JP5944714B2 - Magnesium hydroxide particles and resin composition containing the same - Google Patents

Description

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

  Magnesium hydroxide is added as a flame retardant for the resin composition because it does not generate toxic gas during sintering and is excellent in environmental properties.

  In conventional magnesium hydroxide, fine crystals of magnesium hydroxide aggregate to form particles having an average secondary particle size of about 10 to 100 μm. Magnesium oxides produced using these as raw materials have only been obtained with non-uniform particle sizes. For this reason, when the above magnesium hydroxide or magnesium oxide is used as an additive for the resin, there are problems such as poor dispersibility, insufficient function of the additive, or loss of the original physical properties of the resin. there were. 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 improved dispersibility to some extent because of the shape change, but is not sufficient. Furthermore, since the magnesium hydroxide disclosed in Patent Document 1 contains fine particles and particles having a non-uniform crystal shape, the viscosity of the resin rapidly increases when kneaded with a synthetic resin as an additive, There was a problem that the fluidity and workability deteriorated, the molding speed decreased, and the productivity deteriorated.

JP 2006-306659 A

  An object of the present invention is to solve the above-mentioned problems and provide magnesium hydroxide particles having good fluidity and dispersibility when blended with a resin, and a resin composition containing the magnesium hydroxide particles. is there.

  In order to solve the above-mentioned problems, the present inventors have made various studies. As a result, magnesium hydroxide particles having a uniform crystal shape without containing fine particles and particles having an irregular crystal shape are used as a resin composition. When it was used as an additive, it was found that an excellent effect was obtained, and the present invention was completed. In addition, the present inventors produce magnesium oxide used in the hydration reaction, using a magnesium hydroxide slurry in which the magnesium hydroxide particles contain iron, vanadium, and manganese in predetermined amounts. It has been found that it can be obtained by hydrating this magnesium oxide.

That is, the present invention is a hexagonal columnar particle comprising a hexagonal basal plane of two upper and lower surfaces parallel to each other and a hexagonal prism surface of six outer peripheral surfaces formed between these basal planes, The size of the hexagonal column-shaped particles in the c-axis direction is 0.5 to 1.5 μm, and the size in the c-axis direction is 60% or more of the median particle diameter of the hexagonal column-shaped particles. Water having a curvature diameter of 0.1 to 0.4 μm and an interparticle void of 0.6 × 10 ^{−3 to} 1.0 × 10 ⁻³ m ³ · kg ⁻¹ and having a purity of 98% by mass or more. It relates to magnesium oxide particles.
The present invention relates to the magnesium hydroxide particles described above, 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.
In the present invention, the pore size distribution has a mode diameter of 0.1 to 0.3 μm and a mode volume of 2.3 × 10 ^{−3 to} 2.8 × 10 ⁻³ m ³ · kg ⁻¹ , It relates to the magnesium hydroxide particles described in 1.
The present invention relates to the magnesium hydroxide particles described above, wherein the zeta potential is −20 to −25 mV.
The present invention is a method for producing magnesium hydroxide particles,
(A) A step of adding magnesium hydroxide, iron compound, vanadium compound and manganese compound to a solvent and stirring to obtain a slurry containing magnesium hydroxide, iron, vanadium and manganese. On the other hand, the addition amount of Fe is 100 to 500 ppm, the addition amount of V is 30 to 250 ppm, and the addition amount of Mn is 10 to 150 ppm.
(B) A step of filtering, washing with water and drying a slurry containing magnesium hydroxide, iron, vanadium and manganese to obtain magnesium hydroxide coarse particles,
(C) Magnesium hydroxide coarse particles were calcined at 800 to 1900 ° C. in an air atmosphere to obtain magnesium oxide particles, and (d) obtained by pulverizing and sieving the magnesium oxide particles. Magnesium oxide powder having a median particle size of 3 to 30 μm and a crystallite size of 10 × 10 ⁻⁹ m or more is added to warm water of 100 ° C. or less to which an organic acid is added, and then under high shear stirring. In addition, the present invention relates to a method for producing magnesium hydroxide particles, including a step of obtaining magnesium hydroxide particles by performing a hydration reaction of magnesium oxide, and then filtering off the produced solid content, washing with water and drying.
The present invention provides (I) an epoxy resin, (II) a curing agent, (III) an inorganic filler, and (IV) a flame retardant, the magnesium hydroxide particles described above or the water obtained by the production method described above. The present invention relates to a resin composition containing magnesium oxide particles.
The present invention relates to the resin composition as described above, wherein the compounding amount of the magnesium hydroxide particles is 1 to 35% by mass of the resin composition.
The present invention relates to the resin composition as described above, which is a sealing agent for semiconductors.
The present invention relates to a semiconductor device using the resin composition described above.

  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 are obtained.

It is explanatory drawing which shows the external shape of the magnesium hydroxide particle of this invention.

