TWI458682B - Amorphous vermiculite powder, its production method and use - Google Patents

Description

Amorphous vermiculite powder, its production method and use

The present invention relates to an amorphous vermiculite powder, a method for producing the same, and a use thereof.

In recent years, the semiconductor sealing material used for the sealing of semiconductors has been required to be rendered flame-retardant without using a harmful flame retardant such as a ruthenium compound or a brominated epoxy resin, which has a large environmental load, because of the increased awareness of the protection of the global environment. It is necessary to impart heat resistance to lead-free solder that does not contain lead. The semiconductor sealing material is mainly composed of an epoxy resin, a phenol resin curing agent, a hardening accelerator, an inorganic filler, etc., but in order to satisfy the above-mentioned required characteristics, it is used in an epoxy resin, a phenol resin or the like to contain a large amount of aromatic rings. A method of a structure having high flame retardancy and heat resistance, and a method of highly filling an inorganic filler. However, in such methods, the semiconductor sealing material tends to have a higher viscosity when it is sealed.

On the other hand, in response to the demand for small size, light weight, and high performance of electronic devices, the thinness of the internal structure of semiconductors, the reduction in the diameter of gold wires, the long span, and the high density of wiring pitch are rapidly progressing. . When such a semiconductor is sealed with a high-viscosity semiconductor sealing material, defects such as gold wire deformation, gold wire cutting, semiconductor element tilt, and gap unfilling are increased. Therefore, in the semiconductor sealing material, it is strongly required to have flame retardancy, and it is possible to reduce the viscosity at the time of sealing and to reduce the molding failure.

In order to satisfy such requirements, a method of improving the low viscosity and improving the moldability by improving the method of using an epoxy resin or a phenol resin curing agent used in a semiconductor sealing material has been employed (see Patent Documents 1 and 2). In addition, in order to improve the curing temperature of the epoxy resin, the hardening accelerator is used to protect the reactive matrix by using a component which suppresses the hardening property, that is, a method called potentialization (see Patent Documents 3 and 4). .

The improvement of the inorganic filler is a method of adjusting the particle size distribution so that the viscosity of the sealant does not increase even when it is highly filled (see Patent Documents 5 and 6). However, in such a method, the effect of improving the low-viscosity effect and the formability is insufficient. At present, there is no semiconductor sealing material capable of highly filling the inorganic filler and capable of lowering the viscosity at the time of sealing, and further improving the formability.

CITATION LIST Patent Literature Patent Literature No. JP-A-2007- 225 355 Patent Document No. JP-A-2006- 225 355. JP-A-2005-239892, Patent Document 6: WO/2007/132771

SUMMARY OF THE INVENTION An object of the present invention is to provide a semiconductor sealing material which has a low viscosity at the time of sealing and a further improved formability even when a filler is highly filled, and an amorphous aragonite powder which is suitable for the preparation and a method for producing the same.

The present invention is an amorphous vermiculite powder which is obtained by adsorbing pyridine after the amorphous ochre powder is heated at 450 ° C or higher and less than 550 ° C, and is less than 150 ° C or less. The ratio L/B of the amount of detachment B of pyridine when heated at 250 ° C is 0.8 or less.

Further, in the present invention, in the case where pyridine is adsorbed on the amorphous vermiculite powder, pyridine is heated at 150 ° C or more and less than 250 ° C in the total amount of detached A of pyridine when heated at 150 ° C or more and less than 550 ° C. The ratio (B/A) × 100% occupied by the amount of separation B is preferably 20% or more.

Further, the amorphous vermiculite powder of the present invention has a specific surface area of 0.5 to 45 m 2 /g, an average particle diameter of 0.1 to 60 μm, and an average sphericity of 0.80 or more.

Further, the present invention is an inorganic powder containing the amorphous vermiculite powder of the present invention.

In the present invention, the inorganic powder is preferably an amorphous vermiculite powder and/or an alumina powder other than the present invention.

Further, the present invention provides a method for producing an amorphous vermiculite powder characterized by containing a mixture of a raw material talc powder and an Al source material, and ejecting it into a flame formed by a burner to produce an amorphous material. After the strontium powder, it is kept for 15 to 30 minutes at a temperature of 60 to 150 ° C and a relative humidity of 60 to 90%.

Moreover, the present invention relates to a resin composition containing the amorphous vermiculite powder of the present invention in a resin. The aforementioned tree finger is preferably an epoxy resin.

Further, the present invention is a semiconductor sealing material using the resin compositions.

According to the present invention, it is possible to provide a resin composition excellent in fluidity, viscosity characteristics, and moldability, and a semiconductor sealing material using the resin composition. Further, it is possible to provide a suitable amorphous vermiculite powder for preparing the above resin composition.

Hereinafter, the present invention will be described in detail.

The amorphous vermiculite powder of the present invention is characterized in that when pyridine is adsorbed and heated and detached, the detachment amount L of pyridine when heated at 450 ° C or more and less than 550 ° C is heated at 150 ° C or more and less than 250 ° C. An amorphous vermiculite powder having a ratio of detachment of pyridine B of L/B of 0.8 or less.

