TWI704215B - Curable resin composition and optical semiconductor device - Google Patents

Abstract

A curable resin composition with high transparency, ultraviolet resistance and heat resistance in the ultraviolet region is provided.  The curable resin composition comprises an alkoxy oligomer having an average composition formula represented by formula (1), and a curing catalyst.  The curing catalyst is 3 to 30 parts by weight of H₃ PO₄ with respect to 100 parts by weight of the alkoxy oligomer, or 0.5 to 20 parts by weight of a metal alkoxide with respect to 100 parts by weight of the alkoxy oligomer, wherein the metal of the metal alkoxide is at least one of B, Al, P, Sc, Ga, Y, Zr, Nb, In, Sn, La, Gd, Dy, Yb, Hf, Ta, and W.  In formula (1), R¹ , R² , R³ , R⁴ , R⁵ , and R⁶ are organic groups which are individualy the same or different from one another, each of w, x, y, and z is 0 or a positive number satisfing the equation w＋x＋y＋z＝1, and the atomic ratio of O to Si is 2.3 to 3.5. (R¹ R² R³ SiO_1/2 )_w (R⁴ R⁵ SiO_2/2 )_x (R⁶ SiO_3/2 )_y (SiO_4/2 )_z ···(1)

Description

Curable resin composition and optical semiconductor device

The present invention relates to a curable resin composition and an optical semiconductor device (for example, an ultraviolet LED (Light Emitting Diode)) formed using the curable resin composition. The curable resin composition transmits light in the ultraviolet wavelength region. High performance, and has high UV resistance and high heat resistance.

In recent years, LEDs that emit short-wavelength light such as blue LEDs and ultraviolet LEDs have been developed and used in practical applications. The use of such LEDs has rapidly expanded to, for example, general lighting applications using existing fluorescent lamps and incandescent lamps, ultraviolet curable resins using existing short arc lamps, and UV curable inks. The use of light sources for curing, etc.

Generally, an LED has an LED die with anode electrodes and cathode electrodes formed on the surface. The anode electrode and the cathode electrode are respectively wire bonded to the external electrode, and the LED chip emits light by energizing the external electrode.

In an LED with such a structure, if the LED chip and extremely thin leads (for example, φ30 μm) are exposed to the external space, there is a risk of damage to the LED chip or lead breakage. Therefore, the LED is usually sealed with a sealing material (for example, resin) before use.

In addition, sealing materials with a refractive index higher than air are used for LED When sealing, the refractive index difference between the LED chip and the sealing material is reduced. Therefore, from the perspective of improving light extraction efficiency, sealing the LED with the sealing material is effective.

As such a sealing material, currently, highly transparent epoxy resins, silicone resins, etc. have been used for LEDs that emit visible light (for example, Patent Documents 1 and 2). However, for LEDs that emit short-wavelength light, if the currently used epoxy resins and silicone resins are used, the resin itself will deteriorate under the action of short-wavelength light, causing problems such as coloration and cracks. . In addition, particularly in ultraviolet LEDs used in light sources for curing ultraviolet curable resins and ultraviolet curable inks that emit strong ultraviolet rays, the problem of the sealing material is particularly obvious.

The ultraviolet LED used as a light source for curing of ultraviolet curable resins and ultraviolet curable inks can be, for example, an LED that provides 3W of power to a 1mm square LED chip and emits ultraviolet light with a wavelength of 365nm and 1W. In this case, the amount of irradiated light reaches 1W/mm ² , which is equivalent to 30,000 to 50,000 times the amount of ultraviolet light contained in sunlight. Therefore, for UV LED sealing materials used for curing light sources for UV curing resins and UV curing inks, in addition to high transparency in the emission wavelength region of UV LEDs, resistance to strong ultraviolet rays is also required.

In addition, 2W of the 3W power provided to the UV LED is converted into heat energy to increase the temperature of the LED chip itself. Therefore, for the UV LED sealing material used for the curing light source of UV curing resin and UV curing ink, In addition to UV resistance, resistance to heat (temperature) is also required.

In addition, as a sealing material for LEDs and the like, it has been proposed to use a composition containing an epoxy group-containing polyfunctional polysiloxane and a metal chelate compound (Patent Document 3).

Prior art literature

Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2003-176334

Patent Document 2: Japanese Patent Application Publication No. 2003-277473

Patent Document 3: Japanese Patent Application Publication No. 2010-059359

In addition, the composition of Patent Document 3 is cured by epoxy ring-opening polymerization, and not only has organic covalent bonds (for example, CC bonds) in the structure of the cured product, but also contains metal chelate with strong absorption in the ultraviolet region. Therefore, in the sealing application of high-power ultraviolet LEDs, transparency, ultraviolet resistance, and heat resistance in the ultraviolet region are insufficient.

The present invention has been completed in view of the above circumstances, and its object is to provide a curable resin composition and an optical semiconductor device formed using the curable resin composition, which are compared with conventional UV LED sealing compositions. The curable resin composition has extremely high transparency, ultraviolet resistance, and heat resistance in the ultraviolet region, and even if it is used to seal a high-power ultraviolet LED, it will not crack, peel, or color.

In order to achieve the above object, the inventors considered the raw material of a curable resin composition suitable for sealing of high-power UV LEDs from the viewpoints of required transparency in the ultraviolet region, ultraviolet resistance, heat resistance, and moldability. In-depth study. As a result, it was found that in order to impart stress relaxation ability, an alkoxy oligomer having a non-reactive functional group and a high solid content concentration was used, and phosphoric acid, or selected from B, Al, P, Sc, Ga, Y, A metal alkoxide of at least one of Zr, Nb, In, Sn, La, Gd, Dy, Yb, Hf, Ta, and W can be used as a curing catalyst for accelerating the reaction, and an ideal curable resin composition can be obtained. The present invention has been completed based on the above knowledge.

That is, the curable resin composition of the present invention is a curable resin composition containing an alkoxy oligomer and a curing catalyst, and is characterized in that the alkoxy oligomer has an organopolysiloxane structure, which is selected from One or more structural units in the structural units represented by the following general formulas (1) to (4), and also one or more structural units selected from the structural units represented by the following general formulas (5) to (7), through Formula (1) (R ¹ R ² R ³ SiO _1/2 ). . . (1)

(In the general formula (1), R ¹ , R ² and R ³ are each independently the same or different organic groups.)

General formula (2) (R ⁴ R ⁵ SiO _2/2 ). . . (2)

(In the general formula (2), R ⁴ and R ⁵ are each independently the same or different organic groups.)

General formula (3) (R ⁶ SiO _3/2 ). . . (3)

(In the general formula (3), R ⁶ is an organic group.)

General formula (4) (SiO _4/2 ). . . (4)

General formula (5) (R ⁷ _a (OR ⁸ ) _3-a SiO _1/2 ). . . (5)

(In the general formula (5), a is 0, 1, or 2, R ⁷ and R ⁸ are each independently the same or different organic groups, and when a plurality of R ⁷ or R ^{8 are} contained, each R ⁷ Or R ⁸ may be the same or different from each other.)

General formula (6) (R ⁹ _b (OR ¹⁰ ) _2-b SiO _2/2 ). . . (6)

(In the general formula (6), b is 0 or 1, R ⁹ and R ¹⁰ are each independently the same or different organic groups. When a plurality of R ¹⁰ are contained, each R ¹⁰ may be the same or each other different.)

General formula (7) ((OR ¹¹ )SiO _3/2 ). . . (7)

(In the general formula (7), R ¹¹ is an organic group.)

When all siloxane units constituting the alkoxy oligomer are set to 100 mol%, it contains 90-100 mol% of the structural units represented by general formula (1) to general formula (7), and the alkoxy group is low The atomic ratio of the total amount of O atoms contained in the polymer to the total amount of Si atoms is 2.3 to 3.5, and the curing catalyst is phosphoric acid with a content range of 0.1 to 17.5 parts by weight relative to 100 parts by weight of the alkoxy oligomer , Or the content range of 0.5 to 20 parts by weight relative to 100 parts by weight of the alkoxy oligomer selected from B, Al, P, Sc, Ga, At least one metal alkoxide of Y, Zr, Nb, In, Sn, La, Gd, Dy, Yb, Hf, Ta, and W.

In addition, it is preferable that the alkoxy oligomer and curing catalyst do not contain a sulfur atom or a nitrogen atom.

In addition, it is preferable that R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are methyl groups.

In addition, it is preferable that the curing catalyst does not contain a Ti compound or a chelate compound.

In addition, the amount of alkoxy groups contained in the alkoxy oligomer is preferably in the range of 10 to 30% by mass.

In addition, it is preferable that the alkoxy oligomer is liquid at room temperature.

In addition, it is preferable that when the cured product obtained by curing the curable resin composition is irradiated with ultraviolet light of a predetermined wavelength with an emission intensity of approximately 100 W/cm ² for 500 hours, the transmittance of the cured product to ultraviolet light is 85% or more. In addition, in this case, it is preferable that when the cured product is irradiated with ultraviolet light for 1000 hours, the transmittance of the cured product to ultraviolet light is 85% or more. Furthermore, it is preferable that when the cured product is irradiated with ultraviolet light for 5000 hours, the transmittance of the cured product to ultraviolet light is 80% or more. In addition, it is preferable that the predetermined wavelength is approximately 365 nm.

In addition, from another viewpoint, the optical semiconductor device of the present invention has an optical semiconductor element sealed with the curable resin composition according to any one of the above. In this case, the optical semiconductor element preferably emits light in the ultraviolet region.

As described above, according to the present invention, a curable resin can be realized The composition can further realize the optical semiconductor device formed by using the curable resin composition. Compared with the conventional composition used for UV LED sealing, the curable resin composition has transparency and UV resistance in the ultraviolet region. It has extremely high resistance and heat resistance, and it will not crack, peel, or color even if it is used to seal high-power UV LEDs.

