TWI457383B - The organic - inorganic hybrid material - Google Patents

Description

Organic-inorganic hybrid material

The present invention relates to an organic-inorganic hybrid resin cured product having high heat resistance, and a semiconductor device using the same.

In recent years, due to electrical. The high performance and high speed of electronic equipment and the increase in heat generation from semiconductor elements are increasing, so it is desired to improve the heat resistance of the resin material sealing the semiconductor. Although the organic material exhibits a high elastic modulus and a low thermal expansion property at a low temperature, at a certain temperature or higher, the elastic modulus is lowered and the thermal expansion coefficient is increased. This temperature is called the glass transition temperature and is also one of the indicators of heat resistance. If it becomes higher temperature, the bond is cracked due to intense molecular motion, and then thermally decomposed. In the case of an organic resin material, the temperature at 95% of the initial weight at which the temperature is raised at a constant temperature increase rate is taken as a 5% weight reduction temperature, which is also one of the indexes of heat resistance. As a method of increasing the glass transition temperature or the 5% weight reduction temperature, a method of adding an inorganic substance having a low mobility to a resin has been proposed. For example, Patent Document 1 exemplifies an epoxy cerium oxide mixed product obtained by polycondensation reaction with a hydrolyzable alkoxy decane, and Patent Document 2 exemplifies a polymerization in which polyaminic acid is added and reacted with an organic cerium compound. a mixture of ruthenium and ruthenium dioxide.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-59011

[Patent Document 2] Japanese Patent Laid-Open Publication No. Hei 9-216938

The epoxy-ceria mixture proposed by the prior art has a high glass transition temperature (Tg), but has a problem that the thermal decomposition temperature is as low as 360 °C. Further, although the heat resistance of the polyimide-ceria mixture is extremely high, the curing temperature is also 350 ° C higher, and it is not suitable for the semiconductor seal containing the solder material.

The present invention is intended to provide an organic-inorganic hybrid resin cured product which is hardenable at a low hardening temperature and has a high glass transition temperature or thermal decomposition temperature.

The organic-inorganic hybrid resin cured product of the present invention is characterized in that the inorganic nanoparticle is dispersed in a structure of a thermosetting resin containing a triazine ring and is transparent to visible light.

According to the present invention, it is possible to provide an organic-inorganic hybrid resin cured product in which the glass transition temperature or the thermal decomposition temperature is high and the hardening temperature is low.

The inventors have repeatedly studied carefully in order to achieve the above objectives. As a result, it was found that the organic-inorganic hybrid resin cured product in which the inorganic nano particles were dispersed in the structure of the thermosetting resin containing the triazine ring exhibited a high glass transition temperature and a thermal decomposition temperature. The thermosetting resin is a cyanate resin represented by 2,2-bis(4-cyanooxyphenyl)propane having high heat resistance, or a bismaleimide diphenylethane and 2,2- Copolymers of bis(4-cyanooxyphenyl)propane are desirable. Further, the inorganic nanoparticles dispersed in the resin are composed of at least one type of metal oxide particles of cerium oxide, titanium oxide, aluminum oxide, or zirconium oxide, and the particle diameter of the inorganic nanoparticles is obtained. The high specific surface area effect of the inorganic nanoparticles is ideal from 1 nm to 100 nm. When the particle diameter is 1 nm or less, the molecular motion suppressing effect of the resin skeleton by the inorganic material is not sufficient, and when the particle diameter is 100 nm or more, the specific surface area of the particles is reduced, and a sufficient heat resistance effect cannot be exhibited. Further, the concentration of the inorganic nanoparticles in the cured organic-inorganic hybrid resin may be selected from any amount, and particularly preferably in the range of 0.01% by weight to 10% by weight. When it is 0.01% by weight or less, if the particle diameter of the inorganic nanoparticles is 1 nm, the sufficient effect of the specific surface area cannot be found, and when it is 10% by weight or more, the effect of improving the heat resistance is saturated.

The organic-inorganic hybrid resin cured product of the present embodiment can be produced by the following steps; the metal alkoxide compound is hydrolyzed. The first step of forming an inorganic nanoparticle by polymerization, and hydrolyzing the product formed in the first step and the metal alkoxide compound having a polymerizable functional group and an alkoxy group. a second step of introducing a polymerizable functional group onto the surface of the inorganic nanoparticles by polymerization, a solvent removal by removing the solvent from the reaction solution containing the product produced in the second step by telecentric separation, and then adding an organic solvent to perform solvent replacement. Adding cyanide to the dispersion generated in the third step The fourth step of mixing the resin raw material of the ester compound, the fifth step of removing the organic solvent from the mixed liquid produced in the fourth step, and the sixth step of hardening the product obtained in the fifth step by heat treatment.

The details of the method for producing the cured organic-inorganic hybrid resin of the present embodiment will be described with reference to Fig. 1 .

