JP2008084986A - Sealant for optical semiconductor, and semiconductor optical device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealant for optical semiconductor which is scarcely deteriorated by heat or light and has a long life and a high refractive index. <P>SOLUTION: This sealant contains a cage silsesqioxane compound expressed by the following formula: (AR<SP>1</SP>R<SP>2</SP>SiOSiO<SB>1.5</SB>)<SB>n</SB>(BR<SP>3</SP>R<SP>4</SP>SiOSiO<SB>1.5</SB>)<SB>m-n</SB>(where, A denotes a group having hydrolysis nature, B denotes a substituent or non-substituent alkyl group or hydrogen, R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, and R<SP>4</SP>denote functional groups independently selected from lower alkyl group, phenyl group, and lower arylated alkyl group respectively, m denotes a number selected from 6, 8, 10, and 12, and n denotes an integer 2-m), or cage silsesqioxane compound partial hydrolyzate which is obtained by partially hydrolyzing this compound, and a Ti or Zr compound having two or more hydrolysis groups in the molecule, or partial hydrolyzate of this compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an optical semiconductor encapsulant made of a silsesquioxane compound and a semiconductor optical device encapsulated with the encapsulant.

  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.

  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.

  Furthermore, DVD devices are also required to improve 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 leather power has progressed. In this respect as well, there has been a problem that the sealing material tends to deteriorate when an epoxy-based sealing material is used.

  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.

  In order to solve the above problems, a silicone-based material has been studied as a sealing material excellent in heat resistance and weather resistance (see, for example, Patent Document 1).

However, the refractive index of silicone materials is as low as about 1.4 units, and there is a problem that it is difficult to use as a sealing material for optical systems that require a high refractive index. For example, in the case of a sealing material such as an LED, extraction of light emitted from the light emitting element is greatly influenced by the refractive index of the sealing material that seals the light emitting element, and the refractive index of the sealing material is 1.4 units. In this case, the efficiency of light emission extraction is nearly 30% lower than that when the refractive index is 1.7.
Japanese Patent No. 3412152

  The present invention has been made in view of the above points, and an object of the present invention is to provide an optical semiconductor sealing material that is hardly deteriorated against heat and light, has excellent lifespan, and has a high refractive index. In addition, an object of the present invention is to provide a semiconductor optical device having excellent durability and optical characteristics.

The sealing material for optical semiconductors according to claim 1 of the present invention is:
(AR ¹ R ² SiOSiO _1.5 ) _n (BR ³ R ⁴ SiOSiO _1.5 ) _mn (1)
(In formula (1), A is a hydrolyzable group, B is a substituted or unsubstituted alkyl group or hydrogen, R ¹ , R ² , R ³ and R ⁴ are each independently a lower alkyl group, a phenyl group, A functional group selected from lower arylalkyl groups, m is a number selected from 6, 8, 10, and 12, and n is an integer of 2 to m)
The cage-type silsesquioxane compound represented by the above formula (1), or a cage-type silsesquioxane compound partial hydrolyzate obtained by partial hydrolysis of this compound, and Ti having two or more hydrolyzable groups in the molecule Alternatively, it contains a Zr compound or a partial hydrolyzate of this compound.

  The above cage-type silsesquioxane compound has hydrolyzability because there are two or more hydrolyzable groups via a siloxane bond in the polyhedral silicon atom formed by silicon atoms and oxygen atoms. The group and the hydrolyzable group of other cage-type silsesquioxane compounds are crosslinked and cured by hydrolysis and polycondensation, and the nano-sized cage structure of silica is connected by organic segments. A three-dimensional cross-linked structure that exhibits a glass-like function, is hard to deteriorate even when used in the state of being irradiated with light in the blue / near ultraviolet region, and hardened by heat. Become. A high refractive index can be realized by incorporating Ti or Zr as part of a resin skeleton having a three-dimensional cross-linked structure of a cage silsesquioxane compound or into the resin.

  The invention of claim 2 is characterized in that in claim 1, it contains a complexing agent that forms a complex with a Ti or Zr compound having two or more hydrolyzable groups in the molecule.

  According to this invention, the reactivity of Ti or Zr compound can be adjusted, and Ti or Zr can be easily incorporated into a resin having a three-dimensional cross-linked structure of a cage silsesquioxane compound.

  Further, the invention of claim 3 is the hydrolysis of a Ti or Zr compound partially hydrolyzed Ti or Zr compound of claim 1 having two or more hydrolyzable groups in the molecule in the presence of a complexing agent. It is characterized by being made.

