JPH07142828A - Electronic circuit board - Google Patents

Abstract

PURPOSE:To avoid an electromigration phenomenon without deteriorating the electrical characteristics and curability of board material by a method wherein the specific contents of oxo acid salt of bismuth oxyhydroxide compound and antomonic acid are contained in the material of an electronic circuit board. CONSTITUTION:65-80% of oxo acid salt of bismuth oxyhydroxide compound expressed by formula I and 35-20% of antimonic acid expressed by formula II are contained with the total weight of both materials as a reference value (100%). In the formula I, Y<-a> denotes residue of oxyacid other than nitric acid group and (a) denotes the ion value (absolute value) of the oxyacid residue. Further, (x), (y), (p), (q), (r) and (n) satisfy the formula II and following relations: 1<=x, 1<=y, 0<=n, 0.08x<=p<=0.92x, 0.02x<=aq<=0.92x, 0<=r<=0.2x and 3x=2y+p+aq+r. In the formula II, (m) satisfies a relarion 0<=m.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electronic circuit board having a great effect of preventing an electromigration phenomenon which is a major cause of a short circuit failure of a circuit.

[0002]

2. Description of the Related Art In various printed circuit boards, LSI circuits, pressure film circuits, thin film circuits, capacitors, and other electronic circuit boards, electronic elements, or electronic parts, between insulated metal conductors in the presence of moisture. When a voltage is applied, the metal forming the conductor is ionized, and the surface or inside of the insulating material moves toward the conductor at a negative potential,
The phenomenon of precipitation of metal compounds often occurs in conductors at a negative potential. This phenomenon is called an electromigration phenomenon, and is one of the causes of impairing the reliability of these members and devices, and the thinning of wiring accompanying the recent high integration of electronic elements and electronic components, The frequency of occurrence tends to increase due to the reduction of the wiring interval, the pore formation of the sulfol, and the like.

Metals exhibiting the electromigration phenomenon include silver, gold, copper, tin, lead, platinum, palladium and aluminum, and most of the metals used as conductors of electronic circuits are applicable. Some of these metals ionize and migrate in the presence of water and a voltage is applied, and some of these metals migrate by the addition of impurity ions such as halogen. As a method for preventing such an electromigration phenomenon, the following method has been conventionally tried. Prevents ionization of the conductor metal of the printed wiring board. Generated ions are reduced so that they do not move. The generated ions are insolubilized with a precipitation forming agent. The generated ions are solidified with a chelating agent or a complex forming agent. Deactivates hydroxyl groups on the surface of materials used for manufacturing electronic circuit substrates, electronic elements or electronic components.

Here, the method is a method of alloying the conductive metal of the printed wiring board in order to increase the ionization potential, and there is, for example, a method of replacing silver of the electrode with a silver-palladium alloy. However, in order to obtain a sufficient effect, it is necessary to increase the palladium content, which is expensive. In addition, a method of adding copper to silver and aluminum electrodes has been studied, but a sufficient effect has not been obtained yet. The method is to use aldehyde, hydroquinone, pyrogallo-in the paint applied to the printed wiring board.
However, these additives are chemically unstable and have a drawback that they are easily decomposed by heat or light. This method is a method in which stearic acid, oleic acid, palmitic acid, etc. are added in the same manner as, but in recent years it has been reported that a free organic acid is involved in aluminum wiring corrosion, which is not preferable for mounting. The above method is a method of adding an organic substance such as triazines, benzidine, egg albumin or the like which forms a chelate or a complex. However, most of the functional groups of these compounds are decomposed and deactivated when the temperature exceeds 100 ° C. Therefore, although there is no problem under normal use conditions, it is sufficient that the internal environment will exceed 100 ° C due to internal heat generation due to high integration, or the operating environment itself will exceed 100 ° C for automobiles that are expected to become increasingly electronic. As expected, there are limits to the future use of chelating and complexing agents. Method is a method of treating glass fiber, which is a material of the laminated plate, and quartz used as a filler added to the paint with a silane coupling agent, but it is a partial measure and can be said to be sufficient. Absent.