1. Magnesium hydroxide particles The magnesium hydroxide particles of the present invention have a hexagonal prism shape as shown in FIG. 1, and the size in the c-axis direction (hereinafter referred to as “Lc”) is 0.5 to 1.5 μm. Magnesium hydroxide particles. In the magnesium hydroxide particles of the present invention, Lc is preferably 0.9 to 1.4 μm. Further, the ratio of Lc to the median particle diameter (d) of the magnesium hydroxide particles, that is, Lc / d is 60% or more, Lc / d is preferably 60 to 150%, preferably 65 to 90%. Is more preferable.

  When Lc / d is 60% or more, the fluidity of the magnesium hydroxide particles to the resin is good. This indicates that the larger the value of Lc / d, the more hexagonal columnar particles are developed in the c-axis direction. Some interaction exists at the interface between the magnesium hydroxide particles and the resin, and the particle shape causes the free movement of the resin to be constrained. In general, this tendency is affected by the particle shape. In other words, the effect increases as the degree of shape anisotropy increases. This is because the magnesium hydroxide particles of the present invention are particles sufficiently grown in the c-axis direction, so that they have a smaller shape anisotropy than the conventional particles and there are few factors that hinder the free movement of the resin. The median particle diameter d of the magnesium hydroxide particles is not particularly limited as long as the above-mentioned Lc / d is satisfied, but usually it is preferably in the range of 0.1 to 10 μm.

Note that Lc, which is the size of the magnesium hydroxide particles in the c-axis direction, is a measured value of particles having the maximum length in the field of view when observed with a scanning electron microscope. The median particle diameter is a volume-based cumulative 50% particle diameter (D ₅₀ ) when measured using a laser diffraction / scattering particle size distribution measuring apparatus.

The magnesium hydroxide particles of the present invention have an inflection point diameter of 0.1 to 0.4 μm and an interparticle void of 0.6 × 10 ^{−3 to} 1.0 × 10 ⁻³ m ³ · kg ⁻¹ . is there. In the present invention, the inflection point diameter and interparticle void can be determined from mercury intrusion pore distribution measurement. The relationship curve between the pore diameter and the cumulative pore volume determined from the mercury intrusion pore distribution measurement is called the cumulative pore volume curve.

Specifically, in mercury intrusion type pore distribution measurement, the pore diameter obtained from the indentation pressure is plotted on the horizontal axis, and the cumulative pore volume is plotted on the vertical axis to obtain the cumulative pore volume curve. Conversion from the intrusion pressure of mercury to the pore diameter is performed using the following formula (I) (Washburn formula).
D = − (1 / P) · 4γ · cosψ (I)
Where D: pore diameter (m),
P: Pressure (Pa)
γ: surface tension of mercury (485 dyne / cm (0.485 Pa · m)),
ψ: mercury contact angle (130 ° = 2.26893 rad).

  The inflection point diameter refers to the pore diameter at the point with the largest pore diameter among the inflection points at which the cumulative pore volume curve rises rapidly. The interparticle void amount is the cumulative pore volume at the inflection point diameter. When the inflection point diameter and the interparticle void are within the scope of the present invention, the crystal shape and particle diameter of the magnesium hydroxide particles are uniform, and there are very few aggregates and irregular crystal particles.

  When the inflection point diameter is less than 0.1 μm, the magnesium hydroxide particles contain fine particles having a non-uniform crystal shape. For this reason, when magnesium hydroxide particles having an inflection point diameter of less than 0.1 μm are kneaded with a synthetic resin as an additive, the viscosity of the resin rapidly increases and fluidity deteriorates. On the other hand, when the inflection point diameter exceeds 0.4 μm, the crystal shape of some of the magnesium hydroxide particles becomes indeterminate, and the particles tend to aggregate to form coarse particles. For this reason, when particles having an inflection point diameter exceeding 0.4 μm are kneaded with a synthetic resin as an additive, coarse aggregates are formed, and the particles are likely to settle in the resin, thereby impairing fluidity and workability. In the present invention, the inflection point diameter is preferably 0.2 to 0.3 μm.

When the interparticle gap is less than 0.6 × 10 ⁻³ m ³ · kg ⁻¹ , the magnesium hydroxide particles contain fine particles having a non-uniform crystal shape. Therefore, when kneading into a synthetic resin using magnesium hydroxide particles having an interparticle void of less than 0.6 × 10 ⁻³ m ³ · kg ⁻¹ as an additive, the resin did not penetrate into the particles and could not be dispersed. It becomes easy to form particles and voids. In addition, the fluidity also deteriorates accordingly. Further, when the interparticle void exceeds 1.0 × 10 ⁻³ m ³ · kg ⁻¹ , the crystal shape of some of the particles of magnesium hydroxide becomes indefinite, and the particles tend to aggregate, resulting in coarse particles. It is formed. Therefore, when magnesium hydroxide particles with interparticle voids exceeding 1.0 × 10 ⁻³ m ³ · kg ⁻¹ are kneaded with a synthetic resin as an additive, coarse aggregates are formed, and the particles settle in the resin. It becomes easier and hinders fluidity and workability. In the present invention, the interparticle voids are preferably 0.7 × 10 ^{−3 to} 0.9 × 10 ⁻³ m ³ · kg ⁻¹ .