In the structure of vermiculite, for example, -O-Si-O-Al-O-Si-O-, when Al is substituted for the position of Si, since the coordination number of Si is different from the coordination number of Al, the point becomes a solid acid. The point is also the Lewis acid point (electron pair acceptor). Further, when H ₂ O (water) is bonded to the Lewis acid point, it becomes a Bronsted acid (proton donor). When the pyridine group of the basic substance is bonded to the acid sites on the surface of the amorphous vermiculite powder, the more strongly bonded pyridine is desorbed at a higher temperature upon heating. In the case of an amorphous vermiculite powder, since the structure is irregular compared with the crystallinity, distribution occurs at the acid strength (desorption temperature), and it can be considered that the pyridine system and the fabric are separated at a heating temperature of 150 ° C to 250 ° C. The sulphuric acid point bond is separated from the pyridine group and the Lewis acid point at a heating temperature of 450 ° C to 550 ° C.

When pyridine is adsorbed and heated, the ratio L/B of the detachment amount L of pyridine when heated at 450 ° C or more and less than 550 ° C and the amount of detachment B of pyridine heated at 150 ° C or more and less than 250 ° C is 0.8 or less. , means that the amount of the nibble acid point is 1.25 times or more than the Lewis acid point. When such an amorphous vermiculite is used, a sealing material excellent in fluidity, viscosity characteristics, and moldability can be prepared for the reason described later. On the other hand, when the ratio L/B of the detachment amount L of pyridine heated at 450 ° C or more and less than 550 ° C and the amount of detachment B of pyridine heated at 150 ° C or more and less than 250 ° C is more than 0.8, it means When the amount of the sulphate acid dot is less than 1.25 times as compared with the amount of the Lewis acid point, it is difficult to prepare a sealing material excellent in fluidity, viscosity characteristics, and moldability.

Hereinafter, the reason for discovering the effects of the present invention will be described. That is, the semiconductor sealing material is mainly composed of an epoxy resin, a phenol resin, and a hardening accelerator in addition to the amorphous vermiculite powder. When the semiconductor sealing material is heated to a normal heat curing temperature (forming temperature), that is, about 150 ° C to 200 ° C, the protons of the phenol resin hardener are extracted by the hardening accelerator, and the epoxy resin and the phenol resin hardener are used. The anionic polymerization chain locks the reaction and the sealing material gradually hardens. When the amorphous vermiculite powder of the present invention is used, protons are released from the Bentley acid point by heating. The proton is bonded to the anionic polymerization end, and the sealing material is thermally hardened due to the temporary stop of the polymerization chain reaction. In other words, the amorphous strontium powder of the present invention can potentially thermally harden the sealing material, and can prepare a sealing material having excellent fluidity and viscosity characteristics during molding. When the ratio L of the detachment of pyridine at a temperature of 450 ° C or more and less than 550 ° C and the amount of detachment B of pyridine at a temperature of 150 ° C or more and less than 250 ° C is 0.8 or less, the potential effect is remarkable. Appeared in the ground. An example of the possibility of imparting an amorphous vermiculite powder based on such a mechanism has not existed in the past.

On the other hand, when the ratio L/B of the detachment amount L of pyridine heated at 450 ° C or more and less than 550 ° C and the amount of detachment B of pyridine heated at 150 ° C or more and less than 250 ° C is more than 0.8, not only As described above, the potential for releasing the proton-containing sealing material from the abundance of the amorphous vermiculite powder is difficult to occur, and the oxygen in the Lewis acid dot, the epoxy resin or the phenol resin generates a coordination bond, and conversely In order to prevent the flow of the amorphous vermiculite powder, the fluidity and viscosity characteristics of the sealing material are deteriorated, which is not preferable. The L/B ratio is preferably 0.7 or less, and more preferably 0.6 or less.

The detachment temperature and the amount of detachment of the pyridine from the amorphous vermiculite powder can be measured in the following order.

(1) Preparation of pyridine solution: 7.91 g of spectral analysis was weighed into a 500 ml measuring flask with pyridine, and the volume was measured with n-heptane using spectroscopic analysis. Next, 1 ml of this pyridine solution was taken in a 200 ml volumetric flask and made up to volume with n-heptane.

(2) Adsorption of pyridine on amorphous porphyrite powder: 4.00 g of an amorphous material which was previously dried in the atmosphere at 200 ° C for 2 hours and cooled together with a magnesium perchlorate desiccant in a desiccator A quality stone powder, finely weighed in a 25 ml volumetric flask. 20 ml of the aforementioned pyridine solution was added to the measuring flask and shaken for 3 minutes. The measuring flask was placed in a thermostat set at 25 ° C for 2 hours to adsorb pyridine to the amorphous vermiculite powder.

(3) Washing of amorphous talc powder: In order to wash the pyridine which is physically adsorbed to the amorphous chert powder, the measuring flask taken out from the constant temperature bath is oscillated and mixed and allowed to stand for 10 minutes to make non- The crystalline ochre powder settles. The upper clear liquid of the pyridine solution was discarded, and about 20 ml of n-heptane for spectroscopic analysis was added, and the measuring flask was shaken and mixed and allowed to stand for 10 minutes. The upper clear liquid was placed in a measuring container of an ultraviolet-visible spectrophotometer, and the absorbance at a wavelength of 190 to 340 nm was measured to confirm the absorption of 251 nm of pyridine. The washing operation of the n-heptane was repeated until the absorption of pyridine could not be confirmed by the supernatant liquid of n-heptane. After the absorption of pyridine could not be confirmed, the upper clear liquid of the measuring flask was discarded, and dry nitrogen was blown from the upper portion of the measuring flask at a flow rate of 10 minutes and 100 ml/min, and the amorphous ochre powder was placed in the chamber. Warm and dry.

