WO2006075500A1

WO2006075500A1 - Inorganic anion exchanger composed of yttrium compound and resin composition for electronic component sealing which uses same

Info

Publication number: WO2006075500A1
Application number: PCT/JP2005/023583
Authority: WO
Inventors: Yasuharu Ono
Original assignee: Toagosei Co., Ltd.
Priority date: 2005-01-11
Filing date: 2005-12-22
Publication date: 2006-07-20
Also published as: TWI378827B; JP5176323B2; JPWO2006075500A1; TW200633782A

Abstract

Disclosed is a novel high-performance inorganic anion exchanger which is environment friendly. Specifically disclosed is an inorganic anion exchanger represented by the following formula (1). Y2Ox(OH)y(NO3)z·nH2O (1) (In the formula (1), x, y and z respectively represent 0 or a positive number while satisfying 2x + y + z = 6, and n represents 0 or a positive number.) Also disclosed are a resin composition for electronic component sealing which contains an inorganic anion exchanger represented by the above formula (1), an electronic component sealing resin, and an electronic component. Further disclosed are a varnish, adhesive and paste containing the inorganic anion exchanger, and products containing them.

Description

Specification

Inorganic anion exchanger made of yttrium compound and resin composition for encapsulating electronic components using the same

Technical field

[0001] The present invention relates to an inorganic anion exchanger, and more particularly to an inorganic anion exchanger suitably used for a resin composition for encapsulating electronic components. Furthermore, the present invention relates to a resin composition for encapsulating electronic components containing the inorganic anion exchanger, a resin obtained by curing the resin composition, and an electronic component obtained by sealing an element with the composition. In addition, the present invention relates to a cornice, an adhesive and a paste containing the inorganic anion exchanger, and a product containing them.

Background art

Conventional inorganic anion exchangers include, for example, hydrated talcite, hydrous bismuth, hydrous magnesium oxide, hydrous aluminum oxide, and the like.

In recent years, inorganic anion exchangers are blended in resins for encapsulating electronic components, resins for encapsulating electrical components, resins for electrical products, and the like.

For example, LSIs, ICs, hybrid ICs, transistors, diodes, and thyristors are mostly sealed with epoxy resin. Such an electronic component sealing material suppresses defects caused by ionic impurities in raw materials or moisture entering from the outside, as well as flame retardancy, high adhesion, crack resistance and high volume resistivity. Various characteristics such as electrical characteristics are required.

Epoxy resins that are frequently used as encapsulants for electronic parts include epoxy compounds, which are the main components, as well as epoxy compound curing agents, curing accelerators, inorganic fillers, flame retardants, pigments, and silane coupling agents. Etc.

Furthermore, in recent years, with the high integration of semiconductors, the corrosion of aluminum began to occur at an early stage due to the reduction of the width of the aluminum wiring on the IC chip. This corrosion is mainly promoted by moisture that is used as a sealing material and penetrates into the epoxy resin. In addition, since the heat generated during use increased due to the reduction in wiring width, a large amount of flame retardant such as antimony oxide, brominated epoxy resin, and inorganic hydroxide was added to the epoxy resin. These flame retardant components have further promoted the corrosion of wiring such as aluminum.

[0004] In order to prevent the above corrosion, it has been required to further improve the moisture resistance reliability of the epoxy resin. In order to meet the demand to improve moisture resistance reliability, it is proposed to add hydrotalcites, which are inorganic anion exchangers, to epoxy resins and the like in order to capture impurity ions, especially halogen ions, which are problematic. (For example, see Patent Document 1, Patent Document 2, and Patent Document 3).

Since this compound already has anions such as hydroxide ions and carbonate ions as anions, the anion exchange performance is not sufficient.

[0005] By calcining this hydrated talcite compound, anions in the structure are desorbed to form a hydrated talcite product. Since the fired talcite hydrate does not contain anions in the compound, it excels in anion exchange performance compared to the hydrated talcite compound. This absorbs water and takes a layered structure again.

[0006] Proposals have also been made for blending this fired talcite product with an epoxy resin or the like (see, for example, Patent Document 4). This product has excellent anion exchange performance and is effective in improving the moisture resistance reliability of electronic components, but it is easy to absorb moisture in the air where the moisture absorption is very high. There is an increase in volume. Therefore, when exposed to high temperatures, such as in solder bath or reflow equipment processing, the thermal stress generated by the difference in thermal expansion coefficient of the substrate, etc., and the vapor pressure generated by vaporization of moisture absorption moisture, In addition, peeling may occur between the inserts such as lead frames and the molding material for sealing, which may cause a cage crack or chip damage.

[0007] It is known that a bismuth compound becomes an anion exchanger (see, for example, Patent Document 5 and Patent Document 6). An epoxy resin composition for semiconductor encapsulation containing a bismuth compound which is an anion exchanger is known (for example, see Patent Document 7).

