JP5034283B2 - High refractive material forming composition and cured body thereof, and method for producing high refractive material forming composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a siloxane-based composition giving a high-refractive index cured form of excellent heat resistance, ultraviolet resistance and optical transparency, and to provide a method for producing the composition. <P>SOLUTION: The composition for forming high-refractive index material comprises 100 pts.wt. of (A) microparticles of at least one metal oxide selected from the group consisting of zirconium oxide, titanium oxide, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide and composites thereof and 20-400 pts.wt., on a completely hydrolyzed condensate basis, of (B) a siloxane-based condensate. A cured form made by curing the composition is provided, having a refractive index of 1.55-2.20 for 400 nm wavelength light at 25&deg;C. A cured film of 20&mu;m thick formed by curing the composition is also provided, having a transmittance of greater than 90% for 500-700 nm wavelength light. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a composition used for a highly refractive sealing material used for a light-emitting diode element or the like, a method for producing the same, and a cured product thereof.

  A light emitting diode (LED) element is usually covered with a sealing material in order to protect the LED element and change the color. And in order to take out the light emitted from the LED element efficiently, this sealing material is required to have a high refractive index.

  Conventionally, an epoxy resin has been generally used as a resin used for this sealing material (see, for example, Patent Documents 1 and 2). However, in an LED element using a blue LED element or an ultraviolet LED element as a light emitting element, a blue LED is used. There has been a problem that the epoxy resin sealing material is yellowed in the vicinity of the light emitting element or is thermally deteriorated due to heat generation of the light emitting element due to near ultraviolet light emitted from the element or ultraviolet light emitted from the ultraviolet LED element. In particular, in applications that require high luminance such as electric lamps, the amount of light emitted from blue LED elements and ultraviolet LED elements is large, and yellowing and thermal degradation are likely to occur.

  For this reason, a silicone resin sealing material has been studied as a heat-resistant sealing material that does not cause yellowing due to near-ultraviolet light or ultraviolet light even in a high-luminance environment. However, the silicone resin made of dimethylsiloxane has a problem that the refractive index is low, the adhesiveness with the LED element and the substrate is poor, and further, because it has tackiness, dust and the like are easily attached.

  Patent Documents 3 and 4 disclose a silicone resin composition containing a silicone resin having an alkenyl group bonded to a silicon atom and an organohydrogenpolysiloxane having a Si—H bond. In Patent Documents 3 and 4, this silicone resin composition is crosslinked by a hydrosilylation reaction to form a cured product. However, this cured product has a low refractive index, and since the carbon-carbon bond is present in the crosslinked structure of this cured product, it is decomposed by near ultraviolet light or ultraviolet light and the performance as a sealing material is impaired. was there.

  By the way, a high refractive index film containing highly refractive fine particles and polysiloxane is used for the antireflection film. Patent Document 5 discloses a high refractive index layer made of a cured product of a coating agent containing metal oxide fine particles such as zirconium oxide and a silicone compound having an epoxy group or the like. However, since the carbon-carbon bond is also present in the crosslinked structure of the cured product, there is a problem that it is easily decomposed and deteriorated by near-ultraviolet light or ultraviolet light. Patent Document 6 discloses a high refractive index layer using inorganic fine particles such as zirconium oxide and a binder made of a vinyl group-containing polysiloxane and a thermosetting resin. However, carbon-carbon bonds also exist in the crosslinked structure of the high refractive index layer, and are easily degraded by near-ultraviolet light or ultraviolet light.

On the other hand, a polysiloxane film formed by hydrolysis and condensation of an alkoxysilane monomer is liable to crack when a thick film is formed, and is unsuitable for an LED sealing material.
JP 2000-281868 A JP 2004-339319 A JP 2004-186168 A JP 2004-221308 A JP 2004-117704 A JP 2003-240906 A

  The present invention is intended to solve the problems associated with the prior art as described above, and is excellent in resistance to near ultraviolet light and ultraviolet light (hereinafter referred to as “ultraviolet light resistance”), heat resistance, and light transmittance. An object of the present invention is to provide a siloxane-based composition from which a cured product having a high refractive index can be obtained, and a method for producing the same.

  As a result of diligent research to solve the above problems, the present inventor has found that dispersion stability of highly refractive metal oxide fine particles can be improved by using an alkoxy group-containing siloxane oligomer or a condensate thereof and a condensate of titanium alkoxide in combination. Improved, and a uniform and transparent highly refractive cured product can be obtained, and in particular, when the alkoxy group-containing siloxane oligomer has a specific molecular weight, the above-mentioned characteristics are remarkably exhibited, and the present invention has been completed. It was.

That is, the composition for forming a high refractive material according to the present invention is selected from the group consisting of zirconium oxide, titanium oxide, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, and a composite thereof. It is a composition containing 100 parts by weight of fine particles (A) of at least one metal oxide, and 20 to 400 parts by weight of siloxane-based condensate (B) in terms of complete hydrolysis condensate,
The cured product formed by curing the composition has a refractive index of light having a wavelength of 400 nm at 25 ° C. of 1.55 to 2.20, and a cured film having a thickness of 20 μm formed by curing the composition. The light transmittance at a wavelength of 500 to 700 nm is 90% or more.

Further, the composition for forming a high refractive material according to the present invention is selected from the group consisting of zirconium oxide, titanium oxide, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, and composites thereof. 100 parts by weight of fine particles (A) of at least one metal oxide,
The following average composition formula (1)
R ¹ _a R ² _b SiO _c (OR ³ ) _d (1)
(In the formula, R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ³ is an alkyl group, and R ¹ , R ^2, and R ³ are When there are a plurality of them, they may be the same or different from each other, a and b are independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d Is greater than 0 and less than 4 and a + b + c × 2 + d = 4)
The alkoxy group-containing siloxane oligomer (b1) having a polystyrene-equivalent weight average molecular weight in the range of 1,000 to 100,000 as measured by gel permeation chromatography is 10 to 200% in terms of complete hydrolysis condensate. Part,
It is preferable to contain 10 to 200 parts by weight of the hydroxyl group-containing polysiloxane (b2) in terms of complete hydrolysis condensate and 0.1 to 50 parts by weight of the titanium alkoxide condensate (C) in terms of complete hydrolysis condensate. .

Furthermore, the composition for forming a high refractive material according to the present invention is selected from the group consisting of zirconium oxide, titanium oxide, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, and a composite thereof. 100 parts by weight of fine particles (A) of at least one metal oxide,
The following average composition formula (1)
R ¹ _a R ² _b SiO _c (OR ³ ) _d (1)
(In the formula, R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ³ is an alkyl group, and R ¹ , R ^2, and R ³ are When there are a plurality of them, they may be the same or different from each other, a and b are independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d Is greater than 0 and less than 4 and a + b + c × 2 + d = 4)
A siloxane system of an alkoxy group-containing siloxane oligomer (b1) and a hydroxyl group-containing polysiloxane (b2) having a polystyrene-equivalent weight average molecular weight in the range of 1,000 to 100,000 as measured by gel permeation chromatography It is preferable to contain 20 to 400 parts by weight of the condensate (B) in terms of complete hydrolysis condensate and 0.1 to 50 parts by weight of the condensate (C) of titanium alkoxide in terms of complete hydrolysis condensate.

