TW201343554A - Magnesium hydroxide particle and resin composition containing the same - Google Patents

Abstract

Thin invention provides a magnesium hydroxide particle and a resin composition containing the same, the magnesium hydroxide particle being a hexagonal prism shape particle having a crystal shape composed of hexagonal base planes of two parallel upper and lower surfaces, and prism surfaces of six outer peripheral surfaces formed between the base planes, wherein, the size of a c-axis direction of the hexagonal prism shape particle is 0.5 to 1.5 μ m, the size of the c-axis direction is 60% or more than the median particle diameter of the hexagonal prism shape particle, the inflection point diameter is 0.1 to 0.4 μ m, the inter-particle void is 0.6*10<SP>-3</SP> to 1.0*10<SP>-3</SP>m<SP>3</SP>.kg<SP>-1</SP>, and the purity is 98.0 mass% or higher.

Description

Magnesium hydroxide particles, and a resin composition containing the magnesium hydroxide particles

The present invention relates to magnesium hydroxide particles and a resin composition containing the magnesium hydroxide particles.

Magnesium hydroxide is added as a flame retardant of a resin composition because it does not generate a toxic gas during sintering and is preferred for the environment.

Conventionally, magnesium hydroxide is a fine crystal of magnesium hydroxide, and particles having a secondary particle diameter of about 10 to 100 μm are formed. Magnesium oxide produced from these materials can only produce products having an uneven particle size. Therefore, when the magnesium hydroxide or magnesium oxide is used as a resin additive, there is a problem that the dispersibility is not good, the function as an additive is not sufficiently exhibited, and the physical properties of the resin are impaired. In order to solve such a problem, magnesium hydroxide having a specific shape has been proposed for the purpose of improving dispersibility (Patent Document 1).

However, the magnesium hydroxide disclosed in Patent Document 1 has a certain degree of dispersibility due to a change in shape, but it is still insufficient. In addition, the magnesium hydroxide disclosed in Patent Document 1 contains particles of fine particles or crystals having a non-uniform crystal shape. Therefore, when the resin is kneaded as an additive in the synthetic resin, the resin viscosity is rapidly increased to deteriorate the fluidity and workability, and the molding is performed. The problem of reduced speed reduces productivity.

Advanced technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-306659

An object of the present invention is to provide a magnesium hydroxide particle which is excellent in fluidity and dispersibility when blended in a resin, and a resin composition containing the magnesium hydroxide particle.

In order to solve the problem, the inventors of the present invention conducted various reviews and found that when magnesium hydroxide particles having fine crystal particles and amorphous crystal-shaped particles and having a uniform crystal shape are used as a resin composition additive, excellent effects can be obtained. Thus, the present invention has been completed. Further, the inventors of the present invention have found that the magnesium oxide particles used in the hydration reaction can be produced by using a magnesium hydroxide slurry containing a specific amount of iron, vanadium and manganese, and the magnesium hydroxide particles can be obtained by hydrating the magnesium oxide.

That is, the present invention relates to a magnesium hydroxide particle having a hexagonal column-shaped particle shape, comprising a hexagonal base surface of two upper and lower sides parallel to each other, and an angular cylinder of the outer circumference 6 surface formed between the base surfaces. The hexagonal column-shaped particle has a size in the c-axis direction of 0.5 to 1.5 μm , and the dimension in the c-axis direction is 60% or more of the median diameter of the hexagonal column-shaped particle, and the inflection point diameter is 0.1 to 0.4 μ m, the inter-particle gap is 0.6×10 ^-3 to 1.0×10 ^-3 m ³ . Kg ^-1 , the purity is 98.0% by mass or more.

The present invention relates to the aforementioned magnesium hydroxide particles, wherein the Fe content It is from 100 to 500 ppm, the V content is from 30 to 250 ppm, and the Mn content is from 10 to 150 ppm.

The present invention relates to the aforementioned magnesium hydroxide particles, wherein the mode diameter in the pore distribution is 0.1 to 0.3 μm , and the mode volume is 2.3 × 10 ^-3 to 2.8 × 10 ^-3 m ³ . Kg ^-1 .

The present invention relates to the aforementioned magnesium hydroxide particles, wherein the zeta potential is -20 to -25 mV.

The invention relates to a method for producing magnesium hydroxide particles, comprising: (a) adding magnesium hydroxide, an iron compound, a vanadium compound and a manganese compound to a solvent and stirring, thereby obtaining a slurry containing magnesium hydroxide, iron, vanadium and manganese; a step wherein the amount of Fe added is 100 to 500 ppm, the amount of V added is 30 to 250 ppm, and the amount of Mn added is 10 to 150 ppm with respect to magnesium hydroxide; (b) a slurry containing magnesium hydroxide, iron, vanadium, and manganese a step of filtering, washing with water and drying to obtain coarse particles of magnesium hydroxide; (c) a step of firing magnesium oxide coarse particles in an atmosphere at 800 to 1900 ° C to obtain magnesium oxide particles; and (d) pulverizing Magnesium oxide particles, and a magnesium oxide powder having a median diameter of 3 to 30 μm and a crystal diameter of 10×10 ^-9 m or more is added to warm water having an organic acid content of 100 ° C or less. Next, the hydration reaction of magnesium oxide is carried out under high shear stirring, and then the resulting solid fraction is separated by filtration, washed with water and dried to obtain a magnesium hydroxide particle.

The present invention relates to a resin composition comprising: (I) an epoxy resin, (II) a hardener, (III) an inorganic filler, and (IV) the aforementioned magnesium hydroxide particles as a flame retardant, or Magnesium hydroxide particles obtained by the manufacturing method child.

The present invention relates to the resin composition described above, wherein the magnesium hydroxide particles are blended in an amount of from 1 to 35 mass% of the resin composition.

The present invention relates to the above resin composition, which is a sealing agent for a semiconductor.

