失われるからである。 Furthermore, 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.
Here, 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.
　次に、ｍとｎとの比（ｍ／（ｍ＋ｎ））は１が上限であるが、ｍとｎとの比（ｍ／（ｍ＋ｎ））が大きくなるほど、上記の式（２）に示すハイドロジェン含有ユニットの含有率が高くなり、透明複合体を形成した後もビニル変性シリコーンと未反応のユニットの割合が増加すると考えられる。しかしながら、この未反応ハイドロジェン含有ユニットが透明複合体の特性に及ぼす影響はほとんど無い。従って、側鎖ハイドロジェン変性シリコーンにおけるｍとｎとの比（ｍ／（ｍ＋ｎ））の最大値は１であってよい。 Next, the upper limit of the ratio of m to n (m / (m + n)) is 1. However, as the ratio of m to n (m / (m + n)) increases, 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.
　表面修飾された無機酸化物粒子とシリコーン樹脂とを混合する方法は、特に限定されず、ミキサー、各種ミル、超音波の印加等、従来知られている方法を用いればよい。 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.
　ここで、表面修飾剤により表面が修飾された無機酸化物粒子は、粒子のままの状態でシリコーン樹脂と混合することも可能である。しかしながら、この表面修飾された無機酸化物粒子のシリコーン樹脂中における分散性や混合の容易性を高めるためには、予め、この表面修飾された無機酸化物粒子を使用するシリコーン樹脂に対して相溶性の高い有機溶媒（疎水性溶媒）中に再分散させておき、得られた無機酸化物粒子分散液とシリコーン樹脂とを混合・攪拌することが好ましい。 Here, 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. However, in order to improve the dispersibility of the surface-modified inorganic oxide particles in the silicone resin and the ease of mixing, 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.
　すなわち、無機酸化物粒子を、ある程度の粘度を有するシリコーン樹脂に対して直接投入して撹拌した場合、この無機酸化物粒子を粘性を有するシリコーン樹脂中に均一にかつ粒子の凝集を防ぎつつ分散させることが難しく、得られた分散体中の無機酸化物粒子の分散性も悪く、さらには無機酸化物粒子を粘性を有するシリコーン樹脂中に分散させる工程自体、多大な労力を要する。 That is, when inorganic oxide particles are directly added to a silicone resin having a certain degree of viscosity and stirred, the inorganic oxide particles are uniformly dispersed in the silicone resin having viscosity while preventing aggregation of the particles. It is difficult, the dispersibility of the inorganic oxide particles in the obtained dispersion is poor, and further, the process itself of dispersing the inorganic oxide particles in the viscous silicone resin requires a great deal of labor.
　一方、表面修飾された無機酸化物粒子を一旦、シリコーン樹脂に対して相溶性の高い有機溶媒中に再分散させた場合、有機溶媒自体が低粘度であるから、無機酸化物粒子は有機溶媒中に均一に分散し、低粘度の無機酸化物粒子分散液となる。そこで、この無機酸化物粒子が均一に分散された分散液とシリコーン樹脂とを混合すれば、液体同士が混合されることから、シリコーン樹脂がある程度の粘度を有するものとしても、低粘度の分散液と均一に混合され、その結果、無機酸化物粒子はシリコーン樹脂中に容易かつ均一に分散することとなる。さらには低粘度の無機酸化物粒子分散液と粘性を有するシリコーン樹脂とを混合する工程自体、溶液同士の混合工程であるから、多大な労力を必要としない。 On the other hand, when the surface-modified inorganic oxide particles are once redispersed in an organic solvent highly compatible with the silicone resin, the organic solvent itself has a low viscosity. In the form of a low-viscosity inorganic oxide particle dispersion. Therefore, if 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.
　さらに、表面修飾された無機酸化物粒子とシリコーン樹脂との混合物が高粘度であった場合、この混合物の流動性が悪化し、ひいては後述の透明複合体の成形性の低下や取り扱いの容易性が低下するという問題が生じる場合がある。
　この問題を防ぐためには、無機酸化物粒子とシリコーン樹脂とを混合する際に、適当な溶媒、例えば、表面修飾された無機酸化物粒子の分散性が高くかつシリコーン樹脂との相溶性も高い有機溶媒を添加し、得られた混合物の粘度を低下させておくことが好ましい。 Furthermore, when 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. There may be a problem of degradation.
In order to prevent this problem, when mixing the inorganic oxide particles and the silicone resin, 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.
　このような有機溶媒としては、疎水性溶媒を用いることが好ましく、例えば、ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素、ジクロロメタン、クロロホルム、四塩化炭素等の塩素含有溶媒が好適に用いられ、これらの溶媒のうち１種を単独で、または２種以上を混合して用いることができる。
　また、この有機溶媒の含有率は、上記の溶媒添加効果が得られるものであれば特に限定はされないが、通常、表面修飾された無機酸化物粒子とシリコーン樹脂との合計量に対して４００質量％以下であることが好ましい。有機溶媒の含有率は、より好ましくは１００質量％以下である。その理由としては、有機溶媒が過剰に存在すると、この複合組成物を用いて後述の透明複合体を形成する際に、粘度が低すぎて成形性に難が生じたり、あるいは有機溶媒の除去に時間を要したりするからである。 As such an organic solvent, a hydrophobic solvent is preferably used. For example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and chlorine-containing solvents such as dichloromethane, chloroform, and carbon tetrachloride are suitably used. Of these solvents, one kind can be used alone, or two or more kinds can be mixed and used.
Further, 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.
　表面修飾された無機酸化物粒子とシリコーン樹脂とを混合する具体的な方法としては、例えば、（１）無機酸化物粒子を有機溶媒中に再分散させた後、この分散液にシリコーン樹脂を投入し、混合攪拌する方法、（２）無機酸化物粒子とシリコーン樹脂とを混合した後、この混合物に適宜有機溶媒を添加し、ミキサー等を用いて撹拌・混合することで粘度を調整し、流動性を有する混合物とする方法、等が挙げられる。
　有機溶媒の添加により得られた混合物の粘度が低い場合には、有機溶媒の一部あるいは全部を揮発等で除去することにより、粘度の調整（高粘度化）を行ってもよい。
　以上のようにして、本実施形態の複合組成物を得ることができる。 As a specific method for mixing the surface-modified inorganic oxide particles and the silicone resin, for example, (1) After redispersing the inorganic oxide particles in an organic solvent, the silicone resin is added to the dispersion (2) After mixing the inorganic oxide particles and the silicone resin, 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.
When 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.
As described above, the composite composition of the present embodiment can be obtained.
［透明複合体］
　本実施形態の透明複合体は、シリコーン樹脂中に、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーが結合することにより表面修飾された無機酸化物粒子が平均分散粒子径１ｎｍ以上かつ２０ｎｍ以下にて分散するとともに、前記シリコーン樹脂中にヒドロシリル化反応触媒を含有している透明複合体である。この透明複合体においては、有機溶媒、中でも疎水性溶媒は、基本的には含まれておらず、含まれていてもごく微量である。 [Transparent composite]
In the transparent composite of this embodiment, 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. And 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.
　ここで、「透明複合体」は特定の形状を有するが、この「所定の形状を有する」とは、透明複合体が液状、ゲル状等の不可逆的な変形性を有しておらず、使用の目的や方法に合わせた一定の形状を維持することができることをいう。すなわち、通常のほとんど変形しない固体状の他、ゴム状等の弾性変形性（形状復元性）を有するものを含み、形状自体が特定の形状であることを示していない。 Here, 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).
　この透明複合体は、上記の複合組成物におけるシリコーン樹脂の重合度や架橋度、あるいはシリコーン樹脂と表面修飾剤のシロキサン骨格との間の重合や架橋数を高めることにより、所定の形状を有する状態を得ることができる。したがって、この透明複合体を構成する各成分、すなわち、表面が片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーよりなる表面修飾剤により修飾されている無機酸化物粒子、シリコーン樹脂、反応触媒の３成分については、上述の複合組成物と同一である。 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.
