TW201313829A - Organic-inorganic hybrid prepolymer containing phenyl group, heat resistant organic-inorganic hybrid material and element sealed structure - Google Patents

Abstract

Provided is a heat resistant organic-inorganic hybrid material, wherein the provided organic-inorganic hybrid prepolymer is prepared by subjecting a dehydration condensation of a polydimethylsiloxane and an alkoxide of metal and/or semimetal, and a phenyl group is introduced to all or part of the polydimethylsiloxane and/or the alkoxide of metal and/or semimetal.

Description

Organic-inorganic hybrid material containing phenyl group and heat-resistant organic-inorganic hybrid material and component sealing structure

The present invention relates to a phenyl-containing organic-inorganic hybrid prepolymer and a heat-resistant organic-inorganic hybrid material and a component seal which can be used for a heat-resistant organic-inorganic hybrid material such as a heat-resistant elastic material and a high-temperature heat-generating element sealing material. structure.

Conventionally, a heat-resistant material is used for a film, an adhesive tape, a semiconductor element, or a wiring sealing material for insulating or fixing an electronic component or an electrical component requiring heat resistance. A representative material of the above heat resistant material is an anthrone resin. The above fluorenone resin is generally known as an elastic material having heat resistance, low cost, and high safety. Recently, an organic-inorganic hybrid composition in which an inorganic component is introduced into an fluorenone resin to improve the properties of the above fluorenone resin has been developed.

The organic-inorganic hybrid composition is a material having properties such as flexibility, water repellency, and release property of an fluorenone resin as an organic component, and properties such as heat resistance and thermal conductivity of the inorganic component (for example, Non-Patent Document 1) This material has high heat resistance and flexibility at 200 ° C or higher, and excellent properties such as high electrical insulation or low electrical conductivity at high frequencies (Patent Documents 1 to 4).

[Previous Technical Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 1-113429

[Patent Document 2] Japanese Patent Laid-Open No. 2-182728

[Patent Document 3] Japanese Patent Laid-Open No. 4-227731

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-292970

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2009-164636

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2009-024041

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2004-128468

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2010-118578

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2010-010505

[Patent Document 10] Japanese Patent Laid-Open Publication No. 2004-107652

[Patent Document 11] Japanese Patent Laid-Open Publication No. 2005-320461

[Non-Patent Document 1] G. Philipp and Schmidt, J. Non-Cryst. Solids 63, 283 (1984)

As described above, the above-mentioned organic-inorganic hybrid material is incorporated in a laser diode (LED), an LED (Light Emitting Diode), and an LED print head (LPH, LED Print Head). In the case of a semiconductor element or a wiring sealing material in a charge coupled device (CCD), a IGBT (Insulated Gate Bipolar Transistor) or the like.

As a semiconductor used in these electronic components, a Si semiconductor has been conventionally used, but recently, a SiC semiconductor or a GaN semiconductor has been used instead of the Si semiconductor.

The SiC semiconductor or the GaN semiconductor is expected to be a low-power, high-efficiency power supply element, a high-frequency element, and a semiconductor element excellent in radioactivity resistance, compared with the conventional Si semiconductor. Therefore, in addition to electricity, transportation, and home appliances, there is a high demand in the field of the universe and atomic energy. Recently, semiconductors used in hybrid vehicles have been studied.

For example, compared with Si semiconductor, the SiC semiconductor has a bandgap of 3.25 ev which is 3 times wider. Compared with Si semiconductor, the GaN semiconductor has a band gap of 3 times wider, and the electric field strength of the dielectric breakdown is 3 MV/cm. It is nearly 10 times larger, has excellent thermal conductivity, heat resistance, and chemical resistance, and is also more resistant to radioactivity than Si semiconductors. Therefore, a part of IGBTs or MOSFETs recently used for converter circuits or switching power supplies have been replaced with SiC semiconductors or GaN semiconductors. Thereby achieving high integration and high speed data processing.

However, since the SiC semiconductor or the GaN semiconductor generates high heat of about 200 ° C to 250 ° C, when the conventional organic-inorganic hybrid material is used as a sealing material, the organic-inorganic hybrid material is deteriorated in flexibility due to thermal deterioration. Thus, a phenomenon such as cracking or peeling of the sealing material occurs, and various problems such as deterioration of the sealing material occur, and problems such as loss of transparency or light transmittance of the sealing material occur.

The present invention has been made to solve the above conventional problems, and an object of the present invention is to provide a heat-resistant organic-inorganic hybrid material which can be used as a sealing material in which an element of a SiC semiconductor or a GaN semiconductor is assembled, and the present invention is a polydimethyl methoxyoxane ( Polydimethylsiloxane), and an organic-inorganic hybrid prepolymer prepared by dehydration polycondensation reaction of a metal and/or a semi-alkoxide (alkoxide), the key being the above polydimethyl siloxane, and/or the above A phenyl-containing organic-inorganic hybrid prepolymer having a phenyl group introduced into a part or all of the metal and/or semimetal alkoxide.