100, 200: UV LED

101: substrate

102a, 202a: positive pattern

102b, 202b: negative pattern

103, 203: LED chip

103a, 203a: injection surface

104, 204a, 204b: welding wire

105: frame material

106, 206, 207: cured product

210: Shell

210a: bottom

Fig. 1 is a schematic configuration diagram showing a surface-mounted ultraviolet LED using the curable resin composition of the embodiment of the present invention.

Fig. 2 is a schematic configuration diagram showing an encapsulated ultraviolet LED using the curable resin composition of the embodiment of the present invention.

Figure 3 is a graph showing the transmittance measurement result of the curable resin composition of Example 3 of the present invention.

Fig. 4 is a graph showing the transmittance measurement result of the curable resin composition of Example 7 of the present invention.

Figure 5 is a graph showing the transmittance measurement result of the curable resin composition of Example 9 of the present invention.

Figure 6 is a graph showing the transmittance measurement result of the curable resin composition of Example 10 of the present invention.

Fig. 7 is a graph showing the measurement result of the luminous intensity of the curable resin composition of Example 1 of the present invention.

Fig. 8 is a graph showing the measurement result of the luminous intensity of the curable resin composition of Example 3 of the present invention.

Fig. 9 is a graph showing the measurement result of the luminous intensity of the curable resin composition of Example 7 of the present invention.

Figure 10 shows the transmittance characteristics of the curable resin composition of Comparative Example 1 of the present invention.

Figure 11 shows the transmittance characteristics of the curable resin composition of Comparative Example 2 of the present invention.

Figure 12 shows the transmittance characteristics of the curable resin composition of Comparative Example 3 of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. It should be noted that the description of the components described below is an example of the embodiment of the present invention, and the present invention is not limited to the following, and can be implemented with various modifications within the scope of the gist of the present invention.

The curable resin composition of the embodiment of the present invention can be used for, for example, the sealing of a high-power ultraviolet LED, and it is synthesized from an alkoxy oligomer and a curing catalyst.

[Alkoxy oligomer]

The alkoxy oligomer of this embodiment has an organopolysiloxane structure, which has one or more structural units selected from the structural units represented by the following general formulas (1) to (4), and at the same time has a structure selected from the following One or more structural units among the structural units represented by general formulas (5) to (7).

General formula (1) (R ¹ R ² R ³ SiO _1/2 ). . . (1)

(In the general formula (1), R ¹ , R ² and R ³ are each independently the same or different organic groups.)

General formula (2) (R ⁴ R ⁵ SiO _2/2 ). . . (2)

(In the general formula (2), R ⁴ and R ⁵ are each independently the same or different organic groups.)

General formula (3) (R ⁶ SiO _3/2 ). . . (3)

(In the general formula (3), R ⁶ is an organic group.)

General formula (4) (SiO _4/2 ). . . (4)

General formula (5) (R ⁷ _a (OR ⁸ ) _3-a SiO _1/2 ). . . (5)

(In the general formula (5), a is 0, 1, or 2, R ⁷ and R ⁸ are each independently the same or different organic groups, and when a plurality of R ⁷ or R ^{8 are} contained, each R ⁷ Or R ⁸ may be the same or different from each other.)

General formula (6) (R ⁹ _b (OR ¹⁰ ) _2-b SiO _2/2 ). . . (6)

(In the general formula (6), b is 0 or 1, R ⁹ and R ¹⁰ are each independently the same or different organic groups. When a plurality of R ¹⁰ are contained, each R ¹⁰ may be the same or each other different.)

General formula (7) ((OR ¹¹ )SiO _3/2 ). . . (7)

(In the general formula (7), R ¹¹ is an organic group.)

The structural unit represented by the above general formula (1), that is, the structural unit represented by (R ¹ R ² R ³ SiO _1/2 ) is a monofunctional structural unit (M unit), and the structure represented by the above general formula (2) The unit, that is, the structural unit represented by (R ⁴ R ⁵ SiO _2/2 ) is a bifunctional structural unit (D unit), and the structural unit represented by the above general formula (3), namely (R ⁶ SiO _3/2 ) The structural unit shown is a trifunctional structural unit (T unit), and the structural unit represented by the above general formula (4), that is, the structural unit represented by (SiO _4/2 ) is a tetrafunctional structural unit (Q unit).

In addition, for the structural unit represented by the above general formula (5), that is, the structural unit represented by (R ⁷ _a (OR ⁸ ) _3-a SiO _1/2 ), a is 0, 1, or 2, and in a In the case of 2, it is a bifunctional structural unit having one alkoxy group OR ⁸ represented by (R ⁷ ₂ (OR ⁸ )SiO _1/2 ), and in the case of a is 1, it is (R ⁷ (OR ⁸ ) ₂ SiO _1/2 ) represents a trifunctional structural unit with 2 alkoxy groups OR ⁸ , and when a is 0, it is represented by ((OR ⁸ ) ₃ SiO _1/2 ) with 3 alkane A 4-functional structural unit of the oxy group OR ⁸ .

For the structural unit represented by the above general formula (6), that is, the structural unit represented by (R ⁹ _b (OR ¹⁰ ) _2-b SiO _2/2 ), b is 0 or 1, and when b is 1 Below is a trifunctional structural unit with one alkoxy group OR ¹⁰ represented by (R ⁹ (OR ¹⁰ )SiO _2/2 ). When b is 0, it is ((OR ¹⁰ ) ₂ SiO _2/2 ) Represents a tetrafunctional structural unit having two alkoxy groups OR ¹⁰ .

The structural unit represented by the above general formula (7), that is, the structural unit represented by ((OR ¹¹ )SiO _3/2 ) is a tetrafunctional structural unit having two alkoxy groups OR ¹¹ .

In the compound represented by the general formula (1), R ¹ , R ² and R ³ are each independently the same or different organic groups. In the compound represented by the general formula (2), R ⁴ and R ^{5 is} each independently the same or different organic group, and in the compound represented by the general formula (3), R ⁶ is an organic group.

In addition, in the above general formula (5), R ⁷ and R ⁸ are each independently the same or different organic groups. In the case where a plurality of R ⁷ and R ^{8 are} contained, each R ⁷ and R ⁸ may be the same , Can also be different from each other.

In the compound represented by the general formula (6), R ⁹ and R ¹⁰ are each independently the same or different organic groups. When multiple R ¹⁰ are contained, each R ¹⁰ may be the same or different from each other. .

In the compound represented by the general formula (7), R ¹¹ is an organic group.

As described above, the organic groups represented by R ¹ to R ¹¹ are each independently the same or different organic groups.

The organic group represented by R ¹ to R ¹¹ is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 12 carbon atoms, still more preferably a hydrocarbon group having 1 to 8 carbon atoms, and still more preferably a hydrocarbon group having 1 to 4 carbon atoms, Still more preferably, a hydrocarbon group having 1 to 3 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 2 carbon atoms.

Examples of the above-mentioned hydrocarbon group include one or more groups selected from alkyl groups.

When the above-mentioned hydrocarbon group is an alkyl group, examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and undecyl. , Dodecyl, etc., preferably methyl or ethyl, more preferably methyl.

In the curable resin composition of the present invention, as the alkoxy oligomer, it is preferable that at least one of the organic groups contained in the structural unit constituting the alkoxy oligomer has 1 to 4 carbon atoms. Alkyl groups, organic groups other than the above alkyl groups The group is a hydrocarbon group with 1 to 8 carbon atoms.

In addition, in the curable resin composition of the present invention, as the alkoxy oligomer, at least one of the organic groups contained in the structural unit constituting the alkoxy oligomer is a methyl group, and preferably constitutes an alkoxy group. All organic groups contained in the structural unit of the oligomer are methyl groups.

Generally, the ionic bondability of the Si-O bond as the main chain of polysiloxane is about 50%, which is greater than the C-C bond of ordinary organic resins such as polyethylene. Therefore, compared with the case where the main chain is a CC bond, the chemical stability of the CH bond and CC bond of the side chain of polysiloxane is increased. Generally, polysiloxane is less susceptible to oxidation and ultraviolet rays. Structure.

However, when the side chains of CH bonds, CC bonds, etc. increase and the distance between the atoms constituting the side chains and the Si atoms becomes longer, the problem of lowering of the stabilization effect due to the ionic bond of the Si—O bond occurs. Therefore, it is preferable that the side chain organic group (ie, the organic group represented by R ¹ to R ¹¹ ) has a smaller number of carbon atoms. Among them, since the methyl group is the smallest in the alkyl group, all the atoms ( The distance between the bond with the methyl group and the Si atom is relatively close, and it is easily stabilized by ionic bonds, and there is no CC bond, so the methyl group is most preferred.

In addition, the organic group represented by R ¹ to R ¹¹ preferably does not contain an aromatic ring.

As the organic group represented by R ¹ to R ¹¹ , for example, if a group having an aromatic ring such as a phenyl group is used, the functional group has a double bond, so the π-π* transition of the π electron derived from the double bond will be Absorption occurs from the light region to the visible light region, which easily reduces the transmission characteristics and UV resistance of the ultraviolet region. Therefore, the organic group represented by R ¹ to R ¹¹ is preferably a group that does not contain aromatic rings such as benzene-based aromatic rings, heteroaromatic rings, and non-benzene-based aromatic rings.

In addition, as the organic group represented by R ¹ to R ¹¹ , in order to suppress a decrease in ultraviolet resistance, it is preferable not to include a group containing an N atom (amino group, etc.) and a group containing an S atom (such as a mercapto group). In addition, for the same reason, when the organic groups represented by R ¹ to R ¹¹ are hydrocarbons other than aromatic hydrocarbons, it is preferable that no carbon-carbon bonds (CC bonds, C=C bonds or C≡ C bond) group.