  The magnesium hydroxide particles of the present invention have a purity of 98.0% by mass or more. If it is this range, the elution of an impurity will be suppressed very much and it can use suitably as an additive of resin used as a highly functional material. The purity of the magnesium hydroxide particles of the present invention is preferably 98.5-99.9% by mass.

  In this specification, the purity refers to the impurity element (Ag, Al, B, Ba, Bi, Cd, Cl, Co, Cr, Cu, Fe, Ga, In, K, Li, Mn, Mo, Na in the target particle. , Ni, P, Pb, S, Si, Sr, Tl, V, Zn, Ti, and Zr) are measured, and the total content is subtracted from 100% by mass. Impurity elements to be measured (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), using an ICP emission spectrometer, the sample was dissolved in acid, then the mass was measured, and the Cl amount was measured using a spectrophotometer. Is dissolved in an acid and the mass is measured.

  The magnesium hydroxide particles of the present invention 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. It is preferable. When the content of Fe is 100 to 500 ppm, the content of V is 30 to 250 ppm, and the content of Mn is 10 to 150 ppm, the magnesium hydroxide particles can easily have a uniform crystal shape, Elution of metal impurities is extremely suppressed, and it can be suitably used as an additive, for example, a flame retardant. More preferably, the Fe content is 150 to 400 ppm, the V content is 60 to 120 ppm, and the Mn content is 40 to 80 ppm.

The magnesium hydroxide of the present invention preferably has a mode diameter of 0.1 to 0.3 μm. Moreover, it is preferable that the mode volume of the magnesium hydroxide particles of the present invention is 2.3 × 10 ^{−3 to} 2.8 × 10 ⁻³ m ³ · kg ⁻¹ . Such a mode diameter and mode volume are preferable in that the crystal shape and particle diameter of the magnesium hydroxide particles are more uniform, and there are very few aggregates and amorphous crystal particles.

  The mode volume and mode diameter of the present invention can be obtained from mercury intrusion pore distribution measurement, where the mode volume is the maximum value of the log differential pore volume distribution curve, and the mode diameter is the log differential fine distribution. The pore diameter corresponding to the maximum value of the pore volume distribution curve. When the pore distribution of the magnesium hydroxide particles of the present invention is measured by the mercury intrusion method, the mode diameter corresponds to the diameter of the gap between the magnesium hydroxide particles.

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

2. The manufacturing method of the magnesium hydroxide particle of this invention The magnesium hydroxide particle of this invention can be manufactured as follows, for example.
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. Dry to obtain magnesium hydroxide coarse particles. Next, the magnesium hydroxide raw material is obtained by firing the magnesium hydroxide coarse particles in the range of 800 to 1900 ° C. Subsequently, this magnesium oxide raw material was pulverized and sieved, and a magnesium oxide powder having a median particle diameter of 3 to 30 μm and a crystallite diameter of 10 × 10 ⁻⁹ m or more was added with an organic acid. Magnesium hydroxide added to warm water below ℃, under high shear stirring, hydrated magnesium oxide powder, filtered off solid content, washed with water and dried, according to the production method of the present invention Get particles.

Specifically, the method for producing magnesium hydroxide particles of the present invention includes:
(A) A step of adding magnesium hydroxide, iron compound, vanadium compound and manganese compound to a solvent and stirring to obtain a slurry containing magnesium hydroxide, iron, vanadium and manganese. On the other hand, the addition amount of iron is 100 to 500 ppm, the addition amount of vanadium is 30 to 250 ppm, and the addition amount of manganese is 10 to 150 ppm,
(B) A step of filtering, washing with water and drying a slurry containing magnesium hydroxide, iron, vanadium and manganese to obtain magnesium hydroxide coarse particles,
(C) Magnesium hydroxide coarse particles were calcined at 800 to 1900 ° C. in an air atmosphere to obtain magnesium oxide particles, and (d) obtained by pulverizing and sieving the magnesium oxide particles. Magnesium oxide powder having a median particle size of 3 to 30 μm and a crystallite size of 10 × 10 ⁻⁹ m or more is added to warm water of 100 ° C. or less to which an organic acid is added, and then under high shear stirring. Then, a step of obtaining magnesium hydroxide particles by performing a hydration reaction of magnesium oxide and then filtering off the generated solid, washing with water and drying.

(1) Step (a)
Step (a) is a step of adding a magnesium hydroxide, iron compound, vanadium compound and manganese compound to a solvent and stirring to obtain a slurry containing magnesium hydroxide, iron, vanadium and manganese, In this process, the amount of iron added to magnesium oxide 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.

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

  Examples of the iron compound include iron oxide (ferrous oxide and ferric oxide), iron hydroxide, iron carbonate, iron chloride, and iron nitrate, and iron oxide is preferable. The iron compound may be used alone, or a plurality of iron compounds may be used in combination.