[0008] In addition, an anion exchanger generally adsorbs anions well when the surrounding environment is acidic, but hardly adsorbs anions near neutral or alkaline. Depending on the additive added to the sealing material, the pH of the resin composition may be near neutral, and the effect of the anion exchanger may not be fully exhibited. [0009] As a countermeasure against this, a method has been proposed in which an anion exchanger is mixed with a cation exchanger, which is a solid acid, to lower the apparent pH and improve ion exchange (for example, patent documents). 8). However, when a solid acid is added to the resin, it can damage the resin properties. In addition, since many cation exchangers contain heavy metals, cation exchangers may not be used together due to environmental considerations.

[0010] It is known that an epoxy resin used for a printed wiring board is blended with an inorganic ion exchanger such as a cation exchanger, an anion exchanger, or both ion exchangers (see, for example, Patent Document 9). .

There is known a printed circuit board in which an aramid fiber contains an epoxy resin or a polyphenylene oxide resin and an ion scavenger. Examples of the ion scavenger include an ion exchange resin and an inorganic ion exchanger. As the inorganic ion exchanger, an antimony-bismuth-based material and a dinoleconium-based material are described (for example, see Patent Document 10). ). An insulating varnish containing an ion scavenger is known, and a multilayer printed wiring board is produced using this insulating varnish. Examples of the ion scavenger include activated carbon, zeolite, silica gel, activated alumina, activated clay, hydrated antimony pentoxide, zirconium phosphate, and hydrated talcite (for example, patent documents). 11).

It is known that an inorganic ion adsorbent is blended in an adhesive film for a multilayer wiring board. Examples of the inorganic ion adsorbent include activated carbon, zeolite, silica gel, activated alumina, activated clay, hydrated antimony pentoxide, dinoleconium phosphate, and hydrated talcite (see, for example, Patent Document 12).

An epoxy resin adhesive containing an ion trapping agent is known. Examples of the ion trapping agent include an anion exchanger and a cation exchanger (see, for example, Patent Document 13).

A conductive epoxy resin paste containing an ion scavenger and silver powder is known. Examples of the ion scavenger include hydrated bismuth nitrate, magnesium aluminum hydride talcite, and antimony oxide (see, for example, Patent Document 14).

Among the ion exchangers' ion scavengers described in these documents, there are those which describe the use of hydrated talcite, but these are used as they are or as calcined bodies. [0011] Of these, anodic talcite and hydrous bismuth oxide are used in various applications because they have high anion exchange properties and relatively high chemical resistance and heat resistance. For example, it is used for the purpose of improving the reliability of semiconductor components by mixing it with semiconductor sealing resin in the electronics industry.

However, Hyde mouth talcite is highly soluble under high temperature and high humidity such as hot water of 100 ° C or higher. In addition, the range of use is limited because it is highly hygroscopic and adversely affects the properties of the sealing resin.

On the other hand, bismuth compounds such as hydrated hydrous bismuth have excellent performance and can be used in a wide range. However, copper and alloys can be easily produced, and their use may be limited in terms of recycling.

Patent Document 1: Japanese Patent Application Laid-Open No. 63-252451

Patent Document 2: Japanese Patent Application Laid-Open No. 64-64243

Patent Document 3: JP-A-60-40124

Patent Document 4: JP-A-60-42418

Patent Document 5: Japanese Patent Laid-Open No. 63-060112

Patent Document 6: Japanese Patent Laid-Open No. 02-293325

Patent Document 7: Japanese Patent Laid-Open No. 02-294354

Patent Document 8: JP-A-60-23901

Patent Document 9: Japanese Patent Laid-Open No. 05-140419

Patent Document 10: Japanese Patent Application Laid-Open No. 09-314758

Patent Document 11: JP-A-10-287830

Patent Document 12: JP-A-10-330696

Patent Document 13: Japanese Patent Application Laid-Open No. 10-013011

Patent Document 14: Japanese Patent Laid-Open No. 10-007763

Disclosure of the invention

Problems to be solved by the invention

[0013] Currently known high performance inorganic anion exchangers have the above-mentioned problems. The problem to be solved by the present invention is to create a new inorganic anion exchanger that is environmentally friendly and has high performance. Is to provide.

Means for solving the problem

[0014] As a result of intensive studies to find a novel inorganic anion exchanger that can be used as a semiconductor encapsulant or the like in the electronic industry field, the present inventors have found that an yttrium compound represented by the following formula (1) Was found to have high anion exchange properties, and the present invention was completed.

Y O (OH) (NO) · ηΗ Ο (1)

2 χ y 3 z 2

In the formula (1), x, y, and z are 0 or a positive number, 2x + y + z = 6, and n is 0 or a positive number.

Another aspect of the present invention is an electronic component sealing resin composition containing the inorganic anion exchanger of the present invention, which contains an inorganic cation exchanger as an optional component. Yet another aspect of the present invention is the above-described resin composition for encapsulating electronic components, which contains an epoxy resin and a curing agent.

Another aspect of the present invention is a resin obtained by curing the resin composition for sealing an electronic component described above.

Another aspect of the present invention is an electronic component obtained by sealing an element with the above-described electronic component sealing resin composition.

Another aspect of the present invention is a varnish, adhesive or paste containing the inorganic anion exchanger of the present invention, which may contain an inorganic cation exchanger.

Yet another aspect of the present invention is a product containing the varnish, adhesive or paste described above.

The invention's effect

[0015] According to the present invention, a new inorganic anion exchanger that is environmentally friendly and has high performance can be provided.

