WO2006064568A1 - Anion exchanger and resin composition for electronic part sealing utilizing the same - Google Patents

Abstract

An anion exchanger that realizes exhibiting of low moisture absorption and/or excelling in heat resistance, and further excels in anion exchange performance in the vicinity of neutrality; and a resin composition for electronic parts and electrical parts utilizing the same. Further, there are provided an electronic part or electrical part including the resin composition and a product including the same. In particular, there is provided an anion exchanger comprising a specified hydrotalcite sintering product and/or specified hydrotalcite compound having been treated with a metal salt solution and/or metal alkoxide solution. Furthermore, there is provided an anion exchanger comprising a specified hydrotalcite compound sintering product and a bivalent metal oxide having been treated with a metal salt solution and/or metal alkoxide solution.

Description

 Specification

 Anion exchanger and resin composition for sealing electronic parts using the same

 [oooi] The present invention relates to a calcined product of Hyd mouth Talsai H compound having excellent anion exchange properties. In addition, the present invention relates to a resin composition for encapsulating electronic components excellent in reliability using the fired talcite and a cured product of the composition.

 Background art

 [0002] Hyde mouth talcite has anion exchange properties and is already well known to adsorb chloride ions, etc., which are anions. It is used in the field.

 [0003] Many of these hybrid parts are encapsulated with epoxy resin, such as LSIs, ICs, hybrid ICs, transistors, diodes, and thyristors. Such an electronic component sealing material suppresses defects caused by ionic impurities in raw materials or moisture entering from the outside, and has electrical properties such as flame retardancy, high adhesion, crag resistance and high volume resistivity. Various characteristics such as 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 has increased due to the reduction in wiring width, a large amount of flame retardant such as antimony oxide, brominated epoxy resin, and inorganic hydroxide has been added to the epoxy resin. These flame retardant components have further promoted 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. Already, it becomes a problem to meet this demand to improve moisture resistance reliability. For the purpose of capturing impurity ions, particularly halogen ions, it has been proposed to mix hydrotalcites, which are inorganic anion exchangers, with epoxy resins (for example, Patent Document 1, Patent Document 2, and Patent Document). (See 3 etc.)

 Hyde mouth talcite Ihi compound is the following formula

M ²⁺ M ³⁺ (OH—) (A ⁿ —) -mH O

 a b c d 2

(M ²⁺ is a divalent metal, M ³⁺ is a trivalent metal, and A ⁿ — is an n-valent anion, and a, b, c, d, and m are positive numbers. Specifically, Mg Al (OH) C

 4.5 2 13

○ · 3.5H O, Mg Al (OH) CO · 3.5H 0, Mg Al (OH) C

3 2 4.3 2 12.6 3 2 6 2 16 3 2 Magnesium aluminum hydrate talcite represented by the composition formula is common. 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 Hyde mouth talcite compound, anions in the structure are desorbed, and the following formula

Μ ²⁺ Μ ³⁺ 〇

 x y z

(M ²⁺ represents a divalent metal, M ³⁺ represents a trivalent metal, and x, y, and z are positive numbers). Since this hydrated talcite fired product does not contain anions in the compound, it is superior in anion exchange performance as compared with 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, delamination may occur between the inserts such as lead frames and the molding material for sealing, which may cause a knock crack or chip damage.

[0007] Although an anion exchanger generally adsorbs anions well when the surrounding environment is acidic, it is difficult to adsorb anions near neutral or alkaline. Blended into the encapsulant Depending on the additive, the pH of the resin composition may be near neutral, and the effect of the anion exchanger may not be fully demonstrated.

[0008] 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 performance (for example, patent documents). 5). 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.

[0009] It is known that an epoxy resin used in 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 6). .

 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 ion exchange resins and inorganic ion exchangers, and examples of inorganic ion exchangers include antimony bismuth-based and zirconium-based materials (see, for example, Patent Document 7). ). 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). 8).

 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 9). .

 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 10).

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 11). 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.

 [0010] Patent Document 1: JP-A 63-252451

 Patent Document 2:: Kohei No. 64-64243

 Patent Document 3:: Kokai No. 60--40124

 Patent Document 4:: JP-A-60-42418

 Patent Document 5:: Japanese Patent Publication No. 60-23901

 Patent Document 6: Japanese Patent Laid-Open No. 05-140419

 Patent Document 7:: Japanese Patent Laid-Open No. 09-314758

 Patent Document 8:: Japanese Patent Laid-Open No. 10-287830

 Patent Document 9: JP-A-10-330696

 Patent Document 10: JP-A-10-01301 1

 Patent Document 11: Japanese Patent Laid-Open No. 10-007763

 Disclosure of the invention

 Problems to be solved by the invention

[0011] An object of the present invention is to provide an anion exchanger having low hygroscopicity and / or excellent heat resistance and excellent anion exchange near neutrality, and an electron using the same It is providing the resin composition for components and electrical components. Another object of the present invention is to provide electronic parts, electric parts and products using them using the resin composition. Means for solving the problem

[0012] As a result of intensive studies, the present inventors have determined that a fired talcite fired product represented by the following formula (1) and / or a hydrated talcite compound represented by the following formula (2) are used as a metal. The inventors have found that the above problems can be solved by an anion exchanger treated with a salt solution and / or a metal alkoxide solution, and have completed the present invention.

M ²⁺ M ³⁺ 〇 (1)

または Zn²⁺であり、 M³⁺は Al³⁺ 、 Fe³⁺、 Cr³⁺、 Co³⁺、または In³⁺であり、 x、 y、 zは 0. 1以上の正数であり、 2x+ 3y = 2z であり、そして x >yであり、 x/yの値が 9以下である。 M²⁺ M³⁺ (OH ) (A"") -mH O (2) M ^{2+ in} formula (1) is Mg ²⁺ ,

Or Zn ²⁺ , M ³⁺ is Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Co ³⁺ , or In ³⁺ , x, y, z are positive numbers of 0.1 or more, 2x + 3y = 2z and x> y and x / y value is 9 or less. M ²⁺ M ³⁺ (OH) (A "") -mH O (2)

 1-X X 2 d

M ^{2+ in} formula (2) is Mg ²⁺ , Mn Fe Ni Cu or Zn ²⁺ , and M ³⁺ is Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Co ³⁺ , or In ³⁺ , A ⁿ — are OH—, F—, Cl—, Br—, NO—, CO ² —, SO ² —

 3 3 4

, Fe (CN) ³ —, CH COO—, oxalate ion, or n-valent anion of salicylate ion

 6 3

 X is a positive number not less than 0.1 and not more than 0.33, m is 0 or a positive number, and d is XZn.

 The metal of the metal salt solution and metal alkoxide solution described above is at least one selected from the group consisting of silicon, titanium, zirconium, tin, and aluminum, and is characterized by being treated with these. An anion exchanger.

 The present invention is an anion exchanger obtained by further blending a divalent metal oxide with the anion exchanger described above.

 [0013] One aspect of the present invention is an anion exchanger comprising a fired product of a hydrated talcite compound represented by formula (2) and a divalent metal oxide. An anion exchanger obtained by treating the anion exchanger with a metal salt solution and / or a metal alkoxide solution.

M ²⁺ M ³⁺ (OH) (Α ^π —) -mH Ο (2)

 1-X X 2 d 2

M ^{2+ in} formula (2) is Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu \ or Zn ²⁺ , and M ³⁺ is Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Co ³⁺ , or In ³⁺ , A ⁿ — is OH—, F—, Cl—, Br—, NO—, CO ² —, SO ² —

 3 3 4

, Fe (CN) ³ —, CH COO—, oxalate ion, or n-valent anion of salicylate ion

 6 3

 , X is a positive number not less than 0.1 and not more than 0.33, m is 0 or a positive number, and d is X / n.

 The metal of the metal salt solution and metal alkoxide solution described above is at least one selected from the group consisting of silicon, titanium, zirconium, tin, and aluminum, and is characterized by being treated with these. An anion exchanger.

[0014] Another aspect of the present invention is an electronic component sealing resin composition containing the anion exchanger described above, and at this time, an inorganic cation exchanger may be contained.

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

Another aspect of the present invention is that the device is sealed with the resin composition for sealing an electronic component. This is an electronic component.

 Another aspect of the present invention is a varnish, adhesive or paste containing the anion exchanger as described above, 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.

 Brief Description of Drawings

 [0015] [Fig. 1] is a result of thermal mass spectrometric measurement (TG—DTA) of a hydrated talcite compound Mg Al (OH) CO 3 · 5H ○ (MAH1).

 FIG. 2 is an X-ray diffraction pattern of anion exchanger A-2.

 FIG. 3 is an X-ray diffraction pattern of anion exchanger A-4.

 FIG. 4 is an X-ray diffraction pattern of a product (tMAHl) obtained by firing MAH1 at 550 ° C.

 FIG. 5 is an X-ray diffraction pattern of MAH1.

 Explanation of symbols

[0016] The horizontal axis in FIG. C is shown.

 The left vertical axis in Fig. 1 shows the decrease rate.

 The right vertical axis in FIG. 1 shows an arbitrary value in the differential curve b of the heat loss curve a. In FIG. 1, a indicates a heat loss curve, and b is a differential curve of the heat loss curve a.

 The horizontal axis in Fig. 25 is the diffraction angle (2 Θ) in X-ray diffraction.

 The vertical axis in Figure 2-5 is the value of diffraction intensity in X-ray diffraction.

 BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

 The fired talcite hydrate and the talcite compound represented by the following formula (2) are treated with a metal salt solution and / or a metal alkoxide solution. “Treating” means baking after applying a metal salt and Z or metal alkoxide in a wet or dry manner.

M ²⁺ M ³⁺ 〇 (1)

M ^{2+ in} formula (1) is Mg ²⁺ , Mn Fe Co ²⁺ , Ni ²⁺ , Cu or Zn ²⁺ , and M ³⁺ is Al ³⁺ , Fe Cr ³⁺ , Co ³⁺ , or In ³⁺ , x, y, z are positive numbers greater than or equal to 0.1, 2x + 3y = 2z And x> y and the value of x / y is 9 or less.

M ²⁺ M ³⁺ (OH) (A ⁿ —) -mH O (2)

 1-X X 2 d

Ni Cu または Zn²⁺であり、 M³⁺は Al³⁺ 、 Fe³⁺、 Cr³⁺、 Co³⁺、または In³⁺であり、 Aⁿ—は OH―、 F―、 Cl—、 Br―、 NO―、 CO ²—、 SO ²— M ^{2+ in} formula (2) is Mg ²⁺ , Mn Fe

Ni Cu or Zn ²⁺ , M ³⁺ is Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Co ³⁺ , or In ³⁺ , ^An − is OH−, F−, Cl−, Br ―, NO―, CO ² —, SO ² —

 3 3 4

, Fe (CN) ³ —, CH COO—, oxalate ion, or n-valent anion of salicylate ion

 6 3

 X is a positive number not less than 0.1 and not more than 0.33, m is 0 or a positive number, and d is XZn.