As described above, in the curable resin composition of the present invention, the alkoxy oligomer contains one or more structural units selected from the following structural units: a structural unit having an alkoxy group represented by the general formula (5) , Namely the structural unit represented by (R ⁷ _a (OR ⁸ ) _3-a SiO _1/2 )), the structural unit represented by the general formula (6), namely (R ⁹ _b (OR ¹⁰ ) _2-b SiO ₂ The structural unit represented by _/2 ) is the structural unit represented by the general formula (7), that is, the structural unit represented by ((OR ¹¹ )SiO _3/2 ).

It can be considered that, in the curable resin composition of the present invention, the alkoxy oligomer contains a structural unit having an alkoxy group selected from the structural units represented by the general formula (5) to the general formula (7). When used as a sealing material for an optical semiconductor element constituting an optical semiconductor device, the above-mentioned alkoxy group is strongly chemically bonded to the surface of the wafer, the surface of the substrate, the surface of the wiring pattern, and the like to be sealed.

That is, since a protective layer made of SiO ₂ or the like is provided on the surface of a wafer or the like made of an inorganic substance, and a hydroxyl group is usually present, it can be considered that it is selected from the structural units represented by the general formula (5) to (7) The alkoxy groups in the structural unit are bonded to the hydroxyl groups on the wafer surface and the like through hydrogen bonds and intermolecular forces caused by Van der Waals forces, and dealcoholization is also generated between the alkoxy groups and the hydroxyl groups on the wafer surface. The bond formed by condensation reaction and dehydration reaction makes the two chemically bond firmly.

As described above, when the curable resin composition of the present invention is used as a sealing material, a solid obtained by curing the curable resin composition of the present invention Since the compound is firmly bonded to the wafer or the like, it is considered that even when it is used for sealing applications of high-power ultraviolet LEDs, the cured product of the curable resin composition can be effectively suppressed from cracking and peeling.

In the curable resin composition of the present invention, when all silicone units constituting the alkoxy oligomer are set to 100 mol%, the alkoxy oligomer contains general formula (1) to general formula ( 7) The structural unit shown in 90-100 mol%, preferably contains 95-100 mol% of the structural unit shown in the general formula (1) to the general formula (7), and more preferably contains the general formula (1) to the general formula (7) The structural unit shown is 100 mol%.

That is, in the curable resin composition of the present invention, for the alkoxy oligomer, when all the siloxane units constituting the alkoxy oligomer are set to 100 mol%, the general formula (1 The structural unit shown in) contains mol%, the structural unit shown in general formula (2) contains mol%, the structural unit shown in general formula (3) contains mol%, and the general formula (4) is The structural unit shown contains mole %, the structural unit represented by general formula (5) contains mole %, the structural unit represented by general formula (6) contains mole %, and the general formula (7) The total content of mol% of the structural unit is 90-100 mol%, more preferably 95-100 mol%, and still more preferably 100 mol% (all silicone units constituting the polysiloxane resin are composed of the above Any structural unit represented by general formula (1) to general formula (7)).

Among the structural units constituting the alkoxy oligomer, the composition ratio of the structural units represented by the general formula (1) to the general formula (7) is not particularly limited. If a certain amount of non-reactive functional groups is not included, the When the curable resin composition is cured, the cured product becomes too hard, and the stress generated during heating and cooling cannot be relieved, and the welding wire in the ultraviolet LED may be cut or the LED chip itself may be damaged.

Therefore, in the curable resin composition of the present invention, for the alkoxy oligomer, the atomic ratio of the total amount of O atoms contained in the alkoxy oligomer to the total amount of Si atoms (the alkoxy group is lower The total amount of O atoms contained in the polymer/the total amount of Si atoms contained in the alkoxy oligomer) is preferably 2.3 to 3.5, more preferably 2.3 to 3.4, and still more preferably 2.2 to 3.2.

By making the atomic ratio of the total amount of O atoms contained in the alkoxy oligomer to the total amount of Si atoms within the above-mentioned range, a certain amount of non-reactive functional groups can be contained. Therefore, it can be suitable for alleviating heating and cooling. Stress.

When the atomic ratio of the total amount of O atoms to the total amount of Si atoms contained in the alkoxy oligomer is less than 2.3, the UV resistance is likely to decrease, and when it exceeds 3.5, the cured product of the curable resin composition is likely to crack and break .

The atomic ratio of the total amount of O atoms contained in the alkoxy oligomer to the total amount of Si atoms can be determined by comparing the structural units represented by the general formula (1) to the general formula (7) constituting the alkoxy oligomer. The composition ratio is adjusted to control.

In the curable resin composition of the present invention, for the alkoxy oligomer, the number of moles of the bifunctional structural unit is relative to the total of the bifunctional structural unit and the trifunctional structural unit constituting the alkoxy oligomer. The molar ratio is preferably within a given range.

That is, in the curable resin composition of the present invention, for the alkoxy oligomer, the structural unit represented by the general formula (5) (R ⁷ _a (OR ⁸ ) _3-a SiO _1/2 ) Where a is 2 (R ⁷ ₂ (OR ⁸ )SiO _1/2 ) and the structural unit (R ⁴ R ⁵ SiO _2/2 ) called D unit represented by general formula (2) to the total number of moles of Dn, the structural unit represented by general formula (5) _{^{(R 7 a (OR 8)}} 3-a SiO 1/2) in a structural unit (R ⁷ (OR ⁸⁾ at 1 ₂ SiO _1/2 ), the structural unit represented by the general formula (6) (R ⁹ _b (OR ¹⁰ ) _2-b SiO _2/2 ) when b is 1 (R ⁹ (OR ¹⁰ )SiO _{2 /2} ) and the total molar number of the structural unit (R ⁶ SiO _3/2 ) represented by the general formula (3) called T unit is set to Tn, the ratio represented by Tn/(Dn+Tn) is preferable It is 0.2 to 1, more preferably 0.25 to 1, and even more preferably 0.3 to 1.

The structural unit represented by the general formula (5) (R ⁷ _a (OR ⁸ ) _3-a SiO _1/2 ) where a is 2 in the structural unit (R ⁷ ₂ (OR ⁸ )SiO _1/2 ) is usually prepared In the case of an alkoxy oligomer, part of the alkoxy group of the raw material of the structural unit (R ⁴ R ⁵ SiO _2/2 ) represented by the general formula (2) enters the oligomer in a state where it remains unreacted.

In addition, in the structural unit represented by the general formula (5) (R ⁷ _a (OR ⁸ ) _3-a SiO _1/2 ), the structural unit when a is 1 (R ⁷ (OR ⁸ ) ₂ SiO _1/2 ) , The structural unit represented by the general formula (6) (R ⁹ _b (OR ¹⁰ ) _2-b SiO _2/2 ), the structural unit when b is 1 (R ⁹ (OR ¹⁰ )SiO _2/2 ) is usually prepared In the case of an alkoxy oligomer, part of the alkoxy group of the raw material of the structural unit (R ⁶ SiO _3/2 ) represented by the general formula (3) enters the oligomer without reacting and remaining.

As described above, it can be considered that when the curable resin composition of the present invention is used as a sealing material for an optical semiconductor element constituting an optical semiconductor device, the aforementioned general formula (5) to general formula (7) of the alkoxy oligomer The alkoxy group in the structural unit shown is chemically bonded firmly to the surface of the wafer or the like as the sealing object. For the alkoxy oligomer, considering the balance between the alkoxy group and the organic group, it is preferable that the alkoxy oligomer is composed of only difunctional structural units and trifunctional structural units, but in consideration of In the bonding between the above-mentioned sealing material and the wafer, it is more advantageous to have more Tn than Dn.

By making the ratio represented by Tn/(Dn+Tn) within the above range, the curable resin composition can be well bonded to the wafer surface when used as a sealing material for optical semiconductor elements, even when it is used to apply high-power ultraviolet rays. The sealing of LED etc. Continuously irradiating strong ultraviolet light can also well suppress the occurrence of cracks and peeling at the interface between the surface of the wafer and the cured product of the curable resin composition.

In the curable resin composition of the present invention, the amount of alkoxy groups contained in the alkoxy oligomer is preferably 10 to 30% by mass, more preferably 11 to 27.5% by mass, and still more preferably 12 to 25% by mass.

When the amount of the alkoxy group contained in the alkoxy oligomer is within the above-mentioned range, the desired solid content concentration can be maintained, and three-dimensional bonding can be suppressed, so that the desired stress relaxation ability can be exhibited.

In the curable resin composition of the present invention, the weight average molecular weight of the alkoxy oligomer is not particularly limited, and can be appropriately selected according to the purpose of use. When used as a sealing material for optical semiconductor elements such as ultraviolet LEDs, it can be based on the same Any choice of purpose.

The weight average molecular weight of the alkoxy oligomer is preferably 500 to 4,500, more preferably 750 to 4,250, and still more preferably 1,000 to 4,000. In addition, the amount of the hydroxyl group (OH) contained in the alkoxy oligomer is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

In the curable resin composition of the present invention, the production method of the alkoxy oligomer is not particularly limited.

In the curable resin composition of the present invention, the alkoxy oligomer can be produced in the following manner. For example, the following siloxane units corresponding to the general formula (1) to the general formula (4) The organosiloxanes represented by the general formula (1)' to the general formula (4)' are compounded in respective predetermined amounts, and are produced by hydrolysis and condensation.

R ¹² R ¹³ R ¹⁴ SiOR ¹⁵ . . . (1)'

(In formula (1)', R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently the same or different organic groups.)

R ¹⁶ R ¹⁷ Si (OR ¹⁸ ) (OR ¹⁹ ). . . (2)'

(In formula (2)', R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently the same or different organic groups.)

R ²⁰ Si(OR ²¹ )(OR ²² )(OR ²³ ). . . (3)'

(In formula (3)', R ²⁰ , R ²¹ , R ²² and R ²³ are each independently the same or different organic groups.)