  In the siloxane-based condensate (B), the weight ratio (b1 / b2) in terms of a complete hydrolysis condensate of the alkoxy group-containing siloxane oligomer (b1) and the hydroxyl group-containing polysiloxane (b2) is 1/50 to 50. A condensate obtained by condensation in the range of / 1 is preferred.

  The siloxane-based condensate (B) preferably has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography in the range of 2,000 to 200,000.

  The composition for forming a high refractive material according to the present invention further comprises a trifunctional alkoxy group-containing siloxane oligomer (b3) having a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography in the range of 300 to less than 1,000. 1) to 50 parts by weight in terms of complete hydrolysis condensate.

  The hydroxyl group-containing polysiloxane (b2) has the following formula (2)

(In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ⁴ and R ⁵ are present, they are the same as each other. Or n is an integer of 5 to 2000)
Consisting of one or more hydroxyl group-containing siloxane oligomers represented by
The polystyrene equivalent weight average molecular weight measured by gel permeation chromatography is preferably 500 to 100,000.

The metal oxide fine particles are preferably ZrO ₂ fine particles.
The cured body according to the present invention is obtained by curing the composition for forming a high refractive material, and has a thickness of 10 μm to 1 mm.

The method for producing a composition for forming a high refractive material according to the present invention is selected from the group consisting of zirconium oxide, titanium oxide, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, and composites thereof. 100 parts by weight of the fine particles (A) of at least one kind of metal oxide are 0.1 to 50 parts by weight in terms of a complete hydrolysis condensate and 10 to 200 parts by weight of an alkoxy group-containing siloxane oligomer. A step of dispersing in an organic solvent in the presence of a part of the titanium alkoxide condensate (C);
And a step of mixing the metal oxide fine particle dispersion and 10 to 200 parts by weight of a hydroxyl group-containing polysiloxane (b2) in terms of complete hydrolysis condensate.

The method for producing a composition for forming a high refractive material according to the present invention comprises a step of condensing an alkoxy group-containing siloxane oligomer and a hydroxyl group-containing polysiloxane (b2) to prepare a siloxane-based condensate (B),
100 weights of fine particles (A) of at least one metal oxide selected from the group consisting of zirconium oxide, titanium oxide, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, and composites thereof Parts, 20 to 400 parts by weight of the siloxane-based condensate (B) in terms of complete hydrolysis condensate, and 0.1 to 50 parts by weight of the condensate of titanium alkoxide (C) in terms of complete hydrolysis condensate And mixing in a solvent to disperse the metal oxide fine particles (A) in an organic solvent.

In the method for producing a composition for forming a high refractive material, the condensation is preferably performed by a dealcoholization reaction.
The alkoxy group-containing siloxane oligomer has the following average composition formula (1)
R ¹ _a R ² _b SiO _c (OR ³ ) _d (1)
(In the formula, R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ³ is an alkyl group, and R ¹ , R ^2, and R ³ are When there are a plurality of them, they may be the same or different from each other, a and b are independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d Is greater than 0 and less than 4 and a + b + c × 2 + d = 4)
It is preferable that it is the alkoxy group containing siloxane oligomer (b1) which is represented by these, and the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography exists in the range of 1,000-100,000.

  The hydroxyl group-containing polysiloxane (b2) has the following formula (2)

(In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ⁴ and R ⁵ are present, they are the same as each other. Or n is an integer of 5 to 2000)
Consisting of one or more hydroxyl group-containing siloxane oligomers represented by
The polystyrene equivalent weight average molecular weight measured by gel permeation chromatography is preferably 500 to 100,000.

  The weight ratio (b1 / b2) in terms of the complete hydrolysis condensate between the alkoxy group-containing siloxane oligomer (b1) and the hydroxyl group-containing polysiloxane (b2) is preferably in the range of 1/50 to 50/1.

  According to the present invention, it is possible to obtain a cured product, particularly a polysiloxane thick film, which is excellent in heat resistance, ultraviolet resistance and light transmittance and has a high refractive index. Specifically, it can be used as a sealing material for an LED element using a blue LED element or an ultraviolet LED element as a light emitting element, and can be preferably used particularly as a sealing material for a high-brightness LED element.

First, each component used in the present invention will be described in detail.
(A) Metal oxide fine particles In the present invention, high refractive fine particles are used in order to impart high refraction to the cured product. Such a fine particle is not particularly limited as long as it has a refractive index of light having a wavelength of 400 nm at 25 ° C. of preferably 1.55 or more, more preferably 1.60 or more, particularly preferably 1.70 or more. Metal oxide fine particles (hereinafter referred to as “metal oxide fine particles (A)”) such as zirconium oxide, titanium oxide, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, and composites thereof. Can be mentioned. The titanium oxide is not particularly limited as long as it has a TiO ₂ structure, and examples thereof include an anatase type, a rutile type, and a brookite type. These metal oxide fine particles (A) may be used alone or in combination of two or more. Of these metal oxide fine particles, ZrO ₂ is preferable.

  The primary average particle diameter of the metal oxide fine particles (A) is preferably 0.1 to 100 nm, more preferably 0.1 to 70 nm, and particularly preferably 0.1 to 50 nm. When the primary average particle diameter of the metal oxide fine particles (A) is in the above range, a cured product having excellent light transmittance can be obtained.

(B) Siloxane-based condensate The siloxane-based condensate (B) used in the present invention is not particularly limited as long as the object of the present invention can be achieved. For example, an alkoxy group-containing siloxane oligomer and a hydroxyl group-containing polysiloxane These condensates can be mentioned.

<Alkoxy group-containing siloxane oligomer>
The alkoxy group-containing siloxane oligomer used in the present invention is not particularly limited as long as the object of the present invention can be achieved.
The following average composition formula (1)
R ¹ _a R ² _b SiO _c (OR ³ ) _d (1)
(In the formula, R ¹ and R ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R ³ is an alkyl group, and R ¹ , R ^2, and R ³ are When there are a plurality of them, they may be the same or different from each other, a and b are independently 0 or more and less than 1, a + b is more than 0 and less than 2, c is more than 0 and less than 2, d Is greater than 0 and less than 4 and a + b + c × 2 + d = 4)
And an alkoxy group-containing siloxane oligomer (b1) having a polystyrene-equivalent weight average molecular weight of 1,000 to 100,000 as measured by gel permeation chromatography.

  Of these siloxane oligomers (b1), branched or tertiary crosslinked siloxane oligomers are preferred. Further, hydroxyl groups may remain in the siloxane oligomer (b1) in a range that does not impair the object of the present invention, specifically, in a range that does not inhibit the dealcoholization reaction.

