JP5204393B2 - Semiconductor optical device and transparent optical member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor optical device in which a semiconductor light-emitting element or a semiconductor light-receiving element is sealed with a sealing material, and in which the sealing material is hardly deteriorated and a water absorbing rate is low. <P>SOLUTION: As for a formula (AR<SP>1</SP>R<SP>2</SP>SiOSiO<SB>1.5</SB>)<SB>n</SB>(R<SP>3</SP>R<SP>4</SP>HSiOSiO<SB>1.5</SB>)<SB>p</SB>(BR<SP>5</SP>R<SP>6</SP>SiOSiO<SB>1.5</SB>)<SB>q</SB>(HOSiO<SB>1.5</SB>)<SB>m-n-p-q</SB>is given. In this formula, the character A denotes a group having carbon-carbon unsaturated linkage, B denotes a substituted or unsubstituted alkyl group or hydroxyl group, R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, R<SP>6</SP>each independently denote a functional group selected from among a lower alkyl group, a phenyl group and a lower aryl alkyl group, m denotes a number selected from among 6, 8, 10, 12, n denotes an integer 1 to m-1, p denotes an integer 1 to m-n, and q denotes an integer 0 to m-n-p. The semiconductor light-emitting element or the semiconductor light-receiving element is sealed with a silicon compound containing a cage type silsesquioxane compound represented by the formula or a cage type silsesquioxane compound patial polymer in which this compound performs partial addition reaction. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  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.

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

  In addition, semiconductor light-emitting elements are being developed as lighting fixtures incorporating white LED units, and are expected to become increasingly widespread in the future. Blue and near-ultraviolet LEDs are used as the white LED light source used in the white LED unit, and development is being carried out to achieve high output and high brightness in order to satisfy the requirements of lighting equipment. .

  And since high heat energy and light energy are emitted from the semiconductor light emitting device with high output and high brightness in this way, when such a semiconductor light emitting device is mounted on a substrate and sealed, generally, In the case of the epoxy-based sealing material used, there is a problem that the sealing material deteriorates rapidly and the life becomes relatively short.

  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, low melting point glass, or the like has been studied. For example, Patent Document 1 discloses a semiconductor device obtained by sealing a semiconductor light-emitting element using a metalloxane, which is a metal oxide obtained by a sol-gel method, as a material having excellent heat resistance and light resistance. .

  However, metalloxane, which is a metal oxide obtained by a sol-gel method, has a porous structure and thus has a high water absorption rate, and has a problem that it may absorb moisture during use and cause cracks.

  For recording information, for example, a DVD device that records light by irradiating a resin disk is used. In order to meet the recent demand for high capacity, light in the blue / near ultraviolet region is irradiated. Devices for recording / reading are being studied. When reading the information recorded on the resin disk, the laser light in the blue / 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. Is being read. Such a semiconductor light receiving element is generally sealed and protected by a sealing material, and is irradiated with a high-power laser beam as compared with a conventional one using a red laser beam. When the stop material is used, there is a problem that the sealing material is easily deteriorated.

  In addition, the DVD apparatus is also required to improve the recording speed. The recording speed can be improved by increasing the rotational speed of the disk. However, if the rotational speed is high, the amount of laser light (power density) irradiated on the disk during a certain time is reduced compared to when the rotational speed is low. In order to compensate for this decrease, the increase in laser power has progressed. In this respect as well, there has been a problem that when an epoxy-based sealing material is used, the sealing material tends to deteriorate.

Also, when the laser light in the blue / 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 may be reduced or the optical path may be bent. Since transparent optical members such as lenses and prisms used in this case are also irradiated with relatively high output laser light, there is a problem that they are easily deteriorated when manufactured using an epoxy resin. there were.
Japanese Patent No. 3412152

  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, a semiconductor optical device having an excellent life span in which the sealing material is hardly deteriorated. An object of the present invention is to provide a transparent optical member that is difficult to deteriorate and has a long life in a transparent optical member that is intended to be provided and is used in a portion irradiated with light in the blue / near ultraviolet region. To do.

  The semiconductor optical device according to claim 1 of the present invention contains a cage silsesquioxane compound represented by the following formula (1) or a cage silsesquioxane compound partial polymer obtained by partial addition reaction of this compound. The silicon compound is formed by sealing a semiconductor light emitting element or a semiconductor light receiving element.

(AR ¹ R ² SiOSiO _1.5 ) _n (R ³ R ⁴ HSiOSiO _1.5 ) _p (BR ⁵ R ⁶ SiOSiO _1.5 ) _q (HOSiO _1.5 ) _m- npq (1)
(In the formula (1), A is a group having a cyclohexenyl group , B is a substituted or unsubstituted saturated alkyl group or hydroxyl group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently It represents a functional group selected from a lower alkyl group, a phenyl group, and a lower arylalkyl group, m is a number selected from 6, 8, 10, and 12, n is an integer of 1 to m-1, and p is 1 to m. An integer of -n, q represents an integer of 0 to mnp)
The invention of claim 2 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 (2) is contained. .

^{HR 7 R 8 Si-X-} SiHR 9 R 10 ... (2)
(In formula (2), X represents a divalent functional group or an oxygen atom, and R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents an alkyl group having 1 to 3 carbon atoms 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), a compound represented by the following formula (3) is contained. .
_{H 2 C = CH-Y-} CH = CH 2 ... (3)
(In formula (3), Y represents a divalent functional group)
The transparent optical member according to claim 4 of the present invention contains a cage silsesquioxane compound represented by the following formula (1) or a cage silsesquioxane compound partial polymer obtained by partial addition reaction of this compound. It is characterized by polymerizing a silicon compound.

(AR ¹ R ² SiOSiO _1.5 ) _n (R ³ R ⁴ HSiOSiO _1.5 ) _p (BR ⁵ R ⁶ SiOSiO _1.5 ) _q (HOSiO _1.5 ) _m- npq (1)
(In the formula (1), A is a group having a cyclohexenyl group , B is a substituted or unsubstituted saturated alkyl group or hydroxyl group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently It represents a functional group selected from a lower alkyl group, a phenyl group, and a lower arylalkyl group, m is a number selected from 6, 8, 10, and 12, n is an integer of 1 to m-1, and p is 1 to m. An integer of -n, q represents an integer of 0 to mnp)
The invention of claim 5 is characterized in that, in claim 4, in addition to the cage silsesquioxane compound of the above formula (1), a compound represented by the following formula (2) is contained. .