First, a metal alkoxide compound (B) and a reaction initiator (C) are added to the alcohol (A), and the mixture is stirred at a temperature equal to or lower than the boiling point of the alcohol for 1 hour or more to be hydrolyzed. The polycondensation reaction is carried out to obtain inorganic nanoparticles (G). Next, a metal alkoxide compound (D) having a polymerizable functional group is added and stirred for further 1 hour or longer. At this time, the alkoxy group of the metal alkoxide compound (D) is hydrolyzed with a functional group (hydroxyl or alkoxy group) on the surface of the oxide inorganic particle. The polycondensation polymerizes chemically bonded polymerizable functional groups on the surface of the oxide inorganic particles. Next, the drying of the inorganic particles contained in the solution is suppressed as much as possible while the alcohol (A) or the reaction initiator (C) is removed by telecentric separation, evaporator or the like, and the solvent is replaced with an organic solvent (E). This operation can also be repeated several times. The resin raw material (F) is added to the solution, and the mixture is stirred for 10 minutes or more in a mixed mixer or a ball mill, and sufficiently mixed. Here, if the step of replacing the solvent with the organic solvent (E) is omitted, the resin raw material is hydrolyzed with the alcohol (A) or the above, when the resin raw material (F) is added and mixed. The alcohol reaction formed by the polycondensation reaction is a structure having low heat resistance, which is not preferable. After mixing, it is kept above the boiling point of the organic solvent (E), and at the same time, the organic solvent (E) is completely removed by an aspirator or a vacuum pump or the like. The residual residue was heated at 150 ° C or higher for 1 hour or more to obtain an organic-inorganic hybrid resin cured product.

The alcohol (A) used in the present invention is an alcohol which is liquid at normal temperature. No special restrictions. Examples thereof include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, and 1-octanol. These two or more types may be used in combination.

The metal alkoxide compound (B) used in the present invention may, for example, be a decane compound, a titanium compound, an aluminum compound or a zirconium compound. The decane compound may, for example, be tetraethoxy decane or triethoxy decane, diethoxy decane or the like. The tetraethoxy decane may, for example, be tetramethoxy decane, tetraethoxy decane, tetraisopropoxy decane, tetrabutoxy decane, dimethoxydiethoxy decane or the like. The triethoxy decane may, for example, be an alkyl group or a benzene, such as methyltrimethoxydecane, ethyltrimethoxydecane, propyltrimethoxydecane, phenyltrimethoxynonane or phenyltriethoxydecane. The decane compound may also be vinyltrimethoxydecane, vinyltriethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3- (2-Aminoethyl)aminopropyltrimethoxydecane, 3-cyanopropyltrimethoxydecane γ-(methacryloxypropyl)trimethoxynonane, β-(3,4 a decane compound having a polymerizable functional group such as an epoxycyclohexyl)ethyltrimethoxydecane. The diethoxydecane may, for example, be dimethyldimethoxydecane, dimethyldiethoxydecane, diphenyldimethoxydecane, methylphenyldimethoxydecane or 3-epoxy. Propoxypropylmethyldiethoxydecane, and the like. These may be used alone or in combination. The titanium compound may, for example, be titanium tetraethoxide, titanium tetraisopropoxide, titanium butoxide, titanium dibutoxide, tetra-2-ethylhexyloxytitanate or diisophoric. Propyl bis(ethyl thiopyruvate) titanium, titanium tetraacetyl phthalate, titanium dioctyloxy bis(glycolate), diisopropoxy bis(ethyl acetonitrile) titanium, etc. 2 types can be used as needed Used in combination. The aluminum compound may, for example, be aluminum methoxylate, aluminum ethoxylate, aluminum n-propoxylated, aluminum isopropoxide, aluminum i-butoxylated, sec-butoxylated aluminum, t - Aluminum butoxide, butoxylated aluminum, etc., may be used in combination of two types as necessary. The zirconium compound may, for example, be zirconium tetra-n-propoxide, zirconium tetra-n-butoxide, zirconium tetra-ethyl-mercapto-acetonate, zirconium tributoxyacetate, monobutoxyacetamidacetone Zirconium bis(ethylacetamidine acetate), zirconium dibutoxy bis(ethylacetamidineacetate), zirconium tetraethosylpyruvate, zirconium tributoxide monostearate, etc. Combine 2 types.

The reaction initiator (C) used in the present invention causes hydrolysis with the metal alkoxide compound (B). In the polycondensation reaction, the catalyst may be ammonia such as ammonia, methylamine or dimethylamine, or an aqueous solution containing acetic acid or phosphoric acid, hydrochloric acid or the like, and particularly an aqueous solution containing ammonia.

Hydrolysis of metal alkoxide compound (B). The type of the inorganic nanoparticle (G) produced by the polycondensation reaction can be determined depending on the kind of the metal alkoxide compound (B) used for the synthesis. For example, cerium oxide, titanium dioxide, aluminum oxide, zirconia, etc. may be mentioned, and these two types or more may be combined. The particle diameter of these particles can be controlled by the reaction initiator (C), and is determined by the concentration of the metal alkoxide compound (B), the concentration of water, the amine of the catalyst, or the concentration of the acid. For example, when the concentration of the metal alkoxide compound (B) is 0.2 mol/L and the concentration of water is 10 mol/L, at an ammonia concentration of 0.1 mol/l, about 100 nm of particles are formed, and the ammonia concentration is 0.01 mol. Under the /l, 50nm particles can be obtained. Further, when a secondary or tertiary amine such as methylamine or dimethylamine is used, particles having a smaller particle diameter can be obtained. Such inorganic particles are directly external It is also possible to add dry particles, but it is preferably obtained by the above synthesis method in order to impart higher heat resistance to the cured organic-inorganic hybrid resin.

The inorganic nanoparticles (G) are preferably surface-modified with a metal alkoxide compound (D). By performing this operation, a cured organic-inorganic hybrid resin obtained by uniformly dispersing inorganic nanoparticles in a resin can be obtained. As the metal alkoxide compound (D), the same compound as the metal alkoxide compound (B) can be used, and in particular, a metal alkoxide compound having a polymerizable functional group is preferable. When a metal alkoxide compound substituted with a phenyl group or an alkyl group is used, there is a concern that the organic-inorganic hybrid resin cured product can be plasticized to cause a decrease in the glass transition temperature. Specifically, vinyl trimethoxy decane, vinyl triethoxy decane, 3-glycidoxypropyl triethoxy decane, 3-mercaptopropyl trimethoxy decane, 3-(2- Aminoethyl)aminopropyltrimethoxydecane, 3-cyanopropyltrimethoxydecane γ-(methacryloxypropyl)trimethoxydecane, β-(3,4-epoxy Preferably, cyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, and the like are preferred. The decane compound (B) used in the present invention may be used singly or in combination of plural kinds.

