TWI399243B - Inorganic anionic exchanger made of ammonium compound and resin compound for sealing electrical parts by using it - Google Patents

Description

Inorganic anion exchanger of aluminide and resin composition for sealing electronic parts using the same

The present invention relates to an inorganic anion exchanger, particularly an inorganic anion exchanger which is suitably used in a resin composition for sealing electronic parts. Further, the electronic component resin composition containing the inorganic anion exchanger, the resin obtained by curing the resin, and the electronic component formed by the composition sealing member. Further, the present invention relates to a varnish, an adhesive, and a paste containing the inorganic anion exchanger, and a product containing the same.

Conventionally, inorganic anion exchangers include hydrotalcite, barium hydroxide, magnesium hydroxide, and aluminum hydroxide.

In recent years, inorganic anion exchange systems have been blended in resins for sealing electronic components, resins for sealing electrical components, and resins for electrical products.

For example, many LSIs, ICs, hybrid ICs, transistors, diodes, and thyristor transistors or such hybrid parts are sealed with an epoxy resin. Such an electronic component sealing material is required to have electrical properties such as flame retardancy, high adhesion, crack resistance, and high volume resistivity when suppressing defects due to ionic impurities or external intrusion in the raw material. Etc. Various characteristics.

The epoxy resin-based main component used as the electronic component sealing material is an epoxy compound curing agent, a curing accelerator, an inorganic filler, a flame retardant, a pigment, a decane coupling agent, or the like.

Furthermore, with the high integration of semiconductors in recent years, corrosion of aluminum has occurred early by reducing the width of the aluminum wiring on the IC wafer. This corrosion is promoted by the water mainly immersed in the epoxy resin used as the sealing material. Further, in order to reduce the amount of heat generated during use, a large amount of a flame retardant such as cerium oxide, brominated epoxy resin, or inorganic hydroxide is blended in the epoxy resin by the reduction in wiring width. These flame retardant components can further contribute to the corrosion of wiring such as aluminum.

In order to prevent the above corrosion, it is required to further improve the moisture resistance reliability for the epoxy resin. In fact, it is a proposal to capture a problematic impurity ion, particularly a halogen ion, in order to improve the reliability of the moisture resistance, and a hydrotalcite type of an inorganic anion exchanger is preferably formulated with an epoxy resin or the like (for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

Since this compound contains almost an anion such as a hydroxide ion or a carbonate ion as an anion, the anion exchange performance is not considered to be sufficient.

By calcining the hydrotalcite compound, the anions in the structure are detached to form a hydrotalcite-fired product. Since the hydrotalcite-fired product does not contain an anion in the compound, it is excellent in anion exchange performance as compared with the hydrotalcite compound. They absorb water to form a layered structure.

It is also proposed to blend the hydrotalcite-fired material with an epoxy resin or the like (for example, see JP-A-60-42418). These systems are excellent in anion exchange performance and improve the moisture resistance reliability of electronic components. However, they are highly hygroscopic and easily absorb moisture in the air, so they absorb moisture in electronic parts. It absorbs moisture and increases in volume. Therefore, when it is processed in a high temperature such as a solder bath or a reflow apparatus, thermal stress generated by a difference in thermal expansion coefficient of a substrate or the like, or vapor pressure generated by vaporizing moisture, in a component, a lead frame Peeling between the inserts and the molding material for sealing may cause cracks in the package, damage to the wafer, and the like.

An epoxy resin composition for semiconductor sealing which is a compound of an anion exchanger is known (for example, see JP-A No. 2-294354).

Further, the anion exchange system generally adsorbs anions well in the vicinity of the acidic environment, but it is difficult to adsorb anions near the neutral or near the alkaline. When the pH of the resin composition is in the vicinity of neutrality by the additive of the sealing material, the effect of the anion exchanger may not be sufficiently exhibited.

In the meantime, a method of using a cation exchanger of a solid acid in an anion exchanger to reduce the apparent pH and improve the ion exchange property has been proposed (for example, see JP-A-60-23901). However, in the case where a solid acid is added to the resin, the physical properties of the resin are impaired. Further, many of the cation exchangers contain heavy metals, and since the environmental care is concerned recently, there is a case where the cation exchanger cannot be used in combination.

In the epoxy resin used for the printed wiring board, an inorganic ion exchanger such as a cation exchanger, an anion exchanger, or a two-ion exchanger is known (for example, see JP-A-5-140419). .

A printed substrate containing an epoxy resin or a polyphenylene ether resin and an ion scavenger in an aromatic polyamine is known. The ion-trapping agent is exemplified by an ion-exchange resin or an inorganic ion-exchanger, and an inorganic-ion exchange system has been described in the case of an yttrium-lanthanide or a zirconium-based (see, for example, JP-A-9-314758).

An insulating varnish containing an ion scavenger is known, and the insulating varnish is used to produce a multilayer printed wiring board. The ion scavenger is exemplified by activated carbon, zeolite, cerium oxide gel, activated alumina, activated clay, hydrated pentoxide, zirconium phosphate, and hydrotalcite (see, for example, JP-A-10-287830).

It is known to incorporate an inorganic ion sorbent into an adhesive film for a multilayer wiring board. The inorganic ion sorbent is exemplified by activated carbon, zeolite, cerium oxide gel, activated alumina, activated clay, hydrated pentoxide, zirconium phosphate, and hydrotalcite (see, for example, Japanese Patent Publication No. Hei 10-330696) ).

Epoxy adhesives containing ion-accumulating agents are known. The ion-accepting agent is exemplified by an anion exchanger or a cation exchanger (for example, see JP-A-10-13011).

A conductive epoxy resin paste containing an ion trapping agent, silver powder or the like is known. The ion scavenger is exemplified by hydrated cerium nitrate, magnesium aluminum hydrotalcite, cerium oxide, and the like (for example, see JP-A-10-7763).

The ion exchangers described in them. Among the ion scavengers, there are descriptions using hydrotalcites, and they may be used as they are or as a fired body.

It is known that an inorganic ion exchanger represented by the following formula (2) is blended in the epoxy resin composition (for example, see JP-A-5-125159).

A _x O _y (NO ₃ ) _z (OH) _w . h(H ₂ O) (2)

However, in the formula (2), the A system represents one or two or more kinds of 3 to 5 valence transition metals, and x = 1 to 5, y = 1 to 7, z = 0 to 3, and w = 0.2 to 3, h = 0~2. Among them, the following formula (3) which is different from the aluminide of the present invention is exemplified.

Al ₂ O _{2 . 2} (OH) _{0 . 8} . 0.5H ₂ O (3)

Further, it contains at least one of polyvinyl alcohol and a derivative thereof, at least one of zirconium, titanium, magnesium, aluminum, and antimony, and an inorganic ion exchanger, and (a) has an apparent density of 1.1 to 2.5 g/cm ³ , ( b) a resin-hardened inorganic ion exchange system having an average particle diameter of 0.2 to 20 mm, (c) an ion exchange capacity of 0.1 to 10 meq/g, and (d) a metal component content of 1 to 25% by weight (in terms of metal oxide) is known ( For example, refer to Japanese Laid-Open Patent Publication No. Hei 10-216533.

Among these, the hydrotalcite or the cerium hydroxide-containing lanthanum has high anion exchangeability and is excellent in chemical resistance and heat resistance, and can be used in various applications. For example, a semiconductor sealing resin mixed in an electronic industry region is used for the purpose of improving the reliability of semiconductor components and the like.