  The weight average molecular weight is preferably 1,000 to 80,000, more preferably 1,500 to 70,000. When the siloxane oligomer (b1) having a weight average molecular weight within the above range is used, it is possible to achieve both suppression of crack generation and good curability during formation of the cured product.

  Examples of the monovalent unsubstituted hydrocarbon group include an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group, and a tolyl group. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group. Examples of the monovalent substituted hydrocarbon group include substituted alkyl groups having 1 to 8 carbon atoms. Examples of the substituent of the substituted alkyl group include halogen, amino group, mercapto group, isocyanate group, glycidyl group, glycidoxy group, ureido group and the like.

Examples of the alkyl group represented by R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Of these alkyl groups, a methyl group and an ethyl group are preferable.

This siloxane oligomer (b1) can be produced, for example, by hydrolyzing and condensing polyfunctional alkoxysilane or polyfunctional chlorosilane.
Examples of the polyfunctional alkoxysilane include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane;
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, Phenyltrimethoxysilane, phenyltriethoxysilane,
3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-ureidopropi Trimethoxysilane, trialkoxysilanes such as 3-ureidopropyltriethoxysilane;
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxy Silane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldi Ethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyl Diethoxysilane, diphenyl Silane, dialkoxy silanes such as diphenyl diethoxy silane. These alkoxysilanes can be used individually by 1 type or in mixture of 2 or more types.

  Moreover, in addition to polyfunctional alkoxysilane, monofunctional alkoxysilane can also be used together. Examples of monofunctional alkoxysilanes include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, and triethylethoxysilane. These monofunctional alkoxysilanes are desirably used in an amount of 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less based on the total amount of alkoxysilane used.

  Further, as the siloxane oligomer (b1), X40-9220, X40-9225 (trade name) manufactured by Shin-Etsu Silicone, XR31-B1410, XR31-B0270, XR31-B2733 (trade name, manufactured by GE Toshiba Silicone) Commercially available organosiloxane oligomers such as) can also be used.

<Hydroxyl-containing polysiloxane>
The hydroxyl group-containing polysiloxane (b2) used in the present invention is not particularly limited as long as the object of the present invention can be achieved.
Following formula (2)

(In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and when a plurality of R ⁴ and R ⁵ are present, they are the same as each other. Or n is an integer of 5 to 2000)
It consists of 1 type or 2 types or more of hydroxyl-containing siloxane oligomers represented by these.

  This hydroxyl group-containing siloxane oligomer has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography in the range of 500 to 100,000, preferably 1,000 to 80,000, more preferably 1,500 to 70,000. It is in. When a hydroxyl group-containing siloxane oligomer having a weight average molecular weight in the above range is used, it is possible to achieve both suppression of crack generation and good curability when forming a cured product.

Examples of the substituted or unsubstituted monovalent hydrocarbon group include the same monovalent hydrocarbon groups as exemplified for the siloxane oligomer (b1).
This hydroxyl group-containing siloxane oligomer can be produced, for example, by hydrolyzing and condensing dialkoxysilane or dichlorosilane.

Examples of the dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, Di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane , Di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxy Silane, di-n-cyclohex Such as diethoxymethylsilane silane. These dialkoxysilanes can be used alone or in combination of two or more.

  The hydroxyl group-containing siloxane oligomer can also be produced by ring-opening condensation of a cyclic organosiloxane. Cyclic organosiloxanes include hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, tetilavinyltetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, pentamethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, Examples thereof include tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like.

  Further, as the hydroxyl group-containing siloxane oligomer, commercially available bifunctional organosiloxane oligomers such as XC96-723, YF-3800, YF-3905, and YF-3804 (above, trade names) manufactured by GE Toshiba Silicone Co. can be used. .

<Trifunctional alkoxy group-containing siloxane oligomer>
In the present invention, a trifunctional alkoxy group-containing siloxane oligomer (b3) can be used as necessary in order to disperse the metal oxide fine particles (A) more uniformly. This trifunctional siloxane oligomer (b3) has a polystyrene-reduced weight average molecular weight measured by gel permeation chromatography in the range of 300 to 1,000, preferably 500 to 1,000. When the trifunctional siloxane oligomer (b3) having a weight average molecular weight within the above range is used, the dispersibility of the metal oxide fine particles (A) can be stabilized, cracks are not generated, and the thickness is excellent in light transmittance. A cured product (film) of 10 μm or more can be obtained.

This trifunctional siloxane oligomer (b3) can be produced, for example, by hydrolyzing and condensing polyfunctional alkoxysilane or polyfunctional chlorosilane.
Examples of the polyfunctional alkoxysilane include those similar to the tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes and the like exemplified for the siloxane oligomer (b1). These polyfunctional alkoxysilanes can be used singly or in combination of two or more.

  Moreover, as a trifunctional alkoxy group containing siloxane oligomer, commercially available trifunctional alkoxy group containing siloxane oligomers, such as XC96-B0446 (brand name) by GE Toshiba Silicone, can also be used.

(C) Condensate of titanium alkoxide The condensate (C) of titanium alkoxide used in the present invention is, for example, the following formula (3):
R ⁶ _m Ti (OR ⁷ ) _4-m (3)
(Wherein R ⁶ represents an organic group having 1 to 8 carbon atoms, and when there are a plurality of them, they may be the same or different, and R ⁷ is an alkyl group having 1 to 6 carbon atoms, It represents an organic group selected from the group consisting of an acyl group having 1 to 6 carbon atoms and a phenyl group, and when there are a plurality of them, they may be the same or different, and R ⁶ and R ⁷ are the same Or m may be an integer of 0 to 3)
The condensate of the titanium alcoholate represented by these is mentioned.

In the above formula (3), R ⁶ is an organic group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec- Alkyl groups such as butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group;
Acyl groups such as formyl group, acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group;
Examples thereof include a vinyl group, an allyl group, a cyclohexyl group, a phenyl group, an epoxy group, a glycidyl group, a (meth) acryloxy group, a ureido group, an amide group, a fluoroacetamide group, and an isocyanate group.

Furthermore, examples of R ⁶ include substituted derivatives of the above organic groups. Examples of the substituent of the substituted derivative of R ⁶ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) acryloxy group, A ureido group, an ammonium base, etc. are mentioned. However, the number of carbon atoms of R ⁶ composed of these substituted derivatives is preferably 8 or less including the carbon atoms in the substituent. When a plurality of R ⁶ are present in the formula (3), they may be the same or different from each other.

As R ⁷ which is an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, n
-Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group and the like can be mentioned.

  The titanium alkoxide condensate (C) is one in which the Ti—OH group in the hydrolyzate produced by hydrolysis of the titanium alcoholate is condensed to form a Ti—O—Ti bond. In the present invention, it is not necessary that all of the Ti—OH groups are condensed, and the condensate is obtained by condensing a small part of Ti—OH groups, and most (including all) Ti—OH groups. In addition, a mixture of a condensate in which a Ti—OR group and a Ti—OH group are mixed is also included.