In addition, according to the present invention, it is possible to provide an electronic component sealing resin composition, an electronic component sealing resin, and an electronic component using the inorganic anion exchanger.

Furthermore, according to this invention, the varnish using the said inorganic anion exchanger, an adhesive agent, a base, and the product containing these can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION [0016] Since the inorganic anion exchanger of the present invention is an inorganic anion exchanger composed of the yttrium compound represented by the above formula (1), it is environmentally friendly and has high performance. This is preferable because it can be suitably used in applications where site-based anion exchangers, bismuth-based anion exchangers, and the like cannot be used.

[0017] Yttrium compound

The yttrium compound in the present invention is represented by the above formula (1). X in formula (1) is 0 or a positive number of 3 or less, preferably a positive number of 3 or less, more preferably a positive number of 2.5 or less.

Y in formula (1) is a positive number of 0 or 6 or less, preferably 0 or 5.5 or less, more preferably 5 or less.

Z in the formula (1) is a positive number of 0 or 6 or less, preferably 0 or a positive number of 4 or less, more preferably a positive number of 3 or less.

Specific examples of yttrium compounds in the present invention include Y (OH) (NO) · Η 0, Y

2 5.1 3 0.9 2

〇 (NO), Y O, etc., and Y (OH), Y (OH) (NO), Y (OH) (

2 2 3 2 2 3 2 6 2 4 3 2 2 3

NO), Y (OH) (NO), Y (OH) (NO), Y O (OH), Y〇 (OH) (NO), Y

3 3 2 2 3 4 2 3 5 2 4 2 3 3 2

O (OH) (NO), Y O (OH) (NO), Y 0 (N〇), Y O (OH), Y〇 (OH) (NO

2 3 2 2 3 3 2 3 4 2 2 2 2 2

), Y 2 O (NO 2), etc.

3 2 2 3 2

[0018] As the raw material for obtaining the yttrium compound in the present invention, any raw material can be used as long as it is obtained by the formula (1) and has anion exchange properties. For example, the yttrium compound in the present invention can be obtained by adjusting the aqueous solution of yttrium nitrate to basic to produce a precipitate, which is dried and then heated. Further, for example, yttrium oxide of the present invention can be obtained by solubilizing yttrium oxide with nitric acid and subjecting it to the treatment described above.

[0019] The yttrium compound in the present invention can be obtained, for example, by adjusting the aqueous solution of yttrium nitrate to basic to produce a precipitate, which is dried and then heated. The pH is preferably pH 7.5 to 12 force S, more preferably pH 8 to 11 force S, and more preferably 8.5 to 10 force. The water temperature when this treatment is performed is preferably:! To 80 ° C force S, more preferably 10 to 60 ° C force S, and further preferably 15 to 40 ° C. For pH adjustment, alkali metal hydroxide, carbonate Preferred examples include a rucali metal salt, an alkali metal hydrogen carbonate salt, ammonia, and a compound that generates ammonia by heating (for example, urea, hexamethylenetetramine, etc.). As this alkali metal, sodium and potassium are preferable. More preferable examples of the pH-adjusting agent include ammonia and compounds that generate ammonia by heating (for example, urea, hexamethylenetetramine, etc.).

[0020] The yttrium compound in the present invention can be obtained by, for example, adjusting the aqueous solution of yttrium nitrate to basic to produce a precipitate, heat-treating it, then drying and heat-treating it. . The heating temperature of this heat aging treatment has a preferable temperature depending on the heating time. For example, the heating temperature is preferably 100 to 300 ° C force S, more preferably 130 to 250 ° C, and even more preferably 150 to 200 ° C force S.

The heating time of the heat aging treatment varies depending on the heating temperature. The higher the temperature, the shorter the heating time, but generally 2 to 72 hours are preferred, 10 to 48 hours are more preferred, and 15 to 30 hours are more preferred.

[0021] Drying may be performed at room temperature or by heating in a drying furnace. That is, any treatment may be performed as long as excess water is removed from the precipitate. For example, the drying temperature in the present invention is preferably 80 to 250 ° C. force S, more preferably 110 to 200 ° C. Note that this drying and heating can be performed simultaneously. In this case, it is preferable to lower the temperature until moisture is removed, and then to raise the heating temperature.

[0022] The yttrium compound in the present invention can be obtained by drying the above precipitate and then heat-treating it. This heating temperature has a preferable temperature depending on the heating time. For example, as the caloric heat temperature, 150 to: 1,000 ° C force S is preferable, 180 to 900 ° C force S is more preferable, 200 to

More preferred is 850 ° C.

The heating time for this heat treatment varies depending on the heating temperature. The higher the temperature, the shorter the heating time, but in general:!-72 hours are preferred, 2-48 hours are preferred, 3-30 hours are more preferred.

[0023] The yttrium compound in the present invention obtained as described above can be pulverized according to the purpose to obtain a desired particle size.

The particle size of the yttrium compound in the present invention is not particularly limited, but preferably the average particle size Diameter F. SO. 01 to 10 / im, more preferably ί to 0.05 to 3 / im. Particle size force SO. 01 to: ίθ μΐη is preferable because the particles do not aggregate with each other and when added to the resin, the physical properties are not impaired.