The failure mode due to the electromigration phenomenon occurs in the presence of moisture (for example,
(Observed in silver, gold, lead, etc.) and in the presence of moisture and halogen (for example, observed in gold, silver, palladium, copper, etc.). Is believed to progress. (a) [Electromigration phenomenon occurring in the presence of water] Dissociation of water (H ₂ O → H ⁺ + OH ⁻ ) Oxidative dissolution of metal (anode) (2M + H ₂ O → M ₂ O + H
₂ ) Dissociation (migration) of oxide (M ₂ O + H ₂ O → 2MOH
→ 2M ^{+ +} 2OH ^-) deposition ^{(cathode) (M + + e - →} M) (b) dissociation of water [water and electromigration phenomenon occurs in the presence of halogen] ^{_{(H 2 O → H + +}} OH -) of metal oxide dissolution ^{(anode) (M + Cl - → MCl} +
e ⁻ ) Dissociation (migration) of metal halide (MCl → M ⁺ + C
l ⁻ ) Precipitation (cathode) (M ⁺ + e ⁻ → M) In the above (a) and (b), M is a monovalent metal such as silver is shown, but other metals undergo similar mechanism. It is estimated that In this way, the deposited metal becomes dendritic,
It grows from the cathode toward the anode, and eventually short-circuits so that a current flows between both electrodes. It should be noted that the short circuit here is not limited to the case where both electrodes are directly connected, but a current flows even if both electrodes are close to each other and the number of carriers (ions or holes) having a charge as a conductive substance increases. Is also a short circuit [generally a current of about 300 μA flows (10 ⁶ Ω
When the resistance value is below), it is called a short circuit. ].

The present inventors have previously proposed to prevent the occurrence of the electromigration phenomenon by incorporating an inorganic ion exchanger having an —OH group into a substrate for electronic circuits (Japanese Patent Laid-Open No. 63-45703). . This method involves the migration of an ionic metal ion, such as A
OH for g ⁺ , Cu ⁺ , Cu ²⁺ , Pb ²⁺ , Sn ²⁺ , Au ³⁺
Inorganic anion having an OH group that has a high selective ion adsorption capacity for halogen ion and other impurity ions that promotes ionization by immobilizing them on an inorganic cation exchanger having a group to prevent migration and further promote ionization. It is to be captured by the ion exchanger.

Further, although the present inventors have different technical fields,
By proposing an epoxy resin composition for semiconductor encapsulation, which comprises a bismuth oxyhydroxy oxyacid compound, which is one of the inorganic ion exchangers represented by the following general formula, and by compounding this compound with an epoxy resin, The aluminum composition is prevented from corroding and sealed with the resin composition without reducing the volume resistivity of the resin composition or increasing the electrical conductivity of hot water extracted water of the resin composition. It has been shown that the humidity resistance reliability of the stopped device can be improved (JP-A-2-2).
94354). The electric conductivity of hot water extracted water indicates the concentration of ionic impurities in the epoxy resin composition for semiconductor encapsulation, and the smaller this value is, the smaller the leak current of the encapsulated semiconductor is. Bix Oy (OH) p (Y -a) q (NO 3) r · nH 2
O (however, Y ^-a represents an oxyacid residue other than a nitrate group,
Indicates the ionic value (absolute value) of the oxyacid residue. or,
x, y, p, q, r and n are values satisfying the following formulas. 1 ≦ x, 1 ≦ y, 0 ≦ n, 0.08x ≦ p ≦ 0.9
2x, 0.02x ≦ aq ≦ 0.92x, 0 ≦ r ≦ 0.1
x, 3x = 2y + p + aq + r)

[0008]

As described above, the present inventors have shown that it is possible to prevent the occurrence of electromigration phenomenon in an electronic circuit substrate containing an inorganic ion exchanger having an --OH group. However, as a result of subsequent studies, it has the ability to trap the migrating metal ionized substance, but it will reduce the electrical characteristics (volume resistivity, etc.) of the substrate material and increase the electrical conductivity of hot water extraction water. In some cases, the curability of a substrate material such as an epoxy resin used for a thermosetting resin laminated substrate may be hindered.