　この透明複合体では、これ自体を構成している表面修飾された無機酸化物粒子は、シリコーン樹脂との相溶性及び親和性が高く、シリコーン樹脂中における分散性が良好である。したがって、無機酸化物粒子とシリコーン樹脂とが相分離を起こしたり、無機酸化物粒子の凝集が発生したりすること等がない。よって、これらに起因する、光学的特性、機械的特性、熱的安定性等の劣化を生じさせる虞がなく、良好な特性を維持することができる。 In this transparent composite, 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.
　また、上述したように、このシリコーン樹脂を反応触媒によって硬化させた場合、シリコーン樹脂の硬化速度は、無機酸化物粒子の凝集・相分離速度よりも早い。したがって、得られる透明複合体の中で無機酸化物粒子が凝集することなく透明性も高いものとなる。加えて、透明複合体の形成材料である複合組成物は、キレート化剤を使用していないので、透明複合体に着色が発生する虞もない。 As described above, when this silicone resin is cured by a reaction catalyst, 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. In addition, since 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.
　また、この透明複合体に含まれる無機酸化物粒子の平均分散粒子径を２０ｎｍ以下としている。したがって、平均分散粒子径が２０ｎｍを超えると影響が大きくなるレイリー散乱の発生も低く抑えられており、透明複合体の透明性が低下することもない。
　このように、無機酸化物粒子は、ナノメートルサイズの粒子であるから、この無機酸化物粒子をシリコーン樹脂中に分散させた複合組成物や透明複合体においても、光散乱が小さく、複合組成物や透明複合体の透明性を維持することが可能である。 Further, 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.
Thus, since 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.
　さらに、この透明複合体に含まれる無機酸化物粒子の平均分散粒子径を１ｎｍ以上としているので、この無機酸化物粒子の平均一次粒子径が結晶性の維持が低下する１ｎｍ未満となることがない。したがって、この無機酸化物粒子は結晶性が良好に維持されている。
　このように、無機酸化物粒子の結晶性が維持されているので、無機酸化物粒子自体が有する特性、すなわち屈折率や硬度、耐熱性等の特性が劣化することがない。したがって、無機酸化物粒子をシリコーン樹脂と複合化させた透明複合体としての効果を十分に得ることができる。 Furthermore, since 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.
Thus, since the crystallinity of the inorganic oxide particles is maintained, 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.
　ここで、透明複合体の効果について説明する。
「光学的特性」
　透明複合体の光学的特性としては、屈折率制御が挙げられる。
　シリコーン樹脂の屈折率は１．４程度であるから、シリコーン樹脂と、このシリコーン樹脂より屈折率が高い高屈折率酸化物粒子とを複合化することにより、透明複合体の屈折率をシリコーン樹脂単体の場合に比べて高めることができる。
　特に屈折率が２以上の高屈折率無機酸化物粒子、例えば、正方晶酸化ジルコニウム（屈折率：２．１５）や酸化チタン（屈折率：２．６程度）と複合化することが有効であり、これらの高屈折率無機酸化物粒子を用いることにより、透明複合体の屈折率を、シリコーン樹脂単体と比べて０．１から０．２程度高い１．５から１．６５程度まで高めることが可能である。 Here, the effect of the transparent composite will be described.
"Optical properties"
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.
　この透明複合体の透明性については、上述したとおり、無機酸化物粒子の平均分散粒子径を２０ｎｍ以下とすることで、光散乱を十分低く抑えることができる。したがって、この透明複合体では、透明性が十分に保たれている。
　また、中空シリカ粒子や多孔質シリカ粒子のような、粒子内に空隙を有することで、粒子全体としてシリコーン樹脂より低屈折率となる無機酸化物粒子をシリコーン樹脂と複合化すれば、透明複合体の屈折率をシリコーン樹脂単体の場合に比べて低下させることも可能である。 Regarding the transparency of the transparent composite, as described above, 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.
In addition, if 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.
「機械的特性」
　透明複合体の機械的特性としては、樹脂単体と比較して硬度が向上することが挙げられる。
　通常の無機酸化物粒子は、シリコーン樹脂と比べて硬度が高く、この無機酸化物粒子をシリコーン樹脂と複合化することで、透明複合体の表面硬度をシリコーン樹脂単体の場合に比べて高めることができる。これにより、透明複合体の耐擦傷性を向上させることができ、また、透明複合体自体の寸法精度を向上させることができる。
　特に、酸化ジルコニウムは、酸化物系セラミックスの中でも高硬度であるから、複合化による表面硬度の向上に高い効果を発揮することができる。 "Mechanical properties"
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.
In particular, since zirconium oxide has a high hardness among oxide-based ceramics, it can exhibit a high effect in improving the surface hardness by combining.
「熱的安定性及び化学的安定性」
　シリコーン樹脂は、それ自体が骨格にケイ素（Ｓｉ）を含むので、通常の樹脂と比べて耐熱性や耐薬品性等の熱的安定性や化学的安定性に優れている。一方、無機酸化物粒子は、耐熱性の点でシリコーン樹脂より勝っている。そこで、化学的安定性が高い無機酸化物粒子を選定し、この化学的安定性が高い無機酸化物粒子とシリコーン樹脂とを複合化すれば、得られた透明複合体の熱的安定性や化学的安定性をシリコーン樹脂単体の場合に比べてより高めることができる。 "Thermal and chemical stability"
Since 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. On the other hand, 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.
　ここで、シリコーン樹脂は、疎水性溶媒との相溶性が高いことからも分かるように、疎水性（撥水性）ではあるが、柔軟性に富み、水蒸気に対するガスバリア性は他樹脂と比較して低い。
　本実施形態の透明複合体においては、ガスバリア性に優れる無機酸化物粒子が透明複合体の内部に均一に分散され、さらに無機酸化物粒子とシリコーン樹脂との結合性が高いことから、透明複合体における水蒸気に対するガスバリア性をシリコーン樹脂単体の場合に比べて高い状態へ改善することができる。 Here, as can be seen from the high compatibility with the hydrophobic solvent, the silicone resin is hydrophobic (water repellency), but has high flexibility and low gas barrier property against water vapor compared to other resins. .
In the transparent composite of the present embodiment, 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.
　この透明複合体は、光学レンズ用として好適に用いることができる。その理由として、この透明複合体によれば、高屈折率の無機酸化物粒子、特に酸化ジルコニウムをシリコーン樹脂と複合化させることにより、得られる透明複合体の屈折率を例えばシリコーン樹脂単体の場合である１．４から１．６５程度まで高めることができる。また、シリコーン樹脂単体の場合に比べて硬度が向上することで寸法精度の向上も図ることができる。したがって、光学素子における設計自由度を向上させることができる。
　その結果、例えば、光学レンズに単体のシリコーン樹脂を用いる場合に比べて、小型化、薄厚化、集積化、集光効率の向上、屈折率波長依存性の低減等を行うことができるようになる。よって、このような光学素子を用いる機器であるＣＣＤやＣＭＯＳカメラ等の特性向上、例えば高解像度化や高感度化が期待できる。 This transparent composite can be suitably used for an optical lens. The reason for this is that according to this transparent composite, 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. In addition, 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.
As a result, for example, compared to the case where 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.
　また、この透明複合体は、発光素子であるＬＥＤの封止材として好適に用いることができる。その理由として、この透明複合体は単体のシリコーン樹脂と比べて高屈折率であることから、発光素子であるＬＥＤの封止材として用いた場合には、封止材に覆われる発光体や、発光体を形成するための基板等の屈折率が高い部材（ＬＥＤの発光体である半導体材料の屈折率は２．５程度、半導体材料を成膜する透光性の基板の屈折率は１．７６程度）との屈折率整合性を向上させることができる。したがって、ＬＥＤの発光体から外部に発光を取り出す過程における内部反射を低減することができる。 Also, 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.
