JP2015206019A - composition - Google Patents

Abstract

The present invention provides a composition containing a surface-modified metal oxide for obtaining a cured product having a high refractive index and high transparency, heat resistance and light resistance. A composition comprising particles (1), wherein the particles (1) are a surface modifier (a) having an unsaturated group, and the following general formula (1): R1R2R3Si-Y-SiR4nX3-n (1) {wherein R 1, R 2 and R 3 are each independently a hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted siloxy group, and R 4 is a substituted or unsubstituted saturated alkyl group. X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group, Y is a divalent linking group, and n is 0 to 0 It is an integer of 2. } The composition containing the surface modification metal oxide (A) obtained by surface-modifying the metal oxide (c) with the surface modification agent containing the surface modification agent (b) represented by these. [Selection figure] None

Description

  The present invention relates to a composition containing a surface-modified metal oxide.

  Conventionally, in sapphire and a transparent conductive film on a surface portion of a semiconductor light emitting element such as an LED, members of various materials are arranged on the light emitting surface according to the structure of the light emitting device. However, since there is an angle range in which the total reflection condition is satisfied at the interface between the light emitting element surface and the interface member, light incident on the interface from the inside of the element within this angle range cannot be extracted from the light emitting element.

  Methods for improving light extraction include controlling the sealing shape, growing a semiconductor layer on a sapphire having a fine structure, and providing a light diffusion layer on the surface of the light emitting layer.

  When a light diffusing layer is provided on the surface of the light emitting layer, when a concavo-convex pattern is provided on the light diffusing layer that is close to the substrate or has a refractive index equal to or higher than that of the substrate, The refractive index difference between them is further relaxed, light reflection is suppressed, and the effect of light scattering can be obtained satisfactorily. On the other hand, when there is no concavo-convex pattern, the light that is totally reflected beyond the critical angle at the interface between the light emitting element and the surrounding sealing member and confined inside the light emitting element also changes the light traveling direction. For this reason, it is known that the ratio of falling within the critical angle increases, thereby improving the light extraction amount.

  However, there is a problem that the resin itself is yellowed due to the increase in the amount of heat generated with the recent increase in brightness of the LED and the shortening of the excitation wavelength and emission wavelength of the phosphor. When mounted on the surface, higher transparency and reliability are required. In recent years, in order to solve such problems, silicone compositions containing polyorganosiloxane as a main component and cured products thereof have been used. However, such a silicone resin has a low refractive index, and even when the light diffusion layer is formed on the LED, the light extraction efficiency to the outside is lowered. For these reasons, development of a technology for increasing the refractive index while maintaining resin properties such as transparency and weather resistance is desired, and as one of these, metal oxide fine particles having a high refractive index are contained in these resins. A method of dispersing is being studied. According to this method, it is considered that the refractive index can be increased while ensuring transparency. However, these metal oxides have poor compatibility with the resin as a matrix, and the metal oxides aggregate together, so there is a concern that transparency may deteriorate. Moreover, although surface modification with a surface modifier for a metal oxide has been studied, there is a concern that transparency and weather resistance may be impaired due to deterioration of the surface modifier.

  Patent Document 1 discloses an inorganic oxide transparent dispersion used for dispersing inorganic oxide fine particles in a resin, the surface of the resin being modified by a surface modifier having at least one functional group among the functional groups of the resin. An inorganic oxide transparent dispersion characterized by containing modified inorganic oxide fine particles having an average dispersed particle diameter of 1 nm or more and 20 nm or less is described.

  Patent Document 2 discloses high-refractive-index metal oxide particles obtained by coating high-refractive-index metal oxide fine particles, more specifically, titanium-based fine particles having a rutile crystal structure with a silica-based oxide or a silica-based composite oxide. A coating composition containing fine particles and a curable coating film obtained by applying the coating composition on a substrate are described.

JP 2008-120848 A International Publication No. 2010/073772 Pamphlet

  However, in the inorganic oxide transparent dispersion described in Patent Document 1, the increase in the refractive index is small due to the high content of the modifier and the resin, and the silicone resin used as the modifier has a sufficient dispersibility. It cannot be maintained and transparency is impaired.

  Moreover, in the curable coating film described in patent document 2, the modifier and binder resin mainly contain a large amount of epoxy groups, and the heat resistance and light resistance of the coating film are remarkably lowered.

  In view of the above-described prior art, the problem to be solved by the present invention is a surface-modified metal oxide for obtaining a cured product having a high refractive index and high transparency, heat resistance and light resistance. It is providing the composition containing this.

  In order to solve the above problems, the present inventors have intensively studied and repeated experiments. As a result, they have found that the above problems can be solved by the following solution means, and have completed the present invention. That is, the present invention is as follows.

[1] A composition comprising particles (1),
The particle (1) is a surface modifier (a) having an unsaturated group, and the following general formula (1):
^{R 1 R 2 R 3 Si-} Y-SiR 4 n X 3-n (1)
{Wherein R ¹ , R ² and R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted siloxy group, and R ⁴ is a substituted or unsubstituted saturated alkyl group. X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group, Y is a divalent linking group, and n is 0 It is an integer of ~ 2. }
The composition containing the surface modification metal oxide (A) obtained by surface-modifying the metal oxide (c) with the surface modification agent containing the surface modification agent (b) represented by these.
[2] The composition according to aspect 1, further comprising a resin (2).
[3] The composition according to aspect 2, wherein the resin (2) includes a resin (B) having an unsaturated group.
[4] The composition according to aspect 3, wherein the unsaturated group of the resin (B) is at least one selected from the group consisting of an acryl group, a methacryl group, a styryl group, a vinyl group, and an allyl group. object.
[5] The resin (2) includes a resin (C) having a hydrogen atom directly bonded to silicon or a resin (D) having a thiol group, and the composition further includes a curable catalyst (E). The composition according to any one of the above aspects 2 to 4.
[6] The composition according to any one of the above aspects 2 to 5, wherein the volume ratio of the particles (1) to the total of the particles (1) and the resin (2) is 40 to 99% by volume.
[7] Any one of the above aspects 1 to 6, wherein the unsaturated group of the surface modifier (a) is at least one selected from the group consisting of an acryl group, a methacryl group, a vinyl group, and an allyl group. The composition according to one item.
[8] The composition according to any one of Embodiments 1 to 7, wherein n in the general formula (1) is 0 or 1.
[9] The composition according to any one of the above aspects 1 to 8, wherein the surface-modified metal oxide (A) has a refractive index of 1.8 or more.
[10] The composition according to any one of the above aspects 1 to 9, wherein the metal oxide (c) is titanium oxide, zirconium oxide, or barium titanate.
[11] The surface-modified metal oxide (A) has a structure derived from the surface modifier (a), a structure derived from the surface modifier (b), and a structure derived from the metal oxide (c). The composition according to any one of the above aspects 1 to 10, wherein the ratio of the structure derived from the metal oxide (c) to the total is 70 to 99% by volume.
[12] The composition according to any one of the above aspects 1 to 11, wherein the average primary particle diameter of the particles (1) is 1 nm to 100 nm.
[13] A transparent composite material comprising a cured product of the composition according to any one of the above aspects 1 to 12.
[14] The transparent composite material according to the aspect 13, which has a periodic uneven structure.
[15] An optical element comprising the transparent composite material according to the aspect 13 or 14.
[16] A dispersion comprising particles (1) and a dispersion medium,
The particle (1) is a surface modifier (a) having an unsaturated group, and the following general formula (1):
^{R 1 R 2 R 3 Si-} Y-SiR 4 n X 3-n (1)
In the formula, R ¹ , R ² and R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted siloxy group, and R ⁴ is a substituted or unsubstituted saturated alkyl group. X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group, Y is a divalent linking group, and n is 0 to 0 It is an integer of 2. }
A dispersion comprising a surface-modified metal oxide (A) obtained by surface-modifying a metal oxide (c) with a surface modifier containing the surface-modifier (b) represented by

  ADVANTAGE OF THE INVENTION According to this invention, the composition containing the surface-modified metal oxide for obtaining the hardened | cured material which has a high refractive index and has high transparency, heat resistance, and light resistance can be provided. .

  Hereinafter, modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

This embodiment
A composition comprising particles (1),
The particle (1) is a surface modifier (a) having an unsaturated group (also simply referred to as a surface modifier (a) in the present disclosure), and the following general formula (1):
^{R 1 R 2 R 3 Si-} Y-SiR 4 n X 3-n (1)
{Wherein R ¹ , R ² and R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted siloxy group, and R ⁴ is a substituted or unsubstituted saturated alkyl group. X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group, Y is a divalent linking group, and n is 0 It is an integer of ~ 2. }
Surface-modified metal oxidation obtained by surface-modifying metal oxide (c) with a surface-modifying agent containing a surface-modifying agent (b) represented by the formula (also simply referred to as surface modifying agent (b) in the present disclosure) A composition comprising product (A) is provided.
This embodiment also provides a dispersion comprising the above particles (1) and a dispersion medium.

<Particle (1)>
The particle (1) of this embodiment is a surface-modified metal oxide (A) obtained by surface-modifying a metal oxide (c) with a surface modifier containing a surface modifier (a) and a surface modifier (b). including. The particles (1) may contain, for example, a dispersion aid, an adhesion aid, a curing catalyst, an antioxidant, etc. in addition to the surface-modified metal oxide (A). The product (A) is preferably contained in an amount of 80% by mass or more, more preferably 90% by mass or more. In a further preferred embodiment, the particles (1) can be substantially composed of the surface-modified metal oxide (A). In the present embodiment, a composition having a high refractive index can be obtained by using a metal oxide. In the present embodiment, the surface-modified metal oxide (A) is formed from, for example, a resin (2) described below and curability due to the contribution of the surface modification using the surface modifiers including the surface modifiers (a) and (b). The affinity with the catalyst (E) and the solvent is good, and it can be dispersed well in the composition. Therefore, according to this embodiment, the composition which gives the hardened | cured material which has a high refractive index and transparency is obtained. Good dispersibility as described above is advantageous in that it enables the composition to contain particles (1) in a relatively high proportion. Moreover, the surface modifier containing the surface modifier (a) and the surface modifier (b) is also advantageous in that it does not impair the heat resistance and light resistance of the cured product of the composition.

(Surface modifier (a))
Examples of the surface modifier (a) include a silane coupling agent having an unsaturated group (that is, a functional group containing an unsaturated bond). That is, the surface-modified metal oxide (A) of the present embodiment has an unsaturated group by being surface-modified with the surface modifier (a).

  As the functional group containing an unsaturated bond, vinyl group, allyl group, hexenyl group, cyclohexenyl group, cyclohexenylethyl group, norbornenylethyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, methacryl group, acrylic group An unsaturated carbon double bond-containing group such as a styryl group, a methacrylopropyl group, and an acrylopropyl group, preferably at least selected from the group consisting of an acryl group, a methacryl group, a vinyl group, and an allyl group One.

  Specific compounds include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3 Examples include silane coupling agents such as hydrochloride of aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-isocyanatopropyltriethoxysilane. From the viewpoint of handling and availability, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacrylic Silane coupling agents such as loxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane are preferred. From the viewpoint of dispersibility in the composition of the surface-modified metal oxide (A), vinyltrimethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3- Acryloxypropyltrimethoxysilane is more preferred.

(Surface modifier (b))
The surface modifier (b) is represented by the following general formula (1):
^{R 1 R 2 R 3 Si-} Y-SiR 4 n X 3-n (1)
{Wherein R ¹ , R ² and R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted siloxy group, and R ⁴ is a substituted or unsubstituted saturated alkyl group. X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group, Y is a divalent linking group, and n is 0 It is an integer of ~ 2. }. That is, the surface-modified metal oxide (A) of the present embodiment is surface-modified with the surface modifier (b), whereby the following general formula (1 ′):
R ¹ R ² R ³ Si—Y— (1 ′)
{Wherein R ¹ , R ² and R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted siloxy group, and Y is a divalent linking group. } Will be included.

  Examples of the hydrocarbon group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl group. 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, cyclopentyl group, n -Acyclic and cyclic saturated hydrocarbon groups such as hexyl group, cyclohexyl group, n-heptyl group, 2-methylhexyl group, n-octyl group, n-nonyl group, n-decyl group and octadecyl group, phenyl Group, aromatic hydrocarbon group such as tolyl group, xylyl group, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group, Acyclic and cyclic unsaturated hydrocarbon groups such as chlorhexenylethyl group, norbornenylethyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, styryl group, etc., and benzyl group, phenethyl group, 2-methyl Examples thereof include arylalkyl groups such as benzyl group, 3-methylbenzyl group and 4-methylbenzyl group. In the present disclosure, the compound represented by the general formula (1) and having an unsaturated group is treated as being included in both the surface modifier (a) and the surface modifier (b). Therefore, the usage-amount of such a compound shall be included in both the usage-amount of a surface modifier (a) and the usage-amount of a surface modifier (b). By analyzing the surface modified metal oxide (A) by 1H-NMR or FT-IR, it can be confirmed that the surface modifier (a) and the surface modifier (b) are introduced, respectively. .

