TW201402674A - Surface-modified metal oxide particle material, dispersion, polyoxyxylene resin composition, polyoxymethylene resin composite, optical semiconductor light-emitting device, illumination device, and liquid crystal image device - Google Patents

Abstract

The present invention provides a high heat resistance and a high transparency and gas barrier when used in a sealing material for an optical semiconductor light-emitting device or the like by using a surface-modified metal oxide particle material as follows. Surface-modified metal oxide particle material, dispersion containing the surface-modified metal oxide particle material, polyoxyxene resin composition and polyoxyxene resin composite, and optical semiconductor light-emitting using the polyoxy-oxide resin composite In the device, the illuminating device, and the liquid crystal image device, the surface-modified metal oxide particle material is a surface-modifying material pair having at least a phenyl group and a group capable of crosslinking reaction with a functional group in a polyfluorene-oxygen resin-forming component. The metal oxide particles having an average primary particle diameter of 3 nm or more and 10 nm or less are surface-modified.

Description

Surface-modified metal oxide particle material, dispersion, polyoxyxylene resin composition, polyoxymethylene resin composite, optical semiconductor light-emitting device, illumination device, and liquid crystal image device

The present invention relates to a surface-modified metal oxide particle material, a dispersion liquid, a polyoxyxylene resin composition, a polyoxymethylene resin composite, an optical semiconductor light-emitting device using the same as a sealing material, and an illumination provided with the same. Device and liquid crystal image device.

For example, as described in Patent Document 1, the polysiloxane resin is excellent in properties such as transparency, heat resistance, and light resistance, and is excellent in hardness or rubber elasticity. Therefore, it can be used for a sealing material or an optical waveguide material of an optical semiconductor element. in.

In particular, as a sealing material for a light-emitting diode (LED) of one of the optical semiconductor light-emitting elements, there are, for example, an organically modified polyoxyxylene resin as described in Patent Document 2, and a phenyl group (or methylbenzene). A polyoxyxylene resin or a dimethyl polyphthalide resin as described in Patent Document 3, for example.

On the other hand, although the polyoxyxene resin is excellent in durability, it has a problem of high gas permeability (low gas barrier property), and the industry has attempted to solve this problem by containing metal oxide particles. In order to transparently combine the polyoxyxylene resin with the metal oxide particles, it is necessary to treat the surface of the particles with an organic decane agent. For example, as described in Patent Documents 4 and 5, by performing surface treatment using an epoxy group-containing decane agent or a vinyl group-containing decane agent, it is possible to prevent aggregation of particles during curing of the resin to produce a transparent composite.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2009-076948

Patent Document 2: Japanese Patent Laid-Open Publication No. 2007-270004

Patent Document 3: Japanese Patent Laid-Open No. 2011-096793

Patent Document 4: Japanese Patent Laid-Open Publication No. 2005-200657

Patent Document 5: Japanese Patent Laid-Open No. 2006-70266

However, the polyoxynene resin has a problem of high gas permeability (low gas barrier property), and the metal oxide particles are dispersed in the polyoxynoxy resin and composited to compensate for the disadvantage and improve the function. In particular, there is also a problem that the brightness of the LED is lowered due to corrosion (vulcanization and blackening) of the silver-plated reflector of the LED package due to the sulfur-containing gas in the atmosphere.

In the case where the inorganic particles are dispersed in the polyoxyxene resin, the heat resistance is low by the use of a usual surface treatment agent, so that particle aggregation occurs at a high temperature (particle dispersibility is lowered) or the surface treatment agent itself is colored. As a result, the transmittance is lowered, and thus there is a problem that heat resistance is caused.

Further, in the case of sealing with a dimethylpolyphthalocene resin having a low light extraction efficiency from the LED, the sealing property of the bulb structure or the plating of the light-reflecting sheet of the LED package with high corrosion resistance is improved. There are also problems of lower brightness and higher cost.

On the other hand, although phenyl (or methylphenyl) polyfluorene oxide is less gas permeable (higher gas barrier property) than dimethyl polyoxyn resin, these properties depend on the benzene that can be introduced. The amount of the base is also limited.

Further, when the surface treatment agent has an epoxy group or an unreacted vinyl group remains excessively in the composite, there is a problem that yellowing occurs when a heat load is applied to the composite. Further, when the compatibility between the surface treatment agent and the polyoxyxylene resin is insufficient, the gas barrier properties are not improved, or the particles are aggregated during the heat load (the particle dispersibility is lowered) and the transmittance is increased. Reduce the problem.

The present invention has been made in order to solve the above problems, and an object of the present invention is to provide a heat resistance which is high in heat resistance when used for a sealing material or the like for an optical semiconductor light-emitting device (that is, when it is suppressed by a heat load) a surface-modified metal oxide particle material having a high transparency and gas barrier properties, and a dispersion liquid containing the surface-modified metal oxide particle material, which has a low transmittance due to aggregation of particles during coloring or heat loading. The polyoxynoxy resin composition and the polyoxyxene resin composite, and the optical semiconductor light-emitting device capable of reducing the gas permeability of the sealing material and suppressing the deterioration of the device caused by the permeated gas when the polyoxynoxy resin composite is used as a sealing material An illumination device and a liquid crystal image device including the optical semiconductor light-emitting device.

The present inventors have made an effort to solve the above problems, and as a result, have found that the surface-modified metal oxide particle material can be solved by using at least a phenyl group by using a surface-modified metal oxide particle material. And a surface modification material which can be subjected to a crosslinking reaction with a functional group in the polyoxyxene resin, which is obtained by surface-modifying metal oxide particles having an average primary particle diameter within a specific range. Specifically, it has been found that a polyoxyphthalocene resin composite containing the surface-modified metal oxide particle material in a specific polyoxyxene resin is used for a sealing material of a light-emitting element in an optical semiconductor light-emitting device, and the self-luminous element is not damaged. The light transmissive property can further reduce the gas permeability of the sealing layer, thereby studying the present invention.

That is, the present invention is as follows.

[1] A surface-modified metal oxide particle material which has a mean primary particle diameter by a surface-modifying material having at least a phenyl group and a group capable of undergoing a crosslinking reaction with a functional group in a polyfluorene-oxygen resin-forming component. The metal oxide particles of 3 nm or more and 10 nm or less are surface-modified.

[2] The surface-modified metal oxide particle material according to [1], wherein the above-mentioned poly-polymerizable The group in which the functional group in the epoxy resin forming component is subjected to a crosslinking reaction is an alkenyl group.

[3] The surface-modified metal oxide particle material according to [1], wherein the group which can be cross-linked with the functional group in the polyfluorene oxide-forming component is a hydrogen group.

[4] The surface-modified metal oxide particle material according to [1], wherein the group which can be cross-linked with the functional group in the polyfluorene oxide-forming component is an alkenyl group and a hydrogen group.

[5] A dispersion-containing metal oxide particle material according to any one of [1] to [4].

[6] A polyoxyxylene resin composition comprising the surface-modified metal oxide particle material according to [1], and a component selected from the group consisting of a phenyl polyoxyl resin forming component and a methylphenyl polyoxyl resin forming component. One or more of the polyoxynene resin forming components, and the polyoxynoxy resin forming component has a functional group reactive with a group of the surface modifying material used in the surface-modified metal oxide particle material.

[7] A polyoxyxylene resin composition comprising the surface-modified metal oxide particle material according to [2], and a component selected from the group consisting of a phenyl polyoxymethylene resin forming component and a methylphenyl polyfluorene resin forming component. One or more of the polyoxyxylene resin forming components, and the polyoxyxylene resin forming component has a hydrogen group.

[8] A polyoxyxylene resin composition comprising the surface-modified metal oxide particle material according to [3], and a component selected from the group consisting of a phenyl polyoxyl resin forming component and a methylphenyl polyfluorene resin forming component. One or more of the polyoxynene resin forming components, and the polyoxyxylene resin forming component has one or more selected from the group consisting of alkenyl groups and alkynyl groups.

[9] A polyoxyxylene resin composition comprising the surface-modified metal oxide particle material according to [4], and a component selected from the group consisting of a phenyl polyoxyl resin forming component and a methylphenyl polyoxyl resin forming component. One or more of the polyoxo resin forming components, and the polyoxynoxy resin forming component has one or more selected from the group consisting of alkenyl groups and alkynyl groups, and a hydrogen group.

[10] The polyoxyxylene resin composition according to any one of [6] to [9], wherein the metal oxide particles are contained in an amount of 5 mass% or more.

[11] The polyoxyxylene resin composition according to any one of [6] to [10] further comprising a hydrazine hydrogenation catalyst.

[12] A polyoxyxylene resin composite obtained by curing the polyoxyxylene resin composition according to any one of [6] to [11].

[13] An optical semiconductor light-emitting device which is obtained by sealing a semiconductor light-emitting element with a sealing material, wherein the sealing material comprises the polyoxymethylene resin composite according to [12], and comprises a sealing layer of the sealing material. The thickness is 50 μm or more.

[14] An illumination device 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, it is possible to provide a heat resistance which is high in heat resistance when used for a sealing material or the like for an optical semiconductor light-emitting device (that is, a transmittance which suppresses aggregation of particles by coloring or heat load at the time of heat load) a surface-modified metal oxide particle material which exhibits high transparency and gas barrier properties, a dispersion liquid containing the surface-modified metal oxide particle material, a polyoxyxylene resin composition, and a polyoxyxylene resin composite And when the polyoxyxene resin composite is used for a sealing material, the optical semiconductor light-emitting device having excellent transparency or heat resistance can be provided, which can reduce the gas permeability of the sealing material and suppress deterioration of the device caused by the permeating gas. An illumination device and a liquid crystal image device of the optical semiconductor light-emitting device.

10‧‧‧Lighting device

12‧‧‧Reflection Cup

12A‧‧‧ recess

14‧‧‧Lighting elements

16‧‧‧1st sealing layer

18‧‧‧2nd sealing layer

20‧‧‧Lighting device

Fig. 1 is a cross-sectional view schematically showing an embodiment of an optical semiconductor light-emitting device of the present invention.

2 is a view schematically showing another embodiment of the optical semiconductor light-emitting device of the present invention Sectional view.

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 is a metal oxide having a specific particle diameter by a surface-modifying material having at least a phenyl group and a group capable of crosslinking with a functional group in a polyanthracene resin-forming component. The particles are surface modified. In addition, "polyoxy resin forming component" will be described later.

(metal oxide particles)

The type of the metal oxide particles is not particularly limited, and from the viewpoint of maintaining the transparency of the sealing material or the like, it is preferred to obtain a type of particle diameter of a nanometer size, and examples thereof include zinc oxide, zirconium oxide, and titanium oxide. Silica, alumina, and the like. Further, in consideration of the fact that the refractive index of the sealing material or the like is increased to increase the light extraction efficiency of the optical semiconductor light-emitting device using the sealing material, the refractive index of the metal oxide particles is preferably 1.5. The above is more preferably 1.7 or more, and still more preferably 1.9 or more. As such metal oxide particles, titanium oxide or zirconia is preferable, and zirconia is particularly preferable.

In the present specification, when it is expressed as "X to Y" (X, Y is an arbitrary number), unless otherwise specified, it means "X or more and Y or less".

The average primary particle diameter of the metal oxide particles is 3 to 10 nm. When the average primary particle diameter is less than 3 nm, the surface activity is enhanced in addition to the deterioration of crystallinity, and the interaction between the particles is generated to increase the viscosity of the polyoxyxene resin composition. On the other hand, when the average primary particle diameter becomes larger than 10 nm, the difference in refractive index between the metal oxide and the polyoxynoxy resin containing the surface modifying material is large, so that the decrease in transmittance due to scattering becomes remarkable.

The average primary particle diameter is preferably 4 nm to 8 nm, more preferably 4 nm to 6 nm.

