JPS6023901A - Insulating protective material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an insulating protective material that is effective in protecting electronic and electrical components such as electronic devices.

Semi-conductive function, anti-static function, magnetic function, insulating function,
Electronic devices (e.g. diodes, transistors, varistors,
Insulating protective materials used for the purpose of element protection, contact protection, etc. for capacitors, liquid crystals, thermistors, iC, LSi, etc.) and electronic components (devices) containing these are determined by their application purpose, application parts, application area, Or sealing material, casting material (or casting material) depending on the application method etc.
, botting material, interlayer maintenance material, junction coating material, passivation material, dipping material, sealing material, roller coating material, drip coating material, etc.

These insulating protective materials (hereinafter simply referred to as protective materials) that are applied to sealing materials, casting materials, etc. include low melting point glass as a 72 mix material, epoxy resin as a polymer material, and epoxy resin as a polymer material. - Silicone resins, silicone resins, phenol resins, etc. are known, and polymeric materials are generally used relatively often from the viewpoint of moldability, low cost, and mass production.

These are rarely used alone, but are usually used in combination with fillers, and inorganic substances such as titanic acid, fused silica, β-eucryptite, titanium oxide, and various other substances are included in the composition. . The properties required for such protective feathers are given low importance.

Regarding this insulation, it is said that various inhibiting factors such as the movement of ionic impurities in the protective material, the hygroscopicity of the protective material, and the charge density of the solid surface of the protective material are involved in a complex manner and have an adverse effect. Halogen ions are also said to cause corrosion of electronic elements and lead wires. Various measures have been considered to remove the effects of these, but
In general, the above-mentioned effects on the final product should be avoided by selecting raw materials for the protective material and preventing contamination during purification and manufacturing processes.

Among ionic impurities, alkali metal ions (L+,
Na, K, etc.) and halogen ions (F″″.

The influence of impurities (Cl-1Br-, etc.) cannot be ignored, and it is said that even a few ppm of these impurities can degrade insulation.These ionic impurities can be completely removed in the protective manufacturing process, but in reality Moreover, removing even the smallest amount of material is an extremely large burden both in terms of process and economy.

On the other hand, some fillers constituting protective materials contain alkali metal ions as a main component, and it is also known that this component satisfies a part of the performance as a protective material.

For example, β-nikligetite (Lio2・A I 2
o3・n5io□) has a negative expansion property with respect to heat rise, and there are attempts to use this physical property as a filler for protective materials, but β-nikuriflite is also attracting attention as a lithium ion conductor. , the lithium in the component moves as an ion. However, this should be regarded as an ionic impurity that brings about undesirable results from the viewpoint of the physical property of insulation in the protective material.

The present invention solves the above-mentioned problems regarding the protective material, and the ions that remain as impurities in the protective material or the ions in the main components such as lithium ions in β-nic refractive material are converted into ionic impurities in the protective material. The protective material is characterized in that at least one type of inorganic ion-exchangeable substance having an -OH bond is contained in the components constituting the protective material in order to trap and fix the protective material without being moved.

The protective material in the present invention includes, as described above, low melting point glass, epoxy resin, phenol resin, silicone resin for fusing, and fused silica, β-eucryptite, etc. as fillers as the original protective material components. Selected combinations of known materials are used which are further loaded with at least one of the ion exchange materials listed below.

In other words, these inorganic ion exchange materials can be divided into those that have cation exchange properties, especially those that have exchange properties for alkali metal ions, and those that have anion exchange properties, especially those that have exchange properties for halogen ions. Examples of exchangeable substances include polyvalent metal acids and their salts such as antimonic acid, stannic acid, titanic acid, niobic acid, manganic acid, zirconium phosphate, titanium phosphate, tin phosphate, cerium phosphate, tin arsenate, These include polyvalent metal polybasic acid salts such as titanium arsenate, and heteropolyacids such as molybdic acid and tungstic acid. All of these exhibit ion exchange properties.
This also includes other alkali metal ion exchangeable substances←O that have an I bond, can exchange this H with alkali metal ions, and have similar functions.

