WO2013172476A1 - Surface-modified metal oxide particle material, dispersion liquid, silicone resin composition, silicone resin composite body, optical semiconductor light emitting device, lighting device, and liquid crystal imaging device - Google Patents

Abstract

Provided is a surface-modified metal oxide particle material which is obtained by surface modifying metal oxide particles having an average primary particle diameter of 3-10 nm (inclusive) with a surface modification material having a phenyl group and a group that is crosslinkable with a functional group of a silicone resin-forming component. This surface-modified metal oxide particle material exhibits high heat resistance in cases where the surface-modified metal oxide particle material is used as an encapsulation material for optical semiconductor light emitting devices and the like, while exhibiting high transparency and high gas barrier properties. Also provided are: a dispersion liquid, a silicone resin composition and a silicone resin composite body, each of which contains the surface-modified metal oxide particle material; and an optical semiconductor light emitting device, a lighting device and a liquid crystal imaging device, each of which uses the silicone resin composite body.

Description

Surface-modified metal oxide particle material, dispersion, silicone resin composition, silicone resin composite, optical semiconductor light emitting device, lighting fixture, and liquid crystal image device

The present invention relates to a surface-modified metal oxide particle material, a dispersion, a silicone resin composition, a silicone resin composite, an optical semiconductor light emitting device using the same as a sealing material, a lighting fixture including the optical semiconductor light emitting device, and a liquid crystal The present invention relates to an image device.

Silicone resin has excellent properties such as transparency, heat resistance, and light resistance, and is excellent in hardness and rubber elasticity, as described in Patent Document 1, for example. Used for etc.
In particular, as a sealing material of a light emitting diode (LED) which is a kind of optical semiconductor light emitting element, for example, organic modified silicone resin, phenyl (or methylphenyl) silicone resin as described in Patent Document 2, There is a dimethyl silicone resin as described in Patent Document 3.

On the other hand, although silicone resin is excellent in durability, there is a problem that gas permeability is large (gas barrier property is low). In contrast, attempts have been made to solve this problem by including metal oxide particles. In order to make a transparent composite of silicone resin and metal oxide particles, the particle surface must be treated with an organosilane agent. For example, as described in Patent Documents 4 and 5, surface treatment is performed using an epoxy group-containing silane agent or a vinyl group-containing silane agent, thereby preventing aggregation of particles when the resin is cured and producing a transparent composite. Is possible.

JP 2009-076948 A1 JP 2007-270004 A JP 2011-096793 A Japanese Patent Laying-Open No. 2005-200657 JP 2006-70266 A

However, the silicone resin has a problem of high gas permeability (low gas barrier property), and the metal oxide particles are dispersed and compounded in the silicone resin to compensate for this drawback and improve the function. In particular, the sulfur gas in the atmosphere corrodes (sulfurizes and blackens) the silver-plated reflector of the LED package, so that there is a problem that the brightness of the LED is lowered.
In addition, when inorganic particles are dispersed in a silicone resin, the heat resistance of ordinary surface treatment agents is low, so that particle aggregation occurs at high temperatures (particle dispersibility decreases) and the surface treatment agent itself is colored. As a result, the transmittance is lowered, which may cause a problem in heat resistance.
Furthermore, when sealed with dimethyl silicone resin, which has a low light extraction efficiency from the LED, the brightness is low even when the light bulb structure is hermetically sealed or the light reflection plate of the LED package is plated with high corrosion resistance. There was a problem that the cost was high.

On the other hand, phenyl (or methylphenyl) silicone resin has lower gas permeability (higher gas barrier properties) than dimethyl silicone resin, but these characteristics depend on the amount of phenyl groups that can be introduced, and the introduction amount is also limited. was there.

Further, when the surface treatment agent has an epoxy group or excessively unreacted vinyl groups remain in the composite, there is a problem that the composite is yellowed when a thermal load is applied. In addition, if the consistency between the surface treatment agent and the silicone resin is insufficient, the gas barrier property cannot be improved, or particle agglomeration occurs during heat load (particle dispersibility decreases), resulting in a decrease in transmittance. There was also a problem that.

The present invention has been made in order to solve the above-described problems. Specifically, the present invention has a high heat resistance when used in a sealing material for an optical semiconductor light emitting device (that is, at the time of heat load). A surface-modified metal oxide particle material that is capable of exhibiting high transparency and gas barrier properties, and that has reduced coloration and reduced transmittance due to particle aggregation during heat load) Dispersion liquid containing material, silicone resin composition and silicone resin composite, and device that reduces gas permeability of sealing material and uses this gas when the silicone resin composite is used as a sealing material An object of the present invention is to provide an optical semiconductor light-emitting device capable of suppressing deterioration of the light, a lighting fixture including the optical semiconductor light-emitting device, and a liquid crystal image device.

As a result of intensive studies in order to solve the above problems, the present inventors have made a cross-linking reaction with at least a phenyl group and a functional group in a silicone resin with respect to metal oxide particles having an average primary particle diameter in a predetermined range. The present inventors have found that the problem can be solved by using a surface-modified metal oxide particle material obtained by surface modification with a surface-modifying material having a group capable of being treated. Specifically, by using a silicone resin composite containing the surface-modified metal oxide particle material in a specific silicone resin as a sealing material for a light emitting element in an optical semiconductor light emitting device, light transmission from the light emitting element is achieved. The present inventors have found that the gas permeability of the sealing layer can be further reduced without impairing the properties, and have arrived at the present invention.
That is, the present invention is as follows.

[1] For metal oxide particles having an average primary particle diameter of 3 nm or more and 10 nm or less, surface modification is performed with a surface modification material having at least a phenyl group and a group capable of crosslinking reaction with a functional group in a silicone resin forming component. Performed surface modified metal oxide particle material.
[2] The surface-modified metal oxide particle material according to [1], wherein the group capable of undergoing a crosslinking reaction with the functional group in the silicone resin-forming component is an alkenyl group.
[3] The surface-modified metal oxide particle material according to [1], wherein the group capable of undergoing a crosslinking reaction with the functional group in the silicone resin-forming component is a hydrogen group.
[4] The surface-modified metal oxide particle material according to [1], wherein the functional group and the group capable of undergoing a crosslinking reaction in the silicone resin-forming component are an alkenyl group and a hydrogen group.
[5] A dispersion containing the surface-modified metal oxide particle material according to any one of [1] to [4].
[6] The surface-modified metal oxide particle material according to [1], and a silicone resin-forming component containing at least one selected from a phenylsilicone resin-forming component and a methylphenylsilicone resin-forming component, A silicone resin composition in which a resin-forming component has a functional group capable of undergoing a crosslinking reaction with a group of a surface modification material used for the surface-modified metal oxide particle material.
[7] The surface-modified metal oxide particle material according to [2], and a silicone resin-forming component containing at least one selected from a phenylsilicone resin-forming component and a methylphenylsilicone resin-forming component, A silicone resin composition in which the resin-forming component has a hydrogen group.
[8] The surface-modified metal oxide particle material according to [3] and a silicone resin-forming component containing at least one selected from a phenylsilicone resin-forming component and a methylphenylsilicone resin-forming component, A silicone resin composition having at least one resin-forming component selected from alkenyl groups and alkynyl groups.
[9] The surface-modified metal oxide particle material according to [4], and a silicone resin-forming component containing at least one selected from a phenylsilicone resin-forming component and a methylphenylsilicone resin-forming component, A silicone resin composition wherein the resin-forming component is one or more selected from an alkenyl group and an alkynyl group, and a hydrogen group.
[10] The silicone resin composition according to any one of [6] to [9], which contains 5% by mass or more of the metal oxide particles.
[11] The silicone resin composition according to any one of [6] to [10], further comprising a hydrosilylation catalyst.
[12] A silicone resin composite obtained by curing the silicone resin composition according to any one of [6] to [11].
[13] An optical semiconductor light emitting device in which a semiconductor light emitting element is sealed with a sealing material,
An optical semiconductor light emitting device, wherein the sealing material is made of the silicone resin composite according to [12], and a sealing layer made of the sealing material has a thickness of 50 μm or more.
[14] A lighting fixture comprising the optical semiconductor light-emitting device according to [13].
[15] A liquid crystal image device comprising the optical semiconductor light emitting device according to [13].

According to the present invention, when used as a sealing material for an optical semiconductor light emitting device, etc., high heat resistance (that is, coloring during heat load and decrease in transmittance due to particle aggregation during heat load is suppressed. A surface-modified metal oxide particle material capable of exhibiting higher transparency and gas barrier properties, a dispersion containing the surface-modified metal oxide particle material, a silicone resin composition and a silicone resin composite, and When this silicone resin composite is used as a sealing material, the gas permeability of the sealing material can be reduced, deterioration of the device due to the permeated gas can be suppressed, and light with excellent transparency and heat resistance A semiconductor light-emitting device, a lighting fixture including the optical semiconductor light-emitting device, and a liquid crystal image device can be provided.

It is sectional drawing which shows typically one Embodiment of the optical semiconductor light-emitting device of this invention. It is sectional drawing which shows typically other embodiment of the optical semiconductor light-emitting device of this invention.

Hereinafter, the present invention will be described in detail.
[1. Surface-modified metal oxide particle material]
The surface-modified metal oxide particle material in the present invention has a surface modified by a surface-modified material having at least a phenyl group and a group capable of undergoing a crosslinking reaction with a functional group in the silicone resin-forming component with respect to a metal oxide particle having a specific particle size. It is modified. The “silicone resin forming component” will be described later.
(Metal oxide particles)
The type of metal oxide particles is not particularly limited, but a type capable of obtaining a nanometer size particle diameter from the viewpoint of maintaining transparency such as a sealing material is preferable, and zinc oxide, zirconium oxide, titanium oxide, Silicon (silica), aluminum oxide, etc. are mentioned. In addition, when considering increasing the light extraction efficiency from the optical semiconductor light emitting device using the sealing material by increasing the refractive index of the sealing material or the like, the metal oxide particles The refractive index is preferably 1.5 or more, more preferably 1.7 or more, and even more preferably 1.9 or more. As such metal oxide particles, titanium oxide and zirconium oxide (zirconia) are preferable, and zirconia is particularly preferable.
In this specification, the expression “X to Y” (X and Y are arbitrary numbers) means “X or more and Y or less” unless otherwise specified.

The average primary particle diameter of the metal oxide particles is 3 to 10 nm. If the average primary particle size is less than 3 nm, the crystallinity is deteriorated, the surface activity is strong, and the interaction between particles is generated to increase the viscosity of the silicone resin composition. On the other hand, when the average primary particle size is larger than 10 nm, the transmittance is significantly reduced due to scattering because the difference in refractive index between the metal oxide and the silicone resin containing the surface modifying material is large.
The average primary particle diameter is preferably 4 nm to 8 nm, and more preferably 4 nm to 6 nm.