However, the hydrotalcite is highly soluble in hot water of medium temperature and high humidity of 100 ° C or higher. Further, since the physical properties of the sealing resin having high hygroscopicity are adversely affected, the range of use thereof is limited.

On the other hand, since the ruthenium compound containing ruthenium hydroxide or the like has excellent performance, it can be used in a wide range, but its use is also restricted from the viewpoint of easily recovering the surface of the alloy with copper.

The high-performance inorganic anion exchange system which is now known has been found to have an environmentally superior and high-performance novel inorganic anion exchanger due to the problems as described above and the like.

The present inventors have found that aluminide or amorphous form represented by the following formula (1) is obtained as a result of intensive review in order to find a novel inorganic anion exchanger which can be used for a semiconductor encapsulant or the like in an electronic industrial region. The present invention has been completed by the high anion exchangeability of alumina.

Al ₂ O _x (OH) _y (NO ₃ ) _z . nH ₂ O (1)

In the formula (1), x is a positive number, y is 0 or a positive number, and z is a positive number of 3 or less, and those satisfying the formula of 2x+y+z=6, n is 0 or a positive number.

Another aspect of the present invention is an inorganic anion exchanger having an anion exchange capacity of 0.8 meq/g or more.

Another aspect of the present invention is an inorganic anion exchanger having a supernatant having a conductivity of 200 μS/cm or less in the case where the inorganic anion exchanger is subjected to hot water treatment.

Another aspect of the present invention is an inorganic cation exchanger containing an optional component, and a resin composition for sealing an electronic component containing the inorganic anion exchanger described above.

Another aspect of the present invention is the resin composition for sealing an electronic component described above, which comprises an epoxy resin and a curing agent.

Another aspect of the present invention is an electronic component sealing resin comprising the resin composition for sealing electronic components described above.

Another aspect of the present invention is an electronic component comprising an element sealed by the resin composition for electronic component sealing described above.

Another aspect of the present invention is a varnish, an adhesive, or a paste containing an inorganic cation exchanger as an optional component and the inorganic anion exchanger described above.

Another aspect of the present invention is a product comprising the varnish, the adhesive, or the paste described above.

According to the present invention, it is possible to provide a novel inorganic anion exchanger which is excellent in environmental properties and high in performance.

Moreover, according to the present invention, a resin composition for sealing an electronic component using the above inorganic anion exchanger, a resin for sealing an electronic component, and an electronic component can be provided.

Further, according to the present invention, a varnish, an adhesive, a paste, and a product containing the same, which are used in the above inorganic anion exchanger, can be provided.

[Best Mode for Carrying Out the Invention]

Since the inorganic anion exchange system of the present invention has an inorganic anion exchanger composed of the aluminide represented by the above formula (1) or amorphous alumina, it is excellent in environmental properties and high in performance, and even if the hydrotalcite system cannot be used. The use of an anion exchanger or a ruthenium anion exchanger can also be suitably used, and it is preferable.

○ Aluminide represented by formula (1) (hereinafter, simply referred to as "aluminide")

The aluminide in the present invention is represented by the above formula (1).

The x-form of the formula (1) is preferably a positive number lower than 3, a positive number of 0.5 to 2.9 is preferable, a positive number of 1 to 2.9 is more preferable, and a positive number of 1 to 2.8 is particularly preferable. When x in the formula (1) is 0, the conductivity of the supernatant becomes high, which is not preferable.

The y of the formula (1) is preferably 0 or less than 6 and the positive number of 0 or less is preferably 0, or the positive number of 0 or less is more preferable, and the positive number of 0 or less is due to conductivity. Very good. The smaller number of y is preferable because the conductivity is small.

The z system of the formula (1) is a positive number of 3 or less, a positive number of 2.5 is preferable, and a positive number of 2 or less is particularly preferable. It is preferable that the number of z is small because the amount of nitrate ions is small. In other words, when the aluminide used in the present invention has a nitrate, it is preferable that the degree of conductivity of the supernatant described later becomes small.

The aluminide compound represented by the formula (1) is an example in which x is a positive number of 2.9 or less, y is a positive number of 0 or less, and z is a positive number of 3 or less, and x, y, and z satisfy the formula of 2x+y+z=6. It is better if n is 0 or a positive number.

In the present invention, such as for example aluminum compound may be _{Al 2 O (OH) 3.} 3 (NO 3) 0. 7. H ₂ O, Al ₂ O ₂ (NO ₃ ) ₂ , Al ₂ O _{0 . 5} (OH) ₃ (NO ₃ ) ₂ , Al ₂ O(OH) ₃ (NO ₃ ), Al ₂ O(OH) ₂ ( _{NO 3) 2, Al 2 O} (OH) (NO 3) 3, Al 2 O 2 (OH) (NO 3), Al 2 O 2 (OH) 0. 5 (NO 3) 1. 5, Al 2 O (OH) _{3 . 7} (NO ₃ ) _{0 . 3} . _{H 2 O, Al 2 O 2} . 5 (NO 3), Al 2 O 2. 8 (OH) 0. 3 (NO 3) 0. 1, Al 2 O 2. 7 (OH) 0. 4 (NO 3 _{) 0. 2, Al 2 O} 2 (OH) 1. 4 (NO 3) 0. 6. H ₂ O, Al ₂ O _{2 . 9} (OH) _{0 . 1 5} (NO ₃ ) _{0 . 0 5} , Al ₂ O _{2 . 6} (OH) _{0 . 6} (NO ₃ ) _{0 . 2} , Al ₂ O _{2 . 6 (OH) 0. 2} (NO 3) 0. 6, Al 2 O 2. 5 (OH) 0. 8 (NO 3) 0. 2, Al 2 O 2. 5 (OH) 0. 6 (NO _{3) 0. 4, Al 2} O 2. 5 (OH) 0. 2 (NO 3) 0. 8, Al 2 O 2. 4 (OH) 0. 8 (NO 3) 0. 4, Al 2 O 2 _{. 4 (OH) 0. 4} (NO 3) 0. 8, Al 2 O 2. 3 (OH) 0. 8 (NO 3) 0. 6, Al 2 O 2. 2 (OH) 0. 6 (NO _{3) 1, Al 2 O 2} . 1 (OH) 0. 6 (NO 3) 1. 2 and the like. The aluminide in the present invention is preferred because the conductivity of the nitrate-based supernatant is small.

The raw material of the aluminide represented by the formula (1) in the present invention can be used as long as it is obtained by anion exchange. For example, in the aluminide of the present invention, an aqueous solution of aluminum nitrate is neutralized, and the precipitate is formed and dried, and then obtained by firing or by directly firing a precipitate. In addition, the precipitate is also preferably matured. Further, after directly heating the aluminum nitrate, the aluminide of the present invention can be obtained by firing. Further, aluminum hydroxide, hydroxy aluminum hydroxide, aluminum oxide, metal aluminum or the like may be dissolved in nitric acid or used as a raw material of the aluminide of the present invention. That is, the thus obtained one can be used as the aluminum nitrate of the aluminide raw material of the present invention.

The aluminide in the present invention can be obtained, for example, by neutralizing an aqueous solution of aluminum nitrate at pH 3 to pH 12 to form a shoal, drying it, firing it, or directly firing it. The pH is preferably from 3 to 10, preferably from pH 3.3 to 9, more preferably from pH 3.5 to 8.5. When the pH of the aqueous solution is less than 3, it is difficult to make the precipitation formation system difficult. Further, when the pH of the aqueous solution exceeds 12, the ion exchange property is lowered, which is not preferable.