The present invention relates to a semiconductor device using the above-described resin composition.

According to the present invention, magnesium hydroxide particles having good fluidity and dispersibility when blended with a resin, and a resin composition containing the magnesium hydroxide particles can be obtained.

Fig. 1 is an explanatory view showing the appearance of the magnesium hydroxide particles of the present invention.

Magnesium hydroxide particles

The magnesium hydroxide particles of the present invention are hexagonal column shapes as shown in Fig. 1, and magnesium hydroxide particles having a c-axis direction dimension (hereinafter referred to as "Lc") of 0.5 to 1.5 μm . In the magnesium hydroxide particles of the present invention, Lc is preferably from 0.9 to 1.4 μm . Further, the ratio of Lc to the median diameter (d) of the magnesium hydroxide particles, that is, Lc/d is 60% or more, preferably Lc/d is from 60 to 150%, more preferably from 65 to 90%.

When Lc/d is 60% or more, the flowability of the magnesium hydroxide particles to the resin is good. This is because the larger the Lc/d value, the larger the hexagonal column shape particles are in the c-axis direction. There is an interaction between the magnesium hydroxide particles and the resin, and the particle shape is the cause of the free movement of the bound resin. Generally this tendency is affected by the shape of the particles. That is, the greater the degree of shape anisotropy, the greater the impact. Since the magnesium hydroxide particles of the present invention are particles which are sufficiently grown in the c-axis direction, the shape anisotropy is smaller than that of the conventional one, and the reason for hindering the free movement of the resin is reduced. Further, when the above Lc/d is satisfied, the median diameter d of the magnesium hydroxide particles is not particularly limited, but is usually preferably in the range of 0.1 to 10 μm .

Further, the c-axis direction dimension Lc of the magnesium hydroxide particles is a measured value of particles having the largest length in the field of view when observed by a scanning electron microscope. Further, the median diameter is a 50% particle diameter (D ₅₀ ) cumulative by the volume basis measured by a laser diffraction scattering type particle size distribution analyzer.

The magnesium hydroxide particles of the present invention have an inflection point diameter of 0.1 to 0.4 μm and interparticle voids of 0.6 × 10 ^-3 to 1.0 × 10 ^-3 m ³ . Kg ^-1 . In the present invention, the inflection point diameter and the interparticle voids can be determined by measuring the mercury intrusion pore distribution. The relationship between the pore diameter and the cumulative pore volume determined by the mercury indentation pore distribution measurement is called a cumulative pore volume curve.

Specifically, in the measurement of the mercury-indented pore size distribution, the horizontal axis is the pore diameter obtained by the press-in pressure, and the vertical axis is the cumulative pore volume, and the pore volume curve is obtained. The pore diameter was converted from the pressure of the pressed pressure of mercury, and was converted by the following formula (I) (Washburn type).

D=-(1/P). 4γ. Cosψ (I) here, D: pore diameter (m); P: pressure (Pa); γ: surface tension of mercury (485 dyne/cm (0.485 Pa.m)); ψ: contact angle of mercury (130° = 2.268793 rad).

The inflection point diameter is the diameter of the pore of the largest point of the pore diameter in the inflection point where the cumulative pore volume curve sharply rises. Further, the interparticle gap amount is the cumulative pore volume of the inflection point diameter. When the inflection point diameter and the inter-particle gap are in the range of the present invention, the crystal shape and the particle diameter of the magnesium hydroxide particles are uniform, and the aggregated or amorphous crystal particles are extremely small.

When the inflection point diameter is less than 0.1 μm , the magnesium hydroxide particles contain fine particles having a non-uniform crystal shape. Therefore, when the magnesium hydroxide particles having a recurve point diameter of less than 0.1 μm are kneaded as an additive to the synthetic resin, the resin viscosity is rapidly increased to deteriorate the fluidity. Further, when the radius of recursion exceeds 0.4 μm , the crystal shape of a part of the particles of the magnesium hydroxide particles becomes amorphous, and the particles are easily aggregated to form coarse particles. Therefore, when particles having an inflection point diameter of more than 0.4 μm are kneaded as an additive to the synthetic resin, a coarse aggregate is formed and the particles are easily precipitated in the resin, thereby impeding fluidity or workability. In the present invention, the inflection point diameter is preferably from 0.2 to 0.3 μm .

If the interparticle space is less than 0.6 × 10 ^-3 m ³ . In kg ^-1 , the magnesium hydroxide particles contain fine particles having a non-uniform crystal shape. Therefore, if the interparticle space is less than 0.6 × 10 ^-3 m ³ . When the magnesium hydroxide particles of kg ^{-1 are} kneaded as an additive to the synthetic resin, it is easy to form particles or voids in which the resin cannot penetrate into the particles and cannot be dispersed. At the same time, the liquidity will also deteriorate. In addition, if the interparticle voids exceed 1.0 × 10 ^-3 m ³ . When kg ^-1 , the crystal shape of a part of the particles of magnesium hydroxide becomes amorphous, and the particles are easily aggregated and form coarse particles. Therefore, if interparticle voids are used, it exceeds 1.0 × 10 ^-3 m ³ . When the magnesium hydroxide particles of kg ^{-1 are} kneaded as a additive to the synthetic resin, a coarse aggregate is formed and the particles are easily precipitated in the resin, thereby impeding fluidity or workability. In the present invention, the interparticle voids are preferably from 0.7 × 10 ^-3 to 0.9 × 10 ^-3 m ³ . Kg ^-1 .

The purity of the magnesium hydroxide particles of the present invention is 98.0% by mass or more. If it is in this range, the elution of an impurity can be suppressed extremely, and it can be suitably used for the additive of the resin used as a highly functional material. The purity of the magnesium hydroxide particles of the present invention is preferably from 98.5 to 99.9% by mass.