(surface modification material)

The surface modification material used for surface modification of metal oxide particles contains at least benzene The base and the group which can be cross-linked with the functional group in the polyoxynene resin forming component (hereinafter, simply referred to as "crosslinking reaction group"). Here, the term "crosslinking reaction with a functional group in a polyoxyxylene resin" means a process of polymerizing and curing the following polyoxyxylene resin forming component of the polyoxyxene resin, and the polyoxyxylene resin. The functional group contained in the component is reacted to form a surface-modified metal oxide particle material and a polyoxyxene resin after curing. In addition, examples of the crosslinking reaction include a hydrogenation reaction, a condensation reaction, and a reaction of a hydroxyl group with an epoxy group or an isocyanate group. Examples of the crosslinking reaction group to be used in the crosslinking reaction include a hydrogen group. Alkenyl, alkynyl, hydroxy, epoxy, isocyanate, and the like.

As the above crosslinking reaction, the hydrazine hydrogenation reaction is preferred in that water is not produced as a by-product and coloring by the crosslinking reaction group is suppressed. The crosslinking reaction group to be supplied to the hydroxylation reaction may, for example, be an alkenyl group, an alkynyl group or a hydrogen group, and more preferably an alkenyl group or a hydrogen group.

In addition, the "hydrogen group" in the present invention means hydrogen which is directly bonded to a ruthenium atom in an organic ruthenium compound (H in a Si-H bond).

First, the case where the crosslinking reaction 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 may also be used in combination with a surface modifying material containing a phenyl group and a surface modifying material containing an alkenyl group.

Further, in order to uniformly disperse and stabilize the surface-modified metal oxide particle material in the polyoxymethylene resin composite or the composition, a surface-modifying material having another structure may be used in combination.

The reason why the phenyl group is contained in the surface-modifying material is to ensure the phenyl polyoxyl resin and the methylphenyl polyoxyl resin which are the substrates (hereinafter, these are collectively referred to as "(meth)phenyl group). The interface affinity of the polyoxyl resin and the surface modification of the metal oxide particles by the π-π stacking of the phenyl group of the surface modifying material and the phenyl group of the (meth) phenyl polyoxyl resin The phenyl phthalocyanine resin is close to thereby reducing the polyoxymethylene resin composite The gap in the middle can suppress the gas permeability.

The reason why the surface-modifying material contains an alkenyl group is that the alkenyl group in the surface-modifying material and the hydrogen-based group in the polyoxo-oxygen resin forming component of the matrix are polymerized and hardened (the siloxane polymer) The H (hydrogen) which is directly bonded to Si can be bonded by a crosslinking reaction (hydrazine hydrogenation reaction) to prevent the surface-modified metal oxide particle material from being separated from the matrix polyoxyl resin during the polymerization hardening. Moreover, by crosslinking the surface-modified metal oxide particle material with the matrix polyoxy-oxygen resin, the surface-modified metal oxide particle material can be brought close to the matrix polyoxyl resin to reduce the gap in the polyoxy-resin composite. It can suppress the gas permeability.

Further, by using a surface-modifying material having excellent heat resistance, it is possible to suppress a decrease in transmittance due to aggregation of particles at a high temperature (reduction in particle dispersibility) or coloration of the surface treatment agent itself, and thus, loss of matrix aggregation The heat resistance of the oxygen resin suppresses the gas permeability. Here, the term "heat resistance is excellent" means that the surface modification structure is not changed after the heat load test (150 ° C, 1000 hours) (that is, the surface-modified metal oxide particle material in the resin composition is not present by the heat load) In the case where aggregation occurs, the dispersibility changes, or the surface modification material in the resin composition or the resin composite is colored by heat load, the same applies hereinafter.

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

Formula (1)(C ₆ H ₅ ) _n SiX _4-n

(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 carboxyl group, and when 4-n is 2 or more, all X's may be the same. Or not with)

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

Specific examples thereof include phenyltrimethoxydecane, diphenyldimethoxydecane, phenyl polyfluorene having a single terminal alkoxy group, and methylphenyl polyoxyxoxide having a single terminal alkoxy group. The alkoxy group-containing phenyl polyoxyl resin, the alkoxy group-containing methylphenyl polyoxyl resin, and the like, and the phenyl group-containing surface modifying material may, for example, be benzoic acid, methyl benzoate or toluene. A phenyl-containing organic acid compound such as formic acid or phthalic acid.

Among these, from the viewpoint of excellent heat resistance, phenyltrimethoxydecane, diphenyldimethoxydecane, phenylpolyoxyl which is alkoxy at one terminal, and alkane at the single terminal are preferred. Alkyl phenyl polyfluorene oxy, alkoxy-containing phenyl polyoxyl resin, alkoxy-containing methyl phenyl polyoxyl resin.

The surface-modified 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 represented by the following formulas (3) and (4).

Formula (3) CH ₂ =CH-C _n H _2n -SiX _m (CH ₃ ) _3-m

(In the formula (3), n is an integer of 0 or more, 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 carboxyl group, and when m is 2 or more , all Xs may be the same or different)

(In the formula (4), n is an integer of 1 to 100, m is an integer of 1 to 3; and X is selected from a methoxy group, an ethoxy group, a hydroxyl group, a halogen atom, and a carboxyl group, and when m is 2 or more All Xs may be the same or different)

Specific examples thereof include vinyl trimethoxy decane and a dimethyl phthalocyanine having a single terminal terminal and a single alkoxy group as a vinyl group. Further, examples of the surface-modifying material containing an alkenyl group include a structure of a hydrocarbon chain branch of the formula (3) or a structure containing an alkenyl group in a branched hydrocarbon chain, and methacryloxypropyltrimethoxy group. An acrylic decane coupling agent such as decane or acryloxypropyltrimethoxy decane or a fatty acid having a carbon-carbon unsaturated bond such as methacrylic acid.

Among these, from the viewpoint of excellent heat resistance, vinyl trimethoxy decane, a mono-terminal alkoxy group having a single terminal vinyl group, and a hydrocarbon chain of the formula (3) are preferred. The structure of the branch or the material containing the structure of the alkenyl group on the branched hydrocarbon chain.

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, and examples thereof include styryltrimethoxydecane or The single terminal represented by the formula (5) is a phenyl polyfluorene having a single alkoxy group as a vinyl group, and a methylphenylpolyoxy group having a single terminal terminal and a vinyl group having a single terminal terminal and a vinyl group. These are also excellent in heat resistance.

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

Next, the case where the crosslinking reaction group of the surface modifying material is a hydrogen group will be described. In addition, the "hydrogen group" in the present invention means hydrogen which is directly bonded to a ruthenium atom in an organic ruthenium compound (H in a Si-H bond). Further, the hydrogen group may be referred to 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 may also be used in combination with a surface modifying material containing a phenyl group and a surface modifying material containing a hydrogen group.

Further, in order to uniformly disperse and stabilize the surface-modified metal oxide particle material in the polyoxymethylene resin composite or the composition, a surface-modifying material having another structure may be used in combination.

The reason why the phenyl group is contained in the surface modifying material is as described above.

The reason why the surface-modifying material contains a hydrogen group is that when the polyoxyphthalocene resin composition is polymerized and hardened, the hydrogen group of the surface modifying material and the alkenyl group or alkynyl group in the polyoxon oxide forming component which becomes the matrix can be exchanged. The bonding reaction (hydrazine hydrogenation reaction) is bonded to prevent the surface-modified metal oxide particle material from being separated from the matrix polyoxymethylene resin during the polymerization hardening. Moreover, by crosslinking the surface-modified metal oxide particle material with the matrix polyoxy-oxygen resin, the surface-modified metal oxide particle material can be brought close to the matrix polyoxyl resin to reduce the gap in the polyoxy-resin composite. It can suppress the gas permeability. In addition, the "resin forming component" will be described later.

Thus, by making the surface modification material contain a phenyl group and a hydrogen group, the compatibility of the surface modification material with the matrix polyoxymethylene resin containing the (meth) phenyl polyoxyl resin is improved and integrated. It is prevented from lowering the transmittance due to aggregation of particles during heat load. Moreover, since it is not necessary to have an epoxy group or a vinyl group, the coloring cause itself at the time of a heat load can be eliminated. Further, the phenyl itself has high heat resistance. As described above, the surface treatment material of the present invention has high heat resistance itself.

Moreover, since the matching of the surface modifying material with the matrix polyoxyl resin is improved and integrated, the gas barrier property is also high.

As described above, by using a surface modifying material excellent in heat resistance, the heat resistance of the matrix polyoxynoxy resin can be impaired to suppress the gas permeability.

The surface modification 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, and examples thereof include triethoxydecane, dimethylethoxysilane, and diethoxymethyl. Base decane, dimethyl chlorodecane, ethyl dichlorodecane, and the like.

Among these, from the viewpoint of excellent heat resistance, triethoxydecane, dimethylethoxydecane, and diethoxymethyldecane are preferred.

The surface-modifying material containing both a phenyl group and a hydrogen group is not particularly limited as long as it contains a phenyl group and a hydrogen group (Si-H bond), and is represented by the following formulas (6) and (7). It A material of a structure or a polyoxyxylene material containing a phenyl group and an alkoxy group and further containing a resin structure (three-dimensional network structure) of hydrogen directly bonded to hydrazine.

(6)(C ₆ H ₅ ) _n SiH _m X _4-nm

(In the formula (6), n and m are 1 or 2, and the total of n and m is 3 or less; and X is selected from a methoxy group, an ethoxy group, a hydroxyl group, a halogen atom, and a carboxyl group, and is a 4-nm group. In the case of 2 (in the case of n=m=1), the two Xs may be the same or different)

(In the formula (7), a is an integer from 1 to 100, and b is an integer from 0 to 100; and A, B, C, and D are one selected from the group consisting of a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a hydrogen group. Or two or more, and at least one of A and B is a phenyl group; A, B, C, and D may all be a phenyl group; and, by virtue of Si, A, B, and O, The position and arrangement of the sites composed of Si, C, D, and O are arbitrary, and are a random polymer type; X is selected from a methoxy group, an ethoxy group, a hydroxyl group, a halogen atom, and a carboxyl group, and c is 2 In the above case, all X may be the same or different; when at least one of A, B, C, and D is a hydrogen group, c is an integer of 1 to 3, and d is an integer of 0 to 2, and When the total of c and d is 3 or less, and when A, B, C, and D do not contain a hydrogen group, c and d are 1 or 2, and the total of c and d is 3 or less)

Specific examples thereof include phenyl dichlorodecane, diphenylchlorodecane, phenylchlorodecane, and phenyldiethoxydecane.

In addition, in the polyoxyxylene resin composition or the polyoxymethylene resin composite, the surface modification material which is another structure used for the purpose of uniformly dispersing and stabilizing the metal oxide particles is exemplified by a single terminal. The dimethyloxypolyoxy group of the alkoxy group and the dimethylpolyoxyl group having a single a terminal alkoxy group as a vinyl group, a single-end epoxy polyfluorene oxide, an alkyl decane compound, a fatty acid compound and the like.

Next, the case where the crosslinking reaction 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 groups of a phenyl group, a hydrogen group and an alkenyl group in one surface modifying material, and may be used in combination with one of the three kinds of bases and another type of base. Contains three bases.

That is, in the present invention, the surface modification may be performed by a surface modification material having a hydrogen group, or may be subjected to surface modification using a surface modification material having at least a phenyl group and an alkenyl group. Further, surface modification may be carried out by surface modification with an alkenyl group (or alkynyl group) after surface modification using a surface modification material having at least a phenyl group and a hydrogen group or at the same time as the surface modification. Thereby, both a hydrogen group and an alkenyl group (or an alkynyl group) can be supported and supported on the surface of the metal oxide particle.

The above surface-modified material having an alkenyl group and a surface-modifying material having a hydrogen group are as described above.

Further, in order to uniformly disperse and stabilize the surface-modified metal oxide particle material in the polyoxymethylene resin composite or the composition, a surface-modifying material having another structure may be used in combination.