　すなわち、本実施形態の透明複合体をＬＥＤの封止材に用いることで、ＬＥＤからの光取り出し効率を１０％ないし１５％程度改善することができる。その結果、ＬＥＤの輝度を向上させることができる。
　さらに、この透明複合体は水蒸気に対するガスバリア性が高いことから、外部からの水分滲入を抑え、発光領域の劣化を抑制することができる。したがって、発光素子の長寿命化を図ることができる。 That is, by using 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.
　また、この透明複合体は、有機ＥＬ素子の封止材としても好適に用いることができる。その理由として、この透明複合体を有機ＥＬ素子の封止材として用いた場合には、水蒸気に対するガスバリア性が高いことから、外部からの水分滲入を抑え、発光領域の劣化を抑制することができる。また、透明複合体中の無機酸化物粒子は、酸素ガスの透過を効果的に抑制することができるので、同様に発光領域の劣化を抑制することができる。したがって、本実施形態の透明複合体を有機ＥＬ素子の封止材として用いることにより、有機ＥＬ素子における発光素子の長寿命化を図ることができる。 Moreover, this transparent composite can be suitably used as a sealing material for organic EL elements. The reason for this is that when this transparent composite is used as a sealing material for an organic EL element, 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. . In addition, since 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.
［透明複合体の製造方法］
　本実施形態の透明複合体は、本実施形態の複合組成物を、所定の形状に成形し固化するか、または前記複合組成物を固化した後に所定の形状に成形することで、得ることができる。 [Method for producing transparent composite]
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. .
　本実施形態の製造方法においては、「所定の形状に成形し固化する方法」は、下記のとおりである。
　まず、本実施形態の複合組成物を、金型や型枠を用いて成形したり、金型や型枠状の容器に充填したりすることにより、目的の形状に成形された成形体または充填物を得る。
　この際、使用する複合組成物の粘度が高い場合には、予め、有機溶媒等を添加し撹拌・混合して粘度を低下させ、成形や充填に適した粘度となるように調整しておくことが好ましい。
　一方、使用する複合組成物の粘度が低い場合には、予め、シリコーン樹脂同士やシリコーン樹脂と表面修飾剤の一部を下記の様に重合や架橋させるか、または複合組成物が有機溶媒を含む場合には、この有機溶媒の一部あるいは全部を揮発させる等で除去することで粘度を高め、成形や充填に適した粘度となるように調整しておくことが好ましい。 In the manufacturing method of this embodiment, 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.
On the other hand, when the viscosity of the composite composition to be used is low, 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. In some cases, it is preferable to adjust the viscosity to be suitable for molding and filling by increasing the viscosity by removing part or all of the organic solvent by volatilization.
　次いで、この成形体または充填物を、室温（２５℃程度）のまま、あるいは所定の温度（室温～１５０℃、好ましくは８０℃～１５０℃）に加温して所定時間静置し、この複合組成物中のシリコーン樹脂や表面修飾剤に反応触媒を介して重合や架橋等の反応を生じさせ、シリコーン樹脂同士やシリコーン樹脂と表面修飾剤間での結合度（重合度）を高める。
　また、この成形体または充填物に有機溶媒が残留する場合には、この有機溶媒を揮発除去する。
　これにより、この成形体または充填物は、金型や容器から外した後、外力を加えても、一定の形状を維持できる状態となる。
　以上により、欠陥が無く、光学的特性、機械的特性に優れ、高い熱的安定性や化学的安定性を有する、本実施形態の透明複合体を得ることができる。 Next, 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. 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.
Further, when an organic solvent remains in the molded body or the filling, the organic solvent is removed by volatilization.
Thereby, even if it applies external force after removing this molded object or filling material from a metal mold | die or a container, it will be in the state which can maintain a fixed shape.
As described above, it is possible to obtain the transparent composite of the present embodiment having no defects, excellent optical characteristics and mechanical characteristics, and having high thermal stability and chemical stability.
　また、本実施形態の製造方法においては、「複合組成物を固化した後に所定の形状に成形する方法」は、下記のとおりである。
　まず、本実施形態の複合組成物を固化して、複合組成物の固化物（未成形の透明複合体）を得る。固化方法としては、複合組成物を室温（２５℃程度）のまま、あるいは所定の温度（室温～１５０℃、好ましくは８０℃～１５０℃）に加温して所定時間静置し、この複合組成物中のシリコーン樹脂や表面修飾剤に反応触媒を介して重合や架橋等の反応を生じさせ、シリコーン樹脂同士やシリコーン樹脂と表面修飾剤間での結合度（重合度）を高めてやればよい。
　また、有機溶媒が残留する場合には、この有機溶媒も揮発除去することが好ましい。
　この固化物は、外力を加えても、一定の形状を維持できる状態である。 Moreover, in the manufacturing method of this embodiment, "the method of shape | molding in a predetermined shape after solidifying a composite composition" is as follows.
First, the composite composition of this embodiment is solidified to obtain a solidified product (unformed transparent composite) of the composite composition. As the solidification method, 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. What is necessary is just to raise reaction (polymerization degree) between silicone resins or between a silicone resin and a surface modifier by causing a reaction such as polymerization or cross-linking to a silicone resin or a surface modifier in a product via a reaction catalyst. .
Moreover, when an organic solvent remains, it is preferable to volatilize and remove this organic solvent.
This solidified product is in a state in which a certain shape can be maintained even when an external force is applied.
　次いで、この固化物を切削や型抜き等の機械加工法により、必要な形状に成形する。本実施形態のシリコーン樹脂は、硬化後でも柔軟性を有しており、容易に加工することができる。
　さらに、加工後の成型体においては、シリコーン樹脂同士やシリコーン樹脂と表面修飾剤間での結合度（重合度）を高めたり、残留する有機溶媒を除去することで、より固化を進めてもよい。
　以上によっても、欠陥が無く、光学的特性、機械的特性に優れ、高い熱的安定性や化学的安定性を有する、本実施形態の透明複合体を得ることができる。 Next, 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.
Furthermore, 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. .
As described above, it is possible to obtain the transparent composite of this embodiment having no defects, excellent optical characteristics and mechanical characteristics, and having high thermal stability and chemical stability.
　この透明複合体を透明性を問題にしない分野に適用する場合、透明性を確保する必要がないことから、用いる無機酸化物粒子の平均分散粒子径を１ｎｍ以上かつ２０ｎｍ以下に限定する必要はない。 When this transparent composite is applied to a field where transparency is not a problem, it is not necessary to ensure transparency, and therefore it is not necessary to limit the average dispersed particle size of the inorganic oxide particles used to 1 nm or more and 20 nm or less. .
　例えば、無機酸化物粒子とシリコーン樹脂とを含有する複合体の表面硬度のみの向上を目的とする場合には、平均分散粒子径が２０ｎｍよりも大きい粒子、例えば１００ｎｍの無機酸化物粒子を用いることもできる。
　このような場合であっても、本実施形態の複合組成物の製造方法を適用することにより、複合組成物中での無機酸化物粒子の分散性が高まり、良好な物性を有する成形体または充填物を作製することが可能な複合組成物とすることができる。 For example, when 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.
　以下、実施例及び比較例により本発明を具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。本発明の趣旨を逸脱しない範囲で、構成の付加、省略、置換、およびその他の変更が可能である。
　［実施例１］ EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these Examples. Additions, omissions, substitutions, and other modifications can be made without departing from the spirit of the present invention.