In the present specification, the purity is an impurity element (Ag, Al, B, Ba, Bi, Cd, Cl, Co, Cr, Cu, Fe, Ga, In, K, Li, Mn, Mo, Na, in the particle to be measured). The content of Ni, P, Pb, S, Si, Sr, Tl, V, Zn, Ti, and Zr) is deducted from 100% by mass of the total content of these. Determination of impurities (Ag, Al, B, Ba, Bi, Cd, Co, Cr, Cu, Fe, Ga, In, K, Li, Mn, Mo, Na, Ni, P, Pb, S, Si, Sr, Tl, V, Zn, Ti, and Zr) were measured by dissolving the sample in an acid using an ICP emission spectrometer, and the amount of Cl was measured by dissolving the sample in an acid using a spectrophotometer.

The magnesium hydroxide particles of the present invention preferably have an iron (Fe) content of 100 to 500 ppm, a vanadium (V) content of 30 to 250 ppm, and a manganese (Mn) content of 10 to 150 ppm. When the Fe content is 100 to 500 ppm, the V content is 30 to 250 ppm, and the Mn content is 10 to 150 ppm, the crystal shape of the magnesium hydroxide particles can be easily formed, and the dissolution of the metal impurities can be extremely suppressed. Used as an additive, such as a flame retardant. More preferably, the Fe content is 150 to 400 ppm and the V content is 60 to 120 ppm and Mn content of 40 to 80 ppm.

The mode diameter of the magnesium hydroxide of the present invention is preferably from 0.1 to 0.3 μm . Further, the mode volume of the magnesium hydroxide particles of the present invention is preferably from 2.3 × 10 ^-3 to 2.8 × 10 ^-3 m ³ . Kg ^-1 . In the case of such a mode diameter and a mode volume, the crystal shape and the particle diameter of the magnesium hydroxide particles are more uniform, and the aggregated or amorphous crystal particles are extremely few, and this is preferable.

The modal volume and the modal diameter of the present invention can be obtained by measuring the pore size distribution of the mercury intrusion type. Here, the modal volume is the maximum value of the log differential pore volume distribution curve, and the modal diameter log differential corresponds to the pore size. The pore diameter of the maximum value of the volume distribution curve. When the pore distribution of the magnesium hydroxide particles of the present invention is measured by a mercury intrusion method, the mode diameter corresponds to the diameter of the gap between the magnesium hydroxide particles.

The δ potential of the magnesium hydroxide particles of the present invention is preferably from -20 to -25 mV, more preferably from 21 to -25 mV. When the δ potential is in this range, the dispersibility in the resin is further improved, and sufficient fluidity can be obtained.

2. Method for producing magnesium hydroxide particles of the present invention

The magnesium hydroxide particles of the present invention can be produced, for example, in the following manner.

First, magnesium hydroxide, an iron compound, a vanadium compound, and a manganese compound are added to a solvent and stirred to obtain a slurry containing magnesium hydroxide, iron, vanadium, and manganese, washed with water, and dried to obtain coarse magnesium hydroxide particles. Next, the magnesium hydroxide coarse particles are fired at a temperature in the range of 800 to 1900 ° C, whereby a magnesium oxide raw material is obtained. Next, the magnesium oxide raw material is pulverized, and the obtained magnesium oxide powder having a median diameter of 3 to 30 μm and a crystal diameter of 10×10 ^-9 m or more is added to the warm water of 100 ° C or less to which the organic acid has been added. The hydration reaction of the magnesium oxide powder is carried out under high shear stirring, and the resulting solid fraction is separated by filtration, washed with water and dried to obtain magnesium hydroxide particles according to the production method of the present invention.

Specifically, the method for producing magnesium hydroxide particles of the present invention comprises: (a) adding magnesium hydroxide, an iron compound, a vanadium compound, and a manganese compound to a solvent and stirring, thereby obtaining magnesium hydroxide, iron, vanadium, and manganese. a step of slurry, wherein the amount of iron added is 100 to 500 ppm, the amount of vanadium added is 30 to 250 ppm, and the amount of manganese added is 10 to 150 ppm with respect to magnesium hydroxide; (b) magnesium hydroxide, iron, vanadium and manganese are contained The slurry is filtered, washed with water and dried to obtain coarse magnesium hydroxide particles; (c) a step of calcining the magnesium hydroxide coarse particles in an atmosphere at 800 to 1900 ° C to obtain magnesium oxide particles; and (d) The magnesium oxide particles are pulverized, and the obtained magnesium oxide powder having a median diameter of 3 to 30 μm and a crystal diameter of 10×10 ^-9 m or more is added to the warm water of 100 ° C or less to which the organic acid has been added. Then, the hydration reaction of magnesium oxide is carried out under high shear stirring, and then the resulting solid fraction is separated by filtration, washed with water and dried, thereby obtaining a step of obtaining magnesium hydroxide particles.

(1) Step (a)

Step (a) is a step of adding magnesium hydroxide, an iron compound, a vanadium compound and a manganese compound to a solvent and stirring to obtain a slurry containing magnesium hydroxide, iron, vanadium and manganese, wherein iron is added relative to magnesium hydroxide. The amount is 100 to 500 ppm, the amount of vanadium added is 30 to 250 ppm, and the amount of manganese added is 10 to 150ppm.

The magnesium hydroxide used in the step (a) is not particularly limited as long as it is 95% or more in purity and has a median diameter of about 0.5 to 50 μm . The commercially available magnesium hydroxide is pulverized by a ball mill or the like, whereby magnesium hydroxide having such a median diameter can be obtained. Commercially available magnesium hydroxides include, for example, MAGSTAR #20, MAGSTAR #4, MAGSTAR #5, and MAGSTAR #2 manufactured by Tateho Chemical Industry Co., Ltd.

The iron compound may, for example, be iron oxide (ferrous oxide and ferric oxide), iron hydroxide, iron carbonate, iron chloride or iron nitrate, preferably iron oxide. The iron compound can be used alone or in combination with a plurality of iron compounds.