As described above, the alkenyl group in the surface modifying material can be integrated by the crosslinking reaction (hydrazine hydrogenation reaction) bonding with the hydrogen group in the matrix polyoxyn resin forming component when the polyoxyxene resin composition is polymerized and cured. Further, the hydrogen group in the surface modifying material may be integrated with the alkenyl group or the alkynyl group in the matrix polyoxyn resin forming component by the crosslinking reaction (hydrazine hydrogenation reaction) bonding when the polyoxyxylene resin composition is polymerized and hardened. . And, by the bonding action, aggregation can be prevented The surface-modified metal oxide particle material in the hardening process is separated from the matrix polyoxyxene resin, and the surface-modified metal oxide particle material is brought close to the matrix polyoxyl resin to reduce the gap in the polyoxy-resin composite. Inhibits breathability.

Here, the hardening of the matrix polyoxyl resin forming component is as follows, and it is preferred to select an addition hardening type. The addition hardening refers to a hydrogen group disposed in a siloxane polymer in a polyoxynene resin forming component and an alkenyl group (or alkynyl group) in the same siloxane polymer by using a platinum group metal. It is polymerized by an addition reaction (hydrogenation reaction) of a catalyst, whereby it is hardened. Therefore, the matrix polyoxyn resin forming component contains at least a hydrogen group-containing polyoxyn resin forming component and an alkenyl group containing a alkenyl group (or alkynyl group).

Therefore, by supporting the alkenyl group (or alkynyl group) together with the hydrogen group on the surface of the metal oxide particle, not only the alkenyl group on the surface of the metal oxide particle but also the hydrogen group in the matrix polyoxo resin can be formed. The crosslinking reaction is carried out, and the hydrogen group on the surface of the metal oxide particles can be cross-linked with the alkenyl group (or alkynyl group) in the matrix polyoxo resin forming component, so that the metal oxide particles and the matrix can be further realized. Integration of polyoxyl resin.

Further, when an excess of an alkenyl group or an alkynyl group remains in the polyoxyxene resin composite, there is a possibility of coloration upon heat load. Therefore, it is preferred that the alkenyl group and the alkynyl group contained in the polyoxyxylene resin composition are consumed as much as possible by hydrogenation reaction with a hydrogen group or the like. Therefore, the total amount of the hydrogen groups contained in the polyoxyxene resin composition is preferably an amount greater than the amount of the alkenyl group and the alkynyl group, and is 1.2 times or more (i.e., the hydrogen group is excessive). State) is better. Here, the total amount means a total amount of the amount in the surface modifying material and the amount in the matrix polyoxyl resin forming component.

Examples of the surface modification method of the metal oxide particles by the surface modifying material include a wet method or a dry method. Examples of the wet method include the introduction of metal oxide particles, a surface modifying material, and, if necessary, a catalyst for hydrolyzing a surface modifying material into a solvent, and applying energy from the outside such as heating and stirring or a bead medium to the solvent. A method in which metal oxide particles are surface-modified while being dispersed. Also, the dry method can be cited as one side. A method of obtaining surface-modified metal oxide particles by mixing metal oxide particles and a surface modifying material by a kneading machine or the like.

The surface modification amount (surface modifying material/metal oxide particle) of the surface modifying material with respect to the metal oxide particles is preferably 5 to 40% by mass. When the amount of the surface modification is within this range, the dispersibility of the surface-modified metal oxide particle material in the following polyoxynoxy resin can be maintained high, and the decrease in transparency or the gas permeability can be suppressed.

The surface modification amount is more preferably from 10 to 30% by mass.

Further, the surface modification amount was obtained by heat-treating the surface-modified metal oxide particles dried at 150 ° C at 750 ° C, and calculating the mass reduction amount after the heat treatment as the mass of the surface-modifying material.

[2. Dispersion]

The dispersion liquid 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 of the present invention, since the surface-modified metal oxide particle material of the present invention is dispersed in a dispersion medium, the surface-modified metal oxide can be obtained by combining it with a matrix polyoxyl resin-forming component. The particulate material is dispersed in the matrix polyoxyn resin forming component in a uniform and good dispersion state, whereby a polyoxyxylene resin composition excellent in moldability and workability and excellent in transparency can be obtained, and further hardened. A polyoxymethylene resin composite.

The content of the particulate material in the dispersion liquid of the present invention is preferably 5% by mass or more and 50% by mass or less. By setting the content of the particulate material within this range, the particulate material can be obtained in a well dispersed 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 which can disperse the particulate material, and for example, water; methanol, ethanol, 1-propanol, 2-propanol, butanol, octanol or the like; Ester, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyrolactone and other esters; diethyl ether, ethylene glycol monomethyl ether (methyl cellosolve Ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and other ethers; acetone, methyl Ketones such as ethyl ketone, methyl isobutyl ketone, acetamidine acetone, cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, and ethyl decylamine; dimethylformamide, N, N-di A guanamine such as methyl acetamide or N-methylpyrrolidone may be used alone or in combination of two or more.

Further, in order to improve the dispersibility of the particulate material or the stability of the dispersion, the dispersion of the present invention may contain a dispersant, a surface treatment agent, a water-soluble binder, or the like (dispersant or the like) within a range that does not impair the properties thereof.

As the dispersing agent or surface treating agent, a cationic surfactant, an anionic surfactant, a nonionic surfactant, a decane coupling agent such as an organoalkoxysilane or an organochlorodecane, and a condensing agent B can be preferably used. A polymer dispersant such as a polyimide-based polymer dispersant, a polyurethane-based polymer dispersant, or a polyallylamine-based polymer dispersant, and the dispersant or surface treatment agent is only required to have a particle diameter according to the composite fine particles. The type of the target dispersion medium may be appropriately selected, and one or two or more kinds of the above-mentioned dispersing agents may be used in combination. As the water-soluble binder, polyvinyl alcohol (PVA, polyvinyl alcohol), polyvinyl pyrrolidone (PVP), hydroxy cellulose, polyacrylic acid or the like can be used.

The amount of the dispersing agent or the like (the amount of the solid content component) is preferably in the range of 1 to 15% by mass, more preferably 2 to 10% by mass, based on the particle material.

As a method for carrying out the dispersion treatment, a known dispersion device may be used singly or in combination, and for example, a bead mill, a nanomizer, a jet mill, a homogenizer, a planetary mill may be used alone or in combination. , ultrasonic disperser, etc. Among them, a bead mill which can easily control the dispersed particle diameter by the selection of the bead diameter can be preferably used. The time required for the dispersion treatment may be any time sufficient for uniformly dispersing the particulate material in the dispersion medium.

[3. Polyoxyl resin composition]

The polyoxyxylene resin composition of the present invention comprises at least the surface-modified metal oxide particle material of the present invention and a component selected from the group consisting of a phenyl polyoxyl resin-forming component and a methylphenyl-polyoxyl resin-forming component. The above polyoxyxylene resin is formed into a component, and the polyoxyxylene resin forming component has a combination of functional groups capable of crosslinking reaction with a group of a surface modifying material used in the surface-modified metal oxide particle material. Things.

In addition, the "resin composition" is a non-reversible deformability that cannot be restored to its original shape when it is deformed because it has fluidity, and is a transparent resin composite described below. Raw materials. The state of the resin composition can be, for example, a liquid state or a gel state having a shaken property. In addition, the "resin forming component" is a component for forming a resin component in the following resin composite, and is usually a monomer, oligomer or prepolymer of a resin component, and contains a liquid.

Here, the polyoxyphthalocene resin forming component used in the polyoxyxylene resin composition of the present invention contains one selected from the group consisting of a phenylpolyoxyl resin forming component and a methylphenylpolyoxyl resin forming component. The functional group which can be crosslinked with the group (crosslinking reactive group) of the surface modifying material used in the surface-modified metal oxide particle material is not particularly limited. On the other hand, as described above, as the crosslinking reaction, a hydrogenation reaction is preferred, and as the crosslinking reaction group to be supplied to the hydrogenation reaction, an alkenyl group or a hydrogen group is preferred. In this respect, as a preferable combination of the surface-modified metal oxide particle material and the polyoxynoxy resin-forming component, the following may be mentioned.

(1) When the crosslinking reaction group in the surface-modified metal oxide particle material is an alkenyl group: a polyfluorene-oxygen resin-forming component having a hydrogen group.

(2) When the crosslinking reaction group in the surface-modified metal oxide particle material is a hydrogen group: a polyfluorene oxide resin-forming component having one or more selected from the group consisting of an alkenyl group and an alkynyl group.

(3) When the crosslinking reaction group in the surface-modified metal oxide particle material is an alkenyl group and a hydrogen group: a polyoxygen tree having one or more selected from an alkenyl group and an alkynyl group and a hydrogen group Lipid forming ingredients.

The total amount of the metal oxide particles in the polyoxyxene resin composition is 5% by mass or more based on the total amount of the surface-modified metal oxide particles and the polyoxymethylene resin-forming component. When the content is less than 5% by mass, the effect of reducing the gas permeability of the polyoxymethylene resin composite obtained by curing the resin composition is reduced, so that a substantial effect due to the inclusion of the metal oxide particles cannot be obtained. The content is preferably from 20 to 80% by mass, more preferably from 30 to 70% by mass. Further, here, the content of the metal oxide particles does not include a surface modifying material.

(Polyoxygenated resin forming component)

The polyoxyphthalocene resin-forming component contains at least one selected from the group consisting of a phenylpolyoxyl resin-forming component and a methylphenylpolyoxyl resin-forming component.

Examples of the phenylpolyoxyl resin forming component include those in which a phenyl group is disposed in a siloxane polymer. Examples of the methylphenyl polyfluorene resin forming component include a phenyl group and a methyl group (alkyl group) in the siloxane polymer. Further, there is also a modified polyxanthoxy resin in which a phenyl alkoxy structure having a phenyl group is combined with an epoxy group or another hydrocarbon. As the structure, in addition to the linear shape, there are a chain of two-dimensional structures, a resin of a three-dimensional network structure, a cage structure, and the like.

The phenylpolyoxyl resin forming component and the methylphenyl polyoxynene resin forming component may be used singly or in combination (hereinafter, a phenylpolyoxyl resin is sometimes formed into a component, and a methylphenyl polyoxyl resin is sometimes used. The component and the combination of the two components are collectively referred to as "(meth)phenyl polyfluorene resin forming component"). Further, those having various structures as described above may be combined, and the modified polyxanthoxy resin as described above may be further added.

First, the polyanthracene oxide-forming component having a hydrogen group contains one or more selected from the group consisting of the phenylpolyoxyl resin-forming component and the methylphenylpolysiloxane-forming component, and further has a hydrogen group. Further, the hydrogen group means H (hydrogen) which is directly bonded to Si, that is, H (hydrogen) in the Si-H bond, which forms a polyoxyalkylene resin forming component of a polyoxyxylene resin. Further, the hydrogen group may be referred to as "Si-H group".

Here, in the polyfluorene resin forming component, other polyoxyphthalocene resin forming components may be contained in addition to the (meth) phenylpolyfluorene resin forming component. In other words, the polyanthracene resin forming component in the present invention has a hydrogen group, and means that a hydrogen group can be contained in the (meth)phenyl polyfluorene resin forming component, and hydrogen can be contained in other polyoxyn resin forming components. The base (may be referred to as a "hydrogen oxime resin forming component"), and further may contain a hydrogen group in both of them.

According to the polyoxyxylene resin composition, the surface-modified metal oxide particles in the polymerization hardening process can be prevented by integrating the hydrogen group in the polyoxonium resin forming component and the alkenyl group of the surface modifying material by crosslinking reaction. The phase separation of the material from the matrix polyoxyl resin further brings the surface-modified metal oxide particle material closer to the matrix polyoxyl resin, thereby reducing the gap in the polyoxymethylene resin composite and suppressing the gas permeability.