[Example 1]
　オキシ塩化ジルコニウム８水塩２６１５ｇを純水４０Ｌ（リットル）に溶解させたジルコニウム塩溶液に、２８％アンモニア水３４４ｇを純水２０Ｌに溶解させた希アンモニア水を攪拌しながら加え、ジルコニア前駆体スラリーを調整した。
　次いで、このスラリーに、硫酸ナトリウム３００ｇを５Ｌの純水に溶解させた硫酸ナトリウム水溶液を攪拌しながら加えた。このときの硫酸ナトリウムの添加量は、ジルコニウム塩溶液中のジルコニウムイオンのジルコニア換算値に対して３０質量％であった。 To a zirconium salt solution in which 2615 g of zirconium oxychloride octahydrate is dissolved in 40 L (liter) of pure water, dilute ammonia water in which 344 g of 28% ammonia water is dissolved in 20 L of pure water is added with stirring, and the zirconia precursor slurry is added. It was adjusted.
Next, an aqueous sodium sulfate solution in which 300 g of sodium sulfate was dissolved in 5 L of pure water was added to this slurry with stirring. The amount of sodium sulfate added at this time was 30% by mass with respect to the zirconia-converted value of zirconium ions in the zirconium salt solution.
　次いで、この混合物を、乾燥器を用いて、大気中、１３０℃にて２４時間乾燥させ、固形物を得た。
　次いで、この固形物を自動乳鉢を用いて粉砕した後、電気炉を用いて、大気中、５００℃にて１時間焼成した。
　次いで、この焼成物を純水中に投入し、攪拌してスラリー状とした後、遠心分離器を用いて洗浄を行い、添加した硫酸ナトリウムを十分に除去した後、乾燥器にて乾燥させ、ジルコニア粒子を得た。 Subsequently, this mixture was dried at 130 ° C. for 24 hours in the air using a drier to obtain a solid.
Next, the solid was pulverized using an automatic mortar, and then baked at 500 ° C. for 1 hour in the air using an electric furnace.
Next, 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.
　次いで、このジルコニア粒子１０ｇに、トルエン８５ｇ、カプロン酸５ｇを加えて混合し、ジルコニア粒子の表面を配位子であるカプロン酸により修飾した。その後、分散処理を行い、ジルコニア透明分散液を調製した。
　次いで、このジルコニア透明分散液１００ｇに、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーとしてモノグリシジルエーテル末端ポリジメチルシロキサン（ＰＤＭＳ－Ｇ：数平均分子量５０００：Ａｌｄｒｉｃｈ社製）１０ｇ、ジブチルスズジラウレート０．０１ｇを加え、環流下にて表面修飾を行った。 Next, 85 g of toluene and 5 g of caproic acid were added to and mixed with 10 g of the zirconia particles, 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.
Next, to 100 g of this zirconia transparent dispersion, 10 g of monoglycidyl ether-terminated polydimethylsiloxane (PDMS-G: number average molecular weight 5000: manufactured by Aldrich) as a polydimethylsiloxane skeleton polymer having one functional group at one end, dibutyltin dilaurate 0 .01 g was added and surface modification was performed under reflux.
　反応終了後、溶媒をエバポレータにて除去し、メタノール洗浄と遠心分離を繰り返すことによって、ジルコニア粒子から脱離したカプロン酸、および未反応のモノグリシジルエーテル末端ポリジメチルシロキサンを除去した。回収した表面修飾ジルコニア粒子は１５ｇであった。 After completion of the reaction, the solvent was removed by an evaporator, and methanol washing and centrifugation were repeated to remove caproic acid detached from the zirconia particles and unreacted monoglycidyl ether-terminated polydimethylsiloxane. The recovered surface-modified zirconia particles were 15 g.
　得られた表面処理ジルコニア粒子を、プロトンＮＭＲ（重クロロホルム中）にて測定した結果、２．６から３．５ｐｐｍ近傍のグリシジル基に起因するシグナル強度が、モノグリシジルエーテル末端ポリジメチルシロキサン単体に比べて大きく減少していた。この結果から、モノグリシジルエーテル末端ポリジメチルシロキサンが、エポキシ基の開環及びジルコニア粒子との結合を生じさせていると判断した。 As a result of measuring the obtained surface-treated zirconia particles by proton NMR (in deuterated chloroform), the signal intensity due to glycidyl groups in the vicinity of 2.6 to 3.5 ppm is higher than that of a monoglycidyl ether-terminated polydimethylsiloxane alone. Was greatly reduced. From this result, it was judged that the monoglycidyl ether-terminated polydimethylsiloxane caused ring opening of the epoxy group and bonding with the zirconia particles.
　この表面修飾ジルコニア粒子１５ｇを、トルエン３５ｇへ再分散した後、ビニル変性シリコーンとして側鎖ビニル－ジメチルシリコーンＶＤＴ－１３１（Ｇｅｌｅｓｔ社製）１４．１ｇ、ハイドロジェン変性シリコーンとしてメチルハイドロジェン－ジメチルシリコーンＨＭＳ－１５１（Ｇｅｌｅｓｔ社製）０．９ｇを加え、更に反応触媒として室温硬化用の白金ジビニルテトラメチルジシロキサンＳＩＰ６８３０．３（Ｇｅｌｅｓｔ社製）６ｍｇを加え、実施例１の表面修飾ジルコニア粒子－シリコーン樹脂複合組成物を得た。 After 15 g of the surface-modified zirconia particles were redispersed in 35 g of toluene, 14.1 g of a side chain vinyl-dimethylsilicone VDT-131 (manufactured by Gelest) as a vinyl-modified silicone and methylhydrogen-dimethylsilicone HMS as a hydrogen-modified silicone 0.9 g of -151 (manufactured by Gelest) was added, and 6 mg of platinum divinyltetramethyldisiloxane SIP6830.3 (manufactured by Gelest) for room temperature curing was added as a reaction catalyst, and the surface-modified zirconia particles of Example 1-silicone resin A composite composition was obtained.
　次いで、この表面修飾ジルコニア粒子－シリコーン樹脂複合組成物を攪拌溶解後、ガラス板で組み上げた型の中に流し込み、４０℃の真空下にて有機溶媒を除去しつつ、硬化反応を行い、実施例１の厚みが１ｍｍの透明複合体を得た。
　この透明複合体のジルコニア粒子の含有率は２５質量％であった。 Next, 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.
　得られた実施例１の透明複合体の断面を電解放出型透過電子顕微鏡ＪＥＭ－２１００Ｆ（日本電子社製）を用いて観察し、無作為に１００個選び出した粒子の粒子径を測定し、その平均値を透明複合体内におけるジルコニア粒子の平均分散粒子径とした。この測定の結果、平均分散粒子径は７ｎｍであった。
　この測定結果から、実施例１の複合組成物中のジルコニア粒子の平均分散粒子径も、７ｎｍないしはそれ以下と結論づけられた。
　また、得られた実施例１の透明複合体について、元素分析を行った結果、反応触媒として添加した量と同等量の白金成分を検出できたことから、本発明の透明複合体が得られたことを確認した。
［実施例２］ 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. As a result of this measurement, 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.
Further, as a result of conducting elemental analysis on the obtained transparent composite of Example 1, 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 2]
　ジルコニア粒子を１０ｇ（２５質量％）から１４ｇ（３５質量％）に、ビニル変性シリコーンとして側鎖ビニル－ジメチルシリコーンＶＤＴ－１３１を１４．１ｇ（４７質量％）から８．４ｇ（２８質量％）に、ハイドロジェン変性シリコーンとしてメチルハイドロジェン－ジメチルシリコーンＨＭＳ－１５１を０．９ｇ（３質量％）から０．６ｇ（２質量％）に、それぞれ変更した他は、実施例１に準じて実施例２の表面修飾ジルコニア粒子－シリコーン樹脂複合組成物及び厚みが１ｍｍの透明複合体を得た。
　この透明複合体のジルコニア粒子の含有率は３５質量％であった。 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.