Si(OR ²⁴ )(OR ²⁵ )(OR ²⁶ )(OR ²⁷ ). . . (4)'

(In formula (4)', R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are each independently the same or different organic groups.)

Examples of the organic groups represented by R ¹² to R ²⁷ include the same groups as the organic groups represented by R ¹ to R ¹¹ described above.

In the above-mentioned hydrolysis and condensation reactions, the hydrolysis reaction is not allowed to proceed completely, but a certain amount of alkoxy groups remain in the hydrolyzate. The alkoxy group (-OR ¹⁸ group, -OR ¹⁹ group, -OR ²¹ group, -OR ²² group, -OR ²³ group) constituting the organosiloxane represented by general formula (2)' to general formula (4)' , -OR ²⁴ group, -OR ²⁵ group, -OR ²⁶ group, -OR ²⁷ group) part of the residue, which can be selected from the general formula (5) ~ general formula in the obtained alkoxy oligomer (7) One or more siloxane units among the siloxane units shown in (7).

The remaining amount of the alkoxy group can be controlled by appropriately adjusting the hydrolysis and condensation conditions (the catalyst used, the reaction time, the reaction temperature, etc.).

The compounding ratio of the organosiloxane represented by the general formula (1)' to the general formula (4)' can be appropriately selected according to the alkoxy oligomer to be obtained.

In the curable resin composition of the present invention, as a method for producing an alkoxy oligomer, for example, the following method can be specifically mentioned: methyltrimethoxysilane (representative formula: CH ₃ Si(OCH ₃ ) ₃ , Hereinafter referred to as MTMS), a mixture of MTMS and dimethyldimethoxysilane (indicative formula: (CH ₃ ) ₂ Si(OCH ₃ ) ₂ , hereinafter referred to as DMDMS) is hydrolyzed in the presence of a catalyst and water .

In addition, the alkoxy oligomer in the curable resin composition of the present invention may be a polysiloxane alkoxy oligomer obtained by a method other than the above-mentioned method.

Examples of alkoxy oligomers include polysiloxane alkoxy oligomers X-40-9225, X-40-9246, X-40-9250, KC-89S manufactured by Shin-Etsu Chemical Co., Ltd. , KR-500, and XC-96-B0446, XR31-B1410, XR31-B2230, etc. manufactured by Momentive Performance Materials Japan.

For the curable resin composition of the present invention, when the organosiloxane represented by the general formula (1)' to the general formula (4)' is hydrolyzed and condensed to prepare an alkoxy oligomer, In the presence of a catalyst, it is usually prepared by performing a reaction for several tens of minutes to a day at a temperature of about 0°C to about 100°C.

As a catalyst used in the hydrolysis and condensation of organosiloxanes represented by the above general formula (1)' to general formula (4)', inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, and phosphoric acid can be used , Formic acid, acetic acid and other organic acids. In addition, in order to perform the cohydrolysis/condensation reaction, an organic solvent may be added as necessary. In this case, as the solvent, alcohols such as methanol, ethanol, 1-propanol, and 2-propanol, aromatic compounds such as toluene and xylene, ketones such as acetone, and esters such as ethyl acetate can be used.

In the organosiloxane represented by the general formula (1)' to the general formula (4)', the organic group represented by R ¹² to R ²⁷ preferably does not contain an aromatic ring.

As described above, as the organic group represented by R ¹² to R ²⁷ , for example, if a group having an aromatic ring such as a phenyl group is used, the functional group has a double bond, so π-π* derived from the π electron of the double bond The transition will produce absorption in the ultraviolet region to the visible region, which easily reduces the transmission characteristics and UV resistance in the ultraviolet region. Therefore, the organic group represented by R ¹² to R ²⁷ is preferably a group that does not contain aromatic rings such as benzene-based aromatic rings, heteroaromatic rings, and non-benzene-based aromatic rings.

In addition, as the organic group represented by R ¹² to R ²⁷ , in order to suppress the decrease in ultraviolet resistance, it is preferable not to contain a group containing an N atom (amino group, etc.) and a group containing an S atom (such as a mercapto group). In addition, for the same reason, when the organic groups represented by R ⁹ to R ²⁴ are hydrocarbons other than aromatic hydrocarbons, it is preferable not to contain carbon-carbon bonds (CC bonds, C=C bonds or C≡C bonds as much as possible). ) Of the group.

In the curable resin composition of the present invention, the alkoxy oligomer is preferably a polysiloxane-based material having an organosiloxane structure that is liquid at room temperature (25°C).

In the curable resin composition of the present invention, the alkoxy oligomer can be easily filled and molded by making the alkoxy oligomer liquid at room temperature (25°C).

It should be noted that, in this application file, liquid at room temperature means that the viscosity at room temperature measured in accordance with JIS Z 8803 is 103Pa. The state below s.

In terms of solid content (non-volatile content), the curable resin composition of the present invention preferably contains 50.0 to 99.9% by mass of alkoxy oligomer, and more preferably It contains 70.0-99.5 mass %, More preferably, it contains 90.0-99.0 mass %.

For the curable resin composition of the present invention, by making the content of the alkoxy oligomer within the above range, compared with the existing curable resin composition, the transparency, ultraviolet resistance and heat resistance in the ultraviolet region Very high performance, even if it is used for sealing of high-power UV LEDs, it can easily suppress the occurrence of cracks, peeling, and coloring.

[Curing catalyst]

The curing catalyst of the present embodiment is a substance capable of curing the above-mentioned alkoxy oligomer, specifically, phosphoric acid H ₃ PO ₄ or selected from B, Al, P, Sc, Ga, Y, Zr, Nb , In, Sn, La, Gd, Dy, Yb, Hf, Ta, W alkoxide of at least one metal.

The curing catalyst of this embodiment can use, for example, a solution prepared by mixing phosphoric acid H ₃ PO ₄ and alkoxysilane. Specifically, it can be obtained by mixing an aqueous solution of orthophosphoric acid (indicative formula: H ₃ PO ₄ ) into DMDMS . It should be noted that although H ₂ O is contained in the orthophosphoric acid aqueous solution, as shown in the following chemical reaction formula (8), H ₂ O reacts with the methoxy group (CH ₃ O-) of DMDMS and all is consumed.

(CH ₃ ) ₂ Si(OCH ₃ ) ₂ +2H ₂ O→(CH ₃ ) ₂ Si(OH) ₂ +2CH ₃ OH. . . (8)

In addition, in the above synthesis, DMDMS was used as the alkoxysilane mixed with orthophosphoric acid, but the alkoxysilane represented by the following general formula (9) may also be used.

R ¹ _n Si(OR ² ) _4-n . . . (9)

It should be noted that in the general formula (9), R ¹ and R ² are respectively R ¹ : C _k H _2k+1 -(k=1, 2), R ² : C _m H _2m-1 -(m =1, 2, 3, 4, and 5), and n is an integer of 0-3.

In addition, if the amount of phosphoric acid H ₃ PO ₄ added is too small, problems such as non-curing or slow curing will occur. In addition, if it is too large, the cured product will become too hard, and there will be problems caused by temperature changes accompanying LED lighting/extinguishing. Therefore, it is preferably in the range of 0.1 to 17.5 parts by weight, more preferably in the range of 0.2 to 15.0 parts by weight, and even more preferably 0.3 to 100 parts by weight of the alkoxy oligomer. ~12.5 parts by weight.

In addition, as described above, alcohols of at least one metal selected from B, Al, P, Sc, Ga, Y, Zr, Nb, In, Sn, La, Gd, Dy, Yb, Hf, Ta, and W can be used. Salt instead of phosphoric acid H ₃ PO ₄ . In this case, the amount of metal alkoxide added is in the range of 0.5 to 20 parts by weight relative to 100 parts by weight of the alkoxy oligomer. If the addition amount of the metal alkoxide is less than 0.5 parts by weight, there is a problem of non-curing or too slow curing, and if it is more than 20 parts by weight, the cured product becomes too hard.

It should be noted that, similar to alkoxy oligomers, the curing catalyst does not use substances containing nitrogen (N) or sulfur (S) that deteriorate ultraviolet resistance, and have carbon-carbon bonds (CC, C=C). , C≡C) substances, substances containing Ti. In addition, the curing catalyst does not use strong acid and strong alkaline catalysts that damage the LED chips in the ultraviolet LED, and substances containing alkalis such as Li, Na, and K. In addition, no harmful substances such as Pb, Hg, As, and Cd are used in the curing catalyst.

In addition, a chelating agent (for example, acetone (representative formula: C ₅ H ₈ O ₂ ), ethyl acetone (representative formula: C ₆ H ₉ O ₃ )) is coordinated with a metal ion Since metal chelate compounds are stable, they are often used as curing catalysts. However, due to the π-π* transition of the chelate ring, absorption occurs in the ultraviolet region to the visible region. Although this absorption does not necessarily coincide with the emission peak wavelength of the ultraviolet LED, since the ultraviolet LED usually emits ultraviolet light with a relatively large emission spectrum, absorption of ultraviolet light occurs in a range consistent with the absorption spectrum of the metal chelate compound. As described above, in the case where a metal chelate compound is used as a curing catalyst, the transmission characteristics and UV resistance in the ultraviolet region will be deteriorated, so it is not used as a curing catalyst.

[Preparation of curable resin composition]

The curable resin composition of the present embodiment can be obtained by adding the curing catalyst to the alkoxy oligomer and mixing for a predetermined time. In addition, as long as it is a method which can uniformly mix an alkoxy oligomer and a curing catalyst, the preparation method of a curable resin composition is not specifically limited.

Since the curable resin composition of the present embodiment is liquid at room temperature, when used as a sealing material for an ultraviolet LED, a predetermined amount is injected into the ultraviolet LED package and heated for a predetermined time to dry. It should be noted that the heating conditions are not particularly limited as long as the curable resin composition can be brought into a desired cured state. For example, it is preferable to heat at 100°C to 200°C for about 1 to 2 hours.