  The average condensation degree of the titanium alkoxide condensate (C) is preferably 2 to 20, that is, the condensate is preferably a dimer to a 20-mer, and the average condensation degree is 2 to 15, that is, the condensate is A dimer to a 15-mer is particularly preferable. As this condensate, one or two or more kinds of titanium alcoholates previously hydrolyzed and condensed may be used, or commercially available condensates may be used. Examples of commercially available condensates of titanium alcoholate (from dimer to decamer) include A-10, B-2, B-4, B-7, and B-10 manufactured by Nippon Soda Co., Ltd. It is done. Such a titanium alkoxide condensate (C) may be used alone or in combination of two or more.

<Composition for forming high refractive material>
The composition for forming a high refractive material according to the present invention is the coexistence of the alkoxy group-containing siloxane oligomer and the titanium alkoxide condensate (C) and, if necessary, a trifunctional alkoxy group-containing siloxane oligomer (b3), It can be produced by dispersing the metal oxide fine particles (A) in an organic solvent and mixing the metal oxide fine particle dispersion and the hydroxyl group-containing polysiloxane (b2) (first production method). By dispersing the metal oxide fine particles (A) in an organic solvent as described above, the metal oxide fine particles (A) are uniformly dispersed to form a cured body (film) having excellent uniformity and light transmittance. can do.

In the first production method described above, the alkoxy group-containing siloxane oligomer is 10 to 200 parts by weight, preferably 15 to 180 parts by weight in terms of complete hydrolysis condensate, based on 100 parts by weight of the metal oxide fine particles (A). More preferably 20 to 150 parts by weight; 10 to 200 parts by weight, preferably 15 to 180 parts by weight, more preferably 20 to 150 parts by weight of the hydroxyl group-containing polysiloxane (b2) in terms of complete hydrolysis condensate; trifunctional 1-50 parts by weight, preferably 2-45 parts by weight, more preferably 5-40 parts by weight of the alkoxy group-containing siloxane oligomer (b3) in terms of complete hydrolysis condensate; It is 0.1 to 50 parts by weight, preferably 1 to 45 parts by weight, more preferably 2 to 40 parts by weight in terms of decomposition condensate. Masui. The composition for forming a high refractive material thus produced contains each component in the above range. By using such a composition for forming a high refractive material, a cured body (film) having a uniform and excellent light transmittance can be formed.

  The composition for forming a high refractive material is prepared by mixing the alkoxy group-containing siloxane oligomer and the hydroxyl group-containing polysiloxane (b2) and condensing the siloxane-based condensate (B). The product (B), the metal oxide fine particles (A), the condensate (C) of titanium alkoxide, an organic solvent, and a trifunctional alkoxy group-containing siloxane oligomer (b3) as necessary, It can also be produced by dispersing the metal oxide fine particles (A) in an organic solvent (second production method).

  In the second production method, 20 to 400 parts by weight, preferably 30 to 360 parts by weight of the siloxane-based condensate (B) in terms of the complete hydrolysis condensate with respect to 100 parts by weight of the metal oxide fine particles (A). Parts, more preferably 40 to 300 parts by weight; 1 to 50 parts by weight, preferably 2 to 45 parts by weight, more preferably 5 to 40 parts by weight of the trifunctional alkoxy group-containing siloxane oligomer (b3) in terms of complete hydrolysis condensate. Parts by weight; the condensate (C) of titanium alkoxide is used in the range of 0.1 to 50 parts by weight, preferably 1 to 45 parts by weight, more preferably 2 to 40 parts by weight in terms of complete hydrolysis condensate. preferable. The composition for forming a high refractive material thus produced contains each component in the above range. By using such a composition for forming a high refractive material, a cured body (film) having a uniform and excellent light transmittance can be formed.

  In the second production method, the alkoxy group-containing siloxane oligomer and the hydroxyl group-containing polysiloxane (b2) are preferably condensed by a dealcoholization reaction. Furthermore, you may make it hydrolyze and condense after this dealcoholization reaction. When a polysiloxane condensate prepared by this dealcoholization reaction is used, a cured body (film) that is uniform and excellent in light transmittance can be formed. In addition, when the hydroxyl group-containing polysiloxane (b2) and the alkoxy group-containing siloxane oligomer are hydrolyzed / condensed without causing a dealcoholization reaction, the alkoxy group-containing siloxane oligomer is selectively hydrolyzed / condensed so that it is uniform and light transmissive. It may be difficult to form a cured body (film) having excellent properties.

The temperature of the condensation reaction is preferably 20 to 150 ° C, more preferably 30 to 100 ° C, and particularly preferably 40 to 80 ° C.
Moreover, when performing the said dealcoholization reaction, it is preferable to use the catalyst which promotes this reaction. Examples of the catalyst used in the dealcoholization reaction include acidic compounds, alkaline compounds, salt compounds, amine compounds, organometallic compounds and / or partial hydrolysates thereof (hereinafter referred to as organometallic compounds and / or partial hydrolysates thereof. And “organometallic compounds”).

Examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl titanic acid, p-toluenesulfonic acid, and phthalic acid, and among these, acetic acid is preferable.
Examples of the alkaline compound include sodium hydroxide and potassium hydroxide. Of these, sodium hydroxide is preferable.

Examples of the salt compound include naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and alkali metal salts such as carbonic acid.
Examples of the amine compounds include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-phenylenediamine, p-phenylenediamine, ethanolamine, triethylamine, 3-aminopropyl trimethoxy. Silane, 3-aminopropyl-triethoxysilane, 3- (2-aminoethyl) -aminopropyl-trimethoxysilane, 3- (2-aminoethyl) -aminopropyl-triethoxysilane, 3- (2-aminoethyl) ) -Aminopropyl / methyl / dimethoxysilane, 3-anilinopropyl / trimethoxysilane, alkylamine salts, and quaternary ammonium salts such as tetramethylammonium hydroxide. Various modified amines used as a curing agent for epoxy resins can also be used. Of these, 3-aminopropyl / trimethoxysilane, 3-aminopropyl / triethoxysilane, and 3- (2-aminoethyl) -aminopropyl / trimethoxysilane are preferable.

Examples of the organometallic compounds include the following formula (4):
M (OR ⁸ ) _r (R ⁹ COCHCOR ¹⁰ ) _s (4)
(In the formula, M represents at least one metal atom selected from the group consisting of zirconium, titanium, aluminum and sodium, and R ⁸ and R ⁹ each independently represents a methyl group, an ethyl group, or n-propyl. A monovalent carbon having 1 to 6 carbon atoms such as a group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, etc. R ¹⁰ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, or methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy. Represents an alkoxyl group having 1 to 16 carbon atoms such as a group, t-butoxy group, lauryloxy group, stearyloxy group, and r and s are each independently an integer of 0 to 4, and (r + s) = Satisfies the relationship of (M valence)
(Hereinafter referred to as “organometallic compound (4)”),
A tetravalent tin organometallic compound in which one or two alkyl groups having 1 to 10 carbon atoms are bonded to one tin atom (hereinafter referred to as “organotin compound”), or
These partial hydrolysates are exemplified.