^{HR 7 R 8 Si-X-} SiHR 9 R 10 ... (2)
(In formula (2), X represents a divalent functional group or an oxygen atom, and R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom)
The invention of claim 6 is characterized in that, in claim 4, it contains a compound represented by the following formula (3) in addition to the cage silsesquioxane compound of the above formula (1). .
_{H 2 C = CH-Y-} CH = CH 2 ... (3)
(In formula (3), Y represents a divalent functional group)

  The cage silsesquioxane compound of the formula (1) is a carbon-bonded hydrogen atom bonded via a siloxane bond to a silicon atom having a polyhedral structure formed of silicon atoms and oxygen atoms via a siloxane bond. A group having a carbon unsaturated bond, so that a hydrogen atom undergoes a hydrosilylation reaction with a group having a carbon-carbon unsaturated bond of another cage-type silsesquioxane compound to perform addition polymerization. It is crosslinked and cured to form a three-dimensional crosslinked structure in which silica nano-sized cage structures are connected by organic segments. It exhibits a glass-like function and emits light in the blue and near ultraviolet range. Even if it is used in an irradiated state, it is hard to deteriorate and becomes a cured product having a low water absorption.

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

Further, by reacting the compound of the formula (3) having —CH═CH ₂ groups at both ends with the cage silsesquioxane compound of the formula (1) as a reactive monomer, the cage silsesquioxane compound -CH = CH ₂ is addition polymerization by hydrosilylation reaction of a hydrogen atom, a cage silsesquioxane compound of formula (1) can be cured by crosslinking with a compound of formula (3), unreacted residual It can form a three-dimensional cross-linked structure of a cage silsesquioxane compound with a more uniform network structure with fewer groups, which can suppress stress cracking of the cured product and increase toughness It is also possible to improve the irradiation resistance against short wavelength high energy light such as Blu-ray.

  Therefore, in the present invention, a semiconductor optical device can be formed with a sealing material that is not easily deteriorated and has a long life, and a transparent optical member can be obtained from a material that is hardly deteriorated and has a long life. .

  Moreover, by introducing a hydroxyl group into the cage silsesquioxane compound, the affinity with a heavy metal sol such as TiO or ZrO whose surface is covered with a hydroxyl group can be increased. The hardened | cured material which improved the dispersibility and can raise the refractive index uniformly by introduction | transduction of heavy metal sol can be obtained.

  Hereinafter, the best mode for carrying out the present invention will be described.

  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. Further, an electronic circuit 5 is formed on the substrate 1 and is electrically connected to the semiconductor light emitting element 2 by a bonding wire 6 in the embodiment of FIG.

  As the semiconductor light emitting element 2, a known semiconductor light emitting element 2 can be used. When an element that outputs light having a wavelength of 450 nm or less in blue or near-ultraviolet region is used, the illuminance of the obtained semiconductor optical device This is preferable because the color rendering properties can be improved. As a specific example of the semiconductor light emitting element 2, for example, a semiconductor substrate made of GaAlN, ZnS, ZnSe, SiC, GaP, GaAlAs, AlInGaP, InGaN, GaN, AlInGaN or the like as a light emitting layer is used. it can. The semiconductor light emitting element 2 can be mounted by mounting the semiconductor light emitting element 2 on a portion of the substrate 1 where the semiconductor light emitting element 2 is mounted, and performing wire bonding mounting, flip chip mounting, or the like.

  Moreover, said board | substrate 1 can be obtained by shape | molding resin materials, such as a ceramic material and a thermoplastic resin and a thermosetting resin, in a desired shape by various shaping | molding methods, The shape is not specifically limited. Examples of the ceramic material that can be used for the substrate 1 include alumina, aluminum nitride, zirconia, and silicon carbide. These are formed by known compression molding, injection molding (CIM), or the like and sintered. The substrate 1 can be formed. 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 to efficiently dissipate heat. 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, alumina or the like to the resin material, the thermal conductivity and heat resistance of the substrate 1 can be improved.

  Further, the electric circuit 5 having a predetermined pattern connected to the semiconductor light emitting element 2 is formed on the surface of the substrate 1 as described above. However, the formation method is not particularly limited, and a known method can be used. is there.

  In the embodiment of FIG. 1, the semiconductor optical device according to the present invention has been described with 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 sealed with the sealing material. Needless to say, the semiconductor light receiving device may be used.

  And in this invention, said sealing material 3 is the cage silsesquioxane compound represented by following formula (1), or the cage silsesquioxane compound partial polymer which this compound carried out the partial addition reaction. It is formed by cross-linking the contained silicon compound.

(AR ¹ R ² SiOSiO _1.5 ) _n (R ³ R ⁴ HSiOSiO _1.5 ) _p (BR ⁵ R ⁶ SiOSiO _1.5 ) _q (HOSiO _1.5 ) _m- npq (1)
In the above formula (1), A represents a group having a carbon-carbon unsaturated bond, and is particularly limited as long as it includes a carbon-carbon double bond or a carbon-carbon triple bond as part of the group. Not done. Examples thereof include those containing an alkenyl group, alkynyl group, and cyclohexenyl group. Examples of the group containing an alkenyl group or alkynyl group include a carbon-carbon double bond such as a vinyl group or an allyl group. And a group having a carbon-carbon triple bond such as an ethynyl group and a propynyl 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 can also be mentioned, and the divalent not having this unsaturated group. Examples of the group to which these groups are bonded include a cyclohexenylethyldimethylsiloxy group.

  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 substituted or unsubstituted monovalent saturated hydrocarbon groups having 1 to 8 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group; methoxy group, ethoxy group, etc. Alkoxy groups; aralkyl groups such as 2-phenylethyl group, 2-phenylpropyl group and 3-phenylpropyl group; halogen substitution such as chloromethyl group, γ-chloropropyl group and 3,3,3-trifluoropropyl group A hydrocarbon group etc. can be illustrated. Among these, an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of reducing steric hindrance during the reaction, and a methyl group is particularly preferable. In addition, when it has several B group in one molecule | numerator, ie, when q> = 2, each B group may be the same and may differ.