(Surface modification material)
The surface modifying material used for the surface modification of the metal oxide particles includes at least a phenyl group and a group capable of undergoing a crosslinking reaction with a functional group in the silicone resin forming component (hereinafter, sometimes simply referred to as “crosslinking reactive group”). Contains. Here, “a functional group in the silicone resin can undergo a crosslinking reaction” means that a silicone resin-forming component described later that forms a silicone resin reacts with a functional group contained in the silicone resin-forming component in the process of polymerization and curing. This means that the surface-modified metal oxide particle material and the silicone resin can be integrated after curing. Examples of the crosslinking reaction include hydrosilylation reaction, condensation reaction, reaction of hydroxyl group with epoxy group or isocyanate group, and the like as crosslinking reaction groups used for these crosslinking reactions include hydrogen group, alkenyl group, An alkynyl group, a hydroxyl group, an epoxy group, an isocyanate group, etc. are mentioned.
As the crosslinking reaction, a hydrosilylation reaction is preferable in that water is not generated as a by-product and coloring caused by a crosslinking reactive group is suppressed. Examples of the crosslinking reactive group to be subjected to the hydroxylation reaction include an alkenyl group, an alkynyl group, and a hydrogen group, and an alkenyl group and a hydrogen group are particularly preferable.
In the present invention, the “hydrogen group” means hydrogen (H in Si—H bond) directly bonded to a silicon atom in an organosilicon compound.

First, the case where the crosslinking reactive group of the surface modifying material is an alkenyl group will be described.
In this case, the surface modifying material may contain both a phenyl group and an alkenyl group in one material, and both the surface modifying material containing a phenyl group and the surface modifying material containing an alkenyl group may be used. It may be used in combination.
Further, for the purpose of uniformly dispersing and stabilizing the surface-modified metal oxide particle material in the silicone resin composite or composition, a surface-modifying material having another structure may be used in combination.

The reason for the inclusion of phenyl groups in the surface modification material is to ensure interfacial affinity with the matrix phenylphenyl resin and methylphenylsilicone resin (hereinafter sometimes referred to as “(methyl) phenylsilicone resin”). And the surface-modified metal oxide particles and the (methyl) phenyl silicone resin are in close proximity by the π-π stacking of the phenyl group of the surface modifying material and the phenyl group of the (methyl) phenyl silicone resin. This is because the inside gap can be reduced and gas permeability can be suppressed.

The reason for adding an alkenyl group to the surface modifying material is that when the silicone resin composition is polymerized and cured, the alkenyl group in the surface modifying material and the hydrogen group in the silicone resin forming component that becomes the matrix (directly added to the Si of the siloxane polymer). H (hydrogen)) can be bonded to each other by a crosslinking reaction (hydrosilylation reaction), and phase separation between the surface-modified metal oxide particle material and the matrix silicone resin can be prevented in the polymerization curing process. It is. In addition, the surface-modified metal oxide particle material and the matrix silicone resin undergo a cross-linking reaction so that the surface-modified metal oxide particle material and the matrix silicone resin are close to each other, and the gap in the silicone resin composite can be reduced. This is because the permeability of the film can be suppressed.
Furthermore, by using a surface-modifying material with excellent heat resistance, it is possible to suppress a decrease in transmittance due to the occurrence of particle aggregation (decrease in particle dispersibility) or coloring of the surface treatment agent itself at high temperatures. Therefore, the gas permeability can be suppressed without impairing the heat resistance of the matrix silicone resin. Here, excellent heat resistance means that there is no change in the surface modification structure after the thermal load test (150 ° C., 1000 hours) (that is, the surface-modified metal oxide particle material in the resin composition depends on the thermal load). This means that the dispersibility is changed by agglomeration and that the surface modifying material in the resin composition or the resin composite is not colored by a heat load), and the same applies to the following.

The surface modifying material containing a phenyl group is not particularly limited as long as it contains a phenyl group in the structure. However, the material having a structure represented by the following formulas (1) and (2) and the phenyl group and alkoxy Examples thereof include a silicone material having a resin structure (three-dimensional network structure) containing a group.

(In the formula (1), n is an integer of 1 to 3. X is selected from a methoxy group, an ethoxy group, a hydroxyl group, a halogen atom, and a carboxy group. When 4-n is 2 or more, all Xs are May be the same or different.)

(In the formula (2), a is an integer of 1 to 100, b is an integer of 0 to 100, and c is an integer of 1 to 3. A, B, C, and D are phenyl groups or carbon numbers. 1 to 2 or more selected from 1 to 6 alkyl groups, and at least one of A and B is a phenyl group, and all of A, B, C and D may be a phenyl group. The position and arrangement of the site composed of Si, A, B, and O and the site composed of Si, C, D, and O are arbitrary, and are a random polymer type, where X is a methoxy group, an ethoxy group, When selected from a hydroxyl group, a halogen atom, and a carboxy group and c is 2 or more, all Xs may be the same or different.

Specific examples include phenyltrimethoxysilane, diphenyldimethoxysilane, alkoxy piece-terminated phenyl silicone, alkoxy piece-terminated methylphenyl silicone, alkoxy group-containing phenyl silicone resin, alkoxy group-containing methyl phenyl silicone resin, and the like. Examples of the surface modifying material containing a phenyl group include phenyl group-containing organic acid compounds such as benzoic acid, methyl benzoate, toluic acid, and phthalic acid.
Among these, from the viewpoint of excellent heat resistance, phenyltrimethoxysilane, diphenyldimethoxysilane, alkoxy piece-terminated phenyl silicone, alkoxy piece-terminated methylphenyl silicone, alkoxy group-containing phenyl silicone resin resin, alkoxy group-containing methyl phenyl Silicone resin resins are preferred.

The surface modifying material containing an alkenyl group is not particularly limited as long as it contains an alkenyl group in the structure, and examples thereof include materials having structures represented by the following formulas (3) and (4).

(In the formula (3), n is an integer of 0 or more, and m is an integer of 1 to 3. X is selected from a methoxy group, an ethoxy group, a hydroxyl group, a halogen atom, and a carboxy group, and m is 2 or more. In this case, all Xs may be the same or different.)

(In the formula (4), n is an integer of 1 to 100, and m is an integer of 1 to 3. X is selected from a methoxy group, an ethoxy group, a hydroxyl group, a halogen atom, and a carboxy group, and m is 2) In the above case, all Xs may be the same or different.)

Specific examples include vinyltrimethoxysilane and alkoxy piece-end vinyl piece-end dimethyl silicone. Other surface modifying materials containing an alkenyl group include materials having a branched hydrocarbon chain of the formula (3), materials having an alkenyl group on the branched hydrocarbon chain, methacryloxypropyltrimethoxysilane, acryloxy Examples thereof include acrylic silane coupling agents such as propyltrimethoxysilane, and carbon-carbon unsaturated bond-containing fatty acids such as methacrylic acid.
Among these, from the viewpoint of excellent heat resistance, vinyltrimethoxysilane, alkoxy-terminated vinyl-terminated dimethylsilicone, a structure in which the hydrocarbon chain of formula (3) is branched, and alkenyl on the branched hydrocarbon chain. Materials having a structure containing groups are preferred.

The surface modifying material containing both a phenyl group and an alkenyl group is not particularly limited as long as it contains both a phenyl group and an alkenyl group in the structure, but it is represented by styryltrimethoxysilane or formula (5). Examples thereof include alkoxy one-end vinyl one-end phenyl silicone, alkoxy one-end vinyl one-end methyl phenyl silicone, and the like. These are uniformly excellent in heat resistance.

(In the formula (5), a is an integer of 1 to 100, b is an integer of 0 to 100, and c is an integer of 1 to 3. A, B, C, and D are phenyl groups or carbon numbers. 1 to 2 or more selected from 1 to 6 alkyl groups, and at least one of A and B is a phenyl group, and all of A, B, C and D may be a phenyl group. The position and arrangement of the site composed of Si, A, B, and O and the site composed of Si, C, D, and O are arbitrary, and are a random polymer type, where X is a methoxy group, an ethoxy group, When selected from a hydroxyl group, a halogen atom, and a carboxy group and c is 2 or more, all Xs may be the same or different.

Next, the case where the crosslinking reactive group of the surface modifying material is a hydrogen group will be described. In the present invention, the “hydrogen group” means hydrogen (H in Si—H bond) directly bonded to a silicon atom in an organosilicon compound. Further, the hydrogen group may be expressed as “Si—H group”.
In this case, the surface modifying material may contain both a phenyl group and a hydrogen group in one material, and the surface modifying material containing the phenyl group and the surface modifying material containing the hydrogen group A combination of both may be used.
Further, for the purpose of uniformly dispersing and stabilizing the surface-modified metal oxide particle material in the silicone resin composite or composition, a surface-modifying material having another structure may be used in combination.

The reason for including a phenyl group in the surface modifying material is as described above.
The reason for adding a hydrogen group to the surface modifying material is that when the silicone resin composition is polymerized and cured, the hydrogen group of the surface modifying material and the alkenyl group or alkynyl group in the silicone resin forming component that becomes the matrix are crosslinked. This is because they can be bonded by (hydrosilylation reaction) and phase separation of the surface-modified metal oxide particle material and the matrix silicone resin can be prevented in the polymerization and curing process. In addition, the surface-modified metal oxide particle material and the matrix silicone resin undergo a cross-linking reaction so that the surface-modified metal oxide particle material and the matrix silicone resin are close to each other, and the gap in the silicone resin composite can be reduced. This is because the permeability of the film can be suppressed. The “resin forming component” will be described later.

In this way, by incorporating phenyl groups and hydrogen groups into the surface modifying material, the consistency between the surface modifying material and the matrix silicone resin including the (methyl) phenyl silicone resin is improved and integrated. Further, it is possible to suppress a decrease in transmittance due to particle aggregation during heat load. Further, since it is not necessary to have an epoxy group or a vinyl group, the cause of coloring itself at the time of heat load can be removed. Furthermore, the phenyl group itself has high heat resistance. As described above, the surface treatment material in the present invention has high heat resistance.
And since the consistency of the surface modification material and the matrix silicone resin is improved and integrated, the gas barrier property is also high.
Thus, by using a surface modifying material having excellent heat resistance, gas permeability can be suppressed without impairing the heat resistance of the matrix silicone resin.

The surface modifying material containing a phenyl group is as described above.
The surface modifying material containing a hydrogen group is not particularly limited as long as it contains a hydrogen group (Si—H bond) in the structure. For example, triethoxysilane, dimethylethoxysilane, diethoxymethylsilane , Dimethylchlorosilane, ethyldichlorosilane, and the like.
Of these, triethoxysilane, dimethylethoxysilane, and diethoxymethylsilane are preferable from the viewpoint of excellent heat resistance.

The surface modifying material containing both a phenyl group and a hydrogen group is not particularly limited as long as the structure contains a phenyl group and a hydrogen group (Si—H bond), but the following formula (6) And a material having a structure represented by the formula (7) and a silicone material having a resin structure (three-dimensional network structure) containing a phenyl group and an alkoxy group and further containing hydrogen directly bonded to silicon.

(In Formula (6), n and m are 1 or 2, and the sum of n and m is 3 or less. X is selected from a methoxy group, an ethoxy group, a hydroxyl group, a halogen atom, and a carboxy group, and 4 When -nm is 2 (when n = m = 1), the two Xs may be the same or different.)

(In the formula (7), a is an integer of 1 to 100, and b is an integer of 0 to 100. A, B, C, and D are a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a hydrogen group. And at least one of A and B is a phenyl group, and all of A, B, C, and D may be a phenyl group. The position and arrangement of the site composed of O and the site composed of Si, C, D, and O are arbitrary and are a random polymer type, where X is a methoxy group, an ethoxy group, a hydroxyl group, a halogen atom, and When X is selected from a carboxy group and c is 2 or more, all Xs may be the same or different, and when at least one of A, B, C and D is a hydrogen group, c is An integer from 1 to 3, d is an integer from 0 to 2, and c And when A, B, C, and D do not contain a hydrogen group, c and d are 1 or 2, and the sum of c and d is 3 or less. is there.)