  According to this invention, the reactivity of Ti or Zr compound can be adjusted, and Ti or Zr can be easily incorporated into a resin having a three-dimensional cross-linked structure of a cage silsesquioxane compound.

The invention of claim 4
XSiR ⁵ R ⁶ R ⁷ (2)
(In formula (2), A represents a hydrolyzable group, R ⁵ , R ⁶ and R ⁷ each independently represents a hydrocarbon having 1 to 6 carbon atoms, a phenyl group or a derivative thereof)
The partial hydrolyzate of Ti or Zr compound according to claim 1 is obtained by reacting the partial hydrolyzate of Ti or Zr compound according to claim 3 with the compound of the above formula (2). Is.

  According to this invention, the reactivity of Ti or Zr compound can be adjusted, and Ti or Zr can be easily incorporated into a resin having a three-dimensional cross-linked structure of a cage silsesquioxane compound.

  According to a fifth aspect of the present invention, there is provided a semiconductor optical device comprising the sealing material according to any one of the first to fourth aspects, wherein the semiconductor light emitting element or the semiconductor light receiving element is sealed. .

  As described above, the encapsulant of the present invention hardly deteriorates against heat and light, has excellent lifespan, has a high refractive index, and can obtain a semiconductor optical device excellent in durability and optical characteristics. It can be done.

  According to the present invention, it is possible to obtain a sealing material for optical semiconductors that is not easily deteriorated against heat and light, has excellent lifespan, and has a high refractive index. It is possible to obtain a semiconductor optical device having excellent properties and optical characteristics.

  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, a predetermined electric circuit pattern 5 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 shown in FIG. 1, the semiconductor light emitting device 2 is used as the optical semiconductor and the semiconductor light emitting device 2 is sealed with the sealing material 3. However, the semiconductor light receiving device is sealed as the optical semiconductor. Needless to say, it may be a semiconductor light receiving device sealed with a material.

  In the present invention, the sealing material 3 includes a cage silsesquioxane compound represented by the following formula (1), or a cage silsesquioxane compound partial hydrolyzate obtained by partially hydrolyzing the compound. A silicon compound containing a Ti or Zr compound having two or more hydrolyzable groups in the molecule or a partial hydrolyzate of this compound is formed by crosslinking.

(AR ¹ R ² SiOSiO _1.5 ) _n (BR ³ R ⁴ SiOSiO _1.5 ) _mn (1)
In the above formula (1), A represents a hydrolyzable group and is not particularly limited as long as it is a hydrolyzable group. For example, an alkoxy group, an acetoxy group, an oxime group, an enoxy group And hydrolyzable groups such as amino group, aminoxy group, amide group and halogen. Among these, it is preferable to have an alkoxy group as a hydrolyzable group from the ease of hydrolysis. Moreover, what couple | bonded the divalent group which does not have hydrolyzability, and these hydrolyzable groups may be sufficient. Examples of this include a dimethylethoxysilylethyldimethylsiloxy group.

  In the above formula (1), B represents a substituted or unsubstituted alkyl group or hydrogen. As the substituted or unsubstituted alkyl group, for example, substituted or unsubstituted and not hydrolyzable Mention may be made of monovalent 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 and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; 2-phenylethyl group, Aralkyl groups such as 2-phenylpropyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; chloromethyl group, γ-chloropropyl group, 3, 3, Halogen-substituted hydrocarbon groups such as 3-trifluoropropyl group; substituted hydrocarbon groups such as γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl 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 hydrolysis.

In the above formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represents one functional group selected from a lower alkyl group, a phenyl group and a lower arylalkyl group. And alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group and propyl group, and arylalkyl groups having 7 to 10 carbon atoms such as phenyl group, benzyl group and phenethyl group. Among these, a methyl group is preferable from the viewpoint of reducing the steric hindrance of the reaction, and a phenyl group 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, and n represents an integer of 2 to m.

  Examples of the cage silsesquioxane compound include those represented by the following formulas (3) and (4).

The compound of the formula (3) is a compound in which m = 8, n = 8, R ¹ and R ² are methyl groups (Me) in the above formula (1), and is formed by a silicon atom and an oxygen atom. It has a structure in which a hydrolyzable group A is bonded to eight silicon atoms constituting a hexahedral structure via a siloxane bond (—Si—O—). In addition, the structural formula of Formula (3) simply represents that (—O—SiMe ₂ -A) is bonded to each of eight silicon atoms constituting a substantially hexahedral structure.