In the above formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently one selected from a lower alkyl group, a phenyl group, and a lower arylalkyl group. It represents a functional group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group or a propyl group, or an arylalkyl group having 7 to 10 carbon atoms such as a phenyl group, a benzyl group or a phenethyl group. It can be illustrated. Among these, a methyl group is preferable from the viewpoint of reducing the steric hindrance of the reaction, and phenyl is preferable from the viewpoint of increasing the refractive index.

  Further, in the above formula (1), 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 mn, q represents an integer of 0 to mnp.

  Examples of the cage silsesquioxane compound include those represented by the following formulas (4) and (5).

In the compound of formula (4), m = 8, n = 4, p = 4, q = 0, R ¹ , R ² , R ³ and R ⁴ are methyl groups (Me) in the above formula (1). The group A is bonded to four silicon atoms through eight siloxane bonds (—O—Si—) out of eight silicon atoms that form a substantially hexahedral structure formed of silicon atoms and oxygen atoms. The hydrogen atom is bonded to the other four silicon atoms via a siloxane bond (—O—Si—). In addition, the structural formula of the formula (4) indicates that (—O—SiMe ₂ —A) is bonded to each of four silicon atoms out of the eight silicon atoms constituting the substantially hexahedral structure, and the other four silicon atoms. The fact that (—O—SiMe ₂ H) is bonded to an atom one by one is expressed in a simplified manner (the following structural formula is also expressed in a simplified manner).

In addition, the compound of the formula (5) has the following formula (1): m = 8, n = 3, p = 3, q = 2, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and B is a compound having a methyl group, and among eight silicon atoms constituting a substantially hexahedral structure formed of silicon atoms and oxygen atoms, three silicon atoms are grouped via a siloxane bond (—O—Si—). A is bonded, a hydrogen atom is bonded to the other three silicon atoms via a siloxane bond (—O—Si—), and a B atom is bonded to the remaining two silicon atoms via a siloxane bond (—O—Si—). It has a structure in which the methyl group is bonded. In addition, the structural formula of Formula (5) indicates that (—O—SiMe ₂ —A) is bonded to three silicon atoms one by one among the eight silicon atoms constituting the substantially hexahedral structure, and the other three It is expressed in a simplified manner that (—O—SiMe ₂ H) is bonded to silicon atoms one by one and (—O—SiMe ₃ ) is bonded to the remaining two silicon atoms one by one.

Next, an example of a method for synthesizing the above cage silsesquioxane will be described. First, an octaanion (Si ₈ O ₁₂ ⁸⁻ ) having a substantially hexahedral structure is reacted with a reactive halogen such as chlorohydridodimethylsilane to bond a hydridodimethylsiloxy group to the eight silicon atoms of the octaanion. To prepare octakis [hydridodimethylsiloxy] silsesquioxane (OHSS). Then, by using this OHSS, a compound having two or more carbon-carbon unsaturated groups such as 4-vinyl-1-cyclohexene in the molecule is reacted in an amount less than an equivalent amount, thereby unsaturated some hydridodimethylsiloxy groups. A compound having a carbon-carbon unsaturated bond is bonded to a part of eight silicon atoms constituting an approximately hexahedral structure formed of silicon atoms and oxygen atoms by addition reaction of a compound having two or more groups in the molecule. Then, a cage silsesquioxane compound represented by the formula (4) in which a hydridodimethylsiloxy group is bonded to another silicon atom can be prepared. The octaanion can be obtained by reacting tetramethylammonium hydroxide with tetraethoxysilane.

  Further, by reacting a mixture of a reactive halogen having a carbon-carbon unsaturated group such as dimethylvinylchlorosilane, dimethylallylchlorosilane, chlorocycloalkenyldimethylsilane and chlorohydridodimethylsilane with an octaanion, a silicon atom and an oxygen atom In the formula (4), a group having a carbon-carbon unsaturated bond is bonded to a part of the eight silicon atoms constituting the substantially hexahedral structure formed by the above, and a hydridodimethylsiloxy group is bonded to another silicon atom. Such a cage-type silsesquioxane compound can be prepared.

  Further, when this mixture is reacted with octaanion, an unsaturated group such as chlorotrimethylsilane and a reactive halogen having no active hydrogen are also mixed and reacted to thereby form eight silicons constituting a substantially hexahedral structure. A cage-type silsesquioxane compound represented by the formula (5) in which a non-reactive group is bonded to some of the atoms can be prepared.

  The cage-type silsesquioxane compound obtained as described above comprises a hydrogen atom bonded to a silicon atom having a substantially hexahedral structure formed of silicon atoms and oxygen atoms via a siloxane bond, and a carbon-carbon unsaturated bond. Therefore, the hydrogen atom undergoes a hydrosilylation reaction with an unsaturated group contained in the carbon-carbon unsaturated bond group of another cage-type silsesquioxane compound to undergo addition polymerization. Thus, the resin is cross-linked and cured to form a three-dimensional cross-linked structure. FIG. 2 schematically shows a three-dimensional crosslinked structure in which a substantially hexahedral structure (symbol 7) formed of silicon atoms and oxygen atoms is crosslinked. [Chemical Formula 2] shows a cross-linking reaction of a three-dimensional cross-linked structure of a cage silsesquioxane compound in which A in the formula (4) is a cyclohexenyl group. This three-dimensional crosslinked structure has a structure in which silica (glass) nano-sized squirrel-type structures are connected by organic segments, and can exhibit a glass-like function. .

Here, the reacting carbon-carbon unsaturated bond group and the hydrogen atom are bonded to the polyhedral structure part of silsesquioxane (Si ₈ O ₁₂ ) via a siloxane bond (—O—Si—). Therefore, it is difficult to cause steric hindrance when polymerizing with other cage-type silsesquioxane compounds, and it is possible to obtain a cured product having a high reaction rate, and unreacted residues. As a result, the reliability can be prevented from decreasing due to unreacted residues. Furthermore, since it has a nano-sized cage structure of silica (glass) as described above, a cured product having a high cross-linking density and a low water absorption rate can be obtained as compared with metalloxane obtained by a sol-gel method. It can be done.

  Moreover, 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 silicon atoms constituting the polyhedral structure of silsesquioxane are bonded to four oxygen atoms. Moreover, since the organic group is not directly bonded to the silicon atom, it is difficult to deteriorate even when used in the state of being irradiated with light in the blue / near ultraviolet region.

