WO2008065786A1

WO2008065786A1 - Optical semiconductor device and transparent optical member

Info

Publication number: WO2008065786A1
Application number: PCT/JP2007/066028
Authority: WO
Inventors: Ken-Ichi Shinotani; Takao Hayashi; Shunpei Fujii; Norihiro Takamura
Original assignee: Panasonic Electric Works Co., Ltd.
Priority date: 2006-11-27
Filing date: 2007-08-17
Publication date: 2008-06-05

Abstract

Disclosed is an optical semiconductor device comprising a semiconductor light-emitting element or a semiconductor light-receiving element sealed with a sealing material, wherein the sealing material is hardly deteriorated and has low water absorbability. A silicon compound containing a cage silsesquioxane compound represented by the formula shown below or a partial polymerization product of the compound is used to seal a semiconductor light-emitting element or a semiconductor light-receiving element. (AR1R2SiOSiO1.5)n(R3R4HSiOSiO1.5)p(BR5R6SiOSiO1.5)q(HOSiO1.5)m-n-p-q [wherein A represents a group having a carbon-carbon unsaturated bond or a linear hydrocarbon group having a carbon-carbon unsaturated bond; B represents a substituted or unsubstituted saturated alkyl group or a hydroxy group; R1, R2, R3, R4, R5 and R6 independently represent a functional group selected from a lower alkyl group, a phenyl group and a lower arylalkyl group; m represents a number selected from 6, 8, 10 and 12; n represents an integer of 1 to m-1; p represents an integer of 1 to m-n; and q represents an integer of 0 to m-n-p].

Description

Specification

Semiconductor optical device and transparent optical member

Technical field

TECHNICAL FIELD [0001] The present invention relates to a semiconductor optical device using a silsesquioxane compound as a sealing material, and a transparent optical member using a silsesquioxane compound as a molding material.

Background art

In recent years, semiconductor light emitting devices such as light emitting diodes, laser diodes, and semiconductor lasers have been used as light emission sources. In particular, light-emitting diodes are widely used as long-life, compact light sources for sine light sources and display light sources.

[0003] Semiconductor light-emitting elements are also being developed as lighting fixtures incorporating white LED units, and are expected to become increasingly widespread in the future. The white LED light source used in the white LED unit is a blue / near-ultraviolet LED, and development to achieve high output and high brightness is being promoted in order to satisfy the requirements of lighting equipment. It has been.

[0004] Since a semiconductor light emitting device with such high output and high brightness emits high thermal energy and light energy, such a semiconductor light emitting device is mounted on a substrate and sealed. However, in the case of an epoxy-based sealing material that is generally used, there is a problem that the sealing material deteriorates rapidly, resulting in a relatively short life.

[0005] In order to solve the above problems, a sealing material excellent in heat resistance and weather resistance, for example, a sealing material using a metal oxide such as a siloxane compound or low-melting glass has been studied! / RU For example, Patent Document 1 discloses a semiconductor device obtained by encapsulating a semiconductor light emitting element using metalloxane, which is a metal oxide obtained by a sol-gel method, as a material having excellent heat resistance and light resistance. RU

[0006] However, metalloxane, which is a metal oxide obtained by the sol-gel method, has a problem in that it has a porous structure and therefore has a high water absorption rate and may absorb moisture and cause cracks during use. [0007] In addition, for example, a DVD device that records light by irradiating light onto a resin disk is used as information recording. In order to meet the recent demand for higher capacity, light in the blue region and near ultraviolet region is used. A device that records and reads data by irradiating is being studied. When reading information recorded on a resin disc, the laser light in the blue / near ultraviolet region is irradiated onto the recording surface of the resin disc, and the light reflected on the recording surface is received by the semiconductor light receiving element. Thus, the information is read out. Such semiconductor light receiving elements are generally sealed and protected with a sealing material, and are irradiated with a single laser beam with a higher output than those using conventional red laser light. When using this sealing material, there was a problem that the sealing material was likely to deteriorate.

[0008] Further, there is a demand for an improvement in recording speed in a DVD device. The power to increase the recording speed by increasing the rotational speed of the disk S. When the rotational speed is high, the amount of laser light (power density) irradiated to the disk during a certain period of time decreases compared to when it is slow. In order to compensate for this decrease, the laser power has been increasing, and in this respect as well, there has been a problem that the sealing material tends to deteriorate when using an epoxy type sealing material.

[0009] In addition, when the laser light in the blue region / near ultraviolet region is irradiated onto the recording surface of the resin disk, and the light reflected by the recording surface is received by the semiconductor light receiving element, the diameter of the laser light is reduced, The optical path is bent, and transparent optical members such as lenses and prisms used in this case are also irradiated with relatively high-power laser light. There was a problem that it was easy to deteriorate.

Patent Document 1: Japanese Patent No. 3412152

Disclosure of the invention

Problems to be solved by the invention

The present invention has been made in view of the above points, and in a semiconductor optical device in which a semiconductor light emitting element or a semiconductor light receiving element is sealed with a sealing material, the sealing material is unlikely to deteriorate and has an excellent lifetime. In a transparent optical member used for a portion irradiated with light in a blue region (near ultraviolet region), a transparent optical member that is hardly deteriorated and has an excellent lifetime is provided. It is intended to provide.

Means for solving the problem [0011] As a result of intensive studies in view of the above, the present inventors have developed a glass-like inorganic property when a desired force and a silsesquioxane compound are used as a sealant, and a blue region- It has resistance to near-ultraviolet light and can also be formed into a desired shape due to its organic properties, and its power and type silsesquioxane compounds are used as sealing agents for semiconductor optical devices. The inventors have found that the present invention is optimal and have completed the present invention.

Therefore, the semiconductor optical device according to claim 1 of the present invention includes a cage silsesquioxane compound represented by the following formula (1), or a force obtained by partial addition reaction of this compound, a cage silsesquioxane compound. A silicon compound containing a partial polymer of an oxan compound, wherein the semiconductor light emitting device or the semiconductor light receiving device is sealed.

Here, the equation (1) is (AR R SiOSiO) (R R HSiOSiO) (BR R SiOSiO

1 2 1. 5 n 3 4 1. 5 p 5 6 1. 5

) (HOSiO)… hi)

q 1.5 m— n— p— q

(In the formula (1), A is a group having a carbon-carbon unsaturated bond, B is a substituted or unsubstituted saturated alkyl group or hydroxyl group, and R 1, R 2, R 3, R 4, R 5 and R 5 are each independently a lower alkyl group. The

1 2 3 4 5 6

Represents a functional group selected from an aryl group and a lower arylalkyl group, m is a number selected from 6, 8, 10, and 12, n is an integer from !! to m—1, p is l to m—n , Q represents an integer from 0 to m—n—p).

The invention of claim 2 is characterized in that, in claim 1, in addition to the cage silsesquioxane compound of the above formula (1), a compound represented by the following formula (2) is contained.

[0013] Here, the equation (2) is HR R Si-X- SiHR R · '· (2)

7 8 9 10

(In the formula (2), X represents a divalent functional group or an oxygen atom, and R 1, R 2, R 3, and R 5 are each independently carbon

7 8 9 10

Represents an alkyl group having a prime number of 1 to 3 or a hydrogen atom.

The invention of claim 3 is characterized in that, in claim 1, in addition to the cage silsesquioxane compound of the above formula (1), the compound of the following formula (3) is contained. , Equation (3): HC = CH-Y-CH = CH · '· (3)

twenty two

(In formula (3), Υ represents a divalent functional group).

The invention of claim 4 is the invention according to any one of claims 1 to 3, wherein Α in formula (1) is carbon. The semiconductor optical device is a chain hydrocarbon group having a carbon unsaturated bond.

The transparent optical member according to claim 5 of the present invention is a cage-type silsesquioxane compound represented by the following formula (1) or a partial polymer of a cage-type silsesquioxane compound obtained by partial addition reaction of this compound. It is characterized by polymerizing the contained key compound.

Here, the expression (1) is similar to the above (AR R SiOSiO 2) (R R HSiOSiO 2) (BR R

1 2 1. 5 n 3 4 1. 5 p 5 6

SiOSiO) (HOSiO) ...

1. 5 q 1. 5 m— n— p— q

1 2 3 4 5 6

The invention of claim 6 is characterized in that, in claim 5, it contains a compound represented by the following formula (2) in addition to the cage silsesquioxane compound of the above formula (1).

[0015] Here, the expression (2) is the same as above, HR R Si-X- SiHR R · '· (2)

7 8 9 10

Represents an alkyl group having a prime number of 1 to 3 or a hydrogen atom.

The invention of claim 7 is characterized in that, in claim 5, it contains a compound represented by the following formula (3) in addition to the cage silsesquioxane compound of the above formula (1). , Equation (3) is the same as above, HC = CH-Y-CH = CH · '· (3)

twenty two

(In formula (3), Υ represents a divalent functional group).

Furthermore, the invention of claim 8 is the transparent optical member according to any one of claims 5 to 7, wherein Α in formula (1) is a chain hydrocarbon group having a carbon-carbon unsaturated bond. It is.