  Examples of the vanadium compound include vanadium oxide, vanadium hydroxide, vanadium carbonate, vanadium chloride, and vanadium nitrate, and vanadium oxide is preferable. The vanadium compounds may be used alone or in combination with a plurality of vanadium compounds.

  Examples of the manganese compound include manganese oxide, manganese hydroxide, manganese carbonate, manganese chloride, and manganese nitrate, and manganese oxide is preferable. Manganese compounds may be used alone or in combination of a plurality of manganese compounds.

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

  The amount of iron compound, vanadium compound and manganese compound used is 100 to 500 ppm, preferably 150 to 400 ppm, and the amount of vanadium added is 30 to 250 ppm with respect to magnesium hydroxide. Preferably it is 60-120 ppm, and the addition amount of manganese is 10-150 ppm, Preferably it is 40-80 ppm. If the amount of iron, vanadium, and manganese is the amount of iron, vanadium, and manganese, the amount of iron, vanadium, and manganese is a uniform crystal shape due to firing and further hydration processes. Magnesium hydroxide particles are obtained, and the inflection point diameter and interparticle voids are included in the ranges described in the magnesium hydroxide particles of the present invention.

  In the present invention, the raw material magnesium hydroxide may contain iron, vanadium or manganese. In this case, after measuring the content of iron, vanadium and manganese in magnesium hydroxide as a raw material in advance, the amount of iron is adjusted so that the amount of iron, vanadium and manganese added to magnesium hydroxide is the amount described above. A slurry containing magnesium hydroxide, iron, vanadium, and manganese can be obtained by adding a compound, a vanadium compound, and a manganese compound and stirring.

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

(2) Step (b)
Step (b) is a step of obtaining magnesium hydroxide coarse particles by filtering, washing and drying the slurry containing magnesium hydroxide, iron, vanadium and manganese obtained in step (a). Thereby, the magnesium hydroxide coarse particle containing iron, vanadium, and manganese before baking is obtained. The magnesium hydroxide coarse particles before firing contain iron, vanadium, and manganese derived from a slurry containing magnesium hydroxide, iron, vanadium, and manganese. Filtration can be performed using filter paper or the like, and water washing can be performed by adding 5 to 100 times pure water on a mass basis with respect to magnesium hydroxide.

(3) Step (c)
Step (c) is a step of obtaining magnesium oxide particles by firing the magnesium hydroxide coarse particles obtained in step (b) at 800 to 1900 ° C. in an air atmosphere. The firing of the magnesium hydroxide coarse particles is performed, for example, in an air atmosphere at a temperature rising rate of 1 to 20 ° C./min, preferably 3 to 10 ° C./min, up to 800 to 1900 ° C., preferably 1000 to 1500 ° C. After heating and raising the temperature, it can be carried out by baking at 800 to 1900 ° C, preferably 1000 to 1500 ° C for 0.1 to 5 hours.

(4) Step (d)
In step (d), the magnesium oxide particles obtained in step (c) are pulverized and sieved, and the median particle diameter is 3 to 30 μm, and the crystallite diameter is 10 × 10 ⁻⁹ m or more. Magnesium oxide powder is added to warm water of 100 ° C. or less to which an organic acid is added, and then the magnesium oxide powder is hydrated under high shear stirring, and then the produced solid content is filtered off. This is a step of obtaining magnesium hydroxide particles by washing with water and drying.

The median particle diameter of the magnesium oxide powder obtained by pulverization and sieving used for the hydration reaction is 3 to 30 μm, preferably 5 to 20 μm, and more preferably 5 to 15 μm. If magnesium oxide in this range is used as a raw material, the hydration reaction proceeds sufficiently, and magnesium oxide that cannot be hydrated does not remain, and magnesium hydroxide having a target size can be obtained. Further, the crystallite diameter is a 10 × ^{10 -9} m or more, that is ^{10 × 10 -9 ~40 × 10 -9} m and ^{preferably, 10 × 10 -9 ~30 × 10} -9 m Is more preferable. If magnesium oxide in this range is used as a raw material, the reaction rate during hydration is suppressed and coarse aggregated particles are not formed. The crystallite diameter is a value calculated by the Scherrer equation using the X-ray diffraction method.

  The organic acid is added to suppress the solubility of the raw material magnesium oxide powder. Examples of the organic acid include aliphatic or aromatic organic acids having a carboxyl group, and formic acid, acetic acid, propionic acid, entangling acid, and benzoic acid are preferable. The addition amount of the organic acid is preferably 0.01 to 3.0 mol, more preferably 0.01 to 0.30 mol, with respect to 100 g of the magnesium oxide powder used in the step (d). With such an amount, the rate of crystal precipitation is moderate, and there is little variation in the median particle diameter of the resulting magnesium hydroxide particles.