Further, the final concentration of the inorganic nanoparticles dispersed in the resin can be arbitrarily determined, but it is preferably in the range of 0.05% by weight to 10% by weight. The reason for this is 0.05% by weight or less, the effect is insufficient, and even if it is added to 10% by weight or more, the effect does not change.

The organic solvent (E) used in the present invention may, for example, be acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, acetyl ketone, isophorone, acetophenone or cyclohexane. Ketones such as ketones, especially methyl ethyl ketone, methyl Isobutyl ketone is desirable, but is not limited by these.

The resin raw material (F) in the present invention is a cyanate compound. Further, a maleidene compound, an epoxy resin prepolymer or the like may be mixed in an arbitrary ratio with respect to the cyanate ester compound. A hardening reaction containing a triazine ring excellent in heat resistance can be produced by a hardening reaction of a cyanate compound. Further, when a cyanate compound, a maleic imide compound, an epoxy resin prepolymer, or the like is mixed, a reaction of a cyanate compound with a maleimide compound or an epoxy resin may also be carried out to form a triazine-containing compound. Hardened ring.

The cyanate compound may, for example, be 4,4'-dicyanatobiphenyl, 3,3',5,5'-tetramethyl-4,4'-dicyanoxybiphenyl, bis (4- Cyanoxyphenyl)methane, bis(4-cyanooxy-3-methylphenyl)methane, bis(4-cyanooxy-3-t-butylphenyl)methane, bis(4-cyanooxyl) -3-i-propylphenyl)methane, bis(4-cyanooxy-3,5-dimethylphenyl)methane, bis(2-cyanooxy-3-t-butyl-5-methyl Phenyl)methane, 1,1-bis(4-cyanooxyphenyl)ethane, 1,1-bis(4-cyanooxy-3-methylphenyl)ethane, 1,1-double (4-cyanooxy-3-t-butylphenyl)ethane, 1,1-bis(4-cyanooxy-3-i-propylphenyl)ethane, 1,1-double (4 -Cyanooxy-3,5-dimethylphenyl)ethane, 1,1-bis(2-cyanooxy-3-t-butyl-5-methylphenyl)ethane, 2,2 - bis(4-cyanooxyphenyl)propane, 2,2-bis(4-cyanooxy-3-methylphenyl)propane, 2,2-bis(4-cyanooxy-3-t-butyl) Phenyl)propane, 2,2-bis(4-cyanooxy-3-i-propylphenyl)propane, 2,2-bis(4-cyanooxy-3,5-dimethylphenyl) ) propane, 2,2-bis(2-cyanooxy-3-t-butyl-5-methylphenyl)propane, 2,2-bis(4-cyanooxy-3-t-butyl- 6-methylphenyl)propane, 2,2-bis(3-allyl-4-cyanooxyphenyl)propane , 2,2-bis (4-cyanatophenyl) propane, 1,1-bis (4-cyanatophenyl) butane, 1,1-bis (4-cyano-3-methyl benzene Butane, 1,1-bis(4-cyanooxy-3-t-butylphenyl)butane, 1,1-bis(4-cyanooxy-3-i-propylphenyl) Butane, 1,1-bis(4-cyanooxy-3,5-dimethylphenyl)butane, 1,1-bis(2-cyanooxy-3-t-butyl-5-methyl Phenyl)butane, 1,1-bis(4-cyanooxy-3-t-butyl-6-methylphenyl)butane, 1,1-bis(3-allyl-4- Cyanoxyphenyl)butane, 1,1-bis(4-cyanooxyphenyl)cyclohexane, 1,1-bis(4-cyanooxy-3-methylphenyl)cyclohexane, bis ( 4-cyanooxyphenyl) sulfide, bis(4-cyanooxy-3-methylphenyl) sulfide, bis(4-cyanooxy-3-t-butylphenyl) sulfide, double 4-cyanooxy-3-i-propylphenyl) sulfide, bis(4-cyanooxy-3,5-dimethylphenyl) sulfide, bis(2-cyanooxy-3-t -butyl-5-methylphenyl) sulfide, bis(4-cyanooxyphenyl)anthracene, bis(4-cyanooxy-3-methylphenyl)anthracene, bis(4-cyanooxy-) 3-t-butylphenyl)anthracene, bis(4-cyanooxy-3-i-propylphenyl)anthracene, bis(4-cyanooxy-3,5-dimethylphenyl)anthracene, Bis(2-cyanooxy-3-t-butyl-5-methylphenyl)anthracene, bis(4-cyanooxyphenyl)ether, bis(4-cyanooxy-3-methylphenyl) Ether, bis(4-cyanooxy-3-t-butylphenyl) ether, bis(4-cyanate) -3-i-propylphenyl)ether, bis(4-cyanooxy-3,5-dimethylphenyl)ether, bis(2-cyanooxy-3-t-butyl-5-methyl) Phenyl)ether, bis(4-cyanooxyphenyl)carbonyl, bis(4-cyanooxy-3-methylphenyl)carbonyl, bis(4-cyanooxy-3-t-butylphenyl) a carbonyl group, bis(4-cyanooxy-3-i-propylphenyl)carbonyl, bis(4-cyanooxy-3,5-dimethylphenyl)carbonyl, bis(2-cyanooxy-) Further, two or more kinds of these may be used as necessary, such as 3-t-butyl-5-methylphenyl)carbonyl.