 The fired talcite calcite represented by the formula (1) and the hydrated talcite compound represented by Z or the formula (2) are referred to as “hydride talcite compounds”.

[0018] ○ Hyde mouth talcite compounds

 The calcined talcite used in the present invention is represented by the above formula (1).

^Examples of M ^{2+ in} formula (1) include magnesium, manganese, iron, cobalt, nickel, copper, and zinc. Magnesium and zinc are particularly preferable, with magnesium, zinc, nickel, and cobalt being preferred.

Examples of M ^{3+ in the} formula (1) include anoreminium, iron, chromium, cobalt, indium, and the like, and aluminum is particularly preferable where aluminum, iron, and cobalt are preferred.

 The value of x / y in formula (1) is 9 or less, preferably 7 or less, and more preferably 6 or less. The value of x / y is preferably 2 or more, more preferably 2.1 or more, and particularly preferably 2.2 or more.

 [0019] The fired hydrotalcite used in the present invention can be obtained by firing the hydrotalcite compound represented by the above formula (2). The hide mouth talcite compound used in the present invention is not particularly limited as long as it is represented by the formula (2).

Examples of M ^{2+ in the} formula (2) include magnesium, manganese, iron, cobalt, nickel, copper, zinc, and the like, and magnesium and zinc are particularly preferable, with magnesium, zinc, Nikkenore, and cobalt being preferred.

Examples of M ^{3+ in the} formula (2) include ano-reminium, iron, chromium, cobalt, indium, etc., and aluminum is particularly preferred where ano-remineum, iron, and cobalt are preferred. [0020] X in the formula (2) is 0.1 or more and 0.33 or less, X is preferably 0.15 or more, 0.13 or more is more preferable, and 0.16 or more is more preferable. Yes, particularly preferably 0.2 or more, preferably 0.32 or less, more preferably 0.31 or less.

[0021] In Formula (2), Α ^η — is: Η Η-, F-, Cl-, Br-, NO-, CO ² —, SO ² —, Fe (CN) ³ —, CH

It is preferably an n-valent anion such as COO—, oxalate ion, or salicylate ion, which is calcined and removed from here. Specifically, A ⁿ — in formula (2) is OH, NO—, CO ² —,

CH COO, oxalate ion, or salicylate ion is preferred, more preferably ○ H—

, NO-, or C_〇 ^2, particularly preferably C_〇 ^2.

 [0022] The temperature at which the hydrated talcite compound represented by the formula (2) is calcined is not particularly limited, but is a temperature at which anions in the hydrated talcite compound can be removed. The firing temperature differs depending on the X value of the force equation (2), which is 240 1000 ° C, for example.

 The firing time may be set to an optimum time depending on the type of hydrated talcite, the firing temperature and the amount of firing. For example, the firing time is preferably 24 hours or less, more preferably 15 hours or less, and further preferably 10 hours or less, preferably 0.5 hours or more.

 [0023] When X in formula (2) is 0.29 or more, the calcined product calcined at 240 ° C or higher and lower than 700 ° C has poor anion exchange performance near neutrality. It is necessary to mix and use it. The firing temperature of the fired product is preferably 330 ° C or higher, more preferably 400 ° C or higher, still more preferably 430 ° C or higher, and particularly preferably 500 ° C or higher. If the calcination temperature is low, the anion cannot be removed from the hydrated talcite compound, and therefore the ion exchange performance may be lowered, which is not preferable.

 [0024] When X in the formula (2) is 0.29 or more, a fired product fired at 700 ° C or more and 1000 ° C or less may form a divalent metal oxide. In this case, the fired product does not need to contain a divalent metal oxide. It is more preferable that the fired product is blended with a divalent metal oxide having good anion exchange performance near neutrality. The firing temperature of the fired product is more preferably 900 ° C. or less, and further preferably 850 ° C. or less. If the firing temperature is too high, the anion exchanger may be decomposed and the amount of ion exchange may be reduced, which is not preferable.

[0025] In the formula (2) where X is less than 0.29, firing is performed at 240 ° C or higher and 1000 ° C or lower Products may produce divalent metal oxides. In this case, the fired product does not need to contain a divalent metal oxide. It is more preferable that the fired product is blended with a divalent metal oxide having good anion exchange performance near neutrality. If the value of X is too small, the anion exchange performance near neutrality may deteriorate. The firing temperature of the fired product is 330-1000 ° C force S, preferably 400-950, more preferably 430-950 ° C, and further preferably 500 ° C-900 ° C. Les. Since the firing temperature is low and the anion cannot be removed from the hydrated talcite compound, the ion exchange property of the ion exchanger may be lowered. On the other hand, if the calcination temperature is too high, decomposition of the ion exchanger occurs and the amount of ion exchange may decrease, which is not preferable.

[0026] Whether or not the divalent metal oxide is formed in the fired product of the hydrated talcite beech compound can be examined using X-ray diffraction.

Specifically, for example, when M ²⁺ is Mg ²⁺ , by measuring the force, first X-ray diffraction, and comparison with the diffraction angle (2 Θ) of the fired product, It is possible to confirm the formation of MgO.

 [0027] In a product obtained by merely firing a hydrated talcite compound represented by formula (2), the chlorine exchange rate is preferably more than 70%, more preferably 80% or more, More preferably, it is 90% or more.

 The chlorine ion exchange rate is calculated from the amount of chlorine ions when lg of calcified talcite compound expressed by formula (2) is treated with 50 ml of 0.02 molar sodium chloride aqueous solution. It is calculated.

 [0028] The hygroscopicity of the anion exchanger or anion exchange composition of the present invention is preferably that the rate of weight increase after standing for 24 hours at 35 ° C and 90% relative humidity is 50% or less. Preferably it is 40% or less, more preferably 20% or less.

In the anion exchanger of the present invention, when the chloride ion exchange rate and the hygroscopic property are combined, when the weight increase rate is greater than 40% and less than 50%, the chloride ion exchange rate force is 0% or more. More preferably 90% or more is preferable. When the weight increase rate is 40 or less, the chloride ion exchange rate is preferably 65% or more, more preferably 70% or more, and further preferably 80. / ο or more, particularly preferably 90% or more. [0029] Hyde mouth talcite compounds include Mg Al (OH) C 0 .3. 5H 0, Zn Al (OH

 4.5 2 13 3 2 4.5 2

) CO * 3.5H O, Ni Al (OH) C ○ * 3.5H ○, Mg Fe (OH) CO-3.5H O

13 3 2 4.5 2 13 3 2 4.5 2 13 3 2

, Mg Al (OH) CO-3.5H 0, Mg Al (OH) CO -4H ○ or magnesium and Al

5 1.5 13 3 2 6 2 16 3 2

 For example, those synthesized with a molar ratio of 2.5: 1, 2.75: 1, 4: 1, 5: 1, etc. These calcined products include Mg Al O, Zn Al ○, Ni Al ○, Mg

 0.7 0.3 1.15 0.7 0.3 1.15 0.7 0.3 1.15

Fe O, Mg Al O, Mg Al 〇, Mg AIO, Mg AIO, Mg Al

0.7 0.3 1.15 0.8 0.24 1.16 0.9 0.3 1.35 2.5 4 2.75 4.25 0.8

〇, Mg AIO, Mg AIO, Mg AIO, Mg AIO, Mg AIO etc.

0.24 1.16 1.2 2.7 1.5 3.0 3 4.5 4 5.5 5 6.5

 [0030] Metal salt solution and metal alkoxide solution

 As the metal of the metal salt solution and metal alkoxide solution for treating the hydrated talcite compound, silicon, titanium, zirconium, tin, and aluminum are preferred, and titanium, titanium, dinoleconium, and aluminum are more preferred. Magma and titanium are particularly preferred.

 The method for treating the hydrated talcite compound with a metal salt solution and / or a metal alkoxide solution is not particularly limited. For example, there are the following processing methods.

 • A method in which a hydrated talcite compound is dispersed in a metal salt solution, filtered, washed, dried and calcined.

 • Disperse the hydrated talcite compound in a metal salt solution, add an alkaline substance such as sodium hydroxide or ammonia water, and deposit a metal oxide or metal hydroxide on the surface of the hydrated talcite compound. And then filtering, washing, drying and firing.

 • Disperse the hydrated talcite compound in a metal salt solution, add an amine compound such as urea or hexamethylenetetramine, and heat to form a metal oxide or metal hydroxide on the surface of the hydrated talcite compound. A method of precipitating and then filtering, washing, drying and firing.

• Disperse the hydrated talcite compound in the metal alkoxide solution, hydrolyze the metal alkoxide by adding acid, alkali, or water, or heating to oxidize the metal on the surface of the hydrated talcite compound. A method of depositing a product or metal hydroxide, followed by filtration, washing, drying and firing. • Add a metal alkoxide or metal alkoxide solution to a hydrated talcite compound, mix, heat, and coat the surface of the hydrated talcite compound with a metal oxide or metal hydroxide, then dry and fire how to.

 It is preferable to treat a hydrated talcite compound with a metal salt solution and z or a metal alkoxide solution because an anion exchanger with low hygroscopicity can be obtained.

[0031] In order to use the anion exchanger of the present invention in a resin composition for encapsulating electronic parts, it is preferable that ionic impurities are not contained as much as possible. When treating hydrated talcite compounds with a metal salt solution, the salt must be thoroughly washed away. On the other hand, treatment with a metal alkoxide solution is preferable to a metal salt solution because there is no or a small amount of by-product salt.

 [0032] The metal of the metal salt solution is as described above, and the metal salt solution may be an aqueous solution or a sol solution. Examples of the metal salt include alkali metal salts, halides, and oxides of silicon, titanium, dinoleconium, tin, or aluminum oxoacid. The alkali metal salt is preferably a sodium salt or potassium salt, and the halide is preferably chlorinated or brominated.

 [0033] The metal of the metal alkoxide is as described above. Examples of the metal alkoxide solution include an aqueous solution, a hydrous alcohol solution, and an alcohol solution, and a hydrous alcohol solution or an alcohol solution is preferable.

 Specific examples of the metal alkoxide include tetraethoxysilane, tetramethoxysilane, titanium tetraisopropoxide, aluminum triethoxide, zirconium tetraisopropoxide, tetraethoxytin, tetramethoxytin, and polymers thereof (for example, methyl silicate oligomer). , Ethyl silicate oligomers, propyl silicate oligomers, etc.), and tetraethoxysilane, tetramethoxysilane, and polymers thereof are preferable because they are not so fast to handle. More preferred are a polymer of tetraethoxysilane and a polymer of tetramethoxysilane.

[0034] The calcining temperature of a hydrated talcite fired product represented by the formula (1) mixed with a metal salt solution and / or a metal alkoxide solution is 50-1000. C force S preferred, 100-900. C The force is preferably 200-800 ° C force S, more preferably 400-700 ° C.