Further, as the organometallic compounds, titanium alcoholate represented by the above formula (3) and condensates thereof can be used.
Examples of the organometallic compound (4) include tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetatezirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate). Organic zirconium compounds such as acetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium;
Organic titanium compounds such as tetra-i-propoxy titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetone) titanium ;
Tri-i-propoxyaluminum, di-i-propoxyethyl acetoacetate aluminum, di-i-propoxy acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy bis (acetylacetonate) ) Organoaluminum compounds such as aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethylacetoacetate) aluminum;
Examples include sodium alkoxide such as sodium methoxide.

  As an organic tin compound, for example,

Carboxylic acid type organotin compounds such as;

Mercaptide-type organotin compounds such as

Sulfide-type organotin compounds such as;

Chloride-type organotin compounds such as;
Reaction of organotin oxides such as (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, and ester compounds such as silicates, dimethyl maleate, diethyl maleate and dioctyl phthalate Product;
Etc.

  Of these catalysts, alkoxytitanium, alkoxysilconium, alkoxyaluminum, chelates thereof, and partial hydrolysates thereof, and sodium alkoxide are preferable, and tri-n-butoxyethyl acetoacetate zirconium is more preferable. Di-i-propoxy bis (acetylacetonate) titanium, di-i-propoxy ethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, partial hydrolysates thereof, and sodium methoxide are used.

  The siloxane-based condensate (B) formed in the second production method has a polystyrene-reduced weight average molecular weight of 2,000 to 200,000, preferably 3,000 to 150, measured by gel permeation chromatography. 000, more preferably in the range of 4,000 to 100,000. When the weight average molecular weight is in the above range, a film having the above characteristics, particularly a thick film can be easily formed.

  In addition, the siloxane-based condensate (B) formed in the second production method includes a block (α) derived from an alkoxy group-containing siloxane oligomer and a block (β) derived from a hydroxyl group-containing polysiloxane (b2). ) And. Specifically, it is considered that a block structure in which the block (β) is bonded to both ends of the block (α) is formed. Further, it is preferable that another block (α) is bonded to the block (β) to form a structure in which the block (β) is crosslinked with the block (α). Such a polysiloxane condensate having a block structure is excellent in adhesion and flexibility to a substrate or the like, and easily forms a thick film having a thickness of preferably 10 μm or more, more preferably 20 μm or more, and particularly preferably 100 μm or more. can do. Further, a film excellent in transparency with no light cracking at the time of drying and curing (for example, 150 ° C., 1 hour) and having a light transmittance of a wavelength of 500 to 700 nm is preferably 90% or more, more preferably 95% or more. Can be formed.

  Furthermore, an unreacted siloxane oligomer may remain in the siloxane-based condensate (B) formed in the second production method. In particular, when a siloxane oligomer containing a hydroxyl group remains, the storage stability may be reduced, or the hydroxyl group-containing siloxane oligomer may be separated during curing to form a uniform cured product (film) having excellent light transmittance. For this reason, in this invention, it is preferable to add a polyfunctional alkoxysilane after the said condensation reaction, and to make an unreacted hydroxyl group and an alkoxy group react, and to reduce a hydroxyl group residual amount. The amount of the polyfunctional alkoxysilane added is, for example, preferably 0.1 to 20 parts by weight, more preferably 100 parts by weight (equivalent to a completely hydrolyzed condensate) of the obtained siloxane-based condensate (B). Is 1 to 15 parts by weight, particularly preferably 2 to 10 parts by weight.

  As said polyfunctional alkoxysilane, the thing similar to the polyfunctional alkoxysilane illustrated by the said siloxane oligomer (b1) can be mentioned, It can use individually by 1 type or in mixture of 2 or more types.

In the above production method, when the alkoxy group-containing siloxane oligomer is an alkoxy group-containing siloxane oligomer (b1), the alkoxy group-containing siloxane oligomer (b1) and the hydroxyl group-containing polysiloxane (b2) are weighted in terms of complete hydrolysis condensate. The ratio (b1 / b2) is preferably 1/50 to 50/1, more preferably 1/40 to 40/1, and particularly preferably 1/25 to 25/1. When the siloxane oligomers (b1) and (b2) are reacted at the above ratios, a siloxane-based condensate having excellent stability is obtained when the siloxane-based condensate (B) is produced during the production or formation of the cured product. be able to.

  Examples of the organic solvent include alcohols, aromatic hydrocarbons, ethers, ketones, esters, and the like. Examples of the alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, i-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, Examples include ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, and diacetone alcohol. Aromatic hydrocarbons include benzene, toluene, xylene, etc., ethers include tetrahydrofuran, dioxane, etc., and ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and the like. Examples of the esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate, methyl lactate, ethyl lactate, normal propyl lactate, isopropyl lactate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and the like. . These organic solvents may be used individually by 1 type, or 2 or more types may be mixed and used for them. Of these organic solvents, organic solvents other than alcohols such as methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene and the like are preferable from the viewpoint of promoting the dealcoholization reaction. Moreover, it is preferable to use these organic solvents in the state which gave the dehydration process previously and removed the water | moisture content.

  The amount of the organic solvent used is not particularly limited as long as the metal oxide fine particles (A) can be uniformly dispersed, but the solid content concentration of the obtained composition for forming a high refractive material is preferably 5 to 80 wt. %, More preferably 7 to 70% by weight, particularly preferably 10 to 60% by weight.

  The composition for forming a high refractive material preferably contains glass fibers in order to relieve shrinkage-expansion of the cured body. When a composition containing glass fibers is used, a thick film cured body can be formed. In order to ensure the transparency of the cured product, the siloxane components in the composition (siloxane-based condensate (B), alkoxy group-containing siloxane oligomer (b1) and hydroxyl group-containing polysiloxane (b2)), the glass fiber, The refractive index difference is preferably 0.01 or less, more preferably 0.007 or less, and particularly preferably 0.005 or less.

<Hardened body>
The cured body according to the present invention is a cured body obtained by coating the composition for forming a high refractive material containing an organic solvent on a substrate and the like, and curing the polysiloxane condensate by removing the solvent by drying. (Film) is formed. At this time, the drying conditions are appropriately set depending on the performance of the dryer to be used. For example, the drying temperature is preferably 70 to 250 ° C, more preferably 100 to 230 ° C, and the drying time is preferably 0.1 to 250 ° C. 24 hours, more preferably 0.2 to 3 hours.