(4) Determination of pyridine detachment temperature and detachment amount: 10 mg of the dried amorphous ochre powder was finely weighed in a sample cup of a DOBLE-SHOT PYROLIZER, and a thermal decomposition apparatus was used. The mass spectrum of pyridine was monitored while heating to determine the detachment temperature and the amount of detachment of pyridine. The detachment ratio of pyridine can be calculated from the area of the obtained curve.

In addition, the ultraviolet-visible spectrophotometer used for the presence or absence of the pyridine after physical adsorption is exemplified, and the product name "UV-Vis spectrophotometer UV-1800 type" manufactured by Shimadzu Corporation is used. The measurement was carried out using a container of 10 mm thickness made of quartz glass.

When the reagent used for the preparation of the pyridine solution is exemplified, there are pyridine (a grade for spectral analysis) and n-heptane (a grade for spectral analysis) manufactured by Wako Pure Chemical Industries, Ltd.

In addition, when the apparatus used for measuring the detachment temperature and the detachment amount of the pyridine adsorbed on the amorphous skutter powder is exemplified, there is a thermal decomposition apparatus, the product name "DOBLE-SHOT PYROLIZER PY-2020D" manufactured by FRONTIER LAB, and GC. /MS measuring device, trade name "GC/MSD 6890/5973" manufactured by Agilent.

The measurement conditions of the thermal decomposition furnace are the heating rate: the temperature is raised to 50 to 700 ° C at 25 ° C / min, the ITF temperature is raised to 150 to 300 ° C, and the measurement mode is EGA TEMP PROG. GC/MS measurement conditions column: UADTM-2.5N (no liquid phase) 0.15 mm Φ × 2.5 m, oven temperature: 300 ° C, inlet temperature: 280 ° C, measurement mode: SIM, separation ratio: 30 to 1 Monitoring ions: m/z = 52, 79. Further, the sum of the amounts of detachment of the monitor ions 52 and 79 was taken as the amount of detachment of pyridine.

Since the amount of pyridine to be removed is small, it is difficult to quantitatively quantify the absolute amount, and the amount of pyridine which is heated at 450 ° C or more and less than 550 ° C can be accurately determined based on the abundance measured by the above measurement method. L, the ratio L/B of the detachment amount B of pyridine when heated at 150 ° C or more and less than 250 ° C, or the total amount of detachment A of pyridine when heated at 150 ° C or more and less than 550 ° C, and above 150 ° C The ratio of the detachment amount B of pyridine when heated at less than 250 °C. When the pyridine system is not adsorbed or detached, the existence rate is 0, and the amount of adsorption and the amount of detachment increases. In order to enhance the fluidity, viscosity characteristics, and formability of the present invention, the maximum amount of pyridine release amount when heated at 150 ° C or more and less than 250 ° C must be 100 or more, and more preferably 200 or more. When the maximum value of the existence rate is less than 100, the effect of the present invention is hard to occur even if L/B satisfies a predetermined value.

Further, the existence ratio is a numerical value having a meaning obtained by the above measurement method.

When the amorphous vermiculite powder has the following conditions, it contributes to the effect of improving the fluidity, viscosity characteristics, and formability of the amorphous vermiculite powder of the present invention. That is, in the total amount of detachment A of pyridine when heated at 150 ° C or more and less than 550 ° C, the ratio of the detachment amount B of pyridine (B/A) × 100% when heated at 150 ° C or more and less than 250 ° C is 20 %the above. As described above, the normal heat curing temperature (growth temperature) of the semiconductor sealing material is about 150 ° C to 200 ° C, and the detachment amount of pyridine when heated at 250 ° C or more and less than 550 ° C is not only a semiconductor seal by proton discharge. The potential of the material is not easy to help. The detachment amount L of pyridine when heated at 450 ° C or higher and less than 550 ° C, on the contrary, hinders the flow of the amorphous sillimanite powder, resulting in fluidity and viscosity characteristics of the sealing material. It is not good to change. Therefore, in the total amount of detachment A of pyridine heated at 150 ° C or more and less than 550 ° C, the ratio of the detachment amount B of pyridine (B/A) × 100% when heated at 150 ° C or more and less than 250 ° C is 20 More than % is better. When the ratio is 25% or more, and more preferably 30% or more, the fluidity and viscosity characteristics at the time of lift molding are particularly remarkable.

Further, the effect of improving the fluidity, viscosity characteristics and formability of the present invention is such that the amorphous vermiculite powder has a specific surface area of 0.5 to 45 m 2 /g, an average particle diameter of 0.1 to 60 μm, and an average When the sphericity is 0.80 or more, it can be further promoted.

When the specific surface area of the amorphous vermiculite powder is less than 0.5 m 2 /g, since the contact area between the epoxy resin and the phenol resin hardener and the surface of the amorphous vermiculite powder is too small, proton emission is difficult to occur. The potential effect. On the other hand, when the specific surface area is more than 45 m 2 /g, it means that the amorphous vermiculite powder contains a large amount of small particles or a part or all of the surface of the particles has irregularities, and is sealed with a semiconductor sealing material. When the semiconductor is in a viscosity, the formability is impaired. A preferred specific surface area is in the range of 0.6 to 20 m 2 /g, more preferably 0.7 to 10 m 2 /g.