The invention's effect [0016] The cage silsesquioxane compound of the formula (1) has a polyhedral structure formed of silicon atoms and oxygen atoms, a hydrogen atom bonded to the silicon atom via a siloxane bond, and a siloxane bond. And a group having a carbon-carbon unsaturated bond bonded to each other, so that a hydrogen atom is subjected to a hydrosilylation reaction with a group having a carbon-carbon unsaturated bond of another cage-type silsesquioxane compound, and added. It is crosslinked and cured by polymerization, and is formed by forming a three-dimensional crosslinked structure in which nano-sized cage structures made of silica are connected by organic segments, and it exhibits a glass-like function. Even when used in the blue-near-ultraviolet light, it becomes a cured product that hardly deteriorates and has a low water absorption rate. In addition, the chain hydrocarbon group having a carbon-carbon unsaturated bond has a smaller steric hindrance than the cyclic hydrocarbon group, and the crosslinking reaction by the hydrosilylation reaction proceeds efficiently, and there are few unreacted residues in the cured product. The resistance to Blu-ray irradiation is improved.

[0017] Further, by reacting the compound of the formula (2) having SiH groups at both ends with the cage-type silsesquioxane compound of the formula (1) as a reactive monomer, the force, carbon of the silsesquioxane compound of the type SiH can be hydrosilylated to the carbon unsaturated bond (one C = C) to undergo addition polymerization, and the cage silsesquioxane compound of formula (1) can be crosslinked with the compound of formula (2) and cured. It has a more uniform network structure with fewer unreacted residues, and can form a three-dimensional cross-linked structure of the silsesquioxane compound, which can suppress stress cracking of the cured product and is tough In addition, it can improve the irradiation resistance against short wavelength high energy light such as Blu-ray.

[0018] Further, a compound of formula (3) having CH = CH groups at both ends is used as a reactive monomer.

2

By reacting with the force of (1), a cage silsesquioxane compound, the hydrogen atom of the cage silsesquioxane compound is subjected to addition polymerization by CH = CH force S hydrosilylation reaction,

2

The force of formula (1), the cage silsesquioxane compound can be cross-linked and cured with the compound of formula (3), and it has a more uniform network structure with fewer unreacted residues and a cage silsess Can form a three-dimensional cross-linked structure of a xanthone compound, suppresses stress cracking of the cured product, enhances toughness, and improves irradiation resistance to short wavelength high energy light such as Blu-ray It is something that can be done. Accordingly, in the present invention, a semiconductor optical device can be formed with a sealing material that does not easily deteriorate and has a long life, and a transparent optical member can be obtained with a material that does not easily deteriorate and has a long life.

[0020] Further, by introducing a hydroxyl group into the cage silsesquioxane compound, the affinity of the surface with a heavy metal sol such as TiO or ZrO whose surface is covered with the hydroxyl group can be increased. By increasing the dispersibility between the sol and the heavy metal sol and maintaining the transparency by introducing the heavy metal sol, a cured product having an increased refractive index can be obtained.

Brief Description of Drawings

FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a semiconductor optical device of the present invention.

FIG. 2 is a view schematically showing a three-dimensional crosslinked structure polymer crosslinked by a cage silsesquioxane compound of the present invention.

FIG. 3 is a graph showing the wavelength dependence of the transmittance of the cage silsesquioxane compound according to Example 1.

FIG. 4 is a schematic cross-sectional view illustrating the force according to Example 1 and a method for sealing a cage silsesquioxane compound.

FIG. 5 is a graph showing the luminous flux maintenance factor of the cage silsesquioxane compound according to Example 1.

Yes

[Fig. 6] Far-field image printed in color in the Blu-ray irradiation test. (A) is for Example 4 and (b) is for Reference Example 2.

[FIG. 7] Color-printed images of senalmon observation in the Blu-ray irradiation test. (A) is for Example 4 and (b) is for Reference Example 2.

[Fig. 8] Far-field images are color-printed in the Blu-ray irradiation test. (A) is for Example 5 and (b) is for Example 1.

[FIG. 9] Color-printed images of senalmon observation in the Blu-ray irradiation test. (A) Example 5 and (b) Example 1!

Explanation of symbols

[0022] 2 Semiconductor light emitting device

3 Sealing material

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the present invention will be described.

(Embodiment 1)

FIG. 1 shows an example of a semiconductor optical device. A semiconductor light emitting element 2 is mounted on the surface of a substrate 1, and the entire semiconductor light emitting element 2 and a part of the surface of the substrate 1 are sealed with a sealing material 3. It is. A phosphor layer 4 is formed on the surface of the sealing material 3. An electronic circuit 5 is formed on the substrate 1, and in the embodiment shown in FIG. 1, the electrical circuit 5 is electrically connected to the semiconductor light emitting element 2 by a bonding wire 6.

[0024] As the semiconductor light-emitting element 2, when a device that outputs light having a wavelength in the blue region or near-ultraviolet region of 450 nm or less, which can use the known semiconductor light-emitting device 2, is obtained. It is preferable because it can increase the illuminance of the light device and enhance the color rendering. As a specific example of the semiconductor light-emitting element 2, for example, a semiconductor substrate such as GaAlN, ZnS, ZnSe, SiC, GaP, GaAlAs, AlInGaP, InGaN, GaN, AlInGaN formed as a light emitting layer is used. Can do. The mounting of the semiconductor light emitting element 2 can be performed by placing the semiconductor light emitting element 2 on the portion of the substrate 1 where the semiconductor light emitting element 2 is mounted and performing wire bonding mounting or flip chip mounting.

The substrate 1 can be obtained by molding a resin material such as a ceramic material, a thermoplastic resin or a thermosetting resin into a desired shape by various molding methods. It is not limited. Examples of the ceramic material that can be used for the substrate 1 include alumina, aluminum nitride, zirconium oxide, and carbide carbide. These are formed by known compression molding, injection molding (CIM), etc., and sintered. Can be formed as a substrate 1 by the force S. Since the ceramic material is excellent in thermal conductivity, it can be preferably used from the viewpoint that the heat generated by the semiconductor light emitting element 2 can be diffused throughout the substrate 1 and efficiently radiated. As the resin material, thermoplastic resins such as polyphenylene sulfide (PPS), polyphthalimide (PPA), or liquid crystal polymer (LCP), and thermosetting resins such as epoxy resin and phenol resin can be used. . By adding a filler such as glass, silica, or alumina to this resin material, it is possible to improve the thermal conductivity and heat resistance of the substrate 1 with the force S.

[0026] Further, a predetermined pattern connected to the semiconductor light emitting element 2 as described above is formed on the surface of the substrate 1. The electric circuit 5 is formed! /, The force to be formed This forming method is not particularly limited, and a known method is used to reduce the force S.

In the embodiment of FIG. 1, the semiconductor optical device according to the present invention has been described using a semiconductor light emitting device in which the semiconductor light emitting element 2 is sealed with the sealing material 3. However, the semiconductor light receiving element is made of the sealing material. Even a semiconductor light-receiving device that is sealed! /, Noha! /, Undo! /.

In the present invention, the sealing material 3 includes a cage silsesquioxane compound represented by the following formula (1), or a force obtained by partial addition reaction of this compound, a cage silsesquioxane. It is formed by crosslinking a key compound containing a partial polymer of the compound.

Here, the equation (1) is expressed as (AR R SiOSiO) (R R HSiOSiO) (BR R SiOSiO)

1 2 1. 5 n 3 4 1. 5 p 5 6 1. 5 ¾

(HOSiO)… hi)

1. 5 m— n— p— q

Is represented by

In the above formula (1), A represents a group having a carbon-carbon unsaturated bond, and is not particularly limited as long as it includes a carbon-carbon double bond or a carbon-carbon triple bond as part of the group. For example, those containing an alkenyl group, an alkynyl group, and a cyclohexenyl group can be exemplified. Examples of the group containing an alkenyl group or an alkynyl group include a group having a carbon-carbon double bond such as a bur group and an aryl group, Examples thereof include a group having a carbon-carbon triple bond such as an ether group and a vinyl group. In addition, a group in which a group having a carbon-carbon double bond or a carbon-carbon triple bond and a divalent group not having an unsaturated group are bonded, and a divalent group not having an unsaturated group is bonded. Examples of the group include cyclohexenylethyldimethyloxy group.

[0029] In the above formula (1), B represents a substituted or unsubstituted saturated alkyl group or hydroxyl group. Examples of the substituted or unsubstituted saturated alkyl group include a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, which is substituted or unsubstituted. Specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; Group, alkoxy group such as ethoxy group; aralkyl group such as 2-phenylethyl group, 2 phenylpropyl group, 3-phenylpropyl group; chloromethyl group, Illustrative examples include halogen-substituted hydrocarbon groups such as γ-chloropropyl group and 3,3,3-trifluoropropyl group. Among these, a methyl group, which is preferably an alkyl group having 1 to 4 carbon atoms, is particularly preferable from the viewpoint of reducing steric hindrance during the reaction. In addition, when there are a plurality of Β groups in one molecule, that is, when q≥2, each B group may be the same or different.

[0030] In the above formula (1), R 1, R 2, R 3, R 4, R 5 and R 5 are each independently a lower alkyl group.

1 2 3 4 5 6

It represents one functional group selected from a kill group, a phenyl group, and a lower arylalkyl group, such as an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group, or a phenyl group. Group, aryl group having 7 to 10 carbon atoms such as benzyl group and phenethyl group. Among these, a phenyl group is preferable from the viewpoint of reducing the steric hindrance of the reaction, and a methyl group preferably increasing the refractive index.