The cured product thus obtained does not have a carbon-carbon bond in the crosslinked structure, and is excellent in ultraviolet resistance and heat resistance. For example, the cured product of the polysiloxane condensate does not turn yellow even when irradiated with ultraviolet rays of 5000 mW / m ² for 200 hours, and does not thermally deteriorate even when heated at 150 ° C. for 1000 hours.

  In addition, this cured body (film) has a refractive index of light having a wavelength of 400 nm at 25 ° C. of 1.55 to 2.20, preferably 1.60 to 2.20, more preferably 1.65 to 2.20. is there. Further, at a thickness of 20 μm, the light transmittance at a wavelength of 500 to 700 nm is 90% or more, preferably 93% or more, more preferably 95% or more. Further, the cured body (film) has a light transmittance of 90% or more, preferably 93% or more, more preferably 95% or more at a wavelength of 350 to 400 nm at a thickness of 20 μm. Due to this characteristic, light emitted from the blue LED or the ultraviolet LED element can be extracted without being attenuated.

  Such a cured body is useful as a sealing material for LED elements, and is particularly useful as a sealing material for LED elements in which the light-emitting element is a blue LED element or an ultraviolet LED element because of excellent ultraviolet resistance and heat resistance. It exhibits excellent durability even in a high luminance environment. Further, this sealing material has a high refractive index, and can efficiently extract light from the light emitting element.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the examples and comparative examples, “parts” and “%” indicate “parts by weight” and “% by weight” unless otherwise specified. In addition, various measurements in Examples and Comparative Examples were performed by the following methods.

(1) Storage stability The container was stored tightly for 1 month at room temperature in a polyethylene container, and the presence or absence of gelation was visually determined. About the thing which is not gelatinized, the viscosity was measured with the BM type | mold viscosity meter by Tokyo Keiki Co., Ltd., and the following reference | standard evaluated.
A: Viscosity change rate before and after storage is 20% or less B: Viscosity change rate before and after storage exceeds 20% (2) Dispersed particle size For the fine particles in the obtained composition, the volume average particle size and maximum particle size are This was measured with a Microtrac Ultrafine Particle Size Analyzer (UPA150) manufactured by the company.

(3) Light transmittance The obtained composition was applied on quartz glass so that the dry film thickness was 20 μm, and then dried and cured at 100 ° C. for 1 hour, and then dried and cured at 200 ° C. for 1 hour and cured. The body was made. About this hardening body, the spectral transmittance of wavelength 500-700nm was measured with the ultraviolet visible spectrophotometer, and the following reference | standard evaluated.
A: Light transmittance exceeds 90% B: Light transmittance is 70 to 90%
C: Light transmittance is less than 70% (4) Degree of yellowing The obtained composition was applied on quartz glass so that the dry film thickness was 20 μm, then dried and cured at 100 ° C. for 1 hour, and then 200 A cured product was produced by drying and curing at 1 ° C. for 1 hour. About this hardening body, the light transmittance of wavelength 350-400 nm was measured with the ultraviolet visible spectrophotometer, and the following reference | standard evaluated.
A: Light transmittance exceeds 90% B: Light transmittance is 70 to 90%
C: Light transmittance is less than 70% (5) Refractive index The obtained composition was applied on quartz glass so that the dry film thickness was 20 μm, then dried and cured at 100 ° C. for 1 hour, and then 200 ° C. And dried and cured for 1 hour to prepare a cured product. About this hardening body, the refractive index of light with a wavelength of 400 nm in 25 degreeC was measured with the film thickness measuring apparatus F20 by FILMETRICS.

(6) Light resistance The obtained composition was applied on quartz glass so that the dry film thickness was 20 μm, and then dried and cured at 100 ° C. for 1 hour, and then dried and cured at 200 ° C. for 1 hour to obtain a cured product. Was made. The cured product was irradiated with ultraviolet light having an illuminance of 5000 mW / cm ² using a spot UV irradiation device (USHIO Corporation: SP-V) in which light having a wavelength of 350 nm or less was cut to approximate the emission wavelength of the ultraviolet LED element. Irradiated for 200 hours. The appearance of the cured product after ultraviolet irradiation was visually observed and evaluated according to the following criteria.
A: No change (no coloring, no cracking)
B: Slightly discolored C: Yellowish (7) GPC measurement The weight average molecular weight of siloxane was shown as a polystyrene conversion value measured under the following conditions by gel permeation chromatography.
Apparatus: HLC-8120C (manufactured by Tosoh Corporation)
Column: TSK-gel Multipore H _XL- M (manufactured by Tosoh Corporation)
Eluent: THF, flow rate 0.5 mL / min, load 5.0%, 100 μL

  100 parts of zirconium oxide (primary average particle diameter: 15 nm) as metal oxide fine particles (A), tetramer of tetra n-butoxy titanium as a condensate (C) of titanium alkoxide (trade name: B-, manufactured by Nippon Soda Co., Ltd.) 10) 50 parts of a trifunctional siloxane oligomer (b3), 23 parts of an alkoxy-terminated trifunctional siloxane oligomer (trade name: XC96-B0046, manufactured by Toshiba Silicone Co., Ltd.) having a weight average molecular weight (Mw) of 800, an alkoxy group-containing siloxane oligomer. As (b1), 20 parts of an alkoxy-terminated silicon polymer (product name: XR31-B0270, manufactured by Toshiba Silicone Co., Ltd.) having Mw = 10,000 and 607 parts of methyl isobutyl ketone as an organic solvent are placed in a container, and the particle size is 0.1 mm. 4,000 parts of zirconia beads (Nikkato Co., Ltd.) Zumiru by, 1500 rpm, was stirred for 1 hour to disperse the metal oxide fine particles (A).

  In the obtained metal oxide fine particle (A) dispersion, 6 parts of silanol-terminated polydimethylsiloxane having a Mw = 3500 (trade name: YF-3800, manufactured by Toshiba Silicone) as a hydroxyl group-containing siloxane oligomer (b2), and an organic solvent As a result, 24 parts of methyl isobutyl ketone was added to obtain a composition for forming a high refractive material having a solid concentration of about 20% by weight.

  When this composition was evaluated according to the above method, the storage stability was A, the volume average particle size was 30 nm, the maximum particle size was 60 nm, the transparency was A, the yellowing degree was A, the refractive index was 1.60, and the light resistance. Was A.

  40 parts of alkoxy-terminated silicon polymer (trade name: XR31-B0270, manufactured by Toshiba Silicone Co., Ltd.) having Mw = 10,000 as the alkoxy group-containing siloxane oligomer (b1), and silanol-terminated polysiloxane having Mw = 3500 as the hydroxyl group-containing siloxane oligomer (b2) 19 parts of dimethylsiloxane (trade name: YF-3800, manufactured by Toshiba Silicone Co., Ltd.) and 0.6 part of sodium methoxide diluted 500-fold with propylene bricol monopropyl ether as a condensation catalyst were added and dealcoholized at 60 ° C. for 3 hours. A siloxane-based condensate (B1) was obtained by reaction. Thereafter, 2 parts of glycidoxypropyltrimethoxysilane was added and reacted at 60 ° C. for 2 hours to cap the hydroxyl group of unreacted silanol-terminated polydimethylsiloxane in the siloxane-based condensate (B1). The weight average molecular weight of the obtained siloxane-based condensate (B1) was 15,000.