  Examples of the substituted or unsubstituted siloxy group include, for example, trimethylsiloxy group, methyldiethylsiloxy group, dimethylethylsiloxy group, dimethylbutylsiloxy group, dimethylcyclohexylsiloxy group, dimethylphenylsiloxy group, and methyldiphenylsiloxy group. Examples include siloxy groups having ˜18 hydrocarbon groups.

Among these, from the viewpoint that the surface modification reaction with the metal oxide (c) (typically fine particles) proceeds easily and suppresses the decrease in the refractive index due to the surface modification group, R ^{1 to} R ^3. Are each independently preferably a methyl group, an ethyl group, a trimethylsiloxy group, or a dimethylphenylsiloxy group, and more preferably a methyl group or a trimethylsiloxy group because of excellent heat resistance and light resistance.

In the general formula (1), R ⁴ is a substituted or unsubstituted saturated alkyl group, and preferably has 1 to 4 carbon atoms from the viewpoint that the surface modification reaction with the metal oxide (c) proceeds easily. A saturated alkyl group. Examples of the saturated alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. Among these, from the above viewpoint, R ⁴ is preferably a methyl group.

  In the general formula (1), Y is a divalent linking group, and is preferably a divalent hydrocarbon group having 1 to 6 carbon atoms from the viewpoint of heat resistance, and is a divalent hydrocarbon having 2 to 6 carbon atoms. The hydrocarbon group is more preferable. As a C1-C6 bivalent hydrocarbon group, a C1-C6 linear or branched alkylene group is mentioned, for example. Among these, from the viewpoint of ease of synthesis, Y is preferably a linear or branched alkylene group having 2 or 3 carbon atoms, more preferably a linear or branched alkylene group having 2 carbon atoms. is there.

  In the general formula (1), X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group. Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a t-butoxy group, and an n-hexyloxy group. A cyclohexyloxy group etc. are mentioned as a C3-C6 cycloalkoxy group.

  Among these, X is preferably a hydrogen atom or an alkoxy group from the viewpoint of easy reaction control, and more preferably a methoxy group or an ethoxy group.

  In the said General formula (1), n is an integer of 0-2. From the viewpoint that the surface modification reaction with the metal oxide (c) proceeds easily, n is preferably 0 or 1.

(Method for producing surface modifier (b))
The surface modifier (b) can be produced, for example, by a hydrosilylation reaction between a corresponding hydrosilane compound and a silane compound having an unsaturated carbon double bond (also referred to as an alkenylsilane compound in the present disclosure). Specifically, in a hydrocarbon-based organic solvent or in the absence of a solvent, the hydrosilane compound and the alkenylsilane compound are mixed so that an equimolar amount or one compound is slightly excessive, and a metal catalyst is added and heated and stirred. Can be manufactured.

As said hydrosilane compound and alkenylsilane compound, corresponding to the silicon compound represented by the above general formula (1), the following general formula (2):
R ¹ R ² R ³ Si—H (2)
{Wherein R ^{1 to} R ³ are as defined in the general formula (1). }
And the following general formula (3):
R ⁵ —SiR ⁶ _n X ¹ _(3-n) (3)
{Wherein R ⁵ is an unsaturated carbon double bond-containing hydrocarbon group having 2 to ⁶ carbon atoms, R ⁶ is a saturated alkyl group having 1 to 4 carbon atoms, and X ¹ is a halogen atom or carbon number An alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group, and n is an integer of 0 to 2, preferably 0 or 1. }
A combination with an alkenylsilane compound represented by:
Or the following general formula (4):
R ¹ R ² R ³ Si-R ⁵ (4)
{Wherein R ^{1 to} R ³ are as defined in the general formula (1), and R ⁵ is an unsaturated carbon double bond-containing hydrocarbon group having 2 to 6 carbon atoms. }
And an alkenylsilane compound represented by the following general formula (5):
H-SiR ⁶ _n X ¹ _(3-n) (5)
{In the formula, R ⁶ represents a saturated alkyl group having 1 to 4 carbon atoms; X ¹ represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group; N is an integer of 0 to 2, preferably 0 or 1. }
A combination with a hydrosilane compound represented by the following formula can be used.

Preferred examples of R ⁵ include vinyl group, allyl group, hexenyl group, cyclohexenyl group, methacryl group, acrylic group, and styryl group. Particularly preferred examples are vinyl group, allyl group, acrylic group, and the like. . In the above case, R ^{4 in} the general formula (1) is derived from each R ⁶ described above. Preferred examples of R ⁵ are the same as those exemplified as saturated alkyl having 1 to ⁴ carbon atoms for R ⁴ . Preferred examples of X ¹ are the same as those exemplified for X in the general formula (1) as a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group.

  Although there is no restriction | limiting in particular in the molar ratio of said hydrosilane compound and an alkenylsilane compound, Generally, an alkenylsilane compound is used in 0.9-1.1 mol with respect to 1 mol of hydrosilane compounds. It is preferable.

  Examples of the hydrocarbon-based organic solvent include hexane, octane, toluene, xylene and the like. The organic solvent can be used in any amount.

  Examples of the metal catalyst include platinum group metals such as platinum, palladium, rhodium, and ruthenium, supported catalysts in which the platinum group metal is supported on a carrier such as carbon, alumina, silica, and polymer, chloroplatinic acid, and alcohol-modified platinum chloride. Examples include acids, olefins or acetylene complexes of chloroplatinic acid, vinylsiloxane complexes of platinum, tetrakis (triphenylphosphine) palladium, and chlorotris (triphenylphosphine) rhodium. Among these, chloroplatinic acid (Speier catalyst), platinum tetramethyldivinyldisiloxane complex (Karsttedt catalyst), and chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst) are preferable. These metal catalysts may be used alone or in combination of two or more.

The amount of the metal catalyst used can be typically in the range of 1 × 10 ^{−6 to} 0.01 mol with respect to 1 mol of the hydrosilane compound.

  The reaction temperature of the hydrosilylation reaction is preferably in the range of 0 to 150 ° C., and the reaction time is preferably in the range of 0.5 to 48 hours.

  When the surface modifier (b) represented by the general formula (1) is synthesized by the hydrosilylation reaction, a cis isomer and a trans isomer are formed when the hydrosilane is added to the unsaturated bond site of the alkenyl silane. May be obtained. This isomer mixture can be separated by a separation operation such as distillation and column chromatography, but even a cis-trans isomer mixture is preferably used in the surface modification reaction with the metal oxide (c) described later. Can be used.

  Among the surface modifiers (b), for the silicon compound in which X in the general formula (1) is a hydrogen atom, for example, X in the general formula (1) is a halogen atom, an alkoxy group, a cycloalkoxy group, or an acetoxy After the silicon compound as a group is produced by the above-described method, it can be produced by performing a reduction reaction using a reducing agent such as lithium aluminum hydride or sodium borohydride.

(Metal oxide (c))
The metal oxide (c) is typically a particle and contains a metal atom and an oxygen atom. Examples of the metal oxide include metal oxide particles such as titanium oxide.

  The metal oxide (c) contains one or more selected from the group consisting of Zr, Ti, Sn, Ce, Ta, Nb, Zn, Ba, and Sr from the viewpoint of obtaining a preferable refractive index. Preferred metal oxides include titanium oxide, zirconium oxide, alumina, zinc oxide, tin oxide, magnesium oxide, calcium oxide, cesium oxide, tantalum oxide, niobium oxide, barium titanate, strontium titanate, lead titanate, zirconium silicate. , Lead zirconate, indium tin oxide, antimony tin oxide, lithium niobate, lithium cobaltate, ITO and the like. Among these, titanium oxide, zirconium oxide, and barium titanate are particularly preferable in consideration of the refractive index, availability, and economy.

  The metal oxide (c) is preferably spherical, rod-shaped, plate-shaped or fibrous, or a shape in which two or more of these are combined, and more preferably spherical. In addition, the spherical shape here means a substantially spherical shape including a spheroid, an oval and the like in addition to a true spherical shape.

  The average primary particle diameter of the metal oxide (c) is preferably equal to or less than the wavelength of light used in the intended application in order to avoid adverse effects on transparency due to light scattering. The average primary particle size is preferably 1 nm or more and 100 nm or less, more preferably 1 nm or more and 50 nm or less, and still more preferably 1 nm or more and 40 nm or less. If the average primary particle diameter is 1 nm or more, the dispersibility of the metal oxide (c) is good, and if it is 100 nm or less, the metal oxide (c) is dispersed in an organic solvent or resin. Good transparency. In the present disclosure, the average primary particle diameter means a number average value. The average primary particle diameter can be determined by direct observation with a transmission electron microscope (TEM). Specifically, for example, the major axis of 50 particles is measured, and the number average is obtained.

  Further, as the metal oxide (c), particles having a refractive index of 1.60 or more are preferable from the viewpoint of favorably obtaining the effect of improving the light extraction amount due to the refractive index close to that of the substrate, and particularly the refractive index is 2.00. The above metal oxide particles are preferred.

  The metal oxide (c) can be produced by a hydrothermal method, a sol-gel method, a coprecipitation method or the like, and the average primary particle size can be controlled by changing the production conditions.

(Surface modification)
By carrying out a surface modification reaction by causing a surface modifier (a) having an unsaturated group and a surface modifier (b) represented by the general formula (1) to act on the metal oxide (c). The surface-modified metal oxide (A) having a structural site derived from the surface modifiers (a) and (b) on the surface can be produced.

  The metal oxide (c) used for the surface modification reaction may be a powder obtained by a drying treatment, or may be dispersed in a dispersion medium that is water, an organic solvent, or a mixture thereof.

  When the surface modification reaction is performed using the powdered metal oxide (c), the surface modification reaction may be performed in a dispersion apparatus such as a bead mill, a jet mill (for example, manufactured by Joko Co., Ltd.), or an ultrasonic treatment. .

  The bead mill is a dispersing device including a bead separation mechanism that separates beads, which are a rotor, a stator, and stirring particles. The beads as stirring particles are preferably ultrafine beads, and the particle diameter is preferably 3 to 300 μm, more preferably 10 to 50 μm. If the particle diameter is 3 μm or more, impact energy required for dispersion can be obtained, and if it is 300 μm or less, reaggregation due to excessive impact energy can be suppressed.

  Examples of the stirring particles include zirconia, alumina, silica, glass, silicon carbide, and silicon nitride. Among these, zirconia is preferably used from the viewpoint of excellent strength and stability as stirring particles.

  When surface modification is performed in a state where the metal oxide (c) is dispersed in a dispersion medium, specifically, for example, the surface modification is performed on a uniform dispersion of the metal oxide (c) containing alcohol and water. The surface-modified metal oxide (A) is produced by the step of adding the agents (a) and (b).

  The uniform dispersion may contain water used in the hydrolysis step for producing the metal oxide (c) as it is, and by removing a part of the water or adding water, the water content is reduced. It can also be controlled. The surface modifiers (a) and (b) may be added as they are, or may be added after diluting with alcohol, water or other organic solvents.

  Moreover, as a uniform dispersion of the metal oxide (c), commercially available products can be used, and SZR-W (manufactured by Sakai Chemical), SZR-SW (manufactured by Sakai Chemical), SZR-M (manufactured by Sakai Chemical). ), SZR-K (manufactured by Sakai Chemical), SRD-W (manufactured by Sakai Chemical), SRD-M (manufactured by Sakai Chemical), ZR-40BL (manufactured by Nissan Chemical), ZR-30BS (manufactured by Nissan Chemical), ZR-30BFN (Nissan Chemical), ZR-30AL (Nissan Chemical), ZR-20AS (Nissan Chemical), ZR-30AH (Nissan Chemical), AX-ZP series (Nippon Catalysts), TTO series (Ishihara Sangyo) Zirconia dispersion liquid (manufactured by Sumitomo Osaka Cement) and the like can be used.

  The amount of the surface modifiers (a) and (b) added to the metal oxide (c) is such that the total surface area of the metal oxide (c) and the surface modifiers (a) and (b) can be monomolecularly modified. It can be determined from the ratio to the area (as the theoretical coating surface area).

The surface area (m ² / g) per unit mass of the metal oxide (c) is measured by the BET method. The theoretical coating surface area (m ² / g) per unit mass of the surface modifiers (a) and (b) is calculated by 6.02 × 10 ²³ × 1.3 × 10 ⁻¹⁹ ÷ (molecular weight of the surface modifier). Is done.