If necessary, as the above metal and/or semimetal alkoxide, an oligomer of the above metal and/or semimetal alkoxide can be used.

Specifically, the polydimethyl methoxyoxane to which the phenyl group is introduced is a phenyl group-containing polydimethyl siloxane having the following formula (Chemical Formula 1), a metal into which the phenyl group is introduced, and/or The semimetal alkoxide is a phenyl group-containing alkoxide having the following formula (Chem. 2).

[Chemical 1]

However, R ₁ and R ₂ in the above formula are a linear or branched alkyl group having 1 to 4 carbon atoms, R ₁ and R ₂ are the same or different alkyl groups, and k and l are integers of 1 to 10, m and n are integers of 1 to 300.

[Chemical 2]

However, R in the above formula is a linear or branched alkyl group having 1 to 4 carbon atoms, and R may be the same, partially different, or all different.

Further, the oligomer of the above metal and/or semimetal alkoxide is an alkoxide oligomer having the following formula (Chemical Formula 3).

[Chemical 3]

However, R in the above formula is a linear or branched alkyl group having 1 to 4 carbon atoms, R is an alkyl group which is the same or different, and n is an integer of 4 to 6.

Further, it is preferred to add a third butanol and/or 2-ethoxyethanol as a stabilizing solvent to the phenyl group-containing organic-inorganic hybrid prepolymer.

In the present invention, there is further provided an organic-inorganic hybrid material which is heat-resistant by a gelled product obtained by heating and gelling a phenyl group-containing organic-inorganic hybrid prepolymer. The heat-resistant organic-inorganic hybrid material preferably has a hardness of 80° or less after 1000 hours in an environment of 250° C. by a Shore-E-durometer.

Further, in the present invention, there is provided an element sealing structure in which the heat-resistant organic-inorganic hybrid material is used as a sealing material to seal a heat-generating element. For example, SiC and/or GaN as a semiconductor are incorporated in the above-described heat generating element.

[effect]

In the present invention, polydimethyl methoxyoxane as a raw material of the organic-inorganic mixed prepolymer, and/or phenyl-containing polydimethyl methoxy oxane to which a phenyl group is introduced into a metal and/or a semimetal alkoxide is used. And/or a metal containing a phenyl group and/or a semimetal alkoxide.

The above phenyl group-containing polydimethyl siloxane has the following structure.

[Phenyl-containing polydimethyloxane]

In the above structure, the oxime bond (-Si-O-Si-) is not easily cut by heat by the steric hindrance effect of the phenyl group (C ₆ H ₅ -) and the electron attracting effect.

The following structure exists in the above-mentioned phenyl group-containing metal and/or semimetal alkoxide.

[Alkyl salt containing a phenyl group and/or a semimetal]

In the above structure, by the steric hindrance effect of the phenyl group (C ₆ H ₅ -) and the electron attracting effect, the two ROs at the two coordination sites of Si are not easily hydrolyzed by heat.

Therefore, the phenyl group-containing organic-inorganic hybrid material of the present invention has a main chain or a side chain which is cut by heat, but is restricted by containing a phenyl group, so that it is hard to be decomposed and deteriorated by heat, and is stable to heat. .

[efficacy]

Therefore, the phenyl-containing organic-inorganic hybrid material of the phenyl-containing organic-inorganic hybrid prepolymer gel of the present invention is excellent in heat resistance as a seal for an element in which a SiC semiconductor or a GaN semiconductor which generates high-temperature heat is assembled. Materials are extremely useful.

[definition] (semimetal)

An element of the periodic table that is close to a metal element, also known as a metalloid. Boron, bismuth, antimony, arsenic, antimony, selenium, tellurium, etc.

[Change rate]

The ratio of the oligosaccharide group introduced into the oligomer at both ends or one end of the PDMS by a condensation reaction. For example, a modification rate of 50% means that 50% of the thiol groups contained in the PDMS are introduced with an oligomer.

[mass average molecular weight]

The mass average molecular weight of PDMS was determined by gel permeation chromatography (Gel Permeation Chromatography GPC method). Polystyrene was used as a standard sample and the molecular weight converted to polystyrene was measured.

[Phenyl-containing organic-inorganic hybrid prepolymer]

The phenyl group-containing organic-inorganic hybrid prepolymer (hereinafter, simply referred to as a phenyl group-containing prepolymer) of the present invention is generally exemplified as the following (1) to (5).

In the following description, polydimethyl methoxy oxane is abbreviated as PDMS, phenyl group-containing polydimethyl methoxy oxane is abbreviated as phenyl group-containing PDMS, and organic-inorganic mixed prepolymer is simply referred to as prepolymer. The metal and/or semimetal alkoxide is abbreviated as an alkoxide, and the phenyl group-containing metal and/or semimetal alkoxide is abbreviated as a phenyl group-containing alkoxide.