Further, the compound of the formula (4) is a compound in which m = 8, n = 4, R ¹ , R ² , R ³ , R ⁴ are methyl groups (Me) and B is hydrogen in the above formula (1), Of the eight silicon atoms constituting the substantially hexahedral structure formed of silicon atoms and oxygen atoms, a hydrolyzable group A is bonded to four silicon atoms via a siloxane bond (—Si—O—). The organic group having no hydrolyzability is bonded to the other four silicon atoms via a siloxane bond (—Si—O—). In addition, the structural formula of the formula (4) is that (—O—SiMe ₂ —A) is bonded to four silicon atoms one by one among the eight silicon atoms constituting the substantially hexahedral structure, and the other four The fact that (—O—SiMe ₂ H) is bonded to a silicon atom one by one is expressed in a simplified manner.

  On the other hand, the Ti or Zr compound having two or more hydrolyzable groups in the molecule is not particularly limited as long as it has a hydrolyzable group. For example, an alkoxy group, an acetoxy group, an oxime And Ti or Zr compounds having a hydrolyzable group such as a group, enoxy group, amino group, aminoxy group, amide group and halogen. Among these, it is preferable to have an alkoxy group as a hydrolyzable group from the ease of hydrolysis. The Ti or Zr compound having two or more hydrolyzable groups in the molecule is not particularly limited, but titanium tetrabutoxide, titanium propoxide, titanium tetraisopropoxide, zirconium tetrabutoxide, zirconium tetraiso Various alkoxides such as propoxide can be exemplified.

  This Ti or Zr compound may contain a complexing agent (ligand) that forms a complex with the Ti or Zr compound in order to match the reactivity with the silsesquioxane compound. The complexing agent (ligand) is not particularly limited as long as the reactivity is suppressed, and examples thereof include β diketones such as acetylacetone and ethyl acetoacetate, alkoxy alcohols such as ethoxyethanol and butoxyethanol, and acetic acid. be able to.

  The Ti or Zr compound may be a partially hydrolyzed product obtained by hydrolyzing a Ti or Zr compound having two or more hydrolyzable groups in the molecule in the presence of a complexing agent.

  The blending ratio of the Ti or Zr compound to the silsesquioxane compound is not particularly limited, but is preferably in the range of 10 to 70% by mass ratio.

  Further, as the Ti or Zr compound, a compound obtained by reacting the compound of the following formula (2) with a partial hydrolyzate of the Ti or Zr compound may be used.

XSiR ⁵ R ⁶ R ⁷ (2)
In the above formula (2), X represents a hydrolyzable group and is not particularly limited as long as it is a group that can be hydrolyzed. For example, an alkoxy group, an acetoxy group, an oxime group, an enoxy group And hydrolyzable groups such as a group, amino group, aminoxy group, amide group and halogen.

In the above formula (2), R ⁵ , R ⁶ and R ⁷ are each independently a hydrocarbon having 1 to 6 carbon atoms, a phenyl group or a derivative thereof. Among these, R ⁵ , R ⁶ , and R ⁷ are preferably substituted or unsubstituted alkyl groups. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group Group, alkyl group such as octyl group: cycloalkyl group such as cyclopentyl group and cyclohexyl group; aralkyl group such as 2-phenylethyl group, 2-phenylpropyl group and 3-phenylpropyl group; aryl such as phenyl group and tolyl group Group: alkenyl group such as vinyl group and allyl group; halogen-substituted hydrocarbon group such as chloromethyl group, γ-chloropropyl group, 3,3,3-triple propyl group; γ-methacryloxydipropyl group, γ- Examples include substituted hydrocarbon groups such as glycidoxydipropyl group, 3,4-epoxycyclohexylethyl group, and γ-mercaptopropyl group can do. Among these, the alkyl group of hydrocarbons 1-4 is preferable from the viewpoint of reducing steric hindrance during hydrolysis.

  Specific examples of the compound of the above formula (2) are not particularly limited, and examples thereof include methoxytrimethylsiloxane and chlorotrimethylsiloxane. The addition ratio when the compound of formula (2) is reacted with Ti or Zr compound is not particularly limited, but the mass ratio of the compound of formula (2) to 30 to 90 with respect to Ti or Zr compound. It is preferable to set so as to be in the range of%.