[0031] Further, in the above formula (1), m represents a number selected from 6, 8, 10, and 12, and n represents l to m

1 represents an integer of 1, p represents an integer of l to m-n, and q represents an integer of 0 to m-n-p.

[0032] Examples of the cage silsesquioxane compound include those represented by the following formula (4) and formula (5).

[0033] The compound of the formula (4) has the following formula (1): m = 8, n = 4, p = 4, q = 0, R 1, R 2, R

1 2

, R force A compound of S methyl group (Me), approximately 6 faces formed by silicon atom and oxygen atom

3 4

Of the 8 silicon atoms that make up the body structure, A groups are bonded to 4 silicon atoms via siloxane bonds (O Si), and the other 4 silicon atoms are bonded to siloxane bonds (O — Si). It has a structure in which hydrogen atoms are bonded. It should be noted that the structural formula of formula (4) is as follows. (One OS iMe-A) is bonded to four silicon atoms out of eight silicon atoms constituting an approximately hexahedral structure, and is bonded to the other four silicon atoms. (One O SiMe H)

2 Combine 2 by 2 and express it in a simplified manner! (In the following structural formula,! / Is simplified as well).

[0034] Further, the compound of the formula (5) has the following formula (1): m = 8, n = 3, p = 3, q = 2, R 1, R 2

1 2

, R, R, R, R and B are methyl group compounds formed by silicon and oxygen atoms

3 4 5 6

Of the eight silicon atoms that make up the roughly hexahedral structure, three silicon atoms The A group is bonded through the Sun bond (O Si), the hydrogen atom is bonded through the siloxane bond (one O Si) to the other three silicon atoms, and the siloxane bond (O It has a structure in which the methyl group of B is bonded via Si). The structural formula of formula (5) is that, among the eight silicon atoms constituting the substantially hexahedral structure, (O SiMe-A) is bonded to three silicon atoms one by one, and the other three silicon atoms (-〇

2

SiMe H) are bonded to each other, and (O SiMe) is connected to the remaining two silicon atoms.

2 Connect the three and express it in a simplified way!

[Chemical 1]

Next, an example of a method for synthesizing the above cage silsesquioxane will be described. First, an octacanion with an approximately hexahedral structure (such as Si O ⁸ and chlorohydridodimethylsilane).

8 12

By reacting with a reactive halogen, the hydridodimethylsiloxy group is bonded to the eight silicon atoms of octanion to form octakis [hydridodimethylsilane] silsesquioxane ί. OHSS). Then, by using this OHSS, a compound having two or more carbon-carbon unsaturated groups in the molecule, such as 4-butyl1-1-cyclohexene, is reacted in an amount less than the equivalent, so that some hydridodimethylsiloxy groups are inactivated. Addition reaction of a compound having two or more saturated groups in the molecule forms an approximately hexahedral structure formed by silicon atoms and oxygen atoms. A group having a carbon-carbon unsaturated bond is bonded to some of the eight silicon atoms. Then, a caged silsesquioxane compound represented by the formula (4) in which a hydridodimethylsiloxy group is bonded to another silicon atom can be prepared. The octacanion can be obtained by hydrolytic polycondensation of tetraethoxysilane in the presence of tetramethylammonium hydroxide.

[0037] Further, by reacting a mixture of a reactive halogen having a carbon-carbon unsaturated group such as dimethylvinylchlorosilane, dimethylallylchlorosilane, chlorocycloalkenyldimethylsilane and chlorohydridodimethylsilane with octacanion, A group having a carbon-carbon unsaturated bond is bonded to a part of eight silicon atoms constituting a substantially hexahedral structure formed of silicon atoms and oxygen atoms, and a hydridodimethylsiloxy group is bonded to other silicon atoms. A cage-type silsesquioxane compound such as formula (4) can be prepared.

[0038] Further, when this mixture is reacted with octacanion, an approximately hexahedral structure is formed by mixing and reacting an unsaturated group such as chlorotrimethylsilane and a reactive halogen having no active hydrogen. A cage-type silsesquioxane compound represented by the formula (5) in which a non-reactive group is bonded to a part of one silicon atom can be prepared.

[0039] The force obtained in the manner described above, the gale silsesquioxane compound, in a substantially hexahedral structure formed of silicon atoms and oxygen atoms, has hydrogen atoms bonded to the silicon atoms via siloxane bonds. And a group having a carbon-carbon unsaturated bond group, so that this hydrogen atom is subjected to a hydrosilylation reaction with an unsaturated group contained in the carbon-carbon unsaturated bond group of another cage-type silsesquioxane compound. Then, it is cross-linked and cured by addition polymerization to form a three-dimensional cross-linked structure. Figure 2 schematically shows a three-dimensional cross-linked structure in which an approximately hexahedral structure (symbol 7) formed by silicon atoms and oxygen atoms is cross-linked. [Chemical Formula 2] shows the cross-linking reaction of a three-dimensional cross-linked structure of a cage silsesquioxane compound in which A in formula (4) is a cyclohexenyl group. This three-dimensional cross-linking structure is a nano-sac made of silica (glass). It has a structure in which the cage structure is connected by an organic segment, and can exhibit a glass-like function.

[0040] [Chemical 2]

[0041] Here, the reacting carbon-carbon unsaturated bond group and the hydrogen atom are both bonded to the polyhedral structure part of silsesquioxane (Si 2 O 3) via a siloxane bond (1 O—Si—).

8 12

Therefore, when polymerizing with other cage-type silsesquioxane compounds, steric hindrance is less likely to occur, and it is possible to obtain a cured product with a high reaction rate, and there are few unreacted residues. Thus, it is possible to prevent a decrease in reliability due to unreacted residues. Furthermore, since it has a nano-sized cage structure made of silica (glass), the crosslink density is higher than metalloxane obtained by the sol-gel method, and the water absorption is low. The ability to obtain S.

[0042] Further, the crosslinked structure of the cured product obtained as described above has a structure in which silicon atoms constituting the polyhedral structure of silsesquioxane are bonded to four oxygen atoms to form a glass which is an inorganic material. The structure is close, and the organic group is not directly bonded to the silicon atom, so it is difficult to deteriorate even if it is used under irradiation with light in the blue and near ultraviolet regions.

[0043] Then, as the sealing material 3 for sealing the semiconductor light emitting element 2 or the like, a light transmitting epoxy resin, polyester, polyacrylate, organopolysiloxane or the like that has been used conventionally is used. When the cured product of the cage-type silsesquioxane compound of the present invention is used, an unnecessary absorption peak is likely to appear in the required spectral region due to the presence of crosslinks and absorbing groups contained in Thus, the sealing material 3 having good blue light and ultraviolet light permeability with few absorption peaks is obtained.

[0044] In the molecule of the cage silsesquioxane compound represented by the above formula (1) of the present invention,

Replacement paper (Rule 26) In the polyhedral structure formed of silicon atoms and oxygen atoms, the number of hydrogen atoms bonded to the silicon atom via a siloxane bond and the number of groups having carbon-carbon unsaturated bonds (i.e., n and p) Are preferably the same, but may be slightly different! /, As long as the desired optical and physical properties of the cured product are maintained!

[0045] In sealing the semiconductor light emitting device 2 using the cage silsesquioxane compound of the present invention, it is particularly limited as long as the polymerization / crosslinking reaction of the cage silsesquioxane compound proceeds. Any method can be adopted without any reaction, and the reaction may be carried out using an addition reaction catalyst such as platinum or noradium as necessary. Here, since the cage silsesquioxane compound according to the present invention is a liquid at room temperature or a solid that melts at a relatively low temperature until it is crosslinked, the semiconductor light-emitting element 2 and the like can be easily sealed. Is possible.

[0046] Further, the partial polymer of the cage silsesquioxane compound obtained by partial addition reaction of the cage silsesquioxane compound represented by the above formula (1) of the present invention is represented by the formula (1). Is an oligomer in which about 10 silsesquioxane compounds are polymerized, and has fluidity capable of sealing the semiconductor light-emitting element 2 and the like. Therefore, even when this partially polymerized product is used, it is crosslinked by polymerizing with another cage-type silsesquioxane compound or a partially polymerized product thereof, and, for example, a three-dimensional crosslinked structure as shown in FIG. 2 is formed. . In this case as well, the sealing material 3 can be formed of a cured product that is hardly deteriorated and has a low water absorption even when used in a state of being irradiated with light in the blue region and near-ultraviolet region.

[0047] The encapsulant 3 for encapsulating the semiconductor light emitting device 2 and the like has a cage-type silsesquioxane compound represented by the above formula (1) or a force obtained by partial addition reaction of this compound, In addition to the partially polymerized type silsesquioxane compound, a key compound having addition reactivity may be contained as long as desirable optical and physical properties of the cured product are maintained.

[0048] In the above description, the cage silsesquioxane compound of the above formula (1) has been described in the case of m = 8, but when m is 6, 10, 12, the reaction is performed in the same manner, A partially polymerized product of force, cage silsesquioxane compound or cage silsesquioxane compound can be obtained. Even when these compounds are used, other cage-type silsesquioxane compounds Is formed as a three-dimensional cross-linked structure. In this case as well, even when used in the state of being irradiated with light in the blue region and near-ultraviolet region, it is difficult to deteriorate and has a low water absorption, resulting in a cured product.