  Then, when a conventionally used light-transmitting epoxy resin, polyester, polyacrylate, organopolysiloxane, or the like is used as the sealing material 3 for sealing the semiconductor light emitting element 2 or the like, the cross-linking bond and absorption contained in these are used. Due to the presence of groups, unnecessary absorption peaks are likely to appear in the required spectral region, but when the cured product of the cage silsesquioxane compound of the present invention is used, such absorption peaks are few and good. It becomes the sealing material 3 which has the transmittance | permeability of blue light and ultraviolet light.

  In addition, hydrogen bonded to a silicon atom having a polyhedral structure formed of silicon atoms and oxygen atoms in a molecule of the cage silsesquioxane compound represented by the above formula (1) of the present invention via a siloxane bond. The number of atoms and the number of groups with carbon-carbon unsaturated bonds (ie n and p) are preferably the same, but are somewhat different as long as the desired optical and physical properties of the cured product are maintained. May be.

  In sealing the semiconductor light emitting device 2 using the cage silsesquioxane compound of the present invention, any conditions can be used without particular limitation as long as polymerization and crosslinking of the cage silsesquioxane compound proceed. The method can be employed, and the reaction may be carried out using an addition reaction catalyst such as platinum or palladium as necessary. Here, the cage-type silsesquioxane compound according to the present invention is liquid at room temperature or solid that melts at a relatively low temperature until it is cross-linked, so that the semiconductor light emitting device 2 and the like can be easily sealed. It is possible.

  Moreover, the cage silsesquioxane compound partial polymer obtained by partial addition reaction of the cage silsesquioxane compound represented by the above formula (1) of the present invention is a cage silsesquioxane compound represented by the formula (1). It is an oligomer in which about 2 to 10 oxan compounds are polymerized, and has fluidity capable of sealing the semiconductor light emitting element 2 and the like. Accordingly, 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 to form, for example, a three-dimensional crosslinked structure as shown in FIG. . 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 / near ultraviolet region. .

  The sealing material 3 for sealing the semiconductor light emitting device 2 and the like includes a cage silsesquioxane compound represented by the above formula (1) or a cage silsesquioxane compound portion obtained by partial addition reaction of this compound. In addition to the polymer, a silicon compound having addition reactivity may be contained as long as desirable optical and physical properties of the cured product are maintained.

  In the above description, the cage-type silsesquioxane compound of the above formula (1) has been described in the case of m = 8. However, when m is 6, 10, 12, the cage-type silses A partial polymer of a sesquioxane compound or a cage silsesquioxane compound can be obtained. Even when these compounds are used, they are cross-linked by polymerizing with other cage-type silsesquioxane compounds, etc. to form a three-dimensional cross-linked structure with a polyhedral structure formed of silicon atoms and oxygen atoms in the skeleton. To do. Also in this case, similarly, even when used in a state of being irradiated with light in the blue / near ultraviolet region, it becomes a cured product that is hardly deteriorated and has a low water absorption rate.

  In the cage silsesquioxane compound represented by the above formula (1), when the substituted or unsubstituted alkyl group of B is an alkoxy group and q ≧ 2, the above-mentioned carbon-carbon defect is not detected. In addition to the bond between a group having a saturated bond and a hydrogen atom, it is also possible to crosslink by a hydrolysis / polycondensation bond between the alkoxy groups, which increases the versatility of use and increases the versatility of curing. At this time, when the bond between a group having a carbon-carbon unsaturated bond and a hydrogen atom is a main cross-linked structure, it is preferable because the thickness of the cured product becomes relatively easy, and hydrolysis of alkoxy groups is preferable. It is preferable that the polycondensation bond has a main cross-linked structure because of relatively high transparency. [Chemical Formula 3] shows an example of a cross-linking reaction of a three-dimensional cross-linked structure when A in the formula (1) is a cyclohexenyl group and B is an ethoxy group.

  In the above embodiment, the semiconductor light emitting device or the semiconductor light receiving device is sealed with the cage silsesquioxane compound of the formula (1) or the cage silsesquioxane compound partial polymer obtained by partial addition reaction of this compound. Although the stopped semiconductor optical device has been described, the cage silsesquioxane compound represented by the formula (1) or the cage silsesquioxane compound partial polymer obtained by partial addition reaction of this compound is used as a molding material. A transparent optical member such as a lens or a prism can be produced by molding, polymerizing, and curing this. In addition, it can be used for a transparent optical member such as a protective layer of a Blu-ray disc by being applied and polymerized on the surface of the optical disc.

Here, when applying the cured product of the cage silsesquioxane compound to an optical application such as a transparent encapsulant for LED white illumination, it is necessary to improve the refractive index. In order to form a cured product having a high refractive index, a heavy metal sol such as TiO or ZrO is mixed with a cage silsesquioxane compound, and the heavy metal sol is introduced into a cured product of the cage silsesquioxane compound. Is done. At this time, the cage silsesquioxane compound is generally not compatible with heavy metal sols such as TiO and ZrO, and it is difficult to uniformly disperse the heavy metal sol. For example, as in [Chemical Formula 4], in Formula (1), A is an allyl group, R ¹ , R ² , R ³ , and R ⁴ are methyl groups, m = 8, n = 4, p = 4, q = This is because in a system in which a cage-type silsesquioxane compound that is 0 is subjected to a crosslinking reaction, there is no functional group having an affinity for —OH that covers the surface of the heavy metal sol.

  Therefore, in this case, as shown in the following [Chemical Formula 5], by using a silsesquioxane compound having an OH group in which mnpq is 1 or more in the formula (1). The dispersibility of heavy metal sol can be increased by the affinity between the -OH group of the silsesquioxane compound and the -OH group covering the heavy metal sol. The cage-type silsesquioxane compound and the heavy metal sol are uniformly distributed. And a cured product of a cage-type silsesquioxane compound having a uniform high refractive index can be obtained.

The cage-type silsesquioxane compound represented by [Chemical Formula 5] has the formula (1), wherein A is an allyl group, R ¹ , R ² , R ³ , and R ⁴ are methyl groups, m = 8, n = 3, It is a compound of p = 3 and q = 0, and a siloxane bond (—O—Si—) is bonded to three silicon atoms among eight silicon atoms constituting a substantially hexahedral structure formed of silicon atoms and oxygen atoms. An allyl group is bonded to each other, a hydrogen atom is bonded to three silicon atoms via a siloxane bond (—O—Si—), and a hydroxyl group is bonded to two silicon atoms.

  Such a cage silsesquioxane in which a hydroxyl group is bonded to a part of eight silicon atoms constituting a substantially hexahedral structure can be obtained as follows.