The vanadium compound may, for example, be vanadium oxide, vanadium hydroxide, vanadium carbonate, vanadium chloride or vanadium nitrate, preferably vanadium oxide. The vanadium compound can be used alone or in combination with a plurality of vanadium compounds.

The manganese compound may, for example, be manganese oxide, manganese hydroxide, manganese carbonate, manganese chloride or manganese nitrate, preferably manganese oxide. The manganese compound can be used singly or in combination with a plurality of manganese compounds.

The solvent may be ion-exchanged water. In the slurry containing magnesium hydroxide, iron, vanadium and manganese, the concentration of magnesium hydroxide is not particularly limited, but is preferably 50% by weight or less, more preferably 10 to 40% by weight.

The amount of the iron compound, the vanadium compound and the manganese compound to be used is preferably from 100 to 500 ppm, preferably from 150 to 400 ppm, and the vanadium addition amount is from 30 to 250 ppm, preferably from 60 to 120 ppm, based on the magnesium hydroxide. The amount added is from 10 to 150 ppm, preferably from 40 to 80 ppm. If the amount of the iron compound, the vanadium compound, and the manganese compound can be such that the amount of iron added, the amount of vanadium added, and the amount of manganese added can be achieved by firing and further In the hydration step, magnesium hydroxide particles having a uniform crystal shape can be obtained. Further, the inflection point diameter and the interparticle voids are also within the range described by the magnesium hydroxide particles of the present invention.

The magnesium hydroxide of the raw material in the present invention sometimes contains iron, vanadium or manganese. In this case, the iron, vanadium, or manganese content in the raw material magnesium hydroxide is measured in advance, and then the iron compound, the vanadium compound, and the iron, vanadium, and manganese are added in an amount as described above with respect to the magnesium hydroxide. The manganese compound is stirred and a slurry containing magnesium hydroxide, iron, vanadium and manganese is obtained.

Stirring can be carried out, for example, at a rotational speed of 10 to 50 ° C and 100 to 800 rpm for 0.5 to 5 hours.

(2) Step (b)

The step (b) is a step of filtering, washing and drying the slurry containing magnesium hydroxide, iron, vanadium and manganese obtained in the step (a) to obtain coarse particles of magnesium hydroxide. Thereby, coarse particles of magnesium hydroxide containing iron, vanadium and manganese before firing are obtained. The magnesium hydroxide coarse particles before firing contain iron, vanadium and manganese derived from a slurry containing magnesium hydroxide, iron, vanadium and manganese. The filtration can be carried out using a filter paper or the like, and the water washing can be carried out by putting 5 to 100 times of pure water based on the mass of the magnesium hydroxide.

(3) Step (c)

The step (c) is a step of calcining the magnesium hydroxide coarse particles obtained in the step (b) at 800 to 1900 ° C in an atmosphere to obtain magnesium oxide particles. The calcination of the magnesium hydroxide coarse particles can be carried out, for example, by raising the temperature to 800 to 1900 ° C, preferably 1000, at a temperature increase rate of 1 to 20 ° C / min, preferably 3 to 10 ° C / min in an atmosphere. Up to 1500 ° C, after heating up at 800 to 1900 ° C, It is preferably carried out by firing at 1000 to 1500 ° C for 0.1 to 5 hours.

(4) Step (d)

In the step (d), the magnesium oxide particles obtained in the step (c) are pulverized, and the obtained magnesium oxide powder having a median diameter of 3 to 30 μm and a crystal diameter of 10×10 ^-9 m or more is added to the added The step of obtaining a magnesium hydroxide particle by performing a hydration reaction of the magnesium oxide powder under high shear stirring in a warm water of 100 ° C or less of an organic acid, followed by separating the formed solid fraction, washing with water, and drying.

The pulverized and sieved magnesium oxide powder used in the hydration reaction has a median diameter of 3 to 30 μm , preferably 5 to 20 μm , more preferably 5 to 15 μm . When magnesium oxide in this range is used as a raw material, the hydration reaction can be sufficiently promoted, and magnesium oxide which does not have a hydration reaction is not left, and magnesium hydroxide of a desired size can be obtained. Further, the crystal diameter is 10 × 10 ^-9 m or more, preferably 10 × 10 ^-9 to 40 × 10 ^-9 m, more preferably 10 × 10 ^-9 to 30 × 10 ^-9 m. When magnesium oxide of this range is used for a raw material, the reaction rate at the time of hydration is suppressed, and it does not become coarse aggregated particle. Further, the crystal diameter is a value calculated by the X-ray diffraction method and calculated by the Scherrer equation.

An organic acid is added in order to control the solubility of the raw material magnesium oxide powder. The organic acid may, for example, be an aliphatic or aromatic organic acid having a carboxyl group, and is preferably formic acid, acetic acid, propionic acid, butyric acid or benzoic acid. The organic acid is preferably added in an amount of from 0.01 to 3.0 mol, more preferably from 0.01 to 0.30 mol, based on 100 g of the magnesium oxide powder used in the step (d). If it is such an amount, the precipitation rate of the crystal is appropriate, and the inconsistency of the median diameter of the obtained magnesium hydroxide particles is also small.

The hydration reaction is carried out under high shear stirring at a temperature below 100 ° C, for example from 50 to 100 ° C. The temperature of the warm water is preferably from 60 to 100 °C. In order to avoid the incorporation of impurities, the water used for warm water is preferably ion-exchanged water. The high shear stirring may be carried out by allowing the hydration reaction of magnesium oxide to proceed sufficiently and obtaining the stirring degree of the magnesium hydroxide slurry. For example, it can be carried out using a high-speed mixer having a turbine blade. The peripheral speed of the mixer is preferably from 8 to 18 m/s, more preferably from 9 to 15 m/s. The mixing time may vary depending on the degree of hydration reaction of the magnesium oxide, and may be, for example, 0.5 to 6 hours.