  The hydration reaction is performed under high shear stirring in warm water of 100 ° C. or lower, for example, 50 to 100 ° C. The temperature of the hot water is preferably 60 to 100 ° C. As water used for warm water, ion-exchanged water is preferable in order to avoid contamination of impurities. The high-shear stirring may be performed so long as the hydration reaction of magnesium oxide is sufficiently advanced to obtain a desired magnesium hydroxide slurry, and can be performed by using, for example, a high-speed stirrer equipped with turbine blades. . The peripheral speed of the stirrer is preferably 8 to 18 m / s, more preferably 9 to 15 m / s. The mixing time can be changed according to the degree of hydration reaction of magnesium oxide, and can be, for example, 0.5 to 6 hours.

  The magnesium hydroxide particle manufactured by the manufacturing method of this invention is obtained by said process. 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 can be improved in functions such as affinity for the resin, acid resistance, water repellency, and ultraviolet absorption by performing various surface treatments. As described above, the magnesium hydroxide particles of the present invention have good dispersion in the resin, and even when the function is given by the surface treatment as described above, the function can be sufficiently exhibited.

  Examples of the surface treatment agent for increasing the affinity with the resin include higher fatty acids or alkali metal salts thereof, phosphate esters, silane coupling agents, fatty acid esters of polyhydric alcohols, and the like. In order to improve acid resistance, water repellency and the like, for example, silica coating by hydrolysis of methyl silicate or ethyl silicate, coating with silicone oil, polyfluoroalkyl phosphate ester salt, or the like is performed. Moreover, in order to improve ultraviolet absorptivity, for example, a titanium dioxide sulfate is coated with titanium dioxide by a hydrolysis reaction. The aforementioned surface treatment may be performed in combination.

3. Resin Composition The resin composition of the present invention comprises (I) an epoxy resin, (II) a curing agent, (III) an inorganic filler, and (IV) a flame retardant. Magnesium hydroxide particles obtained by the production method are included.

  The epoxy resin of component (I) is not particularly limited, and known ones can be used. Specific examples include bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins and the like, and cresol novolak type epoxy resins are preferred.

  The curing agent for component (II) is not particularly limited, and known ones can be used. Examples thereof include phenol resins, acid anhydrides, and amine compounds, and phenol resins are preferred.

  Examples of the inorganic filler of component (III) include quartz glass powder, talc, silica powder, alumina powder, calcium carbonate, boron nitride, silicon nitride, and carbon black powder. Of these, silica powder is preferable, and spherical silica powder, particularly spherical fused silica powder is particularly preferable.

  The resin composition of the present invention comprises the magnesium hydroxide particles of the present invention or the magnesium hydroxide particles obtained by the production method of the present invention (I) epoxy resin, (II) curing agent, (III) inorganic filler, etc. And kneaded together. In this resin composition, the compounding amount of the magnesium hydroxide flame retardant is preferably 1 to 35% by mass of the entire resin composition, and more preferably the total of the inorganic substances, that is, the magnesium hydroxide additive and the inorganic It is more preferable that the total blending amount with the filler is 60 to 95% by mass of the entire resin composition.

  The above resin composition is excellent in environmental resistance such as flame retardancy, moisture resistance, and acid resistance, and is useful as a sealing agent for semiconductors. Therefore, various semiconductors sealed with this resin composition The device can be manufactured.

  The method for preparing the semiconductor sealing resin composition is not particularly limited as long as various raw materials can be uniformly dispersed and mixed. Specific examples include, for example, sufficient mixing with a mixer, etc., melt-kneading with a mixing roll, an extruder, etc., cooling, pulverizing, and molding this into granules, dimensions and weight that match the molding conditions Or a mixture of each component of the resin composition received on a pallet, and after cooling it, press rolling, roll rolling, or a mixture of solvent is applied to form a sheet, etc. It can be made into various forms such as one formed into a sheet by a method.

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

  EXAMPLES The present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.

  The median particle diameter, Lc, purity, and pore distribution (inflection point diameter, interparticle void, mode volume, mode diameter) of the magnesium hydroxide particles and the magnesium oxide particles obtained in the examples are as follows. It was measured.

(1) Measurement of Lc Lc of a particle having the maximum length in the visual field in the scanning electron microscope observation was measured.

(2) Measurement of median particle size (volume-based cumulative 50% particle size (D ₅₀ )) Using a laser diffraction scattering type particle size distribution measuring device (trade name: MT3300, manufactured by Nikkiso Co., Ltd.), the median particle size is measured. did.

(3) Mass measurement method of impurity elements in magnesium hydroxide Impurity elements (Ag, Al, B, Ba, Bi, Cd, Co, Cr, Cu, Fe, Ga, In, K, Li, Mn to be measured) , Mo, Na, Ni, P, Pb, S, Si, Sr, Tl, V, Zn, Ti and Zr) using an ICP emission analyzer (trade name: SPS-5100, manufactured by Seiko Instruments Inc.) After dissolving the sample in acid, the mass was measured.
The amount of Cl was measured using a spectrophotometer (trade name: UV-2550, manufactured by Shimadzu Corporation) after dissolving the sample in acid.