[Structure of LED sealed with curable resin composition]

As described above, the curable resin composition of the present embodiment is suitable for use as a sealing material for, for example, a high-power ultraviolet LED. Fig. 1 is a schematic configuration diagram (cross-sectional view) showing an example of a case where the curable resin composition of this embodiment is applied to a surface-mounted ultraviolet LED 100. In addition, Fig. 2 is a schematic configuration diagram (cross-sectional view) showing an example of a case where the curable resin composition of the present embodiment is applied to the encapsulated ultraviolet LED 200.

As shown in FIG. 1, the ultraviolet LED 100 includes a substrate 101, an LED chip 103, and the like. The substrate 101 is a so-called wiring substrate made of an insulating substrate (for example, ceramic (aluminum nitride, alumina, silicon nitride, silicon carbide, etc.)). As shown in FIG. 1, a positive electrode pattern 102a and a negative electrode pattern 102b made of a conductive metal material (for example, copper, aluminum) are formed on the surface of the substrate 101.

The LED chip 103 has a quadrangular prism shape, the upper surface (that is, the emission surface 103a) is provided with a cathode terminal (not shown), and the lower surface is provided with an anode terminal (not shown). The lower surface of the LED chip 103 (that is, the anode terminal) and the positive electrode pattern 102a are mechanically bonded and electrically connected by a chip solder (not shown). In addition, the cathode terminal on the upper surface of the LED chip 103 is electrically connected to the negative electrode pattern 102b through the welding wire 104. Furthermore, when a current is applied between the anode terminal and the cathode terminal via the positive electrode pattern 102a and the negative electrode pattern 102b, the light emitting layer (not shown) inside the LED chip 103 emits ultraviolet light (for example, light with a wavelength of 365 nm), and The emission surface 103a emits.

A frame 105 is provided around the LED chip 103, and the LED chip 103 inside the frame 105 is sealed by the cured product 106 of the curable resin composition of this embodiment.

As a manufacturing method of the ultraviolet LED 100 shown in FIG. 1, the following method can be cited: the LED chip 103 is welded to the positive electrode pattern 102a, and the cathode terminal of the LED chip 103 and the negative electrode pattern 102b are wire-bonded with a wire 104, and then The inside of the frame material 105 is filled with the curable resin composition of this embodiment, and it is heated at 100 degreeC-200 degreeC for about 1 hour-2 hours, and it hardens|cures.

The UV LED 200 shown in Figure 2 is similar to Figure 1 in the following aspects The illustrated ultraviolet LED 100 is different: the cathode terminal (not shown) and the anode terminal (not shown) of the LED chip 203 are formed on the upper surface (ie, the emission surface 203a) of the LED chip 203, and the LED chip 203 is housed in the housing 210 There is a cured product 207 inside and on the cured product 206 of the curable resin composition of this embodiment.

As shown in FIG. 2, the ultraviolet LED 200 includes a housing 210, an LED chip 203, and the like. The case 210 is a cup-shaped member formed of an insulating material (for example, ceramic). As shown in FIG. 2, the bottom 210a of the casing 210 is provided with a positive electrode pattern 202a and a negative electrode pattern 202b formed by extending from the inside to the outside of the casing 210.

The LED chip 203 has a quadrangular prism shape, and the upper surface (that is, the emission surface 203a) is provided with a cathode terminal (not shown) and an anode terminal (not shown). The lower surface of the LED chip 203 is fixed to the bottom 210a of the housing 210 by a chip solder (not shown). In addition, the anode terminal on the upper surface of the LED chip 203 is electrically connected to the positive electrode pattern 202a through the welding wire 204a, and the cathode terminal on the upper surface of the LED chip 203 is electrically connected to the negative electrode pattern 202b through the welding wire 204b. Furthermore, when a current is applied between the anode terminal and the cathode terminal via the positive electrode pattern 202a and the negative electrode pattern 202b, the light-emitting layer (not shown) inside the LED chip 203 emits ultraviolet light (for example, light with a wavelength of 365 nm). The emission surface 203a emits.

The LED chip 203 is surrounded by the wall surface of the housing 210, and the LED chip 203 inside the housing 210 is sealed by the cured product 206 of the curable resin composition of this embodiment. In addition, a cured product 207 of another curable resin composition having a different refractive index and elastic modulus from the curable resin composition of the present embodiment is formed on the cured product 206.

As a method of manufacturing the ultraviolet LED200 shown in Figure 2, you can The following method is mentioned: the LED chip 203 is welded in the housing 210, and the anode terminal and the cathode terminal of the LED chip 203 are connected to the positive electrode pattern 202a and the negative electrode pattern 202b through the wires 204a and 204b, respectively, and then The inside of 210 is filled with the curable resin composition of this embodiment, heated at 100°C to 200°C for about 1 hour to 2 hours to cure it, and then filled with the curable resin composition of the cured product 207, and set it Heat it for a given time at a temperature to cure it.

Example

Hereinafter, the present invention will be further described with examples and comparative examples, but as long as it does not deviate from the gist of the present invention, it is not limited to the following examples. In addition, in Example 2 to Example 10, and Comparative Example 1 to Comparative Example 5, the following matters were applied.

(1) The "difunctional structural unit" may include the structural unit represented by the general formula (5) (R ⁷ _a (OR ⁸ ) _3-a SiO _1/2 ) where a is 2 (R ⁷ ₂ ( OR ⁸ )SiO _1/2 ).

(2) The "trifunctional structural unit" may include the structural unit represented by the general formula (5) (R ⁷ _a (OR ⁸ ) _3-a SiO _1/2 ) in which a is 1 (R ⁷ (OR ⁸ ) ₂ SiO _1/2 ), and the structural unit represented by the general formula (6) (R ⁹ _b (OR ¹⁰ ) _2-b SiO _2/2 ) when b is 1 (R ⁹ (OR ¹⁰ ) SiO _2/2 ).

(3) The "4-functional structural unit" may include the structural unit represented by the general formula (5) (R ⁷ _a (OR ⁸ ) _3-a SiO _1/2 ) where a is 0 ((OR ⁸ ) ₃ SiO _1/2 ), and the structural unit represented by the general formula (7) ((OR ¹¹ )SiO _3/2 ).

[Example 1]

(Synthesis of alkoxy oligomer)

A 500mL four-necked flask equipped with a nitrogen inlet tube, a liebig condenser, and a dropping funnel with a piston is charged with methyltrimethoxysilane (MTMS) Z-6366 manufactured by Dow Corning Toray (indicative formula) : CH ₃ Si(OCH ₃ ) ₃ , molecular weight: 136.2) 68.10 g (0.50 mol) and 32.04 g (1.00 mol) of methanol (representative formula: CH ₃ OH), mixed and stirred at room temperature. Here, in order to hydrolyze the methoxy group of MTMS, hydrochloric acid (indicative formula: HCl) is used as a hydrolysis catalyst, and 13.52 g of 3.70 mol/L hydrochloric acid aqueous solution is added dropwise over 30 minutes under stirring, so that the molar ratio is HCl/MTMS =0.1, H ₂ O/MTMS=1.5, and stir for another 30 minutes. Then, the four-necked flask was set in a bell-type electric heater, refluxed at 80°C for 4 hours, then cooled to room temperature and left for 1 hour to obtain a transparent and uniform viscous liquid (alkoxy oligomer, Amount of alkoxy group: 19% by weight).

(Synthesis of curing catalyst)

While cooling in an ice bath Z-6329 (chemical name: dimethyldimethoxysilane (DMDMS), indicative formula: (CH ₃ ) ₂ Si(OCH ₃ ) ₂ , molecular weight: 120.2) manufactured by Dow Corning Toray ) 100.00g was stirred, 25.93g of orthophosphoric acid (indicative formula: H ₃ PO ₄ ) aqueous solution (H ₃ PO ₄ concentration: 85%) was added dropwise over 15 minutes and mixed, and the mixture was further mixed for 1 hour at room temperature to obtain The phosphoric acid curing catalyst H ₃ PO _{4 is used} . It should be noted that although orthophosphoric acid contains 15% by weight of H ₂ O, as shown in the above chemical reaction formula (2), it reacts with the methoxy group (CH ₃ O-) of DMDMS and all is consumed. In addition, the concentration of the curing catalyst H ₃ PO ₄ contained in the liquid was 17.5% by weight.

(Preparation of curable resin composition)

10.00 g of the curing catalyst (phosphoric acid-based curing catalyst) was added to the viscous liquid (alkoxy oligomer), and mixed at room temperature for 10 minutes. Then, use a rotary evaporator to evaporate and remove CH ₃ OH and H ₂ O, and obtain a transparent uniform containing methyl (CH3-) as an organic group and composed of T unit: D unit = 87.9:12.1 (mole ratio) Liquid (curable resin composition). Relative to the total amount of MTMS and DMDMS, the amount of curing catalyst H ₃ PO ₄ added was 2.30% by weight. In addition, the atomic ratio of O to Si is 2.9.

[Example 2]

The polysiloxane alkoxy oligomer X-40-9225 (organic group: methyl, alkoxy: methoxy, The amount of alkoxy group: 24% by weight, the amount of SiO ₂ : 67% by weight) 100.00 g, and 3.00 g of the phosphoric acid-based curing catalyst prepared in the same manner as in Example 1 were mixed at room temperature for 10 minutes to obtain methyl-containing As an organic group, a transparent and uniform liquid (curable resin composition) composed of T unit: D unit=98.2:1.8 (molar ratio). The addition amount of the curing catalyst H ₃ PO ₄ was 0.52% by weight relative to the polysiloxane alkoxy oligomer X-40-9225. The atomic ratio of O to Si is 3.0. It should be noted that for the structural unit of the polysiloxane alkoxy oligomer X-40-9225, the NMR spectrum of 29Si was carried out using a nuclear magnetic resonance device (NMR) JNM-ECX400 manufactured by JEOL Ltd. (29Si-NMR) measurement and analysis.