Specific examples include phenyldichlorosilane, diphenylchlorosilane, phenylchlorosilane, and phenyldiethoxysilane.

In addition, in the silicone resin composition and silicone resin composite described later, as other surface modification materials used in combination for the purpose of uniformly dispersing and stabilizing the metal oxide particles, alkoxy piece-terminated dimethyl silicone, alkoxy piece Examples include terminal vinyl one-end dimethyl silicone, one-end epoxy silicone, alkylsilane compound, fatty acid compound, and the like.

Next, the case where the crosslinking reactive group of the surface modifying material is a hydrogen group and an alkenyl group will be described.
In this case, the surface modifying material may contain three types of groups, phenyl group, hydrogen group and alkenyl group, in one surface modifying material, and those containing two types of these three types. And those containing other one type of group may be used together, or those containing three types of groups may be used in combination.
That is, in the present invention, after surface modification with a surface modification material having at least a phenyl group and an alkenyl group, or simultaneously with the surface modification, the surface modification may be performed with a surface modification material having a hydrogen group. . Further, after surface modification with a surface modification material having at least a phenyl group and a hydrogen group, or simultaneously with the surface modification, the surface modification may be performed with a surface modification material having an alkenyl group (or alkynyl group). . Thus, both the hydrogen group and the alkenyl group (or alkynyl group) can be modified and supported on the surface of the metal oxide particle.
The surface modifying material having an alkenyl group and the surface modifying material having a hydrogen group are as described above.
Further, for the purpose of uniformly dispersing and stabilizing the surface-modified metal oxide particle material in the silicone resin composite or composition, a surface-modifying material having another structure may be used in combination.

As described above, when the silicone resin composition is polymerized and cured, the alkenyl group in the surface modifying material may be bonded and integrated with the hydrogen group in the matrix silicone resin forming component by a crosslinking reaction (hydrosilylation reaction). it can. In addition, the hydrogen group in the surface modifying material is bonded and integrated with the alkenyl group or alkynyl group in the matrix silicone resin forming component by a crosslinking reaction (hydrosilylation reaction) when the silicone resin composition is polymerized and cured. Can do. This bonding action prevents phase separation between the surface-modified metal oxide particle material and the matrix silicone resin during the polymerization curing process, and the surface-modified metal oxide particle material and the matrix silicone resin are brought close to each other to form a silicone resin composite. The inside gap can be reduced, and the gas permeability can be suppressed.
By the way, the curing of the matrix silicone resin forming component is preferably selected as an addition curing type as described later. This addition curing is an addition reaction (hydrosilylation reaction) of a hydrogen group arranged in a siloxane polymer in a silicone resin forming component and an alkenyl group (or alkynyl group) in the siloxane polymer by a platinum group metal catalyst. ) Is cured by polymerization. Therefore, the matrix silicone resin-forming component contains at least a silicone resin-forming component containing a hydrogen group and a silicone resin-forming component containing an alkenyl group (or alkynyl group).
Therefore, the alkenyl group (or alkynyl group) and the hydrogen group are both modified and supported on the surface of the metal oxide particle to crosslink the alkenyl group on the surface of the metal oxide particle and the hydrogen group in the matrix silicone resin forming component. In addition to the reaction, the hydrogen group on the surface of the metal oxide particles and the alkenyl group (or alkynyl group) in the matrix silicone resin forming component can also undergo a cross-linking reaction, so the metal oxide particles and the matrix silicone resin can be more integrated. be able to.

If excessive alkenyl groups or alkynyl groups remain in the silicone resin composite, coloring may occur during heat load. Therefore, it is preferable that the alkenyl group and alkynyl group contained in the silicone resin composition are consumed as much as possible by a hydrosilylation reaction with a hydrogen group. Therefore, the total amount of hydrogen groups contained in the silicone resin composition is preferably not less than the total amount of alkenyl groups and alkynyl groups and the amount capable of hydrosilylation reaction, which is 1.2 times or more (that is, the hydrogen groups are present). (Excess state) is more preferable. Here, the total amount means the total amount of the amount in the surface modifying material and the amount in the matrix silicone resin forming component.

Examples of the surface modification method for the metal oxide particles using the surface modification material include a wet method and a dry method. In the wet method, metal oxide particles and surface modifying material are added to the solvent, and if necessary, a catalyst for hydrolyzing the surface modifying material is added. Among them, a method of dispersing while surface-modifying is mentioned. The dry method includes a method in which the metal oxide particles and the surface modification material are mixed with a kneader or the like to obtain the surface modification metal oxide particles.

The surface modification amount of the surface modification material with respect to the metal oxide particles (surface modification material / metal oxide particles) is preferably 5 to 40% by mass. If the amount of surface modification is within this range, the dispersibility of the surface-modified metal oxide particle material in the silicone resin described later can be maintained high, and a decrease in transparency and gas permeability can be suppressed.
The surface modification amount is more preferably 10 to 30% by mass.
The surface modification amount is calculated by heat treating the surface-modified metal oxide particles after drying at 150 ° C. at 750 ° C., and calculating the mass reduction amount after the heat treatment as the mass of the surface modification material.

[2. Dispersion]
The dispersion of the present invention is obtained by dispersing the surface-modified metal oxide particle material of the present invention in a dispersion medium. According to the dispersion liquid of the present invention, the surface-modified metal oxide particle material of the present invention is dispersed in a dispersion medium. Therefore, when this is combined with the matrix silicone resin forming component, the surface-modified metal oxide Can be dispersed in a uniform and good dispersion state in the matrix silicone resin forming component, so that the silicone resin composition excellent in moldability and processability and excellent in transparency, and further cured. A silicone resin composite can be obtained.

The content of the particulate material in the dispersion of the present invention is preferably 5% by mass or more and 50% by mass or less. By setting the content rate of the particulate material within this range, the particulate material can be in a good dispersion state. The content of the particulate material is more preferably 10% by mass or more and 30% by mass.

The dispersion medium may be any solvent that can disperse the particulate material. For example, water; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, octanol; ethyl acetate, butyl acetate, lactic acid Esters such as ethyl, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyllactone; diethyl ether, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (Butyl cellosolve), ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; acetone, methyl ethyl , Ketones such as methyl isobutyl ketone, acetylacetone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and ethylamide; amides such as dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone are preferred. One or two or more of these solvents can be used.

In addition, the dispersion of the present invention contains a dispersant, a surface treatment agent, a water-soluble binder, etc. (dispersant, etc.) as long as the properties thereof are not impaired in order to improve the dispersibility of the particulate material and the stability of the dispersion. You may go out.
Dispersants and surface treatment agents include cationic surfactants, anionic surfactants, nonionic surfactants, silane coupling agents such as organoalkoxysilanes and organochlorosilanes, polyethyleneimine polymer dispersants, polyurethane-based agents Polymer dispersants such as polymer dispersants and polyallylamine polymer dispersants are preferably used, and these dispersants and surface treatment agents are appropriately selected depending on the particle diameter of the composite fine particles and the type of the desired dispersion medium. What is necessary is just to use 1 type, or 2 or more types of the said dispersing agent in mixture. As the water-soluble binder, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), hydroxycellulose, polyacrylic acid, or the like can be used.
As a blending amount in the dispersion, the total amount of the dispersant and the like (solid content) is preferably in the range of 1 to 15% by mass, more preferably in the range of 2 to 10% by mass with respect to the particulate material. preferable.

As a method for performing the dispersion treatment, a known dispersion apparatus can be used alone or in combination. For example, a bead mill, a nanomizer, a jet mill, a homogenizer, a planetary mill, an ultrasonic disperser or the like can be used alone or in combination. Can be used. Among these, a bead mill that can easily control the dispersed particle diameter by selecting the bead diameter is preferably used. The time required for the dispersion treatment may be sufficient as long as the particulate material is uniformly dispersed in the dispersion medium.

[3. Silicone resin composition]
The silicone resin composition of the present invention comprises at least a surface-modified metal oxide particle material of the present invention as described above, and a silicone resin forming component containing at least one selected from a phenyl silicone resin forming component and a methylphenyl silicone resin forming component And the silicone resin-forming component has a functional group capable of undergoing a crosslinking reaction with a group of the surface modifying material used for the surface modified metal oxide particle material.
Here, the “resin composition” has fluidity and does not have a specific shape, and has irreversible deformability that does not return to the original shape once deformed. It becomes a raw material of a simple resin composite. As a state of this resin composition, what is in the gel state which has liquid state and thixotropy property can be shown, for example. The “resin-forming component” is a component for forming a resin component in a resin composite described later, and usually includes a resin component monomer, oligomer, or prepolymer that is liquid.

Here, as the silicone resin-forming component used in the silicone resin composition of the present invention, the surface-modified metal oxide particles contain at least one selected from a phenylsilicone resin-forming component and a methylphenylsilicone resin-forming component. The surface modifying material used for the material is not particularly limited as long as it has a functional group capable of crosslinking reaction with a group (crosslinking reaction group). On the other hand, as described above, a hydrosilylation reaction is preferable as the crosslinking reaction, and an alkenyl group and a hydrogen group are preferable as the crosslinking reaction group used for the hydrosilylation reaction. From this, the following can be mentioned as a suitable combination of the surface modified metal oxide particle material and the silicone resin-forming component.
(1) When the crosslinking reactive group in the surface-modified metal oxide particle material is an alkenyl group: a silicone resin-forming component having a hydrogen group.
(2) When the crosslinking reactive group in the surface-modified metal oxide particle material is a hydrogen group: a silicone resin-forming component having at least one selected from an alkenyl group and an alkynyl group.
(3) When the crosslinking reactive group in the surface-modified metal oxide particle material is an alkenyl group and a hydrogen group: a silicone resin-forming component having one or more selected from an alkenyl group and an alkynyl group, and a hydrogen group.

The content of the metal oxide particles with respect to the total amount of the surface-modified metal oxide particles and the silicone resin-forming component in the silicone resin composition is 5% by mass or more. When the content is less than 5% by mass, the gas permeability reduction effect in the silicone resin composite obtained by curing the resin composition is reduced, so that a substantial effect by including metal oxide particles is obtained. It will not be possible. The content is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. Here, the content of the metal oxide particles does not include a surface modifying material.

(Silicone resin forming component)
The silicone resin-forming component contains one or more selected from a phenyl silicone resin-forming component and a methylphenyl silicone resin-forming component.
Examples of the phenyl silicone resin-forming component include those in which a phenyl group is arranged on a siloxane polymer. Examples of the methylphenyl silicone resin forming component include those in which a phenyl group and a methyl group (alkyl group) are arranged on a siloxane polymer. In addition, there are modified silicone resins in which a siloxane structure having a phenyl group and an epoxy group or other hydrocarbon are combined. In addition to the straight chain, the structure includes a two-dimensional chain, a three-dimensional network resin, and a cage structure.
The phenyl silicone resin forming component and the methyl phenyl silicone resin forming component may be used alone or in combination (hereinafter, the phenyl silicone resin forming component, the methyl phenyl silicone resin forming component and the combination of both components are combined. (Sometimes referred to as “(methyl) phenyl silicone resin forming component”). Moreover, you may combine what has the above various structures, and also may add the above modified silicone resins.