When the average particle diameter of the amorphous vermiculite powder is less than 0.1 μm, the viscosity is increased when the semiconductor is sealed by using a semiconductor sealing material, and the moldability is impaired, which is not preferable. Conversely, when the average particle diameter is larger than 60 μm, there is a problem that the semiconductor wafer is damaged, or a package having no unevenness and uniformity cannot be obtained. The preferred average particle size ranges from 2 to 55 microns, with a range from 3 to 50 microns being preferred. Further, the maximum particle diameter is preferably 196 μm or less, more preferably 128 μm or less.

Further, the average sphericity of the amorphous vermiculite powder of the present invention is preferably 0.80 or more, more preferably 0.85 or more.

The average particle diameter of the amorphous vermiculite powder of the present invention is measured based on particle size measurement by a laser diffraction scattering method. For the measurement system, the product name "CIRRUS GRANULOMETER 920" manufactured by CIRRUS Co., Ltd. was used, and the amorphous ochre powder was dispersed in water, and the mixture was subjected to dispersion treatment at an output of 200 W for 1 minute using an ultrasonic homogenizer. Further, the particle size distribution measurement was carried out at a particle diameter of 0.3, 1, 1.5, 2, 3, 4, 6, 8, 12, 16, 24, 32, 48, 64, 96, 128 and 192 μm. In the measured particle size distribution, the cumulative mass was 50% of the average particle diameter, and the cumulative mass was 100% of the particle size.

The specific surface area of the amorphous vermiculite powder of the present invention is measured based on the specific surface area measurement according to the BET method. The specific surface area measuring machine was measured using the product name "MACSORB HM-1208" manufactured by MOUNTECH.

The amorphous vermiculite powder of the present invention can exhibit its effects even when other inorganic powders are mixed. The content of the amorphous vermiculite powder of the present invention in the inorganic powder is preferably 2% by mass or more, more preferably 5% by mass or more. The type of the inorganic powder is preferably an amorphous vermiculite powder and/or an alumina powder other than the present invention. These powders may be used singly or in combination of two or more kinds. When the thermal expansion coefficient of the semiconductor sealing material is lowered or the wear resistance of the mold is reduced, the amorphous vermiculite powder can be selected as the inorganic powder, and when the thermal conductivity of the semiconductor sealing material is imparted, the alumina powder can be selected as the inorganic powder. Further, the amorphous vermiculite powder is preferably 95% or more in terms of an amorphous ratio measured by a method described later, and more preferably 97% or more.

The amorphous vermiculite powder of the present invention has an amorphous ratio measured by the following method, preferably 95% or more, more preferably 97% or more. For the amorphous ratio, a powder X-ray diffraction device (for example, the product name "Mini Flex type" manufactured by RIGAKU Co., Ltd.) is used, and X-ray diffraction analysis is performed in the range of 2θ of 26 ° to 27.5 ° of the CuKα line, and specific The intensity ratio of the diffraction peaks was measured. In the case of vermiculite powder, the main peak of the crystalline vermiculite system is present at 26.7°, and the peak is not present when the amorphous vermiculite is present. When the amorphous vermiculite and the crystalline vermiculite are doped, since the peak height of 26.7° according to the ratio of the crystalline vermiculite can be obtained, the X-ray intensity of the sample from the X-ray intensity to the X-ray intensity of the crystalline vermiculite standard sample In the ratio, the mixing ratio of the crystalline vermiculite (X-ray diffraction intensity of the sample/X-ray diffraction intensity of the crystalline vermiculite) is calculated, and according to the formula: amorphous ratio (%) = (1-crystal enthalpy) The stone doping ratio is ×100 to obtain the amorphous ratio.

The average sphericity of the amorphous vermiculite powder, the inorganic powder and the alumina powder of the present invention is preferably 0.80 or more, more preferably 0.85 or more. Thereby, the viscosity of the resin composition of the present invention can be lowered, and the moldability can be improved. The average sphericity can be used to input a particle image captured by a solid microscope (for example, the product name "SMZ-10" manufactured by NIKON Co., Ltd.) into an image analysis device (for example, the product name "MacView" manufactured by MOUNTECH Co., Ltd.), and the projected area from the photo particle. (A) and perimeter (PM) measurements. Since the area of the perfect circle corresponding to the circumference (PM) is (B), the sphericity of the particles is A/B. When the circumference (PM) of the sample is assumed to be a perfect circle having the same circumference, from PM = 2πr, B=πr ² , B=π×(PM/2π) ² , and the sphericity of the respective particles is sphericity=A/B=A×4π(PM) ² . The sphericity of 200 arbitrary particles obtained in this manner was determined, and the average value thereof was taken as the average sphericity.

For the method of measuring the sphericity other than the above, a particle image analyzer (for example, SYSMEX, Inc.; trade name "FPIA-3000") can be used to obtain the circularity of each particle from quantitative automatic measurement, according to the formula: sphericity = (Circularity) ² Calculated by conversion.

Next, a method for producing the amorphous vermiculite powder of the present invention will be described.