(4) Purity Measurement Method The purity of magnesium hydroxide was calculated as a value obtained by subtracting the total mass of impurity elements measured by the above-mentioned “mass measurement method of impurity elements in magnesium hydroxide” from 100% by mass.

(5) Measurement of pore distribution (inflection point diameter, interparticle void, mode volume and mode diameter) Inflection point diameter, interparticle void, log differential pore volume distribution obtained by mercury intrusion pore distribution measurement The maximum value (mode volume) of the curve and the pore diameter (mode diameter) corresponding to the mode volume were determined under the following conditions. The mercury intrusion pore distribution measuring device was measured using an Autopore 9410 manufactured by Micrometrics. As the mercury, a special grade mercury reagent having a purity of 99.5 mass% or more and a density of 13.5335 × 10 ³ kg / m ³ was used. The measurement cell used was a powder sample cell having an internal volume of 5 × 10 ⁻⁶ m ³ and a stem volume of 0.38 × 10 ⁻⁶ m ³ . The measurement sample was precisely weighed in a mass range of 0.10 × 10 ^{−3 to} 0.13 × 10 ⁻³ kg with a sample having a uniform particle size using a 330 mesh standard sieve (JIS-R8801-87) in advance. The measuring cell was filled. After mounting the measurement cell on the apparatus, the inside of the cell was kept under a reduced pressure at a pressure of 50 μHg (6.67 Pa) or less for 20 minutes. Next, mercury was filled in the measurement cell until the pressure became 1.5 psia (10342 Pa). Thereafter, mercury was injected in a pressure range of 2 psia (13790 Pa) to 60000 psia (413.7 MPa), and the pore distribution was measured.
The following formula (I) was used to convert the intrusion pressure of mercury into the pore diameter.
D = − (1 / P) · 4γ · cosψ (I)
Where D: pore diameter (m),
P: mercury pressure (Pa)
γ: surface tension of mercury (485 dyne · cm ⁻¹ (0.485 Pa · m)),
Ψ: Mercury contact angle (130 ° = 2.26893 rad).

[Example 1]
<Manufacture of magnesium hydroxide particles>
Magnesium hydroxide with a purity of 95% or more and a median particle size of 5.9 μm, and iron oxide with respect to magnesium hydroxide so that the added amount of Fe is 200 ppm and oxidized so that the added amount of V is 100 ppm Vanadium was charged with manganese oxide so that the amount of Mn added was 50 ppm, and ion-exchanged water was added so that the concentration of magnesium hydroxide would be 30% by weight or less, followed by stirring. The resulting white precipitate was then filtered, washed with water and dried. The dried product was pulverized with a ball mill and baked at 1400 ° C. for 2 hours using an electric furnace. The fired product was pulverized with a ball mill for 4 hours and then classified to obtain a magnesium oxide powder. The median particle diameter of the obtained magnesium oxide powder was 10.2 μm, and the crystallite diameter was 28.9 × 10 ⁻⁹ m.

  The obtained magnesium oxide powder was added to a 20 L internal container containing 10 L of acetic acid having a concentration of 0.02 mol / L so that the oxide (MgO) concentration was 100 g / L. While maintaining the obtained magnesium oxide-containing mixed solution at 90 ° C., using a high speed stirrer (trade name: Homomixer, manufactured by Tokushu Kika Co., Ltd.), stirring the peripheral speed of the turbine blade at 10 m / s, 4 A time hydration reaction was performed. Thereafter, filtration, washing with water and drying were performed to obtain magnesium hydroxide particles.

The obtained magnesium hydroxide particles have a magnesium hydroxide purity of 98.8% by mass, an inflection point diameter of 0.22 μm in the pore distribution, and an interparticle void of 0.88 × 10 ^−3. m ³ · kg ⁻¹ , the mode diameter was 0.17 μm, and the mode volume was 2.51 × 10 ⁻³ m ³ · kg ⁻¹ .

<Evaluation test>
The magnesium hydroxide particles were kneaded with the epoxy resin at the 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 is a value representing the fluidity of the thermoplastic resin composition and the thermosetting resin composition. The epoxy resin is a cresol novolac type epoxy resin (epoxy equivalent 198), the curing agent is a phenol novolac resin (hydroxyl equivalent 105), the curing accelerator is triphenylphosphine, and the inorganic filler is a spherical melt. Each silica was used.

(1) Flame Retardancy Measurement Method Using an epoxy resin composition, a flame retardant test piece having a thickness of 1/16 inch was prepared (molding conditions: temperature 175 ° C., time 120 seconds, post cure 175 ° C. × 6 hours). The flame retardancy was evaluated according to the method of UL-94 V-0 standard.

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

(3) Zeta potential measurement method After 0.003 g of magnesium hydroxide particles are ultrasonically dispersed in 300 ml of ultrapure water for about 10 minutes, measurement is performed with a laser data electrometer ELS-8000 (Otsuka Electronics Co., Ltd.). did. The measurement temperature was 25 ° C., and the measurement method was an electrophoretic light scattering method.