[0049] Incidentally, when the substituted or unsubstituted alkyl group of the basket-type silsesquioxane compound represented by formula (1) B is an alkoxy group and q 2, In addition to the bond between a group having a carbon unsaturated bond and a hydrogen atom, it is also possible to crosslink by a hydrolysis / polycondensation bond between these alkoxy groups. Increased properties are preferable. At this time, if the bond between a group having a carbon-carbon unsaturated bond and a hydrogen atom becomes a main cross-linked structure, it is preferable that the thickness of the cured product becomes relatively easy. It is preferable that the decomposition / polycondensation bond is a main cross-linked structure because of relatively high transparency. [Chemical Formula 3] shows an example of a crosslinking reaction of a three-dimensional crosslinked structure when A in the formula (1) is a cyclohexenyl group and B is an ethoxy group.

[0050] [Chemical 3]

[0051] In the above-described embodiment, the cage silsesquioxane compound of the formula (1) or a portion of a cage silsesquioxane compound obtained by partial addition reaction of this compound. The semiconductor optical device in which the semiconductor light emitting element or the semiconductor light receiving element is sealed with the polymer has been described. However, the cage silsesquioxane compound represented by the formula (1) or a partial addition reaction of this compound. A transparent optical member such as a lens or a prism can be produced by using a partially polymerized product of a cage-type silsesquioxane compound as a molding material and molding and polymerizing and curing it. . In addition, it can be used for a transparent optical member such as a protective layer of a Blu-ray disc by coating and polymerizing on the surface of the optical disc.

[0052] Here, the cured product of the force-type silsesquioxane compound is transparently sealed for LED white illumination replacement paper (Rule 26) When applied to optical applications such as materials, it is necessary to improve the refractive index, and in order to form a cured product of a rugged silsesquioxane compound to have a high refractive index, It is preferable to mix a heavy metal sol such as TiO or ZrO and introduce the heavy metal sol into the cured product of the cage silsesquioxane compound. At this time, the cage-type silsesquioxane compound is generally incompatible with heavy metal sols such as TiO and ZrO, and it is difficult to uniformly disperse the heavy metal sol, and as a result, the transparency of the cured product tends to be impaired. For example, as shown in [Chemical Formula 4], in Formula (1), A is an aryl group, R, R,

2

Cage-type silsesquioxane compound in which R and R are methyl groups, m = 8, n = 4, p = 4, q = 0

3 4

This is because there is no functional group having affinity for 1 OH covering the surface of the heavy metal sol in the system in which the product is crosslinked.

[0053] [Chemical 4]

[0054] Therefore, in this case, by using a silsesquioxane compound in which in-n-p-q is 1 or more and a —OH group is introduced in the formula (1), the following [ As shown in Figure 5, the affinity between the OH group of the silsesquioxane compound and the OH group covering the heavy metal sol can increase the dispersibility of the heavy metal sol, and the force-type silsesquioxane compound and the heavy metal sol Can be uniformly dispersed to obtain a cured product of a cage-type silsesquioxane compound having a high refractive index while maintaining transparency.

[0055] [Chemical 5]

Replacement paper (Rule 26)

[0056] The basket-type silsesquioxane compound represented by [Chemical Formula 5] has the formula (1) in which A is an aryl group, R, R, R, R force S methyl group, m = 8, n = 3, p = 3 when q = 0

1 2 3 4

Yes, among the eight silicon atoms that make up the approximately hexahedral structure formed by silicon atoms and oxygen atoms, aryl groups are bonded to three silicon atoms via siloxane bonds (—O—Si—). It has a structure in which a hydrogen atom is bonded to three silicon atoms via a siloxane bond (one O—Si—) and a hydroxyl group is bonded to two silicon atoms.

Such a cage silsesquioxane having a hydroxyl group bonded to a part of eight silicon atoms constituting an approximately hexahedral structure can be obtained as follows.

[0058] The cage silsesquioxane compound such as the above [Chemical 4] is prepared by reacting with the following [Chemical 12] and [Chemical 13] reaction, and eight reaction sites of S and Octanion. In order to substitute allyl dimethyl chlorosilane and dimethyl chlorosilane for all of the above, the amount of allyl dimethyl chlorosilane or dimethyl chlorosilane should be a large excess (for example, 30 times equivalent or more) with respect to octacanion. Must be set. Therefore, when the excess degree of allyldimethylchlorosilane or dimethylchlorosilane relative to octanion is low, some of the eight reaction sites of octanion will not be substituted, and the unsubstituted site will be hydrolyzed to an OH group. Thus, it is possible to prepare allyldimethylsiloxysilsesquioxane in which OH groups are introduced into a part of silicon atoms constituting an approximately hexahedral structure such as [Chemical Formula 5]. In addition, by adjusting this excess, replacement paper for the cage silsesquioxane (Rule 26) The number of introduced OH groups can be controlled.

[0059] Further, in the above-described embodiment, the force-type silsesquioxane compounds are directly crosslinked by hydrosilylation reaction between a carbon-carbon unsaturated bond and a hydrogen atom. For example, as shown in the above [Chemical Formula 4], a cage silsesquioxane compound is cured by directly crosslinking between a SiH group and one CH = CH group. Strength

2

In this case, since the cross-linking reaction proceeds rapidly, the structure freezes when the cross-linking reaction between SiH and CH = CH between the force-type silsesquioxane compound proceeds rapidly to some extent,

2

As a result, a non-uniform cross-linked structure in which a portion where the cross-linking reaction proceeds and a portion where unreacted groups remain coexists may be obtained. Therefore, the structure becomes uneven and the reaction progresses unevenly and rapidly, so that residual strain is accumulated in the cured molecular structure. When the cured product is immersed in a solvent such as acetone, stress is applied. There is a risk that only a brittle cured product may be obtained, such as cracking. In addition, since unreacted groups remain in the cured product, there may be insufficient irradiation resistance to short-wave high-energy light in the blue and near ultraviolet regions such as Blu-ray.

[0060] In this case, therefore, the cage silsesquioxane compound represented by the formula (1) is blended with the following formula (2) or formula (3) as a reactive monomer, and the cage silsesquioxane compound is obtained. The compound is cured by crosslinking with the compound of formula (2) or formula (3).

First, a system using the compound of formula (2) will be described.

[0062] HR R Si-X- SiHR R (2)

5 6 7 8

In the formula (2), X represents a divalent functional group or an oxygen atom. In the formula (2), R 1, R 2, R 3 and R 5 are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom.

5 6 7 8

To express. The compound represented by the formula (2) is not particularly limited, but examples thereof include those represented by the following [Chemical Formula 6].

[0063] [Chemical 6] H

[0064] The amount of the compound of the formula (2) with respect to the force of the formula (1) and the type silsesquioxane compound is not particularly limited. The amount equivalent to the amount of the unreacted A unsaturated group remaining when the hydrosilylation reaction with a hydrogen atom is performed is preferably set slightly higher than the equivalent amount.

[0065] Then, the cage-type silsesquioxane compound is blended with the compound of the formula (2) as a reactive monomer and reacted, thereby producing a force-type silsesquioxane as shown in [Chemical Formula 7]. One SiH force S hydrosilylation reaction of both ends of the compound of formula (2) to one CH-CH group of the xanthane compound

2

Then, the cage-type silsesquioxane compound can be cross-linked with the compound of formula (2) and hardened, and the nano-sized cage structure with silica power is connected by organic segments. Such a three-dimensional crosslinked structure can be formed. Shirusesuki Okisan compounds shown in Formula 7] In the above formula (1), m = 8 n = x s p = 8- xq = 0 A is § Li Le groups, RR, R, with R force S methyl A compound in some cases, silicon atoms and oxygen atoms

1 2 3 4

Out of the six silicon atoms that make up the approximately hexahedral structure formed by the children, the aryl group is bonded to the X silicon atoms through a siloxane bond (one O—Si—) and the other 8—X atoms. It has a structure in which a hydrogen atom is bonded to a silicon atom via a siloxane bond (one O—Si—).

[0066] [Chemical 7] Replacement paper (Rule 26)

[0067] Thus, by reacting a cage silsesquioxane compound with a compound of formula (2) having one SiH at both ends as a reactive monomer, in the sea of the reactive monomer of formula) A force-type silsesquioxane compound of the formula (1) having one CH═CH group is

2

Since the reaction with the compound of formula (2) gradually reacts and crosslinks, the progress of the reaction can be controlled more mildly, and the remaining unreacted CH = Even when the = CH group is generated, the compound of the formula (2) moves to the residue and undergoes a crosslinking reaction. In this way, the progress of the reaction can be controlled mildly to delay structure freezing, and there are fewer unreacted residues and a more uniform network structure with a cage-type silsesquioxane. It is possible to form a three-dimensional cross-linked structure of the product, to suppress the stress cracking of the cured product and to improve the toughness, and to improve the irradiation resistance against short wavelength high energy light such as Blu-ray. Can do.

Next, a system using the compound of formula (3) will be described.

[0069]. H C = CH-Y-CH = CH-(3)

twenty two

In the formula (3), Y represents a divalent functional group, and the compound represented by the formula (3) is not particularly limited, but is represented by the following [Chemical Formula 8]. It can be illustrated.