 The calcining temperature of a mixture of a hydrated talcite compound represented by formula (2) with a metal salt solution and / or a metal alkoxide solution is preferably 400-1000 ° C force S, more preferably 500-900 ° C. A particularly preferred value is 500 700 ° C.

[0035] A compound containing a hydrated talcite compound and a divalent metal oxide may be treated with a metal salt solution and / or a metal alkoxide solution. The processing conditions at this time are the same as above.

 The treatment with the metal salt solution and Z or the metal alkoxide solution is preferably performed before mixing the divalent metal oxide from the viewpoint of anion exchange performance near neutrality.

[0036] Treatment ratio of metal salt solution or metal alkoxide solution

 The treatment ratio of the metal salt solution and / or metal alkoxide solution with respect to the hydracic talcite compound is not particularly limited, but a preferred ratio is that when the hydracic talcite compound is 100 parts by weight, the metal salt solution and / or metal The metal oxide in the alkoxide solution (metal salt solution or metal alkoxide solution converted to oxide) is preferably 3 to 100 parts by weight, particularly preferably 5 to 50 parts by weight. If the metal oxide strength is less than 3 parts by weight, the hygroscopicity may not be suppressed, and if it is more than 100 parts by weight, the ion exchange capacity may be small.

[0037] 〇 Divalent metal oxide

Fe²⁺、 Co²⁺、 CuThe divalent metal oxide used in the present invention is preferably Mg ²⁺ ,

Fe ²⁺ , Co ²⁺ , Cu

Bivalent metals such as Zn ²⁺ . More preferably, it is an oxide of the same metal as the divalent metal in the hydrated talcite compound.

[0038] The particle size of the divalent metal oxide is not particularly limited, but the average particle size is preferably 0.01 am or more and 10 zm or less, more preferably 0.05 zm or more. When the particle size is 0.01 x m or less, aggregation tends to occur, and when the particle size is 10 μm or more, physical properties may be impaired when added to a resin.

[0039] 〇 Divalent metal oxide content

The blending ratio of the hydrated talcite compound and the divalent metal oxide is not particularly limited. When 100 parts by weight of the hydrated talcite compound is treated with a metal salt solution and / or a metal alkoxide solution, the divalent metal oxide is preferably 10 to 500 parts by weight, more preferably 20 to 200 parts. Parts by weight, more preferably 40-100 parts by weight. When the amount of the divalent metal oxide is less than 10 parts by weight, the ion exchange property may not be improved.

[0040] When X in formula (2) is 0.29 or more and the calcined product baked at 240 ° C or more and less than 700 ° C is 100 parts by weight, the divalent metal oxide is preferably 10 1000 parts by weight. Parts, more preferably 20 300 parts by weight, still more preferably 40 200 parts by weight. If the divalent metal oxide is less than 10 parts by weight with respect to the fired product, the ion exchange property may not be improved, and if it is more than 1000 parts by weight, the ion exchange capacity may be reduced.

[0041] When X in formula (2) is 0.29 or more and the anion exchange performance near neutral is not good in the fired product fired at 700 ° C or higher and 1000 ° C or lower, Include oxide. At this time, the divalent metal oxide is preferably 10 to 500 parts by weight, more preferably 20 to 200 parts by weight, and still more preferably 40 to 100 parts by weight with respect to 100 parts by weight of the fired product. It is. If the divalent metal oxide is less than 10 parts by weight with respect to the fired product, the ion exchange performance may not be improved, and if it is more than 500 parts by weight, the ion exchange capacity may be reduced, which is not preferable.

 [0042] When X in formula (2) is less than 0.29 and the anion exchange performance in the vicinity of neutrality is not good in a calcined product calcined at 240 ° C or higher and 1000 ° C or lower, a divalent metal Include oxide. In this case, 10 to 500 parts by weight of divalent metal oxide is preferably used per 100 parts by weight of the fired product, more preferably 20 to 200 parts by weight, and further preferably 40 to 100 parts by weight. Part. If the divalent metal oxide is less than 10 parts by weight with respect to the fired product, the ion exchange performance may not be improved, and if it is more than 500 parts by weight, the ion exchange capacity may be reduced, which is not preferable.

 [0043] 〇 Resin composition for sealing electronic parts

Examples of the resin used in the resin composition for encapsulating electronic components containing the anion exchanger of the present invention include phenol resin, urea resin, melanin resin, unsaturated polyester resin, It may be a thermosetting resin such as an epoxy resin or a thermoplastic resin such as polyethylene, polystyrene, vinyl chloride, or polypropylene, and is preferably a thermosetting resin. 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.

 [0044] 〇 Epoxy resin composition for sealing electronic parts

 The epoxy resin used in the present invention can be used without limitation as long as it is used in 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 of 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 chloride ion content of 1 Oppm or less and a hydrolyzable chlorine content of 1 OOOppm or less.

 [0045] 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. Etc.

[0046] The resin composition for encapsulating electronic components 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, coupling agents for inorganic fillers, colorants, and release agents. All of these components are known as components to be blended with molding epoxy resins. Preferable specific examples of the organic filler include crystalline silica powder, quartz glass powder, fused silica powder, anoremina powder, and talc. Among them, crystalline silica powder, quartz glass powder, and fused silica powder are inexpensive. preferable. Examples of flame retardants include antimony oxide, halogenated epoxy resin, magnesium hydroxide, aluminum hydroxide, red phosphorus compound, phosphate ester Examples of coupling agents include silanes and titanium. Examples of mold release agents include waxes such as aliphatic paraffins and higher aliphatic alcohols.

[0047] 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.

 [0048] A preferred blending ratio of the anion exchanger of the present invention is 0.110 parts by weight, more preferably 115 parts by weight per 100 parts by weight of the resin composition for sealing an electronic component. If it is less than 1 part by weight, the effect of enhancing the anion removability and moisture resistance reliability is small. On the other hand, if it exceeds 10 parts by weight, the effect is not further improved, and the cost is increased.

 [0049] By using an inorganic cation exchanger together with the anion exchanger of the present invention, the anion trapping capacity of the anion exchanger of the present invention is increased, and a cationic ion scavenging effect is expected. be able to. The inorganic cation exchanger is an inorganic substance and has a cation exchange property.

 The blending ratio of the anion exchanger to the inorganic cation exchanger of the present invention is not particularly limited, but is preferably 100: 0-20: 80 by weight. The anion exchanger and the inorganic cation exchanger of the present invention may be blended separately when preparing the resin composition for encapsulating electronic components, and they should be 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.

 [0050] Specific examples of inorganic cation exchangers include antimonic acid (antimony pentoxide hydrate), diobic acid (niobium pentoxide hydrate), manganese oxide, zirconium phosphate, titanium phosphate, phosphorus Examples thereof include tin oxide, cerium phosphate, zeolite, and clay minerals, and antimonic acid (antimony pentoxide hydrate), zirconium phosphate, and titanium phosphate are preferable.

[0051] 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.

 [0052] The anion exchanger of the present invention can be used in various applications such as sealing, coating, and insulation of electronic components or electrical components.

 Furthermore, the anion exchanger of the present invention can be used as a stabilizer for a resin such as vinyl chloride, an antifungal agent, and the like.

 [0053] The resin composition for electronic components containing the anion exchanger of the present invention has a semiconductor chip and a transistor on a support member such as a lead frame, a wired tape carrier, a wiring board, glass or a silicon wafer. It can be used for devices equipped with active elements such as diodes and thyristors, and passive elements such as capacitors, resistors, and coils. Moreover, 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 anion exchanger of the present invention can also 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.

 [0054] ○ 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 adhered to the printed wiring board, and a circuit is produced by etching or the like 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 anion exchanger of the present invention when producing a wiring board. Moreover, corrosion of the wiring board can be prevented by adding the anion exchanger of the present invention to the insulating layer for the wiring board. For this reason, the wiring board containing the 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 15 parts by weight of the anion exchanger of the present invention 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.

[0055] 〇 About blending into adhesive Electronic components and the like are mounted on a substrate such as a wiring board using an adhesive. By adding the anion exchanger of the present invention to the adhesive used at this time, it is possible to suppress the occurrence of defective products due to corrosion or the like. It is preferable to add 0.1 to 15 parts by weight of the anion exchanger of the present invention to 100 parts by weight of the resin solid content in the adhesive. An inorganic cation exchanger may be contained here.

 By adding the anion exchanger of the present invention to a conductive adhesive or the like when connecting or wiring an electronic component or the like to a wiring board, defects caused by corrosion or the like can be suppressed. Examples of the conductive adhesive include those containing a conductive metal such as silver. It is preferable to add 0.1 to 5 parts by weight of the 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 therein.

 [0056] 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 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 0.1 to 5 parts by weight of the anion exchanger of the present invention to 100 parts by weight of the resin solid content. You can also add an inorganic cation exchanger here.

 [0057] About compounding into paste

 The 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 such as soldering. This can suppress the generation of corrosive substances generated from the paste. It is preferable to add 0.1-5 parts by weight of the anion exchanger of the present invention with respect to 100 parts by weight of the resin solid content in the paste. An inorganic cation exchanger may be contained therein.

 [0058] Examples>

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications may be made within a range that can meet the purpose described before and after. In addition, it is also possible to implement, and they are all included in the technical scope of the present invention. In addition, 0.1M M indicates molar concentration,% indicates% by weight, and part indicates part by weight. [0059] <Synthesis Example 1>

 Hyde mouth talcite compound whose composition formula is represented by Mg Al (OH) CO · 3 · 5H〇 (

 4.5 2 13 3 2

 MAH1) is calcined at 550 ° C for 2 hours, and the hydride represented by the composition of MgAlO

 0.7 0.3 1.15

 A mouth talcite fired product (referred to as tMAHl) was obtained.

[0060] ○ Firing test

 The mass change due to heating of MAH1 was measured (thermal mass spectrometry measurement 'TG-DTA, measurement temperature range 30-530 ° C, temperature increase rate 20 ° C / min, measured in air). Figure 1 shows the results.

 From Fig. 1, it can be seen that the firing effect cannot be obtained even if the hydrated talcite compound is fired at a temperature lower than 240 ° C.

[0061] <Synthesis Example 2>

 Hyde mouth talcite compound (NA) represented by the composition formula: Ni Al (OH) CO · 3 · 5H〇

 4.5 2 13 3 2

 H) is fired at 550 ° C for 2 hours, and the hydrotanol represented by the composition of Ni Al 2 O 3

 0.7 0.3 1.15

 A site fired product (referred to as tNAH) was obtained.

[0062] <Synthesis Example 3>

 Hyde mouth talcite compound (ZA) represented by the composition formula Zn Al (OH) CO · 3 · 5H〇

 4.5 2 13 3 2

 Hide) is baked at 550 ° C for 2 hours and is expressed in the composition of Zn Al 2 O 3

 0.7 0.3 1.15

 A site fired product (referred to as tZAH) was obtained.