[0024] Anion exchange capacity

The anion exchange capacity in the present invention is measured using hydrochloric acid. In this measurement, lg sample and 50 ml of 0.1 M / liter hydrochloric acid are placed in a 100 ml polyethylene bottle, shaken at 40 ° C for 24 hours, and then the chloride ion concentration in the supernatant is measured by ion chromatography. Measured by topography. The anion exchange capacity was calculated using the same procedure as described above for the sample without the sample, but measuring the chloride ion concentration as a blank value.

The anion exchange capacity of the inorganic anion exchanger of the present invention is preferably lmeq / g or more, more preferably 1.5 meqZg or more, more preferably 1.8 meqZg or more, and preferably 4.5 meqZg or less. Mashigu 4. Less than 3meq / g is more preferred 4meqZg or less is more preferred.

If the ion exchange amount is within the above range, the performance of the resin blended with the anion exchanger of the present invention is hardly impaired, which is preferable.

[0025] ○ Conductivity

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

The conductivity of the supernatant in the inorganic anion exchanger of the present invention is preferably 200 μS / cm or less, more preferably 150 μS / cm or less, force S, more preferably 100 μS / cm or less, force S, and even more preferably 1 μS / cm or more is preferred 3 μS / cm or more is more preferred 5 μSZcm or more is even more preferred.

If the conductivity of the supernatant is within the above range, the performance of the resin containing the inorganic anion exchanger of the present invention is hardly impaired, which is preferable.

For example, the inorganic anion exchanger of the present invention is preferably an inorganic anion exchanger having an anion exchange capacity of SlmeqZg or more and a supernatant conductivity of 200 μS / cm or less. Good.

[0026] 〇 Resin composition for sealing electronic parts

Examples of the resin used in the resin composition for sealing an electronic component containing the inorganic anion exchanger of the present invention include a thermosetting resin such as a phenol resin, a urea resin, a melanin resin, an unsaturated polyester resin, and an epoxy resin. However, a thermoplastic resin such as polyethylene, polystyrene, salted bull, and polypropylene may be used, and a thermosetting resin is preferable. As the thermosetting resin used in the resin composition for encapsulating electronic parts of the present invention, a phenol resin or an epoxy resin is preferable, and an epoxy resin is particularly preferable.

[0027] Epoxy resin composition for sealing electronic parts

The epoxy resin used in the present invention can be used without limitation as long as it can be used as an electronic component sealing resin. For example, as long as it has two or more epoxy groups in one molecule and can be cured, any type can be used, such as phenol novolac type epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin, etc. Any material used as a molding material can be used. In order to improve the moisture resistance of the composition of the present invention, it is preferable to use an epoxy resin having a salt ion content of 1 Oppm or less and a hydrolyzable chlorine content of 1, OOOppm or less.

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

As the curing agent used in the present invention, any of those known as curing agents for epoxy resin compositions can be used, and preferred specific examples include acid anhydrides, amine-based curing agents, and nopolac-based curing agents. .

As the curing accelerator used in the present invention, any of those known as curing accelerators for epoxy resin compositions can be used, and preferred specific examples include amine-based, phosphorus-based, and imidazole-based accelerators. is there.

[0029] The resin composition for electronic parts of the present invention can be blended with what is known as a component to be blended with the molding resin, if necessary. Examples of this component include inorganic fillers, flame retardants, inorganic filler coupling agents, colorants, and release agents. These ingredients Are known as components to be blended in the molding epoxy resin. Specific examples of preferred inorganic fillers include crystalline silica powder, quartz glass powder, fused silica powder, alumina powder, and talc. Of these, crystalline silica powder, quartz glass powder, and fused silica powder are inexpensive. preferable. Examples of flame retardants include antimony oxide, halogenated epoxy resins, magnesium hydroxide, aluminum hydroxide, red phosphorus compounds, phosphate ester compounds, etc. Examples of coupling agents for inorganic fillers include silane Examples of mold release agents include aliphatic paraffins and higher aliphatic alcohols.

[0030] In addition to the above components, a reactive diluent, a solvent, a thixotropic agent, and the like can also be contained. Specifically, examples of the reactive diluent include butyl phenyl darisidino ether, examples of the solvent include methyl ethyl ketone, and examples of the thixotropic agent include organically modified bentonite.

[0031] A preferred blending ratio of the inorganic anion exchanger of the present invention is 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 an electronic component. . A blending ratio of 0.1 part by weight or more is preferable because it has a large effect of improving the anion removability and moisture resistance reliability. On the other hand, if it is 10 parts by weight or less, it is preferable because it will not only lead to a sufficient effect and cost increase.

[0032] By using an inorganic cation exchanger in combination with the inorganic anion exchanger of the present invention, the anion scavenging ability of the inorganic anion exchanger of the present invention is increased and the effect of capturing cationic ions is improved. Can be added. The inorganic cation exchanger is an inorganic substance and has a cation exchange property.