  A cage-type silsesquioxane compound such as the above [Chemical Formula 4] can be obtained by reacting allyldimethylchlorosilane and dimethylchlorosilane with an octaanion as shown in [Chemical Formula 12] and [Chemical Formula 13] described later. In order to replace allyl dimethyl chlorosilane and dimethyl chloro silane in all eight reaction sites of the octaanion, the amount of allyl dimethyl chlorosilane or dimethyl chlorosilane is larger than that of the octaanion. It is necessary to set the excess (for example, 30 times equivalent or more). Therefore, when the excess of allyldimethylchlorosilane or dimethylchlorosilane relative to the octaanion is small, some of the eight reaction sites of the octaanion are not substituted, and the unsubstituted sites are hydrolyzed to become —OH groups. There can be prepared allyldimethylsiloxysilsesquioxane in which an OH group is introduced into a part of silicon atoms constituting a substantially hexahedral structure as shown in [Chemical Formula 5]. Further, by adjusting the excess degree, the number of —OH groups introduced into the cage silsesquioxane can be controlled.

In the above embodiment, the cage silsesquioxane compounds are directly crosslinked by hydrosilylation reaction of carbon-carbon unsaturated bonds and hydrogen atoms. For example, as in the above [Chemical Formula 4], the cage-type silsesquioxane compound is directly crosslinked between a —SiH group and a —CH═CH ₂ group to be cured. However, in this case, since the cross-linking reaction proceeds rapidly, the structure freezes when the cross-linking reaction of -SiH and -CH = CH ₂ between the cage-type silsesquioxane compounds proceeds rapidly to some extent, and further cross-linking reaction proceeds. As a result, there may be a non-uniform cross-linked structure in which a portion where the cross-linking reaction proceeds and a portion where unreacted groups remain coexist. Therefore, since the structure becomes non-uniform and the reaction progresses non-uniformly and quickly, residual strain is accumulated in the cured molecular structure. When the cured product is immersed in a solvent such as acetone, stress cracking occurs. There is a possibility that only a brittle cured product may be obtained. Moreover, since unreacted groups remain in the cured product, the irradiation resistance to blue / near ultraviolet short wavelength high energy light such as Blu-ray may not be sufficient.

  Therefore, in this case, a compound of the following formula (2) or formula (3) is blended as a reactive monomer into the cage silsesquioxane compound of formula (1), and the cage silsesquioxane compound is represented by the formula (2) or a compound of formula (3) is crosslinked and cured.

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

^{HR 5 R 6 Si-X-} SiHR 7 R 8 ... (2)
In the formula (2), X represents a divalent functional group or an oxygen atom. In the formula (2), R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Although it does not specifically limit as a compound shown by this Formula (2), What can be illustrated to following [Chemical 6] can be illustrated.

  Although the compounding quantity of the compound of Formula (2) with respect to the cage silsesquioxane compound of Formula (1) is not specifically limited, the amount and equivalent of the unsaturated group of A which the compound of Formula (1) has Alternatively, it is preferable to set a little more than the equivalent.

Then, the cage-type silsesquioxane compound is reacted with the compound of the formula (2) as a reactive monomer, and as shown in [Chemical Formula 7], -CH = CH of the cage-type silsesquioxane compound is obtained. -SiH at both ends of the compound of formula (2) can be hydrosilylated into _two groups to undergo addition polymerization, and a cage silsesquioxane compound can be cross-linked with the compound of formula (2) and cured. It is possible to form a three-dimensional cross-linked structure in which these nano-sized cage structures are connected by organic segments. In the above formula (1), the silsesquioxane compound represented by [Chemical Formula 7] is m = 8, n = x, p = 8-x, q = 0, A is an allyl group, R ¹ , R ² , R ³ and R ⁴ are methyl group compounds, and among six silicon atoms constituting a substantially hexahedral structure formed of silicon atoms and oxygen atoms, x silicon atoms are bonded to siloxane bonds (—O—Si—). ) Through which allyl groups are bonded, and hydrogen atoms are bonded to other 8-x silicon atoms through siloxane bonds (—O—Si—).

Thus, by reacting a cage-type silsesquioxane compound with a compound of formula (2) having —SiH at both ends as a reactive monomer, in the sea of the reactive monomer of formula (2), Since the cage silsesquioxane compound of the formula (1) having a —CH═CH ₂ group gradually reacts with the compound of the formula (2) to crosslink, the progress of the reaction can be controlled more mildly. Even if the unreacted remaining —CH═CH ₂ group is generated in the course of the progress of the crosslinking reaction, the compound of the formula (2) moves to the residue portion and undergoes a crosslinking reaction. In this way, it is possible to control the progress of the reaction mildly to delay the structure freezing, and to form a three-dimensional crosslinked structure of the cage silsesquioxane compound with a more uniform network structure with fewer unreacted residues. It can be formed, can suppress stress cracking of the cured body and can improve toughness, and can improve irradiation resistance to short wavelength high energy light such as Blu-ray.

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

_{H 2 C = CH-Y-} CH = CH 2 ... (3)
In the formula (3), Y represents a divalent functional group, and the compound represented by the formula (3) is not particularly limited, but the one represented by the following [Chemical Formula 8] It can be illustrated.

  The compounding amount of the compound of the formula (3) with respect to the cage silsesquioxane compound of the formula (1) is not particularly limited, but the amount and equivalent of the reactive hydrogen atom that the compound of the formula (1) has, Or it is preferable to set a little more than an equivalent.

Then, by adding the compound of the formula (3) as a reactive monomer to the cage-type silsesquioxane compound and reacting it, as shown in [Chemical Formula 9], the -SiH group of the cage-type silsesquioxane compound is converted into the -SiH group. The —CH═CH ₂ groups at both ends of the compound of the formula (3) can be hydrosilylated and subjected to addition polymerization, and the cage silsesquioxane compound can be crosslinked and cured with the compound of the formula (3). A three-dimensional crosslinked structure in which silica nano-sized cage structures are connected by organic segments can be formed.