 Example 1

 [0063] 100 g of tMAHl was added to 2000 ml of a 0.1 M sodium metasilicate aqueous solution, stirred at 90 ° C for 4 hours, filtered and washed with water. This was dried and then calcined at 550 ° C. for 2 hours to obtain an anion exchanger (anion exchanger 1).

 Example 2

 [0064] 100 g of tMAHl was added to 160 g of a 10% titanium tetraisopropoxide isopropanol solution.

 Added in. To this solution, 10 ml of water was added, stirred overnight, filtered and washed with water. This was air-dried for 3 days and then calcined at 550 ° C for 2 hours to obtain an anion exchanger (anion exchanger 2

) Example 3

 [0065] lOOg of tMAHl was added to 160 g of a 10% solution of tetramethoxysilane in methanol, stirred overnight, air-dried for 1 day, and then calcined at 550 ° C for 2 hours for anion exchanger (anion exchanger). 3) was obtained.

 Example 4

 [0066] While stirring lOOg of tMAHl with a mixer, 16 g of tetramethoxysilane was added. After further stirring, the anion exchanger (anion exchanger 4) was obtained by air-drying for 1 day and baking at 550 ° C for 2 hours.

 Example 5

 [0067] lOOg of tNAH was added to 2000 ml of 0.1M-oxyzirconium chloride aqueous solution and adjusted to pH 8 with 0.1M-ammonia aqueous solution. This solution was stirred overnight, filtered and washed with water. This was dried and then calcined at 550 ° C. for 2 hours to obtain an anion exchanger (anion exchanger 5).

 Example 6

 [0068] lOOg of tZAH was added to 160 g of a 10% ethanol solution of tetraethoxysilane, stirred overnight, air-dried for 1 day, and then calcined at 550 ° C for 2 hours for anion exchanger (anion exchanger). 6) was obtained.

 Example 7

 [0069] lOOg of MAH1 was added to 2000 ml of a 0.1 M sodium metasilicate aqueous solution, stirred at 90 ° C for 4 hours, filtered and washed with water. This was dried and then calcined at 550 ° C. for 2 hours to obtain an anion exchanger (anion exchanger 7).

 Example 8

 [0070] lOOg of MAH1 was added to 160 g of a 10% titanium isopropoxide isopropanol solution. To this solution, 10 ml of water was added, stirred overnight, filtered and washed with water. This was air-dried for 3 days and then calcined at 550 ° C. for 2 hours to obtain an anion exchanger (anion exchanger 8).

Example 9 [0071] While stirring lOOg of ZAH with a mixer, 16 g of tetramethoxysilane was added. After further stirring, the anion exchanger (anion exchanger 9) was obtained by air-drying for 1 day and baking at 550 ° C for 2 hours.

 [0072] Measurement of hygroscopicity and chloride ion exchange

 The anion exchanger shown in Table 1 below was heated at 150 ° C. for 4 hours, then left in the atmosphere, and the hygroscopicity was examined by measuring the weight over time.

 The anion exchanger described in Table 1 below was added in an amount of lg to 50 ml of 0.1M hydrochloric acid, and the mixture was stirred at 40 ° C for 24 hours. Thereafter, filtration was performed, and the chloride ion concentration in the filtrate was determined by measuring the chloride ion concentration in the filtrate by ion chromatography. These results are shown in Table 1.

 [0073] [Table 1]

 [0074] As can be seen from Table 1, the anion exchanger of the present invention has a lower hygroscopicity and lower anion than Hyde Mouth Talcite Compound, although the amount of dry anion exchange is lower than that of the calcined Hyde Mouth Talsite. It can be seen that the anion exchanger has excellent exchange performance and is excellent for use in an epoxy resin composition for electronic component sealing.

 Example 10

[0075] 80 parts of cresol novolac type epoxy resin (epoxy equivalent 235), 20 parts of brominated phenol novolac type epoxy resin (epoxy equivalent 275), 50 parts of phenol novolac resin (molecular weight 700-1000), triphenylphosphine 2 parts, 1 part carbana wax, 1 part of carbon black, 370 parts of fused silica and 5 parts of anion exchanger 2 were blended, kneaded in a hot roll at 80 ° C-90 ° C for 3-5 minutes, cooled, and pulverized Thus, a powdery epoxy resin composition was obtained. These were treated with a 100-mesh sieve, and the moisture resistance reliability evaluation element to which the aluminum wiring was connected was sealed using a sample at the passage part at a molding condition of 170 ° C for 3 minutes.

 The sealed device was subjected to a pressure tacker test at 125 ° C., and the time at which disconnection occurred was measured. This test was conducted with 50 samples and the average value was obtained. The sealed element was heat-treated in an IR reflow furnace with a maximum temperature of 245 ° C and the appearance was observed. These results are shown in Table 2.

 Example 11

 An evaluation sample was prepared in the same manner except that the anion exchanger 3 was used instead of the anion exchanger 2 of Example 10. The same evaluation was made and the results are shown in Table 2.

 Example 12

 An evaluation sample was prepared in the same manner except that the anion exchanger 4 was used instead of the anion exchanger 2 of Example 10. The same evaluation was made and the results are shown in Table 2.

 Example 13

 An evaluation sample was prepared in the same manner except that the anion exchanger 5 was used instead of the anion exchanger 2 of Example 10. The same evaluation was made and the results are shown in Table 2.

 Example 14

 An evaluation sample was prepared in the same manner except that the anion exchanger 6 was used instead of the anion exchanger 2 of Example 10. The same evaluation was made and the results are shown in Table 2.

 Example 15

[0080] Anion exchanger 4 and inorganic cation exchanger instead of anion exchanger 2 of Example 10 An evaluation sample was prepared in the same manner except that antimonic acid was used (weight ratio was 5: 5). And it evaluated similarly and the result was described in Table 2.

 Example 16

 [0081] Instead of the anion exchanger 2 of Example 10, an anion exchanger 5 and an inorganic cation exchanger zirconium phosphate were used (weight ratio was 7: 3). An evaluation sample was prepared. And it evaluated similarly and the result was described in Table 2.

[0082] <Comparative Example 1>

 An evaluation sample was prepared in the same manner except that MAH 1 was used instead of the anion exchanger 2 of Example 10. And it evaluated similarly and the result was described in Table 2.

[0083] <Comparative Example 2>

 An evaluation sample was prepared in the same manner except that tMAHl was used instead of the anion exchanger 2 of Example 10. And it evaluated similarly and the result was described in Table 2.

[0084] <Comparative Example 3>

 An evaluation sample was prepared in the same manner as in Example 10 except that the anion exchanger 2 was not used. And it evaluated similarly and the result was described in Table 2.

[0085] [Table 2]

 Example 17

As epoxy resin, bisphenol A type epoxy resin (Asahi Ciba Co., Ltd., trade name: raldite AER-2502) 60 parts, reactive diluent 30 parts butyl phenyl daricidyl ether, epoxy as curing agent 'Amin addition reaction product (epoxy' amine adduct) (Asahi Kasei Kogyo Co., Ltd., trade name: Novaki Yua HX-3721)) 20 parts, with thixotropic agent 1 part of organic modified bentonite, 30 parts of talc as inorganic filler, 8 parts of synthetic zeolite, 0.5 part of red pigment, and 3 parts of anion exchanger 9 are mixed in the resin using three rolls. Solid particles were uniformly dispersed in to obtain a surface-mount adhesive composition. The composition thus prepared was evaluated for each item of insulation reliability, spinnability, application shape, adhesiveness, and gel time, and the results are shown in Table 3.

[0087] Comparative Example 4>

 A surface mounting adhesive composition described in Example 17 was prepared in the same manner without adding the anion exchanger 9. The evaluation was conducted in the same manner as in Example 17, and the results are shown in Table 3.

 [0088] 〇 Insulation reliability

 About the hardened | cured material of the adhesive composition for surface mounting prepared in Example 17 and Comparative Example 4, the surface insulation resistance value was measured according to JIS_Z_3197.

 That is, the composition was applied onto a type II comb substrate by screen printing so as to have a film thickness of 100-150 / im, and cured by heating at 150 ° C. for 10 minutes. Using a minute current measuring instrument, the insulation resistance value of the obtained untreated substrate was measured (A value). Subsequently, the substrate was boiled in water for 2 hours, then left in an environment of 25 ° C and 60% RH for about 1 hour, and the insulation resistance value was measured again (B value). This evaluation is

A / B≤10 ² to `` 〇 '',

10 ² <A / B≤10 ³ is `` △ '',

10 ³ <8/8

 It was. The results are shown in Table 3.

[0089] 〇 Thread properties

 Using a dispenser on a glass epoxy board (FR-4) printed and cured with a solder resist on the entire surface, the adhesive composition prepared in Example 17 and Comparative Example 4 is 0.15 mg per point, coating speed. A coating test of 1000 points at 50 msec per point was performed, and the soiling power of the substrate due to the spinnability was evaluated as “X” for the S1 location, and “○” for the 1 location. .

[0090] 〇 Application shape

The shape of the adhesive composition applied in the evaluation of the spinnability is a conical shape. The diameter D of the bottom of the cone and the height H of the cone were observed and measured with a microscope. The ratio of height to diameter H / D is

 0.5.

 A value in the range 0.5-5.

 1. Five or more items are “△”

 It was.

[0091] 〇 Adhesiveness

 Similar to the evaluation of spinnability, a 2125 resistor chip was adhered to a glass epoxy substrate printed and cured with a solder resist on the surface, and the force required to peel off one chip was measured with a push-pull gauge. That is, the adhesive composition prepared in Example 17 and Comparative Example 4 was applied by applying 0.3 mg per chip and cured by heating in an oven at 150 ° C. for 3 minutes.

[0092] 〇 Gel time

 The time (seconds) until the adhesive composition prepared in Example 17 and Comparative Example 4 of 0.3 ± 0.05 g on a hot plate at 150 ° C was heated and the fluidized state disappeared to reach gelling. ) Was measured.

[0093] [Table 3]

 Example 18

[0094] A liquid crystal sealing material was prepared by the following composition and process. Bisphenol A as epoxy resin Type epoxy resin (Asahi Chiba Co., Ltd., trade name: Araldite AER-2502) 100 parts, Epoxy amine adduct as a curing agent (Asahi Kasei Kogyo Co., Ltd., trade name: Novaki Yua HX-3721), filler Titanium oxide (Ishihara Sangyo Co., Ltd., trade name: Typeta R_630) 60 parts, Colloidal silica (Nippon Aerosil Co., Ltd., trade name: Aerosil R—974) 5 parts

Then, 1 part of antimonic acid, which is an inorganic cation exchanger, 2 parts of anion exchanger 6 was heated to 40 ° C. with a danoleton mixer and stirred for 30 minutes to mix. Then, milling with three rolls was performed 5 times, and the particle size of the contents was confirmed to be 5 μm or less by a grind gauge, and a silica spacer with a particle size of 5 μm was added. Partly added and dispersed uniformly to obtain a composition as a liquid crystal sealant.