　得られた実施例２の透明複合体中のジルコニア粒子の粒子径を実施例１と同様にして測定した結果、平均分散粒子径は８ｎｍであった。
　この結果から、実施例２の複合組成物中のジルコニア粒子の平均分散粒子径も、８ｎｍないしはそれ以下と結論づけられた。
　また、得られた実施例２の透明複合体について、元素分析を行った結果、反応触媒として添加した量と同等量の白金成分を検出できたことから、本発明の透明複合体が得られたことを確認した。
［実施例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]
　ジルコニア粒子を１０ｇ（２５質量％）から１６ｇ（４０質量％）に、ビニル変性シリコーンとして側鎖ビニル－ジメチルシリコーンＶＤＴ－１３１を１４．１ｇ（４７質量％）から５．７ｇ（１９質量％）に、ハイドロジェン変性シリコーンとしてメチルハイドロジェン－ジメチルシリコーンＨＭＳ－１５１を０．９ｇ（３質量％）から０．３ｇ（１質量％）に、反応触媒として白金ジビニルテトラメチルジシロキサンＳＩＰ６８３０．３を６ｍｇ（０．０２質量％）から３ｍｇ（０．０１質量％）に、それぞれ変更した他は、実施例１に準じて実施例３の表面修飾ジルコニア粒子－シリコーン樹脂複合組成物及び厚みが１ｍｍの透明複合体を得た。
　この透明複合体のジルコニア粒子の含有率は４０質量％であった。 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.
　得られた実施例３の透明複合体中のジルコニア粒子の粒子径を実施例１と同様にして測定した結果、平均分散粒子径は１０ｎｍであった。
　この結果から、実施例３の複合組成物中のジルコニア粒子の平均分散粒子径も、１０ｎｍないしはそれ以下と結論づけられた。
　また、得られた実施例３の透明複合体について、元素分析を行った結果、反応触媒として添加した量と同等量の白金成分を検出できたことから、本発明の透明複合体が得られたことを確認した。
［実施例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]
　ビニル変性シリコーンとして側鎖ビニル－ジメチルシリコーンＶＤＴ－１３１を１４．１ｇ（４７質量％）から１１．７ｇ（３９質量％）に、ハイドロジェン変性シリコーンとしてメチルハイドロジェン－ジメチルシリコーンＨＭＳ－１５１の０．９ｇ（３質量％）を、メチルハイドロジェン－ジメチルシリコーンＨＭＳ－０３１（Ｇｅｌｅｓｔ社製）の３．３ｇ（１１質量％）に、それぞれ変更した他は、実施例１に準じて実施例４の表面修飾ジルコニア粒子－シリコーン樹脂複合組成物及び厚みが１ｍｍの透明複合体を得た。
　この透明複合体のジルコニア粒子の含有率は２５質量％であった。 Side chain vinyl-dimethylsilicone VDT-131 was changed from 14.1 g (47% by mass) to 11.7 g (39% by mass) as vinyl-modified silicone, and 0.1% of methylhydrogen-dimethylsilicone HMS-151 as hydrogen-modified silicone. The surface of Example 4 according to Example 1 except that 9 g (3% by mass) was changed to 3.3 g (11% by mass) of methylhydrogen-dimethylsilicone HMS-031 (manufactured by Gelest). A 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 25% by mass.
　得られた実施例４の透明複合体中のジルコニア粒子の粒子径を実施例１と同様にして測定した結果、平均分散粒子径は７ｎｍであった。
　この結果から、実施例４の複合組成物中のジルコニア粒子の平均分散粒子径も、７ｎｍないしはそれ以下と結論づけられた。
　また、得られた実施例４の透明複合体について、元素分析を行った結果、反応触媒として添加した量と同等量の白金成分を検出できたことから、本発明の透明複合体が得られたことを確認した。
［実施例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]
　ビニル変性シリコーンとして側鎖ビニル－ジメチルシリコーンＶＤＴ－１３１の１４．１ｇ（４７質量％）を、側鎖ビニル－ジメチルシリコーンＶＤＴ－７３１（Ｇｅｌｅｓｔ社製）の４．８ｇ（１６質量％）に、ハイドロジェン変性シリコーンとしてメチルハイドロジェン－ジメチルシリコーンＨＭＳ－１５１の０．９ｇ（３質量％）を、メチルハイドロジェン－ジメチルシリコーンＨＭＳ－０３１の１０．２ｇ（３４質量％）に、それぞれ変更した他は、実施例１に準じて実施例５の表面修飾ジルコニア粒子－シリコーン樹脂複合組成物及び厚みが１ｍｍの透明複合体を得た。
　この透明複合体のジルコニア粒子の含有率は２５質量％であった。 As vinyl-modified silicone, 14.1 g (47% by mass) of side-chain vinyl-dimethylsilicone VDT-131 and 4.8 g (16% by mass) of side-chain vinyl-dimethylsilicone VDT-731 (manufactured by Gelest Co., Ltd.) Except that 0.9 g (3% by mass) of methylhydrogen-dimethylsilicone HMS-151 was changed to 10.2 g (34% by mass) of methylhydrogen-dimethylsilicone HMS-031 as the gen-modified silicone, The surface-modified zirconia particle-silicone resin composite composition of Example 5 and a transparent composite having a thickness of 1 mm were obtained according to Example 1.
The content of zirconia particles in this transparent composite was 25% by mass.
　得られた実施例５の透明複合体中のジルコニア粒子の粒子径を実施例１と同様にして測定した結果、平均分散粒子径は７ｎｍであった。
　この結果から、実施例５の複合組成物中のジルコニア粒子の平均分散粒子径も、７ｎｍないしはそれ以下と結論づけられた。
　また、得られた実施例５の透明複合体について、元素分析を行った結果、反応触媒として添加した量と同等量の白金成分を検出できたことから、本発明の透明複合体が得られたことを確認した。
［実施例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]
　ビニル変性シリコーンとして側鎖ビニル－ジメチルシリコーンＶＤＴ－１３１の１４．１ｇ（４７質量％）を、両末端ビニル－ジメチルシリコーンＤＭＳ－Ｖ２１（Ｇｅｌｅｓｔ社製）の１３．５ｇ（４５質量％）に、ハイドロジェン変性シリコーンとしてメチルハイドロジェン－ジメチルシリコーンＨＭＳ－１５１の０．９ｇ（３質量％）を、メチルハイドロジェン－ジメチルシリコーンＨＭＳ－３０１（Ｇｅｌｅｓｔ社製）の１．５ｇ（５質量％）に、それぞれ変更した他は、実施例１に準じて実施例６の表面修飾ジルコニア粒子－シリコーン樹脂複合組成物及び厚みが１ｍｍの透明複合体を得た。
　この透明複合体のジルコニア粒子の含有率は２５質量％であった。 As the vinyl-modified silicone, 14.1 g (47% by mass) of side chain vinyl-dimethylsilicone VDT-131 was added to 13.5 g (45% by mass) of both-end vinyl-dimethylsilicone DMS-V21 (manufactured by Gelest). 0.9 g (3% by mass) of methylhydrogen-dimethylsilicone HMS-151 as a gen-modified silicone, and 1.5 g (5% by mass) of methylhydrogen-dimethylsilicone HMS-301 (manufactured by Gelest), respectively. Except for the change, the surface-modified zirconia particle-silicone resin composite composition of Example 6 and a transparent composite having a thickness of 1 mm were obtained according to Example 1.
The content of zirconia particles in this transparent composite was 25% by mass.