Next, a method for synthesizing a composite oxide composed of the above cage silsesquioxane compound and a Ti or Zr compound 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 cage silsesquioxane compound having a hydrolyzable group such as an ethoxy group by reacting with a silane compound having both a hydrolyzable functional group such as dimethylvinylethoxysilane and an unsaturated group. Can be prepared. The octaanion can be obtained by reacting tetramethylammonium hydroxide with tetraethoxysilane.

  Further, by reacting a mixture of a reactive halogen having hydrolyzability and chlorohydridodimethylsilane with an octaanion, a part of eight silicon atoms constituting a substantially hexahedral structure formed of silicon atoms and oxygen atoms. A cage-type silsesquioxane compound in which a hydrolyzable group is bonded to hydridodimethylsiloxy group is bonded to another silicon atom can be prepared.

  Further, by reacting a mixture of hydrolyzable reactive halogen and chlorotrimethylsilane with octaanion, a part of eight silicon atoms constituting a substantially hexahedral structure formed of silicon atoms and oxygen atoms is formed. A cage-type silsesquioxane compound in which a group having hydrolyzability is bonded and a trimethylsiloxy group is bonded to another silicon atom can be prepared.

  Since the cage silsesquioxane compound obtained as described above has two or more hydrolyzable groups (A) (in formula (1), n is 2 or more), an acid catalyst such as HCl. This hydrolyzable group can be cross-linked and cured by hydrolysis and polycondensation with hydrolyzable groups of other cage silsesquioxane compounds. Then, a three-dimensional cross-linked product is formed. Then, the hydrolyzate of the cage silsesquioxane compound is Ti selected from various alkoxides of Ti and Zr such as titanium tetrabutoxide, titanium propoxide, titanium tetraisopropoxide, zirconium tetrabutoxide and zirconium tetraisopropoxide. Alternatively, a Zr compound can be added in the presence of a complexing agent such as acetylacetone or ethyl acetoacetate and hydrolytically condensed to obtain a cage silsesquioxane-containing three-dimensional crosslinked product incorporating Ti and Zr. It can be done.

  In addition, in advance, Ti or Zr compounds selected from various alkoxides of Ti and Zr such as titanium tetrabutoxide, titanium propoxide, titanium tetraisopropoxide, zirconium tetrabutoxide, zirconium tetraisopropoxide, acetylacetone, ethyl acetoacetate, etc. A complexing agent is added and stirred to synthesize and hydrolyze a Ti or Zr complex partially leaving an alkoxide group, and the hydrolyzate of the cage silsesquioxane compound is converted into a partially hydrolyzed product of the Ti or Zr compound. In addition to the above, a three-dimensional cross-linked product of a cage-type silsesquioxane incorporating Ti and Zr can also be obtained by hydrolytic condensation together.

  Furthermore, the partial hydrolyzate of the Ti or Zr complex leaving a part of the alkoxide group has a formula (2) such as an alkylsilane having only one hydrolyzable group such as methoxytrimethylsilane or chlorotrimethylsilane. By reacting the above compound and suppressing (or eliminating) the hydrolysis reaction activity of the Ti or Zr complex, and hydrolyzing and condensing it together with the hydrolyzate of the cage silsesquioxane compound, A three-dimensional cross-linked product of cage-type silsesquioxane incorporating Ti or Zr can be obtained.

  The cage-type silsesquioxane three-dimensionally crosslinked product incorporating Ti or Zr obtained as described above has an inorganic material in which silicon atoms constituting the polyhedral structure of silsesquioxane are bonded to four oxygen atoms. It has a structure close to that of glass, and is hardly deteriorated even when used in the state of being irradiated with light in the blue / near ultraviolet region, and is also hardly deteriorated against heat. Further, since Ti or Zr is incorporated into the three-dimensional cross-linked product of the cage silsesquioxane, the refractive index can be increased.

  And, as a sealing material for sealing the optical semiconductor, when a conventionally used light-transmitting epoxy resin, polyester, polyacrylate, organopolysiloxane, etc. are used, the presence of crosslinks and absorbing groups contained in these Therefore, an unnecessary absorption peak is likely to appear in a required spectral region. However, when the cage-type silsesquioxane compound of the present invention and Ti or Zr compound are used, such an absorption peak is small and a good blue color is obtained. It becomes a sealing material having transparency of light and ultraviolet light, and has little deterioration against heat, and becomes a sealing material with excellent lifetime. Further, since the refractive index is high, it becomes a sealing material having a high light extraction rate when sealing the optical semiconductor.