 The liquid crystal sealing material obtained here was printed on the seal portion by screen printing leaving a liquid crystal sealing port on a glass substrate on which ITO (transparent electrode) was formed. Next, it was heated to 80 ° C. and held for 3 minutes, pre-dried and fused to the substrate, and then returned to room temperature. Next, the glass substrates on the counter electrode side were combined and pressed for 10 minutes with a hot press heated to 130 ° C to cure the sealing material. After vacuum-suctioning the empty panel obtained here, liquid crystal (Merck Co., Ltd., ZL11636) was injected, the sealing port was sealed with a sealing material, and cured to obtain a liquid crystal panel.

 This liquid crystal panel was evaluated for liquid crystal orientation and memory properties (the ratio that the transmitted light intensity can be maintained over time with respect to the intensity immediately after the application of the pulse voltage decreases with the presence of impurities). The liquid crystal orientation was evaluated by heating the liquid crystal panel to 80 ° C. without applying a voltage and visually observing the width of the black band generated in the vicinity of the sealing material when viewed through the polarizing plate. The case where the width was 0.5 mm or less was designated as “◯”, 0.5—lmm was designated as “△”, and the width exceeding 1 mm was designated as “X”. The results are shown in Table 4.

[0095] Gu Comparative Example 5>

 A liquid crystal sealing material composition was prepared in the same manner without adding antimonic acid and anion exchanger 6 to the composition of Example 18. Evaluation was conducted in the same manner as in Example 18, and the results are shown in Table 4.

[0096] [Table 4] Epoxy resin composition Example 1 8 Comparative Example 5

 Bisph I Nord A Type Epoxy Resin 1 00 1 00

 Epoxy 'amine duct body 40 40

 Titanium oxide 60 60 Colloidal silica 5 5

 Antimonic acid 1 ―

 Anion exchanger 6 2 ―

 Liquid crystal orientation ○ X Memory property (%) 95 42 Example 19

[0097] 5 parts of the anion exchanger 9 are added to 100 parts of a bisphenol A-type epoxy resin having an epoxy equivalent of 450-500 (product name: Araldite AER-2502, manufactured by Asahi Ciba Co., Ltd.). An impregnating resin varnish was prepared by mixing 4 parts of dicyandiamide as an epoxy curing agent, 0.4 part of benzyldimethylamine as a curing accelerator, and 60 parts of a solvent (methylethyl ketone) and mixing them. Next, a 0.2 mm thick low alkali electrical glass cloth was impregnated with the previously prepared resin varnish. Thereafter, drying was performed at 160 ° C. for 5 minutes to prepare a pre-preda. Cut the Puripureda the dimensions of 50 mm X 50 mm, superposing six, initial conditions ^{30kgZcm 2, 1 60 ° C,} 15 min, and then used ^{70kg / cm 2, 165 ° C} , for 1 hour heating press, A laminate having a volume ratio of 50:50 between the resin and the glass cloth substrate and a thickness of about 1.6 mm was obtained.

Silver paste (Dotite XA208 manufactured by Fujikura Kasei Co., Ltd.) is applied to the laminated board by screen printing, and cured by heating at 130 ° C for 1 hour, so that two opposed comb-shaped printed wiring conductors (electrodes) Formed. The shortest distance between the electrodes is lmm, the deviation is lmm, and the thickness is about 20 xm. In order to evaluate the effect of preventing the occurrence of the electret migration phenomenon, a DC voltage of 100 V was applied between the two comb electrodes, and the insulation resistance value between the electrodes was kept at 40 ° C and 95% RH. ^The time when it became ⁶ Ω or less was measured as the time to reach the short circuit.

 As a result, the time to reach the short circuit was more than 3000 hours.

[0098] <Comparative Example 6>

The resin varnish was prepared in the same manner without adding the anion exchanger 9 to the resin varnish of Example 19, and a laminate was prepared. For this laminate, evaluation was made in the same manner as in Example 19. As a result, the time to short circuit was 160 hours.

 Example 20

 [0099] tMAH 1 and magnesium oxide (manufactured by Iwatani Chemical Industry Co., Ltd., MTK-30, hereinafter the same magnesium oxide was used) were mixed well at a weight ratio of 1: 2, and an anion exchange composition 1 to 10 was obtained. It was.

 Example 21

 [0100] tMAHl and magnesium oxide were mixed well at a weight ratio of 1: 1 to obtain an anion exchange composition 1_1.

 Example 22

 [0101] tMAHl and magnesium oxide were mixed well in a weight ratio of 3: 2 to obtain an anion exchange composition 1_2.

 Example 23

 [0102] tMAHl and magnesium oxide were mixed well at a weight ratio of 2: 1 to obtain an anion exchange composition 1_3.

 Example 24

 [0103] MAH1 was calcined at 700 ° C for 2 hours to obtain an anion exchanger A-1. When the composition of this anion exchanger A-1 was measured, it was represented by the composition of Mg Al 2 O 3.

 0.7 0.3 1.15

 Example 25

 [0104] Anion exchanger A-2 was obtained in the same manner as in Example 24 except that the calcination temperature was changed to 800 ° C. The anion exchanger A-2 was measured for X-ray diffraction, and the results are shown in FIG. X-ray diffraction was also measured for tMAH and MAH1, and the results are shown in FIGS. 4 and 5, respectively.

 Example 26

 [0105] Anion exchanger A-3 was obtained in the same manner as in Example 24 except that the calcination temperature was 900 ° C.

 Example 27

[0106] Anion exchange was carried out in the same manner except that the firing temperature in Example 24 was changed to 1000 ° C. Body A-4 was obtained. The X-ray diffraction of this anion exchanger A-4 was measured and the result is shown in FIG.

 [0107] In Figure 2 to Figure 4, the peak at a diffraction angle of 42.9 ° indicates MgO. In Fig. 5 (MAH1), the peak of divalent metal oxide (MgO) is not observed, but in A-2 (Fig. 2) and A-4 (Fig. 3), it is 2 compared to tMAHl (Fig. 4). Many formations of valent metal oxides are observed. In addition, peaks of diffraction angles of 19.0 °, 31.3 °, 36.85 °, and 44.8 ° appeared in A-4, which was fired MAH1 at 1000 ° C. These are considered to be MgAl 2 O peaks. This MgAl〇

 2 4 2 4 Deteriorates the anion exchange performance of the product.

 Example 28

 [0108] A Hyd mouth talcite compound having a ratio of magnesium ion to aluminum ion of 2.5: 1 was calcined at 550 ° C for 2 hours to obtain an anion exchanger B-1. When the composition of this anion exchanger B-1 was measured, it was represented by the composition of Mg AIO.

 2.5 4

 Example 29

 [0109] A hydrated talcite compound having a magnesium ion to aluminum ion ratio of 2.75: 1 was calcined at 550 ° C for 2 hours to obtain an anion exchanger B-2. When the composition of this anion exchanger B-2 was measured, it was represented by the composition of MgAlO.

 2.75 4.25

 Example 30

 [0110] A hydrated talcite compound represented by the composition formula Mg Al (OH) CO 4

 6 2 16 3 2

 And anion exchanger B-3. When the composition of this anion exchanger B-3 was measured, it was represented by Mg AIO yarn.

 3 4.5

 Example 31

 [0111] A hydrated talcite compound in which the ratio of magnesium ion to aluminum ion was 4: 1 was calcined at 550 ° C for 2 hours to obtain anion exchanger B-4. When the composition of this anion exchanger B-4 was measured, it was represented by the composition of Mg AIO.

 4 5.5

 Example 32

[0112] A hydrated talcite compound in which the ratio of magnesium ion to aluminum ion was 5: 1 was calcined at 550 ° C for 2 hours to obtain an anion exchanger B-5. This anion exchanger B-5 When the composition was measured, it was represented by the composition of Mg AIO.

 Example 33

 [0113] A hydrated talcite compound in which the ratio of magnesium ion to aluminum ion was 3: 1 was calcined at 800 ° C for 2 hours to obtain an anion exchanger B-6. When the composition of this anion exchanger B-6 was measured, it was represented by the composition of Mg AIO.

 Example 34

 [0114] A hydrated talcite compound in which the ratio of magnesium ion to aluminum ion was 4: 1 was calcined at 800 ° C for 2 hours to obtain an anion exchanger B-7. When the composition of this anion exchanger B-7 was measured, it was represented by the composition of Mg AIO.

 Example 35

 [0115] A hydrated talcite compound in which the ratio of magnesium ion to aluminum ion was 5: 1 was calcined at 800 ° C for 2 hours to obtain an anion exchanger B-8. When the composition of this anion exchanger B-8 was measured, it was represented by the composition of Mg AIO.

 Example 36

[0116] ○ Ion exchange rate measurement test

 Place an anion exchanger and anion exchange composition shown in Table 5 below in a 100 ml polyethylene bottle, 1. Og, and then add 50 ml of 0.02M sodium chloride aqueous solution. Shake for 24 hours at C. Thereafter, the solution was filtered through a membrane filter having a pore size of 0.1 × m, and the chloride ion concentration of the filtrate was measured by ion chromatography. The anion exchange rate was determined in comparison with the case where the chlorine ion concentration was measured by performing the same operation without inserting any sample. These results are shown in Table 5. The ρ も の of the filtrate of the anion exchanger and the anion exchange composition was alkaline.

[0117] [Table 5] No. e Formula Ion Exchange Rate Example 20 Anion Exchange Composition 1—0 90%

 Example 21 Anion Exchange Composition 1 1 1 98%

 Example 22 anion exchange composition 1 1 2 99%

 Example 23 anion exchange composition 1 1 3 98%

 Example 24 Anion exchanger A— 1 80%

 Example 25 Anion exchanger A_2 98%

 Example 26 Anion exchanger A_3 95%

 Example 27 Anion exchanger A— 4 71%

 Example 28 anion exchanger B— 1 71%

 Example 29 anion exchanger B— 2 75%

 Example 30 anion exchanger B_3 98%

 Example 31 anion exchanger B— 4 99%

 Example 32 Anion exchanger B— 5 98%

 Example 33 anion exchanger B_6 98%

 Example 34 Anion exchanger B_7 95%

 Example 35 anion exchanger B_8 77%

 Comparative example MAH 1 0%

 Comparative example tMAH 1 70%

Comparative Example Mg ₆ AI ₂ (OH) ₁₆ C0 ₃ -4H ₂ 0 0%

 Comparative Example Magnesium oxide 0% Example 37

 The resin used for the sealing material for electronic parts and the anion exchange composition 1 and 2 were blended as described below, and this was kneaded with a hot roll at 80 ° C-90 ° C for 3-5 minutes. .