The maleidin compound may, for example, be 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether double malayan Amine, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene double horse醯imine, 1,6'-double Malay Imine-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylfluorene bismaleimide, 1 , 3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, etc., bismaleimide or malayan A monomaleimide such as an amine or a phenyl maleimide may be used in combination of two or more kinds as necessary.

The epoxy resin prepolymer refers to all of the known epoxy resins having two or more epoxy groups in one molecule. For example, a glycidyl ether type epoxy resin obtained from a phenol or an alcohol and epichlorohydrin, a glycidyl ester type epoxy resin obtained from a carboxylic acid and epichlorohydrin, and an amine and The epoxypropylamine type epoxy resin obtained by epichlorohydrin and the oxidized epoxy resin obtained by oxidizing the double bond of an unsaturated hydrocarbon are not particularly limited by these. Specific examples thereof include a bisphenol type epoxy resin using bisphenol A, F, and S as a raw material, a halogenated epoxy resin obtained from a halogenated phenol, an epoxy resin having a naphthalene skeleton or a biphenyl skeleton, and the like. Bifunctional epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol extended biphenyl type epoxy resin, etc. Polyfunctional epoxy resin, epoxy propyl ether type epoxy resin such as polyhydroxy ether type epoxy resin. In addition, examples of the epoxy propyl ester type epoxy resin include various epoxy propyl ester types obtained by using an aliphatic carboxylic acid, an aromatic carboxylic acid, a cyclic carboxylic acid, or a polymeric fatty acid carboxylic acid as a raw material. Epoxy resin. Further, examples of the epoxy propylamine type epoxy resin include a glycidylamine type epoxy resin obtained by using an aromatic amine, an aminophenol, and a cyclic aliphatic amine as a raw material. Further, the oxidized epoxy resin may, for example, be a cyclic aliphatic epoxy resin. Other examples include an epoxy resin having a naphthalene ring, an anthracene ring, an anthracene ring, a nitrogen-containing epoxy resin, and a phosphorus-containing epoxy resin. , bismuth-containing epoxy resin, liquid crystalline epoxy resin, etc., but are not particularly limited by these. Moreover, these may be used in combination with plural numbers.

4 is a cross-sectional schematic view showing a power semiconductor device. In the power semiconductor device shown in FIG. 4, the back side electrode of the power semiconductor device 101 is electrically connected to the circuit wiring member 102 on the insulating substrate 106 by the bonding material 104, and the main electrode of the power semiconductor device 101 is led by the lead 105 is electrically connected to the wire member 103. A heat dissipation plate for dissipating heat generated by the power semiconductor element 101 to the outside is provided on the back side of the insulating substrate 106. Further, a part of the circuit wiring member 102, the lead member 103, and the heat dissipation plate 107 is exposed, and the periphery of the power semiconductor element 101 is sealed by the sealing resin 108. This sealing resin 108 can be applied to the organic-inorganic hybrid resin cured product of the present invention. Since the organic-inorganic hybrid resin cured product of the present invention has a high glass transition temperature and a small change in the modulus of elasticity or the coefficient of thermal expansion of the temperature amplitude, when used in a sealing material for a power semiconductor device, the accompanying power element can be suppressed. The thermal stress generated by the temperature change due to heat generation is expected to contribute not only to the high reliability of the power semiconductor device but also to the high life of the power semiconductor device due to the high heat resistance. Further, the structure of the power semiconductor device shown in FIG. 4 is only an example, and it is conceivable that the organic-inorganic hybrid resin cured product of the present invention can be applied as a sealing resin around the coated semiconductor element in a semiconductor device having another structure. .

Next, the present invention will be described by way of examples and comparative examples, but the present invention is not limited by the following.

[Examples 1 to 5, Comparative Example 1]

Tetraethoxydecane (TEOS), ammonia and water were added to ethanol, and the mixture was stirred at room temperature for 12 hours. Thereby, cerium oxide having a particle diameter of 10 nm was produced. Next, after adding vinyltrimethoxydecane (VTMS), it was stirred for further 12 hours. Next, the alcohol or ammonia, water was removed using a telecentric separator, and the solvent was replaced with methyl ethyl ketone (MEK). Repeat this operation twice. To this solution, 2,2-bis(4-cyanooxyphenyl)propane (BCPP) was added and treated in a planetary ball mill for 30 minutes to allow thorough mixing. At this time, the amount of BCPP mixed is changed to change the concentration of cerium oxide in the resin. After mixing, the temperature was maintained at 160 ° C and the MEK was completely removed by a vacuum pump. The residue remaining at 160 ° C / 2 h, 250 ° C / 4 h was heated to obtain an organic-inorganic hybrid resin cured product.

Further, a cured product of BCPP resin without added cerium oxide particles was prepared as Comparative Example 1.

The elastic modulus of the cured organic-inorganic hybrid resin was measured by dynamic mechanical analysis (DMA) using TA2000 manufactured by TA Instruments. The temperature increase rate was set to 2 ° C / min, the distance between the clamps was 10 to 20 mm, the sample thickness was about 0.5 mm, and the measurement frequency was 10 Hz. The glass transition temperature was determined from the peak temperature of tan δ by DMA measurement. The 5% weight loss temperature was evaluated using a thermogravimetric analyzer (TGA, TA Instruments, Q500). The measurement conditions were set to atmospheric temperature, a heating rate of 10 ° C/min, and a temperature of 95% of the total weight before measurement was defined as a 5% weight reduction temperature. Further, the inorganic nanoparticle content was determined from the weight fraction of 800 ° C in which the resin component was completely decomposed. And confirm that this value is combined The values placed in Chengzhong are the same.