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

  The obtained magnesium oxide powder was added to a 20 L internal container containing 10 L of acetic acid having a concentration of 0.03 mol / L so that the oxide (MgO) concentration was 100 g / L. While maintaining the obtained magnesium oxide-containing mixed solution at 90 ° C., using a high speed stirrer (trade name: Homomixer, manufactured by Tokushu Kika Co., Ltd.), stirring the peripheral speed of the turbine blade at 10 m / s, 4 A time hydration reaction was performed. Thereafter, filtration, washing with water and drying were performed to obtain magnesium hydroxide particles.

The obtained magnesium hydroxide particles have a magnesium hydroxide purity of 98.7% by mass, an inflection point diameter in the pore distribution of 0.27 μm, and an interparticle void of 0.75 × 10 ^−3. m ³ · kg ⁻¹ , the mode diameter was 0.24 μm, and the mode volume was 2.47 × 10 ⁻³ m ³ · kg ⁻¹ .

[Comparative Example 1]
Without adding iron oxide, vanadium oxide, and manganese oxide, magnesium hydroxide particles having a purity of 95% or more used in Example 1 and ion-exchanged water in a container so that the concentration of magnesium hydroxide is 30% by weight or less. Stir and stir. The resulting white precipitate was then filtered, washed with water and dried. The dried product was pulverized with a ball mill and baked at 1400 ° C. for 2 hours using an electric furnace. The fired product was pulverized with a ball mill for 4 hours and then classified to obtain a magnesium oxide powder. The obtained magnesium oxide powder had a median particle diameter of 11.2 μm and a crystallite diameter of 30.9 × 10 ⁻⁹ m.

  The obtained magnesium oxide powder was added to a 20 L internal container containing 10 L of acetic acid having a concentration of 0.03 mol / L so that the oxide (MgO) concentration was 100 g / L. While maintaining the obtained magnesium oxide-containing mixed solution at 90 ° C., using a high speed stirrer (trade name: Homomixer, manufactured by Tokushu Kika Co., Ltd.), stirring the peripheral speed of the turbine blade at 10 m / s, 4 A time hydration reaction was performed. Thereafter, filtration, washing with water and drying were performed to obtain magnesium hydroxide particles.

The obtained magnesium hydroxide particles have a magnesium hydroxide purity of 98.2% by mass, an inflection point diameter of 0.14 μm in the pore distribution, and an interparticle void of 0.59 × 10 ^−3. m ³ · kg ⁻¹ , the mode diameter was 0.08 μm, and the mode volume was 2.34 × 10 ⁻³ m ³ · kg ⁻¹ .

[Comparative Example 2]
Magnesium hydroxide having a purity of 95% or more used in Example 1 and iron oxide so that the added amount of Fe is 300 ppm and vanadium oxide so that the added amount of V is 300 ppm with respect to magnesium hydroxide. , Manganese oxide was added so that the added amount of Mn was 250 ppm, and ion-exchanged water was put in a container so that the concentration of magnesium hydroxide was 30% by weight or less, followed by stirring. The resulting white precipitate was then filtered, washed with water and dried. The dried product was pulverized with a ball mill and baked at 1400 ° C. for 2 hours using an electric furnace. The fired product was pulverized with a ball mill for 4 hours and then classified to obtain a magnesium oxide powder. The obtained magnesium oxide powder had a median particle diameter of 10.61 μm and a crystallite diameter of 25.9 × 10 ⁻⁹ m.

  The obtained magnesium oxide powder was added to a 20 L internal container containing 10 L of acetic acid having a concentration of 0.03 mol / L so that the oxide (MgO) concentration was 100 g / L. While maintaining the obtained magnesium oxide-containing mixed solution at 90 ° C., using a high speed stirrer (trade name: Homomixer, manufactured by Tokushu Kika Co., Ltd.), stirring the peripheral speed of the turbine blade at 10 m / s, 4 A time hydration reaction was performed. Thereafter, filtration, washing with water and drying were performed to obtain magnesium hydroxide particles.

The obtained magnesium hydroxide particles have a magnesium hydroxide purity of 98.8% by mass, an inflection point diameter in the pore distribution of 0.49 μm, and an interparticle void of 1.1 × 10 ^−3. m ³ · kg ⁻¹ , the mode diameter was 0.34 μm, and the mode volume was 2.86 × 10 ⁻³ m ³ · kg ⁻¹ .

[Comparative Example 3]
Magnesium hydroxide having a purity of 95% or more used in Example 1, and iron oxide so that the added amount of Fe is 200 ppm and manganese oxide so that the added amount of Mn is 50 ppm with respect to magnesium hydroxide. Then, ion-exchanged water was placed in a container and stirred so that the concentration of magnesium hydroxide was 30% by weight or less. The resulting white precipitate was then filtered, washed with water and dried. The dried product was pulverized with a ball mill and baked at 1400 ° C. for 2 hours using an electric furnace. The fired product was pulverized with a ball mill for 4 hours and then classified to obtain a magnesium oxide powder. The obtained magnesium oxide powder had a median particle diameter of 11.52 μm and a crystallite diameter of 28.9 × 10 ⁻⁹ m.