The compounding ratio of the inorganic anion exchanger and inorganic cation exchanger of the present invention is not particularly limited, but is preferably 100: 0 to 20:80 by weight. The inorganic anion exchanger and the inorganic cation exchanger according to the present invention may be blended separately when preparing the resin composition for sealing an electronic component, and these are mixed in advance. You can also. Preferably, a mixture is used. By doing so, the effect of using these components in combination can be further exhibited.

[0033] Specific examples of the inorganic cation exchanger include antimonic acid (antimony pentoxide hydrate), Examples include oxalic acid (niobium pentoxide hydrate), manganese oxide, zirconium phosphate, titanium phosphate, tin phosphate, cerium phosphate, zeolite, and clay minerals. Antimonic acid (antimony pentoxide hydrate) Product), zirconium phosphate, and titanium phosphate.

[0034] The resin composition for sealing an electronic component of the present invention can be easily obtained by mixing the above raw materials by a known method. For example, the respective raw materials are appropriately blended, and the blend is kneaded. The mixture is kneaded while heated in a machine to obtain a semi-cured resin composition, which is cooled to room temperature, pulverized by known means, and tableted as necessary.

[0035] The inorganic anion exchanger of the present invention can be used for various applications such as sealing, coating, and insulation of electronic components or electrical components.

Furthermore, the inorganic anion exchanger of the present invention can also be used for stabilizers, antifungal agents and the like for resins such as polyvinyl chloride.

[0036] A resin composition for electronic components containing the inorganic anion exchanger of the present invention is provided on a support member such as a lead frame, a wired tape carrier, a wiring board, glass, or a silicon wafer, on a semiconductor chip or transistor. It can be used for devices equipped with active elements such as diodes and thyristors, and passive elements such as capacitors, resistors and coils. In addition, the resin composition for encapsulating electronic components of the present invention can also be used effectively for printed circuit boards. An epoxy resin composition for encapsulating electronic components containing the inorganic anion exchanger of the present invention can be used in the same manner.

As a method for sealing an element using the resin composition for sealing an electronic component or the epoxy resin composition for sealing an electronic component of the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, A compression molding method or the like may be used.

[0037] ○ Application to wiring boards

A printed wiring board is formed using thermosetting properties such as an epoxy resin, and a copper foil or the like is bonded to the printed wiring board, and a circuit is produced by etching the film to produce a wiring board. In recent years, corrosion and insulation defects have become problems due to high density of circuits, lamination of circuits, and thinning of insulating layers. Such corrosion can be prevented by adding the inorganic anion exchanger of the present invention when producing a wiring board. Moreover, corrosion of the wiring board can be prevented by adding the inorganic anion exchanger of the present invention to the insulating layer for the wiring board. The Therefore, the wiring board containing the inorganic anion exchanger of the present invention can suppress the generation of defective products due to corrosion or the like. It is preferable to add 0.:! To 5 parts by weight of the inorganic anion exchanger of the present invention with respect to 100 parts by weight of the resin solid content in the wiring board or the insulating layer for the wiring board. An inorganic cation exchanger may be contained therein.

[0038] ○ About blending into adhesive

Electronic components and the like are mounted on a substrate such as a wiring board using an adhesive. At this time, by adding the inorganic anion exchanger of the present invention to the adhesive, the generation of defective products due to corrosion or the like can be suppressed. 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 adhesive. Even if it contains an inorganic cation exchanger, it is acceptable.

By adding the inorganic anion exchanger of the present invention to a conductive adhesive or the like when connecting or wiring an electronic component to a wiring board, it is possible to suppress defects caused by corrosion etc. . Examples of the conductive adhesive include those containing a conductive metal such as silver. It is preferable to add 0.:! To 5 parts by weight of the insoluble anion exchanger of the present invention with respect to 100 parts by weight of the resin solid content in the conductive adhesive. An inorganic cation exchanger may be contained here.

[0039] About compounding into varnish

An electrical product, a printed wiring board, an electronic component, or the like can be produced using the varnish containing the inorganic anion exchanger of the present invention. Examples of the varnish include those mainly composed of a thermosetting resin such as an epoxy resin. It is preferable to add from 0.5 to 5 parts by weight of the inorganic anion exchanger of the present invention to 100 parts by weight of the resin solid content. Inorganic cation exchangers may be included here.

[0040] ○ About compounding into paste

The inorganic anion exchanger of the present invention can be added to a paste containing silver powder or the like. Paste is used to improve the adhesion between connecting metals as an auxiliary agent for soldering. As a result, the generation of corrosive substances generated from the paste can be suppressed. It is preferable to add 0.:! To 5 parts by weight of the inorganic anion exchanger of the present invention with respect to 100 parts by weight of resin solids in the paste. Inorganic cation exchange here A substitute may be included.

[0041] An example of a preferred embodiment relating to a method for producing an inorganic anion exchanger using an yttrium compound is shown below.