(1) Prepolymer I obtained by dehydration polycondensation reaction of phenyl group-containing PDMS and alkoxide

(2) Prepolymer II obtained by dehydration polycondensation reaction of phenyl group-containing PDMS and phenyl group-free PDMS, and phenyl group-free alkoxide

(3) Prepolymer III obtained by dehydration polycondensation of PDMS and phenyl containing alkoxide

(4) Prepolymer IV obtained by dehydration polycondensation reaction of phenyl group-containing PDMS and phenyl group-containing alkoxide

(5) Prepolymer V obtained by dehydration polycondensation reaction of phenyl group-containing PDMS and phenyl group-free PDMS, and phenyl group-containing alkoxide.

The above alkoxide or phenyl group-containing alkoxide may also be an oligomer of a plurality (usually 4 to 6) of alkoxide or a phenyl group-containing alkoxide bonded by polycondensation.

Hereinafter, the raw materials used in the phenyl group-containing prepolymer of the present invention will be described.

[Polydimethyloxane (PDMS)]

The PDMS used in the present invention has a sterol group reactive with a metal and/or a semimetal alkoxide at both ends or at one end, and is represented by the following formula.

(a) Two-terminal sterol-based PDMS

(b) Single-end sterol-based PDMS

Here, in the above chemical formula, R is an alkyl group, and l is an integer of 50 or more.

The mass average molecular weight of the PDMS is preferably 1,500 or more and 100,000 or less.

[PDMS with phenyl]

As a phenyl group-containing PDMS, a single condensation polymer comprising: a phenyl-methyl oxirane in which one methyl group of dimethyloxane is substituted with a phenyl group, and the above phenyl-methyl decane and Co-condensation polymer of dimethyloxane.

The most preferred phenyl group-containing PDMS is a block co-condensation polymer composed of the above phenyl-methyl methoxy olefin condensation polymer block and a dimethyl methoxy olefin condensation polymer block. The above block co-condensation polymer is represented by the following general formula.

[Chemical 1]

However, in the above formula, R ₁ and R ₂ are a linear or branched alkyl group having 1 to 4 carbon atoms, R ₁ and R ₂ are the same or different alkyl groups, and k and l are integers of 1 to 10, m and n are integers of 1 to 300.

[Metal and / or semi-metal alkoxide]

The alkoxide of the above metal and/or semimetal has the following general formula.

M(OR) ₄

Here, the M-based metal or semi-metal, R is an alkyl group having 4 or less carbon atoms, and the above-mentioned four alkyl groups may be the same, or may be partially different or all different.

The type of metal and/or semimetal of the metal and/or semimetal alkoxide used in the present invention may, for example, be cerium, boron, aluminum, titanium, vanadium, manganese, iron, cobalt, zinc, lanthanum or cerium. , alkoxides of zirconium, hafnium, yttrium, lanthanum, cadmium, lanthanum, tungsten, etc., the best metal and / semi-metal lanthanum, titanium, zirconium.

Further, the type of the alkoxide is not particularly limited, and examples thereof include a methoxide, an ethoxide, a n-propoxide, an isopropoxide, a n-butoxide, an isobutoxide, a second butoxide, and a third. Butanol, methoxyethanolate, ethoxyethanolate, etc., but from the viewpoint of stability and safety, it is preferred to use an ethanol salt, a propoxide or an isopropoxide.

As the alkoxide of such metals and/or semimetals, it is especially preferable to use a decyl alkoxide which is easily obtained and stably exists in the atmosphere.

For example, the above sterol salt may, for example, be a tetraalkoxy decane such as tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetraisopropoxy decane or tetrabutoxy decane; Methyltrimethoxydecane, methyltriethoxydecane, methyltripropoxydecane, methyltributoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, n-propyltrimethyl Trialkyloxydecanes such as oxydecane, n-propyltriethoxydecane, isopropyltrimethoxydecane, isopropyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane class. Among them, tetraethoxy decane (TEOS), triethoxymethyl decane (TEOMS), tetrapropoxy decane, tetraisopropoxy decane, tetrabutoxy decane or the like is preferred.

Preferred among the alkoxides of other metals include tetra-iso-propoxide titanium (TTP) and tetra-propoxide zirconium (ZTP).

[Oligomers of metal and/or semimetal alkoxides]

The oligomer of the metal and/or semimetal alkoxide (hereinafter, simply referred to as an oligomer) used in the present invention is a low condensate of a metal and/or a semimetal alkoxide, and has the following general formula.

Here, the M-based metal or semi-metal, R is an alkyl group having 4 or less carbon atoms, and the alkyl group may be the same, or may be partially different or all different, and p is an integer of 4 to 6.

The above oligomers have lower volatility than metal and/or semimetal alkoxide monomers, and the density of functional groups (sterol groups) is smaller, so compared to metal and/or semimetal alkoxides. The monomer is less reactive.

[Phenyl-containing metal and/or semimetal alkoxide]

The phenyl group-containing alkoxide is represented by the chemical formula 2, which is an alkoxide in which one of the four alkoxy groups of the above alkoxide is substituted by a phenyl group.