  In encapsulating an optical semiconductor using the encapsulant of the present invention comprising a cage silsesquioxane compound and Ti or Zr compound, hydrolysis of the cage silsesquioxane compound and Ti or Zr compound Any method can be adopted without particular limitation as long as the crosslinking proceeds by polycondensation, and the reaction may be carried out using an addition reaction catalyst such as a tin catalyst or an amine catalyst as necessary. Anyway. Here, the encapsulant made of the cage silsesquioxane compound and Ti or Zr 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. It can be easily stopped.

  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 hydrolyzate of a sesquioxane compound or a cage silsesquioxane compound can be obtained. Even when these compounds are used, they are crosslinked by hydrolysis polycondensation with other cage-type silsesquioxane compounds, etc., and three-dimensional crosslinking having a polyhedral structure formed of silicon atoms and oxygen atoms in the skeleton. It forms the structure. Moreover, a transparent optical member such as a lens or a prism is manufactured by using a sealing material composed of the cage silsesquioxane compound of the present invention and a Ti or Zr compound as a molding material, and molding and polymerizing and curing the molding material. Is something that can be done. In the above explanation, it has been explained that a Ti or Zr compound having two or more hydrolyzable groups in the molecule or a partial hydrolyzate of this compound is used, but in addition to this, a hydrolyzable group in the molecule. It may contain a solid substance such as Ti or Zr compound, titanium oxide, and zirconia.

  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, liquid separation was performed, and the hexane layer was dehydrated and dried to obtain white solid octakis [hydridodimethylsiloxy] silsesquioxane (OHSS).

  Next, 10 g (10 mmol) of the above OHSS was added to a 250 ml Schlenk flask having a reflux condenser. The flask was gradually heated under vacuum to remove residual air and moisture and then purged with nitrogen. Next, 50 ml of tetrahydrofuran (THF), 3.91 g (30 mmol) of dimethylvinylethoxysilane, and catalyst As a result, 0.1 ml of 2 mM Pt (dvs) -toluene solution was added. The mixture was reacted with stirring at 90 ° C. for 5 hours, and then the solvent was removed to obtain 11.2 g (74 mmol) of a transparent viscous liquid. As a result of analyzing the obtained reaction product by 1H-NMR spectrum and 13C-NMR spectrum, it is a cage silsesquioxane in which the structural formula is formula (1), A is an ethoxy group, and B is hydrogen. Was confirmed.

  Next, the cage-type silsesquioxane compound obtained as described above was replaced with a THF solvent, and then hydrolyzed at 90 ° C. for 6 hours in the presence of water and an HCl catalyst. The hydrolyzate thus obtained was mixed with 10 g of a Ti complex partial hydrolyzate.

The synthesis of the Ti complex partial hydrolyzate is as follows. First, 130 ml of isopropyl alcohol and 11.9 g (35 mmol) of titanium tetrabutoxide (Ti (OBu) ₄ ) were added to a 250 ml flask, and 9.1 g (70 mmol) of ethyl acetoacetate was added thereto and stirred for 8 hours. A yellow solution was obtained. Next, the solution in the flask was cooled to about 5 ° C., and 3.7 g of water and 20 ml of isopropyl alcohol mixed with HCl catalyst (0.1 mol / l) were added dropwise. After completion of the dropwise addition, the mixture was stirred for 10 minutes in an ice bath, the ice bath was removed while continuing stirring, the mixture was further stirred at room temperature for 2 hours, and the reaction was allowed to proceed to complete the stirring at room temperature. Filtration gave a pale yellow solution.

  And by distilling off the solvent of the mixture of the above-mentioned cage silsesquioxane compound hydrolyzate and Ti complex partial hydrolyzate at room temperature and gradually curing it to 120 to 200 ° C., light yellow transparent A cured product was obtained.

  When the cured product there was produced as a thin film on a glass plate and its refractive index was measured with an ellipsometer, a value of around 1.54 was obtained.

(Example 2)
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 116 ml of methylphenylchlorosilane were added to a 1000 ml flask equipped with a reflux tube and a dropping funnel and stirred. The dropping funnel was charged with an octaanion / methanol aqueous solution, the solution in the flask was cooled to about 5 ° C., and the octaanion / methanol solution was added dropwise at about 5 ° C. in a nitrogen atmosphere. About 2 hours after the start of dropping, 334 ml of octaanion / methanol tetramethylammonium hydroxide 334 ml, methanol 164 ml, and water 123 ml were added and stirred. 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 reaction was further continued by stirring at room temperature for 6 hours. After stirring for 6 hours, liquid separation was performed and the hexane layer was dehydrated and dried to obtain a viscous liquid octakis [hydridomethylphenylsiloxy] silsesquioxane.