The transparency of the cured organic-inorganic hybrid resin was visually evaluated.

The infrared absorption spectrum of the cured organic-inorganic hybrid resin was measured by an infrared spectroscopic device (PerkinElmer, Spectrum 100, ATR method). Measurement conditions Measurement 380-4000cm ^-1 range set based measurement interval 1cm ^-1, the cumulative number of 12 times. The evaluation results are shown in Table 1.

The cured product of the cyanate-cerium oxide mixed resin of Examples 1 to 5 was compared with the cured product of the resin without the added cerium oxide of Comparative Example 1, and as a result, the glass transition temperature and the 5% weight reduction temperature were increased. Further, according to Examples 1 to 6, the cyanate-ceria mixed resin cured product was accompanied by the concentration of cerium oxide. The glass transition temperature and the 5% weight reduction temperature also increase, and the cerium oxide concentration is almost 5% or more. When the obtained organic-inorganic hybrid resin cured product was visually observed, it was all transparent. This is considered to be due to the uniform dispersion of particles below visible light (360 nm or more).

[Examples 6 to 10, Comparative Example 2]

Tetraethoxydecane (TEOS), ammonia and water were added to ethanol, and the mixture was stirred at room temperature for 12 hours. Thereby, cerium oxide particles having a particle diameter of 10 nm were produced. Next, after adding vinyltrimethoxydecane (VTMS), it was stirred for further 12 hours. Next, the alcohol or ammonia, water was removed using a telecentric separator, and the solvent was replaced with methyl ethyl ketone (MEK). Repeat this operation twice. To this solution was added 2,2-bis(4-cyanooxyphenyl)propane (BCPP) and bismaleimide diphenylethane (BMI), which was treated in a planetary ball mill for 30 minutes and thoroughly mixed. At this time, the amount of BCPP and BMI mixed is changed to change the concentration of cerium oxide in the resin. After mixing, it was kept at 160 ° C while completely removing the MEK with a vacuum pump. The residue remaining at 160 ° C / 2 h, 250 ° C / 4 h was heated to obtain an organic-inorganic hybrid resin cured product.

Further, a resin cured product containing no cerium oxide particles was prepared as a copolymer of BCPP and BMI as Comparative Example 2.

The elastic modulus of the organic-inorganic hybrid resin cured product was measured by Dynamic Mechanical Analysis (DMA) using TA2000 manufactured by TA Instruments. The heating rate was set to 2 ° C / min, the distance between the clamps was 10 to 20 mm, the thickness of the sample was about 0.5 mm, and the measurement frequency was 10 Hz. Glass transition temperature is measured by DMA from the wave of tan δ The peak temperature is determined. The 5% weight loss temperature was evaluated using a thermogravimetric analyzer (TGA, TA Instruments, Q500). The measurement conditions were set to atmospheric temperature, a heating rate of 10 ° C/min, and a temperature of 95% of the total weight before measurement was defined as a 5% weight reduction temperature. Further, the inorganic nanoparticle content was determined from the weight fraction of 800 ° C in which the resin component was completely decomposed. And confirm that this value is consistent with the value placed in the composition.

The transparency of the cured organic-inorganic hybrid resin was visually evaluated.

The infrared absorption spectrum of the cured organic-inorganic hybrid resin was measured by an infrared spectroscopic device (PerkinElmer, Spectrum 100, ATR method). Measurement conditions Measurement system is set to range 380-4000cm ^-1, measurement interval 1cm ^-1, the cumulative number of 12 times. The evaluation results are shown in Table 2.

The cured organic-inorganic hybrid resin of Examples 6 to 10 was compared with the cured resin of the resin of Comparative Example 2 without adding cerium oxide, and as a result, the glass transition temperature and the 5% weight reduction temperature were increased. Further, according to Examples 6 to 10, when the raw material resin is a BCPP/BMI=50/50 copolymer, the cerium oxide is accompanied. As the concentration increases, the glass transition temperature and the 5% weight reduction temperature also increase, and the cerium oxide concentration becomes almost constant at 2% or more.

2 is a FT-IR spectrum showing the cured organic-inorganic hybrid resin of Example 10. In Fig. 2, the broken line is the FT-IR spectrum of the cured organic-inorganic hybrid resin without the addition of nano-cerium oxide, and the solid line is the FT-IR spectrum of the cured organic-inorganic hybrid resin obtained in Example 10. Example 10 Obtaining organic - inorganic hybrid cured resin was 1360cm ^-1 and 1560 cm ^-1 was found from the absorption of a triazine ring, of silicon dioxide absorption found at 1000 ^{cm -1} ~ 1100cm, which may be known as an inorganic The structure in which the particles of cerium oxide are dispersed in the cured product of the resin containing the triazine ring.

[Examples 11, 12, Comparative Example 3]

To the ethanol, tetraethoxy decane (TEOS) and ammonia (A) of the reaction initiator (C) and water were added, and the mixture was stirred at room temperature for 12 hours. At this time, the particle size of the produced cerium oxide is changed by the amount of ammonia added. Next, vinyl trimethoxydecane (VTMS) was added and stirred for further 12 hours. Next, the alcohol or ammonia and water were removed using a telecentric separator, and the solvent was replaced with methyl ethyl ketone (MEK) of the organic solvent (E). Repeat this operation twice. To this solution, 2,2-bis(4-cyanooxyphenyl)propane (BCPP) and bismaleimide diphenylethane (BMI) of resin raw material (F) were added and treated by a planetary ball mill for 30 minutes. And fully mixed. After mixing, it was kept at 160 ° C while completely removing the MEK with a vacuum pump. The residue remaining at 160 ° C / 2 h, 250 ° C / 4 h was heated to obtain an organic-inorganic hybrid resin cured product.