[0070] [Chemical 8]

Replacement paper (Rule 26) Diaryldiphenylsilane

H ₂ C =: GH -Si- 0 "Si- CH = CH Divinyl 亍 tratyl disiloxane

CH3 CH3

S-CH ₂ -CH = CH ₂

S-CHi>-CH Diaryl disulfide

CH3 CH3

H ₂ G = CH-GH ₂ -Si- O-Si- CH ₂ -CH = GH ₂ diallyl-tramethyldisiloxane

H ₂ C = CH -Si "0- Si- CH = CH ₉ Divinyldiphenyldimethyldisiloxane

CH <¾ CH3 Divinylhexamethyltrisiloxane

[0071] The amount of the compound of formula (3) to the cage silsesquioxane compound of formula (1) is not particularly limited, but the cage silsesquioxane compound of formula (1) It is preferable to set the amount to be equivalent to the amount of unreacted hydrogen atoms remaining when the carbon-carbon unsaturated bond and the hydrogen atom are subjected to a hydrosilylation reaction, or a little less than the equivalent.

[0072] Then, the cage-type silesquioxane compound is compounded with the compound of the formula (3) as a reactive monomer and subjected to an X reaction, as shown in [Chemical Formula 9]. One CH = CH group hydrosilylation reaction at both ends of the compound of formula (3) on one SiH group of the compound

2

In addition, the cage-type silsesquioxane compound can be cross-linked with the compound of formula (3) and cured, and the nano-sized cage structure composed of silica is connected by organic segments. A three-dimensional crosslinked structure can be formed.

[0073] [Chemical 9]

Replacement paper (Rule 26)

[0074] Thus, the cage silsesquioxane compound has one CH = CH at both ends.

2

By reacting the compound of formula (3) as a reactive monomer, a force-type silsesquioxane compound having one SiH group in the reactive monomer sea gradually reacts with the compound of formula (3). As a result of crosslinking, the progress of the reaction can be controlled more mildly, and even if one unreacted SiH group occurs during the course of the crosslinking reaction, the formula (3) The compound moves to the residue and undergoes a crosslinking reaction. As described above, the freezing of the reaction can be controlled mildly to delay the structure freezing, and more uniform network structure with fewer unreacted residues and the cage-type cinresesquioxane compound It is possible to form a tertiary five-crosslinked structure, to suppress stress cracking of the cured body and to improve toughness, and to improve irradiation resistance against short wavelength high-energy energy such as Blu-ray. it can.

[0075] (Embodiment 2)

Next, the cage silsesquioxane compound according to Embodiment 2 of the present invention will be described in detail. The force-type silsesquioxane compound according to Embodiment 2 is a group in which A in the cage-type silsesquioxane compound represented by Formula (1) in Embodiment 1 has a carbon-carbon unsaturated bond. In the second embodiment, however, A is a chain hydrocarbon group having a carbon-carbon unsaturated bond. Different from sesquioxane compounds.

[0076] 'Encapsulant 3 is a cage-type silsesquioxane compound represented by the following formula (1), or a portion of a cage-type silsesquioxane compound obtained by partial addition reaction of this compound. It is formed by cross-linking a key compound containing a polymer.

Here, the formula (1) is similar to the above (AR R SiOSiO) (R R HSiOSiO) (BR R S

1 2 1. 5 n 3 4 1.5 p 5 6 Replacement paper (Rule 26) iOSiO) (HOSiO)… hi)

1. 5 q 1. 5 m— n— p— q

In the formula (1), A is a chain hydrocarbon group having a carbon-carbon unsaturated bond. Here, A is not particularly limited as long as it contains a carbon-carbon double bond or a carbon-carbon triple bond as part of the group. Examples include groups containing alkenyl groups and alkynyl groups. Examples of groups containing alkenyl groups or alkynyl groups include groups having a carbon-carbon double bond such as a buyl group and an allyl group, an ether group, and a vinyl group. Examples thereof include groups having a carbon-carbon triple bond such as a group. Further, a group in which a group having a carbon-carbon double bond or a carbon-carbon triple bond and a divalent group not having an unsaturated group are bonded can also be exemplified. The position of the carbon-carbon unsaturated bond of the chain hydrocarbon group having these carbon-carbon unsaturated bonds is preferably at the terminal from the viewpoint of reducing steric hindrance during hydrolysis.

[0077] Next, an example of a method for synthesizing a cage silsesquioxane according to the second embodiment will be described. First, as in the first embodiment, octacanyon (Si 2 O ⁸ ) having a substantially hexahedral structure and

8 12

, Reacting with a reactive halogen such as chlorohydridodimethylsilane, and bonding hydridodimethyloxy group to eight silicon atoms of octayuon to prepare octakis [hydridodimethyloxy] silsesquioxane (OHSS) To do. Then, by using this OHSS, a chain hydrocarbon having a carbon-carbon unsaturated group such as 1 hexenyl in the molecule is reacted in an amount of less than an equivalent amount, so that some hydridodimethylsiloxy groups are unsaturated chain hydrocarbons. A chain-like group having a carbon-carbon unsaturated bond is bonded to some of the eight silicon atoms that form an approximately hexahedral structure formed by silicon atoms and oxygen atoms, and the other silicon atoms are bonded to other silicon atoms. A cage-type silsesquioxane compound represented by the formula (4) to which a hydridodimethylsiloxy group is bonded can be prepared. The above octanion can be obtained by hydrolysis polycondensation reaction of tetraethoxysilane in the presence of tetramethylammonium salt.

[0078] Further, by reacting a mixture of a reactive halogen having a carbon-carbon unsaturated group such as dimethylvinylchlorosilane, dimethylallylchlorosilane, dimethylhexenole chlorosilane and chlorohydridodimethylsilane with octanion, a silicon atom and Carbon is carbon-saturated to some of the eight silicon atoms that make up the nearly hexahedral structure formed by oxygen atoms. A cage-type silsesquioxane compound represented by the formula (4) in which a chain group having a sum bond is bonded and a hydridodimethylsiloxy group is bonded to another silicon atom can be prepared.

[0079] Further, when this mixture is reacted with octacanion, an approximately hexahedral structure is formed by reacting with an unsaturated group such as chlorotrimethylsilane or a reactive halogen having no active hydrogen. A cage-type silsesquioxane compound represented by the formula (5) in which a non-reactive group is bonded to a part of one silicon atom can be prepared.

[0080] The force obtained as described above, the gale silsesquioxane compound, includes a hydrogen atom bonded to a silicon atom having a substantially hexahedral structure formed of a silicon atom and an oxygen atom through a siloxane bond; And a chain hydrocarbon group having a carbon-carbon unsaturated bond, so that this hydrogen atom is included in the chain hydrocarbon having a carbon-carbon unsaturated bond of another cage silsesquioxane compound. Hydrosilylation reaction with an unsaturated group, followed by addition polymerization to crosslink and cure to form a three-dimensional crosslinked structure.

FIG. 2 schematically shows a three-dimensional cross-linked structure in which a substantially hexahedral structure (symbol 7) formed of silicon atoms and oxygen atoms is cross-linked. Further, in [Chemical Formula 15], a cage-type silsesquialkyl wherein A in the formula (1) is a hexenyl group, m = 8, n = 4, p = 4, q = 0, R, R, R, R force S methyl group.

1 2 3 4

The cross-linking of the oxane compound is shown. The power of [Chemical Formula 15] is that the silsesquioxane of the hexagonal structure has four hydrogen atoms bonded to eight silicon atoms of approximately hexahedral structure via siloxane bonds, and via siloxane bonds. Four hexenyl groups are bonded, and a hydrogen atom and an unsaturated group of hexenyl are crosslinked by hydrosilylation reaction. This three-dimensional cross-linking structure has a structure in which nano-sized cage structures made of silica (glass) are connected by organic segments, and can exhibit a glass-like function. The crosslinked structure of the cured product obtained as described above has a structure close to that of glass, which is an inorganic material, in which the silicon atoms constituting the polyhedral structure of silsesquioxane are bonded to four oxygen atoms. However, since the organic group is not directly bonded to the silicon atom, it is difficult to deteriorate even if it is used in the state of being irradiated with light in the blue region and near ultraviolet region. Furthermore, since it has a nano-sized cage structure that also has silica (glass) force, the cured product has a higher crosslink density and lower water absorption than metalloxane obtained by the sol-gel method. Obtain power S. [0082] [Chemical 15]

[0083] Here, when the cage-type cinolesesquioxane compound is crosslinked by a hydrosilylation reaction between a hydrogen atom and an unsaturated group as described above, the carbon-to-carbon unsaturation of A as shown in [Chemical Formula 16] When a caged silsesquioxane compound in which a cyclic hydrocarbon group such as cyclic vinyl is introduced as a group having a bond is used, the cyclic hydrocarbon has a large steric hindrance, and the carbon-carbon unsaturated bond of cyclohexenyl and hydrogen The cross-linking reaction between atoms (—C = CZ—SiH) does not proceed easily, and unreacted groups are likely to remain as residues in the cured product obtained by cross-linking the cage silsesquioxane compound. If it remains in the unreacted basic cured product in this way, there is a risk of causing problems in durability such as Blu-ray irradiation resistance of the cured product.