A method of producing the powder. The mixture containing the raw gangue powder and the Al source material is sprayed into a flame formed by a burner to melt (amorphize) and spheroidize the raw gangue powder, and to make the Al source material After being fused to the surface of the strontium powder and formed into a -O-Si-O-Al-O-Si-O- structure, it is maintained at a temperature of 60 to 150 ° C and a relative humidity of 60 to 90%. The amount of detachment of pyridine at a temperature of 150 ° C or more and less than 250 ° C and the amount of detachment of pyridine at 450 ° C or more and less than 550 ° C are adjusted for 15 to 30 minutes. Thereby, an amorphous vermiculite powder having the features of the present invention can be produced.

The apparatus containing the mixture of the raw material talc powder and the Al source material, which is sprayed by a flame, melted, fused, and spheroidized, and collected, for example, can be used by connecting a collector to a furnace body having a burner. The furnace body may be of an open type or a closed type, or a vertical type or a horizontal type. The amorphous ochre powder produced can be collected by adjusting one or more gravity sedimentation chambers, cyclones, bag filters, electric dust collectors, and the like in the collecting device. For example, Japanese Laid-Open Patent Publication No. Hei 11-57451, No. Hei 11-71107, and the like. In order to maintain the amorphous vermiculite powder in an environment of a temperature of 60 to 150 ° C and a relative humidity of 60 to 90% for 15 to 30 minutes, for example, a line for supplying steam may be provided in the above-mentioned collecting device, and the temperature may be set to a predetermined temperature. The vapor temperature and the steam supply amount are adjusted in terms of relative humidity. In order to adjust the holding time, the switching time of the discharge valve (used to discharge the amorphous vermiculite powder from the above-mentioned collecting device out of the system) can be adjusted in such a manner as to be a desired time.

Just after the mixture containing the raw ruthenium powder and the Al source material is sprayed into the flame formed by the burner, the -O-Si-O-Al-O-Si-O- structure is affected by the high temperature flame. The acid point is mostly changed to a Lewis acid, and a part of the acid is changed to a H ₂ O bond contained in a combustion gas of a flammable gas used for flame formation. The L/B system has a relationship greater than 0.8. Therefore, in the case of the amorphous vermiculite powder which has not been subjected to the treatment of the production method of the present invention, the fluidity and viscosity characteristics at the time of molding cannot be improved by the potential effect.

When the humidity to be humidified is less than 60%, or the holding time is less than 15 minutes, the change in Lewis acid becomes insufficient for the succinyl acid, and the detachment ratio of pyridine cannot be controlled to 0.8 or less. Further, when the humidity is more than 90% or the holding time is more than 30 minutes, since the amorphous vermiculite powder is agglomerated, the formability of the semiconductor sealing material is lowered, which is not preferable.

The preferred humidification humidity is 65-85%, and the humidification time is in the range of 20-25 minutes. Similarly, when the humidification temperature is less than 60 ° C, H ₂ O is difficult to bond, and the change in Lewis acid is insufficient for the linoleic acid. As a result, the detachment ratio of pyridine cannot be controlled to 0.8 or less. On the other hand, when the temperature is kept higher than 150 ° C, since the temperature is too high, H ₂ O is hard to bond, and L/B cannot be made 0.8 or less. The L/B ratio can be adjusted to 0.8 or less only when the temperature is maintained within the range of 60 to 150 °C. The preferred holding temperature is 70 to 120 ° C, more preferably in the range of 75 to 100 ° C.

The raw ruthenium powder can be a high-purity vermiculite produced by a synthetic method such as high-purity vermiculite, high-purity ceramsite, quartz, crystal, or the like, or a precipitated vermiculite or tannin. A powder or the like is preferably a vermiculite powder in consideration of cost or easy availability. A commercially available product of vermiculite powder is obtained by pulverizing various types of particle diameters by a pulverizer such as vibration milling or ball milling to obtain a desired particle size of the amorphous ochre powder. The way to choose the appropriate particle size.

In the present invention, the Al source material is preferably an alumina powder. Examples of the Al source material include alumina, aluminum hydroxide, aluminum nitrate, aluminum chloride, and an aluminum organic compound. Among them, since the alumina system is close to the melting point of the raw material gangue powder, it is preferably melted on the surface of the raw ruthenium powder when being sprayed from the burner, and the impurity content is also low.

Further, the average particle diameter of the alumina powder is preferably 0.01 to 10 μm. When the average particle diameter is less than 0.01 μm, the powder tends to aggregate, and the composition when it is fused with the vermiculite powder tends to be uneven. Similarly, when it is larger than 10 μm, the composition when it is fused with the vermiculite powder may be uneven. The preferred pattern of the preferred average particle size is 0.03 to 8 μm, preferably 0.05 to 5 μm.

Further, the content of Al ₂ O ₃ in the amorphous vermiculite powder of the present invention is preferably 0.1 to 20% by mass. When the content of Al ₂ O ₃ is less than 0.1% by mass, the increase in acid point is insufficient. On the contrary, when it is more than 20% by mass, the thermal expansion coefficient of the amorphous vermiculite powder becomes too large, and the original The function of the semiconductor sealing material has an adverse effect. The content of Al ₂ O ₃ is preferably 0.15 to 18% by mass, more preferably 0.2 to 15% by mass.