(1) Adjusting the aqueous solution of yttrium nitrate to basic to produce a precipitate, drying the precipitate after heat aging, heating the dried product, or directly drying the precipitate And a method for producing an yttrium compound having anion exchange activity, comprising the step of heating the dried product,

(2) The method includes a step of adjusting the aqueous solution of yttrium nitrate to basic to produce a precipitate, a step of drying the precipitate after heat aging, and a step of heating the dried product. A method for producing an yttrium compound having anion exchange activity,

(3) It has an anion exchange activity characterized by comprising a step of producing a precipitate by adjusting an aqueous solution of yttrium nitrate to basic, a step of directly drying the precipitate, and a step of heating the dried product. Production method of yttrium compound,

(4) Adjusting the aqueous solution of yttrium nitrate to ρΗ7 · 5 ~: 12 to form a precipitate at a water temperature of 1 to 80 ° C, drying the precipitate after heating and aging at 100 to 300 ° C Heating the dried product at 150 to 1,000 ° C, or directly drying the precipitate and heating the dried product at 150 to 1,000 ° C. A method for producing an yttrium compound having an anion exchange activity,

(5) Adjusting the aqueous solution of yttrium nitrate to ρΗ7 · 5 ~: 12 and forming a precipitate at a water temperature of 1 ~ 80 ° C. After the precipitate is heated and aged at 100 ~ 300 ° C Drying at ~ 250 ° C and heating the dried product at 150-1,000 ° C, or drying the precipitate directly at 80-250 ° C, and drying the dried product at 150-: 1, A method for producing an yttrium compound having an anion exchange activity, comprising the step of heating at 000 ° C. The yttrium compound which has the anion exchange activity obtained by the manufacturing method as described in any one of said (1)-(5).

Example

[0042] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition,% is weight% and a part is a weight part. <Example 1>

lOg of yttrium nitrate was dissolved in 100 ml of pure water, and the solution was adjusted to pH 9 with an aqueous ammonia solution while keeping the solution at 25 ° C. Then, after stirring this solution for 1 hour, the precipitate was filtered and washed with pure water.

This precipitate was put into a dryer and heated at 200 ° C. for 24 hours. Thereafter, the mixture was pulverized to obtain an yttrium compound (Compound 1). When this compound 1 was analyzed, Y (OH) (NO

) · It was Η〇.

[0044] Example 2>

Compound 1 synthesized in Example 1 was further heated at 400 ° C. for 4 hours to obtain Compound 2. When this compound was analyzed, it was Y 2 O (NO 2).

[0045] Example 3>

10 g of yttrium nitrate was dissolved in 100 ml of pure water, and the solution was adjusted to pH 9 with an aqueous ammonia solution while keeping the solution at 25 ° C. The solution was stirred for 1 hour, then placed in a polytetrafluoroethylene sealed container and heat-treated at 180 ° C. for 24 hours. Thereafter, the mixture was allowed to cool to room temperature, and the precipitate was filtered and washed with pure water.

This was put into a dryer and heated at 200 ° C. for 24 hours, and further heated at 500 ° C. for 4 hours. Subsequently, it was milled to obtain an yttrium compound (Compound 3). When this compound 3 was analyzed, it was YO.

[Comparative Example 1]

10 g of lanthanum nitrate was dissolved in 100 ml of pure water, and the solution was adjusted to PH9 with an aqueous ammonia solution while maintaining the solution at 25 ° C. After stirring for 1 hour, the precipitate was filtered and washed with pure water.

This precipitate was put into a dryer and heated at 200 ° C. for 24 hours. Thereafter, the mixture was pulverized to obtain a lanthanum compound (Comparative Compound 1). When this comparative compound 1 was analyzed, La (OH

) (NO) · It was 2Η〇.

[0047] <Comparative Example 2>

Comparative compound 1 synthesized in Comparative example 1 was further heated at 400 ° C. for 4 hours to obtain comparative compound 2. When this compound was analyzed, it was La 2 O 3 (NO 3). [0048] <Comparative Example 3>

10 g of lanthanum nitrate was dissolved in 100 ml of pure water, and this solution was adjusted to PH9 with an aqueous ammonia solution while maintaining the solution at 25 ° C. The solution was stirred for 1 hour, then placed in a polytetrafluoroethylene sealed container, and heat-treated at 180 ° C. for 24 hours. Thereafter, the mixture was allowed to cool to room temperature, and the precipitate was filtered and washed with pure water.

This was put into a dryer and heated at 200 ° C. for 24 hours and further at 500 ° C. for 4 hours. Subsequently, the mixture was pulverized to obtain a lanthanum compound (Comparative Compound 3). This comparative compound 3 was analyzed and found to be La 2 O.

twenty three

[0049] <Reference Example 1>

Bismuth trioxide BiO was used as reference compound 1.

twenty three

[0050] Reference Example 2>

Bismuth anion exchanger IXE-500 (manufactured by Toagosei Co., Ltd.) was used as reference compound 2.

[0051] <Ion exchange capacity measurement test>

1. Put Og compound 1 in a 100 ml positive ethylene bottle, add 50 ml of 0.1 M / liter hydrochloric acid, seal tightly and shake at 40 ° C for 24 hours. Then filtered solution using a membrane filter having a pore size 0. 1 _beta m, was measured chlorine ion concentration of the filtrate by ion chromatography grayed Rafi scratch. The anion exchange capacity (meq / g) was measured in comparison with a sample in which the chlorine ion concentration was measured by performing the same operation with no solid content. Table 1 shows the results.