[0084] [Chemical 16] ■

However, as in Embodiment 2, a cage-type silsesquioxane compound into which a chain hydrocarbon group such as chain vinyl is introduced as the group having a carbon-carbon unsaturated bond of A is used. Thus, steric hindrance is less likely to occur, the crosslinking reaction between the hydrogen atom and the carbon-carbon unsaturated bond is significantly accelerated, and the amount of unreacted residues is also reduced. As a result, it is possible to prevent a decrease in reliability due to unreacted residues, and a cured product can be obtained with high durability such as Blu-ray irradiation resistance. Replacement paper (Rule 26) Example

Next, the present invention will be specifically described with reference to examples.

[0087] (Example 1)

Tetramethylammonium hydroxide (334 mL), methanol (164 mL), and water (123 mL) were added to an lOOOOmL flask equipped with a reflux tube and a dropping funnel and stirred. The dropping funnel was charged with 179 mL of tetraethoxysilane (TEOS), and the whole flask was cooled to about 5 ° C in an ice bath, and when the temperature reached about 5 ° C, TEOS was added dropwise. The dripping of 179 mL of TEOS was completed in about 1 hour from the start of dripping. After completion of the dropwise addition, stirring in an ice bath was continued for 10 minutes, then the ice bath was removed, and then the reaction was allowed to proceed by stirring at room temperature for 10 hours. After 10 hours of room temperature stirring, the reaction product was filtered to obtain an octanion / methanol solution as a filtrate.

[0088] Next, 895 mL of hexane and 69 · 7 mL of dimethylchlorosilane were added to an lOOOOmL flask equipped with a reflux tube and a dropping funnel and stirred. Then, the octane / methanol solution was loaded into the dropping funnel, the solution in the flask was cooled to about 5 ° C, and when the temperature reached about 5 ° C in a nitrogen atmosphere, the octaneon / methanol solution was dropped. . The dripping of 334 mL of octacanion / methanol solution was completed in about 2 hours from the start of dripping. After completion of the dropwise addition, the mixture was stirred for 10 minutes in an ice bath, while the stirring was continued, the ice bath was removed, and the mixture was further stirred at room temperature for 6 hours to proceed the reaction. After stirring for 6 hours, the solution in the flask was transferred to a 2 L separatory funnel, and the lower methanol layer was taken out. The upper hexane layer was transferred to a 2 L Erlenmeyer flask, sodium sulfate was added, and the mixture was allowed to stand for about 10 minutes to dry the water in the solution. Also, after extracting the reaction product by adding hexane mL to the lower methanol layer, the upper hexane layer formed by standing was transferred to the 2 L Erlenmeyer flask to which the above hexane layer was transferred, The water in the solution was dried. Next, the dried hexane layer was transferred to a 1 L eggplant type flask, and the hexane was volatilized from the solution using a rotary evaporator and removed from the system. The damp white solid remaining in the 1 L eggplant type flask where hexane was volatilized was further dried under reduced pressure (133 Pa (lmmHg), room temperature) using a vacuum pump. Acetonitrile was added to a 1 L eggplant-shaped flask containing a white solid, the white solid was stirred, and then the solid was filtered off with a suction filter bottle. Next, this filtered white solid was transferred to a lOOmL beaker, further washed with acetonitrile lOOmL, and suction filtered to take out the white solid. This washing operation was repeated twice, followed by drying under reduced pressure using a vacuum pump to obtain white solid octakis [hydridodimethylsiloxy] silsesquioxane (OHSS). The yield at this time was 56%.

Next, 20 g (20 mmol) of the above OHSS was charged into a 250 mL Schlenk flask having a reflux condenser. The flask was heated gradually under vacuum to remove residual air and moisture, then flushed with nitrogen, then toluene (50 mL), 4-bule-1-cyclohexene (8.7 g, 80 mmol), and As a horn beetle medium, 0.2 mM (Pt: 0.4 ppm) of 2 mM Pt (dcp) -tonolenic solution was added. The mixture was reacted with stirring at 90 ° C. for 5 hours, and then the solvent was removed to obtain 27.5 g (0.019 mol) of a white powder product. The yield at this time was 94%.

[0090] As a result of analyzing the obtained reaction product by 1H-NMR spectrum and 13C-NMR spectrum, the structural formula was formula (1), A was a cyclohexenyl group, R 1, R 2, R 3, R force S methyl group,

1 2 3 4

It was confirmed that m is 8, n force, p force, q is 0, and the structural formula is tetrakis (cyclo) represented by the following [Chemical Formula 10].

[0091] [Chemical 10]

Next, the basket-type silsesquioxane compound thus obtained was purified by adding a acetonitrile solvent, and then the white precipitate was filtered. This procedure was repeated three times for purification, and the resulting white powder was dried in vacuo. The purified force, yield of the gale silsesquioxane compound was 3.5 g (2.4 mmol, 24.5%).

[0093] The cage-type silsesquioxane compound thus obtained was poured into a mold made of Teflon (registered trademark), heated and melted at 90 ° C, degassed under reduced pressure, and further maintained under vacuum. The temperature was raised to 00 ° C. and heated for 5 hours to cure to obtain a resin plate. The resin plate had a size of 5 cm x 3 cm and a thickness of about 1 mm.

[0094] The wavelength dependence of the light transmittance of the resin plate was measured using an ultraviolet, visible, and near-infrared spectrophotometer ("UV-3100PC" manufactured by Shimadzu Corporation) at a slit width of 20 nm. For comparison, it does not contain an aromatic component! A resin plate molded and cured using a silicone resin (“KE-006” manufactured by Shin-Etsu Chemical Co., Ltd.) and a light-transmitting alicyclic epoxy resin The same measurement was conducted on a resin plate that was molded and cured. The results are shown in Figure 3. As can be seen in FIG. 3, it was confirmed that the resin plate of this example has high transparency up to a low wavelength.

Next, as shown in FIG. 4, a semiconductor light-emitting element 2 having an emission wavelength peak of 380 ηm is mounted on the bottom of the cavity la of the substrate 1, and the cage silsesquioxane obtained as described above is mounted. The compound was filled into the cavity la and heated at 200 ° C. for 5 hours to cure, thereby sealing the semiconductor light emitting element 2 and fabricating a semiconductor optical device. Then, with this semiconductor optical device at room temperature, the semiconductor light emitting element 2 was turned on, and the maintenance rate of the luminous flux with respect to the illuminance at the start of lighting was measured. At this time, for comparison, a semiconductor optical device sealed with a silicone resin containing no aromatic component (“KE-006” manufactured by Shin-Etsu Chemical Co., Ltd.) and a light-transmitting alicyclic epoxy resin are used for sealing. The same measurement was performed for the stopped semiconductor optical device. The results are shown in Fig. 5. As can be seen in FIG. 5, the semiconductor optical device encapsulated with the cage-type silsesquioxane compound obtained in this example maintains a light flux of nearly 90% even after 1000 hours. It was confirmed that it was high! / And resistant! /.

[0096] Based on this result, the lifetime defined by the time when the luminous flux maintenance factor falls to 50% of the initial value was predicted by the following Lehmann equation, and it was confirmed that the lifetime was 60,000 hours or more. It was.

[0097] Φ (ΐ) = Φ (O) exp (— (t / τ) p)

Φ (t): luminous flux after t time, Φ (0): initial luminous flux, τ: time constant of degradation, ρ: constant

[Example 2]

The OHSS obtained in Example 1 was charged to lg (lmmol) in a lOOmL Schlenk flask having a reflux condenser. The flask was heated under vacuum to remove residual air and moisture, then flushed with nitrogen, and then 5 mL of toluene, 0.32 g of 4-Buyl 1-cyclohexene (2. 9 mmol), 0.25 g (l. 9 mmol) of dimethyl butylethoxysilane, and 2 mM Pt (dcp) -toluene solution as a catalyst were added to a 0 · l mL (Pt: 0.02 ppm) flask. The mixture was reacted with stirring at 90 ° C. for 4 hours, and the solvent was evaporated in vacuum at room temperature to obtain 1.49 g (0.95 mmol) of a white powder. The yield at this time was 95%.

[0099] As a result of analyzing the obtained reaction product by 1H-NMR spectrum and 13C-NMR spectrum, the structural formula was Formula (1), A was a cyclohexenyl group, R 1, R 2, R 3, R 4, R and R are

1 2 3 4 5 6 Tyl group, m is 8, n is 3, p is 3, q is 2, and tris is represented by the following chemical formula: It was confirmed and confirmed that she was a Chile Sesuki-san.

[0100] [Chemical 11] si ₈ . ₁₂

[0101] Tris [cyclohexenylethyldimethylsilane] tris [dimethi] obtained as described above

It was dissolved in THF solvent and hydrolyzed by heating at 90 ° C for 6 hours in the presence of water and HC1 catalyst. The resulting hydrolyzate-concentrated composition is poured into a 10 mL Teflon (registered trademark) mold, heated to 90 ° C to melt, and then degassed under reduced pressure to maintain the vacuum. The resin plate was obtained by raising the temperature to 200 ° C. and heating for 5 hours to cure. The resin plate had a size of 5 cm x 3 cm and a thickness of about 1 mm.