  Next, 12 g (10 mmol) of the above-mentioned octakis [hydridomethylphenylsiloxy] silsesquioxane was added to a 250 ml Schlenk flask having a reflux condenser. The flask was gradually heated under vacuum to remove residual air and moisture, and then purged with nitrogen. Next, 50 ml of tetrahydrofuran (THF), 3.91 g (30 mmol) of dimethylvinylethoxysilane, and a catalyst were used. 0.1 ml of 2 mM Pt (dvs) -toluene solution was added. And after making this mixture react at 90 degreeC for 5 hours stirring, the solvent was removed and the transparent viscous liquid 11.2g was obtained.

  Next, the cage-type silsesquioxane compound obtained above was substituted with a THF solvent, and then hydrolyzed at 90 ° C. for 6 hours in the presence of water and an HCl catalyst. 20 g of a Ti complex partial hydrolyzate was mixed with the obtained hydrolyzate.

The synthesis of the Ti complex partial hydrolyzate is as follows. First, 130 ml of isopropyl alcohol and 11.9 g (35 mmol) of titanium tetrabutoxide (Ti (OBu) ₄ ) were added to a 250 ml flask, and 9.1 g (70 mmol) of ethyl acetoacetate was added thereto, followed by stirring for 8 hours. Solution was obtained. Next, the solution in the flask was cooled to about 5 ° C., and 3.7 g of water and 20 ml of isopropyl alcohol mixed with HCl catalyst (0.1 mol / l) were added dropwise. After completion of the dropwise addition, stirring in an ice bath was continued for 10 minutes, then the ice bath was removed, and the reaction was allowed to proceed by further stirring at room temperature for 2 hours. After completion of stirring at room temperature, the reaction product was filtered. A pale yellow solution was obtained.

By distilling off the solvent of the mixture of the above-mentioned cage silsesquioxane compound hydrolyzate and Ti complex partial hydrolyzate at room temperature and gradually curing from 120 ° C. to 200 ° C., a pale yellow transparent A cured product was obtained.

  When this hardened | cured material was created as a thin film on the glass plate and the refractive index was measured with the ellipsometer, the value around 1.70 was obtained.

  Here, the refractive index of the original condensation cured product of the silsesquioxane is 1.53, whereas the refractive index of about 1.54 in Example 1 is 1. A refractive index of around 70 was obtained, and it was confirmed that the refractive index was improved.

It is a schematic sectional drawing which shows an example of embodiment of the semiconductor optical device of this invention.

Explanation of symbols

2 Semiconductor light receiving element 3 Sealing material

Claims (5)

(AR ¹ R ² SiOSiO _1.5 ) _n (BR ³ R ⁴ SiOSiO _1.5 ) _mn (1)
(In formula (1), A is a hydrolyzable group, B is a substituted or unsubstituted alkyl group or hydrogen, R ¹ , R ² , R ³ and R ⁴ are each independently a lower alkyl group, a phenyl group, A functional group selected from lower arylalkyl groups, m is a number selected from 6, 8, 10, and 12, and n is an integer of 2 to m)
The cage-type silsesquioxane compound represented by the above formula (1), or a cage-type silsesquioxane compound partial hydrolyzate obtained by partial hydrolysis of this compound, and Ti having two or more hydrolyzable groups in the molecule Or the sealing material for optical semiconductors containing a Zr compound or the partial hydrolyzate of this compound.   The encapsulant for optical semiconductors according to claim 1, further comprising a complexing agent that forms a complex with Ti or Zr compound having two or more hydrolyzable groups in the molecule.   The partial hydrolyzate of Ti or Zr compound according to claim 1 is obtained by hydrolyzing a Ti or Zr compound having two or more hydrolyzable groups in the molecule in the presence of a complexing agent. A sealing material for optical semiconductors. XSiR ⁵ R ⁶ R ⁷ (2)
(In formula (2), A represents a hydrolyzable group, R ⁵ , R ⁶ and R ⁷ each independently represents a hydrocarbon having 1 to 6 carbon atoms, a phenyl group or a derivative thereof)
The partial hydrolyzate of Ti or Zr compound according to claim 1 is obtained by reacting the partial hydrolyzate of Ti or Zr compound according to claim 3 with the compound of the above formula (2). Sealing material for optical semiconductors.   5. A semiconductor optical device comprising a semiconductor light-emitting element or a semiconductor light-receiving element sealed with the sealing material according to claim 1.

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