[Example 3]

The polysiloxane alkoxy oligomer X-40-9225 manufactured by Shin-Etsu Chemical Co., Ltd.: 100.00 g and 40.00 g of the phosphoric acid-based curing catalyst prepared in the same manner as in Example 1 were mixed and stirred at room temperature In 10 minutes, a transparent and uniform liquid (curable resin composition) containing a methyl group as an organic group and composed of T unit:D unit=80.2:19.8 (molar ratio) was obtained. The addition amount of the curing catalyst H ₃ PO ₄ was 7.00% by weight relative to the polysiloxane alkoxy oligomer X-40-9225. In addition, the atomic ratio of O to Si is 2.8.

[Example 4]

The polysiloxane alkoxy oligomer X-40-9246 (organic group: methyl group, alkoxy group: methoxy group, etc.) manufactured by Shin-Etsu Chemical Industry Co., Ltd. composed of T unit: D unit = 53.6: 46.4 The amount of alkoxy group: 12% by weight, the amount of SiO ₂ : 72% by weight) 100.00 g and 60.00 g of the phosphoric acid-based curing catalyst prepared in the same manner as in Example 1 were mixed and stirred at room temperature for 10 minutes to obtain a The group is an organic group and is a transparent and uniform liquid (curable resin composition) composed of T unit: D unit=39.9:60.1 (molar ratio). In addition, the addition amount of the curing catalyst H ₃ PO ₄ is 10.50% by weight relative to the polysiloxane alkoxy oligomer X-40-9246. In addition, the atomic ratio of O to Si is 2.4. In addition, the structural unit of polysiloxane alkoxy oligomer X-40-9246 was measured and analyzed for 29Si-NMR spectrum in the same manner as in Example 2.

[Example 5]

Into a 500mL four-necked flask equipped with a nitrogen inlet tube, a Lippy condenser, and a dropping funnel with a piston, was added methyltrimethoxysilane (MTMS) Z-6366 manufactured by Dow Corning Toray: 47.67g (0.35mol), Dimethyldimethoxysilane (DMDMS) Z-6329 manufactured by Dow Corning Toray: 18.03 g (0.15 mol), 32.04 g (1.00 mol) of methanol, and mixing and stirring were performed at room temperature. Here, 13.52g of 3.70mol/L hydrochloric acid (representative formula: HCl) aqueous solution was added dropwise over 30 minutes under stirring, so that the molar ratio was HCl/(MTMS+DMDMS)=0.1, H ₂ O/(MTMS+ DMDMS) =1.5, stirring for another 30 minutes. Then, the four-necked flask was set in a hood-type electric heater, heated at 80°C for 4 hours, then cooled to room temperature and left for 1 hour, thereby obtaining a transparent and uniform viscous liquid (alkoxy oligomer Amount of alkoxy group: 16% by weight). Then, 10.00 g of the phosphoric acid-based curing catalyst used in Example 1 was added to the viscous liquid, and mixed at room temperature for 10 minutes. Then use a rotary evaporator to evaporate and remove CH ₃ OH and H ₂ O, and obtain a transparent and uniform liquid (curable) containing methyl as an organic group and composed of T unit: D unit = 61.6: 38.4 (molar ratio) Resin composition). It should be noted that the addition amount of the curing catalyst H ₃ PO ₄ is 2.66% by weight relative to the total amount of MTMS and DMDMS. In addition, the atomic ratio of O to Si is 2.6.

[Example 6]

In the same manner as in Example 5, methyltrimethoxysilane (MTMS) Z-6366 produced by Dow Corning Toray: 24.52g (0.18mol), dimethyldimethoxysilane produced by Dow Corning Toray (DMDMS) Z-6329: 38.46 g (0.32 mol) was obtained as a transparent and uniform alkoxy oligomer (amount of alkoxy group: 13% by weight). With respect to the alkoxy oligomer, 10.00 g of a phosphoric acid catalyst (same as in Example 1) was used to obtain a methyl group as an organic group and a T unit: D unit = 31.7: 68.3 (molar ratio) The structure is a transparent and uniform liquid (curable resin composition). It should be noted that the addition amount of the curing catalyst H ₃ PO ₄ is 2.78% by weight relative to the total amount of MTMS and DMDMS. In addition, the atomic ratio of O to Si is 2.3.

[Example 7]

To the polysiloxane alkoxy oligomer X-40-9246 manufactured by Shin-Etsu Chemical Co., Ltd.: 100.00 g heated to 60°C, tetra-n-butoxy zirconium manufactured by Nippon Soda Co., Ltd. was added dropwise as a curing catalyst (Indicative formula: Zr(OnC ₄ H ₉ ) ₄ , component concentration: 85% by weight, containing solvent: 1-butanol, referred to as TBZR) 3.00g, mixed for 1 hour, and then cooled to room temperature to obtain a The group is an organic group and is a transparent and uniform liquid (curable resin composition) composed of T unit: D unit = 53.6: 46.4 (molar ratio). In addition, the addition amount of the curing catalyst Zr(OnC ₄ H ₉ ) ₄ is 2.55% by weight relative to the alkoxy oligomer. In addition, the atomic ratio of O to Si is 2.5.

[Example 8]

In place of Example 1, 75.13 g (0.5 mol) of ethyl trimethoxysilane (representative formula: C ₂ H ₅ Si(OCH ₃ ) ₃ , molecular weight: 150.25, hereinafter referred to as ETMS) manufactured by Tokyo Chemical Industry Co., Ltd. Methyltrimethoxysilane (MTMS) Z-6366 manufactured by Dow Corning Toray used for this was operated in the same manner as in Example 1 to obtain a transparent and uniform alkoxy oligomer (alkoxy group: 15% by weight). With respect to the alkoxy oligomer, 10.00 g of a phosphoric acid catalyst (same as in Example 1) was used to obtain an ethyl group (C ₂ H ₅ -) as an organic group and a T unit: D unit = 87.9 : Transparent and uniform liquid (curable resin composition) composed of 12.1 (mole ratio). It should be noted that the addition amount of the curing catalyst H ₃ PO ₄ is 2.11% by weight relative to the total amount of ETMS and DMDMS. In addition, the atomic ratio of O to Si is 2.9.

[Example 9]

3.00 g of pentaethoxy tantalum manufactured by Beixing Chemical Industry Co., Ltd. (indicative formula: Ta(OC ₂ H ₅ ) ₅ ) was used as a curing catalyst instead of the Nippon Soda Co., Ltd. product used as the curing catalyst in Example 7 TBZR was operated in the same manner as in Example 7 to obtain a transparent and uniform liquid (curable resin composition) containing a methyl group as an organic group and composed of T unit:D unit=53.6:46.4 (molar ratio). In addition, the addition amount of the curing catalyst Ta(OC ₂ H ₅ ) ₅ is 3.00% by weight relative to the polysiloxane alkoxy oligomer. In addition, the atomic ratio of O to Si is 2.5.

[Example 10]

The polysiloxane alkoxy oligomer X-40-9246 manufactured by Shin-Etsu Chemical Co., Ltd.: 90.00 g, and the polysiloxane alkoxy group manufactured by COLCOAT, which is composed of only the Q unit polysiloxane Oligomer (methyl silicate 51 (alkoxy group: methoxy group, alkoxy group amount: 66% by weight, SiO ₂ amount: 51% by weight)) 10.00 g was stirred and mixed at room temperature for 1 hour, and then added for implementation 3.00 g of the phosphoric acid curing catalyst used in Example 1 was mixed for 30 minutes at room temperature to obtain a transparent and uniform liquid (curable resin composition) composed of Q unit: T unit: D unit = 7.2: 91.1: 1.7 ). The addition amount of the curing catalyst H ₃ PO ₄ is 0.53% by weight relative to the polysiloxane alkoxy oligomer. In addition, the atomic ratio of O to Si is 3.1.

[Comparative Example 1]

Using B-1 (chemical name: tetra-n-butoxide titanium, indicative formula: Ti(OnC ₄ H ₉ ) ₄ ) manufactured by Nippon Soda Co., Ltd. as a curing catalyst, instead of the phosphoric acid-based curing catalyst of Example 7, In the same manner as in Example 7, a transparent and uniform liquid (curable resin composition) containing a methyl group as an organic group and composed of T unit:D unit=53.6:46.4 (molar ratio) was obtained. The addition amount of the curing catalyst Ti(OnC ₄ H ₉ ) ₄ is 3.50% by weight relative to the polysiloxane alkoxy oligomer. In addition, the atomic ratio of O to Si is 2.5.

[Comparative Example 2]

The aluminum chelate compound D (chemical name: monoacetone bis(ethyl acetylacetate) aluminum alloy manufactured by Kawaken Fine Chemicals Co., Ltd., showing formula: Al(C ₅ H ₇ O ₂ )(C ₆ H ₉ O) ₃ ) _2. Component concentration: 76% by weight, containing solvent: 2-propanol) 6.50 g was used as a curing catalyst instead of the phosphoric acid catalyst of Example 3, and in the same manner as Example 3, a methyl group was obtained as an organic group. A transparent and uniform liquid (curable resin composition) composed of only T units. It should be noted that the amount of curing catalyst Al(C ₅ H ₇ O ₂ )(C ₆ H ₉ O ₃ ) ₂ added was 4.99% by weight with respect to the total amount of polysiloxane alkoxy oligomer. In addition, the atomic ratio of O to Si is 3.0.