First, the silicone resin-forming component having a hydrogen group contains one or more selected from the phenyl silicone resin-forming component and the methylphenyl silicone resin-forming component, and further has a hydrogen group. The hydrogen group means H (hydrogen) directly bonded to Si of the siloxane polymer constituting the silicone resin forming component, that is, H (hydrogen) in the Si—H bond. Further, the hydrogen group may be expressed as “Si—H group”.
Here, the silicone resin forming component may contain other silicone resin forming components in addition to the (methyl) phenyl silicone resin forming component. That is, the silicone resin-forming component in the present invention has a hydrogen group means that a (methyl) phenyl silicone resin-forming component may contain a hydrogen group, and other silicone resin-forming components have a hydrogen group. Group may be contained (this silicone resin-forming component may be referred to as “hydrogen silicone resin-forming component”), and further, both of them may contain a hydrogen group. .

According to this silicone resin composition, the hydrogen group in the silicone resin forming component is integrated by cross-linking reaction with the alkenyl group of the surface modifying material, thereby integrating the surface modified metal oxide particle material and the matrix in the polymerization curing process. Phase separation from the silicone resin can be prevented, and furthermore, the close proximity of the surface-modified metal oxide particle material and the matrix silicone resin can reduce gaps in the silicone resin composite and suppress gas permeability.

Examples of those containing a hydrogen group in the (methyl) phenyl silicone resin forming component include those in which at least a phenyl group and a hydrogen group are arranged in one siloxane polymer. And if it satisfy | fills this condition, the phenyl group and the hydrogen group may be arbitrarily arranged in one siloxane polymer. It is preferable from the viewpoint of polymerization reactivity that two or more hydrogen groups are arranged in one siloxane polymer.

On the other hand, examples of the hydrogen silicone resin forming component include those in which a part of the group bonded to Si of the siloxane polymer is hydrogen (hydrogen group: Si—H bond). It is preferable from the viewpoint of polymerization reactivity that two or more hydrogen groups are arranged in one siloxane polymer. In addition, as a group other than a hydrogen group bonded to Si, an alkyl group such as a methyl group is generally used, but a modified silicone combined with an epoxy group or other hydrocarbon may be used, and the structure is straightforward. In addition to the chain shape, a two-dimensional chain structure, a three-dimensional network structure, a cage structure, or the like may be used.

Next, the silicone resin-forming component having one or more selected from the alkenyl group and the alkynyl group contains one or more selected from the phenylsilicone resin-forming component and the methylphenylsilicone resin-forming component. It has one or more groups selected from a group and an alkynyl group.
Here, the silicone resin forming component may contain other silicone resin forming components in addition to the (methyl) phenyl silicone resin forming component. That is, the silicone resin-forming component in the present invention has one or more groups selected from an alkenyl group and an alkynyl group is one type selected from an alkenyl group and an alkynyl group in the (methyl) phenyl silicone resin-forming component. The above groups may be contained, and one or more groups selected from alkenyl groups and alkynyl groups may be contained in other silicone resin forming components (this silicone resin forming component is referred to as “ It is sometimes referred to as “alkenyl / alkynyl group-containing silicone resin-forming component”), and it means that one or more groups selected from alkenyl groups and alkynyl groups may be contained in both of them.

According to this silicone resin composition, the alkenyl group or alkynyl group of the silicone resin-forming component and the hydrogen group of the surface modification material are combined and integrated by a crosslinking reaction (hydrosilylation reaction), thereby in the polymerization curing process. The phase separation between the surface-modified metal oxide particle material and the matrix silicone resin is prevented, and furthermore, the close proximity between the surface-modified metal oxide particle material and the matrix silicone resin reduces the gap in the silicone resin composite, Permeability can be suppressed.

Examples of the component having one or more groups selected from alkenyl groups and alkynyl groups in the (methyl) phenyl silicone resin forming component are selected from at least phenyl groups, alkenyl groups and alkynyl groups in one siloxane polymer. And one or more groups that are arranged. As long as this condition is satisfied, one siloxane polymer may be arbitrarily arranged with a phenyl group and one or more groups selected from an alkenyl group and an alkynyl group. From the viewpoint of polymerization reactivity, two or more alkenyl groups and alkynyl groups are preferably arranged in one siloxane polymer.

Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group, and a vinyl group is particularly preferable. Examples of the alkynyl group include ethynyl group and propargyl group (propynyl group). These alkenyl groups and alkynyl groups can be arbitrarily combined. For example, one in which a phenyl group and a vinyl group are arranged in one siloxane polymer is general, but is not limited thereto, and one siloxane polymer has a phenyl group, a vinyl group (alkenyl group), and an ethynyl group. (Alkynyl group) may be arranged. Alternatively, a combination of a phenyl group and a vinyl group (alkenyl group) arranged in one siloxane polymer and a phenyl group and ethynyl group (alkynyl group) arranged in another siloxane polymer may be used.

Examples of the alkenyl / alkynyl group-containing silicone resin forming component include those in which one or more groups selected from alkenyl groups and alkynyl groups are arranged on a siloxane polymer. There is no particular limitation on the position of the alkenyl group or alkynyl group in the siloxane polymer, and the alkenyl group or alkynyl group can be arranged at any position. From the viewpoint of polymerization reactivity, 2 alkenyl groups or alkynyl groups are present in one siloxane polymer. It is preferable that at least one is arranged. Further, it may be a modified silicone combined with an epoxy group or another hydrocarbon. Examples of the molecular structure include a straight chain, a partially branched chain, a branched chain, a ring, and a resin. Particularly, a linear or partially branched chain It is preferable that.
The combination of the alkenyl group and the alkynyl group is arbitrary as in the case of having one or more groups selected from the alkenyl group and the alkynyl group in the (methyl) phenyl silicone resin-forming component. Absent. Furthermore, for example, a phenyl silicone resin-forming component having an alkenyl group may be combined with an alkenyl group-containing silicone resin-forming component having an alkynyl group.

The silicone resin forming component having one or more selected from the alkenyl group and alkynyl group and the hydrogen group is selected from the silicone resin forming component having the hydrogen group, and the alkenyl group and alkynyl group. A combination of silicone resin forming components having one or more of the above. The combination and arrangement of one or more selected from alkenyl groups and alkynyl groups in the silicone resin-forming component and hydrogen groups are arbitrary, for example, one selected from alkenyl groups and alkynyl groups in one siloxane polymer. A silicone resin-forming component having one or more selected from alkenyl groups and alkynyl groups and a silicone resin-forming component having a hydrogen group may be used. It may be a mixture.

The silicone resin composition of the present invention contains at least a (methyl) phenyl silicone resin-forming component as a resin component, and a functional group capable of undergoing a crosslinking reaction with a group of the surface modification material used for the surface modification metal oxide particle material In some cases, a silicone resin-forming component necessary for forming a matrix silicone resin is included. The combination of each component is not particularly limited as long as each component has compatibility.

The refractive index and viscosity of the uncured (methyl) phenyl silicone resin forming component and the silicone resin forming component having a functional group capable of crosslinking reaction are determined by the structure and chain length of the siloxane polymer, the phenyl group and the alkyl group in the siloxane polymer. It changes depending on the amount, the number of carbons, etc., and these characteristic values are also reflected in the cured silicone resin. Therefore, by mixing and adjusting a plurality of resin-forming components in an uncured state, it has a refractive index necessary for a matrix silicone resin after curing, and obtains good moldability and workability in the silicone resin composition. be able to. Furthermore, in addition to the combination of the phenyl silicone resin forming component and the methyl phenyl silicone resin forming component, and the combination of the silicone resin forming component having a functional group capable of crosslinking reaction, the kind and amount of the modified silicone resin to be added are adjusted. Thus, it is possible to control properties such as hardness, tackiness, and adhesion to the substrate of the resulting silicone resin composite.
When it is desired to reduce the viscosity of the silicone resin composition from the viewpoint of moldability and workability, it is compatible with (methyl) phenyl silicone resin forming components and silicone resin forming components having functional groups capable of crosslinking reaction. An organic solvent that does not inhibit the dispersibility of the surface-modified metal oxide particles may be added. Examples of such an organic solvent include a dispersion medium used for the dispersion.

As a liquid (uncured) silicone resin-forming component (matrix silicone resin-forming component) that forms a matrix silicone resin in a cured resin composite, an addition-curable silicone composition or a condensation-curable silicone composition may be used depending on the curing method. Things. The addition-curable silicone composition is a composition comprising a silicone resin-forming component containing at least an alkenyl group and a hydrogen group, and a platinum group metal catalyst, and the alkenyl group and the hydrogen group are added. Silicone resin forming components are polymerized and cured by bonding by reaction (hydrosilylation reaction).
Condensation-curable silicone composition is a silane compound containing at least three hydrolyzable groups bonded to a silicon atom and a silicone resin-forming component whose molecular chain end is blocked with a hydroxyl group or a hydrolyzable group. And a condensation catalyst containing an aminoxy group, an amino group, a ketoxime group, etc., and the hydroxyl group or hydrolyzable group and hydrolyzable group are bonded by causing a condensation reaction such as dehydration. By doing so, the silicone resin-forming component and the silane compound are polymerized and cured. Therefore, the silicone resin-forming component contains at least three silicone resin-forming components whose molecular chain ends are blocked with a hydroxyl group or a hydrolyzable group and three or more hydrolyzable groups bonded to a silicon atom in one molecule. A composition comprising a silane compound and a condensation catalyst containing an aminoxy group, an amino group, a ketoxime group and the like. As described above, a phenyl group or a methyl group (alkyl group) is arranged in these silicone resin forming components.

As the matrix silicone resin forming component in the present invention, either an addition curable type or a condensation curable type may be selected.
On the other hand, in the present invention, the functional group capable of crosslinking reaction of the silicone resin forming component and the crosslinking reactive group (alkenyl group, alkynyl group, hydrogen group) of the surface modifying material are integrated by the crosslinking reaction to modify the surface modification. Phase separation between the metal oxide particle material and the matrix silicone resin can be prevented, and the surface-modified metal oxide particle material and the matrix silicone resin can be brought close to each other to suppress gas permeability. Here, the crosslinking reaction and the addition-curing type addition reaction (hydrosilylation reaction) are the same reaction as can be understood from the reactive group and reaction state. Therefore, if an addition curable type is selected as the matrix silicone resin forming component or reaction catalyst, the integration of the surface-modified metal oxide particle material and the matrix silicone resin by crosslinking and the curing of the matrix silicone resin itself can be performed simultaneously. And since it can carry out by a single reaction method, it is preferable. In addition, since by-products such as water are not generated during polymerization in the case of the addition-curing type, it is also preferable that the influence by the presence of by-products and the removal of by-products become unnecessary.
Further, as described above, if metal oxide particles modified and supported by both alkenyl groups and hydrogen groups are used, the alkenyl groups on the surface of the metal oxide particles and the hydrogen groups in the matrix silicone resin forming component are cross-linked. Not only the reaction but also the hydrogen group on the surface of the metal oxide particle and the alkenyl group (or alkynyl group) in the matrix silicone resin forming component can be cross-linked so that the metal oxide particle and the matrix silicone resin can be more integrated. be able to.

In addition, if the condensation curable type is selected as the matrix silicone resin forming component, there is an advantage that the bonding between the surface-modified metal oxide particle material and the matrix silicone resin and the curing of the matrix silicone resin can be individually controlled. However, in this case, it is necessary to first condense the surface-modified metal oxide particle material and the matrix silicone resin through a cross-linking reaction (same as in the case of addition curing type) and then condense and cure the matrix silicone resin. The reason is that when the matrix silicone resin is cured in a state where the surface-modified metal oxide particle material and the matrix silicone resin are not bonded, aggregation and phase separation of the surface-modified metal oxide particle material occur, which is good. It is because there exists a possibility that a novel silicone resin composite may not be obtained.