The quantity ratio of the surface modifiers (a) and (b) to the metal oxide (c) is the theoretical surface area (m ² ) / metal oxide (c) of the surface modifiers (a) and (b). ) Of the total surface area (m ² ) is preferably 0.3 to 3.0, more preferably 0.7 to 2.0. The ratio is preferably 0.3 or more from the viewpoint of dispersibility of the surface-modified metal oxide (A), and preferably 3.0 or less from the viewpoint of workability.

  The surface modification reaction proceeds by a dehydration condensation reaction between a hydroxyl group present on the surface of the metal oxide (c) and an OH group generated by hydrolysis of the surface modifier.

  The amount of water added for hydrolysis is the sum of hydrolyzable groups (for example, groups represented by X in the surface modifier (b)) contained in the surface modifier (a) and the surface modifier (b). The molar ratio is preferably 0.1 to 10 times, more preferably 0.4 to 8 times, and still more preferably 0.8 to 5 times. When the amount of water added is 0.1 times or more, the surface is easily modified, and it is preferably 10 times or less from the viewpoint of suppressing aggregation of the metal oxide (c).

  From the viewpoint of controlling the reaction rate of hydrolysis and condensation, it is more preferable to subject the surface modifiers (a) and (b) to hydrolysis, condensation and surface modification in the presence of a catalyst.

  Examples of the catalyst include an acid catalyst and a base catalyst. For example, examples of the acid catalyst include inorganic acids and organic acids. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, boric acid and the like. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, benzoic acid, and p-aminobenzoic acid. Examples include acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, citraconic acid, malic acid, glutaric acid and the like. Examples of the base catalyst include inorganic bases and organic bases. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; lithium carbonate, potassium carbonate, and carbonate Examples thereof include alkali or alkaline earth metal carbonates such as sodium; metal hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate; and the like. Examples of the organic base include trialkylamines such as triethylamine and ethyldiisopropylamine; N, N-dialkylaniline derivatives having 1 to 4 carbon atoms such as N, N-dimethylaniline and N, N-diethylaniline; pyridine, 2,6 -Pyridine derivatives which may have an alkyl substituent having 1 to 4 carbon atoms, such as lutidine; These catalysts can be used alone or in combination of two or more.

  In producing the surface-modified metal oxide (A), it is preferable in terms of reaction efficiency to add a catalyst in an amount that makes the pH of the reaction system in the range of 0.01 to 6.0, or pH 8 to 14, and more efficient. In order to increase this, it is more preferable to perform the modification reaction under basic conditions of pH 8-14.

  Hydrolysis and condensation for producing the surface-modified metal oxide (A) can also be performed in an organic solvent. Examples of the organic solvent that can be used for the condensation reaction include alcohols, esters, ketones, ethers, aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, amide compounds, and the like.

  Examples of the alcohol include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol; ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, B propylene glycol monopropyl ether, mono ethers of polyhydric alcohols such as propylene glycol monobutyl ether; and the like.

  Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, and γ-butyrolactone. Examples of ketones include acetone, methyl ethyl ketone, and methyl isoamyl ketone.

  Examples of the ether include, in addition to the above monoethers of polyhydric alcohols, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene Examples include polyhydric alcohol ethers obtained by alkyl etherifying all hydroxyl groups of polyhydric alcohols such as glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; tetrahydrofuran; 1,4-dioxane; anisole and the like.

  Examples of the aliphatic hydrocarbon compound include hexane, heptane, octane, nonane, decane, and the like.

  Examples of the aromatic hydrocarbon compound include benzene, toluene, xylene and the like.

  Examples of the amide compound include dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

  Among these solvents, methanol, ethanol, isopropanol, butanol, etc. as alcohols; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. as ketones; ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. as ethers , And amide compounds such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferable because they are easily mixed with water.

  These solvents may be used alone or in combination of a plurality of solvents.

  Although there is no restriction | limiting in particular in the reaction temperature at the time of manufacturing a surface modification metal oxide (A), -50 to 200 degreeC is preferable and 0 to 150 degreeC is more preferable. From the viewpoint of increasing the reaction rate of the hydrolysis and condensation reaction, the reaction temperature is preferably −50 ° C. or higher, and from the viewpoint of suppressing gelation of the surface-modified metal oxide (A), the reaction temperature is 200 ° C. or lower. Preferably there is.

  The reaction time for producing the surface-modified metal oxide (A) is not particularly limited, but is preferably 30 minutes to 24 hours, and more preferably 1 to 6 hours. In order to sufficiently progress hydrolysis of a hydrolyzable group (for example, an alkoxy group), the reaction time is preferably 30 minutes or more, and the reaction temperature is 24 hours or less from the viewpoint of suppressing gelation of the surface modifier. It is preferable that

  The surface modifier that did not contribute to the surface modification of the surface of the metal oxide (c) is washed with an organic solvent in which the surface modified metal oxide (A) does not dissolve and the remaining surface modifier and their condensates dissolve. This can be removed. Specifically, after reprecipitation in the organic solvent, only the surface-modified metal oxide (A) can be isolated by centrifugation or the like. From the viewpoint of further increasing the refractive index of the surface-modified metal oxide (A), it is preferable to remove the surface modifiers (a) and (b) that are not surface-modified.

That the surface modifier is modified on the surface of the metal oxide (c) is that the stretching vibration of the Si—O— metal atom is observed at 930 to 990 cm ⁻¹ by FT-IR (Fourier transform infrared spectroscopy). Can be confirmed.

  For example, when the metal oxide (c) is TiOH, the reaction accompanied by dehydrogenation proceeds spontaneously between TiOH and the hydrogen atom bonded to the silicon atom, and the metal oxide (c ), A bond made of Si—O—Ti is formed.

  The refractive index of the surface-modified metal oxide (A) is preferably 1.8 or more, and preferably 1.9 or more from the viewpoint of further increasing the refractive index of the cured coating film containing the surface-modified metal oxide (A). Furthermore, it is especially preferable that it is 2.0 or more. The upper limit of the refractive index is not particularly limited, but is preferably 2.8 or less and more preferably 2.75 or less because transparency is reduced by absorption due to formation of a conjugated structure.

The concentration of the unsaturated bond functional group contained in the surface modified metal oxide (A) is preferably 0.001 mmol / g or more and 1.0 mmol / g or less. From the viewpoint of the transparency of the cured product coating film, it is preferably 0.001 mmol or more, more preferably 0.003 mmol / g or more, and the dispersibility of the surface-modified metal oxide (A) and the heat resistance viewpoint of the cured product coating film To 1.0 mmol / g or less, more preferably 0.8 mmol / g or less. The concentration can be confirmed by ¹ H-NMR (proton nuclear magnetic resonance spectroscopic analysis described later).

  In the surface-modified metal oxide (A), the metal oxide relative to the sum of the structure derived from the surface modifier (a), the structure derived from the surface modifier (b), and the structure derived from the metal oxide (c) The ratio of the structure derived from (c) is preferably 70 to 99% by volume. The ratio can be calculated by determining the surface functional group concentration by NMR, and by calculating backward from the refractive index of (A) extrapolated from the Maxwell Garnett equation using the measured value with the Abbe refractometer. The above ratio is more preferably 75% by volume or more and 99% by volume or less from the viewpoint of obtaining particles having a high refractive index, and 75% by volume or more from the viewpoint of obtaining surface-modified metal oxide (A) particles having high dispersibility. It is more preferably 97% by volume or less, and particularly preferably 78% by volume or more and 95% by volume or less from the viewpoint of transparency of the cured product.

  The surface modifier may consist of only the surface modifier (a) and the surface modifier (b), or may further contain an additional modifier component. Additional modifier components include organic phosphonic acids, organic carboxylic acids, tetraalkoxysilanes, and the like. Based on the total amount of the surface modifier, the total ratio of the surface modifier (a) and the surface modifier (b) is preferably 10 mol% or more, more preferably 25 mol% or more, even if it is 100 mol%. Good.

  When the surface modifier (a) and the surface modifier (b) are used in combination, the dispersibility of the particles (1) in the composition is improved and transparency is improved as compared with the case of the surface modifier (a) alone. It is advantageous in that it can be improved and can have high heat resistance and light resistance, and compared with the case of only the surface treatment agent (b), the dispersion stability of the particles (1) in the cured product Is advantageous.

  In the surface-modified metal oxide (A), the ratio of the structure derived from the surface modifier (a): the structure derived from the surface treatment agent (b) is a viewpoint of enhancing the dispersibility of the surface-modified metal oxide (A). Therefore, the molar fraction ratio is preferably (a) :( b) = 90: 10 to 10:90, and more preferably 80:20 to 20:80 from the viewpoint of the transparency of the cured product.

The volume ratio and the density are 1 g / mL for the density of the surface modifiers (a) and (b), and the literature values for the density of the metal oxide (c) (for example, according to a safety data sheet such as chemical substances) (for example, oxidation) 4.27 g / mL for titanium, 5.67 g / mL for zirconium oxide, 6.02 g / mL for barium titanate, etc.), and the following equation.
Volume ratio of metal oxide (c) = (mass of (c) / density of (c)) / {(mass of (a) / density of (a)) + mass of (b) / density of (b)) + (C) mass / (c) density)}
Used in the calculation, the amount of actual metal oxide modified surface modifying agent to the surface of the (c) (a) and (b) are dispersed surface-modified metal oxide (A) in the heavy solvent, ¹ It is quantified by measuring H-NMR (proton nuclear magnetic resonance spectroscopy). In addition, the surface-modified metal oxide (A) is subjected to total elemental analysis using XRF (fluorescence X-ray analysis), and atoms of metal atoms derived from the metal oxide and silicon atoms derived from the surface modifier. Calculated by measuring the abundance ratio.

The refractive index of the surface-modified metal oxide (A) is estimated using the following Maxwell-Garnett equation.
Refractive index of surface-modified metal oxide (A) = refractive index of surface modifier × [refractive index of (c) × (1 + 2 × (c) volume fraction) −refractive index of surface modifier) × (2 × (C) volume fraction−2)] / [(surface modifier refractive index) × (2+ (c) volume fraction) + (c) refractive index × (1− (c) volume fraction ]]

  Actually, using a dispersion in which surface-modified metal oxides (A) having different concentrations are dispersed in an organic solvent, the refractive index at a wavelength of 589 nm is measured with an Abbe refractometer, and the refractive index is measured with respect to the surface of the organic solvent. Plotting against the concentration of the modified metal oxide (A), the value obtained by extrapolating the concentration of the surface modified metal oxide (A) to 100% by volume is calculated as the refractive index of the surface modified metal oxide (A). .

<Resin (2) and curable catalyst (E)>
In a preferred embodiment, the composition further comprises a resin (2). In the composition, the particle volume ratio represented by particle (1) / (particle (1) + resin (2)) is preferably 40% by volume or more. Although the said ratio may be 100 volume%, it is preferable that it is 99 volume% or less from a viewpoint of obtaining the advantage by resin (2) favorably. When the composition contains the resin (2), the coating film formed from the composition of the present embodiment has the refractive index of the coating film filled with the resin (2) in the voids between the particles (1). It tends to be higher.

  The particle volume ratio is more preferably 90% by volume or less from the viewpoint of improving the refractive index by satisfactorily filling the voids between the particles (1) with the resin (2), and increasing the content of the particles (1). From the viewpoint of improving the refractive index, it is more preferably 50% by volume or more. From the viewpoint of completely filling the voids and maximizing the refractive index, the particle volume ratio is more preferably 60% by volume to 80% by volume. In the present disclosure, the particle volume ratio is a value calculated from the amount of each component used in the composition.

  In a preferred embodiment, the resin (2) includes a resin (B) having an unsaturated group. In a preferred embodiment, the resin (2) includes a resin (C) having a hydrogen atom directly bonded to silicon or a resin (D) having a thiol group. In this case, the composition can further comprise a curable catalyst (E). In one embodiment, the composition may consist of a surface-modified metal oxide (A) and a resin (B) having an unsaturated group.

  When the composition contains the resin (B) having an unsaturated group, the resin (B) can fill the voids between the surface-modified metal oxides (A) in the coating film formed from the composition. The refractive index of the film can be increased. In addition, the unsaturated group contained in the resin (B) reacts with the unsaturated group on the surface of the surface-modified metal oxide (A) to form a covalent bond, thereby improving the strength of the coating film and improving scratch resistance. improves.

  The composition can further comprise a curable catalyst (E). The presence of the curable catalyst (E) is advantageous in that the film strength after curing of the coating film obtained from the composition is improved.

