JP5204394B2 - 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>, A denotes a chain-like hydrocarbon group having carbon-carbon unsaturated linkage, B denotes a substituted or unsubstituted saturated 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 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 containing a partial polymer of this compound. <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.

A semiconductor optical device according to claim 1 of the present invention includes 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 , A compound containing a compound represented by the following formula (2) , wherein the semiconductor light emitting device or the semiconductor light receiving device is 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 Formula (1), A is a chain hydrocarbon group having a carbon-carbon unsaturated bond, B is a substituted or unsubstituted saturated alkyl group or hydroxyl group, R ¹ , R ² , R ³ , R ⁴ , R ^5. , R ⁶ each independently 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 1 to m−1. Integer, p is an integer from 1 to mn, q is an integer from 0 to mnp )
^{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 semiconductor optical device according to claim 2 of the present invention is 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, A compound containing a compound represented by the following formula (3), wherein the semiconductor light emitting device or the semiconductor light receiving device is 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 Formula (1), A is a chain hydrocarbon group having a carbon-carbon unsaturated bond, B is a substituted or unsubstituted saturated alkyl group or hydroxyl group, R ¹ , R ² , R ³ , R ⁴ , R ^5. , R ⁶ each independently 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 1 to m−1. Integer, p is an integer from 1 to mn, q is an integer from 0 to mnp)
_{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 3 of the present invention is 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 compound containing a compound represented by the following formula (2).
(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 Formula (1), A is a chain hydrocarbon group having a carbon-carbon unsaturated bond, B is a substituted or unsubstituted saturated alkyl group or hydroxyl group, R ¹ , R ² , R ³ , R ⁴ , R ^5. , R ⁶ each independently 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 1 to m−1. Integer, p is an integer from 1 to mn, q is an integer from 0 to mnp )
^{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 transparent optical member according to claim 4 of the present invention is 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 compound containing a compound represented by the following formula (3) .
(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 Formula (1), A is a chain hydrocarbon group having a carbon-carbon unsaturated bond, B is a substituted or unsubstituted saturated alkyl group or hydroxyl group, R ¹ , R ² , R ³ , R ⁴ , R ^5. , R ⁶ each independently 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 1 to m−1. Integer, p is an integer from 1 to mn, q is an integer from 0 to mnp)
_{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. Hydrosilylation reaction with a chain hydrocarbon group having a carbon-carbon unsaturated bond of another cage silsesquioxane compound because it has a chain hydrocarbon group having a carbon unsaturated bond Then, it is crosslinked and cured by addition polymerization to form a three-dimensional crosslinked structure in which silica nano-sized cage structures are connected by organic segments, and expresses a glass-like function. Even if it is used in the state of being irradiated with light in the blue / near ultraviolet region, it is hard to deteriorate and becomes a cured product with low water absorption. Moreover, the chain hydrocarbon group having a carbon-carbon unsaturated bond has less steric hindrance than the cyclic hydrocarbon group, the crosslinking reaction by the hydrosilylation reaction proceeds efficiently, and there are few unreacted residues in the cured product. Thus, the resistance to Blu-ray irradiation is improved.

  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 chain hydrocarbon group having a carbon-carbon unsaturated bond, and includes a carbon-carbon double bond or a carbon-carbon triple bond as part of the group. If there is no particular limitation. Examples thereof include those containing an alkenyl group and an alkynyl group. Examples of the group containing an alkenyl group or alkynyl group include a group having a carbon-carbon double bond such as a vinyl group and an allyl group, and ethynyl. And groups having a carbon-carbon triple bond such as a group and a propynyl group. Moreover, the group which the group which has a carbon-carbon double bond or a carbon-carbon triple bond, and the bivalent group which does not have an unsaturated group may also be mentioned. In addition, it is preferable to have the position of the carbon-carbon unsaturated bond of the chain hydrocarbon group which has these carbon-carbon unsaturated bonds in the terminal from the point of reducing the steric hindrance at the time of hydrolysis.