The temperature of the solution at the time of precipitation from the aqueous solution is preferably from 1 to 100 ° C, more preferably from 10 to 80 ° C, more preferably from 20 to 60 ° C. As the pH adjusting person, for example, an alkali metal hydroxide, an alkali metal carbonate, an alkali metal hydrogencarbonate, ammonia, and a compound which generates ammonia by heating (for example, urea or hexamethylenetetramine) may preferably be mentioned. . The alkali metal is preferably sodium or potassium. As the pH adjusting person, it is more preferable to use ammonia and a compound which generates ammonia by heating (for example, urea or hexamethylenetetramine).

The aluminide in the present invention can also be obtained by subjecting the obtained agglomerated material to the dried material by the above-described operation, followed by drying, baking, or direct firing. This ripening treatment may or may not be carried out. For example, the temperature of the ripening is preferably 10 to 200 ° C, preferably 15 to 120 ° C, and more preferably 20 to 100 ° C.

The time for the ripening treatment is preferably a short heating time at a high temperature, and generally 2 to 72 hours is preferred, 5 to 48 hours is preferred, and 10 to 30 hours is more preferred.

The drying of the precipitate can be carried out at room temperature or by heating. That is, if any excess water can be removed from the shovel, any treatment can be performed. For example, the drying temperature of the precipitate in the present invention is preferably 80 to 250 ° C, more preferably 100 to 200 ° C. Further, the drying and baking may be carried out simultaneously. In this case, it is preferable to reach a slightly lower temperature until the moisture is removed, and then rise to the firing temperature.

The aluminide in the present invention can be obtained by baking after drying the above-mentioned shovel. Further, the drying treatment and the baking may be carried out simultaneously.

The firing temperature varies depending on the firing time and has a different preferred temperature. The firing temperature is preferably 150 to 800 ° C, preferably 200 to 650 ° C, and more preferably 300 to 600 ° C.

The baking treatment time varies depending on the firing temperature and has a different preferred time. The baking treatment time is preferably a short heating time at a high temperature, and is generally preferably 1 to 72 hours, preferably 2 to 48 hours, more preferably 3 to 30 hours.

The aluminide of the present invention can also obtain the aluminide of the present invention by directly heating the aluminum nitrate and then baking it.

The direct heat treatment is preferably carried out at a heating temperature of 140 to 200 ° C and a heating time of 12 to 48 hours. The heating temperature is preferably 150 to 190 °C. When the temperature is outside the range of the heating temperature, the aluminide of the present invention cannot be obtained, which is not preferable. The firing conditions are preferably from 350 to 650 ° C for a period of from 1 to 10 hours. The firing temperature is preferably 400 to 600 ° C. When the range of the firing temperature is outside the range, the aluminide of the present invention cannot be obtained, which is not preferable.

The aluminide of the present invention is formed by neutralizing an aqueous solution of aluminum nitrate, and the precipitate is dried at 80 to 250 ° C, and then fired at 150 to 800 ° C, or by directly depositing the precipitate at 150 ~ After firing at 800 ° C, or directly heating aluminum nitrate at 140 to 200 ° C, it can be obtained by firing at 350 to 650 ° C.

○ Method of making from aluminum hydroxide

The aluminide of the present invention can also be obtained by introducing a nitrate into a compound represented by the following formula (4) and drying it by heating.

Al ₂ O _x (OH) _y . nH ₂ O (4)

In the formula (4), x is a positive number, y is a positive number, and it satisfies the formula of 2x+y=6, and n is 0 or a positive number.

In the present invention, any compound can be used if the compound represented by the above formula (4) can be obtained. For example, it can be obtained by heat-treating aluminum hydroxide. The heat treatment of the aluminum hydroxide is preferably 200 to 700 ° C, more preferably 220 to 600 ° C, and still more preferably 230 to 500 ° C. The time of the heat treatment can be determined according to the temperature of the heat treatment. For example, the heat treatment time is preferably from 0.5 to 24 hours, preferably from 1 to 18 hours, more preferably from 2 to 15 hours.

In the present invention, any condition can be used if the nitrate can be introduced into the compound represented by the formula (4). For example, the compound represented by the formula (4) is treated with an aqueous solution of nitric acid and can be introduced into a nitrate. The concentration of the aqueous nitric acid solution is preferably 0.2 to 10%, more preferably 0.5 to 7%, still more preferably 1 to 5%. The treatment temperature of the aqueous nitric acid solution is preferably 0 to 100 ° C, more preferably 10 to 80 ° C, still more preferably 20 to 60 ° C. The treatment time of the aqueous nitric acid solution can be determined according to the concentration of the aqueous solution of nitric acid and the treatment temperature. For example, the treatment time of the aqueous solution of nitric acid is preferably from 0.5 to 48 hours, more preferably from 2 to 30 hours, more preferably from 5 to 25 hours. In the treatment of the nitric acid aqueous solution, the amount of the compound represented by the formula (4) is preferably from 1 to 50 parts by weight, more preferably from 2 to 30 parts by weight, more preferably from 100 parts by weight to the aqueous solution of the nitric acid. 5 to 25 parts by weight.

In the present invention, when a nitrate is introduced into the compound represented by the formula (4) and then dried by heating to obtain an aluminide represented by the formula (1), any conditions can be used. For example, the heating and drying temperature is preferably from 150 to 700 ° C, more preferably from 200 to 600 ° C, still more preferably from 220 to 500 ° C. The heat drying time is different depending on the temperature of the heat drying. The heating and drying time is preferably a short period of high temperature, and is generally preferably from 1 to 72 hours, preferably from 2 to 48 hours, more preferably from 3 to 30 hours.

○Amorphous alumina

The amorphous alumina in the present invention is alumina and the crystal is amorphous. Further, the amorphous alumina is amorphous. It is not observed by X-ray diffraction analysis.

The raw material for obtaining the amorphous alumina in the present invention can be used if it is obtained. For example, the amorphous alumina in the present invention can be obtained by adjusting an aqueous solution of aluminum nitrate to an alkaline state to form a precipitate, and drying it, heating it, or baking it.

The amorphous alumina in the present invention can be obtained, for example, by adjusting an aqueous solution of aluminum nitrate to be alkaline and causing the formation to be formed, and heating it by drying. The pH is preferably pH 7.5 to 12, preferably pH 8 to 11, and more preferably pH 8.5 to 10. The solution temperature at which the precipitation is formed is preferably from 1 to 100 ° C, preferably from 10 to 80 ° C, more preferably from 20 to 60 ° C. The pH adjustment person may, for example, be an alkali metal hydroxide, an alkali metal carbonate, an alkali metal hydrogencarbonate, ammonia, or a compound which generates ammonia by heating (for example, urea or hexamethylenetetramine). The alkali metal is preferably sodium or potassium. As a pH adjustment, it is more preferable that ammonia is a compound which produces ammonia by heating (for example, urea, hexamethylenetetramine, etc.).

The amorphous alumina in the present invention is obtained by, for example, adjusting an aqueous solution of aluminum nitrate to be alkaline, forming a shovel, and subjecting it to a heating and aging treatment, followed by drying and heat treatment. The heating temperature of the heating and ripening treatment is based on the heating time, and the preferred temperature is different. The heating temperature is preferably 100 to 300 ° C, preferably 130 to 250 ° C, and more preferably 150 to 200 ° C.

The time during which the ripening treatment is carried out is due to the heating temperature, and the preferred time is different. The heating time is preferably high temperature and short heating time. Generally, it is preferably 2 to 72 hours, preferably 10 to 48 hours, and more preferably 20 to 30 hours.