　得られた実施例６の透明複合体中のジルコニア粒子の粒子径を実施例１と同様にして測定した結果、平均分散粒子径は１０ｎｍであった。
　この結果から、実施例６の複合組成物中のジルコニア粒子の平均分散粒子径も、１０ｎｍないしはそれ以下と結論づけられた。
　また、得られた実施例６の透明複合体について、元素分析を行った結果、反応触媒として添加した量と同等量の白金成分を検出できたことから、本発明の透明複合体が得られたことを確認した。
［実施例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]
　ビニル変性シリコーンとして側鎖ビニル－ジメチルシリコーンＶＤＴ－１３１の１４．１ｇ（４７質量％）を、両末端ビニル－ジメチルシリコーンＤＭＳ－Ｖ２２（Ｇｅｌｅｓｔ社製）の１４．７ｇ（４９質量％）に、ハイドロジェン変性シリコーンとしてメチルハイドロジェン－ジメチルシリコーンＨＭＳ－１５１の０．９ｇ（３質量％）を、メチルハイドロジェン－ジメチルシリコーンＨＭＳ－３０１の０．３ｇ（１質量％）に、それぞれ変更した他は、実施例１に準じて実施例７の表面修飾ジルコニア粒子－シリコーン樹脂複合組成物及び厚みが１ｍｍの透明複合体を得た。
　この透明複合体のジルコニア粒子の含有率は２５質量％であった。 As a vinyl-modified silicone, 14.1 g (47% by mass) of side-chain vinyl-dimethylsilicone VDT-131 was added to 14.7 g (49% by mass) of both-end vinyl-dimethylsilicone DMS-V22 (manufactured by Gelest). Except that 0.9 g (3% by mass) of methylhydrogen-dimethylsilicone HMS-151 was changed to 0.3 g (1% by mass) of methylhydrogen-dimethylsilicone HMS-301 as the gen-modified silicone, In accordance with Example 1, the surface-modified zirconia particle-silicone resin composite composition of Example 7 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.
　得られた実施例７の透明複合体中のジルコニア粒子の粒子径を実施例１と同様にして測定した結果、平均分散粒子径は１０ｎｍであった。
　この結果から、実施例７の複合組成物中のジルコニア粒子の平均分散粒子径も、１０ｎｍないしはそれ以下と結論づけられた。
　また、得られた実施例７の透明複合体について、元素分析を行った結果、反応触媒として添加した量と同等量の白金成分を検出できたことから、本発明の透明複合体が得られたことを確認した。
［実施例８］ 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]
　ビニル変性シリコーンとして側鎖ビニル－ジメチルシリコーンＶＤＴ－１３１を１４．１ｇ（４７質量％）から１４．４ｇ（４８質量％）に、ハイドロジェン変性シリコーンとしてメチルハイドロジェン－ジメチルシリコーンＨＭＳ－１５１の０．９ｇ（３質量％）を、メチルハイドロジェン－ジメチルシリコーンＨＭＳ－３０１の０．６ｇ（２質量％）に、それぞれ変更した他は、実施例１に準じて実施例８の表面修飾ジルコニア粒子－シリコーン樹脂複合組成物及び厚みが１ｍｍの透明複合体を得た。
　この透明複合体のジルコニア粒子の含有率は２５質量％であった。 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. Surface modified zirconia particles-silicone of Example 8 according to Example 1 except that 9 g (3% by mass) was changed to 0.6 g (2% by mass) of methyl hydrogen-dimethyl silicone HMS-301. 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.
　得られた実施例８の透明複合体中のジルコニア粒子の粒子径を実施例１と同様にして測定した結果、平均分散粒子径は７ｎｍであった。
　この結果から、実施例８の複合組成物中のジルコニア粒子の平均分散粒子径も、７ｎｍないしはそれ以下と結論づけられた。
　また、得られた実施例８の透明複合体について、元素分析を行った結果、反応触媒として添加した量と同等量の白金成分を検出できたことから、本発明の透明複合体が得られたことを確認した。
［実施例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]
　ビニル変性シリコーンとして側鎖ビニル－ジメチルシリコーンＶＤＴ－１３１の１４．１ｇ（４７質量％）を、側鎖ビニル－ジメチルシリコーンＶＤＴ－７３１の１１．４ｇ（３８質量％）に、ハイドロジェン変性シリコーンとしてメチルハイドロジェン－ジメチルシリコーンＨＭＳ－１５１の０．９ｇ（３質量％）を、メチルハイドロジェン－ジメチルシリコーンＨＭＳ－３０１の３．６ｇ（１２質量％）に、それぞれ変更した他は、実施例１に準じて実施例９の表面修飾ジルコニア粒子－シリコーン樹脂複合組成物及び厚みが１ｍｍの透明複合体を得た。
　この透明複合体のジルコニア粒子の含有率は２５質量％であった。 14.1 g (47% by mass) of side-chain vinyl-dimethylsilicone VDT-131 as vinyl-modified silicone, 11.4 g (38% by mass) of side-chain vinyl-dimethylsilicone VDT-731, 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 3.6 g (12% by mass) of methylhydrogen-dimethylsilicone HMS-301. Thus, the surface-modified zirconia particle-silicone resin composite composition of Example 9 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.
　得られた実施例９の透明複合体中のジルコニア粒子の粒子径を実施例１と同様にして測定した結果、平均分散粒子径は７ｎｍであった。
　この結果から、実施例９の複合組成物中のジルコニア粒子の平均分散粒子径も、７ｎｍないしはそれ以下と結論づけられた。
　また、得られた実施例９の透明複合体について、元素分析を行った結果、反応触媒として添加した量と同等量の白金成分を検出できたことから、本発明の透明複合体が得られたことを確認した。
［実施例１０］ 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]
　ビニル変性シリコーンとして側鎖ビニル－ジメチルシリコーンＶＤＴ－１３１の１４．１ｇ（４７質量％）を、両末端ビニル－ジメチルシリコーンＤＭＳ－Ｖ２２の１４．７ｇ（４９質量％）に、ハイドロジェン変性シリコーンとしてメチルハイドロジェン－ジメチルシリコーンＨＭＳ－１５１の０．９ｇ（３質量％）を、メチルハイドロジェン－ジメチルシリコーンＨＭＳ－３０１の０．３ｇ（１質量％）に、反応触媒として白金ジビニルテトラメチルジシロキサンＳＩＰ６８３０．３を、白金シクロビニルメチルシロキサンＳＩＰ６８３２．２（Ｇｅｌｅｓｔ社製）に、それぞれ変更した他は、実施例１に準じて実施例１０の表面修飾ジルコニア粒子－シリコーン樹脂複合組成物及び厚みが１ｍｍの透明複合体を得た。
　この透明複合体のジルコニア粒子の含有率は２５質量％であった。 14.1 g (47% by mass) of side chain vinyl-dimethylsilicone VDT-131 as vinyl-modified silicone, 14.7 g (49% by mass) of vinyl-dimethylsilicone DMS-V22 at both ends, and methyl as hydrogen-modified silicone 0.9 g (3% by mass) of hydrogen-dimethylsilicone HMS-151 was added to 0.3 g (1% by mass) of methylhydrogen-dimethylsilicone HMS-301, and platinum divinyltetramethyldisiloxane SIP6830. 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.
　得られた実施例１０の透明複合体中のジルコニア粒子の粒子径を実施例１と同様にして測定した結果、平均分散粒子径は９ｎｍであった。
　この結果から、実施例１０の複合組成物中のジルコニア粒子の平均分散粒子径も、９ｎｍないしはそれ以下と結論づけられた。
　また、得られた実施例１０の透明複合体について、元素分析を行った結果、反応触媒として添加した量と同等量の白金成分を検出できたことから、本発明の透明複合体が得られたことを確認した。 As a result of measuring the particle diameter of the zirconia particles in the obtained transparent composite of Example 10 in the same manner as in Example 1, the average dispersed particle diameter 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.
「比較例１」
　ビニル変性シリコーンとして側鎖ビニル－ジメチルシリコーンＶＤＴ－１３１の１４．１ｇ（４７質量％）を、両末端ビニル－ジメチルシリコーンＤＭＳ－Ｖ２１の８．７ｇ（２９質量％）に、ハイドロジェン変性シリコーンとしてメチルハイドロジェン－ジメチルシリコーンＨＭＳ－１５１の０．９ｇ（３質量％）を、メチルハイドロジェン－ジメチルシリコーンＨＭＳ－０３１の６．３ｇ（２１質量％）に、それぞれ変更した他は、実施例１に準じて比較例１の表面修飾ジルコニア粒子－シリコーン樹脂複合組成物及び厚みが１ｍｍの複合体を得た。
　この複合体のジルコニア粒子の含有率は２５質量％であった。
　得られた比較例１の複合体中のジルコニア粒子の粒子径を実施例１と同様にして測定した結果、平均分散粒子径は３５ｎｍであった。 “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. Thus, 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.