Compounds 2 and 3, Comparative compounds 1 to 3, and Reference compounds 1 and 2 were similarly operated to measure the ion exchange capacity. These results are shown in Table 1.

[0052] [Table 1] … ... ion exchange

(meq / g)

Example _{_{1 Y 2 (OH) 5.}} 1 (N0 3) o.9- H 2 0 2

Example 2 Y ₂ 0 ₂ (N0 ₃ ) ₂ 2.5

Example 3 γ ₂ ο ₃ 3.6

Comparative Example 1 La2 (OH) 4 (NOs) 2 * 2n20 0.2

Comparative Example 2 La2 (OH) 4 (NOs) 2 * 2n20 0.4

Comparison 俩 3 La ₂ O _a 1

Reference 1 Bi ₂ 0 ₃ 3.9

Reference 2 IXE-500 3.9

80 parts cresol novolac type epoxy resin (epoxy equivalent 235), 20 parts brominated phenol novolac type epoxy resin (epoxy equivalent 275), 50 parts phenol novolac resin (molecular weight 700 ~: 1,000), 2 3 parts of triphenylphosphine, 1 part carnauba wax, 1 part carbon black, 370 parts fused silica, and 2 parts Compound 1 are mixed in a hot roll at 80 ° C-90 ° C for 3-5 Kneaded for a minute. Then, it cooled and grind | pulverized and the powdery epoxy resin composition A was obtained. The composition A was sieved with a 100 mesh sieve to prepare a 100 mesh pass sample.

Using this 100 mesh pass sample, it was cured at 170 ° C. to produce a resin kneaded body 1. This resin kneaded body 1 was pulverized to a size of 2 to 3 mm. A chlorine elution test was conducted using the ground sample.

A crushed sample of the resin kneaded body 2 was prepared in the same manner as in the preparation of the resin kneaded body 1 except that the compound 2 was used instead of the compound 1.

[Example 6]

A pulverized sample of resin kneaded body 3 was prepared in the same manner as in the preparation of resin kneaded body 1 except that compound 3 was used instead of compound 1.

[0056] <Comparative Example 4>

The same procedure as in the preparation of the resin kneaded body 1 was conducted except that Comparative Compound 1 was used instead of Compound 1. The crushed sample of comparative resin kneaded body 1 was prepared.

[0057] <Comparative Example 5>

A pulverized sample of comparative resin kneaded body 2 was prepared in the same manner as in preparation of resin kneaded body 1 except that comparative compound 2 was used instead of compound 1.

[0058] Gu Comparative Example 6>

A pulverized sample of comparative resin kneaded body 3 was prepared in the same manner as in preparation of resin kneaded body 1 except that comparative compound 3 was used instead of compound 1.

[0059] Gu Comparative Example 7>

A pulverized sample of comparative resin kneaded body 0 was prepared in the same manner as in the preparation of resin kneaded body 1 except that compound 1 was not used. That is, the comparative resin kneaded product 0 is a product containing Compound 1.

[0060] Gu Reference Example 3>

A ground sample of reference resin kneaded body 1 was prepared in the same manner as in preparation of resin kneaded body 1 except that reference compound 1 was used instead of compound 1.

[0061] <Reference Example 4>

A ground sample of reference resin kneaded body 2 was prepared in the same manner as in preparation of resin kneaded body 1 except that reference compound 2 was used instead of compound 1.

[0062] <Chlorine ion extraction test from resin kneaded body>

Put 5 g of each resin kneaded body, comparative resin kneaded body or reference resin kneaded body prepared above and 50 ml of pure water in a polytetrafluoroethylene pressure vessel, and seal at 125 ° C. Heated for 100 hours. After cooling, the water was taken out and the concentration of chloride ions eluted in the water was measured by ion chromatography. The pH of this water was also measured. These results are shown in Table 2.

[0063] [Table 2] ¾J

矣 ί¾ 体 A ノ; 辰 £ ¾_

pH

(ppm)

Example 4 Resin kneaded body 1 19 4.3

Example 5 Resin kneaded body 2 19 4.3

Example 6 Kneaded resin 3 20 4-3

Comparative Example 4 Comparative sallow kneaded body 1 56 4.3

Comparative Example 5 Comparative resin kneaded body 2 53 4,4

Comparative Example 6 Comparative resin kneaded body 3 50 4.3

Comparative Example 7 Comparative resin kneaded body 0 19 4.3

Reference Example 3 Reference resin kneaded body 1 18 4.3

Reference Example 4 Reference resin kneaded body 2 60 4.2

[0064] <Measurement of hygroscopicity>

Compound 1 produced in Example 1 2. Og was placed in an aluminum container and allowed to stand in a constant temperature and humidity chamber at 35 ° C. and 90% humidity for 24 hours. Then, the weight after 24 hours was measured to determine the rate of increase. The results are shown in Table 3.

Compounds 2 and 3, comparative compounds:! To 3, and reference compounds 1 and 2 were also tested in the same manner. The results are shown in Table 3.

[0065] Measurement of conductivity of the supernatant>

0.5 g of Compound 1 was placed in a 100 ml polypropylene bottle, 50 ml of pure water was added, stoppered and kept at 100 ° C. for 24 hours. The bottle has a small hole.