(Resin having an unsaturated group (B))
From the composition, the resin (B) having an unsaturated group is a resin having one or more unsaturated functional groups in one molecule and having two or more unsaturated functional groups in one molecule. It is preferable at the point which improves the film | membrane intensity | strength after hardening of the coating film obtained. The resin (B) may be a monomer or a polymer. The unsaturated group contained in the resin (B) is preferably at least one selected from the group consisting of an acryl group, a methacryl group, a styryl group, a vinyl group, and an allyl group from the viewpoint of versatility. Combining the resin (B) with the particles (1) containing the surface-modified metal oxide (A) is particularly advantageous in obtaining a cured product having good heat resistance and light resistance. The ratio of the resin (B) having an unsaturated group to the total mass of the resin (2) is preferably 30 to 95% by mass, more preferably 50 to 90% by mass.

  Specific examples of the monomer include tetravinylsilane, 1,2-divinyl1,1,2,2-tetramethyldisiloxane, divinyldiphenylsilane, 2,4,6,8-tetramethyl-2,4. , 6,8-tetravinylcyclotetrasiloxane, etc., polyfunctional compounds such as silicon compounds having an unsaturated group, triallyl isocyanurate, and trade names M309, M315, M408, M400, and M403 (all manufactured by Toagosei Co., Ltd.) A meth) acrylate compound is mentioned.

The polymer preferably has a silicone unit skeleton represented by SiO _1/2 , SiO _2/2 , SiO _3/2 , or SiO _4/2 from the viewpoint of heat resistance and light resistance. Can be mentioned. Specific examples include vinyl-terminated polydimethylsilicone, vinyl-terminated diphenylsiloxane, dimethylsiloxane copolymer, vinyl Q resin, and the like.

  The weight average molecular weight of the resin (B) having an unsaturated group is preferably 150 or more and 20,000 or less, more preferably 200 or more and 15,000 or less. In the present disclosure, the weight average molecular weight is a value obtained by converting standard PMMA by gel permeation chromatography (GPC). When the weight average molecular weight of the resin (B) is 150 or more, it is preferable from the viewpoints of heat resistance and curability, and when it is 20,000 or less, the viscosity is lowered and handling properties are improved.

  The unsaturated group concentration of the resin (B) is desirably 0.1 mmol / g or more and 30 mmol / g or less, and is 0.1 mmol / g or more, and further 0.2 mmol / g or more from the viewpoint of solvent resistance. From the viewpoint of film strength, it is more preferably 0.3 mmol / g or more. On the other hand, from the viewpoint of heat resistance, it is preferably 30 mmol / g or less, more preferably 25 mmol / g or less, and from the viewpoint of reducing curing shrinkage and improving crack resistance, 20 mmol / g or less, further 13 mmol / g or less, and further 11 mmol / g. More preferably, it is g or less.

  The viscosity of the resin (B) having an unsaturated group is preferably 2 mPa · s or more and 200 Pa · s or less, and more preferably 2 mPa · s or more and 100 Pa · s or less. When it is 2 mPa · s or more, it is preferable from the viewpoint of dispersion maintaining property of the surface-modified metal oxide (A), and when it is 200 Pa · s or less, it is preferable from the viewpoint of handleability. In the present disclosure, the viscosity is a value measured with an E-type viscometer.

(Resin having hydrogen atom directly bonded to silicon (C) and resin having thiol group (D))
In a preferred embodiment, the resin (2) further includes a resin (C) having a hydrogen atom directly bonded to silicon or a resin (D) having a thiol group, and a curable catalyst (E). In a preferred embodiment, the resin (2) contains the resin (C) or the resin (D) in addition to the resin (B) described above. Use of the resin (C) is advantageous from the viewpoint of coating film strength, while use of the resin (D) is advantageous from the viewpoint of refractive index.
For example, the resin (2) is applied from the composition by having the resin (C) having a hydrogen atom directly bonded to silicon in addition to the resin (B) having an unsaturated group, and the curable catalyst (E). When forming the film, it is possible to satisfactorily fill the gap between the surface-modified metal oxides (A) with the resin, and the refractive index of the coating film can be increased. In this case, the presence of the hydrosilylation catalyst (E1) as the curable catalyst (E) is advantageous in terms of improving the film strength after curing of the coating film obtained from the composition.

  On the other hand, since the resin (2) contains the resin (D) having a thiol group and the curable catalyst (E) in addition to the resin (B), a composition containing a sulfur atom having a large atomic refraction is applied to a thin film. Sometimes it becomes possible to fill the gap, and the refractive index of the coating film can be further increased. In this case, the presence of the radical generator (E2) as the curable catalyst (E) is advantageous in that the film strength after curing of the coating film obtained from the composition is improved.

  In the present disclosure, a resin having both a hydrogen atom directly bonded to silicon and an unsaturated group is treated as being included in both the resin (B) and the resin (C). A resin having both a thiol group and an unsaturated group is handled as being included in both the resin (B) and the resin (D). In addition, a resin having both a hydrogen atom directly bonded to silicon and a thiol group is handled as being included in both the resin (C) and the resin (D). The ratio of the resin (C) having a hydrogen atom directly bonded to silicon to the total mass of the resin (2) is preferably 30 to 95% by mass, more preferably 30 to 90% by mass. Moreover, the ratio of the resin (D) having a thiol group to the total mass of the resin (2) is preferably 30 to 95% by mass, more preferably 50 to 90% by mass.

  Resin (C) having a hydrogen atom directly bonded to silicon has at least one hydrogen atom directly bonded to silicon in one molecule, and has two or more hydrogen atoms directly bonded to silicon in one molecule It is preferable in terms of improving the film strength after curing of the coating film obtained from the composition. Resin (C) may be a monomer or a polymer.

  Specific examples of the monomer include 1,1,2,2-tetramethyldisiloxane, 2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,6,8,10-pentamethyl. -The silicon compound which has Si-H bonds, such as cyclopentasiloxane, is mentioned.

As an example of the polymer, from the viewpoint of heat resistance and light resistance, the resin (C) having a hydrogen atom directly bonded to silicon is SiO _1/2 , SiO _2/2 , SiO _3/2 , or SiO _{4 /} Those having a unit skeleton of silicone represented by ₂ can be preferably exemplified. Specific examples of the polymer include SiH dimethyl silicone at both ends, methyl hydrosiloxane, dimethyl siloxane, methyl hydrosiloxane copolymer, and hydrogenated Q resin.

  The weight average molecular weight of the resin (C) having a hydrogen atom directly bonded to silicon is preferably 150 or more and 20,000 or less, more preferably 200 or more and 15,000 or less. In the present disclosure, the weight average molecular weight is a value obtained by converting standard PMMA by gel permeation chromatography (GPC). When the weight average molecular weight of (B) is 150 or more, it is preferable from the viewpoint of heat resistance and curability, and when it is 20,000 or less, the viscosity is lowered and handling properties are improved.

  The concentration of hydrogen atoms directly bonded to silicon contained in the resin (C) having hydrogen atoms directly bonded to silicon is preferably 0.1 mmol / g or more and 17 mmol / g or less, from the viewpoint of solvent resistance. It is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, and more preferably 0.3 mmol / g or more from the viewpoint of film strength. On the other hand, from the viewpoint of heat resistance, it is preferably 17 mmol / g or less, more preferably 13 mmol / g or less, and more preferably 11 mmol / g or less from the viewpoint of reducing curing shrinkage and improving crack resistance.

  The viscosity of the resin (C) having a hydrogen atom directly bonded to silicon is preferably 2 mPa · s to 200 Pa · s, more preferably 2 mPa · s to 100 Pa · s. When it is 2 mPa · s or more, it is preferable from the viewpoint of dispersion maintaining property of the surface-modified metal oxide (A), and when it is 200 Pa · s or less, it is preferable from the viewpoint of handleability.

  From the viewpoint of the strength of the cured film, the ratio of the unsaturated group-containing resin (B) and the resin (C) having a hydrogen atom directly bonded to silicon is the concentration of the unsaturated group (B / M) in the resin (B). 1. The ratio of the hydrogen atoms directly bonded to silicon in the resin (C) having a hydrogen atom directly bonded to silicon and the resin (C) (ie, [hydrogen atom directly bonded to silicon] / [unsaturated group]) It is preferably 0 to 0.3, and more preferably 1.8 to 0.5. The above ratio is 0.3 or more, more preferably 0.5 or more, from the viewpoint of avoiding that the unsaturated group remaining in the cured product of the composition is oxidized and causing yellowing and from the viewpoint of heat resistance. Further, it is preferably 0.6 or more, and more preferably 2.0 or less, further 1.8 or less, and further preferably 1.6 or less from the viewpoint of improving the crosslinking density.

The curable catalyst (E) preferably contains a hydrosilylation catalyst (E1). The hydrosilylation catalyst (E1) is a catalyst for promoting an addition reaction between a carbon-carbon unsaturated bond site in an unsaturated group and a hydrogen atom directly bonded to a silicon atom. A known hydrosilylation catalyst can be used as the hydrosilylation catalyst (E1). Examples of hydrosilylation catalysts include platinum group metals such as platinum (including platinum black), rhodium and palladium; H ₂ PtCl ₄ · nH ₂ O, H ₂ PtCl ₆ · nH ₂ O, NaHPtCl ₆ · nH ₂ O, KHPtCl ₆ · nH ₂ O, Na ₂ PtCl ₆ · nH ₂ O, K ₂ PtCl ₄ · nH ₂ O, PtCl ₄ · nH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ · nH ₂ O {where n is 0 It is an integer of ˜6, preferably 0 or 6. }, Such as platinum chloride, chloroplatinic acid and chloroplatinate; alcohol-modified chloroplatinic acid; complex of chloroplatinic acid and olefins; platinum group metals such as platinum black and palladium supported on a support such as alumina, silica and carbon Rhodium-olefin complex; chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst); platinum chloride, chloroplatinic acid or chloroplatinate and vinyl group-containing siloxane, divinyltetramethyldisiloxane platinum complex or vinyl group-containing And a complex with a cyclic siloxane. These hydrosilylation catalysts may be used alone or as a mixture of two or more hydrosilylation catalysts.

  The content of the hydrosilylation catalyst (E1) in the composition was directly bonded to the surface-modified metal oxide (A), the resin (B) having an unsaturated group, and silicon in terms of platinum group metal mass. 0.01-1000 ppm is preferable and 0.2-100 ppm is more preferable on the basis of the total amount with the resin (C) having a hydrogen atom. The content is preferably 0.01 ppm or more from the viewpoint of reaction efficiency, and preferably 1000 ppm or less from the viewpoint of transparency of the cured product.

  The composition containing the resin (C) and the curable catalyst (E) may further contain various additives. Examples of the additive include one or more selected from an adhesion assistant, a curing retarder, an additional resin (thermosetting resin and thermoplastic resin), an antioxidant, and an ultraviolet absorber.

  The resin (D) having a thiol group preferably has at least one thiol group in the molecule and two or more thiol groups in the molecule from the viewpoint of improving the cured film strength. The resin (D) may be a monomer or a polymer.