As a result of measuring the particle diameter of the zirconia particles in the obtained composite of Comparative Example 1 in the same manner as in Example 1, the average dispersed particle diameter was 35 nm.
「比較例２」
　ビニル変性シリコーンとして側鎖ビニル－ジメチルシリコーンＶＤＴ－１３１の１４．１ｇ（４７質量％）を、両末端ビニル－ジメチルシリコーンＤＭＳ－Ｖ２２の１３．２ｇ（４４質量％）に、ハイドロジェン変性シリコーンとしてメチルハイドロジェン－ジメチルシリコーンＨＭＳ－１５１の０．９ｇ（３質量％）を、メチルハイドロジェン－ジメチルシリコーンＨＭＳ－０３１の１．８ｇ（６質量％）に、それぞれ変更した他は、実施例１に準じて比較例２の表面修飾ジルコニア粒子－シリコーン樹脂複合組成物及び厚みが１ｍｍの複合体を得た。
　この複合体のジルコニア粒子の含有率は２５質量％であった。
　得られた比較例２の複合体中のジルコニア粒子の粒子径を実施例１と同様にして測定した結果、平均分散粒子径は４２ｎｍであった。 "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. Thus, 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.
As a result of measuring the particle diameter of the zirconia particles in the obtained composite of Comparative Example 2 in the same manner as in Example 1, the average dispersed particle diameter was 42 nm.
「比較例３」
　実施例１と同様にして作製したジルコニア粒子１０ｇに、トルエン８５ｇ、カプロン酸５ｇを加えて混合し、ジルコニア粒子の表面を配位子であるカプロン酸により修飾した。その後、分散処理を行い、ジルコニア透明分散液を調製した。
　反応終了後、溶媒をエバポレータにて除去し、アセトン洗浄と遠心分離を繰り返すことによって、ジルコニア粒子と未反応のカプロン酸を除去した。回収した、表面が配位子であるカプロン酸により修飾されたジルコニア粒子は１１ｇであった。 “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.
　ジルコニア粒子として、本カプロン酸修飾ジルコニア粒子１０ｇ（２５質量％）を用い、ビニル変性シリコーンとして側鎖ビニル－ジメチルシリコーンＶＤＴ－１３１を１４．１ｇ（４７質量％）から１８．８ｇ（６３質量％）に、ハイドロジェン変性シリコーンとしてメチルハイドロジェン－ジメチルシリコーンＨＭＳ－１５１を０．９ｇ（３質量％）から１．２ｇ（４質量％）に、反応触媒として白金ジビニルテトラメチルジシロキサンＳＩＰ６８３０．３を６ｍｇ（０．０２質量％）から９ｍｇ（０．０３質量％）に、それぞれ変更した他は、実施例１に準じて比較例３の表面修飾ジルコニア粒子－シリコーン樹脂複合組成物及び厚みが１ｍｍの複合体を得た。
　この複合体のジルコニア粒子の含有率は２５質量％であった。
　得られた比較例３の複合体中のジルコニア粒子の粒子径を実施例１と同様にして測定した結果、平均分散粒子径は４５ｎｍであった。 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. Further, 0.9 g (3 mass%) to 1.2 g (4 mass%) of methyl hydrogen-dimethyl silicone HMS-151 as hydrogen-modified silicone and 6 mg of platinum divinyltetramethyldisiloxane SIP6830.3 as a reaction catalyst The surface-modified zirconia particle-silicone resin composite composition of Comparative Example 3 and the composite having a thickness of 1 mm are the same as in Example 1, except that the amount is changed from (0.02% by weight) to 9 mg (0.03% by weight). Got the body.
The content of zirconia particles in this composite was 25% by mass.
As a result of measuring the particle diameter of the zirconia particles in the obtained composite of Comparative Example 3 in the same manner as in Example 1, the average dispersed particle diameter was 45 nm.
「評価」
　実施例１～１０それぞれの透明複合体及び比較例１～３それぞれの複合体について、下記の装置または方法により透明性、屈折率及び耐久性の評価を行った。 "Evaluation"
The transparency, refractive index and durability of each of the transparent composites of Examples 1 to 10 and Comparative Examples 1 to 3 were evaluated by the following apparatus or method.
（１）透明性
　分光光度計（日本分光社製）を用いて可視光線の透過率を測定した。
　ここでは、透明複合体（または複合体）の厚み方向（Ｌ＝１ｍｍ）の可視光線透過率を測定し、可視光線透過率が８０％以上を「○」、８０％未満を「×」とした。
（２）屈折率
　日本工業規格ＪＩＳ Ｋ ７１４２「プラスチックの屈折率測定方法」に準拠し、アッベ屈折計により測定した。
　ここでは、ジルコニア粒子を添加していない樹脂単体を基準として、屈折率が０．０３以上向上した場合を「○」、屈折率が０．０３未満しか向上しなかった場合を「×」とした。 (1) Transparency The transmittance of visible light was measured using a spectrophotometer (manufactured by JASCO Corporation).
Here, the visible light transmittance in the thickness direction (L = 1 mm) of the transparent composite (or composite) was measured, and the visible light transmittance was 80% or more as “◯” and less than 80% as “x”. .
(2) Refractive index The refractive index was measured with an Abbe refractometer in accordance with Japanese Industrial Standard JIS K 7142 “Plastic Refractive Index Measuring Method”.
Here, on the basis of a single resin not added with zirconia particles, a case where the refractive index is improved by 0.03 or more is “◯”, and a case where the refractive index is improved by less than 0.03 is “X”. .
（３）耐久性
　透明複合体（または複合体）を温度１５０℃の環境下に２４時間放置した後、取り出し、透明複合体（または複合体）の外観を目視にて観察し、黄変が無いものを「○」、黄変したものを「×」とした。
　実施例１～１０及び比較例１～２各々の複合組成物の組成及び透明複合体（または複合体）の評価結果を表１に示す。 (3) Durability The transparent composite (or composite) is allowed to stand for 24 hours in an environment at a temperature of 150 ° C. and then taken out. The appearance of the transparent composite (or composite) is visually observed, and there is no yellowing. The thing was set as "(circle)" and the thing yellowed was set as "x".
Table 1 shows the composition of each composite composition of Examples 1 to 10 and Comparative Examples 1 and 2 and the evaluation results of the transparent composite (or composite).
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表１によれば、実施例１～１０各々の透明複合体は、透明性、屈折率及び耐久性の全ての点で優れたものであった。
　一方、比較例１、２の複合体は、可視光線の透過率が０％～２０％と極めて低く、また、屈折率を測定することができなかった。
　この理由は、ハイドロジェン変性シリコーン及びビニル変性シリコーン共に架橋密度が小さいので、無機酸化物粒子の凝集・相分離速度がシリコーン樹脂の硬化速度よりも速くなり、その結果、無機酸化物粒子とシリコーン樹脂との硬化の際に透明性が失われたことによると考えられる。
　また、比較例３の複合体は、可視光線の透過率が１０％以下と極めて低く、屈折率を測定することができなかった。この理由は、無機酸化物粒子の表面修飾が不十分なために、無機酸化物粒子とシリコーン樹脂との複合組成物中において無機酸化物粒子が凝集し、その結果、複合体における透明性が得られなかったためと考えられる。さらに、耐久性においては、１５０℃で２４時間放置した後に、微黄変が見られたことから、カプロン酸による変色の影響が確認された。 According to Table 1, each of the transparent composites of Examples 1 to 10 was excellent in all of transparency, refractive index, and durability.
On the other hand, 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.