[Comparative Example 3]

Used ZC-540 manufactured by Matsumoto Fine Chemical Company (chemical name: zirconium tributoxy monoacetone, indicative formula: Zr(OnC ₄ H ₉ ) ₃ (C ₅ H ₇ O ₂ ), component concentration: 45 weight %, containing solvent: toluene, 1-butanol, butyl acetate) 3.00g as a curing catalyst instead of the phosphoric acid-based curing catalyst of Example 3, the same operation as Example 3, obtained containing methyl as an organic group, And a transparent and uniform liquid (curable resin composition) composed only of T cells. The addition amount of the curing catalyst Zr(OnC ₄ H ₉ ) ₃ (C ₅ H ₇ O ₂ ) is 1.35 wt% with respect to the polysiloxane alkoxy oligomer. In addition, the atomic ratio of O to Si is 3.0.

[Comparative Example 4]

In the same manner as in Example 5, a transparent and uniform alkoxy oligomer (amount of alkoxy groups; 12% by weight) was obtained from 14.98 g (0.11 mol) of MTMS and 46.88 g (0.39 mol) of DMDMS. With respect to the alkoxy oligomer, 10.00 g of the phosphoric acid catalyst used in Example 1 was used to obtain a composition containing a methyl group as an organic group and consisting of T unit: D unit = 19.3: 80.7 (molar ratio) The transparent liquid (curable resin composition). With respect to the total amount of MTMS and DMDMS, the addition amount of the curing catalyst H ₃ PO ₄ was 2.83% by weight. In addition, the atomic ratio of O to Si is 2.2.

[Comparative Example 5]

In the same manner as in Example 5, a transparent and uniform alkoxy oligomer (amount of alkoxy group: 17% by weight) was obtained from 54.48 g (0.40 mol) of MTMS and 12.02 g (0.10 mol) of DMDMS. With respect to the alkoxy oligomer, 15.65 g of an orthophosphoric acid aqueous solution (H ₃ PO ₄ concentration: 85%) was used instead of the phosphoric acid catalyst of Example 5 to obtain a methyl group as an organic group and a T unit : D unit = 80.0: a transparent liquid (curable resin composition) composed of 20.0 (mole ratio). With respect to the total amount of MTMS and DMDMS, the amount of curing catalyst H ₃ PO ₄ added was 20.00% by weight. In addition, the atomic ratio of O to Si is 2.8.

[Evaluation/Measurement]

The curable resin compositions of the above-mentioned Examples 1 to 10 and Comparative Examples 1 to 5 were evaluated for the occurrence of cracks/fractures, transmittance measurement, and ultraviolet resistance evaluation as described below. The results are summarized in Tables 1 to 4.

(Evaluation of whether cracks/fractures have occurred)

Put 6.0 g of each of the above sealing materials (curable resin composition) into a petri dish made of polymethylpentene resin with an inner diameter of φ84mm and a height of 14mm, and cover with polymethyl A cap made of pentene resin (inner diameter φ87mm, height 8mm) was left at room temperature and cured. The solidification is determined by placing one end of the petri dish on a metal block with a height of 20 mm and tilting it (approximately 13°), and determining whether the liquid in the petri dish has fluidity. After curing, the lid was removed and placed at room temperature. Visual inspection was used to confirm whether cracks or breaks occurred. It should be noted that the evaluation results are shown in Tables 1 to 4 "whether cracks/fractures occur", the cases where there are no cracks and fractures are "None", and the cases where there are cracks and fractures are "Yes".

(Transmittance measurement/evaluation)

A petri dish made of polymethylpentene resin with an inner diameter of φ84mm and a height of 14mm is filled with the above-mentioned sealing materials (curable resin composition) with a capacity to obtain a cured product with a thickness of 1mm and covered with polymethylpentene resin Cover (inner diameter φ87mm, height 8mm) and solidify it. After curing, the temperature was raised to 150°C and kept at 150°C for 1 hour to dry. The transmittance of the obtained cured product was measured in a wavelength range of 200 to 1200 nm using an ultraviolet-visible spectrophotometer U-4100 manufactured by Hitachi High Technologies. Then, the smallest transmittance in the wavelength range of 300 to 350 nm was evaluated.

Figures 3 to 6 are graphs showing an example of the transmittance measurement results. Figure 3 shows the transmittance measurement results of Example 3, Figure 4 shows the transmittance measurement results of Example 7, Figure 5 shows the transmittance measurement results of Example 9, and Figure 6 The transmittance measurement result of Example 10 is shown. In Example 3, according to Figure 3, the smallest transmittance in the wavelength range of 300 to 350 nm was evaluated as 91.8%. In addition, in Example 7, according to Fig. 4, the smallest transmittance in the wavelength range of 300 to 350 nm was evaluated as 90.5%. In addition, in Example 9, according to Fig. 5, the smallest transmittance in the wavelength range of 300 to 350 nm was evaluated as 87.4%. In addition, in Example 10, according to Fig. 6, the smallest transmittance in the wavelength range of 300 to 350 nm was evaluated as 91.1%. As described above, based on the transmittance measurement results of each of the above-mentioned sealing materials (curable resin compositions), the results of the minimum transmittance in the wavelength range of 300 to 350 nm are shown in Tables 1 to 4 in "Tmin _300-350 ". It should be noted that the case where "Tmin _300-350 " is 85% or more is regarded as a pass.

(Evaluation of UV resistance)

The packaged ultraviolet LED manufactured by Nichia Chemical Industry Co., Ltd. with the glass window removed: NC4U133B (luminous peak wavelength: 365nm) was mounted on an aluminum star-shaped substrate, and the star-shaped substrate was interposed with Teflon (registered (Trademark) spacers are fixed on the aluminum radiator with screws. Then, a current of about 1.0A was passed through the encapsulated ultraviolet LED to emit about 100W/cm ² of ultraviolet light, and the thickness of the spacer made of Teflon (registered trademark) was adjusted so that the junction temperature (Tj) was 100°C . The junction temperature was measured using a thermal resistance tester AT-205 manufactured by YUASA ELECTRONICS. Each of the above-mentioned sealing materials (curable resin compositions) was filled in the recesses of the encapsulated ultraviolet LED, left at room temperature to be cured, then the temperature was raised to 150°C, and then kept at 150°C for 1 hour to dry. A current of 1.0A was passed through the sealed packaged ultraviolet LED to continuously light up, and the luminous intensity was continuously measured using an integrating sphere (manufactured by Labsphere, model: 3P-GPS-020-SL, inner diameter: φ2 inches). For the measurement of the luminous intensity, an ultraviolet cumulative light meter UIT-150 manufactured by Ushio Electric Co., Ltd. and a receiver UVD-S365 for ultraviolet cumulative light meter were used. LED has the property that the luminous intensity decreases with the lapse of lighting time. Therefore, in the evaluation of the ultraviolet resistance of the sealing material (curable resin composition), the unsealed encapsulated ultraviolet LED and the sealed encapsulated ultraviolet LED They were lit together under the same conditions, and after 5000 hours, the luminous intensities of the two were compared. Then, as described later, the luminous intensity after 500 hours (correction value), the luminous intensity after 1000 hours (correction value), and the luminous intensity after 5000 hours (correction value) in the evaluation of ultraviolet resistance , The case where the luminous intensity (corrected value) after at least 500 hours has passed is 85% or more is regarded as a pass.

Figures 7 to 9 are graphs showing an example of changes in luminous intensity over time. Figure 7 shows the time-dependent changes in the luminous intensity of Example 1, Figure 8 shows the time-dependent changes in the luminous intensity of Example 3, and Figure 9 shows the time-dependent changes in the luminous intensity of Example 7 . In Figures 7-9, the graphs indicated by "○" and the dotted line are graphs showing the time-dependent changes (measured values) of the luminous intensity of each example. The luminous intensity immediately after the LED is lit It is a graph that is 100% and expressed as a relative value. In addition, in Figs. 7-9, the graphs indicated by "●" and the solid line are corrected for the actual measured values indicated by "○" and the dotted line in consideration of the luminous intensity of the unsealed packaged UV LED. The obtained graph (correction value) is, specifically, a graph showing the aforementioned correction value with respect to the emission intensity of an unsealed packaged ultraviolet LED. That is, the graph represented by "●" and the solid line (ie, the correction value) is the luminous intensity of ultraviolet light passing through the cured product of each sealing material (curable resin composition) relative to the luminous intensity of the unsealed encapsulated ultraviolet LED The intensity ratio, that is, shows the transmittance of the cured product of each sealing material (curable resin composition) to ultraviolet light.

In Example 1, according to Figure 7, the luminous intensity (correction value) after 500 hours was evaluated as 95% or more, the luminous intensity after 1000 hours (correction value) was evaluated as 95% or more, and the luminous intensity (correction value) after 1000 hours was evaluated as 95% or more. The luminous intensity (corrected value) after hours is evaluated to be 90% or more. In Example 3, according to Figure 8, the luminous intensity (correction value) after 500 hours was evaluated as 95% or more, the luminous intensity after 1000 hours (correction value) was evaluated as 95% or more, and the luminous intensity (correction value) after 1000 hours was evaluated as 95% or more. Glow after hours The intensity (corrected value) is evaluated as 90% or more. In Example 7, according to Figure 9, the luminous intensity (correction value) after 500 hours is evaluated to be 95% or more, and the luminous intensity (correction value) after 1000 hours is evaluated to be 95% or more. The luminous intensity (corrected value) after hours is evaluated to be 90% or more. As described above, based on the measurement results of the luminous intensity of LEDs sealed with each of the above-mentioned sealing materials (curable resin compositions), the luminous intensity (corrected value) after 500 hours and the luminous intensity after 1000 hours (Correction value), the results of the luminous intensity after 5000 hours (correction value) are shown in Tables 1 to 4 in the ultraviolet resistance (1) (luminous intensity after 500 hours (correction value)), ultraviolet resistance ( 2) (Luminous intensity after 1000 hours (correction value)) and UV resistance (3) (Luminous intensity after 5000 hours (correction value)). It should be noted that for the eligibility criteria for the ultraviolet resistance evaluation of this example, the luminous intensity (corrected value) after at least 500 hours has passed (that is, the transmittance of ultraviolet light after 500 hours has passed) is 85% The above case is regarded as a pass, but the pass standard for the evaluation of ultraviolet resistance can be appropriately changed according to the specifications required for the LED, and it is more preferably 87.5% or more, and still more preferably 90% or more. In addition, as a pass criterion for the evaluation of ultraviolet resistance, the emission intensity (correction value) after 1000 hours (that is, the transmittance of ultraviolet light after 1000 hours) may be added. In this case, the emission intensity (correction value) after 1000 hours has passed is preferably 85% or more, more preferably 87.5% or more, and still more preferably 90% or more. In addition, as a pass criterion for the evaluation of ultraviolet resistance, the luminous intensity (correction value) after 5000 hours (that is, the transmittance of ultraviolet light after 5000 hours) may be added. In this case, the emission intensity (correction value) after 5000 hours has passed is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. As shown in Table 3 and Table 4, for Comparative Examples 1 to 7, the UV resistance (1) and (2) (ie, after 500 The luminous intensity after hours (correction value) and the luminous intensity after 1000 hours (correction value) are both evaluated as 85% or less, so UV resistance is not performed (3) (luminous intensity after 5000 hours (correction value) )evaluation of.