  The thiol group possessed by the resin (D) is intended to encompass an unsubstituted thiol group (that is, —SH group) and a substituted thiol group (for example, those listed below) in the present disclosure. In the present disclosure, a substituted thiol group intends a group in which hydrogen of an unsubstituted thiol group is substituted with another group such as a substituted or unsubstituted alkyl group. As the substituted thiol group, a substituted or unsubstituted alkylthio group such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, n-hexylthio group, iso-hexylthio group, 2-ethylhexylthio group, 3,5,5-trimethylhexylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group A cycloalkylthio group having 5 to 10 carbon atoms in total, such as a linear or branched alkylthio group having 1 to 10 carbon atoms, a cyclopentylthio group, a cyclohexylthio group, a methoxyethylthio group, and an ethoxyethylthio group. Group, n-propoxyethylthio group, iso-propoxyethylthio group N-butoxyethylthio group, iso-butoxyethylthio group, tert-butoxyethylthio group, n-pentyloxyethylthio group, iso-pentyloxyethylthio group, n-hexyloxyethylthio group, iso-hexyloxy Alkylalkylthio group such as ethylthio group, n-heptyloxyethylthio group and the like having 12 to 10 carbon atoms in total, aralkylthio group such as benzylthio group, methylthioethylthio group, ethylthioethylthio group, n-propylthioethyl Thio group, iso-propylthioethylthio group, n-butylthioethylthio group, iso-butylthioethylthio group, tert-butylthioethylthio group, n-pentylthioethylthio group, iso-pentylthioethylthio group N-hexylthioethylthio group, iso-hexyl An alkylthioalkylthio group having a total carbon number of 12 to 10 such as a thioethylthio group and n-heptylthioethylthio group, a substituted or unsubstituted arylthio group, a phenylthio group, a naphthylthio group, a 2-methylphenylthio group, and a 3-methylphenyl group Thio group, 4-methylphenylthio group, 2-ethylphenylthio group, propylphenylthio group, butylphenylthio group, hexylphenylthio group, cyclohexylphenylthio group, 2,4-dimethylphenylthio group, 2,5- Dimethylphenylthio group, 2,6-dimethylphenylthio group, 3,4-dimethylphenylthio group, 3,5-dimethylphenylthio group, 3,6-dimethylphenylthio group, 2,3,4-trimethylphenylthio Group, 2,3,5-trimethylphenylthio group, 2,3,6-trimethyl An unsubstituted or alkyl-substituted arylthio group having a total carbon number of 12 or less, such as a ruphenylthio group, 2,4,5-trimethylphenylthio group, 2,4,6-trimethylphenylthio group, 3,4,5-trimethylphenylthio group 2-methoxyphenylthio group, 3-methoxyphenylthio group, 4-methoxyphenylthio group, 2-ethoxyphenylthio group, propoxyphenylthio group, butoxyphenylthio group, hexyloxyphenylthio group, cyclohexyloxyphenylthio group A monoalkoxyarylthio group having a total carbon number of 12 or less, a 2,3-dimethoxyphenylthio group, a 2,4-dimethoxyphenylthio group substituted by a substituted or unsubstituted alkyloxy group having 6 or less carbon atoms, such as 2, 5-dimethoxyphenylthio group, 2,6-dimethoxyphenylthio group, 3, -Dimethoxyphenylthio group, 3,5-dimethoxyphenylthio group, 3,6-dimethoxyphenylthio group, 4,5-dimethoxy-1-naphthylthio group, 4,7-dimethoxy-1-naphthylthio group, 4,8- Total carbon number 12 substituted by a substituted or unsubstituted alkyloxy group having 6 or less carbon atoms such as dimethoxy-1-naphthylthio group, 5,8-dimethoxy-1-naphthylthio group, 5,8-dimethoxy-2-naphthylthio group, etc. The following dialkoxyarylthio groups, chlorophenylthio groups, dichlorophenylthio groups, trichlorophenylthio groups, bromophenylthio groups, dibromophenylthio groups, iodophenylthio groups, fluorophenylthio groups, chloronaphthylthio groups, bromonaphthylthio groups , Difluorophenylthio group, trifluorophenylthio group, teto And arylthio groups having a total carbon number of 12 or less substituted with halogen atoms such as a rafluorophenylthio group and a pentafluorophenylthio group. From the viewpoint of heat resistance, the substituted or unsubstituted alkylthio group is methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, sec-butylthio group, t-butylthio group. Group, n-pentylthio group, iso-pentylthio group, n-hexylthio group, iso-hexylthio group, 2-ethylhexylthio group, 3,5,5-trimethylhexylthio group, n-heptylthio group, n-octylthio group, n -A linear or branched alkylthio group having 1 to 10 carbon atoms in total, such as a nonylthio group, is preferable, and a methylthio group, an ethylthio group, an n-propylthio group, and an i-propylthio group are more preferable from the viewpoint of refractive index.

  Specific compounds suitable as the resin (D) having a thiol group include saturated or unsaturated hydrocarbon thiol compounds in terms of excellent heat resistance, such as methanedithiol, 1,1-ethanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,2,3-propanetrithiol, 2,3-butanedithiol, 1,2-butane Dithiol, 1,4-butanedithiol, bis (2-mercaptoethyl) sulfide, 3,7-dithia-1,9-nonanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzene Examples include dithiol and 1,3,5-benzenetrithiol. As these resins (D), for example, the above compounds can be used alone or in combination of two or more.

When the resin (D) is a polymer, a silicone unit skeleton represented by SiO _1/2 , SiO _2/2 , SiO _3/2 , or SiO _4/2 is used from the viewpoint of heat resistance and light resistance. It is more preferable to have it.

  The thiol group concentration contained in the resin (D) having a thiol group is preferably 0.1 mmol / g or more and 25 mol / g or less, and from the viewpoint of solvent resistance, 0.1 mmol / g or more, and further 0.2 mmol / g. It is preferably g or more, and more preferably 0.3 mmol / g or more from the viewpoint of film strength. On the other hand, from the viewpoint of heat resistance, it is preferably 25 mmol / g or less, more preferably 24 mmol / g or less, and more preferably 20 mmol / g or less from the viewpoint of reducing curing shrinkage and improving crack resistance.

  The weight average molecular weight of the resin (D) having a thiol group is preferably 150 or more and 20,000 or less, more preferably 200 or more and 15,000 or less. In the present disclosure, the weight average molecular weight is a value obtained by converting standard PMMA by gel permeation chromatography (GPC). When the weight average molecular weight of the resin (D) is 150 or more, it is preferable from the viewpoints of heat resistance and curability, and when it is 20,000 or less, the viscosity is lowered and handling properties are improved.

  The viscosity of the resin (D) having a thiol group is preferably 2 mPa · s or more and 200 Pa · s or less, and more preferably 2 mPa · s or more and 100 Pa · s or less. When it is 2 mPa · s or more, it is preferable from the viewpoint of dispersion maintaining property of the surface-modified metal oxide (A), and when it is 200 Pa · s or less, it is preferable from the viewpoint of handleability.

  As a ratio of the resin (B) having an unsaturated group and the resin (D) having a thiol group, the concentration (mmol / g) of the unsaturated group that the resin (B) has and the resin (D) having a thiol group It is preferable that it is 2.0-0.3 as [thiol group] / [unsaturated group] which is a ratio with the thiol group density | concentration to have, and it is 1.8-0.5 from a viewpoint of the intensity | strength of a cured film. It is more preferable. From the viewpoint of avoiding that the remaining unsaturated groups are oxidized and causing yellowing, and from the viewpoint of heat resistance, the ratio is more preferably 0.6 or more, and from the viewpoint of improving the crosslinking density. More preferably, it is 6 or less.

  When the resin (D) having a thiol group is used, the curable catalyst (E) contains the radical generator (E2). The resin (B) has a carbon-carbon unsaturated bond site and the resin (D). Contributes to radical growth-chain transfer reaction with thiol groups. Since this reaction proceeds spontaneously by heat or ultraviolet rays even in the absence of a catalyst, it is not always necessary to use a radical generator, but the reaction rate is remarkably improved by using a radical generator, and a cured product is obtained. It is preferable to use a radical generator from the viewpoints of improving the molecular weight and improving mechanical properties, heat resistance and light resistance.

  Examples of the radical generator (E2) that can be used in the present embodiment include a thermal radical generator and a photo radical generator. The thermal radical generator is not particularly limited as long as it generates radicals by heat. Specific examples include organic peroxides such as benzoyl peroxide, lauryl peroxide, t-butyl peroxide, and cumene hydroperoxide; azo compounds such as azobisisobutyronitrile. Specifically, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries), 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) 2,2′-azobisisobutyronitrile (V-60, manufactured by Wako Pure Chemical Industries), and 2,2 ″ -azobis (2-methylbutyronitrile) (V -59, manufactured by Wako Pure Chemical Industries, Ltd.); octanoyl peroxide (Perroyl (registered trademark) O, manufactured by NOF), lauroyl peroxide (Perroyl (registered trademark) L, manufactured by NOF), stearoyl peroxide ( Parroyl (registered trademark) S, manufactured by NOF), succinic acid peroxide (Perroyl (registered trademark) SA, manufactured by NOF), benzoyl peroxide (NIPER (registered trademark) BW, manufactured by NOF), ISOBU Ril peroxide (Perroyl (registered trademark) IB, manufactured by NOF), 2,4-dichlorobenzoyl peroxide (Nyper (registered trademark) CS, manufactured by NOF), and 3,5,5-trimethylhexanoyl peroxide ( Diacyl peroxides such as Parroyl (registered trademark) 355, manufactured by NOF Corporation; di-n-propyl peroxydicarbonate (Perroyl (registered trademark) NPP-50M, manufactured by NOF Corporation), diisopropyl peroxydicarbonate (parroyl ( (Registered trademark) IPP-50, manufactured by NOF Corporation), bis (4-t-butylcyclohexyl) peroxydicarbonate (Perroyl (registered trademark) TCP, manufactured by NOF Corporation), di-2-ethoxyethyl peroxydicarbonate (parroyl) (Registered trademark) EEP, manufactured by NOF Corporation), di-2-ethoxyhexylperoxydicarbonate (Paroyl (registered trademark) OPP, manufactured by NOF), di-2-methoxybutyl peroxydicarbonate (paroyl (registered trademark) MBP, manufactured by NOF), and di (3-methyl-3-methoxybutyl) par Peroxydicarbonates such as oxydicarbonate (Perroyl (registered trademark) SOP, manufactured by NOF Corporation); t-butyl hydroperoxide (Perbutyl (registered trademark) H-69, manufactured by NOF Corporation), and 1,1,3 , 3-tetramethylbutyl hydroperoxide (Perocta (registered trademark) H, manufactured by NOF Corporation), etc .; di-t-butyl peroxide (Perbutyl (registered trademark) D, manufactured by NOF Corporation), 2 , 5-dimethyl-2,5-bis (t-butylperoxy) hexane (Perhexa (registered trademark) 25B, manufactured by NOF Corporation) and the like; α, α'-bis (neodecanoylperoxy) diisopropylbenzene (Daiper (registered trademark) ND, manufactured by NOF), cumylperoxyneodecanoate (PARKMILL (registered trademark) ND, manufactured by NOF), 1, 1,3,3-tetramethylbutylperoxyneodecanoate (Perocta® ND, manufactured by NOF), 1-cyclohexyl-1-methylethylperoxyneodecanoate (Percyclo®ND), NOF), t-hexyl peroxyneodecanoate (Perhexyl (registered trademark) ND, manufactured by NOF), t-butyl peroxyneodecanoate (perbutyl (registered trademark) ND, manufactured by NOF), t -Hexyl peroxypivalate (perhexyl (registered trademark) PV, manufactured by NOF Corporation), t-butyl peroxypivalate (perbutyl (registered trademark) PV, JP 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Perocta® O, manufactured by NOF Corporation) 2,5-dimethyl-2,5-bis (2- Ethylhexanoylperoxy) hexane (Perhexa (registered trademark) 250, manufactured by NOF), 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate (Percyclo (registered trademark) O, manufactured by NOF), t-hexylperoxy 2-ethylhexanoate (perhexyl (registered trademark) O, manufactured by NOF), t-butylperoxy 2-ethylhexanoate (perbutyl (registered trademark) O, manufactured by NOF), t- Butyl peroxyisobutyrate (Perbutyl (registered trademark) IB, manufactured by NOF Corporation), t-hexyl peroxyisopropyl monocarbonate (Perhexyl (registered trademark) I, NOF Corporation) ), And t-butyl peroxymaleic acid (Perbutyl (registered trademark) MA, manufactured by NOF), t-amylperoxy 2-ethylhexanoate (Trigonox (registered trademark) 121, manufactured by Kayaku Akzo), Examples thereof include organic peroxides such as peroxyesters such as t-amylperoxy 3,5,5-trimethylhexanoate (Kayaester (registered trademark) AN, manufactured by Kayaku Akzo). Moreover, these thermal radical generators can be used alone or in combination of two or more.

The photoradical generator is not particularly limited as long as it generates radicals by light. Preferred examples thereof include the following compounds having absorption with respect to light having a wavelength of 365 nm.
(1) benzophenone derivatives; for example, benzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone, etc. (2) acetophenone derivatives For example, trichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -Phenyl} -2-methylpropan-1-one, pheny Methyl glyoxylate, (2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one) (manufactured by BASF Corporation) (3) thioxanthone derivatives; for example, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, etc. (4) benzyl derivatives; for example, benzyl, benzyldimethyl ketal, benzyl-β-methoxy (5) benzoin derivatives such as ethyl acetal; for example, benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1phenylpropan-1-one, etc. (6) oxime compounds; such as 1-phenyl-1,2- Butanedione-2- (O-Met Xoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl -1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O- Benzoyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] (IRGACURE (registered trademark) OXE-01 manufactured by BASF Corporation), ethanone-1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxy ) (Manufactured by BASF Co., Ltd. IRGACURE (registered trademark) OXE02), etc.