  Next, 100 parts of zirconium oxide (primary average particle size: 15 nm) as the metal oxide fine particles (A), tetramer of tetra n-butoxy titanium as a condensate of titanium alkoxide (C) (trade name, manufactured by Nippon Soda Co., Ltd.) : B-10) 50 parts, 80 parts of the siloxane-based condensate (B1) as a siloxane-based condensate (B), and 770 parts of methyl isobutyl ketone as an organic solvent are placed in a container, and zirconia beads having a particle diameter of 0.1 mm Add 4000 parts (made by Nikkato Co., Ltd.) and stir with a bead mill at 1500 rpm for 1 hour to disperse the metal oxide fine particles (A) to obtain a composition for forming a high refractive material having a solid concentration of about 20% by weight. It was.

  When this composition was evaluated according to the above method, the storage stability was A, the volume average particle size was 30 nm, the maximum particle size was 65 nm, the transparency was A, the yellowing degree was A, the refractive index was 1.56, and the light resistance. Was A.

  For forming a high refractive material having a solid content concentration of about 20% by weight, as in Example 2, except that the siloxane-based condensate (B1) was changed from 80 parts to 34 parts and methyl isobutyl ketone was changed from 770 parts to 586 parts. A composition was obtained.

  When this composition was evaluated according to the above method, the storage stability was A, the volume average particle size was 35 nm, the maximum particle size was 70 nm, the transparency was A, the yellowing degree was A, the refractive index was 1.64, and light resistance. Was A.

  40 parts of alkoxy-terminated silicon polymer (trade name: XR31-B0270, manufactured by Toshiba Silicone Co., Ltd.) having Mw = 10,000 as the alkoxy group-containing siloxane oligomer (b1), and silanol-terminated polysiloxane having Mw = 3500 as the hydroxyl group-containing siloxane oligomer (b2) 19 parts of dimethylsiloxane (trade name: YF-3800, manufactured by Toshiba Silicone Co., Ltd.), 0.2 part of an i-propyl alcohol solution of di-i-propoxy / ethyl acetoacetate aluminum (concentration 75% by weight) as a condensation catalyst, A dealcoholization reaction was performed at 60 ° C. for 3 hours to obtain a siloxane-based condensate (B2). Thereafter, 2 parts of glycidoxypropyltrimethoxysilane was added and reacted at 60 ° C. for 2 hours to cap the hydroxyl group of unreacted silanol-terminated polydimethylsiloxane in the siloxane-based condensate (B2). The weight average molecular weight of the obtained siloxane-based condensate (B2) was 25,000.

A composition for forming a high refractive material having a solid concentration of about 20% by weight was obtained in the same manner as in Example 2 except that the siloxane-based condensate (B2) was used as the siloxane-based condensate (B).
When this composition was evaluated according to the above method, storage stability was A, volume average particle size was 30 nm, maximum particle size was 60 nm, transparency was A, yellowing degree was A, refractive index was 1.56, light resistance. Was A.

  A composition for forming a high refractive material having a solid content concentration of about 20% by weight was obtained in the same manner as in Example 1 except that rutile type titanium oxide (primary average particle size: 30 nm) was used as the metal oxide fine particles (A). Obtained.

  When this composition was evaluated according to the above method, the storage stability was A, the volume average particle size was 40 nm, the maximum particle size was 70 nm, the transparency was A, the yellowing degree was B, the refractive index was 1.61, and the light resistance. Was A.

[Comparative Example 1]
100 parts of hydrogenated bisphenol A glycidyl ether (Japan Epoxy Resin, Epicoat YX8000) and 90 parts of methylhexahydrophthalic anhydride (MH700) were sufficiently stirred and mixed, then dried and cured at 100 ° C for 1 hour, and then 150 ° C. And dried for 1 hour. When the obtained cured product was evaluated according to the above method, the transparency was A, the yellowing degree was B, and the light resistance C.
Met.

[Comparative Example 2]
100 parts of zirconium oxide (primary average particle size: 15 nm) as the metal oxide fine particles (A), and a tetramer of n-butoxytitanium tetramer as the condensate (C) of titanium alkoxide (product name: B -10) 50 parts, 450 parts of methyl isobutyl ketone as an organic solvent are put in a container, 4000 parts of zirconia beads having a particle size of 0.1 mm (made by Nikkato Co., Ltd.) are added thereto, and the mixture is stirred at 1500 rpm for 1 hour by a bead mill. The metal oxide fine particles (A) were dispersed, but could not be separated from the zirconia beads due to poor dispersion.

[Comparative Example 3]
100 parts of zirconium oxide (primary average particle size: 15 nm) as metal oxide fine particles (A), alkoxy-terminated trifunctional siloxane oligomer of Mw = 800 as trifunctional siloxane oligomer (b3) (trade name: XC96- B0046) 23 parts, 20 parts of alkoxy-terminated silicon polymer (product name: XR31-B0270, manufactured by Toshiba Silicone Co., Ltd.) having Mw = 10,000 as the alkoxy group-containing siloxane oligomer (b1), and 607 parts of methyl isobutyl ketone as the organic solvent Into this, 4000 parts of zirconia beads having a particle size of 0.1 mm (made by Nikkato Co., Ltd.) were added, and the mixture was stirred at 1500 rpm for 1 hour by a bead mill to disperse the metal oxide fine particles (A). Therefore, it could not be separated from zirconia beads.

[Reference Example 1]
Instead of 80 parts of the siloxane-based condensate (B1), 40 parts of the siloxane-based condensate (B1) and an oxyalkylene group-containing organosiloxane oligomer having a Mw of 10,000 (manufactured by Nippon Unicar Co., Ltd., trade name: MAC-2101) ) A composition for forming a highly refractive material having a solid content concentration of about 20% by weight was obtained in the same manner as in Example 2 except that 30 parts were used.

  When this composition was evaluated according to the above method, the storage stability was A, the volume average particle size was 35 nm, the maximum particle size was 70 nm, the transparency was A, the yellowing degree was B, the refractive index was 1.56, and light resistance. Was A.