In addition, examples of halogen ion exchange substances include those having -OH bonds similar to those mentioned above, such as ), idrotalcite (M
#aA12 (OH)+6CO3・4H20), ferric acid,
Hydrous oxides such as zirconic acid and bismuth acid can be mentioned, and these can also be used in combination with the above-mentioned alkali metal ion exchangeable substances. Further, these ion-exchangeable substances may be used alone, in mixtures, or in various forms such as double salts, and can be used appropriately depending on the purpose.

Among the various inorganic ion exchange substances mentioned above, particularly useful ones are antimonic acid and its salts, zirconium phosphate, cerium phosphate, tin phosphate, titanium phosphate, hydrated bismuth oxide, hydrated manganese oxide, and hydrated tin oxide. etc.

The use of such inorganic ion-exchangeable substances is determined by the type and amount of ions to be captured in the protective material, as well as the consideration of other physical properties of the protective material, but usually the proportion of such inorganic ion exchange substances is determined based on the total amount of the protective material. The amount is preferably 40% (wt%; the same applies hereinafter) or less, and 1.5 to 25% is particularly preferable; if this is too small, capturing and fixing the ionic impurities cannot be achieved, and if too much is added. This affects the original sealing effect of the protective material and is also economically unfavorable.

In general, ion exchange is achieved in a system in which a liquid and an ion exchange material are in contact with each other, and is said to be difficult to occur in a solid-solid ion exchange material system. This method causes ion exchange to capture and fix ionic impurities in the protective material, and this brings about great effects as will be clear from the Examples described later.

This is considered to be due to the ion exchange material used in the present invention depending on the target ion, etc.

Among the inorganic ion-exchangeable substances used in the present invention, the cationic ion-exchangeable substance is preferably in the H-form, but may also be in the salt form partially substituted with other metal ions.

This is because inorganic fillers are generally considered to contain alkaline ionic impurities, and because unnecessary metal ion impurities are not increased. When the inorganic ion exchange material is in the monobasic acid form of MO-H+, the ionic impurity AOH is as follows.

MOH1A OH→MOA +H20 Moisture is liberated in this reaction, but this moisture is a protective material and can be removed from the system by heat treatment when protecting electronic elements, etc., and can contribute to improving insulation.

Further, the form of the anion exchange substance is more preferably OI-1 form.

In the present invention, the inorganic ion-exchangeable substance may be used simply in a uniformly mixed state as a protective material composition, or may be used to cover the surface of the inorganic filler.

The present invention will be explained below with reference to Examples and Comparative Examples.

Example 1 and Comparative Example 1 Antimony hexaoxide and stannic chloride were mixed in a side number with an atomic ratio of antimony and tin of 2:1 at a ratio of 4:1 (HCI!:HN
O3) Dissolved in water. Next, add the solution to an acid concentration of 2N to 3N.
The mixture was hydrolyzed to N and heated and aged at 75°C for 8 hours. After this, the product was filtered through a 1μ precision filter,
After thorough washing with water, a composite of antimonic acid and stannic acid was obtained. (Hereinafter, this will be referred to as tin antimonate (2:1)).

Tin antimonate (2:1) was fired at 230°C to remove attached moisture and residual acid.

0.4 g of tin antimonate (2:1) obtained by the above method, 4.0 g of β-eucryptite, 1.9 g of D-cresol novolac type epoxy resin, and 0 imidazole curing agent.
6J in a ball mill (mix, put in a mold press, 1
75℃, 10tJkg/d, 60rnm for 45 minutes
It was hardened and molded into a board measuring 60mm x 2mm thick.

Next, the cured plate was cut out with a knife into a 1 cm x 14 square plate to prepare a sample plate. Take around 2g of this sample, put it in a Pyrex glass container, and add 20ml of water to it.
was injected. This Pyrex glass container was placed in an autoclave at a gauge pressure of 1 m/cri and at 100 to 120°C.
The container was heated under these conditions to elute the alkali metal ions. After cooling, the container was taken out and the alkali metal ions (sodium ions) eluted into the water were analyzed. (Example 1) Separately, a blank test (analysis of sodium, potassium, and lithium ions) was conducted in the same manner without tin antimonate (2:1). (Comparative Example 1) As a result, less than 1/10 of the sodium ions were eluted compared to the case without tin antimonate (2:1) shown in Table 1, and the sodium ions were immobilized in the protective material. That was clear.