(7) α-hydroxy ketone compounds; for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl -1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane and the like (8) α-aminoalkylphenone Compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE (registered trademark) 369 manufactured by BASF Corporation), 2-dimethylamino-2- (4- (9) phosphine oxide compounds such as methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one; (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl -Phosphine oxide (DAOCURE (registered trademark) TPO manufactured by BASF Corporation) and the like (10) Titanocene compounds; for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3 -(1H-pyrrol-1-yl) phenyl) titanium and the like (11) benzoate derivatives; for example, ethyl-p- (N, N-dimethylaminobenzoate) and the like (12) acridine derivatives; for example, 9-phenylacridine and the like These photo radical generators may be used alone or in combination of two or more. It can be used. Further, a heat radical generator and a photo radical generator may be mixed and used.

  The amount of the radical generator (E2) is 0.1 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the total mass of the surface-modified metal oxide (A), the resin (B), and the resin (D). Is preferably 0.23 parts by mass or more and 5 parts by mass or less. More preferably, it is 0.32 parts by mass or more and 3 parts by mass or less. Curing proceeds favorably when the amount is 0.1 parts by mass or more, and when the amount is 10 parts by mass or less, the cured product after curing by light or heat is less colored.

  Moreover, in order to improve the stability of a composition more, the compound which suppresses a radical reaction can be mix | blended as a polymerization inhibitor. In particular, when the radical generator mentioned above is used, the stability of the composition tends to be lowered, and therefore it is preferable to use such a compound in combination. Examples of such compounds include phosphorus compounds such as triphenylphosphine and triphenyl phosphite; p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2, 6-di-tert-butyl-p-cresol, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol) Radical), N-nitrosophenylhydroxylamine aluminum salt, diphenylnitrosamine and other radical polymerization inhibitors; benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, diaza Tertiary amines such as bicycloundecene; 2-methylimidazole, 2- Examples include imidazoles such as ethyl-4-methylimidazole, 2-ethylhexylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole and the like.

  Of the phosphorus compounds, triphenyl phosphite is preferable because it has a high radical reaction suppressing effect, is liquid at room temperature, and is easy to handle. When a phosphorus compound (especially triphenyl phosphite) is blended in the composition, the amount of the phosphorus compound (especially triphenyl phosphite) depends on the surface-modified metal oxide (A) and the resin (B). From a viewpoint of the effect which suppresses a radical reaction with respect to 100 mass parts of total mass with resin (D), 0.1 mass part or more is preferable, and it is preferable that it is 10 mass parts or less from a sclerosing | hardenable viewpoint.

  Of the radical polymerization inhibitors, nitrosophenylhydroxylamine aluminum salts are preferable because they have a high effect of suppressing radical reaction even in a small amount and are excellent in the color tone of the resulting cured product. When a radical polymerization inhibitor (especially nitrosophenylhydroxylamine aluminum salt) is added to the composition, the amount of radical polymerization inhibitor (especially nitrosophenylhydroxylamine aluminum salt) depends on the surface-modified metal oxide (A) and the resin. The total mass of 100 parts by mass of (B) and the resin (D) is preferably 0.0001 parts by mass or more from the viewpoint of the effect of suppressing radical polymerization, and 0.1 mass parts or less from the viewpoint of curability. preferable.

  Of the tertiary amines, benzyldimethylamine is preferred because it has a high effect of suppressing radical reaction even in a small amount and is liquid at room temperature and easy to handle. When a tertiary amine (especially benzyldimethylamine) is blended in the composition, the amount of the tertiary amine (especially benzyldimethylamine) depends on the surface-modified metal oxide (A), resin (B) and resin. From the viewpoint of radical polymerization inhibition, 0.001 part by mass or more is preferable with respect to the total mass of 100 parts by mass of (D), and preferably 5 parts by mass or less from the viewpoint of heat resistance.

  The composition of this embodiment includes a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, a release agent, a foaming agent, a nucleating agent, a coloring agent, a crosslinking agent, and a dispersion aid. Further, a plasticizer, a flame retardant and the like can be blended. These materials are preferably mixed with other components of the composition using a known method such as centrifugation, and the resulting mixture is preferably defoamed by a known method such as vacuum defoaming.

<Solvent>
Moreover, a solvent can be added to the composition of this embodiment as needed. A conventionally well-known thing can be arbitrarily used as a solvent. In order to prevent curing, foaming at the time of molding, and residual solvent in the cured product, the content of the solvent is preferably 1900 parts by mass or less with respect to 100 parts by mass of the solid content of the composition, and 900 parts by mass The following is more preferable. Content of the said solvent may be 50 mass parts or more with respect to 100 mass parts of solid content of a composition, Furthermore, 1100 mass parts or more may be sufficient.

<Dispersion>
The present disclosure also provides a dispersion comprising the particles (1) described above and a dispersion medium. As the dispersion medium, a conventionally known medium similar to the above solvent can be arbitrarily used. The amount of the dispersion medium is preferably 1900 parts by mass or less, more preferably 1500 parts by mass or less, preferably 100 parts by mass or less with respect to 100 parts by mass of the particles (1). 100 parts by mass or more, more preferably 150 parts by mass or more. The dispersion can be suitably used for preparing the aforementioned composition. Alternatively, a cured product can be formed using the dispersion and, if necessary, a curable catalyst.

<Transparent composite material>
Another aspect of the present embodiment is a transparent composite material containing a cured product of the above-described composition. In a preferred embodiment, the transparent composite material has a periodic uneven structure. Examples of the periodic concavo-convex structure include those described below for the concavo-convex structure layer.

  In an exemplary embodiment, the transparent composite can be produced by coating the composition of the present disclosure onto a transparent substrate. As a coating method, methods such as a spin coater, a bar coater, a capillary coater, an R & R coater, a slot die coater, a lip coater, a comma coater, and a gravure coater can be used. From the viewpoint of productivity and film thickness, coating with a gravure coater, capillary coater, or lip coater is preferred. Examples of the transparent substrate include glass, sapphire, PET, TAC, PEN, acrylic resin, and the like.

  The transparent composite material can be obtained by drying, heating, or exposing the composition disclosed in the present embodiment on the transparent substrate, or heating after drying / exposure.

  The thickness of the transparent composite material to be produced is preferably about 1 nm to 100 μm, preferably 2 nm or more, more preferably 5 nm or more from the viewpoint of moldability. Moreover, from a viewpoint of transparency, 50 micrometers or less are more preferable, and from a viewpoint of crack resistance, 30 micrometers or less are still more preferable.

  Various curing temperatures can be set for producing the transparent composite material, but 30 to 300 ° C. is preferable and 70 to 200 ° C. is more preferable from the viewpoint of the curing rate and molding processability.

  Curing may be performed at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Rather than performing curing at a constant temperature, it is preferable that the reaction is carried out while raising the temperature in a multistage or continuous manner in that a uniform cured product with less distortion is easily obtained and cracks are less likely to occur.

  In the case of performing a curing treatment with light, for example, visible light, ultraviolet light, far ultraviolet light, or the like can be used. Examples of the light source include a low-pressure or high-pressure mercury lamp, deuterium lamp, or discharge light of a rare gas such as argon, krypton, or xenon, YAG laser, argon laser, carbon dioxide laser, or XeF, XeCl, XeBr, KrF, An excimer laser such as KrCl, ArF or ArCl can be used. The output of these light sources is preferably 10 to 5,000 W.

<Uneven structure layer>
An example of the use of the composition of the present disclosure is not particularly limited thereto, but includes use as an uneven microstructure layer formed on the element surface for improving the luminance of the semiconductor light emitting element. For example, the above-described transparent composite material can be formed by forming such an uneven structure layer on a transparent substrate.

  The shape of the concavo-convex structure is a line-and-space structure in which a plurality of fence-like bodies are arranged, a dot structure in which a plurality of dot (convex parts, protrusions) -like structures are arranged, and a hole structure in which a plurality of hole (concave) -like structures are arranged. Can be adopted. Examples of the dot structure and the hole structure include a cone, a cylinder, a truncated cone, a quadrangular pyramid, a quadrangular column, a hexagonal pyramid, a hexagonal column, a polygonal pyramid, a polygonal column, a double ring shape, and a multiple ring shape. These shapes include a shape in which the outer diameter of the bottom surface is distorted and a shape in which the side surface is curved. The dot structure is a structure in which a plurality of convex portions are arranged independently of each other. That is, each convex part is separated by a continuous concave part. In addition, each convex part may be smoothly connected by the continuous recessed part. On the other hand, the hole structure is a structure in which a plurality of recesses are arranged independently of each other. That is, each recessed part is separated by the continuous convex part. In addition, each recessed part may be smoothly connected by the continuous convex part. The concavo-convex structure layer typically has a large number of protrusions as the concavo-convex structure. The protrusions may be arranged periodically or not arranged periodically, and may have long-term order. Examples of the periodic uneven structure include, but are not limited to, a regular hexagonal arrangement, a hexagonal arrangement, a quasi-hexagonal arrangement, a quasi-tetragonal arrangement, a tetragonal arrangement, and a regular tetragonal arrangement. Moreover, the shape of each protrusion may be the same or different. For each projection, a top and bottom can be defined. The size of the concavo-convex structure is preferably such that the width of the concavo-convex structure (typically, the width of the bottom of the protrusion) is equal to or less than the emission wavelength of the light-emitting layer, and the height of the concavo-convex structure ( Typically, the height from the bottom to the top of the protrusion is preferably equal to or higher than the emission wave of the light emitting layer. In this case, the refractive index difference between them at the interface between the light emitting element and the surrounding sealing member is further relaxed to suppress the reflection of light, and the effect of light scattering can be obtained satisfactorily. As a result, when there is no concavo-convex structure, light that is totally reflected beyond the critical angle at the interface between the light emitting element and the surrounding sealing member, and is confined inside the transparent layer or the semiconductor layer, Since the traveling direction of light changes due to the presence of light, the amount of light extraction is improved by increasing the ratio within the critical angle.

  In particular, the height of the concavo-convex structure (typically, the height from the bottom to the top of the protrusion) is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 200 nm or more, and still more preferably 350 nm or more. is there. The height of the concavo-convex structure in the concavo-convex structure layer is preferably 1500 nm or less, more preferably 1300 nm or less, and still more preferably 1200 nm or less. When the height of the concavo-convex structure is 50 nm or more, the refractive index difference between them at the interface between the light emitting element and the surrounding sealing member is further relaxed to suppress light reflection, and the effect of light scattering. Is obtained satisfactorily. As a result, when there is no concavo-convex structure, light that is totally reflected beyond the critical angle at the interface between the light emitting element and the surrounding sealing member, and is confined inside the transparent layer or the semiconductor layer, Since the traveling direction of light changes due to the presence of light, the amount of light extraction is improved by increasing the ratio within the critical angle. When it is 1500 nm or less, it is advantageous in terms of productivity.

  The refractive index of the concavo-convex structure layer is preferably a refractive index closer to that of the substrate used in the semiconductor light emitting device, preferably 1.50 or more, more preferably 1.60 or more, from the viewpoint of light extraction efficiency. More preferably, it is 70 or more. The refractive index is preferably 2.00 or less, and more preferably 1.95 or less, from the viewpoint of the transparency of the uneven microstructure layer.

  The structure layer on which the desired unevenness is formed can be dried or light after various methods, for example, a method of etching after forming a smooth film, forming unevenness on an uncured coating film, transferring unevenness using a shaping mold, Alternatively, it can be formed by a method such as curing by heat, a known processing method such as press working or injection molding. Alternatively, it can be formed by separately producing an optical sheet having a structure with irregularities and attaching it to a substrate. This optical sheet can be dried by various methods, for example, a method of etching a substrate, a method of etching after forming a smooth film, formation of unevenness on an uncured coating film, transfer of unevenness using a shaping mold, and drying or light. Alternatively, it can be formed by a method such as curing by heat, a known processing method such as press working or injection molding. Among these, the method of attaching the optical sheet to the substrate is advantageous from the viewpoint of productivity. In the case where the optical sheet is an optical sheet having a structure area with unevenness and a gap, it is possible to increase the dicing productivity associated with the separation of the light emitting elements.

  A well-known method can be used for alignment for forming the concavo-convex structure at a desired position on the substrate. For example, there are a method of arranging a mask, a method of arranging a concavo-convex shaping mold, a method of sticking a sheet, etc. using an orientation flat or engraving of a substrate as a mark. When using the method of sticking a sheet, the sheet can be engraved. Use of a method for marking a sheet makes it possible to easily perform alignment and is advantageous from the viewpoint of productivity.

<Optical element>
Another aspect of the present invention provides an optical element including the transparent composite material.
The optical element can be manufactured by separating a laminate including a light emitting layer, a substrate, and the concavo-convex structure layer disclosed above. The light emitting element is preferable in that light extraction efficiency is improved by reducing light loss due to total reflection at the interface.