The magnesium hydroxide particles produced by the production method of the present invention can be obtained by the above steps. The magnesium hydroxide particles obtained by the production method of the present invention are preferably the magnesium hydroxide particles of the present invention.

The magnesium hydroxide particles of the present invention are subjected to various surface treatments, whereby the functions such as affinity for the resin, acid resistance, water repellency, and ultraviolet absorbing property can be improved. The magnesium hydroxide particles of the present invention are preferably dispersed in a resin as described above, and can sufficiently exhibit this function when subjected to a surface treatment imparting function as described above.

The surface treatment agent for improving the affinity with the resin may, for example, be a higher fatty acid or an alkali metal salt thereof, a phosphate ester, a decane coupling agent or a fatty acid ester of a polyhydric alcohol. Further, in order to improve acid resistance, water repellency, and the like, for example, ruthenium coating by decomposing methyl decanoate or ethyl decanoate, coating with decyl alkane oil, polyfluoroalkyl phosphate, or the like may be performed. . Further, in order to increase the ultraviolet absorbing property, for example, titanium sulfate is hydrolyzed and hydrolyzed to coat titanium dioxide. The foregoing surface treatment may be combined to carry out plural kinds.

3. Resin composition

The resin composition of the present invention comprises (I) an epoxy resin, (II) a hardener, (III) an inorganic filler, and (IV) a magnesium hydroxide particle of the present invention as a flame retardant or a magnesium hydroxide particle obtained by the production method of the present invention.

The epoxy resin of the component (I) is not particularly limited, and a known one can be used. Specific examples thereof include a bisphenol A type epoxy resin, a phenol varnish type epoxy resin, a cresol varnish type epoxy resin, a biphenyl type epoxy resin, and the like, and a cresol type epoxy resin is preferable.

The curing agent of the component (II) is not particularly limited, and a known one may be used, and examples thereof include a phenol resin, an acid anhydride, and an amine compound, and a phenol resin is preferable.

Examples of the inorganic filler of the component (III) include quartz glass powder, talc, cerium oxide powder, alumina powder, calcium carbonate, boron nitride, tantalum nitride, and carbon black powder. Among them, a cerium oxide powder, particularly a spherical cerium oxide powder, and more preferably a spherical molten cerium oxide powder is preferable.

The resin composition of the present invention is obtained by kneading the magnesium hydroxide particles of the present invention or the magnesium hydroxide particles obtained by the method of the present invention together with (I) an epoxy resin, (II) a hardener, (III) an inorganic filler, and the like. Income. In the resin composition, the blending amount of the magnesium hydroxide flame retardant is preferably from 1 to 35 mass% of the total of the resin composition, more preferably the total of the inorganic materials, that is, the total blend of the magnesium hydroxide additive and the inorganic filler. The amount is 60 to 95% by mass based on the entire resin composition.

The resin composition described above is excellent in environmental resistance such as flame retardancy, moisture resistance, and acid resistance, and can be used as a sealing agent for a semiconductor, and various semiconductor devices sealed with the resin composition can be produced.

The resin composition for semiconductor encapsulation is not particularly limited as long as it can uniformly disperse and mix various raw materials. Specific examples can be mentioned For example, it is sufficiently mixed by a mixer or the like, and kneaded by a mixing roll, an extruder, or the like, and then cooled and pulverized to form a granule; the granule is sized according to the size and weight of the molding conditions; or A mixture of the components of the above-mentioned resin composition is placed on a carriage, and after cooling, it is formed into a sheet shape or the like by press rolling, roll rolling, or flaking by coating a solvent.

The method of sealing the semiconductor element using the resin composition for semiconductor encapsulation thus obtained is not particularly limited, and for example, a known molding method such as normal transfer molding is used.

(Example)

The present invention will be more specifically described by the examples, but the present invention is not limited to the examples below.

The median diameter, Lc, purity, and pore distribution (recurve point diameter, interparticle void volume, modal volume, and mode diameter) of the magnesium hydroxide particles and magnesium oxide particles obtained in the examples were determined by the following methods. Determination.

(1) Determination of Lc

The Lc of the particles having the largest length in the field of view observed by the scanning electron microscope was measured.

(2) Determination of the median diameter (accumulated 50% particle diameter (D ₅₀ ) of the volume basis)

The median diameter was measured using a laser diffraction scattering type particle size distribution measuring apparatus (trade name: MT3300, manufactured by Nikkiso Co., Ltd.).

(3) Determination of the quality of impurities in magnesium hydroxide

Determination of impurities in the object (Ag, Al, B, Ba, Bi, Cd, Cl, Co, Cr, Cu, Fe, Ga, In, K, Li, Mn, Mo, Na, Ni, P, Pb, S, Si, Sr, Tl, V, Zn, Ti, and Zr) were measured by dissolving the sample in an acid using an ICP emission spectrometer (trade name: SPS-5100, manufactured by SII).

The amount of Cl was measured by using a spectrophotometer (trade name: UV-2550, manufactured by Shimadzu Corporation), and the sample was dissolved in acid to measure the mass.

(4) Purity determination method

The purity of the magnesium hydroxide is a value obtained by subtracting the mass of the impurity element measured by 100 mass% of the above-mentioned "mass measurement method of the impurity element in magnesium hydroxide".