The Al ₂ O ₃ content (equivalent oxide) of the amorphous vermiculite powder of the present invention can be measured by the following procedure using atomic absorption spectrometry. That is, 1 gram of the amorphous ochre powder is finely weighed in a white gold dish, and the test reagent super hydrofluoric acid and the test drug super perchloric acid are each 20 ml and 1 ml. The platinum blood was placed on a sand bath heated to 300 ° C for 15 minutes, cooled to room temperature, and transferred to a 25 ml volumetric flask and made up to volume with pure water. The amount of Al in the solution was quantified by a calibration curve method using an atomic absorption spectrophotometer. The Al content was converted into Al ₂ O ₃ to calculate the content ratio in the amorphous vermiculite powder. The atomic absorption photometer is exemplified by the product name "Atomic Absorbance Photometer AA-969" manufactured by OPTRONIC Corporation of Japan. When the standard solution used for the calibration curve is prepared, an Al standard solution for atomic absorption by Toki Chemical Co., Ltd. (concentration: 1000 ppm) is used. Further, the flame at the time of measurement was quantified using an acetylene-nitrogen monoxide flame and measuring the absorbance at a wavelength of 309.3 nm.

Further, in the present invention, the amount of the Al source material which can be fused to the surface of the raw ruthenium powder can be sized by the amount of pyridine removed and the detachment temperature when the amorphous iridium powder is adsorbed and detached by heating. The amount, the humidification holding condition, the specific surface area, the average particle diameter, and the like are adjusted.

The specific surface area and the average particle diameter of the amorphous vermiculite powder can be adjusted by the particle size composition of the raw vermiculite powder, the flame temperature, and the like. Further, the average sphericity and the amorphous ratio can be adjusted by the amount of the raw material strontium powder supplied to the flame, the flame temperature, and the like. In addition, by preparing a plurality of kinds of amorphous vermiculite powders having different sizes, amounts, humidification holding conditions, specific surface areas, and average particle diameters of the fused Al source material, and mixing the two or more types as appropriate, An amorphous vermiculite powder obtained by further specifically adsorbing pyridine and heating off, the detachment amount of pyridine, the detachment temperature, the specific surface area, and the average particle diameter are obtained.

The resin composition of the present invention contains a resin composition of the amorphous vermiculite powder of the present invention or the inorganic powder of the present invention in a resin. The content of the amorphous vermiculite powder or the inorganic powder in the resin composition is preferably from 10 to 95% by mass, more preferably from 30 to 90% by mass.

The resin can be used as an epoxy resin, an anthracene resin, a phenol resin, a melamine resin, a urea resin, an unsaturated polyester, a fluororesin, a polyimine, a polyamidimide, a polyether phthalimide, or the like. Polyesters such as butylene phthalate, polyethylene terephthalate, polyphenylene sulfide, aromatic polyester, polyfluorene, liquid crystal polymer, polyether fluorene, polycarbonate, maleicene An amine-modified resin, an ABS resin, an AAS (acrylonitrile-acrylic rubber-styrene) resin, an AES (acrylonitrile-ethylene-propylene-diene rubber-styrene) resin, or the like.

Among these, the resin for the semiconductor sealing material is preferably one or more epoxy resins in one molecule. When exemplified, there are a phenol novolak type epoxy resin, an o-cresol novolac type epoxy resin, and a phenol phenol and an aldehyde novolak resin epoxidized, and bisphenol A, bisphenol F, and A propylene glycol epoxy resin, a linear aliphatic epoxy resin, or an alicyclic epoxy resin obtained by reacting a polycarboxylic acid such as a bisphenol S or a polyacrylic acid such as a decyl phenol or a dimer acid with epichlorohydrin , heterocyclic epoxy resin, alkyl modified polyfunctional epoxy resin, β-naphthol novolak epoxy resin, 1,6-dihydroxynaphthalene epoxy resin, 2,7-dihydroxynaphthalene epoxy A resin, a bishydroxybiphenyl type epoxy resin, and an epoxy resin obtained by introducing a halogen such as bromine to impart flame retardancy. Among them, in terms of moisture resistance or solder flow resistance, an o-cresol novolak epoxy resin, a bishydroxybiphenyl type epoxy resin, a naphthalene skeleton epoxy resin or the like is preferable.

The epoxy resin used in the present invention contains a curing agent for an epoxy resin, a curing agent for an epoxy resin, and a curing accelerator for an epoxy resin. The hardener of the epoxy resin may, for example, be selected from the group consisting of phenol, cresol, xylenol, resorcinol, chlorophenol, t-butylphenol, nonylphenol, isopropylphenol and octylphenol. a novolak resin, a poly-p-hydroxystyrene resin, a bisphenol A or a bisphenol S obtained by reacting a mixture of one or more of them in a group with formaldehyde, p-formaldehyde or p-xylene under an oxidation catalyst. a tri-functional phenol such as a bisphenol compound, a gallic phenol or a fluoroglycerol, an acid anhydride such as maleic anhydride, phthalic anhydride or pyrogallanic acid, m-phenylenediamine, diaminodiphenylmethane or diamine. An aromatic amine such as a diphenyl hydrazine.

Further, in order to promote the reaction between the epoxy resin and the curing agent, a curing accelerator such as triphenylphosphine, benzyldimethylamine or 2-methylimidazole can be used.