(Survey)

As shown in Tables 1 and 2, for each of the sealing materials (curable resin compositions) of Examples 1 to 8, the atomic ratio of O to Si of any alkoxy oligomer is in the range of 2.3 to 3.5 And the curing catalyst is phosphoric acid with a content in the range of 3 to 30 parts by weight relative to 100 parts by weight of alkoxy oligomer, or a content in the range of 0.5 to 20 parts by weight relative to 100 parts by weight of alkoxy oligomer At least one metal alkoxide selected from B, Al, P, Sc, Ga, Y, Zr, Nb, In, Sn, La, Gd, Dy, Yb, Hf, Ta, and W. Therefore, no cracks/fractures were found after curing, "Tmin _300-350 " was 85% or more, and "luminous intensity after 500 hours (correction value)" (ie, "ultraviolet resistance (1)") was Over 85%. Therefore, the transparency, ultraviolet resistance, and heat resistance of each sealing material (curable resin composition) of Examples 1 to 8 in the ultraviolet region were evaluated as extremely high.

Figure 10 shows the transmittance characteristics of the curable resin composition of Comparative Example 1 produced using titanium tetra-n-butoxide as a curing catalyst. As shown in Fig. 10, it can be seen that the tetra-n-butoxide titanium of Comparative Example 1 contains Ti and absorbs light in the wavelength region of less than 350 nm. Therefore, when it is used as a curing catalyst, the transmission characteristics and UV resistance in the ultraviolet region deteriorate (Table 3), and therefore it is not suitable for use as a curing catalyst.

Figure 11 shows the use of monoacetone bis (ethyl acetone) aluminum alloy The transmittance characteristics of the curable resin composition of Comparative Example 2 prepared as a curing catalyst. As shown in Fig. 11, it can be seen that a metal chelate compound such as monoacetone bis(ethylacetate)aluminum absorbs light in a wavelength range of less than 350 nm. Therefore, when it is used as a curing catalyst, the transmission characteristics and UV resistance in the ultraviolet region deteriorate (Table 3), and therefore it is not suitable for use as a curing catalyst.

Figure 12 shows the transmittance characteristics of the curable resin composition of Comparative Example 3 produced using zirconium tributoxymonoacetone acetonate as a curing catalyst. As shown in Figure 12, it can be seen that zirconium tributoxymonoacetone also absorbs light in the wavelength region below 350 nm. Therefore, when it is used as a curing catalyst, the transmission characteristics and UV resistance in the ultraviolet region deteriorate (Table 3), and therefore it is not suitable for use as a curing catalyst.

From Comparative Example 4, it can be seen that if D units are relatively increased and the ratio of T units/(D units + T units) is decreased, the atomic ratio of O to Si is less than 2.3, and therefore the UV resistance is deteriorated (Table 4).

It can be seen from Comparative Example 5 that if the amount of the catalyst is too large, the material becomes too hard, the ability to relax the stress caused by the temperature change accompanying the turning on/off of the LED is significantly reduced, and the UV resistance is deteriorated (Table 4) .

The foregoing is a description of the embodiments and examples of the present invention, but the present invention is not limited to the above-mentioned configuration, and various changes can be made within the scope of the technical idea of the present invention.

For example, in the description of the embodiments of the present invention, as the use of the curable resin composition, the sealing of ultraviolet LEDs is cited, but the use of the curable resin composition is not limited to this. For example, it can also be used as a laser. Diodes and other semiconductor light-emitting devices (optical semiconductor devices), photodetectors, electro-optical displays, Sealing materials for light-emitting elements used in organic semiconductors, organic light-emitting diodes, electroluminescent displays, organic solar cell devices, lighting devices, etc.

In addition, it should be considered that the embodiments disclosed in the present application are illustrative in every respect and not restrictive. The scope of the present invention is not the above description, but the scope shown in the scope of the patent application, and includes the meaning equivalent to the scope of the patent application and the meaning of various changes within the scope.

100‧‧‧UV LED

101‧‧‧Substrate

102a‧‧‧Anode pattern

102b‧‧‧Negative pattern

103‧‧‧LED chip

103a‧‧‧Ejection surface

104‧‧‧Wire

105‧‧‧Frame material

106‧‧‧cured material

Claims (14)

A curable resin composition containing an alkoxy oligomer and a curing catalyst, wherein the alkoxy oligomer has an organopolysiloxane structure, which is selected from the following general formulas (1)~( 4) One or more structural units in the structural unit shown, and also one or more structural units selected from the structural units shown in the following general formulas (5) to (7), the general formula (1)(R ¹ R ² R ³ SiO _1/2 ). . . (1) In the general formula (1), R ¹ , R ² and R ³ are each independently the same or different hydrocarbon groups, and the general formula (2) (R ⁴ R ⁵ SiO _2/2 ). . . (2) In the general formula (2), R ⁴ and R ⁵ are each independently the same or different hydrocarbon groups, and the general formula (3) (R ⁶ SiO _3/2 ). . . (3) In the general formula (3), R ⁶ is a hydrocarbon group, and the general formula (4) (SiO _4/2 ). . . (4) General formula (5) (R ⁷ _a (OR ⁸ ) _3-a SiO _1/2 ). . . (5) In the general formula (5), a is 0, 1, or 2, R ⁷ and R ⁸ are each independently the same or different hydrocarbon groups, and when a plurality of R ⁷ or R ^{8 are} contained, each R ⁷ or R ^{8 are the} same or different from each other, the general formula (6) (R ⁹ _b (OR ¹⁰ ) _2-b SiO _2/2 ). . . (6) In the general formula (6), b is 0 or 1, R ⁹ and R ¹⁰ are each independently the same or different hydrocarbon groups. When a plurality of R ¹⁰ are contained, each R ^{10 is the} same or different from each other , General formula (7) ((OR ¹¹ )SiO _3/2 ). . . (7) In the general formula (7), R ¹¹ is a hydrocarbon group, and when all siloxane units constituting the alkoxy oligomer are set to 100 mol%, the general formula (1) is contained ~ The structural unit represented by the general formula (7) is 90-100 mol%, and the atomic ratio of the total amount of O atoms contained in the alkoxy oligomer to the total amount of Si atoms is 2.3-3.5, the The curing catalyst is phosphoric acid in a content range of 0.1 to 17.5 parts by weight relative to 100 parts by weight of the alkoxy oligomer, or a content range of 0.5 to 20 parts relative to 100 parts by weight of the alkoxy oligomer. Parts by weight of at least one metal alkoxide selected from B, Al, P, Sc, Ga, Y, Zr, Nb, In, Sn, La, Gd, Dy, Yb, Hf, Ta, and W. The curable resin composition according to claim 1, wherein the alkoxy oligomer and the curing catalyst do not contain a sulfur atom or a nitrogen atom. The curable resin composition according to item 1 or 2 of the scope of patent application, wherein the R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are methyl groups. Curable resin composition as described in item 1 or 2 of the scope of patent application Wherein, the curing catalyst does not contain Ti compound or chelating compound. The curable resin composition according to claim 1 or 2, wherein the amount of alkoxy groups contained in the alkoxy oligomer is in the range of 10 to 30% by mass. The curable resin composition according to item 1 or 2 of the scope of patent application, wherein the alkoxy oligomer is liquid at room temperature. The curable resin composition described in item 1 or 2 of the scope of the patent application, wherein the cured product obtained by curing the curable resin composition is irradiated with a predetermined wavelength with a luminous intensity of about 100 W/cm ² for 500 hours In the case of ultraviolet light, the transmittance of the cured product to the ultraviolet light is more than 85%. The curable resin composition according to claim 7, wherein when the cured product is irradiated with the ultraviolet light for 1000 hours, the transmittance of the cured product to the ultraviolet light is 85% or more. The curable resin composition according to claim 8, wherein when the cured product is irradiated with the ultraviolet light for 5000 hours, the transmittance of the cured product to the ultraviolet light is 80% or more. The curable resin composition described in item 7 of the scope of patent application, wherein the predetermined wavelength is about 365 nm. The curable resin composition described in item 8 of the scope of patent application, wherein the predetermined wavelength is about 365 nm. The curable resin composition described in item 9 of the scope of patent application, wherein the predetermined wavelength is about 365 nm. An optical semiconductor device having an optical semiconductor element sealed with a curable resin composition as described in item 1 or 2 of the scope of patent application. The optical semiconductor device as described in item 13 of the scope of patent application, wherein the optical semiconductor element emits light in the ultraviolet region.

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