The elastic modulus of the hardened organic-inorganic hybrid resin is measured by dynamic viscoelasticity The amount (Dynamic Mechanical Analysis, DMA) was measured using TA2000 manufactured by TA Instruments. The heating rate was set to 2 ° C / min, the distance between the clamps was 10 to 20 mm, the thickness of the sample was about 0.5 mm, and the measurement frequency was 10 Hz. The glass transition temperature was determined from the peak temperature of tan δ by DMA measurement. The 5% weight loss temperature was evaluated using a thermogravimetric analyzer (TGA, TA Instruments, Q500). The measurement conditions were set to atmospheric temperature, a heating rate of 10 ° C/min, and a temperature of 95% of the total weight before measurement was defined as a 5% weight reduction temperature. Further, the inorganic nanoparticle content was determined from the weight fraction of 800 ° C in which the resin component was completely decomposed. And confirm that this value is consistent with the value placed in the composition.

The transparency of the cured organic-inorganic hybrid resin was visually evaluated.

The infrared absorption spectrum of the cured organic-inorganic hybrid resin was measured by an infrared spectroscopic device (PerkinElmer, Spectrum 100, ATR method). Measurement conditions Measurement system is set to range 380-4000cm ^-1, measurement interval 1cm ^-1, the cumulative number of 12 times. The evaluation results are shown in Table 3.

According to Examples 13 and 14, when the particle diameter was 100 nm or less, the resin cured product of Comparative Example 2 without added cerium oxide was found to have a glass transition temperature and a thermal decomposition temperature. On the other hand, according to Comparative Example 3, when the particle diameter was 200 nm or more, it was found that the heat resistance was the same as that of the resin cured product without the added cerium oxide of Comparative Example 2. From this result, the particle diameter of the inorganic particles to be added is preferably less than 200 nm, and more preferably 100 nm or less.

[Examples 13 to 17]

Tetraethoxydecane (TEOS), ammonia and water were added to ethanol, and the mixture was stirred at room temperature for 12 hours. Next, vinyltrimethoxydecane (VTMS), allyltrimethoxydecane (ATMS), methacryloxypropyltrimethoxydecane (MPTMS), and ethyltrimethoxydecane (ETMS) were added, respectively. After hexyltrimethoxydecane (HTMS), it was stirred for more than 1 hour. Next, the alcohol or ammonia, water was removed using a telecentric separator, and the solvent was replaced with methyl ethyl ketone (MEK). Repeat the operation twice. To this solution was added 2,2-bis(4-cyanooxyphenyl)propane (BCPP) and bismaleimide diphenylethane (BMI), which was treated in a planetary ball mill for 30 minutes and thoroughly mixed. After mixing, it was kept at 160 ° C while completely removing the MEK with a vacuum pump. The residue remaining at 160 ° C / 2 h, 250 ° C / 4 h was heated to obtain an organic-inorganic hybrid resin cured product.

The elastic modulus of the organic-inorganic hybrid resin cured product was measured by Dynamic Mechanical Analysis (DMA) using TA2000 manufactured by TA Instruments. The heating rate was set to 2 ° C / min, the distance between the clamps was 10 to 20 mm, the thickness of the sample was about 0.5 mm, and the measurement frequency was 10 Hz. The glass transition temperature was determined from the peak temperature of tan δ by DMA measurement. The 5% weight loss temperature was evaluated using a thermogravimetric analyzer (TGA, TA Instruments, Q500). The measurement conditions were set to atmospheric temperature, a heating rate of 10 ° C/min, and a temperature of 95% of the total weight before measurement was defined as a 5% weight reduction temperature. Further, the inorganic nanoparticle content was determined from the weight fraction of 800 ° C in which the resin component was completely decomposed. And confirm that this value is consistent with the value placed in the composition.

The transparency of the cured organic-inorganic hybrid resin was visually evaluated.

The infrared absorption spectrum of the cured organic-inorganic hybrid resin was measured by an infrared spectroscopic device (PerkinElmer, Spectrum 100, ATR method). Measurement conditions Measurement system is set to range 380-4000cm ^-1, measurement interval 1cm ^-1, the cumulative number of 12 times. The evaluation results are shown in Table 4.

In any of Examples 13 to 17, the glass transition temperature and the 5% weight reduction temperature were improved as compared with the resin cured product of the cerium oxide which was not added in Comparative Example 2. On the other hand, a polymerizable functional group having a vinyl group, an allyl group, a methacryl group or the like is used as compared with the examples 13 to 15. In the case of the metal alkoxide compound, the glass transition temperature and the 5% weight reduction temperature are improved. When the metal alkoxide compound substituted with ethyl or hexyl is used in Examples 16 and 17, the heat resistance improving effect becomes Smaller. On the other hand, it is considered that the affinity of the cerium oxide to the resin is high because a metal alkoxide compound having a polymerizable functional group is used.