After 24 hours, the solution was cooled, the solution was filtered through a 0.1 μm membrane filter, and the conductivity of the filtrate was measured. The results are shown in Table 3.

Compounds 2 and 3 and comparative compounds:! To 3 and reference compounds 1 and 2 were also tested in the same manner. The results are shown in Table 3.

[0066] [Table 3] Hygroscopic conductivity J

Cwt%) (jLi S / cm)

Compound 1 4.1 26

Compound 2 2.7 35

Compound 3 0.5 10

Comparative compound 1> 10> 100

Comparative compound 2> 10> 100

Comparative compound 3> 10> 100

Reference compound 4 0.5 8

Reference compound 5 0.5 10

[0067] <Combination with cation exchanger>

Compound 1 synthesized in Example 1 and zirconium arsenate, which is a cation exchanger, were well mixed at a weight ratio of 1: 1 to prepare mixture 1. This mixture 1 was used to measure the ion exchange rate.

Compound 2, Compound 3, Reference Compound 1, and Reference Compound 2 were also operated in the same manner as described above to prepare Mixture 2, Mixture 3, Reference Mixture 4, and Reference Mixture 5. These materials were used to measure the ion exchange rate.

[0068] <Ion exchange rate measurement test>

1. Og mixture 1 was placed in a 100 ml polypropylene bottle, 50 ml of 0.02M aqueous sodium chloride solution was added, sealed, 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. The same procedure was performed using only a sodium chloride aqueous solution, and the chloride ion concentration was measured. The anion exchange rate of mixture 1 was calculated from these measured values and shown in Table 4.

The same procedure was performed for mixture 2, mixture 3, reference mixture 1, and reference mixture 2, and the ion exchange rate was calculated and shown in Table 4. In addition, compound 1, compound 2, compound 3, reference compound 1 and reference compound 2 were similarly operated, and the ion exchange rate was calculated and shown in Table 4.

[0069] [Table 4] ion

Exchange rate

Mixture 1 Compound 1 + Zirconium phosphate 98%

Mixture 2 Compound 2+ Zirconium phosphate 99%

Mixture 3 Compound 3 + Zirconium phosphate 95%

Reference mixture 1 Reference compound 1 + Zirconium oxalate 96%

Reference mixture 2 Reference compound 2 + Zirconium phosphate 99%

Compound _{_{1 Υ 2 (ΟΗ) 5.}} 1 (ΝΟ 3) 0Α · Η 2 Ο 20%

Compound 2 Y ₂ 0 ₂ (N0 ₃ ) ₂ 40%

Compound 3 Υ ₂ Ο ₃ 2%

Reference compound 1 Bi ₂ 0 ₃ 5%

Reference compound 2 IXE- 500 70%

[0070] As is apparent from Tables 1 to 4, the inorganic anion exchanger of the present invention has a low ion solubility and a low hygroscopic property even under high temperature and high humidity with a large ion exchange capacity. In addition, even if added to the encapsulant resin, there is an effect of suppressing elution of chlorine ions. As a result, it is possible to provide a highly reliable sealing material composition in a wide range.

Further, by using a resin composition containing a cation exchanger, a higher ion exchange rate is exhibited.

Industrial applicability

[0071] The inorganic anion exchanger of the present invention is one made of an environment and excellent in anion exchange properties.

In addition, the inorganic anion exchanger of the present invention is an inorganic anion exchanger that does not use a high-mouth talcite or a bismuth compound, which is problematic in terms of hygroscopicity or recycling. Even if the inorganic anion exchanger of the present invention is added to the resin, there is an effect of suppressing the elution of this force of anions. Thus, the inorganic anion exchanger of the present invention can be used for various purposes such as sealing, coating, and insulation of highly reliable electronic parts or electric parts over a wide range. In addition, the inorganic anion exchanger of the present invention can also be used as a resin stabilizer such as bull chloride, an antifungal agent, and the like.

Claims

The scope of the claims

An inorganic anion exchanger represented by the following formula (1).

Y O (OH) (NO) · ηΗ Ο (1)

2 χ y 3 z 2

(In the formula (1), x, y, and z are 0 or a positive number, 2x + y + z = 6, and n is 0 or a positive number.)

A resin composition for encapsulating electronic parts, comprising the inorganic anion exchanger according to claim 1. The resin composition for sealing an electronic component according to claim 2, comprising an inorganic cation exchanger. A resin obtained by curing the resin composition for sealing an electronic component according to claim 2. An electronic component obtained by sealing an element with the resin composition for sealing an electronic component according to claim 2.

[6] A varnish containing the inorganic anion exchanger according to claim 1.

7. The varnish according to claim 6, comprising an inorganic cation exchanger.

[8] A product comprising the varnish according to claim 6 or 7.

[9] An adhesive comprising the inorganic anion exchanger according to claim 1.

10. The adhesive according to claim 9, containing an inorganic cation exchanger.

[11] A product comprising the adhesive according to claim 9 or 10.

[12] A paste containing the inorganic anion exchanger according to claim 1.

13. The paste according to claim 12, comprising an inorganic cation exchanger.

[14] A product comprising the paste according to claim 12 or 13.