  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). A group A is bonded to four silicon atoms through a siloxane bond (—O—Si—) out of eight silicon atoms that constitute a substantially hexahedral structure formed of silicon atoms and oxygen atoms. It has a structure in which hydrogen atoms are bonded to the other four silicon atoms via siloxane bonds (—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 chain hydrocarbon having a carbon-carbon unsaturated group such as 1-hexenyl in the molecule is reacted in an amount less than an equivalent amount, whereby an unsaturated chain carbonized group is partially converted into a hydridodimethylsiloxy group. A chain group having a carbon-carbon unsaturated bond is bonded to a part of eight silicon atoms constituting an approximately hexahedron structure formed by silicon atoms and oxygen atoms by adding a hydrogen group to another silicon. A cage-type silsesquioxane compound represented by the formula (4) in which a hydridodimethylsiloxy group is bonded to an atom can be prepared. The octaanion can be obtained by reacting tetramethylammonium hydroxide with tetraethoxysilane.

  Also formed by reacting a mixture of reactive halogen-carbon reactive groups such as dimethylvinylchlorosilane, dimethylallylchlorosilane, dimethylhexenylchlorosilane and chlorohydridodimethylsilane with octaanion to form silicon and oxygen atoms. A chain group having a carbon-carbon unsaturated bond is bonded to a part of eight silicon atoms constituting the substantially hexahedral structure, and a hydridodimethylsiloxy group is bonded to another silicon atom. A cage-type silsesquioxane compound such as 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 is an unsaturated group contained in the chain hydrocarbon having a carbon-carbon unsaturated bond of another cage silsesquioxane compound and hydrosilyl group. It undergoes a chemical reaction and is crosslinked by addition polymerization to cure and form a three-dimensional crosslinked 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. Further, in [Chemical Formula 2], A in formula (1) is a hexenyl group, m = 8, n = 4, p = 4, q = 0, and R ¹ , R ² , R ³ , and R ⁴ are methyl groups The cross-linking of the type silsesquioxane compound is shown. In the cage silsesquioxane of [Chemical Formula 2], four hydrogen atoms are bonded to eight silicon atoms having a substantially hexahedral structure via a siloxane bond, and four hexenyls are bonded via a siloxane bond. A group is bonded, and a hydrogen atom and an unsaturated group of hexenyl are crosslinked by a hydrosilylation reaction. 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. . 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. 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.

Here, when the cage silsesquioxane compound is crosslinked by a hydrosilylation reaction between a hydrogen atom and an unsaturated group as described above, the present inventors have previously used a group having a carbon-carbon unsaturated bond of A. A cage-type silsesquioxane compound into which a cyclic hydrocarbon group such as cyclic vinyl has been introduced has been studied. In [Chemical Formula 3], as a cage silsesquioxane compound corresponding to Formula (1), A in Formula (1) is a cyclohexenyl group, and m = 8, n = 4, p = 4, q = 0. , R ¹ , R ² , R ³ , and R ⁴ represent a silsesquioxane in which a methyl group is present, and four hydrogen atoms are bonded to eight silicon atoms having a substantially hexahedral structure through a siloxane bond. In addition, four cyclohexenyl groups are bonded via a siloxane bond. A cage silsesquioxane compound can be crosslinked and cured by hydrosilylation reaction of a hydrogen atom and an unsaturated group of cyclohexenyl.

  However, the cyclic hydrocarbon has a large steric hindrance, and the cross-linking reaction between the carbon-carbon unsaturated bond of cyclohexenyl and the hydrogen atom (-C = C / -SiH) is difficult to proceed. Unreacted groups are likely to remain as residues in the crosslinked cured product. If unreacted groups remain in the cured product in this way, there is a possibility that problems such as resistance to Blu-ray irradiation of the cured product may occur.

  On the other hand, by using a cage silsesquioxane compound in which a chain hydrocarbon group such as chain vinyl is introduced as a group having a carbon-carbon unsaturated bond of A as in the present invention, steric hindrance is unlikely to occur. Thus, the crosslinking reaction between the hydrogen atom and the carbon-carbon unsaturated bond is remarkably promoted, 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 having high durability such as Blu-ray irradiation resistance can be obtained.

  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.

  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 silsesquioxane compound that is 0 is subjected to a crosslinking reaction, there is no functional group having an affinity for —OH covering the surface of the heavy metal sol.