In the case where the hydrogen group is contained in the (meth) phenyl polyfluorene resin forming component, for example, at least a phenyl group and a hydrogen group are disposed in one siloxane polymer. Further, as long as the condition is satisfied, a phenyl group and a hydrogen group may be arbitrarily disposed in one of the siloxane polymers. In terms of polymerization reactivity, it is preferred to dispose two or more hydrogen groups in one siloxane polymer.

On the other hand, examples of the hydrogen polyoxynene resin forming component include hydrogen (hydrogen group: Si-H bond) in which a part of the Si-bonded base of the siloxane polymer is hydrogen. In terms of polymerization reactivity, it is preferred to dispose two or more hydrogen groups in one siloxane polymer. Further, the group other than the hydrogen group bonded to Si is usually an alkyl group such as a methyl group, but may be a modified polyfluorene oxygen in which an epoxy group or another hydrocarbon is combined, and has a structure other than a linear chain. It can also be a chain of two-dimensional structures or a three-dimensional network structure, a cage structure, and the like.

In the above, the polyanthracene resin forming component having one or more selected from the group consisting of an alkenyl group and an alkynyl group contains at least one selected from the group consisting of the phenylpolyoxyl resin forming component and the methylphenyl polyfluorene resin forming component. Further, it has one or more selected from the group consisting of an alkenyl group and an alkynyl group.

Here, in the polyfluorene resin forming component, other polyoxyphthalocene resin forming components may be contained in addition to the (meth) phenylpolyfluorene resin forming component. In other words, the polyoxyphthalocene resin-forming component in the present invention has one or more selected from the group consisting of an alkenyl group and an alkynyl group, and means that the (meth) phenyl polyfluorene resin-forming component contains an alkenyl group. And one or more of the alkynyl groups may contain one or more selected from the group consisting of an alkenyl group and an alkynyl group in the other polyoxo-oxygen resin-forming component (sometimes the polyoxy-oxyl resin-forming component is referred to as an "alkenyl group". The polyoxymethylene resin forming component of the acetylene group may further contain one or more selected from the group consisting of an alkenyl group and an alkynyl group.

According to the polyoxyxylene resin composition, the alkenyl group or the alkynyl group which forms a component of the polyoxyxylene resin and the hydrogen group of the surface modifying material are bonded by a crosslinking reaction (hydrazine hydrogenation reaction) to prevent polymerization hardening. The phase-modified metal oxide particle material in the process is separated from the matrix polyoxyxene resin, thereby bringing the surface-modified metal oxide particle material close to the matrix polyoxyl resin, thereby narrowing the gap in the polyoxymethylene resin composite. , inhibits breathability.

In the above-mentioned (meth) phenyl polyfluorene resin forming component, one or more selected from the group consisting of an alkenyl group and an alkynyl group, for example, at least a phenyl group and at least one siloxane group are disposed. One or more bases selected from the group consisting of alkenyl groups and alkynyl groups. In addition, as long as the condition is satisfied, one of a phenyl group and one or more selected from the group consisting of an alkenyl group and an alkynyl group may be optionally disposed in one siloxane polymer. In terms of polymerization reactivity, it is preferred to dispose two or more alkenyl groups or alkynyl groups in one siloxane polymer.

The alkenyl group may, for example, be a vinyl group, an allyl group, a butenyl group, a pentenyl group or a hexenyl group, and more preferably a vinyl group. Further, examples of the alkynyl group include an ethynyl group and a propynyl group. Also, the alkenyl or alkynyl groups may be arbitrarily combined. For example, a phenyl group and a vinyl group are usually disposed in one siloxane polymer, but it is not limited thereto, and a phenyl group, a vinyl group (alkenyl group), and an ethynyl group may be disposed in one siloxane polymer. (alkynyl). Further, it may be used in combination with a phenyl group and a vinyl group (alkenyl group) in one oxoxane polymer and a phenyl group and an ethynyl group (alkynyl group) in another oxoxane polymer. .

In addition, examples of the alkenyl group-containing alkynyl group-forming polyoxymethylene resin component include a base selected from the group consisting of an alkenyl group and an alkynyl group. The position of the alkenyl group or the alkynyl group in the siloxane polymer is not particularly limited, and may be disposed at any position. Further, in terms of polymerization reactivity, it is preferred to dispose two in one siloxane polymer. More than one alkenyl or alkynyl group. Further, it may be a modified polyoxane combined with an epoxy group or other hydrocarbons. The molecular structure may, for example, be a linear chain, a part of a linear chain having a branch, a branch, a ring, or a resin, and more preferably a linear or a part of a linear chain having a branch.

In addition, the combination of the alkenyl group or the alkynyl group is not particularly limited as long as it has one or more selected from the group consisting of an alkenyl group and an alkynyl group in the component (meth) phenyl polyfluorene resin. Further, for example, a polyphenylene oxide resin-forming component having an alkenyl group-containing phenylpolyfluorene resin-forming component and an alkynyl group-containing alkenyl group may be combined.

Further, the polyanthracene oxide-forming component having one or more selected from the group consisting of an alkenyl group and an alkynyl group and a hydrogen group is a component of the above-mentioned polyfluorene oxide-forming resin having a hydrogen group, and the above-mentioned one having an alkenyl group and an alkynyl group. One or more kinds of polyoxyxylene resin forming components are combined. The combination or arrangement of one or more selected from the group consisting of alkenyl groups and alkynyl groups in the polyoxynene resin forming component and the hydrogen group is arbitrary, and for example, it may be selected from an alkenyl group and an alkynyl group in one alkoxyalkylene polymer. One or more of them and a hydrogen group may be a mixture of a polyfluorene-oxygen resin-forming component having one or more selected from the group consisting of an alkenyl group and an alkynyl group, and a polyfluorene-oxygen resin having a hydrogen group.

The polyoxyxylene resin composition of the present invention has a case where at least a (meth) phenylpolyfluorene resin forming component is contained as a resin component, and a surface modifying material having a surface-modified metal oxide particle material is used. The polyoxyxyl resin forming component having a functional group for performing a crosslinking reaction further contains a polyoxyxylene resin forming component required for forming a matrix polyoxyalkylene resin. The combination of each component is not particularly limited as long as the components are compatible.

Unhardened (methyl) phenyl polyfluorene resin forming component or having crosslinkable The refractive index or viscosity of the polyoxyxyl resin forming component of the functional group varies depending on the structure or chain length of the siloxane polymer, the amount of phenyl or alkyl group in the siloxane polymer, or the carbon number, etc. These characteristic values are also reflected in the hardened polyoxynoxy resin. Therefore, by mixing and adjusting a plurality of resin-forming components in an uncured state, it has a refractive index required as a matrix-polyoxyl resin after hardening, and good formability of the polyoxyxene resin composition can be obtained or Workability. Further, in addition to the combination of the phenyl polyoxyl resin forming component and the methylphenyl polyoxyl resin forming component or the polyoxyxyl resin forming component having a functional group capable of undergoing a crosslinking reaction, By adjusting the type or amount of the modified polyxanthene resin to be added, it is possible to control characteristics such as hardness, contact property, and adhesion to the substrate of the obtained polyoxymethylene resin composite.

Further, in the case of the moldability or the workability, when the polyoxyxene resin composition is to have a low viscosity, it may be added with a (meth) phenyl polyfluorene resin or may have a component. The polyoxyxyl resin forming component of the functional group capable of crosslinking reaction has compatibility and does not inhibit the organic solvent of the surface-modified metal oxide particles. Examples of such an organic solvent include a dispersion medium used in the above dispersion liquid.

In the resin composite after hardening, as a liquid (unhardened) polyoxyl resin forming component (matrix polyoxyl resin forming component) which forms a matrix polyoxyn resin, according to the hardening method, addition hardening is mentioned A polyoxygenated composition or a condensed hardening polydecaneoxy composition. The addition-hardening polyoxymethylene composition is a composition comprising at least an alkenyl group and a hydrogen group-containing polyanthracene resin-forming component and a platinum group-based catalyst, and the alkenyl group and the hydrogen group are reacted by addition reaction. (矽 hydrogenation reaction) and bonding, whereby the polyoxymethylene resin forming components are polymerized and hardened.

The condensation-hardening polyoxosiloxane composition is a polydecane-oxygen resin-forming component having at least a terminal of a molecular chain blocked by a hydroxyl group or a hydrolyzable group, and a decane compound containing at least three hydrolyzable groups bonded to a ruthenium atom in one molecule. And a composition comprising a condensation catalyst of an aminooxy group, an amine group, a ketoximino group or the like, which is dehydrated by the above hydroxyl group or a hydrolyzable group and a hydrolyzable group The condensation reaction is carried out to bond, so that the polyoxyphthalocene resin forming component is polymerized with the decane compound to be hardened. Therefore, the polyoxon resin-forming component contains at least a polyfluorene-oxygen resin-forming component whose molecular chain terminal is blocked by a hydroxyl group or a hydrolyzable group, and one molecule containing three or more hydrolyzable groups bonded to a ruthenium atom. A composition of a decane compound and a condensation catalyst containing an amineoxy group, an amine group, a ketoximino group or the like. Further, as described above, a phenyl group or a methyl group (alkyl group) is disposed in the polyoxyphthalocene resin forming component.

As the matrix polyoxymethylene resin forming component in the present invention, either of an addition hardening type and a condensation hardening type can be selected.

On the other hand, in the present invention, the crosslinkable reactive group (alkenyl group, alkynyl group, hydrogen group) of the functional group capable of undergoing the crosslinking reaction of the polyfluorene oxide forming component and the surface modifying material is subjected to a crosslinking reaction. The integration prevents the phase-modified metal oxide particle material from separating from the matrix polyoxyl resin, and the surface-modified metal oxide particle material is adjacent to the matrix polyoxyl resin to suppress gas permeability. Here, the addition reaction of the crosslinking reaction with the addition hardening type (hydrazine hydrogenation reaction) can be understood from the reaction group or the reaction state, and is the same reaction. Therefore, as long as the additive hardening type is selected as the matrix polyoxyl resin forming component or the reaction catalyst, the surface modified metal oxide particle material and the matrix polyoxyl resin can be crosslinked at the same time by a single reaction method. It is preferred to carry out the integration and hardening of the matrix polyoxyl resin itself. Further, in the case of the addition curing type, by-products such as water are not generated during the polymerization, and it is also preferable to remove the influence or by-products caused by the presence of by-products in the mixture.

Further, as described above, when the metal oxide particles supporting both the alkenyl group and the hydrogen group are modified, not only the alkenyl group on the surface of the metal oxide particles but also the hydrogen group in the matrix polyoxo resin forming component can be used. The crosslinking reaction, and the hydrogen group on the surface of the metal oxide particles and the alkenyl group (or alkynyl group) in the matrix polyoxo resin forming component can also be cross-linked, thereby further realizing the metal oxide particles and the matrix. Integration of oxygen resin.

Furthermore, if a condensation hardening type is selected as the matrix polyoxyl resin forming component, there is The advantages of the bonding of the surface-modified metal oxide particle material to the matrix polyoxyl resin and the hardening of the matrix polyoxyl resin can be separately controlled. However, in this case, it is necessary to first bond the surface-modified metal oxide particle material to the matrix polyoxyl resin by using a crosslinking reaction (the same as in the case of the addition curing type), on the basis of which the matrix polyoxyl resin is used. Condensation hardening. The reason for this is that when the surface-modified metal oxide particle material and the matrix polyoxyl resin are not bonded, the matrix polyoxyl resin is hardened, and the surface-modified metal oxide particle material is agglomerated or phase-separated. There is no way to obtain a good polyoxymethylene resin composite.

(矽hydrogenation catalyst)

In the present invention, the crosslinking reaction group of the functional group capable of undergoing the crosslinking reaction of the polyfluorene resin forming component and the surface modifying material is integrated by a crosslinking reaction (hydrazine hydrogenation reaction). Therefore, the polyoxyxylene resin composition of the present invention preferably contains a rhodium hydrogenation catalyst.