[0102] The resulting tris [cyclohexenoreethinoresi methinoresoxy] tris [dimethino lescioxy] di [dimethenoreethoxysilino retinoresin methinoresoxy] cinolessesquixane was produced by Teflon (registered trademark) It was put into a mold, heated to 90 ° C to melt, and then deaerated under reduced pressure. Thereafter, the mixture was heated at 90 ° C. for 30 minutes, and the resulting solid was dissolved in THF solvent and hydrolyzed at 90 ° C. for 6 hours in the presence of water and HC1 catalyst. The composition obtained by concentrating the obtained hydrolyzate was poured into a 10 mL Teflon (registered trademark) mold and cured by heating at 200 ° C. for 5 hours to obtain a resin plate. The resin plate had a size of 5 cm x 3 cm and a thickness of about 1 mm. [0103] As a result, the tris [cyclohexenylethyldimethylsilane] tris [dimethylsilaneoxy] di [dimethyl ethersilylethyldimethylsiloxy] cinolesesquioxane obtained as described above was used for curing. It was confirmed that the addition reaction could be cured after hydrolysis polycondensation, and it was confirmed that the addition could be cured by hydrolysis polycondensation after the addition reaction.

[Example 3]

An apparatus equipped with a dropping funnel, thermometer, and reagent injection valve was assembled in a three-necked flask, and 376inL of hexane, 33.8 mL of ali / redimethylchlorosilane, and 4.3 mL of dimethyl chronoresyllan were added to the three-layer flask. Next, the whole system in the three-necked flask is cooled in an ice bath to 5 ° C or less, and after confirming that the temperature in the system is 5 ° C or less, dripping funnel canyon under a deaeration flow 140 mL was added dropwise at a rate of 1-2 drops Z seconds. At this time, in order to replace allyl dimethyl chlorosilane and dimethyl chlorosilane at all eight reaction sites of octanion, the amount of allyl dimethyl chlorosilane and dimethyl chlorosilane is very large with respect to octan anion. There is a necessary power S to be set. .

[0105] After completion of the dropwise addition, the ice bath was removed, the mixture was stirred at room temperature for 6 hours, and the Octano reaction solution was extracted three times with hexane as shown in [Chemical Formula 12], and the hexane layer was extracted with a desiccant (sodium sulfate). After drying, suction filtration was performed. The obtained filtrate is passed through an evaporator to distill off hexane, and the reaction product obtained by further removing hexane. Unreacted raw materials are removed by heating at 45 ° C with a vacuum pump and purified. Hexalylsilsesquian xanthone with two SiH groups was obtained.

[0106]! [匕 12]

(Aryldimethylchlorosilane)

₆

(Octanion) (Dimethylchloro) (Hexalylsilsesquioxane)

[0107] Hexalylsilsesquioxane 1 · Og synthesized as shown in [Chemical Formula 12] was mixed with 0.24 _g of tetramethyldisiloxane as the compound of formula (2), and 3.0 Add 10% to ³ % by weight Pt (cts) toluene solution to the entire system and mix evenly, then in the air, 12 replacement paper (Rule 26) It was cured by heating at 0 ° C. for 3 hours to obtain a colorless and transparent resin plate.

[0108] (Reference Example 1)

In Example 3, in the method of synthesizing hexarylsilsesquioxane having two SiH groups in [Chemical Formula 12], 19.8 mL of allyldimethylchlorosilane was added to 376 mL of hexane. As shown in the above [Chemical 4], except that 14.6 mL of dimethylchlorosilane was added and octanion was allowed to react, it was shown in the above [Chemical 4]. Axane was synthesized.

[0109] Then, tetraylsilsesquioxane in [Chemical Formula 4] is added with 3.0 X 1CT ³ wt% Pt

(cts) lppm of toluene solution was added and mixed uniformly, and then cured by heating in air at 120 ° C for 3 hours to obtain a colorless and transparent resin plate.

[0110] The resin plates obtained in Example 3 and Reference Example 1 were immersed in an acetone solution (RT), and stress cracking was evaluated based on the presence or absence of cracks in the resin plate during the immersion. As a result, the resin plate of Reference Example 1 in which the cage-type silsesquioxane compound was directly crosslinked was cross-linked with a reactive monomer. The cage-type silsesquioxane compound was instantly cracked by immersion in an acetone solution. The resin plate of Example 3 was not cracked.

[0111] (Example 4)

Assemble a three-neck flask with a dropping funnel, thermometer, and reagent injection valve.

8. Charged 7 mL. Next, the whole system in the three-necked flask is cooled in an ice bath to 5 ° C or lower, and after confirming that the temperature in the system has decreased to 5 ° C or lower, from the dropping funnel under a nitrogen stream. 140 mL of Octanion was added dropwise at a rate of 1 to 2 drops / second. At this time, since all of the eight reaction sites of octanion are substituted with gallium dimethyl chlorosilane and dimethyl chlorosilane, the amount of allyl dimethyl chlorosilane and dimethyl chlorosilane is excessively large with respect to octanion. It is necessary to set as follows.

[0112] After completion of the dropwise addition, the ice bath was removed, the mixture was stirred at room temperature for 6 hours, and the Octano reaction solution was extracted three times with hexane as shown in [Chemical Formula 13], and the hexane layer was extracted with a desiccant (sodium sulfate). After drying, suction filtration was performed. The obtained filtrate is subjected to an evaporator to distill off hexane, and further By removing the unreacted raw material from the reaction product obtained by removing hexane in the vacuum pump while heating at 45 ° C with a vacuum pump, and purifying it, a diarylsilsesquioxane having 6 SiH groups was obtained. .

[Chemical 13]

0 -Si- ° ~ -si-0-Si- H

(Octaani n)

[0114] Then, 1.137 g of divinyltetramethyldisiloxane as a compound of the formula (3) is mixed with 1 · Og of diarylsilsesquioxane 1 · Og synthesized as in [Chem. Add ¹ ppm of Pt (cts) toluene solution with a concentration of ³ % by mass of 1CT, mix uniformly, and then cure by heating at 120 ° C for 4 hours in air to obtain a colorless and transparent resin plate It was.

[0115] (Reference Example 2) / 1-o

丄 so-A three-necked flask equipped with a dropping funnel, thermometer, and reagent injection valve? Attach 188 mL of hexane, dimethylhexenol chlorosilane 12.16 mL, and dimethino chloronorolesilane 7.5 mL to a three-necked flask, and cool the whole system with a water bath to 5 ° C or less. When the inside temperature became 5 ° C. or lower, 70 mL of Octanion was added dropwise from the dropping funnel at a rate of 1 to 2 / s drop Z seconds. After completion of the dropwise addition, the water bath was removed and the reaction was allowed to stir at room temperature for 6 hours. The obtained reaction solution was extracted 3 times with 40 mL of hexane, and the hexane layer was dried with a desiccant (sodium sulfate) and then filtered with suction. As shown in [Chemical Formula 14], the obtained filtrate is evaporated to remove hexane, and the reaction product power obtained is removed by purification while heating at 50 ° C with a vacuum pump. A tetrahexenyl silsesquioxane having four SiH groups was obtained.

[0116] Then, as in [Chemical Formula 14], the diallyl silsesquioxane obtained in [Chemical Formula 13] above and tetrahexenylsilsesquioxane are mixed in a mass ratio of 30:70, By heating at 120 ° C for 4 hours, the spaces were directly crosslinked and cured to obtain a colorless and transparent resin plate.

[0117] [Formula 14] Replacement paper (Rule 26)

[0118] The resin plate obtained in Example 4 and the resin plate obtained in Reference Example 2 were evaluated for BluRay irradiation resistance. In the test, each resin plate was irradiated with 405 nm Blu-ray under the conditions of power density 1.1 W / wake ² and spot size 200 m, and the time-dependent change of the irradiated part screen enlarged image (far field image) was observed. Senna / lemon observation was performed on the sample after completion of the irradiation test.

FIG. 6 (a) shows the time-dependent change of the far field image of Example 4, and FIG. 6 (b) shows the time-dependent change of the far field image of Reference Example 2. As seen in Fig. 6 (a) and (b), compared to the reference example 2 in which silsesquioxane was directly crosslinked, the example 4 crosslinked with a reactive monomer was used before the Blu-ray irradiation ( The change in far-field image was small compared to O r). After 240 hours of irradiation (240 r), the change was almost unchanged. .

[0120] Fig. 7 (a) shows the senalmon observation of Example 4, and Fig. 7 (b) shows the senalmon observation of Reference Example 2. In the case of Reference Example 2, a slight irradiation mark is seen at the center as shown in Fig. 7 (b), but in the case of Example 4, the irradiation mark was not seen as shown in Fig. 7 (a). .

[0121] Therefore, it was confirmed that the product of Example 4 in which silsesquioxane was crosslinked with a reactive monomer and hardened was improved in the resistance to Blu-ray irradiation.

[0122] Further, the resin plates obtained in Example 4 and Reference Example 2 were immersed in an acetone solution (RT), and stress cracking was evaluated based on the presence or absence of cracks in the resin plate during the immersion. As a result, the resin plate of Reference Example 2 was instantly cracked when immersed in an aceto solution.