  Therefore, in this case, a silsesquioxane compound having an —OH group, in which mnpq is 1 or more in the formula (1), is used. As shown in the following [Chemical Formula 5], the dispersibility of the heavy metal sol can be enhanced by the affinity between the —OH group of the silsesquioxane compound and the —OH group covering the heavy metal sol. A cured product of a cage silsesquioxane compound having a uniform high refractive index can be obtained by uniformly dispersing an oxan compound and a heavy metal sol.

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, A compound with p = 3 and q = 0, and an allyl group is bonded to three silicon atoms constituting a substantially hexahedral structure formed of silicon atoms and oxygen atoms through siloxane bonds (—O—Si—). In addition, hydrogen 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 having a hydroxyl group 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] is obtained by reacting allyldimethylchlorosilane and dimethylchlorosilane with an octaanion as shown in [Chemical Formula 10] and [Chemical Formula 14] 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) and a compound of formula (3) are 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 compounds having a methyl group, and among eight silicon atoms constituting an approximately hexahedral structure formed by 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 the stress cracking of the cured product and can improve the toughness, and can improve the irradiation resistance against short wavelength high energy light such as Blu-ray.

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

Example 1
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 at all eight reaction sites of the octaanion, the compounding amount of allyl dimethyl chlorosilane and dimethyl chlorosilane is set to a large excess with respect to the octaanion. There is a need.

  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 10]. 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, the unreacted raw material was removed from the reaction product obtained by removing hexane by heating at 45 ° C. with a vacuum pump, and purified to obtain —SiH. A diallyl silsesquioxane having 6 groups was obtained.

  A dropping funnel, a thermometer, and a reagent injection valve were attached to the three-necked flask, and 188 ml of hexane, 12.16 ml of dimethylhexenylchlorosilane, and 7.5 ml of dimethylchlorosilane were added to the three-necked flask. Next, the whole system in the three-necked flask was cooled with an ice bath so as to be 5 ° C. or less, and when the temperature in the system became 5 ° C. or less, 70 ml of octaanion was added at 1 to 2 drops / second from the dropping funnel. It was dripped at a speed. At this time, in order to substitute dimethylhexenylchlorosilane and dimethylchlorosilane for all eight reaction sites of the octaanion, it is necessary to set the blending amount of dimethylhexenylchlorosilane and dimethylchlorosilane to a large excess with respect to the octaanion. There is.

  After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature for 6 hours to react the octaanion with dimethylhexenylchlorosilane and dimethylchlorosilane as shown in [Chemical Formula 11]. 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. By evaporating the obtained filtrate to distill off hexane and further removing hexane from the reaction product obtained by removing unreacted raw materials while heating at 45 ° C. with a vacuum pump, purification is performed. A tetrahexenylsilsesquioxane having four —SiH groups was obtained.

Then, as in [Chemical Formula 12], 0.4 g of diallyl silsesquioxane and 0.8 g of tetrahexenyl silsesquioxane are blended, and a Pt (cts) toluene solution having a concentration of 3.0 × 10 ⁻³ mass% is further added. Then, 1 ppm of the whole system was added and mixed uniformly, and then cured by heating in air at 120 ° C. for 4 hours to obtain a colorless and transparent resin plate.

(Comparative 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 represented by the following [Chemical Formula 13], wherein m is 8, n is 4, p is 4, 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 resin plate obtained in Example 1 and the resin plate obtained in Comparative Example 1 were evaluated for BluRay irradiation resistance. In the test, each resin plate was irradiated with 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 irradiated portion screen enlarged image (far field image) was observed, and senalmon was observed.

  FIG. 3A shows the change over time of the far field image of Example 1, and FIG. 3B shows the change of the far field image of Comparative Example 1 over time. As seen in FIGS. 3 (a) and 3 (b), in Comparative Example 1 where A in the formula (1) is cyclic vinyl, the center of the far field image becomes darker after irradiation 48hr, whereas the formula ( In Example 1 in which 1) A is a chain-end terminal vinyl, there is no change in the center of the far field image even after irradiation for 183 hours, and no significant change is observed in the entire far field image.

  4A shows the senalmon observation of Example 1, and FIG. 4B shows the senalmon observation of Comparative Example 1. FIG. The thing of the comparative example 1 has an irradiation trace like FIG.4 (b), and a damage is seen. On the other hand, some damage is observed in Example 1 after irradiation for 183 hours as shown in FIG. 4A, but the damage is extremely small compared to that in Comparative Example 1.