The catalyst for the hydrogenation reaction in the present invention may, for example, be a platinum-based catalyst, a ruthenium-based catalyst or a palladium-based catalyst. In particular, in terms of a smooth hydrogenation reaction, a platinum-based catalyst is preferred. . Examples of the platinum-based catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, and an alkenyl alkoxylate complex of platinum.

The amount of the catalyst for the hydrogenation reaction may be an amount sufficient for crosslinking the surface-modified material of the polyfluorene resin-forming component and the surface-containing modifying material containing the crosslinking reaction group. Specifically, when a platinum-based catalyst is used as the catalyst for the hydrogenation reaction, it is preferred that the platinum metal has a mass relative to the above-mentioned alkenyl or alkynyl group-containing polyoxyl resin-forming component and hydrogen-containing group. The total amount of the surface-modifying materials is 0.1 to 100 ppm, particularly in terms of smooth hydrogenation reaction, and it is not easy to produce coloration in the polyoxymethylene resin composite obtained by the reaction, and more preferably Amount within the range of 1 to 50 ppm.

Further, in the case where the addition curing type is selected as the matrix polyoxyl resin forming component, since the hardening of the matrix polyoxyl resin is also dependent on the hydrogenation reaction, it is preferred to increase the amount of the catalyst in such a manner as to satisfy the above conditions. That is, the quality of the platinum metal relative to the alkenyl group or The total amount of the alkynyl group-containing polyoxo resin forming component, the hydrogen group-containing polyoxynoxy resin forming component, and the hydrogen group-containing surface modifying material is preferably 0.1 to 100 ppm, more preferably 1 to 50 ppm.

Further, as described above, when a metal oxide particle carrying a hydrogen group and an alkenyl group or an alkynyl group is modified, a base or alkynyl group on the surface of the metal oxide particle is formed with a matrix polyoxyl resin. Since the hydrogen group in the component also undergoes a crosslinking reaction, it is preferred to increase the amount of the catalyst in the same manner. That is, the mass of the platinum metal is relative to the polyoxyxylene resin-forming component containing an alkenyl group or an alkynyl group, the polyoxyxylene resin-forming component containing a hydrogen group, the surface-modifying material containing a hydrogen group, and the surface containing an alkenyl group or an alkyne group. The total amount of the modifying materials is preferably from 0.1 to 100 ppm, more preferably from 1 to 50 ppm.

When the mixed surface-modified metal oxide particle material and the matrix polyoxyl resin are used as a component, a method of directly introducing the surface-modified metal oxide particle material into the matrix polyoxyl resin-forming component and using a machine such as a kneading machine is exemplified. a method of mixing the ground; or dispersing the surface-modified metal oxide particle material in a dispersion medium such as an organic solvent to form a surface-modified metal oxide particle material dispersion, and polymerizing the dispersion with the substrate The method of mixing the epoxy resin-forming component with a stirrer or the like, followed by removal of an organic solvent.

The polydecane resin composition of the present invention can be obtained by mixing the two by any of the above methods. Further, the polyoxyxylene resin composition of the present invention may be one which contains an organic solvent or the like used in the above mixing process.

[4. Polyoxyl resin composite]

The polyoxyxylene resin composite of the present invention can be obtained by subjecting the matrix polyoxyl resin forming component in the above polyoxyxylene resin composition of the present invention to polymerization hardening by an addition reaction or a condensation reaction or the like, and The surface-modifying material of the metal oxide particles and the matrix polyoxyl resin-forming component are bonded by a crosslinking reaction to integrate the surface-modified metal oxide particles with the matrix polyoxy-resin.

Here, the "resin composite" has a specific shape, but the "specific shape" means that the resin composite does not have irreversible deformability such as liquid or gel, and can be maintained depending on the purpose of use or The fixed shape of the method. In other words, in addition to the solid shape which is hardly deformed in general, the elastic deformability (shape recovery property) such as rubber is also included, and the shape itself does not show a specific shape.

The shape of the polyoxymethylene resin composite is not particularly limited, and the shape thereof may be selected according to the use. Here, the polyoxyxylene resin used in the present invention is hardened by an addition reaction or a polymerization reaction, and does not exhibit thermoplasticity or solvent solubility as indicated by a usual resin. Therefore, the formation of the polyoxyxene resin composite is preferably carried out when the polyfluorene oxide resin composition is cured to form a polyoxyxene resin composite, or the hardened polyoxyxene resin is processed by cutting or the like. The complex is carried out. Here, a case where the polyoxyxene resin composition is cured to form a polyoxyxene resin composite will be described.

First, the polyoxyxylene resin composition of the present invention is molded using a mold or a mold, or filled in a mold or a frame-shaped container, whereby a molded body or a filler formed into a target shape is obtained. At this point in time, the formed body or the filler is in a fluid state.

In this case, when the viscosity of the polyoxyxene resin composition to be used is high and the formability is poor, an organic solvent or the like may be added in advance, and the mixture may be stirred and mixed to lower the viscosity, and adjusted to a viscosity suitable for molding or filling. .

On the other hand, in the case where the viscosity of the polyoxyxene resin composition to be used is low, it may be carried out by previously making a part of the matrix polyoxyl resin forming component or a part of the matrix polyoxyl resin forming component and the surface modifying material. Polymerization or cross-linking to increase the viscosity and adjust to a viscosity suitable for forming or filling. Further, when the polyoxyxene resin composition contains an organic solvent, it may be removed by partially or completely volatilizing one or more of the organic solvent, thereby increasing the viscosity. Further, the polyfluorene oxide resin composition may be used as a master batch in other resins.

Then, by directly or heating the shaped body or filler at room temperature (about 25 ° C) Allowing to a specific temperature (room temperature ~ 150 ° C, preferably 80 ° C ~ 150 ° C) for a specific time, or irradiating the shaped body or filler with an electron beam or light having any wavelength from the ultraviolet region to the infrared region (active energy ray), wherein the matrix polyoxyl resin forming component in the polyoxyxene resin composition is hardened by an addition reaction or a polymerization reaction or the like, and the surface modification material of the metal oxide particles is condensed with the matrix. The oxygen resin forming component is bonded by a crosslinking reaction to integrate the surface-modified metal oxide particles with the matrix polyoxyalkylene resin.

Further, in the case where an organic solvent remains in the molded body or the filler, it is preferred to volatilize the organic solvent in advance.

Thereby, a polyoxymethylene resin composite in a state in which the molded body or the filler can be maintained in a fixed shape by applying an external force after being taken out from the mold or the container can be obtained.

Furthermore, as long as there is no problem in use, it is not necessary to take out the polyoxymethylene resin composite from the mold or the container. For example, in the optical semiconductor light-emitting device described below, the device itself forms a shape of a container.

When the polyoxyxylene resin composite of the present invention is used for a sealing material of an optical semiconductor light-emitting device or the like, the refractive index thereof is preferably higher than 1.54, more preferably 1.56 or more, and further preferably 1.58 or more. If it is 1.6 or more, it is the best. By increasing the refractive index of the sealing material, the light extraction efficiency of the light-emitting semiconductor light-emitting device can be increased and the luminance can be increased.

Further, when the optical path length is 0.5 mm, the transmittance at a wavelength of 450 nm is preferably 40% or more, more preferably 60% or more, and still more preferably 70% or more. When the transmittance is within this range, for example, when a polyoxyxylene resin composite is used as an optical component, it is possible to suppress a decrease in light transmission loss as a constituent member.

The refractive index or transmittance of the polyoxyxene resin composite can be adjusted by appropriately adjusting the kind or particle diameter of the metal oxide particles, the composition of the matrix polyoxyl resin, the amount of the metal oxide particles in the polyoxyxene resin composite, and the like. Set to the desired range. In the polyoxyxene 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 high, so that the surface modification material does not become a high polyoxymethylene resin composite. The inhibition of refractive index.

Further, the refractive index of the polyoxyxene resin composite may be measured by a known method, and for example, by using a composite (1 mm thick) formed on an aluminum substrate, a tantalum coupler can be used at room temperature. The value of the wavelength of 594 nm was measured and found. The method of measuring the transmittance will be described later.

The use of the polyoxyxylene resin composite of the present invention is not particularly limited. In particular, it can be preferably used as an optical component or the like which utilizes the above-described excellent characteristics of the polyoxymethylene resin composite. Examples of the optical function device including the optical component include various display devices (such as a liquid crystal display or a plasma display), various projection devices (such as an OHP (Over Head Projector), a liquid crystal projector, and the like), and an optical fiber communication device. (optical waveguide, optical amplifier, etc.), an imaging device such as a camera or a video camera, an illumination device such as an LED illumination device, or the like.

[5. Optical semiconductor light-emitting device]

The optical semiconductor light-emitting device of the present invention is obtained by sealing a semiconductor light-emitting device with a sealing material, and the sealing material comprises the polyoxymethylene resin composite of the present invention, and the thickness of the sealing layer containing 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 sufficiently suppressed. The thickness of the sealing layer is preferably 100 μm or more, and more preferably 200 μm or more.

In the constitution of the sealing layer of the present invention, the entire sealing layer of the optical semiconductor light-emitting device may be a layer of the polyoxy-oxygen resin composite of the present invention (the first aspect), or may be a part of the sealing layer of the optical semiconductor light-emitting device. The layer of the polyoxymethylene resin composite of the invention is laminated with another sealing layer (second aspect). Further, the sealing layer may contain a phosphor.

Since the optical semiconductor light-emitting device of the present invention has excellent gas barrier properties as described above, deterioration of, for example, a silver-plated reflector provided in a light-emitting diode (LED) package can be suppressed, and the light-emitting diode can be removed. The brightness of the emitted light of the package is kept high and the decrease thereof is reduced, so that it can be effectively used as an illumination device or a liquid crystal image device having the same.

The optical semiconductor light-emitting device will be specifically described. Furthermore, the invention is not particularly Limited to the following examples.

As shown in FIG. 1, the first aspect (light-emitting device 10) of the present invention is such that the light-emitting element 14 is disposed in the concave portion 12A of the reflector cup 12, and is formed in contact with the light-emitting element 14 and buried in the concave portion. The first sealing layer 16 composed of a sealing material of the epoxy resin composite.

With this device, the light emitted from the light-emitting element 14 passes through the boundary surface with the sealing material, passes through the inside of the sealing material, and is directly or reflected by the wall surface of the reflecting cup 12 and is extracted to the outside.

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 can be exemplified ( For example, a blue light-emitting diode of light having a wavelength of 450 nm. The light-emitting diode may have a so-called face-up configuration or a flip-chip structure. In other words, the light-emitting diode system 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, and a structure in which light from the light-emitting layer is emitted to the outside through the substrate.

More specifically, the light-emitting diode has, for example, a first cladding layer including 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. a layer and a second cladding layer including a compound semiconductor layer having a second conductivity type (for example, p-type) formed on the active layer, and including a first electrode electrically connected to the first cladding layer, and a second electrode electrically connected to the second cladding layer. The layer constituting the light-emitting diode may be composed of a well-known compound semiconductor material depending on the light-emitting wavelength.

Here, the refractive index of the light-emitting layer of the light-emitting diode is, for example, about 3.5 in the GaAs system, about 3.2 in the GaP system, and about 2.5 in the GaN system, and the refractive index of the commonly used sapphire substrate is Around 1.75, it is quite high in either case. However, first The refractive index of the sealing material such as polyoxynoxy resin or epoxy resin which has been used before is at most about 1.4 to 1.5, and the refractive index difference between the luminescent layer and the sealing material or between the sapphire substrate and the sealing material is large. Therefore, most of the light from the light-emitting layer is totally reflected at the interfaces and enclosed in the light-emitting layer or the sapphire substrate, and the light extraction efficiency cannot be improved.

In the optical semiconductor light-emitting device of the present invention, by increasing the refractive index of the sealing material, the amount of light that is totally reflected between the light-emitting layer and the sealing material or between the sapphire substrate and the sealing material can be reduced, and the light extraction efficiency can be improved. In this respect, the refractive index of the sealing material is preferably higher than 1.54, more preferably 1.56 or more, more preferably 1.58 or more, and most preferably 1.6 or more. 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, still more preferably 70% or more.