(Light emitting layer)
The configuration of the light emitting layer may be a common one in a semiconductor light emitting device and is not particularly limited. For example, a GaN-based semiconductor light emitting layer can be used. The GaN-based semiconductor light emitting layer includes an n-semiconductor layer, a p-semiconductor layer, a conductive layer, an electrode, and the like. The n-semiconductor layer is a laminated body of a GaN layer as a first n-type cladding layer and an In _0.02 Ga _0.98 N layer as a second n-type cladding layer. In addition, as a structure of a semiconductor light-emitting element, the thing of a homo structure, a hetero structure, or a double hetero structure can be used. Furthermore, a quantum well structure (single quantum well structure or multiple quantum well structure) can also be adopted.

  A method for forming the light emitting layer is not particularly limited and can be a general one used in a semiconductor light emitting device. For example, a semiconductor layer made of a well-known nitride compound semiconductor is formed by using a well-known metal organic chemical vapor deposition method (MOCVD method). ), Molecular beam crystal growth method (MBE method), halide vapor phase epitaxy method (HVPE method), sputtering method, ion plating method, electron shower method and the like.

(substrate)
As the substrate, a gallium nitride such as GaN, a semiconductor substrate such as silicon carbide or silicon, an oxide substrate such as sapphire, spinel, zinc oxide, or magnesium oxide, zirconium boride, or the like can be used. GaN, silicon carbide, and sapphire are preferable from the viewpoint of versatility, and sapphire is particularly preferable from the viewpoint of productivity.

(Manufacturing method of light emitting element)
Dicing can be used as a method of dividing the laminate into individual light emitting elements. Types of dicing include blade dicing which mechanically cuts the substrate, a method of cutting the substrate by causing ablation on the substrate surface using a laser, and dicing which forms a modified layer inside the substrate with a laser and cuts the substrate. A known method is used. In the case of using dicing in which a modified layer is formed inside the substrate with a laser and is cut, it is advantageous from the viewpoint of productivity because the area for removal and removal is small and it is difficult to cause chipping.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these.

  The surface modifier (b), metal oxide (c) and surface modified metal oxide (A) synthesized in the following examples were measured according to the following (1) to (5).

(1) Structural identification of the synthesized surface modifier (b) The synthesized surface modifier (b) was dissolved in deuterated chloroform, and the pulse width was determined using 1HNMR (JEOL NMR (nuclear magnetic resonance) apparatus GSX400). Integration was performed with 0.5 seconds, a waiting time of 2 seconds, and an integration count of 16.

(2) Measurement of the particle diameter of the metal oxide (c) The particle dispersion is dropped on a fine sample capturing film (collodion film), dried, and then used with a JEOL 2000-FX transmission electron microscope (TEM). The number average of the primary particle diameters of 50 particles was calculated.

(3) Identification of Metal Oxide (c) Particles Part of the particle dispersion was dried, powder X-ray diffraction was performed using a Rigaku X-ray diffractometer RU-200X, and identified from diffraction patterns described in the literature.

(4) Measurement of volume ratio of metal oxide (c) in surface-modified metal oxide (A) and measurement of density of (A) The volume ratio and density are determined by the surface modifiers (a) and (b). ) Is 1 g / mL, and the density of the metal oxide (c) is a literature value, that is, 4.27 for titanium oxide, 5.67 for zirconium oxide, 6.02 g / mL for barium titanate. And calculated by the following formula.
Volume ratio of metal oxide (c) = (mass of metal oxide (c) / density of metal oxide (c)) / {mass of surface modifier (a) / density of surface modifier (a)) + Surface modifier (b) mass / surface modifier (b) density) + metal oxide (c) mass / metal oxide (c) density)}
The amount of the surface modifiers (a) and (b) actually used on the surface of the metal oxide (c) used in the above calculation is determined by dispersing the surface modified metal oxide (A) in deuterated THF and adding toluene. An internal standard was used and quantified by measuring 1H-NMR. From the 1H-NMR measurement result of the prepared sample solution, the peak area (3H) of the hydrogen atom of the functional group corresponding to (a), or the peak area of the hydrogen atom of the functional group corresponding to (b) (that is, D-TMS). Of the surface modifiers (a) and (b) per 1 g of the surface-modified metal oxide (A) based on the ratio of the peak area (5H) of the benzene ring of toluene to the SiCH ₃ group 21H) The amount was quantified. The concentration of unsaturated functional groups in the surface-modified metal oxide (A) was calculated from the double bond peak (peak area (3H) of hydrogen atoms of the functional group corresponding to (a)).

(5) Measurement of Refractive Index of Surface-Modified Metal Oxide (A) The refractive index of the surface-modified metal oxide (A) was estimated using the following formula (Maxwell-Garnett formula).

Refractive index of dispersion = refractive index of surface modifier × [refractive index of metal oxide (c) × (1 + 2 × volume fraction of metal oxide (c)) − refractive index of surface modifier) × (2 × Volume fraction of metal oxide (c) -2)] / [(refractive index of surface modifier) × (2 + volume fraction of metal oxide (c)) + refractive index of metal oxide (c) × ( 1-Volume fraction of metal oxide (c))]

  A dispersion in which surface modified metal oxides (A) having different concentrations, 1.5% by volume, 3% by volume, 5% by volume, or 8% by volume are dispersed in an organic solvent (in methyl isobutyl ketone or tetrahydrofuran). In addition, the refractive index at a wavelength of 589 nm was measured with an Abbe refractometer. The refractive index is plotted against the concentration of the surface modified metal oxide (A) with respect to the organic solvent, and the value obtained by extrapolating the surface modified metal oxide (A) concentration to 100% by volume is the surface modified metal oxide (A). Was calculated as the refractive index.

[Synthesis Example 1]
Toluene (made by Wako Pure Chemicals, dehydrated) 800 g, 1,1,1,3,5,5,5-heptamethyltrisiloxane 128.6 g (manufactured by Tokyo Chemical Industry) Then, 71.4 g of trimethoxyvinylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was weighed, and 110 μL of a 2 wt% xylene solution (manufactured by Gelest) of a tetramethyldivinyldisiloxane complex of platinum (Karstedt catalyst) was added. A reflux tube was set, and the reaction was heated at 60 ° C. using an oil bath under a nitrogen atmosphere. After 8 hours, it was cooled to room temperature. The conversion of trimethoxyvinylsilane by GC was 100%. Toluene was distilled off at 4 kPa and 70 ° C. using an evaporator. Further purification was carried out by distillation under reduced pressure at 0.57 kPa and 120 ° C. (boiling point 103 ° C., 0.57 kPa) to obtain bis (trimethylsiloxy) methylsilylethyltrimethoxysilane (D-TMS). The production ratio of bis (trimethylsiloxy) methylsilylethyltrimethoxysilane and bis (trimethylsiloxy) methylsilylethyltrimethoxysilane identified by 1H-NMR was 90:10 by mass ratio, and the purity measured by GC was 99. %Met.

[Synthesis Example 2]
Toluene (made by Wako Pure Chemicals, dehydrated) 800 g, 1,1,1,3,5,5,5-heptamethyltrisiloxane 134.4 g (manufactured by Tokyo Chemical Industry) Then, 65.6 g (manufactured by Tokyo Chemical Industry Co., Ltd.) of dimethoxymethylvinylsilane was weighed, and 110 μL of a 2 wt% xylene solution (manufactured by Gelest) of a tetramethyldivinyldisiloxane complex of platinum (Karstedt catalyst) was added. A reflux tube was set, and the reaction was heated at 60 ° C. using an oil bath under a nitrogen atmosphere. After 8 hours, it was cooled to room temperature. The conversion of trimethoxyvinylsilane by GC was 100%. Toluene was distilled off at 4 kPa and 70 ° C. using an evaporator. Further, the residue was purified by distillation under reduced pressure at 0.57 kPa and 120 ° C. to obtain bis (trimethylsiloxy) methylsilylethyldimethoxymethylsilane (D-DMS). The production ratio of bis (trimethylsiloxy) methylsilylethyldimethoxymethylsilane and bis (trimethylsiloxy) methylsilylethyldimethoxymethylsilane identified by 1H-NMR was 89:11 by mass ratio, and the purity measured by GC was 99. %Met.

[Synthesis Example 3]
500 mL of 2-methoxyethanol (manufactured by Wako Pure Chemical Industries, Ltd., purity 99% or more) was placed in a separable flask having a volume of 1 L that was replaced under a nitrogen atmosphere. Degassed by bubbling 2-methoxyethanol with nitrogen for 2 hours under a nitrogen atmosphere. Put metal barium 54.9g (0.4M) (Kanto Chemical, purity 99% or more), tetraethoxy titanium 83.7mL (0.4M) (Tokyo Chemical, purity 97% or more) with stirring. Heating at 130 ° C. for 2 hours completely dissolved the metal barium and tetraethoxytitanium. After 2 hours, 144 mL of ion-exchanged water dissolved in 2-methoxyethanol was bubbled with N 2 and added so that the total liquid volume was 1100 mL. The mixture was stirred for 3 hours at 130 ° C. using an oil bath to obtain a dispersion of barium titanate. Nanoparticles with an average of 45 nm were obtained by TEM, and it was confirmed that the XRD diffraction peak coincided with barium titanate.

[Synthesis Example 4]
In a 300 mL three-necked flask, 50 g of SRD-M (manufactured by Sakai Chemical, 17% by mass titanium oxide methanol dispersion), D-TMS 6.99 g synthesized in Synthesis Example 1, vinyltrimethoxysilane (VTMS) (manufactured by Tokyo Chemical Industry) 2 .81 g was added. 1.22 g of 1N aqueous sodium hydroxide solution was slowly added dropwise and stirred at 20 ° C. for 24 h. The obtained solution was re-precipitated in 250 g of acetone, and centrifuged at 11,000 rpm for 10 minutes to remove the supernatant. Further, 115 g of acetone was added and suspended, and the surface-modified titanium oxide was precipitated again by centrifugation. Washing acetone was removed, 120 g of methyl isobutyl ketone (MIBK) (manufactured by Wako Pure Chemical Industries, Ltd.) was added and redispersed in ultrasonic waves. Residual acetone was removed using an evaporator to obtain a 15 mass% MIBK surface-modified metal oxide dispersion. Each characteristic is shown in Table 1.

[Synthesis Example 5]
In a 300 mL three-necked flask, 50 g of SZR-M (manufactured by Sakai Chemical, 33 mass% zirconium oxide methanol dispersion), 15.45 g of D-TMS, and 2.06 g of vinyltrimethoxysilane (manufactured by Tokyo Chemical Industry) were placed. 0.60 g of 1N sodium hydroxide aqueous solution was slowly added dropwise and stirred at 20 ° C. for 24 hours. The obtained solution was re-precipitated in 250 g of acetone, and centrifuged at 11,000 rpm for 10 minutes to remove the supernatant. Further, 115 g of acetone was added and suspended, and the surface-modified titanium oxide was precipitated again by centrifugation. Washing acetone was removed, 120 g of tetrahydrofuran (THF) (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and redispersed in ultrasonic waves. The residual acetone was removed using an evaporator to obtain a surface-modified metal oxide dispersion of 20% by mass of THF. Each characteristic is shown in Table 1.

[Synthesis Example 6]
Similar to Synthesis Example 4 except that 50 g of the barium titanate dispersion of Synthesis Example 3 was used.

[Synthesis Example 7]
The same as synthesis example 4 except that D-TMS was changed to D-DMS 9.98 g.

[Synthesis Example 8]
D-TMS was set to 10.48 g, and Synthesis Example 4 was followed except that 3-methacryloxypropyltrimethoxysilane (MEMO) 2.34 g was used instead of vinyltrimethoxysilane (VTMS).

[Synthesis Example 9]
D-TMS was set to 10.48 g, and Synthesis Example 4 was followed except that 2.11 g of p-styryltrimethoxysilane was used instead of vinyltrimethoxysilane (VTMS).

[Synthesis Example 10]
The surface modifier used was D-TMS 13.98 g, and the same as in Synthesis Example 4 except that vinyltrimethoxysilane (VTMS) was not used.

[Synthesis Example 11]
D-TMS was not used, but according to Synthesis Example 4 except that vinyltrimethoxysilane (VTMS) was changed to 5.59 g.

[Synthesis Example 12]
As a surface treatment agent, D-TMS and vinyltrimethoxysilane (VTMS) were not used, and the same as synthesis example 5 except that 9.36 g of 3-methacryloxypropyltrimethoxysilane (MEMO) was used.