Thus, by reacting a cage silsesquioxane compound with a compound of formula (3) having —CH═CH ₂ at both ends as a reactive monomer, a —SiH group in the sea of reactive monomers Since the cage-type silsesquioxane compound having a reaction with the compound of the formula (3) gradually reacts and crosslinks, the progress of the reaction can be controlled more mildly, and in the course of the progress of the crosslinking reaction, Even if the -SiH group remaining in the reaction is generated, the compound of the formula (3) moves to the residue part and undergoes a crosslinking reaction. In this way, it is possible to control the progress of the reaction mildly to delay the structure freezing, and to form a three-dimensional crosslinked structure of the cage silsesquioxane compound with a more uniform network structure with fewer unreacted residues. It can be formed, can suppress stress cracking of the cured body and can improve toughness, and can improve irradiation resistance to short wavelength high energy light such as Blu-ray.

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

Example 1
A 1000 ml flask equipped with a reflux tube and a dropping funnel was charged with 334 ml of tetramethylammonium hydroxide, 164 ml of methanol, and 123 ml of water and stirred. The dropping funnel was charged with 179 ml of tetraethoxysilane (TEOS), the whole flask was cooled to about 5 ° C. in an ice bath, and TEOS was added dropwise at about 5 ° C. The addition of 179 ml of TEOS was completed in about 1 hour from the start of the addition. 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 was completed, the reaction product was filtered to obtain an octaanion / methanol solution in the filtrate.

  Next, 895 ml of hexane and 69.7 ml of dimethylchlorosilane were charged into a 1000 ml flask equipped with a reflux tube and a dropping funnel and stirred. The dropping funnel was charged with an octaanion / methanol solution, the solution in the flask was cooled to about 5 ° C, and the octaanion / methanol solution was added dropwise at about 5 ° C under a nitrogen atmosphere. The dripping of 334 ml of the octaanion / methanol solution was completed in about 2 hours from the start of the dropping. 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. Further, 100 ml of hexane was added to the lower methanol layer, and the reaction product was extracted, and then the upper hexane layer formed by standing was transferred to the 2 l Erlenmeyer flask to which the above hexane layer was transferred. Water was dried. Next, the dried hexane layer was transferred to a 1 L eggplant-shaped flask, and hexane was volatilized from the solution using a rotary evaporator and removed from the system. The damp white solid remaining in the 1-liter eggplant type flask in which hexane was volatilized was further dried under reduced pressure (133 Pa (1 mmHg), 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 100 ml beaker, further washed with 100 ml of acetonitrile, and suction filtered to take out the white solid. After this washing operation was repeated twice, the white solid octakis [hydridodimethylsiloxy] silsesquioxane (OHSS) was obtained by drying under reduced pressure using a vacuum pump. 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 gradually heated under vacuum to remove residual air and moisture, then flushed with nitrogen, then 50 ml of toluene, 8.7 g (80 mmol) of 4-vinyl-1-cyclohexene, and 2 mM as catalyst. 0.2 ml of Pt (dcp) -toluene solution (Pt: 0.4 ppm) was added. And after making this mixture react at 90 degreeC for 5 hours stirring, the solvent was removed and the white powdery product 27.5g (0.019 mol) was obtained. The yield at this time was 94%.

As a result of analyzing the obtained reaction product by 1H-NMR spectrum and 13C-NMR spectrum, the structural formula is formula (1), A is a cyclohexenyl group, R ¹ , R ² , R ³ , and R ⁴ are methyl. A tetrakis (cyclohexenylethyldimethylsiloxy) tetrakis (dimethylsiloxy) silsesquioxane whose structural formula is represented by the following [Chemical Formula 10], wherein m is 8, n is 4, p is 4, and q is 0. It was confirmed.

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

  The cage-type silsesquioxane compound thus obtained is poured into a Teflon (registered trademark) mold, heated and melted at 90 ° C., degassed under reduced pressure, and further heated to 200 ° C. while maintaining the vacuum. And the resin board was obtained by making it harden | cure by heating for 5 hours. The resin plate had a size of 5 cm × 3 cm and a thickness of about 1 mm.

  The wavelength dependence of the light transmittance of this resin plate was measured at a slit width of 20 nm using an ultraviolet / visible / near infrared spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation). For comparison, a resin plate molded and cured using 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. The same measurement was performed on the molded and cured resin plate. The results are shown in FIG. As can be seen in FIG. 3, it was confirmed that the resin plate of this example had high transparency up to a low wavelength.

  Next, as shown in FIG. 4, the semiconductor light emitting device 2 having a peak emission wavelength of 380 nm is mounted on the bottom of the cavity 1a of the substrate 1, and the cage silsesquioxane compound obtained as described above is added to the cavity 1a. The semiconductor light-emitting element 2 was sealed by filling the inside and heating and curing at 200 ° C. for 5 hours to produce a semiconductor optical device. Then, the semiconductor light emitting device 2 was turned on with this semiconductor optical device at room temperature, and the maintenance rate of the luminous flux relative 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. As 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 to have high resistance.

  Based on this result, the lifetime defined by the time when the maintenance factor of the luminous flux 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.

Φ (t) = Φ (0) exp (− (t / τ) p)
Φ (t): luminous flux after t time, Φ (0): initial luminous flux, τ: time constant of deterioration, p: constant (Example 2)
1 g (1 mmol) of OHSS obtained in Example 1 was charged into a 100 ml Schlenk flask having a reflux condenser. The flask was heated under vacuum to remove residual air and moisture, then flushed with nitrogen, then 5 ml of toluene, 0.32 g (2.9 mmol) of 4-vinyl-1-cyclohexene, dimethylvinylethoxysilane. Was added to a 0.1 ml (Pt: 0.02 ppm) flask with 2 mM Pt (dcp) -toluene solution as a catalyst. The mixture was reacted at 90 ° C. with stirring for 4 hours, and then the solvent was evaporated in vacuum at room temperature to obtain 1.49 g (0.95 mmol) of white powder. The yield at this time was 95%.

As a result of analyzing the obtained reaction product by 1H-NMR spectrum and 13C-NMR spectrum, the structural formula is formula (1), A is a cyclohexenyl group, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ is a methyl group, m is 8, n is 3, p is 3, q is 2, and the structural formula is represented by the following [Chemical Formula 11] tris [cyclohexenylethyldimethylsiloxy] tris [dimethylsiloxy] Di [dimethylethoxysilylethyldimethylsiloxy] silsesquioxane was confirmed.