In the second aspect (light-emitting device 20) of the present invention, as shown in FIG. 2, the first sealing layer 16 is formed to cover the surface of the light-emitting element 14, and the optical semiconductor element sealing composition of the present invention is formed on the outer side thereof. The second sealing layer 18 having a different composition is the same as the first aspect.

Examples of the material of the second sealing layer 18 having different compositions include a resin such as methyl polyfluorene oxide, modified polyfluorene oxide, acrylic resin, epoxy resin, and polyimide resin, or a resin composite. In order to further reduce the interface reflection between the first sealing layer 16 and the second sealing layer 18 and further reduce the interface reflection between the second sealing layer 18 and the outside, the refractive index of the second sealing layer 18 is preferably the first sealing layer 16 The refractive index is equal to or lower than 1 (the refractive index of the atmosphere) or more. Further, in order to adjust the refractive index of the second sealing layer 18, the surface-modified metal oxide particles of the present invention may be contained in the second sealing layer.

Moreover, the optical semiconductor light-emitting device of the present invention may 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 that is in contact with the optical semiconductor element is the above-described polyoxyxene resin composite of the present invention, but The first sealing layer contains, for example, a YAG (Yttrium Aluminum Garnet) phosphor for blue InGaN or a RGB (Red Green Blue) phosphor for ultraviolet light. Just fine. The phosphor may be contained in a polyoxyxylene resin composition for forming a polyoxymethylene resin composite as a sealing material of the present invention, and a method of directly mixing the phosphor with the phosphor may be mentioned. a method in a silicone resin composition, a method of mixing a phosphor in a phenylpolyoxyl resin forming component or a methylphenylpolyoxyl resin forming component, and dispersing a phosphor in an organic solvent or the like. A method in which a liquid is mixed in a polyoxyxylene resin composition, an organic solvent or the like is removed, and the like.

In particular, in consideration of the case where the amount of use of the phosphor is reduced in terms of cost, or when the phosphor is concentrated in the vicinity of the light-emitting element to improve the light conversion efficiency, it is preferable to make the first of the second aspect. The sealing layer contains a phosphor. The phosphor is preferably 5 to 80% by mass, more preferably 20 to 70% by mass, based on the mass of the first sealing layer. Further, a phosphor may be contained in the second sealing layer.

As such an optical semiconductor light-emitting device in which a light-emitting element and a phosphor are combined, a white light-emitting diode (for example, a light-emitting diode in which ultraviolet light or a blue light-emitting diode and a phosphor particle are combined to emit white light) can be exemplified. body).

[Examples]

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the Examples.

Various measurements and evaluations were carried out in the following manner in the following examples.

(average primary particle size of metal oxide particles)

The average primary particle diameter of the metal oxide particles is set to a Scherrer particle diameter obtained by calculation from a half-value width of the X-ray diffraction peak. The reason for this is that if the primary particle diameter is a nanometer size, the possibility that one particle is composed of a plurality of crystallites is lowered, whereby the average primary particle diameter is substantially the same as the Xerox particle diameter.

(Transmission rate of polyoxyl resin composite)

The transmittance of the polyoxymethylene resin composite was measured using a composite (0.5 mm thick) of an example formed on a glass substrate and using a spectrophotometer (integral sphere). Further, in Examples A1 to A5 and Comparative Examples A1 to A4, the amount of decrease in transmittance at a wavelength of 450 nm with respect to the polyoxyxylene resin monomer (Comparative Example 1) was less than 10%, and it was set to "A". 10% or more is set to "B". Further, in Examples B1 to B5 and Comparative Examples B1 to B6, the transmittance at a wavelength of 450 nm was determined.

(heat resistance of polyoxymethylene resin composite)

In Examples A1 to A5 and Comparative Examples A1 to A4, the heat resistance of the polyoxyxene resin composite was carried out by applying the above-mentioned 0.5 mm thick composite (hardened body) to an electric furnace at 150 ° C for 500 hours. The transmittance was measured using a spectrophotometer (integral sphere) and evaluated. When the transmittance at a wavelength of 450 nm after the heat load is reduced by 30% or more compared with the initial value (before the heat load), it is set to "B", and when the amount of decrease is less than 30%, it is set to "A".

On the other hand, in Examples B1 to B5 and Comparative Examples B1 to B6, the composite (0.5 mm thick) of the example formed on the glass substrate was used, and the transmission was measured using a spectrophotometer (integral sphere). Rate and evaluate. Specifically, the polyoxyxylene resin composite is put into a dryer at 120 ° C, and the transmittance and the initial transmittance at 450 nm after 1000 hours are compared, and the reduction rate with respect to the initial transmittance is less than 5 % is set to "A", 5% or more and less than 25% are set to "B", and 25% or more is set to "C".

(The gas permeability (gas barrier property) of the polyoxymethylene resin composite)

The gas permeability (gas barrier property) of the polyoxymethylene resin composite was evaluated in the following manner.

First, the polyoxyxene resin composition was sealed in an LED package having a silver-plated reflector, and the polyoxyxene resin composition was heat-treated at 150 ° C for 3 hours to be hardened to obtain a composite of the examples. The package was sealed with 0.3 g of sulfur powder in a 500 ml pressure-resistant glass container and kept at 80 °C. Visually observing the change in the appearance of the silver-plated reflector over time (corrosion of silver plating due to sulfur-containing gas (blackening discoloration)), in Examples A1 to A5, Comparative Examples A1 to A4, and without metal Oxide particles of oxide particles (comparison In the case of the example A1), the time required for the discoloration to be slower and the equivalent blackening is 1.5 times or more is set to be "A", and the discoloration is slower than that of the polyoxyxylene resin. It is set to "B" when the blackening time is less than 1.5 times, and it is set to "C" when it is discolored similarly to polyoxyl resin.

On the other hand, in Examples B1 to B5 and Comparative Examples B1 to B6, the blackening of the appearance of the silver-plated reflector (corrosion of silver plating by black-containing gas (blackening discoloration)) was visually observed to The evaluation was carried out until the same time as the other prepared reference plate (the black-plated reflector was directly blackened by the sulfur-containing gas). Furthermore, the lower the gas barrier property, the shorter the time until blackening.

(Evaluation of hardness of polyoxyl resin composite)

The hardness evaluation of the polyoxymethylene resin composite was "A" in the case where no polysulfide resin composite was produced, and "B" in the case where cracks occurred (Examples B1 to B5, Comparative Examples) B1~B6).

(including the thickness of the sealing layer of the polyoxymethylene resin composite)

The thickness of the sealing layer containing the polyoxymethylene resin composite was measured by observing the cross section of the package by SEM (Scanning Electron Microscope).

[Example A1] (Production of zirconia particles)

In the zirconium salt solution obtained by dissolving 2615 g of zirconium oxychloride octahydrate in 40 L (liter) of pure water, the diluted ammonia water obtained by dissolving 344 g of 28% aqueous ammonia in 20 L of pure water was stirred to prepare oxidation. Zirconium precursor slurry.

Then, a sodium sulfate aqueous solution obtained by dissolving 300 g of sodium sulfate in 5 L of pure water was added to the slurry while stirring. The amount of sodium sulfate added at this time was 30% by mass in terms of zirconium oxide equivalent value of zirconium ions in the zirconium salt solution.

Then, using a drier, the mixture is dried in the atmosphere at 130 ° C for 24 hours. When it is obtained, solid matter is obtained.

Then, the solid matter was pulverized by an automatic mortar, and then fired in the air at 500 ° C for 1 hour in an electric furnace.

Then, the calcined product is poured into pure water, stirred to obtain a slurry, and then washed with a centrifugal separator to sufficiently remove the added sodium sulfate, and then dried by a dryer to obtain an average primary particle diameter. 4 nm zirconia particles.

(Surface modification of zirconia particles: production of surface-modified zirconia particles)

Then, 8 g of toluene and 5 g of a methoxy group-containing phenyl polyfluorene resin (manufactured by Shin-Etsu Chemical Co., Ltd., KR217) were added to 10 g of zirconia particles and mixed, and the beads were removed by a bead mill for 6 hours to remove the beads. grain. Then, 3 g of vinyltrimethoxydecane (KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and surface modification and dispersion treatment were carried out at 130 ° C for 6 hours under circulation, thereby preparing a surface-modifying material having a phenyl group and A transparent dispersion of surface-modified zirconia particles having a surface modification material of a vinyl group as an alkenyl group.

(Production of polyoxyl resin composition)

Mn-6520 (manufactured by Dow Corning Toray Co., Ltd., refractive index 1.54, A liquid/B liquid ratio = 1/1) was added to 50 g of the transparent dispersion of the zirconia particles. g (3.8 g of liquid A, 3.8 g of liquid B) and stirred, and then toluene was removed by drying under reduced pressure to obtain a polyoxyxylene resin containing surface-modified zirconia particles, phenyl polyoxyl resin, and reaction catalyst. Composition (zirconia particle content: 30% by mass).

Further, regarding OE-6520, the presence of a Si-H bond was confirmed by NMR (Nuclear Magnetic Resonance) analysis, and it was found that a hydrogen group was contained in the polyoxyxyl resin forming component. Therefore, OE-6520 can be integrated by crosslinking reaction with a vinyl (alkenyl group) of vinyl trimethoxynonane which is surface-modified with zirconia particles.

Further, regarding OE-6520, it was confirmed by NMR analysis that an alkenyl group, that is, a C=C double bond (vinyl group), and platinum was confirmed by luminescence analysis. That is, OE-6520 is by adding An addition-hardening polyoxyxylene resin which is formed into a reaction (hydrazine hydrogenation reaction) and polymerized and hardened. Therefore, it can be judged that OE-6520 uses platinum as a catalyst, and the vinyl group in the surface modification material of the zirconia particle is bonded to the hydrogen group in OE-6520 by a crosslinking reaction, and is made in OE-6520. The vinyl group is subjected to an addition reaction with a hydrogen group, whereby the polyfluorene oxide resin component is polymer-cured while maintaining the dispersed state of the zirconia particles.

(Production of polyoxyl resin composite)

The polyoxyphthalocene resin composition was heat-treated at 150 ° C for 3 hours to be hardened, whereby a polyoxymethylene resin composite was obtained.

The above various evaluations were carried out using the polyoxymethylene resin composite. Further, in the evaluation of the gas permeability, the thickness of the sealing layer was set to 500 μm.

[Example A2] (Production of zirconia particles)

Zirconium oxide particles were produced in the same manner as in Example A1.

(Production of surface modification materials containing both phenyl and alkenyl groups)

Preparation of surface modification material A: (CH ₂ =CH)(CH ₃ ) ₂ SiO(SiO(C ₆ H ₅ ) ₂ ) ₄₅ Si(OC ₂ H ₅ ) ₃

1.8 g of dimethylvinylstanol was dissolved in 60 ml of tetrahydrofuran (THF, tetrahydrofuran) solvent under a nitrogen atmosphere, and 1.2 g of n-butyllithium dissolved in n-hexane was added dropwise thereto at a temperature of 0 ° C while stirring. After reacting for 3 hours, lithium dimethylvinyl stanol was obtained (refer to the formula (A)).

Then, a solution obtained by dissolving 160.5 g of hexaphenylcyclotrioxane in a solvent of THF was added dropwise, and reacted at a temperature of 0 ° C for 12 hours to obtain lithium phenylvinylorganoalkanol (see Formula (B)). ).

Then, 3.6 g of triethoxymethane chloride was added, and the mixture was reacted at a temperature of 0 ° C for 12 hours (refer to the formula (C)).

Then, after mixing n-hexane to form a precipitate of lithium chloride, the lithium chloride is removed by filtration. A surface modification material A containing both a phenyl group and an alkenyl group was obtained.

The surface modification material obtained was confirmed by 1 H-NMR.