[Chemical 2]

However, R in the above formula is a linear or branched alkyl group having 1 to 4 carbon atoms, and R may be the same, may be partially different, or all different.

[Oligomers of phenyl-containing metals and/or semimetal alkoxides]

The phenyl group-containing alkoxide oligomer has the following four types.

(oligomer I)

(oligomer II)

(oligomer III)

(oligomer IV)

Here, the M-based metal or semi-metal, R is an alkyl group having 4 or less carbon atoms, and the alkyl group may be the same, or may be partially different or all different, and p is an integer of 4 to 6.

[Manufacture of organic-inorganic hybrid prepolymer sol]

In the present invention, as described above, the above-mentioned phenyl group-containing PDMS, or phenyl group-free PDMS (hereinafter referred to as (phenyl group-containing) PDMS), and the above-mentioned phenyl group-containing alkoxide or oligomer or not An alkoxide or oligomer of phenyl group (hereinafter referred to as (containing phenyl) alkoxide (oligomer)) is dehydrated and polycondensed to form a phenyl-containing organic-inorganic hybrid prepolymer. In this dehydration polycondensation reaction, hydrolysis of the sterol group of the above (containing phenyl) alkoxide (oligomer) is accompanied.

In the above dehydration polycondensation reaction, stannousoctoate, dibutyl tin dilaurate, dibutyltin di-2-ethylhexoate, ortho-benzene are usually used. A condensation catalyst such as sodium phenolate or tetra(2-ethylhexyl) titanate.

In the above dehydration polycondensation reaction, in order to stably hydrolyze (containing phenyl) PDMS or (containing phenyl) alkoxide (oligomer), the container used in the reaction is filled with an inert gas. Hydrolysis and condensation are preferably carried out by heating. The inert gas may, for example, be nitrogen or an 18th element (cerium, neon, argon, neon, xenon, etc.) as a rare gas. Also, it is also possible to use these gases in combination.

a phenyl-containing prepolymer in the presence of the above-mentioned condensation catalyst by using a mixture containing the above (containing phenyl) alkoxide (oligomer) and the above (containing phenyl) PDMS in the presence of the above-mentioned inert catalyst It is prepared by performing hydrolysis and polycondensation reaction (that is, dehydration polymerization reaction). The above (containing phenyl) alkoxide (oligomer) is more easily hydrolyzed in the presence of water than the above (phenyl-containing) PDMS, so that the alkoxy group of the above (containing phenyl) alkoxide (oligomer) becomes Highly reactive sterol group (-OH).

That is, the alkoxy group of the above (containing phenyl) alkoxide (oligomer) which has been hydrolyzed becomes an -OH group, and is heated by a phenolic group at the end of the (containing phenyl) PDMS in the presence of an inert gas. The dehydration polycondensation reaction occurs. When an oligomer is used as the above alkoxide, the condensation reaction of PDMS and the hydrolyzed oligomer can be smoothly carried out without accelerating the individual condensation of the alkoxide. The condensation reaction proceeds smoothly by the homogeneous reaction of the above oligomer and the above (phenyl group-containing) PDMS.

In other words, the hydrolysis reaction of the unnecessary oligomer caused by the presence of moisture in the air is suppressed by the hydrolysis reaction and the polycondensation reaction in the atmosphere of the inert gas, and the phenyl group containing the phenyl group as the organic component is promoted. A condensation reaction between an alcohol group and a plurality of alkoxy groups as an inorganic component (containing a phenyl group) oligomer, thereby smoothly producing a phenyl group-containing organic-inorganic hybrid prepolymer as a sol.

Further, a low molecular weight decane which is a problem in (containing phenyl) PDMS is contained in a phenyl group-containing organic-inorganic hybrid prepolymer or volatilized upon heating, so it exists as a monomer in prepolymerization. The amount of low molecular weight oxane in the material becomes extremely small or becomes completely absent.

According to the above, the phenyl-containing organic-inorganic hybrid prepolymer sol obtained from the present invention, or the phenyl-containing organic-inorganic hybrid gel (hardened material) which has been gelated by the above prepolymer sol Among them, since there is no culster as an inorganic component, it is possible to provide a heat-resistant bonding material, a heat-resistant sealing material, or a heat conductive material which is higher in quality than conventional ones.

[mixing ratio]

The compounding ratio (A/B) of the above (including phenyl) PDMS (A) and the above (containing phenyl) alkoxide or oligomer (B) is set to a molar ratio of 0.1 to 10 as a molar ratio. It is preferably from 0.5 to 1.5, more preferably from 0.8 to 1.2.

When the Mohr of A/B exceeds 10, for example, the sol becomes unstable, so that gelation is liable to occur, and the gelation is liable to shrink. On the other hand, when the molar amount of A/B is less than 0.1, the dehydration-polycondensation reaction does not proceed smoothly, and gelation is unlikely to occur, so that low molecular weight decane will remain.