In the resin composition of the present invention, the following components can be further prepared as necessary. In other words, the low-stressing agent may be a rubber-like substance such as a silicone rubber, a polysulfide rubber, an acrylic rubber, a butadiene rubber, a styrene block copolymer or a saturated elastomer, or various thermoplastic resins. A resinous substance such as a phthalocyanine resin, or a resin obtained by modifying a part or all of an epoxy resin or a phenol resin using an amine oxime, an epoxy oxime, an alkoxy oxime or the like. Examples of the decane coupling agent include epoxy decane such as γ-glycidoxypropyltrimethoxydecane and β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and aminopropyltriethyl ethane. Aminodecane, phenyltrimethoxydecane, methyltrimethoxydecane, octadecyl, such as oxydecane, ureidopropyltriethoxydecane, N-phenylaminopropyltrimethoxydecane, etc. A hydrophobic decane compound such as trimethoxy decane or a thiodecane or the like. Examples of the surface treatment agent include a Zr-clamping agent, a titanate coupling agent, and an aluminum-based coupling agent. Examples of the flame retardant auxiliary include Sb ₂ O ₃ , Sb ₂ O ₄ , and Sb ₂ O ₅ . Examples of the flame retardant include a halogenated epoxy resin or a phosphorus compound. Examples of the colorant include carbon black, iron oxide, a dye, a pigment, and the like. Further, examples of the release agent include natural waxes, synthetic waxes, metal salts of linear fatty acids, guanamines, esters, and paraffin waxes.

The resin composition of the present invention can be used by blending the above materials in a prescribed amount using a blender or a Henschel Mixer, etc., using a heating roll, a kneader, a uniaxial or biaxial extruder. After the kneaded material is cooled, it is pulverized and manufactured.

The semiconductor sealing material-based resin composition of the present invention contains an epoxy resin and is composed of a curing agent containing an epoxy resin and a curing accelerator of an epoxy resin.

The semiconductor sealing material of the present invention is used to seal the semiconductor, and conventional molding means such as transfer molding or vacuum printing molding can be used.

Example

Hereinafter, the embodiments of the present invention are explained in more detail, but are not to be construed as being limited to the same.

Examples 1 to 10 and Comparative Examples 1 to 8

The raw material used for producing the amorphous porphyrite powder of the present invention is a crystalline vermiculite powder (SiO ₂ content: 99.9% by mass) manufactured by KINSEIMATE Co., Ltd., and an alumina powder and an aluminum hydroxide powder manufactured by Nippon Light Metal Co., Ltd. Each of the powders is pulverized and classified to have a particle size adjustment, and various raw material shale powders and Al source materials having different average particle diameters are prepared. In the apparatus described in Japanese Laid-Open Patent Publication No. Hei 11-57451, a steam generating boiler and a steam supply line are provided in the collecting apparatus, and the steam temperature and the steam supply amount can be adjusted to obtain a required temperature and Relative humidity is used. Using this apparatus, melting, fusion, spheroidization, and humidification holding treatment were carried out in a flame to produce various amorphous vermiculite powders shown in Tables 1 and 2. Further, these powders were appropriately blended to produce amorphous vermiculite powders and inorganic powders shown in Tables 3 and 4.

In addition, the amount of detachment of pyridine and the temperature of detachment of pyridine when pyridine is adsorbed by the amorphous porphyrite powder are changed by the size, amount, and humidification condition of the Al source material fused on the surface of the raw gangue powder. , specific surface area, average particle size, etc. to adjust.

The specific surface area and the average particle diameter of the amorphous vermiculite powder are adjusted by the particle size composition of the raw vermiculite powder or the flame temperature, and the average sphericity and amorphous ratio of the amorphous vermiculite powder are The amount of the raw material strontium powder supplied to the flame, the flame temperature, and the like are adjusted. Further, the formation of the flame uses LPG and oxygen, and the carrier gas for carrying the raw material powder to the burner also uses oxygen. The maximum temperature of the flame is in the range of about 2,000 ° C to 2,300 ° C.

The measurement of the detachment temperature and the amount of detachment of pyridine from the amorphous vermiculite powder and the pyridine from the amorphous vermiculite powder was carried out in accordance with the method described in the paragraph (0014).

The amorphous ratio of the obtained amorphous vermiculite powder is 99.5% or more. The specific surface area, the average particle diameter, the average sphericity, the pyridine detachment temperature, and the detachment amount of the powders were measured to calculate the amount of detachment L of pyridine when heated at 450 ° C or more and less than 550 ° C, and 150 ° C or more and less than 250 The ratio of the detachment amount B of the pyridine when heated at °C to L/B, and the total amount of detachment of pyridine at a temperature of 150 ° C or more and less than 550 ° C, the amount of pyridine detachment when heated at 150 ° C or more and less than 250 ° C The ratio of B occupancy (B/A) × 100%. The results are shown in Tables 3 and 4.

The characteristics of the obtained amorphous vermiculite powder and inorganic powder as a filler of a semiconductor sealing material were evaluated. That is, 7.8 parts of a biphenyl type epoxy resin (YX-4000H manufactured by JAPAN EPOXY RESINS) and 5.1 parts of a phenol aralkyl resin (XLC-LL manufactured by Mitsui Chemicals Co., Ltd.) were added to each of 87.8 parts by mass of the same powder. ), 0.2 parts of triphenylphosphine, 0.6 parts of an epoxy resin coupling agent, 0.1 part of carbon black, and 0.3 part of carnauba wax, and dry blended using a Hansel mixer. Subsequently, the same direction nip biaxial extruder (screw diameter D = 25 mm, kneading disc length 10 Dmm, paddle rotation speed 50 to 120 rpm, discharge amount of 2.5 kg / hour, mixing temperature of 99 to 100 ° C) was used for heating and kneading. The kneaded material (discharged material) was pressurized and cooled by a press machine, and then pulverized to produce a semiconductor sealing material. The viscosity characteristics (hardened viscoelasticity tester torque), formability (linear deformation rate), and fluidity (spiral flow) of the semiconductor sealing material obtained by the following evaluation were evaluated.