Here, the outline of the synthesis scheme of the surface modification material containing both a phenyl group and an alkenyl group is shown below.

[化10]

(Surface modification of zirconia particles: production of surface-modified zirconia particles)

Then, 80 g of toluene and 5 g of methoxypolyphenyl phthalocyanine resin (manufactured by Shin-Etsu Chemical Co., Ltd., KR217) were added to 10 g of zirconia particles and mixed, and the beads were removed by a bead mill for 6 hours. grain. Then, 3 g of the above surface modifying material A was added, and surface modification and dispersion treatment were carried out at 130 ° C under a 6-hour circulation, whereby a surface-modifying material having a phenyl group and a phenyl group and an alkenyl group were prepared together. A transparent dispersion of surface-modified zirconia particles of a surface modification material of vinyl).

(Production of polyoxyxylene resin composition and polyoxymethylene resin composite)

Polyfluorene was produced in the same manner as in Example A1 except that the above-mentioned methoxy-containing phenylpolyoxyl resin and the transparent dispersion of the surface-modified zirconia particles by the surface-modifying material A were used. The resin composition was further prepared into a polyoxymethylene resin composite, and various evaluations were carried out.

[Example A3]

A polyoxyphthalocene resin composition was produced in the same manner as in Example A1 except that the thickness of the sealing layer was changed to 30 μm, and a polyfluorene oxide resin composite was produced, and various evaluations were carried out.

[Example A4] (Production of titanium dioxide particles)

242.1 g of titanium tetrachloride and 111.9 g of tin(IV) chloride pentahydrate were placed in 1.5 L (liter) of pure water at 5 ° C and stirred to prepare a mixed solution.

Then, the mixed solution was heated to adjust the temperature to 25 ° C, and an aqueous solution of ammonium carbonate having a concentration of 10% by mass was added to the mixed solution to adjust the pH to 1.5, followed by aging at 25 ° C for 24 hours. Thereafter, excess chloride ions are removed by ultrafiltration.

Then, the water was removed from the mixed solution obtained by removing the chloride ions using an evaporator, and then dried to prepare titanium oxide particles. The average primary particle diameter of the obtained titanium oxide particles was 4 nm.

The surface modification was carried out in the same manner as in Example A1 except that the titanium oxide particles were used, and a transparent dispersion of titanium dioxide was produced, and then a polyoxyxylene resin composition was produced, and a polyoxyxylene resin composite was produced, and various evaluations were carried out. .

[Example A5] (Production of cerium oxide particles)

20 g of ammonia water having a concentration of 24%, 0.8 g of 10 N NaOH, and 4 g of a polyoxyethylene alkyl ether (trade name: Emulgen 707, manufactured by Kao Corporation) as a surfactant were mixed in 80 g of methanol. 4 g of tetraethyl phthalate (trade name: Ethyl Silicate 28, manufactured by Colcoat Co., Ltd.) diluted with methanol was added dropwise thereto. The mixture was stirred at 20 ° C for 1 hour. After completion of the stirring, the precipitate was separated by decantation, and the operation was repeated by redispersing in methanol and decanting to remove residual ions.

The obtained wet cerium oxide particles were dried under reduced pressure to dry methanol, and the produced cerium oxide particles were obtained. The average primary particle diameter of the obtained cerium oxide particles was 4 nm.

A cerium oxide transparent dispersion was prepared by the same method as in Example A1 except that the cerium oxide particles were used, and then a polyfluorene oxide resin composition was produced, and a polyoxyxylene resin composite was produced. And carry out various evaluations.

[Comparative Example A1]

Various evaluations similar to those in Example 1 were carried out on the polyoxyxylene resin used in Example A1 (but no metal oxide particles were added). Further, in the three aspects of the transmittance of the polyoxyxene resin composite, the heat resistance of the polyoxyxene resin composite, and the gas permeability of the polyoxyxene resin composite, the comparative example A1 containing no metal oxide particles is used. The value is the reference value.

[Comparative Example A2]

A zirconia particle having an average primary particle diameter of 2 nm was produced in the same manner as in Example A1 except that the baking temperature of the electric furnace in the production of the zirconia particles was changed to 500 ° C from 500 ° C. A polyfluorene oxide resin composition was produced in the same manner as in Example A1 except that the zirconia particles were used, and a polyfluorene oxide resin composite was produced, and various evaluations were carried out.

[Comparative Example A3]

A zirconia particle having a primary particle diameter of 15 nm was produced in the same manner as in Example A1 except that the baking temperature of the electric furnace in the production of the zirconia particles was changed to 500 ° C from 500 ° C. A polyfluorene oxide resin composition was produced in the same manner as in Example A1 except that the zirconia particles were used, and a polyfluorene oxide resin composite was produced, and various evaluations were carried out.

[Comparative Example A4]

A surface was produced in the same manner as in Example A1 except that the surface modification material used in Example A1 was changed to 6 g of methacryloxypropyltrimethoxydecane and 2 g of isopropyltrimethoxydecane. The zirconia particles were modified, and a polyoxyxylene resin composition was produced in the same manner as in Example A1, and a polyoxyxylene resin composite was produced, and various evaluations were carried out.

The details and evaluation results of the polyoxyxene resin composites in the above respective Examples and Comparative Examples are collectively shown in Tables 1 and 2.

The transmittance of the polyoxymethylene resin composites in Examples A1 to A5 was the same as the value of the reference polyoxyxylene resin monomer (Comparative Example A1), and no significant decrease was observed. Further, regarding the heat resistance of the polyoxymethylene resin composite, the transmittance after the heat load was not reduced by 30% or more as compared with the initial value, and there was no problem.

The gas permeability of the polyoxyxene resin composites of Examples A1, A2, A4, and A5 was 1.5 in comparison with the standard polyoxyxylene resin monomer (Comparative Example A1). When the ratio is more than the above, it is confirmed that the gas permeability is lowered, that is, the gas barrier property is clearly improved. Further, in Example A3, the decrease in gas permeability was also confirmed, which was lower than that of the other examples. The reason is considered to be that the thickness of the sealing layer is thinner than 30 μm.

On the other hand, regarding Comparative Example A2, the gas permeability was high and sufficient gas barrier properties could not be obtained. The reason for this is considered to be that since the particle diameter of the metal oxide is small, the viscosity of the polyoxymethylene resin composition is high, so workability is poor, and the seal itself cannot be sufficiently performed.

Further, regarding Comparative Example A3, the light transmittance was lowered. The reason is considered to be that scattering of light occurs due to the large particle size of the metal oxide.

Further, in Comparative Example A4, both the light transmittance and the heat resistance were lowered. It is believed to be caused by a surface modifying material. That is, the reason why the transmittance of light is lowered is that since the surface modification material of this example does not contain an alkenyl group, it does not have a component with a matrix polyoxyl resin. Bonding property, and further, since the phenyl group is not contained, the affinity with the matrix polyoxyl resin forming component is low, and therefore, when the polyoxyxylene resin composite is formed (when the polyoxyxene resin composition is hardened), the metal is oxidized. The reason why the particles of the particles are agglomerated and the heat resistance is lowered is that the surface modifying material of this example does not have a phenyl group or the like and has low heat resistance.

[Example B1] (Production of zirconia particles)

In the zirconium salt solution obtained by dissolving 2615 g of zirconium oxychloride octahydrate in 40 L (liter) of pure water, the diluted ammonia water obtained by dissolving 344 g of 28% aqueous ammonia in 20 L of pure water was stirred to prepare oxidation. Zirconium precursor slurry.

Then, a sodium sulfate aqueous solution obtained by dissolving 300 g of sodium sulfate in 5 L of pure water was added to the slurry while stirring. The amount of sodium sulfate added at this time was 30% by mass in terms of zirconium oxide equivalent value of zirconium ions in the zirconium salt solution.

Then, the mixture was dried in the air at 130 ° C for 24 hours using a drier to obtain a solid matter.

Then, the solid matter was pulverized by an automatic mortar, and then fired in the air at 500 ° C for 1 hour in an electric furnace.

Then, the calcined product is poured into pure water, stirred to obtain a slurry, and then washed with a centrifugal separator to sufficiently remove the added sodium sulfate, and then dried by a dryer to obtain an average primary particle diameter. 4 nm zirconia particles.

(Surface modification of zirconia particles: production of surface-modified zirconia particles)

Then, 8 g of toluene and 5 g of a methoxy group-containing phenyl polyfluorene resin (manufactured by Shin-Etsu Chemical Co., Ltd., KR217) were added to 10 g of zirconia particles and mixed, and the beads were removed by a bead mill for 6 hours to remove the beads. grain. Then, 3 g of dimethyl ethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., LS490) was added, and surface modification and dispersion treatment were carried out at 130 ° C for 6 hours under a circulation to prepare a surface-modifying material having a phenyl group and having hydrogen. A surface-treated zirconia particle transparent dispersion of a surface-modified material.

(Production of polyoxyl resin composition)

Mn-6520 (manufactured by Dow Corning Toray Co., Ltd., refractive index 1.54, A liquid/B liquid ratio = 1/1) 7.6 g was added to 50 g of the zirconia particle transparent dispersion. (3.8 g of liquid A, 3.8 g of liquid B) and stirred, and then toluene was removed by drying under reduced pressure to obtain a polyoxyxylene resin combination containing surface-modified zirconia particles, phenyl polyoxyl resin, and reaction catalyst. (zirconia particle content: 30% by mass).

Further, regarding OE-6520, the presence of an alkenyl group, that is, a C=C double bond (vinyl group) and a Si-H bond (hydrogen group) was confirmed by NMR analysis, and the presence of platinum was confirmed by luminescence analysis. That is, OE-6520 is an addition hardening type polyoxymethylene resin which is polymerized and hardened by a hydrogenation reaction. Therefore, it can be judged that the hydrogen group in the surface modification material of the zirconia particles and the vinyl group in the OE-6520 can be bonded by hydrogenation reaction of the ruthenium, and, in addition, the platinum as the ruthenium hydrogenation catalyst contained in the OE-6520 The catalyst is added in an amount sufficient for the polyanthracene resin forming component in the OE-6520 to be subjected to hydrogenation polymerization curing, so that even if a surface-modifying material is added (a small amount relative to the polyoxy-oxygen resin), it is sufficient. Has the amount or effect as a catalyst.

(Production of polyoxyl resin composite)

The polyoxyphthalocene resin composition was heat-treated at 150 ° C for 3 hours to be hardened, whereby a polyoxymethylene resin composite was obtained.

The above various evaluations were carried out using the polyoxymethylene resin composite. Further, in the evaluation of gas barrier properties, the thickness of the sealing layer was set to 500 μm.

[Example B2] (Production of titanium dioxide particles)

Into 1.5 L (liter) of pure water at 5 ° C, 242.1 g of titanium tetrachloride and 111.9 g of tin (IV) chloride pentahydrate were charged and stirred to prepare a mixed solution.

Then, the mixed solution was heated to adjust the temperature to 25 ° C, and an aqueous solution of ammonium carbonate having a concentration of 10% by mass was added to the mixed solution to adjust the pH to 1.5, and thereafter, after aging at 25 ° C for 24 hours, Excess chloride ions are removed by ultrafiltration.

Then, the evaporator is used to remove moisture from the mixed solution, and then dried. A titanium oxide particle was produced. The obtained titanium oxide (titanium dioxide) particles had an average primary particle diameter of 4 nm.

A surface modification by a surface modification material having a phenyl group and a surface having a hydrogen group was carried out in the same manner as in Example B1 except that the content of the metal oxide particles was 20% by mass. A transparent dispersion of titanium dioxide particles having a surface treated with a material was prepared, and then a polyoxyxylene resin composition was produced in the same manner as in Example B1, and a polyoxyxylene resin composite was produced, and various evaluations were carried out.