[0123] (Example 5)

An apparatus equipped with a dropping funnel, thermometer, and reagent injection valve was assembled in a three-necked flask, and 376 mL of hexane, 33.8 mL of allyldimethyl chronolesilane, and 4.3 niL of dimethinorechlorsilane were added to the three-flask. Next, the whole system in the three-necked flask is cooled in an ice bath to 5 ° C or less, and after confirming that the temperature in the system is 5 ° C or less, the dropping funnel replacement paper ( (Rule 26) Force Octanion 140 mL was added dropwise at a rate of 1-2 drops per second. At this time, in order to substitute allyldimethylcyclosilane and dimethylchlorosilane for all eight reaction sites of octanion, the compounding amount of allyldimethylchlorosilane and dimethylchlorosilane was much larger than octanion. It is necessary to set so that

[0124] After completion of the dropwise addition, the permanent bath was removed, the mixture was stirred at room temperature for 6 hours, and the Octano solution was extracted three times with hexane as shown in [Chemical Formula 17], and the hexane layer was extracted with a desiccant (sodium sulfate). After drying, suction filtration was performed. Reactive biological force obtained by evaporating the obtained filtrate through an evaporator and further removing hexane and removing unreacted raw materials with a vacuum pump at 45 ° C. As a result, diallyl silsesquioxane having 6 SiH groups was obtained.

[0125] [Chemical 17]

2

(Octanion) (Dimethylchlorosilane) (Diarylsilsesquioxane)

[0126] In addition, a dropping funnel into a three-necked flask, a thermometer fitted with a reagent injection valve, three-necked: flask hexane to 188 mL, hexenyl dimethylcyclohexyl Le Chrono les silane 12. 16 mL _s-dimethyl chlorobenzene sila emissions 7. charged with 5 mL. Next, the whole system in the three-necked flask is cooled in a water bath so that the temperature is 5 ° C or less, and when the temperature in the system becomes 5 ° C or less, it is 70 m from the dropping funnel.

L was dropped at a rate of 1 to 2 drops / second. At this time, in order to replace dimethylhexenylchlorosilane and dimethylchlorosilane in all of the eight reaction sites of octanion, the amount of dimethylhexenylchlorosilane and dimethylchlorosilane was much larger than octanion. It is necessary to set so that

[0127] After completion of the dropwise addition, the ice bath was removed, and the mixture was stirred at room temperature for 6 hours to react octanion with dimethylhexenoylchlorsilane and dimethylchlorosilane as shown in [Chemical Formula 18]. The obtained reaction solution was extracted with 40 mL of hexane three times, and the hexane layer was replaced with a desiccant (sodium sulfate). Replacement paper (Rule 26) After 'drying', it was filtered with suction. The obtained filtrate was evaporated to distill off hexane, and further removed by heating at 45 ° C., followed by purification to obtain a tetrahexenoresinoleseschi-born xylene having four 1 SiH groups.

[0128] [Chemical 18]

(Dimethylhexenylchlorosilane)

(Octanion) (dimethylchlorosilane) (シラン trahexenylsilsesquioxane)

[0129] Then, as in [Formula 19], to di § Li Lucille sesquicarbonate O hexanes 0. 4g and tetra blended Kisenirushiruse Sukiokisan 0. 8 g, further 3. 0 X 10 one ³ mass ^_0/0 concentration of Pt ( cts) Toluene solution was added at lppm of the whole system, mixed uniformly, and then cured by heating in air at 120 ° C for 4B to obtain a colorless and transparent resin plate.

[0130] [Chemical 19]

Cure

(Dialylsilsesquioxane) (Tera Hexenile Silsesquioxane)

[0131] With respect to the resin plate obtained in Example 5 and the resin plate obtained in Example 1, the blu-ray irradiation resistance was evaluated. In the test, each resin plate was irradiated with benoray ray under the conditions of a power density of 1.1 W, 讓² and a spot size of 200 am, and the time-dependent changes in the screen image of the irradiated area (far field image) were observed. did.

FIG. 8 (a) shows the time-dependent change of the far field image of Example 5, and FIG. 8 (b) shows the time-dependent change of the far field image of Example 1. FIG. As seen in Figs. 8 (a) and 8 (b), in Example 1 where A in the formula (1) is cyclic vinyl, the center of the far field image becomes darker after 48 hours of irradiation, whereas the formula ( In Example 1 of 1) where A is a chain-end vinyl, the far-field image where the center of the far-field image does not change after irradiation for 183 hours Replacement paper (Rule 26) There is no big change in the whole.

FIG. 9 (a) shows the senalmon observation of Example 5, and FIG. 9 (b) shows the senalmon observation of Example 1. In Example 1, there is an irradiation mark as shown in FIG. On the other hand, the force of Example 5 shows a slight damage after 183 hr irradiation as shown in FIG. 9 (a). The damage is extremely small compared to that of Example 1.

[0134] Therefore, it was confirmed that the Blu-ray irradiation resistance was improved by forming a group having a carbon-carbon unsaturated bond of silsesquioxane with a chain hydrocarbon group.

[Example 6]

The diarylsilsesquioxane 1. Og of [Chemical Formula 17] synthesized in Example 5 was combined with 1.137 g of dibule tetramethyldisiloxane as a compound of the formula (3), and then 3.0. X 1CT Add ³ ppm by mass of Pt (cts) toluene solution at a concentration of ³ % by mass, mix uniformly, and then cure by heating at 120 ° C for 4 hours in air to obtain a colorless and transparent resin plate It was.

[0136] (Reference Example 3)

In Example 6, in a method for synthesizing hexarylsilsesquioxane having two SiH groups of [Chemical Formula 17], 19.8 mL of allyldimethylchlorosilane was added to 376 mL of hexane. The reaction was purified in the same manner except that 14.6 mL of dimethylchlorosilane was mixed and reacted with octananion, so that tetraallylsilsesquioxane having four SiH groups shown in [Chemical 4] above was obtained. Was synthesized.

[0137] And this tetra § Li Lucille sesquicarbonate O-hexane of Formula 4] 3. 0 X 1CT ³ mass ^_0/0 concentration of Pt

[0138] The resin plates obtained in Examples 3 and 6 and Reference Example 3 were immersed in an acetone solution (RT), and stress cracking was evaluated based on the presence or absence of cracks in the resin plate during the immersion. As a result, the resin plate of Reference Example 3 in which the force and gale silsesquioxane compound were directly cross-linked was obtained by immersing the resin plate in Reference Example 3 in acetone solution. No cracks occurred in the resin plates of Example 3 and Example 6 crosslinked with the reactive monomer.

Claims

Claims [1] A cage-containing silsesquioxane compound represented by the following formula (1), or a cage-containing silsesquioxane compound partial polymer formed by partial addition reaction of this compound A semiconductor optical device comprising a semiconductor light emitting element or a semiconductor light receiving element sealed with a compound. (AR R SiOSiO) (RR HSiOSiO) (BR R SiOSiO) (HOSiO) 1 2 1. 5 n 3 4 1. 5 p 5 6 1. 5 ¾ 1.5 in- n ••• (l) 11

1 2 3 4 5 6

Represents a functional group selected from an aryl group and a lower arylalkyl group, m is a number selected from 6, 8, 10, and 12, n is an integer from !! to m—1, p is l to m—n Integer, q represents an integer from 0 to m—np)

[2] The cage silsesquioxane compound represented by the above formula (1), or a cage silsesquioxane compound partial polymer obtained by partial addition reaction of this compound, and the following formula (2): 2. The semiconductor optical device according to claim 1, wherein the semiconductor light-emitting element or the semiconductor light-receiving element is sealed with a composition containing the compound represented.

HR R Si-X- SiHR R (2)

7 8 9 10

Represents an alkyl group of 1 to 3 prime numbers or a hydrogen atom)

[3] A cage silsesquioxane compound represented by the above formula (1), or a cage silsesquioxane compound partial polymer obtained by partial addition reaction of this compound, and the following formula (3): 2. The semiconductor optical device according to claim 1, wherein the semiconductor light-emitting element or the semiconductor light-receiving element is sealed with a composition containing the compound represented.

H C = CH-Y-CH = CH…)

twenty two

(In formula (3), Y represents a divalent functional group)

[4] The semiconductor optical device according to any one of [1] to [3] above, wherein in the formula (1), A is a chain hydrocarbon group having a carbon-carbon unsaturated bond.

[5] A cage silsesquioxane compound represented by the following formula (1), or a part of this compound A transparent optical member obtained by polymerizing a carbon compound containing a cage-type silsesquioxane compound partial polymer obtained by an addition reaction.

(AR R SiOSiO) (R R HSiOSiO) (BR R SiOSiO) (HOSiO)

1 2 1. 5 n 3 4 1. 5 p 5 6 1. 5 ¾ 1. 5 in— n

••• (l)

11

1 2 3 4 5 6

The cage-type silsesquioxane compound represented by the above formula (1), or a cage-type silsesquioxane compound partial polymer obtained by partial addition reaction of this compound, and the following formula (2) 6. The transparent optical member according to claim 5, wherein a composition containing the compound is polymerized.

HR R Si-X- SiHR R (2)

7 8 9 10

Represents an alkyl group of 1 to 3 prime numbers or a hydrogen atom)

The cage-type silsesquioxane compound represented by the above formula (1) or a cage-type silsesquioxane compound partial polymer obtained by partial addition reaction of this compound and the following formula (3) 6. The transparent optical member according to claim 5, wherein a composition containing the compound is polymerized.

H C = CH-Y-CH = CH…)

twenty two

(In formula (3), Y represents a divalent functional group)

The transparent optical member according to any one of claims 5 to 7, wherein A in the formula (1) is a chain hydrocarbon group having a carbon-carbon unsaturated bond.