(5) Determination of pore distribution (recurved point diameter, interparticle void, modal volume and mode diameter)

The measurement was carried out by measuring the pore size distribution of mercury, and the maximum value (modal volume) of the curve of the inflection point, the inter-particle gap, the log differential pore volume distribution, and the pores corresponding to the modal volume were obtained by the following conditions. Diameter (modal diameter). The mercury push-in type pore distribution measuring apparatus was measured using Autopore 9410 manufactured by MicroMetrics. Mercury uses a special mercury sample having a purity of 99.5 mass% or more and a density of 13.5335 × 10 ³ kg/m ³ . The measurement cell (cell) is a powder sample tank having a groove internal volume of 5 × 10 ^-6 m ³ and a tube volume of 0.38 × 10 ^-6 m ³ . The sample was previously preliminarily sampled using a 330 mesh standard sieve (JIS-R8801-87), and the mass was measured to a mass of 0.10×10 ^-3 to 0.13×10 ^-3 kg. Filled in the measuring tank. The measuring chamber is mounted on the apparatus, the pressure inside the tank is 50 μ Hg (6.67Pa) of the reduced pressure state for 20 minutes. The measurement tank was then filled with mercury to increase the pressure to 1.5 psia (10342 Pa). Mercury was then pressed in at a pressure ranging from 2 psia (13790 Pa) to 60,000 psia (413.7 MPa) to determine the pore distribution. The pore diameter was converted from the press-in pressure of mercury using the following formula (I).

D=-(1/P). 4γ. CosΨ (I) Here, D: pore diameter (m); P: mercury intrusion pressure (Pa); γ: mercury surface tension (485dyue.cm ^-1 (0.485Pa.m)); Ψ: mercury Contact angle (130° = 2.268793 rad).

[Example 1] <Manufacture of Magnesium Hydroxide Particles>

Magnesium hydroxide having a purity of 95% or more and a median diameter of 5.9 μm was added to the vessel, and iron oxide was added in such a manner that the amount of Fe added was 200 ppm with respect to magnesium hydroxide to make V relative to magnesium hydroxide. The vanadium oxide was added in such a manner that the amount of addition was 100 ppm, and manganese oxide was added so that the amount of Mn added was 50 ppm with respect to magnesium hydroxide, and ion-exchanged water was added and stirred so that the magnesium hydroxide concentration became 30 weight% or less. The resulting white precipitate was then filtered, washed with water and dried. The dried product was pulverized in a ball mill and fired at 1400 ° C for 2 hours using an electric furnace. The fired product was pulverized in a ball mill for 4 hours, and then classified to obtain a magnesium oxide powder. The obtained magnesium oxide powder had a median diameter of 10.2 μm and a crystal diameter of 28.9 × 10 ^-9 m.

The obtained magnesium oxide powder was added to a container having an internal volume of 20 L of 10 L of acetic acid having a concentration of 0.02 mol/L, so that the concentration of the oxide (MgO) was 100 g/L. While maintaining the obtained mixed solution containing magnesium oxide at 90 ° C, a hydration reaction was carried out for 4 hours while stirring at a turbine blade peripheral speed of 10 m/s using a high-speed stirrer (manufactured by Seiko Co., Ltd., trade name: Homomixer). Thereafter, the mixture was filtered, washed with water, and dried to obtain magnesium hydroxide particles.

The obtained magnesium hydroxide particles had a magnesium hydroxide purity of 98.8% by mass, a pore diameter distribution of 0.22 μm in the pore distribution, and an interparticle void of 0.88 × 10 ^-3 m ³ . kg ^-1, modal diameter of 0.17 μ m, modal volume of 2.51 × 10 ^-3 m ^3. Kg ^-1 .

<evaluation test>

The magnesium hydroxide particles were kneaded in an epoxy resin at a ratio shown in Table 1, and the spiral flow and flame retardancy of the obtained resin composition were measured under the following conditions. Here, the spiral flow system represents the value of the fluidity of the thermoplastic resin composition and the thermosetting resin composition. In addition, the epoxy resin uses a cresol varnish type epoxy resin (epoxy equivalent 198), the hardener uses a phenol varnish resin (hydroxyl equivalent: 105), the hardening accelerator uses triphenylphosphine, and the inorganic filler uses spherical sulphurized cerium oxide. .

(1) Method for measuring flame retardancy

A flame retardancy test piece having a thickness of 1/16 Å was prepared using an epoxy resin composition (forming conditions: temperature 175 ° C, time 120 seconds, post-curing 175 ° C × 6 hours), according to UL-94 V- The method of 0 specification evaluated the flame retardancy.

(2) Spiral flow measurement method

The spiral flow value was measured according to EMMI 1-66 using a mold for spiral flow measurement under the conditions of a temperature of 175 ° C and a pressure of 6086 MPa.

(3) Method for determining the bound potential

After ultrasonic wave dispersion of 0.003 g of magnesium hydroxide particles in 300 ml of ultrapure water for about 10 minutes, the laser data potentiometer ELS-8000 (大冢电 The measurement was carried out by a subsidiary company. The measurement temperature was 25 ° C, and the measurement method was measured by electrophoretic light scattering.

[Embodiment 2]

To the vessel, magnesium hydroxide having a purity of 95% or more used in Example 1 was added, and iron oxide was added so that the amount of Fe added in the magnesium hydroxide was 100 ppm, so that the amount of V added in the magnesium hydroxide was 100 ppm. In the vanadium oxide, manganese oxide was added so that the amount of Mn added to the magnesium hydroxide was 50 ppm, and ion-exchanged water was added and stirred so that the magnesium hydroxide concentration became 30% by weight or less. The resulting white precipitate was then filtered, washed with water and dried. The dried product was pulverized in a ball mill and fired at 1400 ° C for 2 hours using an electric furnace. The fired product was pulverized in a ball mill for 8 hours, and then classified to obtain a magnesium oxide powder. The obtained magnesium oxide powder had a median diameter of 6.8 μm and a crystal diameter of 29.9 × 10 ^-9 m.

The obtained magnesium oxide powder was added to a container having an internal volume of 20 L of 10 L of acetic acid having a concentration of 0.03 mol/L, so that the concentration of the oxide (MgO) was 100 g/L. While maintaining the obtained mixed solution containing magnesium oxide at 90 ° C, a hydration reaction was carried out for 4 hours while stirring at a turbine blade peripheral speed of 10 m/s using a high-speed stirrer (manufactured by Seiko Co., Ltd., trade name: Homomixer). Thereafter, the mixture was filtered, washed with water, and dried to obtain magnesium hydroxide particles.