(Hydrosilylation catalyst)
In the present invention, the functional group capable of crosslinking reaction of the silicone resin forming component and the crosslinking reactive group of the surface modifying material are integrated by a crosslinking reaction (hydrosilylation reaction). Therefore, the silicone resin composition of the present invention preferably contains a hydrosilylation catalyst.
Examples of the hydrosilylation reaction catalyst in the present invention include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst. In particular, a platinum-based catalyst is preferable because the hydrosilylation reaction proceeds smoothly. Examples of the platinum-based catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, and an alkenylsiloxane complex of platinum.

The blending amount of the hydrosilylation reaction catalyst may be an amount sufficient to cause a crosslinking reaction between the silicone resin-forming component and the crosslinking reactive group-containing surface modifying material. Specifically, when a platinum-based catalyst is used as the hydrosilylation reaction catalyst, the total amount of the silicone resin-forming component containing the alkenyl group or alkynyl group and the surface modification material containing a hydrogen group The amount of platinum metal is preferably such that the mass of platinum metal is 0.1 to 100 ppm, particularly since the hydrosilylation reaction proceeds smoothly and the silicone resin composite obtained by the reaction is less likely to be colored. More preferred is an amount in the range of 1 to 50 ppm.
In addition, when the addition curing type is selected as the matrix silicone resin forming component, the curing of the matrix silicone resin is also caused by the hydrosilylation reaction, so that the amount of the catalyst is preferably increased so as to meet the above conditions. That is, the mass of platinum metal is based on the total amount of the silicone resin-forming component containing an alkenyl group or an alkynyl group, the silicone resin-forming component containing a hydrogen group, and the surface modification material containing a hydrogen group. 0.1 to 100 ppm is preferable, and 1 to 50 ppm is more preferable.
Further, as described above, when metal oxide particles in which both a hydrogen group and an alkenyl group or alkynyl group are modified and supported are used, the alkenyl group or alkynyl group on the surface of the metal oxide particle and the matrix silicone are used. Since the hydrogen group in the resin forming component also undergoes a crosslinking reaction, it is preferable to increase the amount of the catalyst in the same manner. That is, the mass of platinum metal is a silicone resin forming component containing an alkenyl group or an alkynyl group, a silicone resin forming component containing a hydrogen group, a surface modifying material containing a hydrogen group, an alkenyl group or an alkynyl group. The content is preferably 0.1 to 100 ppm, more preferably 1 to 50 ppm, based on the total amount with the surface-modifying material containing.

In order to mix the surface-modified metal oxide particle material and the matrix silicone resin-forming component, a method in which the surface-modified metal oxide particle material is directly introduced into the matrix silicone resin-forming component and mechanically mixed with a kneader or the like, As in the case of the dispersion, the surface-modified metal oxide particle material is dispersed in a dispersion medium such as an organic solvent to form a surface-modified metal oxide particle material dispersion, and the dispersion and the matrix silicone resin-forming component are stirred. And the like, and then the organic solvent is removed.
The silicone resin composition of the present invention can be obtained by mixing both by any of the above methods. In addition, the silicone resin composition of this invention may contain the organic solvent etc. which are used in the said mixing process.

[4. Silicone resin composite]
In the silicone resin composite of the present invention, the matrix silicone resin forming component in the silicone resin composition of the present invention is polymerized and cured by addition reaction or condensation reaction, and the surface modification material of the metal oxide particles and the matrix silicone resin are formed. It is obtained by combining the components with a cross-linking reaction to integrate the surface-modified metal oxide particles and the matrix silicone resin.
Here, “resin composite” has a specific shape, but this “having a predetermined shape” means that the resin composite does not have irreversible deformability such as liquid or gel. This shows that a certain shape can be maintained according to the purpose and method. That is, in addition to a normal solid state that hardly deforms, it includes a rubber-like one having elastic deformability (shape restoring property), and does not indicate that the shape itself is a specific shape.

The shape of the silicone resin composite is not particularly limited, and the shape may be selected according to the application. Here, the silicone resin used in the present invention does not exhibit the thermoplasticity and solvent solubility as shown by general resins after being cured by addition reaction or polymerization reaction. For this reason, the silicone resin composite is preferably molded when the silicone resin composition is cured to form a silicone resin composite, or the cured silicone resin composite is preferably processed by machining such as cutting. Here, a case where molding is performed when the silicone resin composition is cured to form a silicone resin composite will be described.

First, the silicone resin composition of the present invention is molded using a mold or a mold, or filled into a mold or a mold-shaped container, thereby forming a molded body or a filling molded into a target shape. Get things. At this point, the molded body and the filling are in a fluid state.
At this time, when the viscosity of the silicone resin composition to be used is high and the moldability is poor, the viscosity is lowered by adding an organic solvent or the like in advance and stirring and mixing so that the viscosity is suitable for molding and filling. You may adjust it.
On the other hand, when the viscosity of the silicone resin composition to be used is low, a part of the matrix silicone resin forming component or a part of the matrix silicone resin forming component and the surface modifying material may be polymerized or crosslinked in advance. The viscosity can be increased and adjusted to a viscosity suitable for molding and filling. Moreover, when a silicone resin composition contains an organic solvent, a viscosity can also be raised by removing by volatilizing a part or all of this organic solvent. Furthermore, you may mix and use the said silicone resin composition for other resin as a masterbatch.

Next, the molded body or filling is left at room temperature (about 25 ° C.), heated to a predetermined temperature (room temperature to 150 ° C., preferably 80 ° C. to 150 ° C.), and left to stand for a predetermined time, or The matrix silicone resin-forming component in the silicone resin composition is subjected to an addition reaction by irradiating the molded body or filler with an electron beam or light having an arbitrary wavelength from the ultraviolet region to the infrared region (active energy ray). And the surface modification material of the metal oxide particles and the matrix silicone resin forming component are bonded by a crosslinking reaction to integrate the surface modification metal oxide particles and the matrix silicone resin.
In addition, when an organic solvent remains in this molded object or a filling, it is preferable to volatilize and remove this organic solvent beforehand.
Thereby, even if external force is applied after removing this molded object or filling material from a mold or a container, a state where a certain shape can be maintained, that is, a silicone resin composite is obtained.
It should be noted that the silicone resin composite does not necessarily have to be removed from the mold or container if there is no problem in use. For example, in an optical semiconductor light emitting device to be described later, the device itself has a shape in which a container is formed.

When the silicone resin composite of the present invention is used for a sealing material such as an optical semiconductor light emitting device, the refractive index is preferably higher than 1.54, more preferably 1.56 or more, and 1.58. More preferably, it is more preferably 1.6 or more. By increasing the refractive index of the sealing material, the light extraction efficiency from the optical semiconductor light emitting device can be improved and the luminance can be increased.
Further, the transmittance at a wavelength of 450 nm when the optical path length is 0.5 mm is preferably 40% or more, more preferably 60% or more, and further preferably 70% or more. If the transmittance is within this range, for example, when a silicone resin composite is used as an optical component, a decrease in light transmission loss as a component can be suppressed.

The refractive index and transmittance of the silicone resin composite can be adjusted by appropriately adjusting the type and particle diameter of the metal oxide particles, the composition of the matrix silicone resin, the amount of the metal oxide particles in the silicone resin composite, and the like. It can be a range. In the silicone resin composite of the present invention, since the surface modification material of the metal oxide particles has a phenyl group, the refractive index itself is increased, and the surface modification material is used to increase the refractive index of the silicone resin composite. There is no hindrance.
The refractive index of the silicone resin composite may be measured using a known method. For example, a composite (1 mm thickness) formed on an aluminum substrate is used, and a value of a wavelength of 594 nm is measured at room temperature using a prism coupler. It is obtained by measuring. A method for measuring the transmittance will be described later.

The use of the silicone resin composite of the present invention is not particularly limited. In particular, the silicone resin composite can be suitably used as an optical component utilizing the excellent characteristics of the silicone resin composite. Examples of the optical functional device provided with such optical components include various display devices (liquid crystal display, plasma display, etc.), various projector devices (OHP, liquid crystal projector, etc.), optical fiber communication devices (optical waveguide, optical amplifier, etc.), camera, etc. Illuminating devices such as LED lighting devices and the like, and imaging devices such as video and video.

[5. Optical semiconductor light emitting device]
In the optical semiconductor light emitting device of the present invention, the semiconductor light emitting element is sealed with a sealing material, the sealing material is made of the silicone resin composite of the present invention, and the thickness of the sealing layer made of the sealing material. Is 50 μm or more. If the thickness of the sealing layer is less than 50 μm, the gas permeability cannot be suppressed sufficiently low. The thickness of the sealing layer is preferably 100 μm or more, and more preferably 200 μm or more.

In the configuration of the sealing layer according to the present invention, the entire sealing layer of the optical semiconductor light emitting device may be the layer of the silicone resin composite of the present invention (first aspect), and a part of the sealing layer of the optical semiconductor light emitting device. Is a layer of the silicone resin composite of the present invention, and other sealing layers may be laminated (second embodiment). Moreover, you may contain a fluorescent substance in these sealing layers.
Since the optical semiconductor light-emitting device of the present invention is excellent in the gas barrier property of the sealing layer as described above, it is possible to suppress deterioration of a silver-plated reflector provided in, for example, a light-emitting diode (LED) package and to emit radiation from the light-emitting diode package. Since the decrease in light intensity can be reduced while keeping the luminance of light high, it can be effectively used as a lighting fixture or a liquid crystal image device provided with the same.

The said optical semiconductor light-emitting device is demonstrated concretely. In addition, this invention is not specifically limited to the following examples.
As shown in FIG. 1, the first aspect (light emitting device 10) according to the present invention is such that the light emitting element 14 is disposed in the concave portion 12 </ b> A of the reflecting cup 12 and the concave portion is embedded in contact with the light emitting element 14. The 1st sealing layer 16 comprised with the sealing material which consists of this silicone resin composite_body | complex is formed.
According to such an apparatus, the light emitted from the light emitting element 14 passes through the boundary surface with the sealing material, passes through the sealing material, and is reflected directly or by the wall surface of the reflecting cup 12 and is extracted to the outside. It is.

Examples of the light emitting element constituting the light emitting device include a light emitting diode (LED) and a semiconductor laser. Here, as the light emitting diode, a red light emitting diode that emits red light (for example, light having a wavelength of 640 nm), a green light emitting diode that emits green light (for example, light having a wavelength of 530 nm), and blue light (for example, having a wavelength of 450 nm). An example is a blue light emitting diode that emits light). The light emitting diode may have a so-called face-up structure or a flip chip structure. That is, the light-emitting diode includes a substrate and a light-emitting layer formed on the substrate, and may have a structure in which light is emitted from the light-emitting layer to the outside, or light from the light-emitting layer passes through the substrate. It is good also as a structure radiate | emitted outside.

More specifically, the light emitting diode includes, for example, a first cladding layer made of a compound semiconductor layer having a first conductivity type (for example, n-type) formed on a substrate, and an active layer formed on the first cladding layer. The first clad layer has a structure in which a second clad layer made of a compound semiconductor layer having a second conductivity type (for example, p-type) formed on the active layer is laminated, and is electrically connected to the first clad layer. An electrode and a second electrode electrically connected to the second cladding layer are provided. The layer constituting the light emitting diode may be made of a known compound semiconductor material depending on the emission wavelength.