Drying can be carried out at room temperature or in a drying oven. In other words, if any excess water can be removed from the sediment, any treatment can be performed. For example, the drying temperature in the present invention is preferably from 80 to 250 ° C, more preferably from 110 to 200 ° C. In addition, the drying and heating can also be carried out simultaneously. In this case, it is preferable to reach a slightly lower temperature until the moisture is removed, and then rise to the heating temperature.

The amorphous alumina in the present invention can be obtained by drying the above-mentioned slab and then heat-treating it. Further, the drying treatment and the heat treatment may be simultaneously performed.

The heating temperature is different depending on the heating time. The heating temperature is preferably, for example, a heating temperature of 360 to 800 ° C, preferably 380 to 700 ° C, and more preferably 400 to 600 ° C.

The heat treatment time is different depending on the heating temperature. The heating time is preferably at a high temperature and a short heating time. Generally, 1.5 to 72 hours is preferred, 2 to 48 hours is preferred, and 3 to 30 hours is more preferred.

The aluminide of the present invention and the amorphous alumina obtained as described above are pulverized according to the purpose, and a desired particle diameter can be obtained.

The particle size of the aluminide and the amorphous alumina in the present invention is not limited, but the average particle diameter is preferably 0.01 to 10 μm, more preferably 0.05 to 3 μm. When the particle diameter is 0.01 to 10 μm, the particles do not aggregate with each other, and it is preferable that the resin is added to the resin without impairing the physical properties.

○ Anion exchange capacity

The anion exchange capacity in the present invention is measured using hydrochloric acid. In the measurement, 1 g of the sample and 50 ml of a 0.1 M/liter hydrochloric acid were placed in a 100 ml polyethylene bottle and shaken at 40 ° C for 24 hours. Thereafter, the supernatant was subjected to ion chromatography at a chloride ion concentration. The method is determined. The ion exchange capacity was calculated as a blank test value by measuring the chloride ion concentration without performing a sample and performing the same operation.

The anion exchange capacity of the inorganic anion exchanger of the present invention is preferably 0.8 meq/g or more, more preferably 0.9 meq/g or more, more preferably 1 meq/g or more, and preferably 4.5 meq/g or less, 4 meq. The following is preferably /g or less, and more preferably 3 meq/g or less.

When the anion exchange capacity is in the above range, it is preferred that the resin properties of the inorganic anion exchanger of the present invention are not impaired.

○ Conductivity

The conductivity of the supernatant is obtained by charging pure water in a sample, stirring it, and measuring the conductivity of the supernatant. In the measurement, 0.5 g of the sample and 50 ml of pure water were placed in a 100 ml polypropylene bottle and kept at 100 ° C for 24 hours, after which the conductivity of the supernatant was measured.

The supernatant conductivity in the inorganic anion exchanger of the present invention is preferably 200 μS/cm or less, more preferably 150 μS/cm or less, more preferably 100 μS/cm or less, still more preferably 1 μS/cm or more, and 3 μS/cm or more. Preferably, it is more preferably 5 μS/cm or more.

When the conductivity of the supernatant is in the above range, it is preferred that the performance of the resin of the inorganic anion exchanger of the present invention is not impaired.

For example, the inorganic anion exchange system of the present invention preferably has an anion exchange capacity of 0.8 meq/g or more and an inorganic anion exchanger having a superconductivity of 200 μS/cm or less.

The aluminide of the present invention is preferably one which does not contain crystal water, and can further reduce the conductivity of the supernatant.

○Resin composition for electronic parts sealing

The resin used in the resin composition for sealing electronic components of the inorganic anion exchanger of the present invention may be a thermosetting resin such as a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, or an epoxy resin. The thermoplastic resin such as polyethylene, polystyrene, vinyl chloride, or polypropylene is preferably a thermosetting resin. The thermosetting resin used in the resin composition for sealing electronic parts of the present invention is preferably a phenol resin or an epoxy resin, and particularly preferably an epoxy resin.

○ Epoxy resin composition for electronic parts sealing

The epoxy resin used in the present invention can be used without limitation if it can be used for a resin for sealing electronic parts. For example, if there are two or more epoxy groups in one molecule and can be cured, in particular, regardless of the type, phenol novolac type epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin, etc. One can also be used as a molding material. Moreover, in order to improve the moisture resistance of the composition of the present invention, it is preferred that the epoxy resin has a chloride ion content of 10 ppm or less and a water-decomposable chlorine content of 1,000 ppm or less.

In the present invention, the epoxy resin composition for electronic component sealing preferably contains a curing agent and a curing accelerator.

As the curing agent used in the present invention, any one of curing agents known as an epoxy resin composition can be used, and preferred examples thereof are an acid anhydride, an amine curing agent, and a novolac-based curing agent.

The hardening accelerator used in the present invention may be any one of curing accelerators known as epoxy resin compositions, and preferred examples are amine-based, phosphorus-based, and imidazole-based accelerators.

The resin composition for electronic parts of the present invention may be blended with a component known as a resin for blending molding as needed. Examples of the component include inorganic fillers, flame retardants, coupling agents for inorganic fillers, colorants, and release agents. These components are known as a component which blends any molding epoxy resin. Specific examples of the inorganic filler include, for example, crystalline cerium oxide powder, quartz glass powder, molten cerium oxide powder, alumina powder, and talc, among which crystalline cerium oxide powder, quartz glass powder, and molten sinter are particularly used. Cerium oxide powder is preferred because it is cheap. Examples of the flame retardant include cerium oxide, halogenated epoxy resin, magnesium hydroxide, aluminum hydroxide, ruthenium-based compound, and phosphate ester compound, and examples of the coupling agent include decane-based and titanium-based agents. Examples thereof include waxes of aliphatic paraffin, higher aliphatic alcohols, and the like.

In addition to the above components, a reactive diluent, a solvent or a thixotropic agent may be contained. Specifically, the reactive diluent may, for example, be butylphenyl glycidyl ether, the solvent may be exemplified by methyl ethyl ketone, and the thixotropic agent may, for example, be an organically modified bentonite.

The ratio of the inorganic anion exchanger of the present invention is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight per 100 parts by weight of the resin composition for sealing electronic parts. When the blending ratio is 0.1 part by weight or more, the effect of improving anion removal property or moisture resistance reliability is large. On the other hand, when it is 10 parts by weight or less, a sufficient effect is obtained, and it is preferable because the cost is not hindered.

By using the inorganic anion exchanger of the present invention in combination with the inorganic cation exchanger, the anion trapping energy of the inorganic anion exchanger of the present invention can be increased, and the trapping effect of the cationic ions can be added. The inorganic cation exchange system is an inorganic substance and has a cation exchange property.

The compounding ratio of the inorganic anion exchanger of the present invention to the inorganic cation exchanger is not particularly limited, but the weight ratio is preferably from 100:0 to 20:80. The blending of the inorganic anion exchanger of the present invention and the inorganic cation exchanger can be carried out separately when the resin composition for electronic component sealing is used, or can be carried out by uniformly mixing them in advance. It is preferred to use a mixture. By performing as described above, the effects of using these components can be further exerted.

Specific examples of the inorganic cation exchanger include citric acid (ruthenium pentoxide hydrate), citric acid (ruthenium pentoxide hydrate), manganese oxide, zirconium phosphate, titanium phosphate, tin phosphate, strontium phosphate, zeolite, and talc. Minerals and the like are preferably citric acid (nitricium pentoxide hydrate), zirconium phosphate, and titanium phosphate.