The obtained magnesium hydroxide particles which magnesium hydroxide having a purity of 98.7% by mass, pore distribution, the inflection point diameter is 0.27 μ m, the gap between the particles is 0.75 × 10 ^-3 m ^3. Kg ^-1 , the mode diameter is 0.24 μ m and the modal volume is 2.47×10 ^-3 m ³ . Kg ^-1 .

[Comparative Example 1]

The iron oxide particles having a purity of 95% or more used in Example 1 were added to the vessel without adding iron oxide, vanadium oxide, and manganese oxide, and ion-exchanged water was added and stirred with the magnesium hydroxide concentration of 30% by weight or less. . The resulting white precipitate was then filtered, washed with water and dried. The dried product was pulverized in a ball mill and fired at 1400 ° C for 2 hours using an electric furnace. The fired product was pulverized in a ball mill for 4 hours, and then classified to obtain a magnesium oxide powder. The obtained magnesium oxide powder had a median diameter of 11.2 μm and a crystal diameter of 30.9 × 10 ^-9 m.

The obtained magnesium oxide powder was added to a container having an internal volume of 20 L of 10 L of acetic acid having a concentration of 0.03 mol/L, so that the concentration of the oxide (MgO) was 100 g/L. While maintaining the obtained mixed solution containing magnesium oxide at 90 ° C, a hydration reaction was carried out for 4 hours while stirring at a turbine blade peripheral speed of 10 m/s using a high-speed stirrer (manufactured by Seiko Co., Ltd., trade name: Homomixer). Thereafter, the mixture was filtered, washed with water, and dried to obtain magnesium hydroxide particles.

The obtained magnesium hydroxide particles had a magnesium hydroxide purity of 98.2% by mass, a pore diameter distribution of an inflection point of 0.14 μm , and an interparticle void of 0.59 × 10 ^-3 m ³ . Kg ^-1 , the mode diameter is 0.08 μ m, and the modal volume is 2.34×10 ^-3 m ³ . Kg ^-1 .

[Comparative Example 2]

To the container, magnesium hydroxide having a purity of 95% or more used in Example 1 was added, and iron oxide was added so that the amount of Fe added was 300 ppm with respect to magnesium hydroxide, so that the amount of V added was changed with respect to magnesium hydroxide. Magnesium oxide was added in an amount of 300 ppm, and manganese oxide was added so that the amount of Mn added was 250 ppm with respect to magnesium hydroxide, and ion-exchanged water was added and stirred so that the magnesium hydroxide concentration became 30 weight% or less. The resulting white precipitate was then filtered, washed with water and dried. The dried product was pulverized in a ball mill and fired at 1400 ° C for 2 hours using an electric furnace. The fired product was pulverized in a ball mill for 4 hours, and then classified to obtain a magnesium oxide powder. The obtained magnesium oxide powder had a median diameter of 10.61 μm and a crystal diameter of 25.9 × 10 ^-9 m.

The obtained magnesium oxide powder was added to a container having an internal volume of 20 L of 10 L of acetic acid having a concentration of 0.03 mol/L, so that the concentration of the oxide (MgO) was 100 g/L. While maintaining the obtained mixed solution containing magnesium oxide at 90 ° C, a hydration reaction was carried out for 4 hours while stirring at a turbine blade peripheral speed of 10 m/s using a high-speed stirrer (manufactured by Seiko Co., Ltd., trade name: Homomixer). Thereafter, the mixture was filtered, washed with water, and dried to obtain magnesium hydroxide particles.

The obtained magnesium hydroxide particles had a magnesium hydroxide purity of 98.8% by mass, a pore diameter distribution of 0.49 μm in the pore distribution, and an interparticle void of 1.1 × 10 ^-3 m ³ . Kg ^-1 , the mode diameter is 0.34 μ m, and the modal volume is 2.86×10 ^-3 m ³ . Kg ^-1 .

[Comparative Example 3]

To the container, magnesium hydroxide having a purity of 95% or more used in Example 1 was added, and iron oxide was added so that the amount of Fe added was 200 ppm with respect to magnesium hydroxide, so that the amount of Mn added was changed with respect to magnesium hydroxide. Manganese oxide was added in a manner of 50 ppm, and ion-exchanged water was added and stirred with a magnesium hydroxide concentration of 30% by weight or less. The resulting white precipitate was then filtered, washed with water and dried. The dried product was pulverized in a ball mill and fired at 1400 ° C for 2 hours using an electric furnace. The fired product was pulverized in a ball mill for 4 hours, and then classified to obtain a magnesium oxide powder. The obtained magnesium oxide powder had a median diameter of 11.52 μm and a crystal diameter of 28.9 × 10 ^-9 m.

The obtained magnesium oxide powder was added to a container having an internal volume of 20 L of 10 L of acetic acid having a concentration of 0.03 mol/L, so that the concentration of the oxide (MgO) was 100 g/L. While maintaining the obtained mixed solution containing magnesium oxide at 90 ° C, a hydration reaction was carried out for 4 hours while stirring at a turbine blade peripheral speed of 10 m/s using a high-speed stirrer (manufactured by Seiko Co., Ltd., trade name: Homomixer). Thereafter, the mixture was filtered, washed with water, and dried to obtain magnesium hydroxide particles.

The obtained magnesium hydroxide particles had a magnesium hydroxide purity of 98.7% by mass, a pore diameter distribution of 0.48 μm in the pore distribution, and an interparticle void of 1.25 × 10 ^-3 m ³ . Kg ^-1 , the mode diameter is 0.38 μ m, and the modal volume is 2.92×10 ^-3 m ³ . Kg ^-1 .