Claims (14)

100 parts by weight of fine particles (A) of at least one metal oxide selected from the group consisting of zirconium oxide, titanium oxide and composites thereof,
10 to 200 parts by weight gain helper molecular weight distribution The weight average molecular weight in terms of polystyrene measured by chromatography is in the range of 1,000 to 100,000 alkoxy group-containing siloxane oligomer (b1) in the product of complete hydrolysis and condensation terms,
10 to 200 parts by weight of hydroxyl group-containing polysiloxane (b2) in the product of complete hydrolysis and condensation conversion, and condensates of the titanium alkoxide (C) the product of complete hydrolysis and condensation terms a high refractive you 0.1 to 50 parts by weight A material forming composition comprising:
The alkoxy group-containing siloxane oligomer (b1) is tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxy Silane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyl Triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di -N-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, Di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane The At least one polyfunctional alkoxysilane selected from the group consisting of -n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane, or It is obtained by hydrolyzing and condensing polyfunctional chlorosilane,
The composition for forming a high refractive material, wherein the titanium alkoxide condensate (C) has an average degree of condensation of 2 to 20. 100 parts by weight of fine particles (A) of at least one metal oxide selected from the group consisting of zirconium oxide, titanium oxide and composites thereof,
Gate helper siloxane condensate having a weight average molecular weight in terms of polystyrene measured by permeation chromatography is an alkoxy group-containing siloxane oligomer (b1) in the range of 1,000 to 100,000 and hydroxyl group-containing polysiloxane (b2) ( B)
Is a composition for forming a high refractive material containing 20 to 400 parts by weight in terms of a complete hydrolysis condensate and 0.1 to 50 parts by weight of a condensate (C) of titanium alkoxide in terms of a complete hydrolysis condensate. ,
The alkoxy group-containing siloxane oligomer (b1) is tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxy Silane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyl Triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di -N-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, Di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane The At least one polyfunctional alkoxysilane selected from the group consisting of -n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane, or It is obtained by hydrolyzing and condensing polyfunctional chlorosilane,
The composition for forming a high refractive material, wherein the titanium alkoxide condensate (C) has an average degree of condensation of 2 to 20 .   The siloxane-based condensate (B) is a mixture of the alkoxy group-containing siloxane oligomer (b1) and the hydroxyl group-containing polysiloxane (b2) in a weight ratio (b1 / b2) in terms of a complete hydrolysis condensate of 1/50 to 50. The composition for forming a high refractive material according to claim 2, wherein the composition is a condensate obtained by condensing within a range of / 1.   The siloxane-based condensate (B) has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography in the range of 2,000 to 200,000. A composition for forming a refractive material.   Further, a trifunctional alkoxy group-containing siloxane oligomer (b3) having a polystyrene-reduced weight average molecular weight measured by gel permeation chromatography in the range of 300 to less than 1,000 is 1 to 50 weights in terms of complete hydrolysis condensate. The composition for forming a high refractive material according to any one of claims 1 to 4, wherein the composition is contained. The hydroxyl group-containing polysiloxane (b2), the weight average molecular weight in terms of polystyrene measured by gate helper permeation chromatography is 500 to 100,000,
The hydroxyl group-containing polysiloxane (b2) is dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyl. Dimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n- Hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n -Cyclohexyldimethoxysilane, and di- -Obtained by hydrolyzing and condensing dialkoxysilane or dichlorosilane selected from the group consisting of cyclohexyldiethoxysilane, or hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, tetilavinyltetramethylcyclotetrasiloxane , Hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, pentamethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane at least one serial cyclic organosiloxane to claim 1, characterized in that it is obtained by engaged opening condensation High refractive index material forming composition. The composition for forming a high refractive material according to claim 1, wherein the metal oxide fine particles are ZrO ₂ fine particles or composite fine particles containing ZrO ₂ . It is obtained by curing the composition for forming a high refractive material according to claim 1 and has a thickness of 1.
Hardened | cured material characterized by being 0 micrometer-1 mm. 100 parts by weight of fine particles (A) of at least one metal oxide selected from the group consisting of zirconium oxide, titanium oxide and composites thereof, containing 10 to 200 parts by weight of alkoxy groups in terms of complete hydrolysis condensate A step of dispersing in an organic solvent in the presence of 0.1 to 50 parts by weight of a titanium alkoxide condensate (C) in terms of a completely hydrolyzed condensate;
Met production method of the metal oxide fine particle dispersion and the product of complete hydrolysis and condensation hydroxyl group-containing polysiloxane 10 to 200 parts by weight in terms of (b2) that have a a step of mixing a high-refractive index material forming composition And
The method for producing a highly refractive material-forming composition, wherein the titanium alkoxide condensate (C) has an average degree of condensation of 2 to 20 . A step of condensing an alkoxy group-containing siloxane oligomer and a hydroxyl group-containing polysiloxane (b2) to prepare a siloxane-based condensate (B);
100 parts by weight of fine particles (A) of at least one metal oxide selected from the group consisting of zirconium oxide, titanium oxide and composites thereof, and the siloxane-based condensate (B) in terms of complete hydrolysis condensate 20 to 400 parts by weight, and 0.1 to 50 parts by weight of the titanium alkoxide condensate (C) in terms of complete hydrolysis condensate are mixed in an organic solvent, and the metal oxide fine particles (A) are mixed with the organic solvent. a method of manufacturing a high-refractive index material forming composition that having a the step of dispersing in,
The method for producing a highly refractive material-forming composition, wherein the titanium alkoxide condensate (C) has an average degree of condensation of 2 to 20 . The method for producing a composition for forming a high refractive material according to claim 10, wherein the condensation is carried out by a dealcoholization reaction. The alkoxy group-containing siloxane oligomer, Ri alkoxy group-containing siloxane oligomer (b1) der in weight average molecular weight in terms of polystyrene measured by gate helper permeation chromatography is in the range of 1,000 to 100,000,
The alkoxy group-containing siloxane oligomer (b1) is tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxy Silane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyl Triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di -N-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, Di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane The At least one polyfunctional alkoxysilane selected from the group consisting of -n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane, or It is obtained by hydrolyzing and condensing polyfunctional chlorosilane, The manufacturing method of the composition for highly refractive material formation in any one of Claims 9-11 characterized by the above-mentioned. The hydroxyl group-containing polysiloxane (b2) is a weight average molecular weight in terms of polystyrene measured by gate helper permeation chromatography is Ri der 500 to 100,000,
The hydroxyl group-containing polysiloxane (b2) is dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyl. Dimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n- Hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n -Cyclohexyldimethoxysilane, and di- -Obtained by hydrolyzing and condensing dialkoxysilane or dichlorosilane selected from the group consisting of cyclohexyldiethoxysilane, or hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, tetilavinyltetramethylcyclotetrasiloxane , Hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, pentamethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane to claim 9-12, characterized in that it is obtained by engaged opening condensation of at least one cyclic organosiloxane Process for producing a high refractive index material forming composition of the mounting. The weight ratio (b1 / b2) in terms of complete hydrolysis condensate between the alkoxy group-containing siloxane oligomer (b1) and the hydroxyl group-containing polysiloxane (b2) is in the range of 1/50 to 50/1. A method for producing a composition for forming a high refractive material according to claim 12 or 13.