The resin composition for sealing an electronic component of the present invention can be easily obtained by mixing the above-mentioned raw materials by a known method. For example, the above respective raw materials are appropriately blended, and the complex is kneaded in a kneading machine in a heated state to form a semi-hardened resin. After cooling the composition to room temperature, it is pulverized by a well-known means, and it can be obtained by ingot.

The inorganic anion exchanger of the present invention can be used for various applications such as sealing, coating, and insulation of electronic parts and electrical parts.

Further, the inorganic anion exchanger of the present invention can also be used in a resin stabilizer such as vinyl chloride or a rust inhibitor.

The resin composition for an electronic component of the inorganic anion exchanger of the present invention can be used for mounting a semiconductor wafer or a transistor in a support member such as a lead frame or a transfer tape for wiring, a wiring board, a glass, or a germanium wafer. An element such as an active element such as a diode or a thyristor, a component such as a capacitor, a resistor, or a coil, or the like. Moreover, the resin composition for electronic component sealing of this invention can also be used effectively in a printed circuit board. An epoxy resin composition for electronic component sealing in which the inorganic anion exchanger of the present invention is blended can also be used in the same manner.

The method of sealing the element by using the resin composition for electronic component sealing of the present invention or the epoxy resin composition for sealing electronic parts, the low pressure transfer molding method is the most common, and an injection molding method, a compression molding method, or the like can be used.

○About application of wiring board

A thermosetting property such as an epoxy resin is used as a printed wiring board, and a copper foil or the like is adhered thereto, and an electric circuit is formed by etching or the like to form a wiring board. However, in recent years, there has been a problem of corrosion or poor insulation due to high density of circuits, lamination of circuits, and thinning of an insulating layer. When the wiring board is produced, such corrosion can be prevented by adding the inorganic anion exchanger of the present invention. Moreover, by adding the inorganic anion exchanger of the present invention to the insulating layer for the wiring board, it is possible to prevent corrosion of the wiring board and the like. Thereby, the wiring board containing the inorganic anion exchanger of the present invention can suppress the occurrence of defective products due to corrosion or the like. It is preferable to add 0.1 to 5 parts by weight of the inorganic anion exchanger of the present invention to 100 parts by weight of the resin solid content in the wiring board or the wiring board insulating layer. It is preferred to contain an inorganic cation exchanger here.

○About the admixture of adhesives

An adhesive is used to encapsulate an electronic component or the like on a substrate such as a wiring board. At this time, by adding the inorganic anion exchanger of the present invention to the adhesive to be used, it is possible to suppress the occurrence of defective products due to corrosion or the like. It is preferred to add 0.1 to 5 parts by weight of the inorganic anion exchanger of the present invention to 100 parts by weight of the resin solid content in the adhesive. It is preferred to contain an inorganic cation exchanger here.

By adding the inorganic anion exchanger of the present invention to a conductive adhesive or the like used for connecting or wiring electronic components or the like, it is possible to suppress the occurrence of defective products due to corrosion or the like. The conductive adhesive can be exemplified by a conductive metal containing silver or the like. It is preferred to add 0.1 to 5 parts by weight of the inorganic anion exchanger of the present invention to 100 parts by weight of the resin solid content in the conductive adhesive. It is preferred to contain an inorganic cation exchanger here.

○About the varnish blending

An electric product, a printed wiring board, an electronic component, or the like can be produced by using a varnish containing the inorganic anion exchanger of the present invention. The varnish can be exemplified by a thermosetting resin such as an epoxy resin. It is preferred to add 0.1 to 5 parts by weight of the inorganic anion exchanger of the present invention to 100 parts by weight of the resin solid content. It is preferred to contain an inorganic cation exchanger here.

○About the blending of paste

The inorganic anion exchanger of the present invention may be added to a paste containing silver powder or the like. The paste is used as a supplementary agent for imparting a pattern or the like, and is used for adhering the connection metals to each other. Thereby, the occurrence of corrosive substances by the paste can be suppressed. It is preferred to add 0.1 to 5 parts by weight of the inorganic anion exchanger of the present invention to 100 parts by weight of the resin solid content in the paste. It is preferred to contain an inorganic cation exchanger here.

○Implementation

Regarding the production method of the anion exchanger according to the present invention, the preferred embodiment is as follows.

<1> A method for producing an aluminide having anion exchange activity, comprising the steps of: neutralizing an aqueous solution of aluminum nitrate, forming a slab to obtain a shovel, and drying the precipitate at 80 to 250 ° C, The firing is carried out at 150 to 800 ° C, or the precipitate is directly calcined at 150 to 800 ° C, or the aluminum nitrate is directly heated at 140 to 200 ° C, and then calcined at 350 to 650 ° C. The steps.

<2> A method for producing an aluminide having anion exchange activity, comprising the steps of: neutralizing an aqueous solution of aluminum nitrate, forming a slab to obtain a step of smear, and drying the precipitate at 80 to 250 ° C. And the step of baking the dried shovel at 150~800 °C.

<3> A method for producing an aluminide having anion exchange activity, comprising the steps of: neutralizing an aqueous solution of aluminum nitrate, forming a slab to obtain a step, and directly performing the precipitate at 150 to 800 ° C. The step of firing.

<4> A method for producing an aluminide having anion exchange activity, comprising the steps of: heating aluminum nitrate directly at 140 to 200 ° C, and heat-treating aluminum nitrate at 350 to 650 ° C for firing The steps to become.

<5> The aluminide represented by the formula (1) obtained by the production method according to any one of the above <1> to <4>.

Regarding the production method of the anion exchanger according to the amorphous alumina, examples of preferred embodiments are as follows.

<6> A method for producing amorphous alumina having anion exchange activity, comprising the steps of: adjusting an aqueous solution of aluminum nitrate to be alkaline, forming a slab to obtain a shovel, and subjecting the shovel to heating and aging Thereafter, the step of drying, heating the dried product, or directly drying the sediment, and heating the dried product are carried out.

<7> A method for producing amorphous alumina having anion exchange activity, comprising the steps of: adjusting an aqueous solution of aluminum nitrate to be alkaline, forming a slab to obtain a step of smear, and subjecting the smudge to heating and aging treatment The step of drying and the step of heating the dried product.

<8> A method for producing an amorphous alumina having an anion exchange activity, comprising the steps of: adjusting an aqueous solution of aluminum nitrate to be alkaline, forming a step of obtaining a slab to obtain a shoal, and directly drying the shovel; and The step of heating the dried product.

<9> A method for producing amorphous alumina having anion exchange activity, comprising the steps of: adjusting an aqueous solution of aluminum nitrate to a pH of 7.5 to 12, and forming a sap in a water temperature of 1 to 100 ° C to obtain a shoal And the step of heating the matured material to treat the sediment, the step of drying the heat treated material, the step of heating the dried product, or the step of directly drying the suspended matter, and the step of heating the dried product.

<10> A method for producing amorphous alumina having anion exchange activity, comprising the steps of: adjusting an aqueous solution of aluminum nitrate to a pH of 7.5 to 12, and forming a sap in a water temperature of 1 to 100 ° C to obtain a shoal And the step of performing the ripening treatment at 100 to 300 ° C, the step of drying the cooked treatment, and the step of heating the dried product at 360 to 800 ° C, or making the sediment The step of drying directly at 80 to 250 ° C, and the step of heating the dried product at 360 to 800 ° C.

<11> The method for producing any one of the above <6> to <10>, which comprises the obtained anion exchange activity amorphous alumina.

Example

Hereinafter, the present invention will be described in further detail by way of examples and comparative examples, but the invention is not limited thereto. Further, % is % by weight and parts are parts by weight.