[Synthesis Example 13]
In a separable flask with a capacity of 2 L that was replaced under a nitrogen atmosphere, 800 g of toluene (manufactured by Wako Pure Chemicals, dehydrated), 73.5 g of trimethylvinylsilane (manufactured by Tokyo Chemical Industry), and 126.5 g of triethoxysilane (manufactured by Tokyo Chemical Industry) were weighed. Then, a reflux tube was set, and the reaction was heated at 60 ° C. using an oil bath in a nitrogen atmosphere. After 2 hours, it was cooled to room temperature. The conversion of trimethylvinylsilane by GC was 100%. Toluene was distilled off at 4 kPa and 70 ° C. using an evaporator. Further, it was purified by distillation under reduced pressure at 0.3 kPa and 90 ° C. (boiling point 65 ° C., 0.3 kPa) to obtain trimethylsilylethyltriethoxysilane. The production ratio of 2-trimethylsilylethyltriethoxysilane and 1-trimethylsilylethyltriethoxysilane identified by 1H-NMR was 87:13 in mass ratio.

[Synthesis Example 14]
The same procedure as in Synthesis Example 4 was followed, except that the surface modifier was changed to 4.98 g of trimethylsilylethyltriethoxysilane synthesized in Synthesis Example 13 and 2.81 g of vinyltrimethoxysilane (VTMS) (manufactured by Tokyo Chemical Industry).

[Synthesis Example 15]
The same as Synthesis Example 5 except that the surface modifier was changed to 15.45 g of D-TMS and 4.68 g of 3-methacryloxypropyltrimethoxysilane (MEMO).

  The compositions prepared in the following examples and their cured products were measured according to the following (6) to (9).

(6) Refractive index measurement A composition corresponding to each example was applied on a silicon wafer to a thickness of 10 nm using a spin coater, and heated and cured at 120 ° C. for 60 minutes (or a photoinitiator was added). Was exposed and cured at 1,000 mJ / cm ² , and the refractive index at a wavelength of 589 nm was measured with an automatic ellipsometer (DVA-36LA, manufactured by Mizoji Optical Co., Ltd.).

(7) Transparency A composition having a thickness of 1 μm is coated on a 5 cm square glass substrate and heated and cured at 120 ° C. for 60 minutes (or 1,000 mJ / cm for those containing a photoinitiator). ² was exposed and cured). Using a UV-Visible spectrophotometer UV-1600PC manufactured by Shimadzu Corporation, the transmittance at a wavelength of 800 nm to 300 nm is measured, and when the transmittance at 400 nm is 80% or more, ○, and when 80% or less, × did.

(8) Heat resistance A composition having a thickness of 1 μm is coated on a 5 cm square glass substrate and heated and cured at 130 ° C. for 60 minutes (or 1,000 mJ / cm for those containing a photoinitiator). ² was exposed and cured). The heat resistance test was performed in an oven at 120 ° C. for 400 hours in the atmosphere. Measure YI (E313) at 0 hours and YI (E313) after 400 hours with a spectrocolorimeter CM-3600 (manufactured by Konica Minolta). The difference between YI (313) is ΔYI, and ΔYI is 1 or less. ◯, exceeding 1 and 3 or less, Δ, exceeding 3 and 5 or more.

(9) Light resistance A composition having a thickness of 1 μm is applied on a 5 cm square glass substrate, and heated and cured at 120 ° C. for 60 minutes (or 1,000 mJ / cm for those containing a photoinitiator). ² was exposed and cured). The obtained cured product was subjected to an exposure test for 144 hours at 50 ° C. with a 7 W 365 nm UV-LED light source. Measure YI (E313) at 0 hours and YI (E313) after 400 hours with a spectrocolorimeter CM-3600 (manufactured by Konica Minolta). The difference between YI (313) is ΔYI, and ΔYI is 1 or less. ◯, exceeding 1 and 4 or less, Δ, exceeding 4 and 5 or more.

[Example 1]
10 g of the surface-modified titanium oxide nanoparticle MIBK 15% by mass dispersion of Synthesis Example 4, 0.132 g of DMS-V05 (manufactured by Gelest), 2,4,6,8,10-pentamethyl-1,3,5,7,9- Pentaoxa-2,4,6,8,10-pentasilacyclodecane (manufactured by Aldrich) 0.0269 g, (2-ethyl-1-hydroxyhexyl) acetylene (Tokyo Kasei) 1.97 mg, 1,3-divinyl-1 , 1,3,3-Tetramethyldisiloxane platinum (0) complex solution (manufactured by Aldrich) 2 wt% xylene solution was mixed well so that the Pt content was 3 ppm with respect to the solid matter, To prepare a composition. After curing using a bar coater on a 5 cm square glass substrate, it was applied at a thickness of 1 μm and cured at 120 ° C. for 2 hours to obtain a transparent composite material thin film.

[Example 2] to [Example 3] and [Example 8] to [Example 9]
The preparation method and curing were in accordance with Example 1, and the compositions were prepared at the blending ratios in Table 1 and thermally cured.

[Example 4]
10 g of the surface-modified titanium oxide nanoparticle MIBK 20% by mass dispersion of Synthesis Example 7, 0.184 g of 1,3-benzenedithiol (manufactured by Aldrich), 0.073 g of tetravinylsilane (manufactured by Shin-Etsu Silicone), and bis (2,4,6- 0.04 g of trimethylbenzoyl-phenylphosphine oxide (Irgacure (registered trademark) 819 (manufactured by BASF Corp.)), N-nitrosophenylhydroxylamine aluminum salt (manufactured by Wako Pure Chemical Industries, Ltd .: trade name “Q-1301”) 0.06 mg was mixed and mixed well to obtain a composition, which was coated on a 5 cm square glass substrate with a bar coater at a thickness of 1 μm, and a metal halide lamp (CV-110Q-G manufactured by Fusion UV Systems Japan). ) With UV light at a light intensity of 1000 mJ / cm ² A material thin film was obtained.

[Example 5] to [Example 7] and Example 10
The preparation method and curing were in accordance with Example 4 and the compositions were prepared at the blending ratios in Table 1 and photocured.

[Comparative Example 1] to [Comparative Example 2]
The preparation method and curing were in accordance with Example 1, and the compositions were prepared at the blending ratios in Table 1 and thermally cured. Titanium oxide precipitated in the cured product, and a transparent cured film could not be obtained.

[Comparative Example 3]
The preparation method and curing were in accordance with Example 4 and the compositions were prepared at the blending ratios in Table 1 and photocured.

  According to the following examples, the uneven shaped structure of the prepared composition was measured according to the following (10) to (12).

(10) Measurement of pitch height and aspect ratio of concavo-convex microstructure layer A chip after dicing was attached to a 1-inch SEM table using carbon paste, and osmium-deposited was used as FE-SEM (Hitachi High-Tech Field Emission) Using a scanning electron microscope, SU-8010), the height and width of the microstructure of the concavo-convex microstructure layer were confirmed by observation at 50,000 times. In the electron microscopic image, the bottom B and the top T of the protrusion as the concavo-convex microstructure were defined, and the height h of the microstructure was determined. Further, the aspect ratio = h / w was determined as the width w of the protrusion as the concave-convex microstructure.

(11) Evaluation of light extraction property An LED sealing material (SCR1016, manufactured by Shin-Etsu Silicone) was molded into a 3 mmφ hemispherical lens type on a light emitting element separated into 1 mm □, and 5 hours at 150 ° C. for 1 hour at 100 ° C. The semiconductor light emitting element was produced by heating for a period of time. About the produced semiconductor light emitting element, the amount of light emission is measured, the light emission amount is 1.2 times or more with respect to the reference, ◎, 1.1 times or more and less than 1.2 times, ○, 1.05 times Those having a value less than 1.1 times were evaluated as Δ, and those having a value less than 1.05 were rated as ×.

(12) Light long-term stability test In the device prepared in (11), the external temperature was set to 85 ° C. so that Tj was 180 ° C., and the current was continuously supplied at 100 mA. For the semiconductor light emitting device after 96 hours, the amount of luminescence was measured, and the amount of luminescence was 0.9 times or more before the current test, ◯, 0.8 times or more and less than 0.9 times △, Those less than 0.8 times were rated as x.

[Example 11]
The laminated body was formed by sticking the optical sheet which has the uneven structure of Table 1 on the surface on the opposite side to the light emitting layer of said board | substrate with a light emitting layer using the composition of Example 1. A light emitting device in which the laminate was separated into 1 mm square pieces was produced. The results are shown in Table 2.

[Example 12] Using the composition of Example 2, according to Example 11, an individual light emitting device having an uneven structure was produced.
[Example 13]
Using the composition of Example 3, according to Example 11, an individual light-emitting element having an uneven structure was manufactured.
[Example 14]
Using the composition of Example 4, according to Example 11, an individual light-emitting element having an uneven structure was manufactured.
[Example 15]
Using the composition of Example 5, according to Example 11, an individual light-emitting element having an uneven structure was manufactured.
[Example 16]
Using the composition of Example 6, according to Example 11, an individual light-emitting element having an uneven structure was manufactured.
[Example 17]
Using the composition of Example 7, according to Example 11, an individual light-emitting element having an uneven structure was manufactured.
[Example 18]
Using the composition of Example 8, according to Example 11, an individual light-emitting element having an uneven structure was produced.
[Example 19]
Using the composition of Example 9, according to Example 11, an individual light-emitting element having an uneven structure was manufactured.
[Example 20]
Using the composition of Example 10, according to Example 11, an individual light-emitting element having an uneven structure was manufactured.

[Comparative Example 4]
Using the composition of Comparative Example 3, an individual light-emitting element having a concavo-convex structure was produced according to Example 11.

  The composition of the present invention is useful as a material for light-emitting diode elements and other optical devices or optical components. Specifically, it can be suitably used for a protective film on the light emitting element and a light scattering layer on the upper surface of the light emitting element.

Claims (16)

A composition comprising particles (1),
The particle (1) is a surface modifier (a) having an unsaturated group, and the following general formula (1):
^{R 1 R 2 R 3 Si-} Y-SiR 4 n X 3-n (1)
{Wherein R ¹ , R ² and R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted siloxy group, and R ⁴ is a substituted or unsubstituted saturated alkyl group. X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group, Y is a divalent linking group, and n is 0 It is an integer of ~ 2. }
The composition containing the surface modification metal oxide (A) obtained by surface-modifying the metal oxide (c) with the surface modification agent containing the surface modification agent (b) represented by these.   The composition according to claim 1, further comprising a resin (2).   The composition according to claim 2, wherein the resin (2) includes a resin (B) having an unsaturated group.   The composition according to claim 3, wherein the unsaturated group of the resin (B) is at least one selected from the group consisting of an acryl group, a methacryl group, a styryl group, a vinyl group, and an allyl group.   The resin (2) comprises a resin (C) having a hydrogen atom directly bonded to silicon or a resin (D) having a thiol group, and the composition further comprises a curable catalyst (E). The composition as described in any one of 2-4.   The composition as described in any one of Claims 2-5 whose volume ratio of the said particle | grains (1) with respect to the sum total of the said particle | grains (1) and the said resin (2) is 40-99 volume%.   The unsaturated group of the surface modifier (a) is at least one selected from the group consisting of an acryl group, a methacryl group, a vinyl group, and an allyl group. The composition as described.   The composition according to any one of claims 1 to 7, wherein n in the general formula (1) is 0 or 1.   The composition as described in any one of Claims 1-8 whose refractive index of the said surface modification metal oxide (A) is 1.8 or more.   The composition according to any one of claims 1 to 9, wherein the metal oxide (c) is titanium oxide, zirconium oxide, or barium titanate.   In the surface modified metal oxide (A), the metal relative to the sum of the structure derived from the surface modifier (a), the structure derived from the surface modifier (b), and the structure derived from the metal oxide (c) The composition according to any one of claims 1 to 10, wherein a ratio of a structure derived from the oxide (c) is 70 to 99% by volume.   The composition as described in any one of Claims 1-11 whose average primary particle diameters of the said particle | grain (1) are 1 nm-100 nm.   The transparent composite material containing the hardened | cured material of the composition as described in any one of Claims 1-12.   The transparent composite material according to claim 13, which has a periodic uneven structure.   An optical element comprising the transparent composite material according to claim 13. A dispersion comprising particles (1) and a dispersion medium,
The particle (1) is a surface modifier (a) having an unsaturated group, and the following general formula (1):
^{R 1 R 2 R 3 Si-} Y-SiR 4 n X 3-n (1)
In the formula, R ¹ , R ² and R ³ are each independently a hydrocarbon group having 1 to 18 carbon atoms, or a substituted or unsubstituted siloxy group, and R ⁴ is a substituted or unsubstituted saturated alkyl group. X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or an acetoxy group, Y is a divalent linking group, and n is 0 to 0 It is an integer of 2. }
A dispersion comprising a surface-modified metal oxide (A) obtained by surface-modifying a metal oxide (c) with a surface modifier containing the surface-modifier (b) represented by