Here, the refractive index of the light emitting layer of the light emitting diode is, for example, about 3.5 for GaAs, about 3.2 for GaP, and about 2.5 for GaN, and the refractive index of a commonly used sapphire substrate is It is about 1.75, which is quite high in any case. However, the refractive index of conventionally used sealing materials such as silicone resin and epoxy resin is about 1.4 to 1.5 at most, and between the light emitting layer and the sealing material or between the sapphire substrate and the sealing material. Because of the large refractive index difference between them, most of the light from the light-emitting layer is totally reflected at these interfaces and confined in the light-emitting layer or sapphire substrate, which can increase the light extraction efficiency. There wasn't.
In the optical semiconductor light-emitting device of the present invention, by increasing the refractive index of the encapsulant, the amount of emitted light that is totally reflected between the emissive layer and the encapsulant or between the sapphire substrate and the encapsulant is reduced, and light is extracted. Efficiency can be increased. From this point, the refractive index of the sealing material is preferably higher than 1.54, more preferably 1.56 or more, further preferably 1.58 or more, and most preferably 1.6 or more. preferable. Further, the transmittance at a wavelength of 450 nm when the optical path length is 0.5 mm is preferably 40% or more, more preferably 60% or more, and further preferably 70% or more.

As shown in FIG. 2, the second aspect (light emitting device 20) according to the present invention is formed so that the first sealing layer 16 covers the surface of the light emitting element 14, and the outer side of the first sealing layer 16 is the surface of the present invention. The second embodiment is the same as the first embodiment except that the second sealing layer 18 having a composition different from that of the optical semiconductor element sealing composition is formed.
Examples of the material of the second sealing layer 18 having a different composition include resins such as methyl silicone, modified silicone, acrylic resin, epoxy resin, and polyimide resin, or resin composites. The refractive index of the second sealing layer 18 reduces the interface reflection between the first sealing layer 16 and the second sealing layer 18 and reduces the interface reflection between the second sealing layer 18 and the outside. Therefore, it is preferable that the refractive index is equal to or lower than the refractive index of the first sealing layer 16 and equal to or higher than 1 (the refractive index of the atmosphere). Further, for the purpose of adjusting the refractive index of the second sealing layer 18, the surface-modified metal oxide particles according to the present invention may be contained in the second sealing layer.

The optical semiconductor light emitting device of the present invention can also be an optical semiconductor light emitting device in which a light emitting element and a phosphor are combined. According to the optical semiconductor light emitting device of the present invention, the first sealing layer in contact with the optical semiconductor element is the above-described silicone resin composite of the present invention. For example, for the blue InGaN, A phosphor such as a YAG phosphor or an RGB phosphor for ultraviolet light may be contained. This phosphor may be preliminarily contained in the silicone resin composition for forming the silicone resin composite that is the sealing material of the present invention. As the method, the phosphor is directly contained in the silicone resin composition. A method of mixing, a method of mixing a phosphor in a phenylsilicone resin forming component or a methylphenylsilicone resin forming component, a dispersion in which the phosphor is dispersed in an organic solvent, etc., and then mixing the organic solvent, etc. The method of removing, etc. can be mentioned.
In particular, considering the case of reducing the amount of phosphor used in terms of cost or the case of increasing the light conversion efficiency by intensively arranging the phosphor in the vicinity of the light emitting element, the first sealing layer in the second mode It is preferable to contain a phosphor. The phosphor is preferably 5 to 80% by mass, more preferably 20 to 70% by mass with respect to the mass of the first sealing layer. Note that the second sealing layer can also contain a phosphor.
As such an optical semiconductor light emitting device combining a light emitting element and a phosphor, a white light emitting diode (for example, a light emitting diode that emits white light by combining an ultraviolet or blue light emitting diode and phosphor particles) is exemplified. be able to.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

For this example, various measurements and evaluations were performed as follows.
(Average primary particle diameter of metal oxide particles)
The average primary particle diameter of the metal oxide particles was the Scherrer diameter obtained by calculation from the half width of the X-ray diffraction peak. This is because if the primary particle diameter is nanometer size, the possibility that one particle is composed of a plurality of crystallites is reduced, and the average primary particle diameter and the Scherrer diameter are substantially the same. It is.

(Transmissivity of silicone resin composite)
The transmittance of the silicone resin composite was measured with a spectrophotometer (integrating sphere) using the composite (0.5 mm thickness) of the example formed on the glass substrate. In Examples A1 to A5 and Comparative Examples A1 to A4, the transmittance reduction amount at a wavelength of 450 nm for the silicone resin alone (Comparative Example 1) was less than 10% as “A”, and 10% or more as “B”. . In Examples B1 to B5 and Comparative Examples B1 to B6, transmittance at a wavelength of 450 nm was obtained.

(Heat resistance of silicone resin composite)
With respect to the heat resistance of the silicone resin composites, in Examples A1 to A5 and Comparative Examples A1 to A4, the 0.5 mm-thick composites (cured bodies) were subjected to a load at 150 ° C. for 500 hours in an electric furnace. Then, it evaluated by measuring the transmittance | permeability using a spectrophotometer (integral sphere). “B” indicates that the transmittance at a wavelength of 450 nm after heat load is 30% or more lower than the initial value (before heat load), and “A” if the decrease is less than 30%.
On the other hand, in Examples B1 to B5 and Comparative Examples B1 to B6, the transmittance was measured using a spectrophotometer (integrating sphere) using the composite (0.5 mm thickness) of the example formed on the glass substrate. I went more than that. Specifically, the silicone resin composite is put into a dryer at 120 ° C., and the transmittance decrease rate compared to the initial transmittance at 450 nm after 1000 hours is less than 5%. Is “A”, 5% or more and less than 25% is “B”, and 25% or more is “C”.

(Gas permeability (gas barrier property) of silicone resin composite)
The gas permeability (gas barrier property) of the silicone resin composite was evaluated as follows.
First, a silicone resin composition was sealed in an LED package having a silver-plated reflector, and the silicone resin composition was cured by heat treatment at 150 ° C. for 3 hours to obtain a composite of the example. The package was sealed in a 500 ml pressure-resistant glass container together with 0.3 g of sulfur powder and kept at 80 ° C. Changes in appearance of silver-plated reflector over time (corrosion of silver plating due to sulfur gas (blackening discoloration)) were visually observed, and Examples A1 to A5 and Comparative Examples A1 to A4 did not contain metal oxide particles. Discoloration is slower than that of silicone resin (Comparative Example A1), and the time required to exhibit equivalent blackening is 1.5 times or more as “A” because gas permeability is low, and discoloration is slower than silicone resin “B” indicates that the blackening time is less than 1.5 times, while “C” indicates that the color changed to the same level as that of the silicone resin or that changed more quickly.
On the other hand, in Examples B1 to B5 and Comparative Examples B1 to B6, blackening of the appearance of the silver-plated reflecting plate (corrosion of silver plating by sulfur gas (blackening discoloration)) was visually observed, and a separately prepared reference plate ( Evaluation was made based on the time until the silver-plated reflector was directly blackened with sulfur gas). In addition, the time until blackening is shorter as the composite has a lower gas barrier property.

(Evaluation of hardness of silicone resin composite)
The hardness of the silicone resin composite was evaluated as “A” when there was no crack when the silicone resin composite was produced, and “B” when a crack occurred (Examples B1 to B5, Comparative Examples B1 to B6). ).

(Thickness of sealing layer made of silicone resin composite)
The thickness of the sealing layer made of the silicone resin composite was measured by observing the cross section of the package with an SEM.

[Example A1]
(Preparation of zirconia particles)
To a zirconium salt solution in which 2615 g of zirconium oxychloride octahydrate is dissolved in 40 L (liter) of pure water, dilute ammonia water in which 344 g of 28% ammonia water is dissolved in 20 L of pure water is added with stirring, and the zirconia precursor slurry is added. Prepared.
Next, an aqueous sodium sulfate solution in which 300 g of sodium sulfate was dissolved in 5 L of pure water was added to this slurry with stirring. The amount of sodium sulfate added at this time was 30% by mass with respect to the zirconia-converted value of zirconium ions in the zirconium salt solution.

Subsequently, this mixture was dried at 130 ° C. for 24 hours in the air using a drier to obtain a solid.
Next, the solid was pulverized in an automatic mortar and then baked at 500 ° C. for 1 hour in the air using an electric furnace.
Next, the fired product is put into pure water, stirred to form a slurry, washed using a centrifuge, and after sufficiently removing the added sodium sulfate, dried in a dryer, Zirconia particles having an average primary particle diameter of 4 nm were obtained.

(Surface modification to zirconia particles: Preparation of surface-modified zirconia particles)
Next, 82 g of toluene and 5 g of a methoxy group-containing phenyl silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., KR217) were added to 10 g of zirconia particles, mixed, subjected to surface modification treatment for 6 hours with a bead mill, and then the beads were removed. . Next, 3 g of vinyltrimethoxysilane (KBE1003, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and surface modification and dispersion treatment were performed under reflux at 130 ° C. for 6 hours. A transparent dispersion of zirconia particles surface-modified with a surface modifying material having a certain vinyl group was prepared.

(Preparation of silicone resin composition)
7.6 g of the above-mentioned transparent dispersion of zirconia particles as a phenyl silicone resin, trade name: OE-6520 (manufactured by Dow Corning Toray, refractive index 1.54, A / B mixture ratio = 1/1) A liquid 3.8 g and B liquid 3.8 g) were added and stirred, and then toluene was removed by drying under reduced pressure, and a silicone resin composition (containing zirconia particles) containing surface-modified zirconia particles, phenyl silicone resin, and a reaction catalyst. Amount: 30% by mass) was obtained.
As for OE-6520, the presence of Si—H bond was confirmed by NMR analysis, and it was found that a hydrogen group was contained in the silicone resin forming component. Therefore, OE-6520 can be integrated by cross-linking reaction with the vinyl group (alkenyl group) of vinyltrimethoxysilane which is modifying the surface of the zirconia particles.
As for OE-6520, it was confirmed by NMR analysis that a C═C double bond (vinyl group), which is an alkenyl group, was present and platinum was present by emission analysis. That is, OE-6520 is an addition-curable silicone resin that is polymerized and cured by an addition reaction (hydrosilylation reaction). Therefore, OE-6520 uses platinum as a catalyst to bond the vinyl group in the zirconia particle surface modifying material and the hydrogen group in OE-6520 by a cross-linking reaction, and the vinyl group and hydrogen group in OE-6520 As a result of the addition reaction, it can be determined that the silicone resin-forming component is polymerized and cured while maintaining the dispersed state of the zirconia particles.

(Production of silicone resin composite)
A silicone resin composite was obtained by curing the silicone resin composition by heating at 150 ° C. for 3 hours.
Various evaluations described above were performed using this silicone resin composite. In the gas permeability evaluation, the thickness of the sealing layer was 500 μm.

[Example A2]
(Preparation of zirconia particles)
Zirconia particles were produced in the same manner as Example A1.