[Component Seal Construction]

The element related to the present invention mainly refers to an element formed of a semiconductor, or an element in which a semiconductor is assembled, or an element in which the above element is mounted on a substrate. The above elements are a transistor, a diode, a rectifying element, a negative resistance (NDR) element, a photoelectric element, a photoconductive element, a light emitting element, a magnetoelectric element, or a logic element incorporated in a logic device.

For example, in the above-mentioned photovoltaic element, photoconductive element, light-emitting element, or the like, in the light-emitting and light-receiving element (collectively referred to as an optical element), the light-emitting surface or the light-receiving surface is covered with a sealing material in order to protect the light-emitting surface or the light-receiving surface.

Further, in the component mounted on the substrate, the terminal provided on the surface of the substrate and the terminal provided on the component are electrically connected by wire bonding, but the component and the wiring are simultaneously covered by the sealing material.

[Method of manufacturing components]

In the present invention, a method of fabricating an element of a semiconductor element mounted on the substrate will be described by way of an example of an optical element.

When an element of an optical element is mounted on the surface of the substrate, first, the optical element is mounted on the surface of the substrate using a mounting machine that is generally sold in the market. When there is a terminal under the optical element, wiring is sometimes unnecessary. However, when a terminal is provided on the upper surface of the optical element, the terminal provided on the surface of the substrate and the terminal provided on the optical element are electrically connected by a wiring.

Then, at least on the light-emitting surface and/or the light-receiving surface of the optical element, a sealing material containing the phenyl-containing prepolymer of the present invention as a main component is applied and sealed. At this time, care must be taken not to allow air bubbles to enter the above-mentioned sealing material. The method of applying the sealing material is not particularly limited, but generally, as described later, it is preferable to use a coating device capable of quantitatively applying (sealing) the sealing material. The seal can also be sealed in such a way that the seal material covers the entire light element.

Thereafter, the element to which the sealing material is applied is placed in a high-temperature furnace (also referred to as an oven) and heated to gel the sealing material to form a solid or semi-solid gel, and the gel The above-mentioned sealing material is formed into a desired shape.

Further, as a method of gelling the sealing material, a method of mixing an additive (curing agent) in the sealing material and gelling it without heating may be employed.

The fluorenone resin or the organic-inorganic hybrid composition used in the prior art deteriorates white turbidity or yellowing over time, so that it is difficult to find foreign matter adhering to the surface of the sealing material, and if a defect occurs inside, It is difficult to analyze the cause of the problem. However, the sealing material made of the phenyl-containing organic-inorganic hybrid material of the present invention does not deteriorate over time, and is always colorless and transparent, so that foreign matter can be easily found. Further, the sealing material of the present invention can maintain the transparency and light transmittance of the sealing material even after long-term irradiation with near ultraviolet rays. Further, even in a high-temperature environment of 200 ° C to 250 ° C, the sealing material of the present invention does not cause cracking or peeling such as cracking due to high heat generated by semiconductor elements such as SiC or GaN. The problem of deterioration of components, disconnection of wiring, and deterioration of insulation does not occur, so that high-quality semiconductor elements can be provided.

[Examples]

The invention will be more specifically illustrated by the examples.

In the examples, "parts" and "%" are not described in terms of quality (mass parts, mass%).

Further, the manufacturing method capable of controlling the reforming rate is not limited to the illustrated embodiment. The evaluation of the reforming rate in the examples was carried out by using SHODEX GPC-101 manufactured by Showa Denko Co., Ltd. for molecular weight measurement. The fractionation tube used was connected to K-806M and K-802.5 manufactured by SHODEX.

Further, the present invention is not limited to the embodiments.

[Example 1] [Manufacture of PDMS-TEPS Organic-Inorganic Mixed Prepolymer A (Prepolymer III)]

In a reaction vessel (a flask having a plurality of insertion ports) equipped with a stirring device, a thermometer, and a dropping tube, nitrogen gas as an inert gas was used, and nitrogen gas was sufficiently filled in the reaction vessel. At this time, nitrogen gas manufactured by a nitrogen gas production apparatus (UNX-200, manufactured by Japan Unix Corporation) was used.

Next, in the above-mentioned reaction vessel which is sufficiently filled with nitrogen, a dimethyl alcohol oxime which is a phenyl group-free PDMS (YF3057, which has an average molecular weight equivalent to 32,000, is added to the reaction vessel which is sufficiently filled with nitrogen gas. Further, triethoxyphenyl decane (TEPS) (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a phenyl group-containing alkoxide, is added in an amount of 2 mol to the above-mentioned PDMS.

In addition, 0.1 mol of hydrazine (2-ethylhexyl) titanate (manufactured by Matsumoto Fine Chemical Co., Ltd.) was diluted with a dehydrated ethanol (manufactured by Wako Pure Chemical Industries Co., Ltd.) to a concentration of 5 times, and then dropped into the reaction container. The mixture was stirred at room temperature (23 ° C to 25 ° C) for 30 minutes to obtain a raw material liquid A.