  The obtained magnesium oxide powder was added to a 20 L internal container containing 10 L of acetic acid having a concentration of 0.03 mol / L so that the oxide (MgO) concentration was 100 g / L. While maintaining the obtained magnesium oxide-containing mixed solution at 90 ° C., using a high speed stirrer (trade name: Homomixer, manufactured by Tokushu Kika Co., Ltd.), stirring the peripheral speed of the turbine blade at 10 m / s, 4 A time hydration reaction was performed. Thereafter, filtration, washing with water and drying were performed to obtain magnesium hydroxide particles.

The obtained magnesium hydroxide particles have a magnesium hydroxide purity of 98.7% by mass, an inflection point diameter of 0.48 μm in pore distribution, and an interparticle void of 1.25 × 10 ^−3. m ³ · kg ⁻¹ , the mode diameter was 0.38 μm, and the mode volume was 2.92 × 10 ⁻³ m ³ · kg ⁻¹ .

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

  The obtained magnesium oxide powder was added to a 20 L internal container containing 10 L of acetic acid having a concentration of 0.03 mol / L so that the oxide (MgO) concentration was 100 g / L. While maintaining the obtained magnesium oxide-containing mixed solution at 90 ° C., using a high speed stirrer (trade name: Homomixer, manufactured by Tokushu Kika Co., Ltd.), stirring the peripheral speed of the turbine blade at 10 m / s, 4 A time hydration reaction was performed. Thereafter, filtration, washing with water and drying were performed to obtain magnesium hydroxide particles.

The obtained magnesium hydroxide particles have a magnesium hydroxide purity of 98.2% by mass, an inflection point diameter in the pore distribution of 0.42 μm, and an interparticle void of 1.33 × 10 ^−3. m ³ · kg ⁻¹ , the mode diameter was 0.41 μm, and the mode volume was 3.03 × 10 ⁻³ m ³ · kg ⁻¹ .

  The results are summarized in Table 2 and Table 3. In addition, the quantity of Fe, V, and Mn in a table | surface is the quantity in the obtained magnesium hydroxide particle.

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

  Since the magnesium hydroxide particles of the present invention do not contain fine particles or irregular particles, the entire particles are composed of a uniform crystal shape, and thus 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 with respect to the resin. Therefore, it is extremely useful as a sealing resin filler for semiconductor devices such as transistors, ICs, and LSIs.

Claims (8)

A hexagonal columnar particle having a hexagonal basal plane of two upper and lower surfaces parallel to each other and six outer peripheral prismatic surfaces formed between these basal planes, The size in the c-axis direction is 0.5 to 1.5 μm, the size in the c-axis direction is 60% or more of the median particle diameter of the hexagonal columnar particles, and the inflection point diameter is 0. a 1～0.4Myuemu, Ri interparticle voids is ^{0.6 × 10 -3 ~1.0 × 10 -3} m 3 · kg -1 der, the Fe content is 100 to 500 ppm, of V Magnesium hydroxide particles having a purity of 98.0% by mass or more, wherein the content is 30 to 250 ppm and the content of Mn is 10 to 150 ppm . In the pore distribution, a mode diameter 0.1 to 0.3 [mu] m is, the mode volume is ^{2.3 × 10 -3 ~2.8 × 10 -3} m 3 · kg -1, placing claim 1 Symbol Magnesium hydroxide particles. Magnesium hydroxide particles according to claim 1 or 2 , wherein the zeta potential is -20 to -25 mV. 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 to obtain a slurry containing magnesium hydroxide, iron, vanadium, and manganese, the magnesium hydroxide On the other hand, 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.
(B) A step of filtering, washing with water and drying a slurry containing magnesium hydroxide, iron, vanadium and manganese to obtain magnesium hydroxide coarse particles,
(C) Magnesium hydroxide coarse particles were calcined at 800 to 1900 ° C. in an air atmosphere to obtain magnesium oxide particles, and (d) obtained by pulverizing and sieving the magnesium oxide particles. Magnesium oxide powder having a median particle size of 3 to 30 μm and a crystallite size of 10 × 10 ⁻⁹ m or more is added to warm water of 100 ° C. or less to which an organic acid is added, and then under high shear stirring. A method for producing magnesium hydroxide particles, comprising a step of obtaining magnesium hydroxide particles by performing a hydration reaction of magnesium oxide, and then filtering off the generated solid, washing with water and drying. (I) epoxy resin,
(II) curing agent,
(III) an inorganic filler, and as (IV) a flame retardant, according to claim 1 to 3 resin composition comprising magnesium particles child hydroxide according to any one. The resin composition of Claim 5 whose compounding quantity of the said magnesium hydroxide particle is 1-35 mass% of the said resin composition. The resin composition according to claim 5 or 6 , which is a sealing agent for a semiconductor. The semiconductor device comprising the resin composition of any one of claims 5-7.

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