<Inorganic anion exchanger composed of aluminide>

(Example 1) While dissolving 10 g of aluminum nitrate in 100 ml of pure water and maintaining the solution at 25 ° C, it was adjusted to pH 9 with an aqueous ammonia solution. Further, after stirring for 1 hour, the sediment was filtered and washed with pure water. The shovel was placed in a dryer and treated at 200 ° C for 24 hours. Thereafter, it was pulverized to obtain aluminide 1 (anion exchanger 1). When the compound was analyzed for _{Al 2 O (OH) 3.} 3 (NO 3) 0. 7. H ₂ O.

(Example 2) While dissolving 10 g of aluminum nitrate in 100 ml of pure water and maintaining the solution at 25 ° C, it was adjusted to pH 9 with an aqueous ammonia solution. Further, after stirring for 1 hour, the sediment was filtered and washed with pure water. The shovel was placed in a dryer and treated at 200 ° C for 24 hours. This was heated at 350 ° C for 2 hours to obtain aluminide 2 (anion exchanger 2). When the analysis of the compound was carried out, it was Al ₂ O ₂ (NO ₃ ) ₂ .

(Example 3) While dissolving 10 g of aluminum nitrate in 100 ml of pure water and maintaining the solution at 25 ° C, it was adjusted to pH 9 with an aqueous ammonia solution. After the solution was stirred for 1 hour, it was placed in a sealed container made of polytetrafluoroethylene, and heat-treated at 180 ° C for 24 hours. After that, let it cool to room temperature, filter the sediment, and wash it with pure water.

This was placed in a dryer and heated at 200 ° C for 24 hours. Thereafter, it was pulverized to obtain aluminide 3 (anion exchanger 3). When the compound was analyzed for _{Al 2 O (OH) 3.} 7 (NO 3) 0. 3. H ₂ O.

(Example 4) The aluminide 3 obtained in Example 3 was further heated at 350 ° C for 2 hours to obtain aluminide 4 (anion exchanger 4). When the analysis of the compound was carried out, it was Al ₂ O _{2 . 5} (NO ₃ ).

(Example 5) While dissolving 10 g of aluminum nitrate in 100 ml of pure water and maintaining the solution at 25 ° C, it was adjusted to pH 5.5 with an aqueous ammonia solution. After the solution was stirred for 1 hour, the precipitate was filtered and washed with pure water. It was heated at 450 ° C for 4 hours. Thereafter, it was pulverized to obtain aluminide 5 (anion exchanger 5). When the compound was analyzed for _{Al 2 O 2. 8 (OH} ) 0. 3 (NO 3) 0. 1.

(Example 6) 10 g of aluminum nitrate was placed in a dryer as it was and heated at 155 ° C for 24 hours. It was further heated at 500 ° C for 4 hours, allowed to cool to room temperature, and pulverized to obtain aluminide 6 (anion exchanger 6). When the compound was analyzed for _{Al 2 O 2. 7 (OH} ) 0. 4 (NO 3) 0. 2.

(Example 7) 10 g of aluminum nitrate was placed in a dryer as it was and heated at 155 ° C for 24 hours. It was further heated at 400 ° C for 4 hours, allowed to cool to room temperature, and pulverized to obtain aluminide 7 (anion exchanger 7). When the compound was analyzed for _{Al 2 O 2 (OH) 1} . 4 (NO 3) 0. 6. H ₂ O.

(Example 8) While dissolving 10 g of aluminum nitrate in 100 ml of pure water and maintaining the solution at 25 ° C, it was adjusted to pH 7 with an aqueous ammonia solution. After the solution was stirred for 1 hour, the precipitate was filtered and washed with pure water. It was heated at 450 ° C for 4 hours. Thereafter, it was pulverized to obtain aluminide 8 (anion exchanger 8). When the compound was analyzed for _{Al 2 O 2. 9 (OH} ) 0. 1 5 (NO 3) 0. 0 5.

(Example 9) Aluminum hydroxide was heated at 300 ° C for 4 hours, and allowed to cool to room temperature. 100 g of this product was placed in 1 L of a 2% aqueous solution of nitric acid, and stirred at 40 ° C for 20 hours. Thereafter, the conductivity to the filtrate was 50 μS/cm or less. Further, it was dried at 250 ° C for 8 hours to obtain aluminide 9 (anion exchanger 9). When the compound was analyzed for _{Al 2 O 2 (OH) 1} . 9 5 (NO 3) 0. 0 5.

(Comparative Example 1) While dissolving 10 g of aluminum nitrate in 100 ml of pure water and maintaining the solution at 25 ° C, it was adjusted to pH 9 with an aqueous ammonia solution. Further, after stirring for 1 hour, the sediment was filtered and washed with pure water.

The sediment was placed in a dryer and heated at 100 ° C for 24 hours. Thereafter, it was pulverized to obtain a comparative aluminide (Comparative Compound 1). When the compound was analyzed for _{Al 2 (OH) 5. 1} (NO 3) 0. 9. H ₂ O.

(Comparative Example 2) The washed sediment obtained in Comparative Example 1 was heated at 300 ° C for 1 hour. Thereafter, it was pulverized to obtain a comparative aluminide (Comparative Compound 2).

(Comparative Example 3) Alumina hydroxide was obtained by heating at 500 ° C for 4 hours as a comparative aluminide (comparative compound 3).

(Comparative Example 4) α-alumina was used as Comparative Compound 4.

(Comparative Example 5) γ alumina was used as Comparative Compound 5.

(Comparative Example 6) While dissolving 10 g of aluminum nitrate in 100 ml of pure water and maintaining the solution at 25 ° C, it was adjusted to pH 9 with an aqueous ammonia solution. Further, after stirring for 1 hour, the sediment was filtered and washed with pure water. The slab was heated at 900 ° C for 1 hour. Thereafter, it was pulverized to obtain Comparative Compound 6. When the analysis of the compound is carried out, it is Al ₂ O ₃ .

(Comparative Example 7) Aluminum hydroxide was used as Comparative Compound 7.

(Comparative Example 8) Aluminum hydroxide was obtained by heating at 500 ° C for 4 hours as a comparative aluminide (comparative compound 8). When the analysis of the compound was carried out, it was AlO(OH).

<Ion exchange capacity measurement test>

1.0 g of the anion exchanger 1 was placed in a 100 ml polyethylene bottle, and then 50 ml of 0.1 M/liter hydrochloric acid was added thereto, and the plug was shaken and shaken at 40 ° C for 24 hours. Thereafter, the solution was filtered through a membrane filter having a pore size of 0.1 μm, and the chloride ion concentration in the filtrate was measured by ion chromatography. The same operation was carried out without any solid components, and the anion exchange capacity was determined in comparison with the measured chloride ion concentration. The results are shown in Table 1.

The anion exchange capacities were measured by performing the same treatment on the anion exchangers 2 to 9 and the comparative compounds 1 to 8. Their results are shown in Table 1.

<Measurement of Conductivity of Supernatant>

0.5 g of the anion exchanger 1 was placed in a 100 ml polypropylene bottle, and then 50 ml of pure water was added thereto, and the mixture was kept at 100 ° C for 24 hours (the bottle was pierced with a small hole). After 24 hours, the solution was cooled, filtered through a 0.1 μm membrane filter, and the conductivity of the filtrate was measured. The results are shown in Table 1.

The anion exchangers 2 to 9 and the comparative compounds 1 to 8 were also subjected to the same treatment to measure the conductivity. Their results are shown in Table 1.