  Tris [cyclohexenylethyldimethylsiloxy] tris [dimethylsiloxy] di [dimethylethoxysilylethyldimethylsiloxy] silsesquioxane obtained as above was dissolved in THF solvent, and at 90 ° C. in the presence of water and HCl catalyst. It was hydrolyzed by heating for 6 hours. The composition obtained by concentrating the obtained hydrolyzate is poured into a 10 ml Teflon (registered trademark) mold, heated to 90 ° C. and melted, degassed under reduced pressure, and maintained at 200 ° C. while maintaining the vacuum. The resin plate was obtained by heating and curing by heating for 5 hours. The resin plate had a size of 5 cm × 3 cm and a thickness of about 1 mm.

  After the obtained tris [cyclohexenylethyldimethylsiloxy] tris [dimethylsiloxy] di [dimethylethoxysilylethyldimethylsiloxy] silsesquioxane was placed in a Teflon (registered trademark) mold and heated to 90 ° C. to melt And degassed under reduced pressure. Then, it heated at 90 degreeC for 30 minutes, the obtained solid content was melt | dissolved in the THF solvent, and it hydrolyzed at 90 degreeC for 6 hours by water and HCl catalyst presence. 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 × 3 cm and a thickness of about 1 mm.

  As a result, the tris [cyclohexenylethyldimethylsiloxy] tris [dimethylsiloxy] di [dimethylethoxysilylethyldimethylsiloxy] silsesquioxane obtained as described above was subjected to an addition reaction after hydrolysis polycondensation in curing. It was confirmed that it may be cured, or may be subjected to hydrolysis polycondensation after addition reaction.

(Example 3)
An apparatus equipped with a dropping funnel, a thermometer, and a reagent injection valve was assembled in a three-necked flask, and 376 ml of hexane, 33.8 ml of allyldimethylchlorosilane, and 4.3 ml of dimethylchlorosilane were charged into the three-necked flask. Next, the whole system in the three-necked flask was cooled with an ice bath so that the temperature was 5 ° C. or less, and after confirming that the temperature in the system was 5 ° C. or less, 140 ml of octaanion was added from the dropping funnel under a nitrogen stream. The solution was dropped at a rate of 1 to 2 drops / second. At this time, in order to substitute all eight dimethyl chlorosilanes and dimethyl chlorosilanes in all eight reaction sites of the octaanion, the compounding amount of allyl dimethyl chlorosilane and dimethyl chlorosilane must be set to a large excess with respect to the octaanion. There is.

  After completion of the dropping, the ice bath was removed, and the mixture was stirred at room temperature for 6 hours to react the octaanion with allyldimethylchlorosilane and dimethylchlorosilane as shown in [Chemical Formula 12]. The obtained reaction solution was extracted three times with hexane, and the hexane layer was dried with a desiccant (sodium sulfate) and then filtered with suction. The obtained filtrate was subjected to an evaporator to distill off hexane, and further, hexane was removed from the reaction product obtained by removing unreacted raw materials while heating at 45 ° C. with a vacuum pump, and purification was performed. A hexaallyl silsesquioxane having two groups was obtained.

Then, 1.04 g of hexaallyl silsesquioxane synthesized as in [Chemical Formula 12] is mixed with 0.24 g of tetramethyldisiloxane as a compound of the formula (2), and further a concentration of 3.0 × 10 ⁻³ mass% After adding 1 ppm of the Pt (cts) toluene solution of the whole system and mixing uniformly, it hardened | cured by heating at 120 degreeC in the air for 3 hours, and the colorless and transparent resin plate was obtained.

(Reference Example 1)
In the method of synthesizing hexaallyl silsesquioxane having two —SiH groups of [Chemical Formula 12] in Example 3, 19.8 ml of allyldimethylchlorosilane and 14.6 ml of dimethylchlorosilane were mixed with 376 ml of hexane. The tetraallyl silsesquioxane having four —SiH groups shown in the above [Chemical Formula 4] was synthesized by reacting and purifying in the same manner except that the octaanion was reacted.

Then, 1 ppm of a Pt (cts) toluene solution having a concentration of 3.0 × 10 ⁻³ mass% is added to the tetraallyl silsesquioxane of [Chemical Formula 4] and mixed uniformly, and then heated in air at 120 ° C. for 3 hours. To obtain a colorless and transparent resin plate.

  The resin plate obtained in Example 3 and Reference Example 1 was immersed in an acetone solution (RT), and stress cracking was evaluated based on whether the resin plate was cracked during immersion. As a result, the resin plate of Reference Example 1 in which the cage-type silsesquioxane compound was directly crosslinked was cracked instantaneously when immersed in an acetone solution, but the cage-type silsesquioxane compound was reacted with the reactive monomer. No cracking occurred in the resin plate of Example 3 crosslinked with 1.

Example 4
An apparatus equipped with a dropping funnel, a thermometer, and a reagent injection valve was assembled in a three-necked flask, and 376 ml of hexane, 14 ml of allyldimethylchlorosilane, and 18.7 ml of dimethylchlorosilane were charged into the three-necked flask. Next, the whole system in the three-necked flask was cooled with an ice bath so that the temperature was 5 ° C. or less, and after confirming that the temperature in the system was 5 ° C. or less, 140 ml of octaanion was added from the dropping funnel under a nitrogen stream. The solution was dropped at a rate of 1 to 2 drops / second. At this time, in order to substitute all eight dimethyl chlorosilanes and dimethyl chlorosilanes in all eight reaction sites of the octaanion, the compounding amount of allyl dimethyl chlorosilane and dimethyl chlorosilane must be set to a large excess with respect to the octaanion. There is.

  After completion of the dropping, the ice bath was removed, and the mixture was stirred at room temperature for 6 hours to react the octaanion with allyldimethylchlorosilane and dimethylchlorosilane as shown in [Chemical Formula 13]. The obtained reaction solution was extracted three times with hexane, and the hexane layer was dried with a desiccant (sodium sulfate) and then filtered with suction. The obtained filtrate was subjected to an evaporator to distill off hexane, and further, hexane was removed from the reaction product obtained by removing unreacted raw materials while heating at 45 ° C. with a vacuum pump, and purification was performed. A diallyl silsesquioxane having 6 groups was obtained.

Then, 1.137 g of divinyltetramethyldisiloxane as a compound of the formula (3) is added to 1.0 g of diallyl silsesquioxane synthesized as in [Chemical Formula 13], and further a concentration of 3.0 × 10 ⁻³ mass% A Pt (cts) toluene solution of 1 ppm was added to the whole system and mixed uniformly, and then cured by heating at 120 ° C. for 4 hours in air to obtain a colorless and transparent resin plate.