[Examples 18 to 21]

Tetraethoxydecane (TEOS), i-propoxytitanium (TIP), zirconium butoxide (ZB), and i-propoxylated aluminum (AP) were added to ethanol, and reactions were added thereto. Ammonia and water of the initiator (C) were stirred at room temperature for 12 hours. Next, vinyltrimethoxydecane (VTMS), allyltrimethoxydecane (ATMS), methacryloxypropyltrimethoxydecane (MPTMS), and ethyltrimethoxydecane (ETMS) were added, respectively. After that, it was stirred for another 12 hours. Next, the alcohol or ammonia, water was removed using a telecentric separator, and the solvent was replaced with methyl ethyl ketone (MEK). Repeat this operation twice. To this solution was added 2,2-bis(4-cyanooxyphenyl)propane (BCPP) and bismaleimide diphenylethane (BMI), which was treated in a planetary ball mill for 30 minutes and thoroughly mixed. After mixing, it was kept at 160 ° C while completely removing the MEK with a vacuum pump. The residue remaining in the residue was heated at 160 ° C / 2 h and 250 ° C / 4 h to obtain an organic-inorganic hybrid resin cured product.

The elastic modulus of the organic-inorganic hybrid resin cured product was measured by Dynamic Mechanical Analysis (DMA) using TA2000 manufactured by TA Instruments. Set the heating rate to 2 ° C / min, the distance between the clamps 10 ~ 20 mm, the thickness of the sample is about 0.5 mm, measurement Frequency 10Hz. The glass transition temperature was determined from the peak temperature of tan δ by DMA measurement. The 5% weight loss temperature was evaluated using a thermogravimetric analyzer (TGA, TA Instruments, Q500). The measurement conditions were set to atmospheric temperature, a heating rate of 10 ° C/min, and a temperature of 95% of the total weight before measurement was defined as a 5% weight reduction temperature. Further, the inorganic nanoparticle content was determined from the weight fraction of 800 ° C in which the resin component was completely decomposed. And confirm that this value is consistent with the value placed in the composition.

The transparency of the cured organic-inorganic hybrid resin was visually evaluated.

The infrared absorption spectrum of the cured organic-inorganic hybrid resin was measured by an infrared spectroscopic device (PerkinElmer, Spectrum 100, ATR method). Measurement conditions Measurement system is set to range 380-4000cm ^-1, measurement interval 1cm ^-1, the cumulative number of 12 times. The evaluation results are shown in Table 5.

In Examples 18 to 21, an organic-inorganic hybrid resin cured product obtained by dispersing inorganic nanoparticles having different types of cerium oxide particles, titanium oxide particles, zirconium oxide particles, and alumina particles was prepared. Under any of the conditions, the glass transition temperature and the 5% weight reduction temperature of the cured resin having no added cerium oxide of Comparative Example 2 were increased, and almost no difference due to the type of the inorganic nanoparticle was observed. Inorganic nai The size of the rice particles is sufficiently small that the material volume characteristics do not occur.

[Comparative Example 4]

The metal alkoxide compound (B) was replaced with ethanol, and cerium oxide particles having a particle diameter of 1 μm were added thereto, and ammonia and water were added thereto, and vinyltrimethoxydecane (VTMS) was added thereto, followed by stirring for 12 hours. Next, the alcohol or ammonia, water was removed using a telecentric separator, and the solvent was replaced with methyl ethyl ketone (MEK). Repeat this operation twice. To this solution was added 2,2-bis(4-cyanooxyphenyl)propane (BCPP) and bismaleimide diphenylethane (BMI), which was treated in a planetary ball mill for 30 minutes and thoroughly mixed. After mixing, it was kept at 160 ° C while completely removing the MEK with a vacuum pump. The residue remaining at 160 ° C / 2 h, 250 ° C / 4 h was heated to obtain an organic-inorganic hybrid resin cured product.

The elastic modulus of the organic-inorganic hybrid resin cured product was measured by Dynamic Mechanical Analysis (DMA) using TA2000 manufactured by TA Instruments. The heating rate was set to 2 ° C / min, the distance between the clamps was 10 to 20 mm, the thickness of the sample was about 0.5 mm, and the measurement frequency was 10 Hz. The glass transition temperature was determined from the peak temperature of tan δ by DMA measurement. The 5% weight loss temperature was evaluated using a thermogravimetric analyzer (TGA, TA Instruments, Q500). The measurement conditions were set to atmospheric temperature, a heating rate of 10 ° C/min, and a temperature of 95% of the total weight before measurement was defined as a 5% weight reduction temperature. Further, the inorganic nanoparticle content was determined from the weight fraction of 800 ° C in which the resin component was completely decomposed. And confirm that this value is consistent with the value placed in the composition.

The transparency of the cured organic-inorganic hybrid resin was visually evaluated.

The infrared absorption spectrum of the cured organic-inorganic hybrid resin was measured by an infrared spectroscopic device (PerkinElmer, Spectrum 100, ATR method). Measurement conditions Measurement system is set to range 380-4000cm ^-1, measurement interval 1cm ^-1, the cumulative number of 12 times.

As a result of the measurement, the appearance was opaque. Further, the glass transition temperature was 270 ° C, and the 5% weight loss temperature was 410 ° C, that is, almost the same as the resin alone.

[Comparative Example 5]

TEOS ammonia and water were added to ethanol, and stirred at room temperature for 12 hours. Next, after adding vinyltrimethoxydecane (VTMS), it was stirred for further 12 hours. Secondly, solvent replacement was not carried out with MEK, and 2,2-bis(4-cyanooxyphenyl)propane (BCPP) and bismaleimide diphenylethane (BMI) were added as a resin material to a planetary ball mill. Treat for 30 minutes and mix thoroughly. After mixing, the temperature was maintained at 160 ° C while the solvent was completely removed by a vacuum pump. The residue remaining at 160 ° C / 2 h, 250 ° C / 4 h was heated to obtain an organic-inorganic hybrid resin cured product.