<Use of aluminide resin mixed body>

(Example 10) 80 parts of a cresol novolac type epoxy resin (epoxy equivalent 235), 20 parts of a brominated phenol novolak type epoxy resin (epoxy equivalent 275), and 50 parts of a phenol novolac Resin (molecular weight 700-1,000), 2 parts of triphenylphosphine, 1 part of carnauba wax, 1 part of carbon black, 370 parts of molten cerium oxide, and 2 parts of anion exchanger 1 at 80 ° C The hot roll of ~90 ° C is kneaded for 3 to 5 minutes. Thereafter, the mixture was cooled and pulverized to obtain a powdery epoxy resin composition 1. Further, the composition 1 was sieved with a 100 mesh sieve to prepare a 100-mesh sample.

The 100-mesh sample was hardened at 170 ° C to prepare a resin mixed body 1. This resin was mixed into the body 1 and pulverized to a size of 2 to 3 mm. The pulverization sample was used to carry out a elution test of chloride ions.

(Example 11) A pulverized sample of the resin mixed body 2 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 2 was used instead of the anion exchanger 1.

(Example 12) A pulverized sample of the resin mixed body 3 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 3 was used instead of the anion exchanger 1.

(Example 13) A pulverized sample of the resin mixed body 4 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 4 was used instead of the anion exchanger 1.

(Example 14) A pulverized sample of the resin mixed body 5 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 5 was used instead of the anion exchanger 1.

(Example 15) A pulverized sample of the resin mixed body 6 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 6 was used instead of the anion exchanger 1.

(Example 16) A pulverized sample of the resin mixed body 7 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 7 was used instead of the anion exchanger 1.

(Example 17) A pulverized sample of the resin mixed body 8 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 8 was used instead of the anion exchanger 1.

(Example 18) A pulverized sample of the resin mixed body 9 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 9 was used instead of the anion exchanger 1.

(Comparative Example 9) A pulverized sample of the comparative resin mixed body 1 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 1 was replaced with the comparative compound 1.

(Comparative Example 10) A pulverized sample of the comparative resin mixed body 2 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 1 was replaced with the comparative compound 2.

(Comparative Example 11) A pulverized sample of the comparative resin mixed body 3 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 1 was replaced with the comparative compound 3.

(Comparative Example 12) A pulverized sample of the comparative resin mixed body 4 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 1 was replaced with the comparative compound 4.

(Comparative Example 13) A pulverized sample of the comparative resin mixed body 5 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 1 was replaced with the comparative compound 5.

(Comparative Example 14) A pulverized sample of the comparative resin mixed body 6 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 1 was replaced with the comparative compound 6.

(Comparative Example 15) A pulverized sample of the comparative resin mixed body 7 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 1 was replaced with the comparative compound 7.

(Comparative Example 16) A pulverized sample of the comparative resin mixed body 8 was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 1 was replaced with the comparative compound 8.

(Comparative Example 17) A pulverized sample in which the comparative resin mixed body 0 was produced was produced in the same manner as in the production of the resin mixed body 1 except that the anion exchanger 1 was not used. That is, the resin incorporation body 0 does not contain an inorganic anion exchanger.

<Chlorine ion extraction test from resin mixed body>

5 g of the resin mixed body 1 and 50 ml of pure water were placed in a pressure-resistant container made of polytetrafluoroethylene, sealed, and heated at 125 ° C for 100 hours. After cooling, water was taken out, and the concentration of chloride ions eluted in water was measured by ion chromatography. The results are shown in Table 2. Further, the pH of the supernatant was measured, and the results are shown in Table 2.

The same tests were carried out for the resin blends 2 to 9 and the comparative resin blends 1 to 8 and 0, and the results are shown in Table 2.

As is apparent from Tables 1 and 2, the inorganic anion exchange system of the present invention using aluminide has a large ion exchange capacity, and is added to the sealing material resin to suppress the elution of chloride ions. Accordingly, a wide range of highly reliable sealing material compositions can be provided.

<blending with cation exchanger>

The anion exchanger 1 synthesized in Example 1 and the α-zirconium phosphate group of the cation exchanger were sufficiently mixed at a weight ratio of 6:4 to prepare a mixture 1. This mixture 1 was used for the measurement of the ion exchange rate.

The anion exchanger 2, the anion exchanger 3, the anion exchanger 4, the anion exchanger 5, the anion exchanger 6, the anion exchanger 7, the anion exchanger 8, and the anion exchanger 9 are also operated in the same manner as described above. Mix 2, Mix 3, Mix 4, Mix 5, Mix 6, Mix 7, Mix 8, and Mix 9. They are used for the determination of ion exchange rate.

<Ion exchange rate measurement test>

2.0 g of the mixture 1 was placed in a 100 ml bottle made of polypropylene, and 50 ml of a 0.02 M aqueous sodium chloride solution was added thereto, and the mixture was stoppered and shaken at 40 ° C for 24 hours. Thereafter, the solution was filtered through a membrane filter having a pore size of 0.1 μm, and the concentration of chloride ions in the filtrate was measured. The same operation was carried out for those containing only aqueous sodium chloride solution to determine the chloride ion concentration. The anion exchange ratio of the mixture 1 was calculated from the values measured by the above, as shown in Table 3.

With respect to the mixture 2, the mixture 3, the mixture 4, the mixture 5, the mixture 6, the mixture 7, the mixture 8, and the mixture 9, the same operation was carried out, and the ion exchange ratio was calculated as shown in Table 3. Further, the anion exchanger 1, the anion exchanger 2, the anion exchanger 3, the anion exchanger 4, the anion exchanger 5, the anion exchanger 6, the anion exchanger 7, the anion exchanger 8, and the anion exchanger 9 are also subjected to The ion exchange rate was calculated in the same manner as shown in Table 3.

<Inorganic anion exchanger composed of amorphous alumina>

(Example 19) While dissolving 10 g of aluminum nitrate in 100 ml of pure water and maintaining the solution at 25 ° C, it was adjusted to pH 9 with an aqueous ammonia solution. After the solution was stirred for 1 hour, it was placed in a sealed container made of polytetrafluoroethylene, and heat-treated at 180 ° C for 24 hours. After that, let it cool to room temperature, filter the sediment, and wash it with pure water.

The washed sediment was placed in a dryer, heated at 200 ° C for 24 hours, and then heated at 500 ° C for 4 hours. It is then pulverized to obtain an aluminide (anion exchanger A). When the analysis of the compound is carried out, it is amorphous Al ₂ O ₃ . The X-ray diffraction was measured for the anion exchanger A, and the results are shown in Fig. 1.

(Example 20) The washed sediments prepared in Example 19 were placed in a dryer, heated at 200 ° C for 24 hours, and then heated at 400 ° C for 4 hours. It is then pulverized to obtain an aluminide (anion exchanger B). When the analysis of the compound is carried out, it is amorphous Al ₂ O ₃ .

(Example 21) While dissolving 10 g of aluminum nitrate in 100 ml of pure water and maintaining the solution at 25 ° C, it was adjusted to pH 9 with an aqueous ammonia solution. Further, after stirring for 1 hour, the sediment was filtered and washed with pure water. The shovel was placed in a dryer and treated at 200 ° C for 24 hours. It was then heated at 500 ° C for 4 hours. It is then pulverized to produce an aluminide (anion exchanger C). When the analysis of the compound is carried out, it is amorphous Al ₂ O ₃ .

(Comparative Example 18) While dissolving 10 g of aluminum nitrate in 100 ml of pure water and maintaining the solution at 25 ° C, it was adjusted to pH 9 with an aqueous ammonia solution. Further, after stirring for 1 hour, the sediment was filtered and washed with pure water.