The results are shown in Tables 3 and 4.

(1) Viscosity characteristics (hardened viscoelasticity test machine torque)

The viscosity characteristics of the obtained semiconductor sealing material were measured as follows. The semiconductor sealing material was heated to 110 ° C using a hardened viscoelasticity tester (for example, the product name "CURASTMETER 3P-S type" manufactured by JSR TRADING Co., Ltd.), and the torque after 30 seconds was used as the viscosity index. The smaller the value is, the better the viscosity characteristic is.

(2) Formability (linear deformation rate)

The moldability of the obtained semiconductor sealing material was measured as follows. In a BGA (Ball Grid Array) substrate, two pieces of analog semiconductor elements having a size of 8 mm × 8 mm × 0.3 mm were overlapped by a die attach adhesive film, and connected by a gold wire. Subsequently, each of the semiconductor sealing materials was used, and after forming into a package size of 38 mm × 38 mm × 1.0 mm using a transfer molding machine, post-baking was performed at 175 ° C for 8 hours to manufacture a BGA type semiconductor. The gold wire portion of the semiconductor was observed using a soft X-ray transmitting device to measure the gold wire deformation rate. The gold wire deformation rate is determined by measuring the shortest distance X of the sealed line and the maximum displacement amount Y of the sealed line to obtain (Y/X) × 100%. This value is the average of the deformation rate of the 12 gold wires. Further, the gold wire has a diameter of Φ 30 μm and an average length of 5 mm. The transfer molding conditions were a mold temperature of 175 ° C, a molding pressure of 7.4 MPa, and a dwell time of 90 seconds. The smaller the value, the smaller the amount of deformation of the wire and the better the formability.

(3) Fluidity (rotary flow)

The measurement of each semiconductor sealing material was carried out using a transfer molding machine equipped with a mold for rotating flow measurement according to EMMI-I-66 (Epoxy Molding Material Institute; Society of Plastic Industry) Rotate the flow value. Further, the transfer molding conditions were a mold temperature of 175 ° C, a molding pressure of 7.4 MPa, and a dwell time of 120 seconds. When the value is larger, it means that the fluidity is good.

As is clear from the comparison between the examples and the comparative examples, the amorphous cherish powder according to the present invention can prepare a resin composition, particularly a semiconductor seal, which is more excellent in fluidity, viscosity characteristics and formability when compared with the comparative example. material.

Industrial use possibility

The amorphous strontium powder of the present invention can be used as a filler in a semiconductor sealing material used in automobiles, portable electronic devices, personal computers, home electric products, and the like, and laminated sheets mounted on semiconductors. In addition to the semiconductor sealing material, the resin composition of the present invention can be formed by immersing and curing glass woven fabric, glass nonwoven fabric, and other organic substrates, and is used as, for example, a prepreg for a printed substrate, or various Engineering plastics, etc.

The entire disclosure of Japanese Patent Application No. 2008-129122, filed on-

Claims (8)

An amorphous strontium powder characterized in that pyridine is desorbed at a temperature of 450 ° C or more and less than 550 ° C after adsorption of pyridine by an amorphous vermiculite powder, and is less than 250 ° C and less than 250 ° C. The ratio L/B of the detachment amount B of pyridine during heating is 0.8 or less. The amorphous strontium powder according to claim 1, wherein the amorphous strontium powder is adsorbed with pyridine, and the total detachment amount A of pyridine when heated at 150 ° C or more and less than 550 ° C is 150. The ratio (B/A) × 100% of the detachment amount B of pyridine when heated at a temperature of ° C or more and less than 250 ° C is 20% or more. The amorphous vermiculite powder according to claim 1 or 2 has a specific surface area of 0.5 to 45 m 2 /g, an average particle diameter of 0.1 to 60 μm, and an average sphericity of 0.80 or more. An inorganic powder containing 2% by mass or more of the amorphous vermiculite powder according to any one of claims 1 to 3, and further comprising an amorphous vermiculite powder other than the present invention and/or Or alumina powder. A method for producing an amorphous strontium powder according to any one of claims 1 to 3, which is characterized in that it contains a raw material talc powder and A1. The mixture of the source materials is sprayed into a flame formed by a burner to produce an amorphous vermiculite powder, and then maintained at a temperature of 60 to 150 ° C and a relative humidity of 60 to 90% for 15 to 30 minutes. A resin composition containing 10 to 95% by mass of an amorphous strontium powder or an inorganic powder according to any one of claims 1 to 4 of the patent application. end. The resin composition of claim 6, wherein the resin composition is a resin-based epoxy resin. A semiconductor sealing material which is obtained by using a resin composition as claimed in claim 6 or 7, and when the resin composition is an epoxy resin, is hardened by a hardener containing an epoxy resin and an epoxy resin. The composition of the accelerator is composed of.