Table 1 Example 2 and Example 6 Based on the synthesis of tin antimonate (2:1) in Example 1, antimony trioxide and bismuth trioxide were mixed at a metal atomic ratio of 6:1. Acid complex acid (
Hereinafter referred to as bismuth antimonate (3:1)) was obtained. Example 1 This bismuth antimonate (3:1)
It was washed with water and fired in the same way.

A cured plate was prepared in the same manner as in Example 1, and an elution test was conducted in hot water to examine the elution of sodium and potassium ions (Example 2). Based on the synthesis, the metal atomic ratio of antimony hexaoxide and metal manganese (
3:2), a complex acid of antimonic acid and manganic acid (
Hereinafter referred to as manganese antimonate (RO:2)) was obtained. After washing this manganese antimonate (3:2) with water and firing, a cured plate was prepared in the same manner as in Example 1, and an elution test was conducted in hot water to check the elution of sodium and potassium ions.

(Example 5) The results of Example 2 and Example 6 are shown in Tables 2 and 3 below. Compared to the blank test of Comparative Example 1, sodium and potassium ions were overwhelmingly suppressed. It is clear that it is captured and fixed in the protective material.

Table 2 Table 6 Example 4 Using zirconium carbonate and concentrated phosphoric acid under conditions of excess phosphoric acid,
The reaction mixture was heated, filtered, and washed with water to synthesize zirconium phosphate. The obtained zirconium phosphate was semi-neutralized with NaOH to obtain a neutral form of zirconium phosphate. This compound was thoroughly washed with water and then calcined at 200°C. The resulting neutral form of zirconium phosphate was referred to as ZrNaHP.

Taking this ZrNaHP 0.411, β-eucryptite, epoxy resin,
A cured plate was obtained using the same proportion of the curing agent. Thereafter, a hot water elution test was conducted using the method of Example 1, and sodium and potassium ions were analyzed.

This is shown in Table 4 in comparison with the elution results of sodium and potassium ions in the blank test piece obtained in Comparative Example 1. This shows that both sodium and potassium ions are immobilized.

Table 4 Example 5 Using a method similar to the synthesis method of zirconium phosphate in Example 4, using cerium sulfate, tin tetrachloride, and titanium tetrachloride as raw materials, neutral cerium phosphate, tin phosphate, and titanium phosphate were prepared. The shapes were synthesized. A protective material using these as ion exchange materials was constructed in the same manner as in Example 1, and an alkali metal ion elution test was conducted. The results obtained were almost the same as in Example 4.

Example 6 Potassium pyroantimonate and tin tetrachloride were mixed at a molar ratio of antimony and tin of 1:2.5, and hydrochloric acid was added so that the acid concentration of the aqueous solution was 2 to 3N.
The mixture was heated for 5 hours, and then filtered, washed with water, and dried to obtain a complex of tin antimonate C1:2.3) containing antimonic acid and stannic acid in a 1:2.3 mole ratio.

0.51 of the obtained tin antimonate (1:2.6) was sampled, and 4.5% of the obtained tin antimonate (1:2.6) was collected. Og, novolak type epoxy resin 2.1g, imidazole curing agent 0. !
M was mixed uniformly to prepare a food preservation material composition.

This composition was thermally cured by the method of Example 1, and a hot water elution test was conducted on the prepared plate. The results obtained are shown in Table 5 together with the blank test results (Comparative Example 1) for sodium and lithium ions.The effect was also shown for Li ions.

Table 5 Examples 7 to 9 and Comparative Example 2 Antimony chloride and titanium tetrachloride in a molar ratio of 6:2.5 Antimony chloride and zirconium oxychloride in a molar ratio of 6:2
．． Titanium antimonate (3:2), zirconium antimonate (5:2), and antimonic acid were synthesized using the same method as in Example 1 using antimony pentachloride alone under three conditions. It was made into an androgynous form by adultery.

015g each of the ion exchange material thus obtained
, fused silica 4.5g, O-cresol novolak type epoxy resin 2.1g, imidazole type curing agent 0.
11 was uniformly mixed and cured by the method of Example 1.

(Examples 7 to 9) The same hot water elution test as in Example 1 was conducted on these and the same blank test plate (Comparative Example 2)
The results of the comparison are shown in Table 6.

Claims (1)

[Claims] An insulating protective material comprising at least one component of an inorganic ion exchange substance having an -OH bond.