Further, in the raw material liquid A, 3 parts by weight (3 wt%) of the third butanol as a stabilizing solvent was added dropwise to the PDMS under a nitrogen atmosphere, and the mixture was stirred for 30 minutes to obtain a prepolymer 1.

[Manufacture of Prepolymer B (Prepolymer II) using PDMS containing phenyl]

In a reaction vessel (a flask having a plurality of insertion ports) equipped with a stirring device, a thermometer, and a dropping tube, nitrogen gas as an inert gas was used, and nitrogen gas was sufficiently filled in the reaction vessel. At this time, nitrogen gas manufactured by a nitrogen gas production apparatus (UNX-200, manufactured by Japan Unix Corporation) was used.

Next, 1 mol of phenyl group-containing PDMS (YF3804, manufactured by Momentive Co., Ltd., average molecular weight equivalent to 6000) was added to the reaction vessel sufficiently filled with nitrogen gas, and 2 mol of the above was used for the purpose of improving the reaction. Tetraethoxy decane oligomer (n=4 to 6) ethyl silicate (manufactured by Tama Chemical Industry Co., Ltd., citrate 40 n=4 to 6 or citrate 45 n=6 To 8), and a polydimethyl oxane (YF3905, manufactured by Momentive Co., Ltd., YF3905, having an average molecular weight of 20,000) which is equivalent to 1 mol of a phenyl group-free PDMS having a sterol group at both ends or one end. Raw material liquid B was obtained.

Further, in the raw material liquid B, 3 parts by weight (3 wt%) of the third butanol as a stabilizing solvent was added dropwise to the PDMS under a nitrogen atmosphere, and the mixture was stirred for 30 minutes to obtain a prepolymer 2.

[Evaluation 1] (Evaluation sheet 1)

The sol of the prepolymer A prepared in the present Example 1 was injected into a mold surface-treated with tetrafluoroethylene/perfluoroalkoxy vinyl ether copolymer (PFA) in such a manner as to be 4 mm thick after completion ( In the case of 15 mm □), the temperature was raised from normal temperature of 23 ° C to 250 ° C over 10 hours, and then subjected to a dry baking treatment for 2 hours. Thereafter, it was separated from the mold to form a sheet 1 for evaluation (150 mm in width × 150 mm in length × 4 mm in thickness).

(Evaluation sheet 2)

The sol of the prepolymer B prepared in the present Example 1 was injected into a PFA surface-treated mold (15 mm □) in a manner of reaching a thickness of 4 mm after completion, and was heated from a normal temperature of 23 ° C to 250 over 10 hours. After °C, the dry baking treatment was maintained for 2 hours. Thereafter, it was separated from the mold to form a sheet 2 for evaluation (150 mm in width × 150 mm in length × 4 mm in thickness).

[Comparative Example 1] (previous prepolymer)

In a reaction vessel equipped with a stirring device, a thermometer, and a dropping tube, 1.0 g of ethyl decanoate (manufactured by Tama Chemical Industry Co., Ltd., citrate 40 n = 4 to 6 or citrate 45 n = 6 to 8) Further, in the atmosphere (room temperature), 32.0 g of PDMS (mass average molecular weight; equivalent to 32,000) (HBSIL039 manufactured by Arakawa Chemical Co., Ltd.) modified with both ends of ethyl citrate was stirred and mixed together. In a minute, a raw material liquid A of the mixture was obtained.

Then, the raw material liquid A was stirred and mixed by dropping 0.93 g of the necessary amount of water over 1 hour in the hydrolysis step and the condensation step.

Thereafter, the mixture was naturally cooled to room temperature by stirring for about 30 minutes to prepare a conventional prepolymer sol.

The conventional prepolymer sol prepared as the above-mentioned comparison was injected into a PFA surface-treated mold (15 mm□) so as to have a thickness of 4 mm after completion, and was heated from a normal temperature of 23 ° C to 250 ° C over 10 hours. Further, a dry baking treatment was carried out for 2 hours. Thereafter, it was separated from the mold to form a comparative sample sheet 1 (150 mm in width × 150 mm in length × 4 mm in thickness).

[evaluation method] (heat resistance temperature evaluation)

The heat-resistant temperature is a convection drying oven in which the evaluation sheet and the comparative sample sheet are each stored in an atmosphere at 250 ° C, and the electronic balance is used at regular intervals up to 500 hours (New Classic MF by Mettler Toledo Co., Ltd. (Model: ML204) Measurement, the change rate of weight relative to the original weight was measured [[weight change rate = (initial weight - current weight) / initial weight] × 100]

(hardness measurement evaluation)

For the hardness measurement evaluation, the evaluation sheet and the comparative sample sheet are each stored in a convection drying oven at 250 ° C in the atmosphere, and soft rubber (based on JIS K 6253, ISO 7619) is used at regular intervals. Hardness) The hardness was measured using an E-type hardness tester.