 Cresol novolac epoxy resin (epoxy equivalent 235) 80 parts Brominated phenol novolac epoxy resin (epoxy equivalent 275) 20 parts phenol novolac resin (molecular weight 700-1000) 50 parts

 Triphenylphosphine 2 parts

 Carnauba wax 1 part

 1 part of carbon black

 370 parts of fused silica

 Anion exchange composition 1 2 2 parts

Thereafter, the mixture was cooled and pulverized to obtain a powdery epoxy resin composition A-12. The composition A-1-2 was sieved and divided 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 product A-1-12. This resin kneaded body A-1 1-2 was pulverized to a size of 2-3 mm. Using this ground sample, a chlorine ion elution test was conducted.

 Example 38

 [0119] The anion exchange composition of Example 37, except that anion exchanger A-2 was used in place of 1-2, was operated in the same manner as in Example 37, and resin kneaded body A2-2-2 was prepared. Produced. And it grind | pulverized similarly to Example 37 and produced the grind | pulverized sample.

 Example 39

 [0120] The anion exchange composition of Example 37, except that anion exchanger B-3 was used instead of 1 or 2, was operated in the same manner as in Example 37, and resin kneaded product A-3-3 was prepared. Produced. And it grind | pulverized similarly to Example 37 and produced the grind | pulverized sample.

[0121] <Comparative Example 7>

 A comparative resin kneaded body A-1 was produced in the same manner as in Example 37 except that MAH1 was used in place of the anion exchange composition 1-12 of Example 37. And it grind | pulverized like Example 37 and produced the grind | pulverized sample.

[0122] <Comparative Example 8>

 A comparative resin kneaded body A-2 was produced in the same manner as in Example 37 except that tMAH 1 was used instead of the anion exchange composition 1 and 2 of Example 37. And it grind | pulverized like Example 37 and produced the grind | pulverized sample.

[0123] <Comparative Example 9>

 Anion exchange composition of Example 37 Composition formula Mg Al (OH) CO 4Η instead of 1-2

 6 2 16 3 2

A comparative resin kneaded body Α-3 was produced in the same manner as in Example 37 except that the heel talcite mixture was used. And it grind | pulverized like Example 37 and produced the grind | pulverized sample.

[0124] <Comparative Example 10>

A comparative resin kneaded body A was produced in the same manner as in Example 37 except that the anion exchange composition 1 or 2 was not used. And it grind | pulverized like Example 37 and produced the grind | pulverized sample. That is, the comparative resin kneaded body A does not contain a fired composition. Example 40

 [0125] The resin used for the sealing material for electronic parts and the anion exchange composition 1 and 2 are blended as described below, and this is mixed with a hot roll at 80 ° C and 90 ° C for 35 minutes. Kneaded.

 Cresolol novolac epoxy resin (epoxy equivalent 235) 80 parts Brominated phenol novolac epoxy resin (epoxy equivalent 275) 20 parts phenol novolac resin (molecular weight 700-1000) 50 parts DBU 3 parts

 Amine-based silane coupling agent (3-part 3 parts

 1 copy

 Carbon black 1 part Fused silica 370¾

 Anion exchange composition 1 2 2 parts Thereafter, the mixture was cooled and powdered to obtain a powdery epoxy resin composition Β-2. Then, this composition B-1-2 was sieved with a 100 mesh sieve to prepare a 100 mesh pass sample, and the 100 mesh pass sample was cured at 170 ° C. B—1 1 2 was made. This resin kneaded body B-1 1 2 was pulverized to a size of 23 mm. Using this ground sample, a chlorine ion elution test was conducted.

 Example 41

 [0126] Resin kneaded product B-2-2 was produced in the same manner as in Example 40 except that anion exchanger A-2 was used instead of anion-exchange composition 12 of Example 40. did. And it grind | pulverized similarly to Example 40 and produced the grind | pulverized sample.

 Example 42

 [0127] The anion exchange composition of Example 40 was operated in the same manner as in Example 40 except that the anion exchanger B-3 was used instead of 1 and 2, and the resin kneaded body B-3-3 was used. Produced. And it grind | pulverized similarly to Example 40 and produced the grind | pulverized sample.

 [0128] <Comparative Example 11>

Example 40 Anion Exchange Composition 1 Example 1 except that MAH1 was used instead of 2 In the same manner as in 0, comparative resin kneaded body B-1 was produced. Then, it was pulverized in the same manner as in Example 40 to prepare a pulverized sample.

<Comparative Example 12>

 A comparative resin kneaded body B-2 was produced in the same manner as in Example 40 except that tMAHl was used in place of the anion exchange composition 1 and 2 of Example 40. And it grind | pulverized similarly to Example 40 and produced the grind | pulverized sample.

[0130] <Comparative Example 13>

 Anion exchange composition of Example 40 Composition formula Mg Al (OH) CO · 4Η instead of 1-2

 6 2 16 3 2

A comparative resin kneaded body Β-3 was produced in the same manner as in Example 40 except that the heel talcite mixture was used. And it grind | pulverized similarly to Example 40 and produced the grind | pulverized sample.

[0131] <Comparative Example 14>

 A comparative resin kneaded body was prepared in the same manner as in Example 40 except that the anion exchange composition 1 or 2 was not used. And it was dusted like Example 40, and the powder sample was produced. That is, the comparative resin kneaded material Β does not contain a fired composition.

 Example 43

 [0132] 〇 Chlorine ion extraction test from resin kneaded material

 5 g of each resin kneaded body or comparative resin kneaded body prepared above and 50 ml of pure water were placed in a polytetrafluoroethylene pressure vessel and sealed, and heated at 125 ° C. 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. These results are shown in Table 6.

[0133] [Table 6]

N O. Sample ¾ί (ppm) pH Example 37 Resin kneaded body A—1 1 2 1 9 4. 6 Example 38 Resin kneaded body A—2— 2 1 9 4.6 Example 39 Resin kneaded Embedded body A— 3— 3 20 4. 6 Comparative example 7 Comparative resin kneaded body A— 1 56 4. 3 Comparative example 8 Comparative resin kneaded body A— 2 25 4. 5 Comparative example 9 Comparative resin kneaded body A — 3 55 4. 3 Comparative Example 10 Comparative Resin Kneaded Body A 60 4.2 Example 40 Resin Kneaded Body B— 1 1 2 20 6. 8 Example 41 Resin Kneaded Body B— 2— 2 22 6. 8 Example 42 Resin kneaded body B— 3— 3 22 6. 8 Comparative example 1 1 Comparative resin kneaded body B— 1 61 6. 7 Comparative example 1 2 Comparative resin kneaded body B— 2 55 6. 8 Comparison Example 1 3 Comparative resin kneaded body B— 3 60 6. 7 Comparative example 1 4 Comparative resin kneaded body B 62 6. 8

As is clear from Table 5 and Table 6, the anion exchanger of the present invention has a high ion exchange rate near neutrality. Moreover, even when added to the encapsulant resin, it has the effect of suppressing elution of chloride ions regardless of whether the pH of the extract of the encapsulant composition is acidic or near neutral. As a result, it is possible to provide a highly reliable sealing material composition in a wide range.

 Example 44

 [0135] 100 g of tMAHl was added to 200 g of a 10% methanol solution of methyl silicate monomer (manufactured by Tama Chemical), stirred overnight, and then air-dried for 1 day. Thereafter, this was calcined at 550 ° C. for 2 hours to obtain an anion exchanger (anion exchanger 10).

 Example 45

 [0136] 100 g of tMAHl was added to 160 g of a 10% methanol solution of methyl silicate oligomer (manufactured by Tama Chemical Co., Ltd., trade name: methyl silicate 51. The same thing was used hereinafter) and stirred for 1 day. Air dried. Thereafter, this was calcined at 550 ° C. for 2 hours to obtain an anion exchanger (anion exchanger 11).

 Example 46

[0137] 100 g of anion exchanger B-3 was added to 200 g of a 10% methanol solution of methyl silicate monomer (manufactured by Tama Chemical), stirred overnight, and then air-dried for 1 day. Thereafter, an anion exchanger (anion exchanger B-9) was obtained by baking at 550 ° C. for 2 hours. Example 47

 [0138] lOOg of anion exchanger B_3 was added to 160 g of a 10% methanol solution of methyl silicate oligomer (manufactured by Tama Chemical), stirred overnight, and then air-dried for 1 day. Then, an anion exchanger (anion exchanger B-10) was obtained by baking at 550 ° C. for 2 hours.

 Example 48

 [0139] An anion exchanger (anion exchange composition 115) was obtained by mixing 60 g of the anion exchanger 10 and 40 g of magnesium oxide which is a divalent metal oxide.

 Example 49

 [0140] An anion exchanger was obtained by mixing 60 g of anion exchanger 11 and 40 g of magnesium oxide which is a divalent metal oxide (anion exchange composition 1-6).

 Example 50

 [0141] 60 g of tMAHl and 40 g of divalent metal oxide magnesium oxide were mixed to obtain an anion exchanger (anion exchange composition 14).

 Example 51

 [0142] lOOg of anion exchange composition 1-4 was added to 200 g of a 10% methanol solution of methyl silicate monomer (manufactured by Tama Chemical), stirred overnight, and then air-dried for 1 day. Thereafter, it was baked at 550 ° C. for 2 hours to obtain an anion exchanger (anion exchange composition 1-7). Example 52

 [0143] lOOg of anion exchange composition 1 to 4 was added to 160 g of a 10% methanol solution of methyl silicate oligomer (manufactured by Tama Chemical), stirred overnight, and then air-dried for 1 day. Thereafter, it was calcined at 550 ° C. for 2 hours to obtain an anion exchanger (anion exchange composition 118). Example 53

 [0144] Anion exchanger (anion exchange composition 2-1) was obtained by mixing 60 g of anion exchanger B-3 and 40 g of magnesium oxide which is a divalent metal oxide.

 Example 54

[0145] An anion exchanger (anion exchange composition 2_2) was obtained by mixing 60 g of an anion exchanger B-9 with 40 g of divalent metal oxide magnesium oxide. Example 55

 [0146] An anion exchanger (anion exchange composition 2-3) was obtained by mixing 60 g of an anion exchanger B_10 and 40 g of magnesium oxide which is a divalent metal oxide.

 Example 56

 [0147] 100 g of anion exchange composition 2-1 was added to 200 g of a 10% methanol solution of methyl silicate monomer (manufactured by Tama Chemical), stirred overnight, and air-dried for 1 day. Then, an anion exchanger (anion exchange composition 2-4) was obtained by baking at 550 ° C. for 2 hours.

 Example 57

 [0148] 100 g of anion exchange composition 2-1 was added to 160 g of a 10% methanol solution of methyl silicate oligomer (manufactured by Tama Chemical Co., Ltd., methyl silicate 51), stirred overnight, and air-dried for 1 day. Then, an anion exchanger (anion exchange composition 2-5) was obtained by baking at 550 ° C. for 2 hours.

 Example 58

 [0149] ○ Hygroscopicity test

 Each of the anion exchangers and anion exchange compositions listed in Table 7 below was heated at 150 ° C for 4 hours, then left in 90% humidity and 35 ° C, and the weight was measured over time. The hygroscopicity (weight increase rate) was examined. Of these, Table 7 shows the results of weight gain after 24 hours.