(Production of surface modification material containing both phenyl and alkenyl groups)
Surface Modification Material A: Preparation of (CH ₂ ═CH) (CH ₃ ) ₂ SiO (SiO (C ₆ H ₅ ) ₂ ) ₄₅ Si (OC ₂ H ₅ ) ₃ in 60 ml of tetrahydrofuran (THF) solvent under nitrogen atmosphere Into this solution, 1.8 g of dimethylvinylsilanol was dissolved, and 1.2 g of n-butyllithium dissolved in n-hexane was dropped at a temperature of 0 ° C. with stirring to react for 3 hours to obtain lithium dimethylvinylsilanolate ( (See formula (A)).

Subsequently, a solution obtained by dissolving 160.5 g of hexaphenylcyclotrisiloxane in a THF solvent was dropped, and the mixture was reacted at a temperature of 0 ° C. for 12 hours to obtain lithium phenylvinylorganosilanolate (see formula (B)).

Subsequently, 3.6 g of chlorotriethoxysilane was added and reacted at a temperature of 0 ° C. for 12 hours (see formula (C)).

Next, n-hexane was mixed to form a lithium chloride precipitate, and then the lithium chloride was removed by filtration to obtain a surface modifying material A containing both phenyl and alkenyl groups.
The structure of the obtained surface modifying material was confirmed by 1H-NMR.

Here, the outline of the synthesis flow of the surface modifying material containing both the phenyl group and the alkenyl group is shown below.

(Surface modification to zirconia particles: Preparation of surface-modified zirconia particles)
Next, 10 g of zirconia particles were added with 80 g of toluene and 5 g of methoxy group-containing phenyl silicone resin (manufactured by Shin-Etsu Kogyo Kagaku Co., Ltd., KR217), mixed, subjected to surface modification treatment with a bead mill for 6 hours, and then the beads were removed. . Next, 3 g of the surface modification material A is added, and surface modification and dispersion treatment are performed under reflux at 130 ° C. for 6 hours, so that both the surface modification material having a phenyl group and the phenyl group and the alkenyl group (vinyl group) are present. A transparent dispersion of zirconia particles surface-modified with the surface modifying material having was prepared.

(Production of silicone resin composition and silicone resin composite)
A silicone resin composition and a silicone resin composite were prepared in the same manner as in Example A1, except that the methoxy group-containing phenyl silicone resin and a transparent dispersion of zirconia particles surface-modified with the surface modifying material A were used. Various evaluations were made.

[Example A3]
Except that the thickness of the sealing layer was 30 μm, a silicone resin composition and further a silicone resin composite were produced in the same manner as Example A1, and various evaluations were performed.

[Example A4]
(Production of titania particles)
242.1 g of titanium tetrachloride and 111.9 g of tin (IV) chloride pentahydrate were put into 1.5 L (liter) of pure water at 5 ° C. and stirred to prepare a mixed solution.
Next, the mixed solution is heated to adjust the temperature to 25 ° C., and an aqueous ammonium carbonate solution having a concentration of 10% by mass is added to the mixed solution to adjust the pH to 1.5. After aging for a period of time, excess chloride ions were removed by ultrafiltration.
Next, using an evaporator, moisture was removed from the mixed solution after removing the chloride ions, followed by drying to produce titanium oxide particles. The average primary particle diameter of the obtained titanium oxide particles was 4 nm.

The surface modification was performed in the same manner as in Example A1 except that the titania particles were used to prepare a titania transparent dispersion, and then a silicone resin composition and further a silicone resin composite were prepared and subjected to various evaluations.

[Example A5]
(Preparation of silica particles)
80 g of methanol was mixed with 20 g of 24% aqueous ammonia, 0.8 g of 10N NaOH, and 4 g of polyoxyethylene alkyl ether (trade name: Emulgen 707, manufactured by Kao Corporation) as a surfactant. Thereto, 4 g of tetraethyl silicate diluted with methanol (trade name: ethyl silicate 28, manufactured by Colcoat Co.) was dropped. The mixture was stirred at 20 ° C. for 1 hour. After completion of the stirring, the precipitate was separated by decantation, redispersed in methanol and decanted repeatedly to remove residual ions.

The obtained wet silica particles were dried under reduced pressure to dry methanol to obtain the produced silica particles. The average primary particle diameter of the obtained silica particles was 4 nm.
Surface modification was performed in the same manner as in Example A1 except that the silica particles were used to prepare a silica transparent dispersion, and then a silicone resin composition and a silicone resin composite were prepared and subjected to various evaluations.

[Comparative Example A1]
Various evaluation similar to Example 1 was performed about the silicone resin (however, metal oxide particle addition-free) used in Example A1. In addition, about three points of the transmittance | permeability of a silicone resin composite, the heat resistance of a silicone resin composite, and the gas permeability of a silicone resin composite, the value of this comparative example A1 which does not contain a metal oxide particle is set as a reference value. did.

[Comparative Example A2]
Zirconia particles having an average primary particle diameter of 2 nm were produced in the same manner as in Example A1, except that the electric furnace firing temperature in the production of zirconia particles was changed from 500 ° C to 450 ° C. Except for using the zirconia particles, a silicone resin composition and a silicone resin composite were prepared in the same manner as in Example A1, and various evaluations were performed.

[Comparative Example A3]
Zirconia particles having a primary particle diameter of 15 nm were produced in the same manner as in Example A1, except that the electric furnace firing temperature in the production of zirconia particles was changed from 500 ° C to 600 ° C. Except having used the said zirconia particle | grain, it carried out similarly to Example A1, and produced the silicone resin composition and also the silicone resin composite, and performed various evaluation.

[Comparative Example A4]
Surface modified zirconia particles were prepared in the same manner as in Example A1 except that the surface modifying material used in Example A1 was changed to 6 g and 2 g of methacryloxypropyltrimethoxysilane and isopropyltrimethoxysilane, respectively. Similarly, a silicone resin composition and a silicone resin composite were produced and various evaluations were performed.
The details and evaluation results of the silicone resin composites in the above Examples and Comparative Examples are shown in Tables 1 and 2 together.

The transmittance of the silicone resin composites in Examples A1 to A5 was equal to the value of the reference silicone resin alone (Comparative Example A1), and no significant reduction was observed. Further, regarding the heat resistance of the silicone resin composite, there was no problem with the transmittance after heat load being found to be 30% lower than the initial value.
Regarding the gas permeability of the silicone resin composites of Examples A1, A2, A4, and A5, the time required for exhibiting blackening equivalent to that of the standard silicone resin alone (Comparative Example A1) is 1.5. It was confirmed that the gas permeability was lowered, that is, the gas barrier property was clearly improved. Moreover, although the fall of gas permeability was confirmed also in Example A3, the grade was low compared with the other Example. This is considered because the sealing layer thickness is as thin as 30 μm.
On the other hand, Comparative Example A2 has high gas permeability and a sufficient gas barrier property cannot be obtained. This is presumably because workability was poor because the particle size of the metal oxide was small and the viscosity of the silicone resin composition was high, and the sealing itself could not be performed sufficiently.
Further, the light transmittance of Comparative Example A3 was lowered. This is presumably because light scattering occurs due to the large particle size of the metal oxide.
In Comparative Example A4, both light transmittance and heat resistance were also decreased. This is considered due to the surface modifying material. That is, the light transmittance is reduced because the surface modifying material of this example does not contain an alkenyl group and thus has no binding property with the matrix silicone resin forming component, and further does not contain a phenyl group. It is considered that the metal oxide particles aggregated during the formation of the silicone resin composite (during the curing of the silicone resin composition) due to low affinity, and the decrease in heat resistance was caused by the surface modification material of this example. This is probably because there is no phenyl group and the heat resistance is low.

[Example B1]
(Preparation of zirconia particles)
To a zirconium salt solution in which 2615 g of zirconium oxychloride octahydrate is dissolved in 40 L (liter) of pure water, dilute ammonia water in which 344 g of 28% ammonia water is dissolved in 20 L of pure water is added with stirring, and the zirconia precursor slurry is added. Prepared.
Next, an aqueous sodium sulfate solution in which 300 g of sodium sulfate was dissolved in 5 L of pure water was added to this slurry with stirring. The amount of sodium sulfate added at this time was 30% by mass with respect to the zirconia-converted value of zirconium ions in the zirconium salt solution.

Subsequently, this mixture was dried at 130 ° C. for 24 hours in the air using a drier to obtain a solid.
Next, the solid was pulverized in an automatic mortar and then baked at 500 ° C. for 1 hour in the air using an electric furnace.
Next, the fired product is put into pure water, stirred to form a slurry, washed using a centrifuge, and after sufficiently removing the added sodium sulfate, dried in a dryer, Zirconia particles having an average primary particle diameter of 4 nm were obtained.

(Surface modification to zirconia particles: Preparation of surface-modified zirconia particles)
Next, 82 g of toluene and 5 g of methoxy group-containing phenyl silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd .: KR217) were added to 10 g of zirconia particles, mixed, and subjected to surface modification treatment with a bead mill for 6 hours, and then the beads were removed. . Next, 3 g of dimethylethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: LS490) was added, surface modification and dispersion treatment were performed at 130 ° C. for 6 hours under reflux, and a surface modification material having a phenyl group and a surface having a hydrogen group A transparent dispersion of zirconia particles surface-treated with a modifying material was prepared.

(Preparation of silicone resin composition)
Product name: OE-6520 (refractive index 1.54 A liquid / B liquid mixture ratio = 1/1) manufactured by Toray Dow Corning Co., Ltd. as a phenyl silicone resin in 50 g of the above zirconia particle transparent dispersion liquid (A liquid 3 After adding and stirring, the toluene was removed by drying under reduced pressure, and a silicone resin composition containing the surface-modified zirconia particles, the phenyl silicone resin, and the reaction catalyst (zirconia particle content: 30). Mass%).
As for OE-6520, the presence of C═C double bond (vinyl group) and Si—H bond (hydrogen group), which are alkenyl groups, was confirmed by NMR analysis. The existence is confirmed. That is, OE-6520 is an addition curing type silicone resin that is polymerized and cured by a hydrosilylation reaction. Therefore, the hydrogen group in the zirconia particle surface modifying material and the vinyl group in OE-6520 can be bonded by a hydrosilylation reaction, and the platinum catalyst as a hydrosilylation catalyst contained in OE-6520 is: Since a sufficient amount of the silicone resin-forming component in the OE-6520 is hydrolyzed and polymerized and cured, even if a surface modifying material (a small amount with respect to the silicone resin) is added to the OE-6520 as a catalyst. It can be judged that the amount and the effect are sufficient.

(Production of silicone resin composite)
A silicone resin composite was obtained by curing the silicone resin composition by heating at 150 ° C. for 3 hours.
Various evaluations described above were performed using this silicone resin composite. In the evaluation of gas barrier properties, the thickness of the sealing layer was 500 μm.

[Example B2]
(Production of titania particles)
242.1 g of titanium tetrachloride and 111.9 g of tin (IV) chloride pentahydrate were put into 1.5 L (liter) of pure water at 5 ° C. and stirred to prepare a mixed solution.
Next, the mixed solution is heated to adjust the temperature to 25 ° C., and an aqueous ammonium carbonate solution having a concentration of 10% by mass is added to the mixed solution to adjust the pH to 1.5. After aging for a period of time, excess chloride ions were removed by ultrafiltration.
Next, moisture was removed from this mixed solution using an evaporator, and then dried to produce titanium oxide particles. The average primary particle diameter of the obtained titanium oxide (titania) particles was 4 nm.