[evaluation result]

The heat-resistant temperature evaluation results are shown in the graph of Fig. 1.

According to the graph of Fig. 1, it is possible to determine the comparative sample sheet 1 formed by the evaluation sheets 1 and 2 and the conventional mixed composition of the mixed material of the present invention (referred to as the sample sheet 1 in the drawing) For comparison, the comparative sample sheet 1 formed of the conventional mixed composition was subjected to weight reduction in a short period of time at 250 ° C, and cracked (fractured) occurred in 200 hours, but was formed of the mixed material of the present invention. The sheet 1 for evaluation showed a gentle weight reduction even in an environment of 250 ° C, and thus exhibited heat resistance maintenance of 500 hours or more, and the sheet 2 for evaluation showed a gentle weight reduction even in an environment of 250 ° C. And the weight reduction rate after only 500 hours passed was only below 4%, thereby showing its excellent thermal stability.

Further, it is understood that the mixed material of the present invention can be obtained by introducing a phenyl group, thereby obtaining a cured product having less reactivity and having less unreacted portions, and improving heat resistance characteristics due to thermal stability of the phenyl group in the molecule.

That is, the sheet 1 for evaluation can be determined, and a hardened material having low hardness and high flexibility can be obtained by stabilizing a phenyl group derived from a phenyl group-containing alkoxide, and the sheet 2 for evaluation is obtained from The stabilizing action of the phenyl group of the phenyl group-containing PDMS can obtain a high hardness, heat stable cured product.

The results of the hardness measurement evaluation are shown in the graph of Fig. 2.

According to the graph of Fig. 2, the comparative sample sheet 1 formed by the evaluation sheets 1 and 2 of the mixed material of the present invention and the conventional mixed composition can be identified (referred to as the sample sheet 1 in the drawing) In comparison, the comparative sample sheet 1 made of the conventional mixed composition promoted the surface polycondensation reaction in an environment of 250 ° C, and the hardness increased in a short time, and cracking (fracture) occurred in 200 hours. Further, after 200 hours passed, the hardness of the comparative sample sheet 1 was measured, and after 437 hours passed, the range which can be measured by the E-type durometer was exceeded, that is, the maximum hardness measurement range of 80 was exceeded.

Further, it can be confirmed that the sheet 1 for evaluation prepared from the mixed material of the present invention exhibits a hardness within a range of usable hardness of 80 ° C or less which is equivalent to a comparative sample sheet obtained by the conventional mixed composition even in an environment of 250 ° C. The sheet 2 for evaluation which is formed by the mixed material of the present invention has no hardness change even in an environment of 250 ° C, and the hardness change after only 500 hours is only about +10 °. Further, the sheet 1 for evaluation was hardly changed to have a hardness of 60 or less after 700 hours in an environment of 250 ° C, and the sheet 2 for evaluation was hardly maintained at 70 or less after 500 hours in an environment of 250 ° C.

Further, it is possible to determine the mixed material of the present invention, and by introducing a phenyl group, it is possible to obtain a cured product having less reactivity, an unreacted portion, and an improved heat resistance property due to thermal stability of the phenyl group in the molecule.

That is, the sheet 1 for evaluation made of the mixed material of the present invention is thermally stable over a long period of time, and can maintain a low hardness after passing for 500 hours or more at 250 ° C, and can maintain a low level of 60 or less after 1000 hours at 250 ° C. hardness. Further, the evaluation sheet 2 made of the mixed material of the present invention has almost no change in hardness even after storage at 250 ° C for 500 hours, and maintains a low hardness of 70 or less after 1000 hours at 250 ° C, and is thermally stable. Excellent in sex, less thermal decomposition and no abnormal heat. This means that intense decomposition, volatilization, heat generation, and the like due to thermal decomposition do not occur, and it can be said that it is an effective characteristic as a heat-resistant component.

From the above, the mixed material of the present invention can be determined, and among the two items evaluated, the characteristics are higher than those of the conventional mixed composition.

Further, it can be confirmed that the mixed material of the present invention does not cause cracking (fracture) or the like after 1000 hours in an environment of 250 ° C, and the hardness measured by the Shore-E hardness meter is preferably 80 or less, and preferably 75 or less. , 70 or less is the best.

[Modification]

The present invention is not limited to the above-described embodiments, and those having ordinary knowledge in the art can be changed, deleted, or added without departing from the technical idea of the present invention from the scope of the patent application and the description.

In the above embodiments, it is not limited thereto, and metal and/or semimetal alkoxides of different types/characteristics may be used.

Different molecular weight distributions can also be used for PDMS. For example, if a PDMS having a uniform molecular weight distribution with a narrow molecular weight distribution is used, a mixed composition having a very small unreacted portion can be obtained, and characteristics excellent in hardness or surface water repellency can be exhibited.