 [0150] 〇 Ion exchange rate measurement test

 Place 1.0 g of the anion exchanger and anion exchange composition shown in Table 7 below into a 100 ml polyethylene bottle, and then add 50 ml of 0.02 M aqueous sodium chloride solution, and seal tightly. Shake for 24 hours at ° C. Thereafter, the solution was filtered through a membrane filter having a pore size of 0.:m, and the chloride ion concentration in the filtrate was measured by ion chromatography. The chloride concentration was measured for the same operation without an anion exchanger. In comparison with this, the anion exchange rate of an anion exchanger was determined. These results are shown in Table 7.

[0151] [Table 7] No. Sample Weight increase rate Ion exchange rate Example 44 Anion exchanger 1 0 8% 70% Example 45 Anion exchanger 1 1 4% 67% Example 30 Anion exchanger B— 3 47% 97% Example 46 Anion exchanger B— 9 1 1% 71% Example 47 Anion exchanger B_ 1 0 7% 70% Example 50 Anion exchange composition 1 1 4 43% 98% Example 48 Anion exchange composition 1 1 5 1 2% 95% Example 49 Anion exchange composition 1 _6 6% 95% Example 51 Anion exchange composition 1 1 7 1 1% 71% Example 52 Anion exchange composition 1 1 8 5% 66% Example 53 Anion exchange composition 2-1 45% 99% Example 54 Anion exchange composition 2-2 2 1 2% 96% Example 55 Anion exchange composition 2-3 3 8% 96% Example 56 Anion exchange composition 2—4 1 0% 67% Example 57 Anion exchange composition 2—5 6% 65% Comparative example tMAH I 45% 70% Comparative example AH 1 1% 0% Example 59

 The composition used for the encapsulant for electronic parts and the anion exchange composition 1-5 were combined as follows, and this composition was kneaded with a hot roll at 80 ° C-90 ° C for 35 minutes. .

 Cresol novolac epoxy resin (epoxy equivalent 235) 80 parts Brominated phenol novolac epoxy resin (epoxy equivalent 275) 20 parts phenol novolac resin (molecular weight 700-1000) 50 parts

 Triphenylphosphine 2 parts

 Carnauba wax 1 part

 1 part of carbon black

 370 parts of fused silica

 Anion exchange composition 1 1 5 2 parts

Then, it cooled and grind | pulverized and obtained powdery epoxy resin composition A-Z-1. The composition AZ-1 was sieved with a 100 mesh sieve, a 100 mesh pass sample was prepared, and the 100 mesh pass sample was cured at 170 ° C to obtain a resin kneaded body A— Make Z—1 Made. This resin kneaded body A—Z-1 was pulverized to a maximum diameter of 2-3 mm. Using this pulverized sample, a chloride ion elution test was conducted.

 Example 60

 [0153] The anion exchange composition used in the production of the resin kneaded body A_Z_1 1-11 The procedure was the same as in Example 59 except that the anion exchange composition 1-6 was used instead of 5, and the resin kneaded The body A_Z_2 was produced. This was similarly pulverized to prepare a pulverized sample. Chlorion elution test was performed using this ground sample.

 [0154] <Comparative Example 15>

 Resin kneaded body A—H—1 was used in the same manner as in Example 59 except that tMAHl was used instead of the anion exchange composition 15 used in the production of resin A—Z—1. Produced. This was pulverized in the same manner to prepare a pulverized sample. Using this ground sample, a chloride ion elution test was conducted.

 Example 61

 [0155] The anion exchange composition used in the production of the resin kneaded body A_Z_1 1 Except that the anion exchanger 10 was used in place of 5, an operation was performed in the same manner as in Example 59, and the resin kneaded body AZ- 3 was produced. This was similarly pulverized to prepare a pulverized sample. This ground sample was used to conduct a chloride ion elution test.

 Example 62

 [0156] Resin kneaded body AZ-4 was prepared in the same manner as in Example 59 except that anion exchanger composition 11 was used instead of anion exchange composition 15 used in the preparation of resin kneaded body A_Z_1. Produced. This was similarly pulverized to prepare a pulverized sample. This ground sample was used for a chlorine ion elution test.

 [0157] <Comparative Example 16>

Resin kneaded material A_H_3 was produced in the same manner as in Example 59 except that MAH1 was used instead of the anion exchange composition 115 used in the production of resin kneaded material A_Z_1. This was pulverized in the same manner to prepare a pulverized sample. Using this ground sample, a chloride ion elution test was conducted. Example 63

 [0158] The anion exchange composition used in the production of the resin kneaded body A_Z_1 1 An operation was performed in the same manner as in Example 59 except that the anion exchange composition 1-14 was used instead of 5, and the resin kneaded body was used. A_Z_5 was made. This was similarly pulverized to prepare a pulverized sample. Chlorion elution test was performed using this ground sample.

 Example 64

 [0159] The anion exchange composition used in the production of the resin kneaded body A_Z_1 1 In the same manner as in Example 59 except that the anion exchange composition 1-7 was used instead of 5, the resin kneaded body A—Z—6 was produced. This was similarly pulverized to prepare a pulverized sample. Chlorion elution test was performed using this ground sample.

 Example 65

 [0160] The anion exchange composition used in the production of the resin kneaded body A_Z_1 1 In the same manner as in Example 59 except that the anion exchange composition 1-8 was used instead of 5, the resin kneaded body A—Z—7 was produced. This was similarly pulverized to prepare a pulverized sample. Chlorion elution test was performed using this ground sample.

 Example 66

 [0161] Anion exchange composition used in the preparation of resin kneaded body A_Z_1 11 The procedure was the same as in Example 59 except that anion exchanger B-9 was used instead of 5, and resin kneaded body A_Z_8 Was made. This was similarly pulverized to prepare a pulverized sample. This ground sample was used to conduct a chloride ion elution test.

 Example 67

 [0162] The anion exchange composition used in the production of the resin kneaded body A_Z_1 1 In the same manner as in Example 59 except that the anion exchanger B-10 was used instead of 5, the resin kneaded body A — Z— 9 was produced. This was similarly pulverized to prepare a pulverized sample. This ground sample was used to conduct a chloride ion elution test.

 Example 68

[0163] Anion exchange composition used in preparation of resin kneaded body A_Z_1 A resin kneaded body AZ-10 was produced in the same manner as in Example 59 except that the exchange composition 2-2 was used. This was similarly pulverized to prepare a pulverized sample. Chlorion elution test was performed using this ground sample.

 Example 69

 [0164] Anion exchange composition used in preparation of resin kneaded body A_Z_1 1 In the same manner as in Example 59 except that anion exchange composition 2-3 was used instead of 5, resin kneaded body A_Z_11 was produced. This was similarly pulverized to prepare a pulverized sample. Chlorion elution test was performed using this ground sample.

 Example 70

 [0165] The anion exchange composition used in the production of the resin kneaded body A_Z_1 1 In the same manner as in Example 59 except that the anion exchange composition 2-4 was used instead of 5, the resin kneaded body A_Z_12 was produced. This was similarly pulverized to prepare a pulverized sample. Chlorion elution test was performed using this ground sample.

 Example 71

 [0166] Resin kneaded product A was prepared in the same manner as in Example 59 except that the anion exchange composition 2-5 was used instead of the anion exchange composition 15 used in the preparation of the resin kneaded product A_Z_1. — Z— 13 was fabricated. This was similarly pulverized to prepare a pulverized sample. Chlorion elution test was performed using this ground sample.

 Example 72

 [0167] The anion exchange composition used in the production of the resin kneaded body A_Z_1 1 The procedure was the same as in Example 59 except that the anion exchanger B-3 was used instead of 5, and the resin kneaded body A_Z_14 Was made. This was similarly pulverized to prepare a pulverized sample. This ground sample was used to conduct a chloride ion elution test.

 Example 73

[0168] Resin kneaded product AZ was operated in the same manner as in Example 59 except that anion exchange composition 2-1 was used instead of anion exchange composition 15 used in the production of resin kneaded product A_Z_1. -15 was produced. This was similarly pulverized to prepare a pulverized sample. Using this ground sample, chlorine On dissolution test was performed

 [0169]

 A comparative resin kneaded body A was produced in the same manner as in Example 59 except that the anion exchange composition 1-5 was not used. This was similarly pulverized to prepare a pulverized sample. Using this ground sample, a chlorine ion elution test was conducted.

 Example 74

 [0170] The composition used for the sealing material for electronic parts and the anion exchange composition 1-5 were blended as described below, and this was mixed for 3-5 minutes with a hot roll at 80 ° C-90 ° C. Kneaded.

 Cresolol novolac epoxy resin (epoxy equivalent 235) 80 parts Brominated phenol novolac epoxy resin (epoxy equivalent 275) 20 parts

'One novolak resin (molecular weight 700-1000) 50 parts

 DBU 3 parts

 Amine-based silane coupling agent (3-a 3 parts Carnauba wax 1 part Carbon black 1 part Fused silica 370 parts

 Anion exchange composition 1 1 5 2 parts Thereafter, the mixture was cooled and pulverized to obtain a powdery epoxy resin composition Β_Ζ_1. Then, this composition B-Z-1 was sieved with a 100-mesh sieve to produce a 100-mesh pass sample.

 Using this 100 mesh pass sample, it was cured at 170 ° C to produce a resin kneaded body B_Z_1. This resin kneaded body B_Z_1 was pulverized to a maximum diameter of 23 mm. Using this pulverized sample, a chloride ion elution test was conducted.

 Example 75

[0171] The same procedure as in Example 74 was carried out except that the anion exchange composition 1-6 was used instead of the anion exchange composition 1-5 used in the production of the resin kneaded body B-Z-1. Resin kneaded body B-Z-2 was produced. A pulverized sample was prepared by pulverizing in the same manner. Chlorion elution test was performed using this ground sample. [0172] <Comparative Example 18>

 Resin kneaded product B—Z—1 was used in the same manner as in Example 74 except that tMAHl was used in place of 1 to 5 to prepare the resin kneaded product B—H—1. Produced. In the same manner, pulverization was performed to prepare a pulverized sample.

 Example 76

 [0173] The anion exchange composition used for the production of the resin kneaded body B_Z_1 1 In the same manner as in Example 74 except that the anion exchanger 10 was used instead of 5, the resin kneaded body BZ-3 Was made. A pulverized sample was prepared by pulverizing in the same manner.

 Example 77

 [0174] Anion-exchange composition used for preparation of resin kneaded body B_Z_1 1-11 A resin-kneaded body B_Z_4 was prepared in the same manner as in Example 74 except that anion exchanger 11 was used instead of 5. did. A pulverized sample was prepared by pulverizing in the same manner.