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

(Example 2)
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 at all eight reaction sites of the octaanion, the compounding amount of allyl dimethyl chlorosilane and dimethyl chlorosilane is set to a large excess with respect to the octaanion. There is a need.

  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 14]. 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, the unreacted raw material was removed from the reaction product obtained by removing hexane by heating at 45 ° C. with a vacuum pump, and purified to obtain —SiH. A hexaallyl silsesquioxane having two groups was obtained.

Then, 1.04 g of hexaallyl silsesquioxane synthesized as in [Chemical Formula 14] is blended 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.

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

(Reference Example 1)
In Example 2, in the method for synthesizing hexaallyl silsesquioxane having two —SiH groups of [Chemical Formula 14], 19.8 ml of allyldimethylchlorosilane and 14.6 ml of dimethylchlorosilane were mixed with 376 ml of hexane. Then, except that the octaanion was reacted, tetraallylsilsesquioxane having four —SiH groups shown in the above [Chemical Formula 4] was synthesized by reacting and purifying in the same manner.

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 plates obtained in Examples 2 to 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 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. Cracks did not occur in the resin plates of Example 2 and Example 3 crosslinked with 1.

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 the figure which carried out the color printing of the far field image in the Blu-ray irradiation test, (a) is Example 1, (b) is the comparative example 1. FIG. It is the figure which color-printed Senarmon observation in the Blu-ray irradiation test, (a) is Example 1, (b) is Comparative Example 1.

Explanation of symbols

1 Semiconductor Light Emitting Device 3 Sealing Material

Claims (4)

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, and a compound represented by the following formula (2). A semiconductor optical device comprising a semiconductor light-emitting element or a semiconductor light-receiving element sealed with a 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 Formula (1), A is a chain hydrocarbon group having a carbon-carbon unsaturated bond, B is a substituted or unsubstituted saturated alkyl group or hydroxyl group, R ¹ , R ² , R ³ , R ⁴ , R ^5. , R ⁶ each independently 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 1 to m−1. Integer, p is an integer from 1 to mn, q is an integer from 0 to mnp)
^{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) Cage silsesquioxane compound represented by the following following formula (1), or a polyhedral oligomeric silsesquioxane compounds partially polymerized product which this compound has partial addition reaction, and a compound represented by the following formula (3) in compounds containing, semi-conductor light device characterized by comprising sealing the semiconductor light-emitting element or a semiconductor light receiving device.
(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 Formula (1), A is a chain hydrocarbon group having a carbon-carbon unsaturated bond, B is a substituted or unsubstituted saturated alkyl group or hydroxyl group, R ¹ , R ² , R ³ , R ⁴ , R ^5. , R ⁶ each independently 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 1 to m−1. Integer, p is an integer from 1 to mn, q is an integer from 0 to mnp)
_{H 2 C = CH-Y-} CH = CH 2 ... (3)
(In formula (3), Y represents a divalent functional group) Cage silsesquioxane compound represented by the following following formula (1), or a polyhedral oligomeric silsesquioxane compounds partially polymerized product which this compound has partial addition reaction, and a compound represented by the following formula (2) A transparent optical member obtained by polymerizing a contained 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 Formula (1), A is a chain hydrocarbon group having a carbon-carbon unsaturated bond, B is a substituted or unsubstituted saturated alkyl group or hydroxyl group, R ¹ , R ² , R ³ , R ⁴ , R ^5. , R ⁶ each independently 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 1 to m−1. Integer, p is an integer from 1 to mn, q is an integer from 0 to mnp)
^{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 following 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) A transparent optical member obtained by polymerizing a compound to be polymerized.
(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 Formula (1), A is a chain hydrocarbon group having a carbon-carbon unsaturated bond, B is a substituted or unsubstituted saturated alkyl group or hydroxyl group, R ¹ , R ² , R ³ , R ⁴ , R ^5. , R ⁶ each independently 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 1 to m−1. Integer, p is an integer from 1 to mn, q is an integer from 0 to mnp)
_{H 2 C = CH-Y-} CH = CH 2 ... (3)
(In formula (3), Y represents a divalent functional group)