The elastic modulus of the organic-inorganic hybrid resin cured product was measured by Dynamic Mechanical Analysis (DMA) using TA2000 manufactured by TA Instruments. The heating rate was set to 2 ° C / min, the distance between the clamps was 10 to 20 mm, the thickness of the sample was about 0.5 mm, and the measurement frequency was 10 Hz. The glass transition temperature was determined from the peak temperature of tan δ by DMA measurement. The 5% weight loss temperature was evaluated using a thermogravimetric analyzer (TGA, TA Instruments, Q500). Measuring condition In the atmosphere, the heating rate was 10 ° C / min, and the temperature of 95% of the total weight before the measurement was defined as a 5% weight reduction temperature. Further, the inorganic nanoparticle content was determined from the weight fraction of 800 ° C in which the resin component was completely decomposed. And confirm that this value is consistent with the value placed in the composition.

The transparency of the cured organic-inorganic hybrid resin was visually evaluated.

The infrared absorption spectrum of the cured organic-inorganic hybrid resin was measured by an infrared spectroscopic device (PerkinElmer, Spectrum 100, ATR method). Measurement conditions Measurement system is set to range 380-4000cm ^-1, measurement interval 1cm ^-1, the cumulative number of 12 times.

As a result of the measurement, the glass transition temperature was 200 ° C, and the 5% weight loss temperature was 350 ° C. The glass transition temperature was lowered by 70 ° C and the 5% weight loss temperature was lowered by 60 ° C compared with the addition of inorganic nano cerium oxide.

Fig. 3 is a view showing the FT-IR spectrum of the cured organic-inorganic hybrid resin synthesized in Comparative Example 5. In Fig. 3, the broken line is the FT-IR spectrum of the cured organic-inorganic hybrid resin without the addition of nano-cerium oxide, and the solid line is the organic-inorganic hybrid obtained by adding 10% by weight of nano-cerium oxide obtained in Comparative Example 5. FT-IR spectrum of cured resin. It may be made of known organic Comparative Example 5 - inorganic hybrid cured resin, without adding the silicon dioxide without adding an organic - inorganic hybrid Seen from the resin was cured at 1360cm ^-1 and 1560cm ^-1 of the triazine ring from Absorption disappears. On the other hand, it is considered that the catalyst is not subjected to solvent replacement by MEK, and the resin is deteriorated by the reaction of the cyanate compound and the alcohol, and the heat resistance is further lowered.

101‧‧‧Power semiconductor components

102‧‧‧Circuit wiring components

103‧‧‧Wire members

104‧‧‧Material

105‧‧‧Lead

106‧‧‧Insert substrate

107‧‧‧heat plate

108‧‧‧ Sealing resin

Fig. 1 is a view showing a method of producing an organic-inorganic hybrid resin cured product.

Fig. 2 is a FT-IR spectrum chart showing the cured organic-inorganic hybrid resin synthesized in Example 10.

Fig. 3 is a FT-IR spectrum chart showing the cured organic-inorganic hybrid resin synthesized in Comparative Example 5.

Fig. 4 is a schematic cross-sectional view of a power semiconductor device.

Claims (7)

An organic-inorganic hybrid resin cured product characterized in that the inorganic nanoparticle is dispersed in a structure of a thermosetting resin containing a triazine ring and is transparent to visible light; and the thermosetting resin is 2,2-bis (4) a polymer of -cyanooxyphenyl)propane having a vinyl, allyl or methacrylic group-polymerizable functional group chemically bonded to the surface of the inorganic nanoparticle, and containing the above-mentioned inorganic naphthene at 0.05% by weight to 10% by weight Rice particles. The organic-inorganic hybrid resin cured product according to claim 1, wherein the inorganic nanoparticle particles are chemically bonded to a vinyl polymerizable functional group on the surface. The organic-inorganic hybrid resin cured product according to claim 1, wherein the inorganic nanoparticle particles are chemically bonded with an allyl polymerizable functional group on the surface. The organic-inorganic hybrid resin cured product of claim 1, wherein the inorganic nanoparticle is chemically bonded to a methacrylic group-based polymerizable functional group on the surface. The organic-inorganic hybrid resin cured product according to claim 1, wherein the inorganic nanoparticle is composed of at least one metal oxide particles of at least one of ceria, titania, alumina, and zirconia, and has a particle diameter of 1 nm. 100nm. An organic-inorganic hybrid resin cured product, which is characterized by the organic-inorganic hybrid resin cured product according to claim 1, which is produced by the following steps; and is selected from the group consisting of a decane compound, a titanium compound, an aluminum compound, and a zirconium compound. At least one compound is hydrolyzed. a first step of forming an inorganic nanoparticle by polymerization; forming a product formed in the first step and at least one compound selected from the group consisting of a decane compound, a titanium compound, an aluminum compound, and a zirconium compound having a polymerizable functional group and an alkoxy group a second step of introducing a polymerizable functional group on the surface of the inorganic nanoparticles by hydrolysis or polymerization; removing the solvent from the reaction solution containing the product produced in the second step by centrifugation and adding an organic solvent to replace the solvent a third step; a fourth step of adding an epoxy resin raw material containing a cyanate compound to the dispersion formed in the third step; and a fifth step of removing the organic solvent from the mixed liquid formed in the fourth step; The sixth step of heat-treating to harden the product obtained in the fifth step. A semiconductor device which is a semiconductor device having a structure in which a periphery of a semiconductor element is sealed by a sealing material, and the organic-inorganic hybrid resin cured product according to any one of claims 1 to 6 is used in the sealing material.