[Example B3]

The average primary particle diameter of the zirconia particles was changed from 4 nm to 5 nm, and the surface modification material was changed from dimethyl ethoxy decane to diethoxymethyl decane (manufactured by Shin-Etsu Chemical Co., Ltd., LS880), and further In the same manner as in Example B1, except that the vinyl group was added to the hydrogen group/vinyl group, the vinyl trimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1003) was subjected to surface modification and dispersion treatment. A transparent dispersion of zirconia particles surface-treated with a surface modification material having a phenyl group, a surface modification material having a hydrogen group, and a surface modification material having a vinyl group was produced in the same manner as in Example B1. The polyoxyxene resin composition and the polyoxymethylene resin composite were subjected to various evaluations.

[Example B4]

In the dimethyl ethoxy decane which is a surface modification material, vinyl trimethoxy decane is added in such a manner that the hydrogen group/vinyl group is 6 in terms of a molar ratio, and surface modification and dispersion treatment are carried out, and other methods are used. A transparent dispersion of zirconia particles surface-treated with a surface modification material having a phenyl group, a surface modification material having a hydrogen group, and a surface modification material having a vinyl group was produced in the same manner as in Example B1, and then used and implemented. In the same manner as in Example B1, a polyoxyxylene resin composition and a polyoxyxylene resin composite were produced, and various evaluations were carried out.

[Example B5]

Using an average primary particle size of 6 nm of cerium oxide particles (Snowtex XS, Nissan Chemical Manufactured by an industrial company as a metal oxide particle.

To 10 g of the cerium oxide particles, 5 g of toluene and 5 g of a methoxypolyoxyl resin containing methoxy groups were added and mixed, and the surface modification treatment was performed for 6 hours in a bead mill to remove the beads. Then, 3 g of ethyl dichloromethane (manufactured by Shin-Etsu Chemical Co., Ltd., LS140) was added, and surface modification and dispersion treatment were carried out at 130 ° C under a 6-hour circulation. The chloride ion is removed to 1 mass ppm or less by passing the obtained dispersion liquid through a column filled with an alumina gel. Further, the amount of chlorine is determined by a chlorine ion meter. Thereafter, the surface-modified cerium oxide particles were again dispersed in toluene to prepare a transparent dispersion of cerium oxide particles surface-treated with a surface-modifying material having a phenyl group and a surface-modifying material having a hydrogen group.

Then, a polyfluorene oxide resin composition and a polyoxymethylene resin composite were produced in the same manner as in Example B1, and various evaluations were carried out.

[Comparative Example B1]

The polyoxyxylene resin used in Example B1 (but without the addition of metal oxide particles) was heat-treated at 150 ° C for 3 hours to be hardened, and the hardened body was subjected to various evaluations similar to those in Example B1.

[Comparative Example B2]

In the same manner as in Example B1, the surface modification of the metal oxide particles of Example B1 was carried out in the same manner as in Example B1 except that dimethyl ethoxy decane was used as the vinyl methoxy decane. a surface-modified material and a surface-treated zirconium oxide particle dispersion having a surface modification material of a vinyl group, and then a polyxanthoxy resin composition was produced in the same manner as in Example B1, thereby producing a polyoxymethylene resin composite, and Conduct various evaluations.

[Comparative Example B3]

A table having a phenyl group was produced in the same manner as in Example B1 except that the average primary particle diameter of the zirconia particles in Example B1 was changed from 4 nm to 20 nm. a surface-treated zirconium oxide particle dispersion having a surface-modified material and a surface-modified material having a hydrogen-based surface, and then a polyfluorene oxide resin composition was produced in the same manner as in Example B1, thereby producing a polyoxymethylene resin composite, and Conduct various evaluations.

[Comparative Example B4]

In the surface modification of the metal oxide particles of Example B3, the mixing ratio of diethoxymethyl decane and vinyl trimethoxy decane is set to be hydrogen ratio/vinyl group = 0.1 in terms of molar ratio, and A surface-treated zirconia particle dispersion having a surface modification material having a phenyl group, a surface modification material having a hydrogen group, and a surface modification material having a vinyl group was produced in the same manner as in Example B3, and then A polyoxyphthalocene resin composition was produced in the same manner as in Example B1, and a polyoxyxylene resin composite was produced, and various evaluations were carried out.

[Comparative Example B5]

In the same manner as in Example B1, the surface modification of the metal oxide particles of Example B1 was carried out in the same manner as in Example B1 except that dimethylethoxy decane was used as the dodecyltrimethoxydecane. A surface-modified zirconia particle dispersion having a surface-modified material and a surface modification material having a carbon chain, and then a polyfluorene oxide resin composition was produced in the same manner as in Example B1, thereby producing a polyoxyxylene resin composite. And conduct various evaluations.

[Comparative Example B6]

A surface-modifying material having a phenyl group and a surface-modifying material having a hydrogen group were produced in the same manner as in Example B1 except that the average primary particle diameter of the zirconia particles in the example B1 was changed to 2 nm from 4 nm. The surface-treated zirconium oxide particle dispersion was prepared in the same manner as in Example B1, and a polyfluorene oxide resin composite was produced, and various evaluations were carried out.

The details and evaluation results of the polyoxyxene resin composites in the above respective Examples and Comparative Examples are collectively shown in Tables 3 and 4.

In the examples B1 to B5, since the metal oxide particles having an average primary particle diameter of 3 nm or more and 10 nm or less are used, and the particles are surface-modified by a surface-modifying material having a phenyl group and a hydrogen group, it is good. The state maintains the light transmittance, heat resistance, and gas barrier properties of the polyoxymethylene resin composite produced by using the surface-modified metal oxide particle material.

In particular, regarding gas barrier properties, Comparative Example B1, which is a polyoxyxylene resin monomer as a reference, has been shown to be clearly improved, and is considered to be based on dimethyl ethoxy decane or diethoxymethyl used as a surface modifying material. The hydrogen group in the surface modifying material of the decane and ethyl dichlorodecane is bonded to the vinyl group in the OE-6520 as a raw material of the matrix polyoxyl resin by crosslinking reaction by hydrogenation reaction of hydrazine. The effect of integrating metal oxide particles with a matrix polyoxyl resin.

Moreover, in these examples, in particular, Examples B3 and B4 have a high gas barrier property. It is believed that it is based not only on the bond formed by the hydrogenation reaction of the hydrogen group in the surface modification material with the hydrogenation reaction of the vinyl group in the OE-6520 which is the raw material of the matrix polyoxyl resin, but also based on The vinyl group in the surface modification material of the vinyl trimethoxy decane used as the surface modification material and the hydrogen group in the OE-6520 as the base material of the matrix polyoxyl resin The effect of bonding the metal oxide particles and the matrix polyoxyl resin more firmly by the crosslinking reaction and bonding.

On the other hand, in Comparative Example B2, yellowing was observed after the heat resistance evaluation test. The reason for this is considered to be that vinyl trimethoxy decane is used instead of dimethyl ethoxy decane as a surface modifying material, so that unreacted vinyl groups remain excessively in the polyoxymethylene resin composite. Further, although the gas barrier property is improved as compared with the polyoxynoxy resin monomer, it is considered that the vinyl group in the surface modification material and the hydrogen in the OE-6520 which is the raw material of the matrix polyoxymethylene resin are based on the resin composition. The effect of the crosslinking reaction is carried out by a hydrogenation reaction during hardening.

Further, regarding Comparative Example B3, the light transmittance was lowered. The reason is considered to be that scattering of light occurs due to the large particle size of the metal oxide.

Further, in Comparative Example B4, yellowing was observed after the heat resistance evaluation test. The reason is considered to be that diethoxymethyl decane is used and a large amount of vinyl trimethoxy decane is used as the surface modification material, so that unreacted vinyl groups remain excessively in the polyoxymethylene resin composite. Further, although the gas barrier property is improved as compared with the polyoxynoxy resin monomer, it is considered to be used in combination with the following effects: a hydrogen group in a surface modifying material based on diethoxymethyldecane and a polycondensation as a matrix The effect of crosslinking polymerization by the hydrogenation reaction of the vinyl group in the OE-6520 of the oxygen resin raw material during the curing of the resin composition, and the vinyl group in the surface modification material and the OE-6520 as the raw material of the matrix polyoxyl resin The hydrogen in the middle is subjected to a crosslinking reaction by a hydrogenation reaction upon hardening of the resin composition.

Further, in Comparative Example B5, yellowing was observed after the heat resistance evaluation test. The reason is considered to be that since the dodecyltrimethoxydecane is used instead of dimethylethoxydecane as the surface modifying material, the carbon chain portion of dodecyltrimethoxydecane is thermally deteriorated.

Further, in Comparative Example B6, the gas permeability was high and sufficient gas barrier properties could not be obtained. The reason for this is considered to be that since the particle diameter of the metal oxide is small, the viscosity of the polyoxymethylene resin composition is high, so workability is poor, and the seal itself cannot be sufficiently performed.

[Industrial availability]

The present invention can of course be used as a sealing material for a semiconductor light-emitting element (LED or the like), and can be used as a material or a member or the like in various other industrial fields.

Claims (15)

A surface-modified metal oxide particle material having a mean primary particle diameter of 3 nm or more by a surface-modifying material having at least a phenyl group and a group capable of crosslinking reaction with a functional group in a polyfluorene-oxygen resin-forming component The metal oxide particles of 10 nm or less are surface-modified. The surface-modified metal oxide particle material according to claim 1, wherein the group which can be cross-linked with the functional group in the polyfluorene oxide-forming component is an alkenyl group. The surface-modified metal oxide particle material according to claim 1, wherein the group which can be cross-linked with the functional group in the polyanthracene resin-forming component is a hydrogen group. The surface-modified metal oxide particle material according to claim 1, wherein the group which can be cross-linked with the functional group in the polyfluorene oxide-forming component is an alkenyl group and a hydrogen group. A dispersion containing the surface-modified metal oxide particle material according to any one of claims 1 to 4. A polyoxyxylene resin composition comprising the surface-modified metal oxide particle material of claim 1 and one or more selected from the group consisting of a phenyl polyoxyl resin forming component and a methylphenyl polyoxyl resin forming component. The polyoxynene resin forming component has a functional group capable of crosslinking reaction with a group of the surface modifying material used in the surface-modified metal oxide particle material. A polyoxyxylene resin composition comprising the surface-modified metal oxide particle material of claim 2, and one or more selected from the group consisting of a phenyl polyoxyl resin forming component and a methylphenyl polyoxyl resin forming component. The polyoxyxene resin forms a component, and the polyoxymethylene resin forming component has a hydrogen group. A polyoxyxylene resin composition comprising the surface-modified metal oxide particle material of claim 3, and a component selected from the group consisting of phenyl polyoxyl resin and methylphenyl One or more polyoxyphthalocene resin forming components of the polyoxyphthalocene resin forming component, and the polyoxyxylene resin forming component has one or more selected from the group consisting of an alkenyl group and an alkynyl group. A polyoxyxylene resin composition comprising the surface-modified metal oxide particle material of claim 4, and one or more selected from the group consisting of a phenyl polyoxyl resin forming component and a methylphenyl polyoxyl resin forming component. The polyoxyphthalocene resin forming component has one or more selected from the group consisting of an alkenyl group and an alkynyl group, and a hydrogen group. The polyoxyxylene resin composition according to any one of claims 6 to 9, which comprises the above metal oxide particles in an amount of 5 mass% or more. The polyoxyxylene resin composition according to any one of claims 6 to 10, which further contains a rhodium hydrogenation catalyst. A polyoxyxylene resin composite obtained by hardening the polyoxyxylene resin composition according to any one of claims 6 to 11. An optical semiconductor light-emitting device which is obtained by sealing a semiconductor light-emitting element with a sealing material, wherein the sealing material comprises the polyoxymethylene resin composite according to claim 12, and a sealing layer containing the sealing material has a thickness of 50 μm or more . An illumination device comprising the optical semiconductor light-emitting device of claim 13. A liquid crystal image device comprising the optical semiconductor light-emitting device of claim 13.