The reason for this is that 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. As a result, the inorganic oxide particles and the silicone resin This is thought to be due to the loss of transparency during curing.
Further, 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. This is because the surface modification of the inorganic oxide particles is insufficient, so that the inorganic oxide particles aggregate in the composite composition of the inorganic oxide particles and the silicone resin, resulting in transparency in the composite. It is thought that it was not possible. Further, in terms of durability, slight yellowing was observed after standing at 150 ° C. for 24 hours, and thus the influence of discoloration by caproic acid was confirmed.
　本発明は、屈折率、機械的特性およびガスバリア性の向上が可能な無機酸化物粒子をシリコーン樹脂中に分散した場合に、分散性が高く、しかも、硬化時の相分離・白化を防止し、透明性の確保を可能とする無機酸化物粒子とシリコーン樹脂との複合組成物及び透明複合体を提供することができる。
　本発明の無機酸化物粒子とシリコーン樹脂との複合組成物は、無機酸化物粒子をシリコーン樹脂中に分散してなる複合組成物であり、少なくとも、無機酸化物粒子であって、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーが結合することにより表面修飾されるとともに平均分散粒子径が１ｎｍ以上かつ２０ｎｍ以下である無機酸化物粒子と、シリコーン樹脂と、反応触媒とを含有してなる。これにより、無機酸化物粒子とシリコーン樹脂とを複合化した複合体の透明性、耐熱性及び耐光性を維持しつつ、屈折率が制御された透明複合体を得ることができる。そのため、半導体発光素子（ＬＥＤ）の封止材、液晶表示装置用基板、有機ＥＬ表示装置用基板、カラーフィルタ用基板、タッチパネル用基板、太陽電池用基板等の光学シート、透明板、光学レンズ、光学素子、光導波路、接着剤等はもちろんのこと、これ以外の様々な工業分野においても、その利用可能性は大である。 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. Thereby, the transparent composite body with which the refractive index was controlled can be obtained, maintaining the transparency, heat resistance, and light resistance of the composite body which combined the inorganic oxide particle and the silicone resin. Therefore, 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, In addition to optical elements, optical waveguides, adhesives, etc., the applicability is great in various other industrial fields.

Claims (8)

  1. 　少なくとも、無機酸化物粒子であって、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーが結合することにより表面修飾されるとともに平均分散粒子径が１ｎｍ以上かつ２０ｎｍ以下である無機酸化物粒子と、シリコーン樹脂と、反応触媒とを含有してなる複合組成物であって、
    　前記シリコーン樹脂は、ビニル変性シリコーン及びハイドロジェン変性シリコーンを含有し、
    　前記反応触媒は、ヒドロシリル化反応触媒を含有してなる無機酸化物粒子とシリコーン樹脂との複合組成物。     At least inorganic oxide particles which 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; A composite composition comprising a silicone resin and a reaction catalyst,
    The silicone resin contains vinyl-modified silicone and hydrogen-modified silicone,
    The reaction catalyst is a composite composition of inorganic oxide particles containing a hydrosilylation reaction catalyst and a silicone resin.
  2. 　前記ポリジメチルシロキサン骨格ポリマーは、モノグリシジルエーテル末端ポリジメチルシロキサンおよび／またはモノヒドロキシエーテル末端ポリジメチルシロキサンである請求項１記載の無機酸化物粒子とシリコーン樹脂との複合組成物。 The composite composition of inorganic oxide particles and a silicone resin according to claim 1, wherein the polydimethylsiloxane skeleton polymer is monoglycidyl ether-terminated polydimethylsiloxane and / or monohydroxyether-terminated polydimethylsiloxane.
  3. 　前記ビニル変性シリコーンは、両末端ビニル－ジメチルシリコーン、両末端ビニルジフェニル－ジメチルシリコーン、両末端ビニル－フェニルメチルシリコーン、両末端ビニル－ジエチルシリコーン、側鎖ビニル－ジメチルシリコーン、ビニルメチルシリコーン、ビニルメトキシシリコーン、ビニルレジン分散体からなる群から選択された１種または２種以上である請求項１または２記載の無機酸化物粒子とシリコーン樹脂との複合組成物。 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. The composite composition of inorganic oxide particles and a silicone resin according to claim 1 or 2, which is one or more selected from the group consisting of vinyl resin dispersions.
  4. 　前記ハイドロジェン変性シリコーンは、両末端ハイドロジェン－ジメチルシリコーン、メチルハイドロジェン－ジメチルシリコーン、メチルハイドロジェンシリコーン、エチルハイドロジェンシリコーン、メチルハイドロジェン－フェニルメチルシリコーン、ハイドライドレジンからなる群から選択された１種または２種以上である請求項１ないし３のいずれか１項記載の無機酸化物粒子とシリコーン樹脂との複合組成物。 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. The composite composition of inorganic oxide particles according to any one of claims 1 to 3 and a silicone resin.
  5. 　前記ハイドロジェン変性シリコーンは、下記の式（１）
    Figure JPOXMLDOC01-appb-C000001
     　（但し、Ｒ１～Ｒ８は相互に独立な任意の有機基（Ｈを除く）、ｍは１以上の整数、ｎは０を含む正の整数である）
    に示す側鎖ハイドロジェン変性シリコーンを含有してなり、
    　前記側鎖ハイドロジェン変性シリコーンにおけるｍとｎとの比（ｍ／（ｍ＋ｎ））は０．２５以上かつ１以下である請求項１ないし４のいずれか１項記載の無機酸化物粒子とシリコーン樹脂との複合組成物。     The hydrogen-modified silicone has the following formula (1):
    Figure JPOXMLDOC01-appb-C000001
     (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)
    Containing the side chain hydrogen-modified silicone shown in
    The inorganic oxide particles and the silicone resin according to any one of claims 1 to 4, wherein a ratio of m to n (m / (m + n)) in the side chain hydrogen-modified silicone is 0.25 or more and 1 or less. And a composite composition.
  6. 　シリコーン樹脂中に、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーが結合することにより表面修飾された無機酸化物粒子が平均分散粒子径１ｎｍ以上かつ２０ｎｍ以下にて分散するとともに、前記シリコーン樹脂中にヒドロシリル化反応触媒を含有してなる透明複合体。 In the silicone resin, inorganic oxide particles whose surface is modified by bonding with a polydimethylsiloxane skeleton polymer having one functional group at one end are dispersed at an average dispersed particle diameter of 1 nm to 20 nm, and the silicone resin A transparent composite comprising a hydrosilylation reaction catalyst therein.
  7. 　請求項１ないし５のいずれか１項記載の無機酸化物粒子とシリコーン樹脂との複合組成物を、所定の形状に成形し固化するか、または前記複合組成物を固化した後に成形してなる透明複合体。 A transparent composition formed by molding and solidifying the composite composition of inorganic oxide particles according to any one of claims 1 to 5 and a silicone resin into a predetermined shape, or solidifying the composite composition. Complex.
  8. 　無機酸化物粒子の表面を、片末端に１官能基を有するポリジメチルシロキサン骨格ポリマーにより修飾し、表面が修飾された平均分散粒子径が１ｎｍ以上かつ２０ｎｍ以下の無機酸化物粒子を得る工程と、
    　前記表面が修飾された平均分散粒子径が１ｎｍ以上かつ２０ｎｍ以下の無機酸化物粒子と、シリコーン樹脂と、反応触媒とを混合する工程とを含む、
    　請求項１ないし５のいずれか１項記載の無機酸化物粒子とシリコーン樹脂との複合組成物の製造方法。     Modifying the surface of the inorganic oxide particles with a polydimethylsiloxane skeleton polymer having one functional group at one end to obtain inorganic oxide particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less with the modified surface;
    A step of mixing 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 surface of which is modified,
    The manufacturing method of the composite composition of the inorganic oxide particle of any one of Claim 1 thru | or 5, and a silicone resin.
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