(Reference Example 2)
Attach a dropping funnel, thermometer, and reagent injection valve to the three-necked flask, and add 188 ml of hexane, 12.16 ml of dimethylhexenylchlorosilane, and 7.5 ml of dimethylchlorosilane to the three-necked flask. When the temperature in the system became 5 ° C. or less, 70 ml of octaanion was dropped from the dropping funnel at a rate of 1 to 2 drops / second. After completion of the dropwise addition, the ice bath was removed and the reaction was allowed to stir at room temperature for 6 hours. The obtained reaction solution was extracted three times with 40 ml of hexane, and the hexane layer was dried with a desiccant (sodium sulfate) and then filtered with suction. The obtained filtrate is evaporated to distill off hexane, and unreacted raw materials are removed from the obtained reaction product while heating at 50 ° C. with a vacuum pump for purification, as shown in [Chemical Formula 14]. Tetrahexenylsilsesquioxane having four na-SiH groups was obtained.

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

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 a 405 nm Blu-ray under the conditions of a power density of 1.1 W / mm ² and a spot size of 200 μm, and the time-dependent change of the irradiation screen enlarged image (far field image) was observed. did.

  FIG. 6A shows the change over time of the far field image of Example 4, and FIG. 6B shows the change over time of the far field image of Reference Example 2. As seen in FIGS. 6 (a) and 6 (b), compared with the reference example 2 in which silsesquioxane was directly crosslinked, the example 4 crosslinked with a reactive monomer was subjected to the irradiation before Blu-ray irradiation. There was little change in the far field image with respect to (0 hr), and almost no change after 240 hours irradiation (240 hr).

  FIG. 7A shows the senalmon observation of Example 4, and FIG. 7B shows the senalmon observation of Reference Example 2. In the case of Reference Example 2, a slight irradiation mark is observed at the center as shown in FIG. 7B, but in the case of Example 4, the irradiation mark is not observed at all as shown in FIG. 7A. It was.

  Therefore, it was confirmed that the thing of Example 4 which made the silsesquioxane bridge | crosslink and harden | cure with a reactive monomer has improved the Blu-ray irradiation tolerance.

  Moreover, the resin plate obtained in Example 4 and Reference Example 2 was immersed in an acetone solution (RT), and stress cracking was evaluated based on the presence or absence of cracking of the resin plate during immersion. As a result, the resin plate of Reference Example 2 was instantly cracked when immersed in an acetone solution, but the resin plate of Example 4 was not cracked.

It is a schematic sectional drawing which shows an example of embodiment of the semiconductor optical device of this invention. It is a figure which shows typically the three-dimensional crosslinked structure polymer which the cage-type silsesquioxane compound of this invention bridge | crosslinked. It is a figure which shows the wavelength dependence of the transmittance | permeability of Example 1. FIG. 2 is a schematic cross-sectional view illustrating a sealing method of Example 1. FIG. It is a figure which shows the light beam maintenance factor of Example 1. FIG. It is the figure which carried out the color printing of the far field image in the Blu-ray irradiation test, (a) is Example 4 and (b) is the reference example 2. FIG. It is the figure which color-printed the cenalmon observation in the Blu-ray irradiation test, (a) is Example 4 and (b) is Reference Example 2.

Explanation of symbols

2 Semiconductor light emitting device 3 Sealing material

Claims (6)

A silicon light-emitting device or a semiconductor light-receiving device comprising a cage-type silsesquioxane compound represented by the following formula (1) or a silicon compound containing a cage-type silsesquioxane compound partial polymer obtained by partial addition reaction of this compound. A semiconductor optical device characterized by being sealed.
(AR ¹ R ² SiOSiO _1.5 ) _n (R ³ R ⁴ HSiOSiO _1.5 ) _p (BR ⁵ R ⁶ SiOSiO _1.5 ) _q (HOSiO _1.5 ) _m- npq (1)
(In the formula (1), A is a group having a cyclohexenyl group , B is a substituted or unsubstituted saturated alkyl group or hydroxyl group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently It represents a functional group selected from a lower alkyl group, a phenyl group, and a lower arylalkyl group, m is a number selected from 6, 8, 10, and 12, n is an integer of 1 to m-1, and p is 1 to m. An integer of -n, q represents an integer of 0 to mnp) A 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 a compound represented by the following formula (2) The semiconductor optical device according to claim 1, wherein the semiconductor light-emitting element or the semiconductor light-receiving element is sealed with the compound to be used.
^{HR 7 R 8 Si-X-} SiHR 9 R 10 ... (2)
(In formula (2), X represents a divalent functional group or an oxygen atom, and R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom) A 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 a compound represented by the following formula (3) The semiconductor optical device according to claim 1, wherein the semiconductor light-emitting element or the semiconductor light-receiving element is sealed with the compound to be used.
_{H 2 C = CH-Y-} CH = CH 2 ... (3)
(In formula (3), Y represents a divalent functional group) A cage-type silsesquioxane compound represented by the following formula (1), or a silicon compound containing a cage-type silsesquioxane compound partial polymer obtained by partial addition reaction of this compound is polymerized. A transparent optical member.
(AR ¹ R ² SiOSiO _1.5 ) _n (R ³ R ⁴ HSiOSiO _1.5 ) _p (BR ⁵ R ⁶ SiOSiO _1.5 ) _q (HOSiO _1.5 ) _m- npq (1)
(In the formula (1), A is a group having a cyclohexenyl group , B is a substituted or unsubstituted saturated alkyl group or hydroxyl group, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently It represents a functional group selected from a lower alkyl group, a phenyl group, and a lower arylalkyl group, m is a number selected from 6, 8, 10, and 12, n is an integer of 1 to m-1, and p is 1 to m. An integer of -n, q represents an integer of 0 to mnp) A 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 a compound represented by the following formula (2) transparent optical member according to claim 4, a to that of compound, characterized by comprising polymerizing.
^{HR 7 R 8 Si-X-} SiHR 9 R 10 ... (2)
(In formula (2), X represents a divalent functional group or an oxygen atom, and R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom) A 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 a compound represented by the following formula (3) The transparent optical member according to claim 4, wherein the compound is polymerized.
_{H 2 C = CH-Y-} CH = CH 2 ... (3)
(In formula (3), Y represents a divalent functional group)