 Example 78

 [0175] Anion exchange composition used for preparation of resin kneaded body B_Z_1 1 An operation was carried out in the same manner as in Example 74 except that anion exchange composition 11-4 was used instead of 5, and the resin kneaded body was used. B—Z—5 was produced. A pulverized sample was prepared by pulverizing in the same manner.

 Example 79

 [0176] Anion exchange composition used for production of resin kneaded body B_Z_1 1 In the same manner as in Example 74 except that anion exchange composition 1-7 was used instead of 5, resin kneaded body B_Z_6 was made. A pulverized sample was prepared by pulverizing in the same manner.

 Example 80

 [0177] Anion exchange composition used for preparation of resin kneaded body B_Z_1 1 An operation was performed in the same manner as in Example 74 except that anion exchange composition 1-8 was used instead of 5, and a resin kneaded body was used. B—Z—7 was produced. A pulverized sample was prepared by pulverizing in the same manner.

 [0178] <Comparative Example 19>

Resin kneaded product B_H_3 was produced in the same manner as in Example 74 except that MAH1 was used instead of the anion exchange composition 115 used to prepare resin kneaded product B_Z_1. Same as this A pulverized sample was prepared.

 Example 81

 [0179] Anion exchange composition used for preparation of resin kneaded body B_Z_1 1 The procedure was the same as in Example 74 except that anion exchanger B-9 was used instead of 5, and resin kneaded body B_Z_8 Was made. A pulverized sample was prepared by pulverizing in the same manner.

 Example 82

 [0180] The anion exchange composition used for the production of the resin kneaded body B_Z_1 1 The procedure was the same as in Example 74 except that the anion exchanger B-10 was used instead of the resin kneaded body B — Z— 9 was produced. A pulverized sample was prepared by pulverizing in the same manner.

 Example 83

 [0181] Anion exchange composition used for preparation of resin kneaded body B_Z_1 1 In the same manner as in Example 74 except that anion exchange composition 2-2 was used instead of 5, resin kneaded body B_Z_10 was made. A pulverized sample was prepared by pulverizing in the same manner.

 Example 84

 [0182] Anion exchange composition used for preparation of resin kneaded body B_Z_1 1 Resin kneaded body was operated in the same manner as in Example 74 except that anion exchange composition 2-3 was used instead of 5. B_Z_11 was made. A pulverized sample was prepared by pulverizing in the same manner.

 Example 85

 [0183] Anion exchange composition used for preparation of resin kneaded body B_Z_1 1 In the same manner as in Example 74 except that anion exchange composition 2-4 was used instead of 5, resin kneaded body B—Z—12 was produced. A pulverized sample was prepared by pulverizing in the same manner.

 Example 86

 [0184] Anion exchange composition used for production of resin kneaded body B_Z_1 1 In the same manner as in Example 74 except that anion exchange composition 2-5 was used instead of 5, resin kneaded body B_Z_13 was made. A pulverized sample was prepared by pulverizing in the same manner.

 Example 87

[0185] Anion exchange composition used for preparation of resin kneaded body B—Z— 1 1 1 Anion instead of 5 A resin kneaded body B-Z-14 was produced in the same manner as in Example 73 except that the exchange composition B-3 was used. A pulverized sample was prepared by pulverizing in the same manner.

 Example 88

 [0186] Anion exchange composition used for preparation of resin kneaded body B_Z_1 1 In the same manner as in Example 74 except that anion exchange composition 2-1 was used instead of 5, resin kneaded body B_Z_15 was made. A pulverized sample was prepared by pulverizing in the same manner.

[0187] <Comparative Example 20>

 A comparative resin kneaded body B was prepared in the same manner as in Example 74 except that the anion exchange composition 115 was not used. This was similarly pulverized to prepare a pulverized sample. The ground sample was used for a chloride ion elution test.

 Example 89

 [0188] 〇 Chlorine ion extraction test from resin kneaded material

 The resin kneaded materials shown in Table 8 and Table 9 below were sealed in 5 ml of 50 ml pure water and a polytetrafluoroethylene pressure vessel, and heated at 125 ° C for 100 hours. After cooling, water was taken out, the pH of the water was measured, and the concentration of chloride ions eluted in the water was measured by ion chromatography. These results are shown in Table 8 and Table 9.

[0189] [Table 8]

No. Material im¾i; Degree (ppm) pH Example 59 Resin kneaded body Α—Ζ— 1 18 4.4 Example 60 Resin kneaded body A—Z— 2 19 4.4 Example 61 Resin kneaded body A—Z — 3 19 4.4 Example 62 Resin kneaded body A—Z— 4 19 4.5 Example 63 Resin kneaded body A—Z— 5 17 4.4 Example 64 Resin kneaded body A—Z_ 6 18 4.4 Example 65 Resin kneaded body A—Z— 7 19 4.4 Example 66 Resin kneaded body A—Z— 8 18 4.3 Example 67 Resin kneaded body A—Z— 9 19 4.3 Example 68 Resin kneaded body A—Z— 10 17 4.5 Example 69 Resin kneaded body A—Z— 11 17 4.5 Example 70 Resin kneaded body A_Z— 12 18 4. 3 Example 71 Resin kneaded body A—Z— 13 19 4.4 Example 72 Resin kneaded body Embedded body A—Z— 14 17 4.5 Example 73 Resin kneaded body A—Z—15 16 4.4 Comparative example 15 Comparative resin kneaded body A—H— 1 19 4.4 Comparative example 16 Comparative resin kneaded body A—H— 3 55 4.3 Comparative Example 17 Comparative resin kneaded body A 60 4. 2]

No. 5 ^ material Chlorine ion is (ppm) pH Example 74 Resin kneaded product B—Z— 1 19 6. 8 Example 75 Resin kneaded product B—Z— 2 20 6.8 Example 76 Resin kneaded product B—Z— 3 41 6.7 Example 77 Resin kneaded body B—Z— 4 45 6.7 Example 78 Resin kneaded body B—Z— 5 18 6.8 Example 79 Resin kneaded body B—Z— 6 39 6.8 Implementation Example 80 Resin kneaded body B—Z— 7 40 6. 8 Example 81 Resin kneaded body B—Z— 8 40 6.8 Example 82 Resin kneaded body B—Z— 9 41 6.7 Example 83 Resin kneaded body B—Z—10 20 6.8 Example 84 Resin kneaded body B—Z—11 20 6.8 Example 85 Resin kneaded body B—Z—12 41 6. 8 Example 86 Resin kneaded body B—Z—13 42 6.7 Example 87 Resin kneaded body B—Z— 14 40 6.8 Example 88 Resin kneaded body BZ— 15 18 6.9 Comparative example 18 Comparative resin kneaded body B—H— 1 40 6. 8 Comparative example 19 Comparative resin kneaded Embedded B_H— 3 58 6.8 Comparative Example 20 Comparative resin kneaded body B 62 6.8 [0191] As is clear from Table 7, Table 8, and Table 9, these anion exchangers have high ion exchange rates near neutrality. Furthermore, the hygroscopicity is low. In addition, when the anion exchanger of the present invention is added to a sealing material resin such as an electronic component, the effect of suppressing the elution of chloride ions from the sealing resin regardless of whether the pH of the sealing resin extract is acidic or near neutral. There is. As a result, it is possible to provide a highly reliable sealing material composition in a wide range.

 Industrial applicability

[0192] The anion exchanger of the present invention has low hygroscopicity and / or excellent heat resistance, and has a high anion exchange rate even near neutrality. Even if the anion exchanger of the present invention is added to the resin, there is an effect of suppressing the elution of anions from now on. From this, the anion exchanger of the present invention can be used for various applications such as sealing, covering, and insulating of electronic parts or electric parts with high reliability in a wide range. The anion exchanger of the present invention can also be used as a stabilizer for a resin such as vinyl chloride and an antifungal agent.

Claims

Claims [1] A fired talcite hydrate represented by formula (1) and a talcite H composite represented by Z or formula (2) are mixed with a metal salt solution and / or a metal alkoxide solution. Anion exchanger processed. M2 + M3 + O (1) xyz (M ^{2+ in} formula (1) is Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , C. ²⁺ , Ni Cu or Zn ²⁺ , M ³⁺ is Al ³⁺ , Fe ³⁺ , Cr ^{3 +} , Co ³⁺ , or In ³⁺ , x, y, z is a positive number greater than or equal to 0.1, 2x + 3y = 2z, and x> y, and the value of x / y is 9 or less.) M ²⁺ M ³⁺ (OH) (Α ^π —)-mH Ο (2)  1-Χ X 2 d 2 (Μ ^{2+ in} formula (2) is Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , Co ²⁺ , Ni Cu or Zn ²⁺ , and M ³⁺ is Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Co ³⁺ , or In ³⁺ , A ⁿ — is 〇H—, F—, Cl—, Br—, NO—, CO ² —, SO ² —,  3 3 4 Fe (CN) ³ —, CH COO—, oxalate ion, or n-valent anion of salicylate ion  6 3  , X is a positive number not less than 0.1 and not more than 0.33, m is 0 or a positive number, and d is X / n. )  [2] The metal of the metal salt solution or the metal alkoxide solution according to claim 1 is at least one selected from the group consisting of silicon, titanium, dinoleconium, tin, and aluminum. Item 2. The anion exchanger according to Item 1. [3] The anion exchanger according to claim 1, further comprising a divalent metal oxide.  [4] The anion exchanger according to claim 2, further comprising a divalent metal oxide.  [5] An anion exchanger comprising a fired talcite compound compound represented by formula (2) and a divalent metal oxide. M ²⁺ M ³⁺ (OH) (Α ^π —)-mH Ο (2)  1-Χ X 2 d 2 (Μ ^{2+ in} formula (2) is Mg ²⁺ , Mn ²⁺ , Fe ²⁺ , C. ²⁺ , Ni Cu or Zn ²⁺ , M ³⁺ is Al ³⁺ , Fe ³⁺ , Cr ^{3 +} , Co ³⁺ , or In ³⁺ , A ⁿ — is 〇H-, F-, Cl Br-, NO-, CO ² —, SO ² —,  3 3 4 Fe (CN) ³ —, CH COO—, oxalate ion, or n-valent anion of salicylate ion  6 3  , X is a positive number not less than 0.1 and not more than 0.33, m is 0 or a positive number, and d is X / n. ) [6] The anion exchanger according to claim 5, wherein the anion exchanger is dissolved in a metal salt solution and / or a metal alkoxide. An anion exchanger characterized by being treated with a liquid.  [7] The resin composition for encapsulating an electronic component containing the anion exchanger according to any one of [1] to [16], which may contain an inorganic cation exchanger.  [8] An electronic component sealing resin obtained by curing the electronic component sealing resin composition according to claim 7.  [9] An electronic component obtained by sealing an element with the electronic component sealing resin composition according to claim 7. [10] The varnish, adhesive or paste containing the anion exchanger according to any one of claims 1 to 6, which may contain an inorganic cation exchanger. [11] A product containing the varnish, adhesive or paste according to claim 10.