Using the above titania particles, the surface was modified in the same manner as in Example B1 except that the content of the metal oxide particles was 20% by mass, and surface treatment was performed using a surface modifying material having a phenyl group and a surface modifying material having a hydrogen group. A titania particle transparent dispersion was prepared, and then a silicone resin composition and a silicone resin composite were prepared in the same manner as in Example B1, and various evaluations were performed.

[Example B3]
The average primary particle size of zirconia particles was changed from 4 nm to 5 nm, dimethylethoxysilane was changed to diethoxymethylsilane (manufactured by Shin-Etsu Chemical Co., Ltd .: LS880) as a surface modifying material, and vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) was further changed. Surface modification having a phenyl group in the same manner as in Example B1, except that surface modification and dispersion treatment were carried out by adding KBM-1003) in a molar ratio of hydrogen group / vinyl group = 4. A transparent dispersion of zirconia particles surface-treated with a material, a surface modifying material having a hydrogen group and a surface modifying material having a vinyl group is prepared, and then a silicone resin composition and a silicone resin composite are prepared in the same manner as in Example B1. A body was prepared and subjected to various evaluations.

[Example B4]
Except for adding dimethylethoxysilane as a surface modifying material and adding vinyltrimethoxysilane in a molar ratio of hydrogen group / vinyl group = 6 to perform surface modification and dispersion treatment, the same as Example B1 Then, a surface-modified material having a phenyl group, a surface-modified material having a hydrogen group, and a surface-modified zirconia particle-transparent dispersion liquid having a vinyl group are prepared. Then, in the same manner as in Example B1, A silicone resin composition and a silicone resin composite were prepared and subjected to various evaluations.

[Example B5]
As metal oxide particles, silica particles having an average primary particle diameter of 6 nm (Snowtex XS, manufactured by Nissan Chemical Industries, Ltd.) were used.
To 10 g of the silica particles, 82 g of toluene and 5 g of a methoxy group-containing phenyl silicone resin were added, mixed, and subjected to surface modification treatment with a bead mill for 6 hours, and then the beads were removed. Next, 3 g of ethyldichlorosilane (manufactured by Shin-Etsu Chemical Co., Ltd .: LS140) was added, and surface modification and dispersion treatment were performed under reflux at 130 ° C. for 6 hours. By passing the obtained dispersion through a column filled with alumina gel, chloride ions were removed until it became 1 mass ppm or less. The amount of chlorine is measured by a chlorine ion meter. Thereafter, the surface-modified silica particles were dispersed again in toluene to prepare a transparent dispersion of silica particles surface-treated with a surface modifying material having a phenyl group and a surface modifying material having a hydrogen group.
Next, in the same manner as in Example B1, a silicone resin composition and a silicone resin composite were produced and subjected to various evaluations.

[Comparative Example B1]
The silicone resin used in Example B1 (with no addition of metal oxide particles) was cured by heat treatment at 150 ° C. for 3 hours, and various evaluations similar to Example B1 were performed on this cured product.

[Comparative Example B2]
In the surface modification of the metal oxide particles of Example B1, except that dimethylethoxysilane was changed to vinyltrimethoxysilane, the surface modification material having a phenyl group and the surface modification material having a vinyl group were used in the same manner as in Example B1. A surface-treated zirconia particle dispersion was prepared, and then a silicone resin composition and a silicone resin composite were prepared and evaluated in the same manner as in Example B1.

[Comparative Example B3]
Except for changing the average primary particle diameter of the zirconia particles in Example B1 from 4 nm to 20 nm, the surface treatment was performed with the surface modifying material having a phenyl group and the surface modifying material having a hydrogen group in the same manner as in Example B1. A zirconia particle dispersion was prepared, and then a silicone resin composition and a silicone resin composite were prepared in the same manner as in Example B1, and various evaluations were performed.

[Comparative Example B4]
Example B3, except that in the surface modification of the metal oxide particles of Example B3, the mixing ratio of diethoxymethylsilane and vinyltrimethoxysilane was such that the hydrogen group / vinyl group = 0.1 in terms of molar ratio. In the same manner as in Example 1, a surface-modified material having a phenyl group, a surface-modified material having a hydrogen group, and a surface-modified material having a vinyl group are surface-treated, and then treated in the same manner as in Example B1. Then, a silicone resin composition and a silicone resin composite were prepared and various evaluations were performed.

[Comparative Example B5]
In the surface modification of the metal oxide particles of Example B1, except that dimethylethoxysilane was changed to dodecyltrimethoxysilane, the surface modification material having a phenyl group and the surface modification material having a carbon chain were used in the same manner as in Example B1. A surface-treated zirconia particle dispersion was prepared, and then a silicone resin composition and a silicone resin composite were prepared and evaluated in the same manner as in Example B1.

[Comparative Example B6]
Zirconia surface-treated with a surface modifying material having a phenyl group and a surface modifying material having a hydrogen group in the same manner as in Example B1, except that the average primary particle size of the zirconia particles in Example B1 was changed from 4 nm to 2 nm. A particle dispersion was prepared, and then a silicone resin composition and a silicone resin composite were prepared and evaluated in the same manner as in Example B1.
The details and evaluation results of the silicone resin composites in the above Examples and Comparative Examples are shown in Table 3 and Table 4.

In Examples B1 to B5, metal oxide particles having an average primary particle diameter of 3 nm or more and 10 nm or less were used, and the particles were surface-modified with a surface modification material having a phenyl group and a hydrogen group. The light transmittance, heat resistance, and gas barrier properties of the silicone resin composite produced using the particulate material could be maintained in a good state.
In particular, it is shown that the gas barrier property is clearly improved with respect to Comparative Example B1, which is a standard silicone resin alone. This is because dimethylethoxysilane and diethoxymethylsilane used as surface modification materials are used. And the hydrogen group in the surface modification material based on ethyldichlorosilane and the vinyl group in OE-6520, which is a matrix silicone resin raw material, are bonded by a cross-linking reaction by a hydrosilyl reaction during the curing of the resin composition. This is considered to be an effect in which the product particles and the matrix silicone resin are integrated.
Among these examples, Examples B3 and B4 were particularly high in gas barrier properties. This is based on vinyltrimethoxysilane used as a surface modifying material, as well as bonding by a crosslinking reaction by a hydrosilyl reaction between a hydrogen group in the surface modifying material and a vinyl group in OE-6520, which is a matrix silicone resin raw material. The vinyl group in the surface modification material and the hydrogen group in OE-6520, which is a matrix silicone resin raw material, are bonded by cross-linking reaction, so that the metal oxide particles and the matrix silicone resin are more firmly integrated. It is considered an effect.

On the other hand, Comparative Example B2 was yellowed after the heat resistance evaluation test. This is presumably because an unreacted vinyl group remained in the silicone resin composite because vinyltrimethoxysilane was used instead of dimethylethoxysilane as the surface modifying material. The gas barrier property was improved as compared with that of the silicone resin alone. This is because the vinyl group in the surface modifying material and the hydrogen group in OE-6520, which is a matrix silicone resin raw material, are cured by the resin composition. It is thought that this is sometimes the effect of crosslinking reaction by hydrosilyl reaction.
Moreover, about the comparative example B3, the transmittance | permeability of light fell. This is presumably because light scattering occurs due to the large particle size of the metal oxide.
Further, Comparative Example B4 was yellowed after the heat resistance evaluation test. This is presumably because an excessive amount of unreacted vinyl groups remained in the silicone resin composite because a large amount of vinyltrimethoxysilane was used together with diethylmethylsilane as the surface modifying material. The gas barrier property was improved as compared with that of the silicone resin alone. This is because the hydrogen group in the surface modifying material based on dietoxymethylsilane and the vinyl group in OE-6520, which is a matrix silicone resin raw material. The effect of cross-linking polymerization by the hydrosilyl reaction during curing of the resin composition, the vinyl group in the surface modifying material, and the hydrogen group in OE-6520, which is a matrix silicone resin raw material, are hydrosilylated during the curing of the resin composition. This is considered to be combined with the effect of crosslinking reaction.
Further, Comparative Example B5 was yellowed after the heat resistance evaluation test. This is presumably because the carbon chain portion of dodecyltrimethoxysilane is thermally altered because dodecyltrimethoxysilane is used as the surface modifying material instead of dimethylethoxysilane.
Moreover, about comparative example B6, gas permeability was high and sufficient gas barrier property was not acquired. This is presumably because workability was poor because the particle size of the metal oxide was small and the viscosity of the silicone resin composition was high, and the sealing itself could not be performed sufficiently.

The present invention can be used not only as a sealing material for semiconductor light emitting devices (LEDs and the like) but also as materials and members in various other industrial fields.

Claims (15)

1. Surface modification in which metal oxide particles having an average primary particle diameter of 3 nm or more and 10 nm or less are surface-modified by a surface modification material having at least a phenyl group, a functional group in a silicone resin forming component, and a group capable of crosslinking reaction Metal oxide particle material.
2. The surface-modified metal oxide particle material according to claim 1, wherein the group capable of undergoing a crosslinking reaction with the functional group in the silicone resin-forming component is an alkenyl group.
3. The surface-modified metal oxide particle material according to claim 1, wherein the group capable of undergoing a crosslinking reaction with the functional group in the silicone resin-forming component is a hydrogen group.
4. 2. The surface-modified metal oxide particle material according to claim 1, wherein the group capable of undergoing a crosslinking reaction with the functional group in the silicone resin-forming component is an alkenyl group and a hydrogen group.
5. A dispersion containing the surface-modified metal oxide particle material according to any one of claims 1 to 4.
6. A surface-modified metal oxide particle material according to claim 1, and a silicone resin-forming component containing at least one selected from a phenylsilicone resin-forming component and a methylphenylsilicone resin-forming component, the silicone resin-forming component However, the silicone resin composition which has a functional group which can carry out a crosslinking reaction with the group which the surface modification material used for the said surface modification metal oxide particle material has.
7. A surface-modified metal oxide particle material according to claim 2 and a silicone resin-forming component containing at least one selected from a phenylsilicone resin-forming component and a methylphenylsilicone resin-forming component. Is a silicone resin composition having a hydrogen group.
8. A surface-modified metal oxide particle material according to claim 3, and a silicone resin-forming component containing at least one selected from a phenylsilicone resin-forming component and a methylphenylsilicone resin-forming component, the silicone resin-forming component Is a silicone resin composition having one or more selected from alkenyl groups and alkynyl groups.
9. A surface-modified metal oxide particle material according to claim 4, and a silicone resin-forming component containing at least one selected from a phenylsilicone resin-forming component and a methylphenylsilicone resin-forming component. Is a silicone resin composition having at least one selected from an alkenyl group and an alkynyl group, and a hydrogen group.
10. The silicone resin composition according to any one of claims 6 to 9, wherein the metal oxide particles are contained in an amount of 5% by mass or more.
11. The silicone resin composition according to any one of claims 6 to 10, further comprising a hydrosilylation catalyst.
12. A silicone resin composite obtained by curing the silicone resin composition according to any one of claims 6 to 11.
13. An optical semiconductor light emitting device in which a semiconductor light emitting element is sealed with a sealing material,
    An optical semiconductor light-emitting device, wherein the sealing material is made of the silicone resin composite according to claim 12, and a sealing layer made of the sealing material has a thickness of 50 μm or more.
14. A lighting fixture comprising the optical semiconductor light-emitting device according to claim 13.
15. A liquid crystal image device comprising the optical semiconductor light emitting device according to claim 13.

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