The sediment was placed in a dryer and heated at 100 ° C for 24 hours. Thereafter, it was pulverized to obtain a comparative aluminide (Comparative Compound A). When the compound was analyzed for _{Al 2 (OH) 5. 1} (NO 3) 0. 9. H ₂ O.

(Comparative Example 19) Aluminum hydroxide was heated at 500 ° C for 4 hours to obtain a comparative aluminide (Comparative Compound B). The X-ray diffraction was measured for the comparative compound B, and the results are shown in Fig. 2.

(Comparative Example 20) Activated alumina (manufactured by Iwatani Chemical Industry Co., Ltd., RK-30) was used as Comparative Compound C. X-ray diffraction was measured for the comparative compound C, and the results are shown in Fig. 3.

(Comparative Example 21) α-alumina was used as Comparative Compound D. The X-ray diffraction was measured for Comparative Compound D, and the results are shown in Fig. 4.

(Comparative Example 22) γ alumina was used as Comparative Compound E. X-ray diffraction was measured for the comparative compound E, and the results are shown in Fig. 5.

The anion exchangers A to C and the comparative compounds A to E were treated in the same manner as the above-described ion exchange capacity measurement test, and the anion exchange capacity was measured. Their results are shown in Table 4.

Further, the anion exchangers A and B and the comparative compounds A, D, and E were treated in the same manner as the measurement of the conductivity of the supernatant to measure the conductivity. Their results are shown in Table 4.

<Resin mixed with amorphous alumina>

(Example 22) 80 parts of a cresol novolac type epoxy resin (epoxy equivalent 235), 20 parts of a brominated phenol novolak type epoxy resin (epoxy equivalent 275), and 50 parts of a phenol novolac Resin (molecular weight 700-1,000), 2 parts of triphenylphosphine, 1 part of carnauba wax, 1 part of carbon black, 370 parts of molten cerium oxide, and 2 parts of anion exchanger A, at 80 ° C The hot roll of ~90 ° C is kneaded for 3 to 5 minutes. Thereafter, it was cooled and pulverized to obtain a powdery epoxy resin composition A. Further, the composition A was sieved with a sieve of 100 mesh to prepare a sample of 100 mesh.

The 100-mesh sample was hardened at 170 ° C to prepare a resin mixed body A. The resin was mixed into the body A and pulverized to a size of 2 to 3 mm. The pulverization sample was used for the elution test of chloride ions.

(Comparative Example 23) A pulverized sample of the comparative resin mixed body A was produced in the same manner as in the production of the resin mixed body A except that the comparative compound A was used instead of the anion exchanger A.

(Comparative Example 24) A pulverized sample of the comparative resin mixed body D was produced in the same manner as in the production of the resin mixed body A except that the comparative compound D was used instead of the anion exchanger A.

(Comparative Example 25) A pulverized sample of the comparative resin mixed body E was produced in the same manner as in the production of the resin mixed body A except that the comparative compound E was used instead of the anion exchanger A.

(Comparative Example 26) A pulverized sample in which the comparative resin mixed body N was produced was produced in the same manner as in the production of the resin mixed body A except that the anion exchanger A was not used. That is, the comparative resin mixture N is not containing an inorganic anion exchanger.

The resin mixed body A and the comparative resin mixed bodies D, E, and N were tested in the same manner as the chloride ion extraction test of the resin mixed body, and the results are shown in Table 5.

As is apparent from Tables 4 and 5, the inorganic anion exchange system of the present invention using amorphous alumina has a large ion exchange capacity, and is added to the sealing material resin to have an effect of suppressing elution of chloride ions. Accordingly, a wide range of highly reliable sealing material compositions can be provided.

<blending with cation exchanger>

The anion exchanger A synthesized in Example 19 and the α-zirconium phosphate of the cation exchanger were sufficiently mixed at a weight ratio of 6:4 to prepare a mixture A. Using the mixture A, the ion exchange rate with respect to the aqueous sodium chloride solution was measured in the same manner as above.

The anion exchanger B and the anion exchanger C were also operated in the same manner as described above to prepare a mixture B and a mixture C. Further, regarding the mixture B, the mixture C, the anion exchanger A, the anion exchanger B, and the anion exchanger C, the ion exchange rate with respect to the sodium chloride aqueous solution was measured in the same manner as described above.

The results of these measurements are shown in Table 6 below.

[Industrial availability]

The inorganic anion exchange system of the present invention is excellent in environmental properties or anion exchange properties. Further, the inorganic anion exchange system of the present invention is an inorganic anion exchanger which does not use hydrotalcite or a ruthenium compound which is problematic in hygroscopicity or recycling surface. Further, by incorporating the inorganic anion exchanger of the present invention into the resin, it is also possible to suppress the effect of anion elution. Therefore, the inorganic anion exchanger of the present invention can be used for various applications such as sealing, coating, and insulation of electronic parts or electrical parts of a wide range and high reliability. Further, the inorganic anion exchanger of the present invention may be used in a resin stabilizer such as vinyl chloride or a rust inhibitor.

The horizontal axis of the first to fifth figures is the diffraction angle (2θ) of the X-ray diffraction.

The vertical axis of the first to fifth figures is the value of the diffraction intensity of the X-ray diffraction.

Figure 1 is an X-ray diffraction pattern of an anion exchanger A.

Figure 2 is a comparison of the X-ray diffraction pattern of Compound B.

Figure 3 is a comparison of X-ray diffraction of Compound C (activated alumina RK-30).

Figure 4 is a comparison of the X-ray diffraction pattern of Compound D (alpha alumina).

Figure 5 is a comparison of X-ray diffraction of compound E (gamma alumina).

Claims (10)

An inorganic anion exchanger characterized by being aluminide represented by the following formula (1) or amorphous alumina, and Al ₂ O _x (NO ₃ ) _z . nH ₂ O (1) (in the formula (1), x is in the range of 0.5 to 2.9, z is in the range of 0.05 to 3, and those satisfying the formula of 2x + z = 6, and n is in the range of 0 to 1) . The inorganic anion exchanger of claim 1, wherein the anion exchange capacity is 0.8 to 4.5 meq/g. An inorganic anion exchanger according to claim 1, wherein 0.5 g of the inorganic anion exchanger and 50 ml of pure water are placed in a 100 ml polypropylene bottle and kept at 100 ° C for 24 hours to obtain a supernatant. The conductivity is 1 to 200 μS/cm. A resin composition for sealing an electronic component, characterized in that it contains 0.1 to 10 parts by weight of the inorganic anion exchanger as claimed in claim 1 per 100 parts by weight of the resin composition for sealing an electronic component. The resin composition for sealing an electronic component according to claim 4, which comprises an inorganic cation exchanger, and the mixing ratio of the inorganic anion exchanger to the inorganic cation exchanger is 100:0 to 20:80 by weight ratio. . A resin for sealing an electronic component, which is characterized by being cured by a resin composition for sealing an electronic component according to the fourth or fifth aspect of the patent application. An electronic component characterized by being sealed by a resin composition for electronic component sealing as disclosed in claim 4 or 5. A varnish characterized by containing 0.1 to 5 parts by weight of the inorganic anion exchanger according to item 1 of the patent application with respect to 100 parts by weight of the resin solid content. An adhesive comprising 0.1 to 5 parts by weight of an inorganic anion exchanger according to item 1 of the patent application with respect to 100 parts by weight of the resin solid content. A paste comprising 0.1 to 5 parts by weight of an inorganic anion exchanger according to item 1 of the patent application with respect to 100 parts by weight of the resin solid content.