In the above embodiment, the organic-inorganic hybrid compound is coated with a sol to form a solid or semi-solid (colloidal) molded article, and the organic-inorganic hybrid prepolymer sol is coated on a disk such as a mold. And hardened (gelled) by dry baking treatment. The shape to be formed is not particularly limited, and is generally formed into a sheet shape or a plate shape.

Further, the inert gas used for the replacement may be a purity of 80% or more and a moisture content of 20% or less.

When the organic-inorganic hybrid material of the present invention is used as a heat-resistant elastic material, for example, a composite ceramic filler for the purpose of imparting thermal conductivity, and an adjustable scale-shaped insulating filler for the purpose of imparting electrical insulation.

Further, in optical applications requiring transparency, it is possible to harden a single material without mixing a filler or the like.

In the bonding application, it is provided in a semi-hardened state for the purpose of curing by heat treatment at the time of use.

According to the synthesis method of the present invention, the modification rate can be set in various applications such as a sealing material, a binder, a heat conductive sheet, and an insulating sheet, thereby providing a mixed prepolymer sol suitable for the purpose of use.

The application technique of the organic-inorganic hybrid prepolymer of the present invention can also be applied to a bonding agent or a coating material other than the sealing material.

The cured product (gelled product) of the organic-inorganic hybrid prepolymer sol of the present invention has characteristics of elastic properties at a high temperature, and is excellent in thermal expansion relaxation ability of the bonded material according to thermal shock. Therefore, it can be used as a bonding layer for relieving thermal stress by separating it between the bonded materials of different materials.

In addition, as an application technique of the organic-inorganic hybrid compound of the present invention, it can also be used for a sealing material or a potting used for a semiconductor element such as a light-emitting element such as a laser diode or a photosensitive element such as an image sensor.

[Industrial availability]

The phenyl-containing organic-inorganic hybrid prepolymer of the present invention imparts a heat-resistant gel compound which is used as a sealing material for a heat generating element, or a binder or an electronic component, an electric component, or the like. It can be used in the industry for film or tape for insulation or fixing.

Fig. 1 is a graph showing the results of evaluation of the heat resistant temperature in the examples of the present invention.

Fig. 2 is a graph showing the results of hardness measurement evaluation in the examples of the present invention.

Since the diagram of this case is an example evaluation chart, it is not a representative figure of this case.

Therefore, there is no designated representative map in this case.

Claims (10)

A phenyl-containing organic-inorganic hybrid prepolymer which is an organic compound obtained by dehydration polycondensation reaction of polydimethylsiloxane and metal and/or semimetal alkoxide (alkoxide) An inorganic mixed prepolymer, wherein a phenyl group is introduced into the above-mentioned polydimethylsiloxane, and/or a part or all of the above metal and/or semimetal alkoxide. The phenyl-containing organic-inorganic hybrid prepolymer according to claim 1, wherein the metal and/or semimetal alkoxide is an oligomer of the above metal and/or semimetal alkoxide ( Oligomer). The phenyl-containing organic-inorganic hybrid prepolymer according to the first or second aspect of the invention, wherein the phenyl group-introduced polydimethyl siloxane is a benzene-containing compound having the following formula Polydimethyl oxane, [Chemical 1] However, R ₁ and R ₂ in the above formula are a linear or branched alkyl group having 1 to 4 carbon atoms, R ₁ and R ₂ are the same or different alkyl groups, and k and l are integers of 1 to 10, m and n are integers of 1 to 300. The phenyl group-containing organic-inorganic hybrid prepolymer according to any one of claims 1 to 3, wherein the phenyl group-introduced metal and/or semimetal alkoxide has the following a phenyl-containing alkoxide of the formula, [Chemical 2] However, R in the above formula is a linear or branched alkyl group having 1 to 4 carbon atoms, and R may be the same, partially different, or all different. The phenyl-containing organic-inorganic hybrid prepolymer according to any one of claims 2 to 4, wherein the oligomer of the above metal and/or semimetal alkoxide has the following Alkoxide oligomer, [Chemical 3] However, R in the above formula is a linear or branched alkyl group having 1 to 4 carbon atoms, R is an alkyl group which is the same or different from each other, and n is an integer of 4 to 6. The phenyl-containing organic-inorganic hybrid prepolymer according to any one of claims 1 to 5, wherein the phenyl-containing organic-inorganic hybrid prepolymer is added as a stabilizer The third butanol and/or 2-ethoxyethanol of the solvent. A heat-resistant organic-inorganic hybrid material which is a gelled product obtained by heating and gelling a phenyl-containing organic-inorganic hybrid prepolymer according to any one of claims 1 to 6. Adult. The heat-resistant organic-inorganic hybrid material according to the seventh aspect of the invention, wherein the hardness is measured after 1000 hours in a 250 ° C environment by a Shore-E-durometer For those below 80. An element sealing structure characterized in that the heat-generating element is sealed by using an organic-inorganic hybrid material having heat resistance as described in claim 7 or 8 as a sealing material. The element sealing structure according to claim 9, wherein the heat generating element incorporates SiC and/or GaN as a semiconductor.