[Comparative Example 4]

To the container, magnesium hydroxide having a purity of 95% or more used in Example 1 was added, and iron oxide was added so that the amount of Fe added was 200 ppm with respect to magnesium hydroxide, so that the amount of V added was changed with respect to magnesium hydroxide. Vanadium oxide was added in a manner of 100 ppm, and ion-exchanged water was added and stirred with a magnesium hydroxide concentration of 30% by weight or less. The resulting white precipitate was then filtered, washed with water and dried. The dried product was pulverized in a ball mill and fired at 1400 ° C for 2 hours using an electric furnace. The fired product was pulverized in a ball mill for 4 hours, and then classified to obtain a magnesium oxide powder. The obtained magnesium oxide powder had a median diameter of 10.24 μm and a crystal diameter of 29.1 × 10 ^-9 m.

The obtained magnesium oxide powder was added to a container having an internal volume of 20 L of 10 L of acetic acid having a concentration of 0.03 mol/L, so that the concentration of the oxide (MgO) was 100 g/L. While maintaining the obtained mixed solution containing magnesium oxide at 90 ° C, a hydration reaction was carried out for 4 hours while stirring at a turbine blade peripheral speed of 10 m/s using a high-speed stirrer (manufactured by Seiko Co., Ltd., trade name: Homomixer). Thereafter, the mixture was filtered, washed with water, and dried to obtain magnesium hydroxide particles.

The obtained magnesium hydroxide particles had a magnesium hydroxide purity of 98.2% by mass, a pore diameter distribution of 0.42 μm , and an interparticle void of 1.33 × 10 ^-3 m ³ . Kg ^-1 , the mode diameter is 0.41 μ m, and the modal volume is 3.03×10 ^-3 m ³ . Kg ^-1 .

The results are summarized in Tables 2 and 3. Further, the amounts of Fe, V and Mn in the table are the amounts in the obtained magnesium hydroxide particles.

As is apparent from the results of Tables 2 and 3, the magnesium hydroxide particles of the present invention have a Lc of 0.5 to 1.5 μm , an Lc/d of 60% or more, an inflection point diameter of 0.1 to 0.4 μm , and interparticle spaces. 0.6×10 ^-3 to 1.0×10 ^-3 m ³ . Kg ^-1 magnesium hydroxide particles. Further, when the magnesium hydroxide particles of the present invention were kneaded as an additive to a resin, it was confirmed that the spiral flow was larger than the conventional magnesium hydroxide particles and the fluidity was good. On the other hand, when the magnesium hydroxide particles of the comparative example were kneaded as an additive as a resin, the fluidity was poor.

(industrial availability)

Since the magnesium hydroxide particles of the present invention do not contain fine particles or amorphous particles, they are composed of a uniform crystal shape of the entire particles, and therefore have good affinity for the resin. From the above, the magnesium hydroxide particles of the present invention are excellent in flame retardancy and fluidity and dispersibility to resins. Therefore, it is extremely useful as a filling material for a resin for sealing a semiconductor device such as a transistor, an IC, or an LSI.

Claims (9)

A magnesium hydroxide particle having a hexagonal column shape particle in a crystal shape, comprising a hexagonal base surface of two upper and lower sides parallel to each other, and an angular cylinder surface of the outer circumference 6 surface formed between the base surfaces, wherein the hexagonal column shape particle c The dimension in the axial direction is 0.5 to 1.5 μm , and the dimension in the c-axis direction is 60% or more of the median diameter of the hexagonal column-shaped particles, the inflection point diameter is 0.1 to 0.4 μm , and the inter-particle gap is 0.6×. 10 ^-3 to 1.0 × 10 ^-3 m ³ . Kg ^-1 , the purity is 98.0% by mass or more. The magnesium hydroxide particles according to claim 1, wherein the Fe content is 100 to 500 ppm, the V content is 30 to 250 ppm, and the Mn content is 10 to 150 ppm. The magnesium hydroxide particles according to claim 1 or 2, wherein the pore diameter has a mold diameter of 0.1 to 0.3 μm and a mold volume of 2.3 × 10 ^-3 To 2.8 × 10 ^-3 m ³ . Kg ^-1 . The magnesium hydroxide particles according to any one of claims 1 to 3, wherein the δ potential is -20 to -25 mV. A method for producing magnesium hydroxide particles, comprising the steps of: (a) adding magnesium hydroxide, an iron compound, a vanadium compound and a manganese compound to a solvent and stirring, thereby obtaining a slurry containing magnesium hydroxide, iron, vanadium and manganese; a step wherein the amount of iron added is 100 to 500 ppm, the amount of vanadium added is 30 to 250 ppm, and the amount of manganese added is 10 to 150 ppm with respect to magnesium hydroxide; (b) a slurry containing magnesium hydroxide, iron, vanadium, and manganese a step of filtering, washing with water and drying to obtain coarse particles of magnesium hydroxide; (c) a step of firing magnesium oxide coarse particles in an atmosphere at 800 to 1900 ° C to obtain magnesium oxide particles; and (d) pulverizing Magnesium oxide particles, and the obtained magnesium oxide powder having a median diameter of 3 to 30 μm and a crystal diameter of 10×10 ^-9 m or more is added to warm water of 100 ° C or lower to which the organic acid has been added, and then The hydration reaction of magnesium oxide is carried out under high shear stirring, and then the solid portion formed is separated by filtration, washed with water and dried to obtain a step of obtaining magnesium hydroxide particles. A resin composition comprising: (I) an epoxy resin; (II) a hardener; (III) an inorganic filler; and (IV) a flame retardant according to any one of claims 1 to 4 Magnesium hydroxide particles, or magnesium hydroxide particles obtained by the production method described in claim 5 of the patent application. The resin composition according to claim 6, wherein the magnesium hydroxide particles are blended in an amount of from 1 to 35 mass% of the resin composition. The resin composition according to claim 6 or 7, which is a sealing agent for a semiconductor. A semiconductor device using the resin composition according to any one of claims 6 to 8.