The present invention solves the above problems and provides an electronic circuit substrate which prevents the occurrence of the electromigration phenomenon without impairing the electrical characteristics and curability of the substrate material.

[0010]

SUMMARY OF THE INVENTION The present inventors have proposed an inorganic ion exchanger to be contained in a substrate material used in an electronic circuit, which has an electromigration preventing effect, electric characteristics of the substrate material, and thermosetting which constitutes the substrate. As a result of a detailed study on the curability of a conductive material, in order to obtain an electronic circuit substrate that solves the above problems, the bismuth oxyhydroxylated oxyacid compound represented by the following formula [1] and the following formula [2] are used. It has been found that it is extremely effective to contain the antimonic acid shown in the electronic circuit substrate in a specific ratio, and the present invention has been completed. That is, the present invention is based on the total weight of the bismuth oxyhydroxy oxyate compound represented by the following formula [1] and the antimonic acid represented by the following formula [2]. Is contained in 35 to 20%. Bix Oy (OH) p (Y -a) q (NO 3) r · nH 2 O (1) (where, Y ^-a represents an oxy acid residue other than nitric acid radical, a
Indicates the ionic value (absolute value) of the oxyacid residue. or,
x, y, p, q, r and n are values satisfying the following formulas. 1 ≦ x, 1 ≦ y, 0 ≦ n, 0.08x ≦ p ≦ 0.9
2x, 0.02x ≤ aq ≤ 0.92x, 0 ≤ r ≤ 0.2
x, 3x = 2y + p + aq + r) Sb ₂ O ₅ · mH ₂ O [2] (where m is a number satisfying 0 ≦ m).

The present invention will be described in detail below. Bismuth oxyhydroxide bismuth oxyacid compound The bismuth oxyhydroxide oxymuth compound used in the present invention is an inorganic anion exchanger represented by the above general formula [1], and an oxyacid residue ( Y) is represented by a unit obtained by removing a hydrogen atom from an oxyacid other than nitric acid,
As an oxyacid other than nitric acid, if it contains oxygen atoms and dissociates hydrogen ions in an aqueous solution to anionize,
The type does not matter. Preferred specific examples of the oxyacid include, for example, carbonic acid, bicarbonate, metasilicic acid, orthosilicic acid, metaboric acid, orthoboric acid, phosphoric acid, carboxylic acid such as oxalic acid, and a compound or a combination of two or more thereof. is there. Among the above oxyacids, because of good electrical properties such as electrical insulation when contained in the electronic circuit substrate,
Carbonic acid, bicarbonate, metasilicic acid, orthosilicic acid, metaboric acid, orthoboric acid and the like are preferable, and further, metasilicic acid and orthosilicic acid are particularly preferable since they have low electric conductivity in hot water extraction.

In the above formula [1], when r is large, the conductivity of hot water extraction water is increased and the electric characteristics are deteriorated. Therefore, the range of r is 0 ≦ r ≦ 0.2x. More preferably 0 ≦
The range is r ≦ 0.08x. Also, p is large and a
If q is too small, the halogen ion scavenging ability is lowered. Conversely, if p is too small and aq is too large, the volume resistivity of the bismuth compound in the present invention tends to be lowered.
The ranges of p and aq are 0.08x ≦ p ≦ 0.92x and 0.02x ≦ aq ≦ 0.92x, and more preferably 0.
5x ≦ p ≦ 0.92x and 0.08x ≦ aq ≦ 0.5x
Is the range.

The bismuth oxyhydroxy oxyacid compound used in the present invention can be easily produced, for example, by the following method. That is, an aqueous alkali solution such as sodium hydroxide is added to the aqueous bismuth nitrate solution to generate bismuth oxynitrate. Then, the target product can be obtained by adding an aqueous solution of an alkali metal salt of oxyacid and substituting a target ratio of the nitric acid group with the oxyacid and the hydroxyl group.

Antimonic Acid Antimonic acid in the present invention is an inorganic cation exchanger represented by the following general formula [2], and is a known compound for which various production methods are known. Sb ₂ O ₅ · mH ₂ O [2] (where m is a number satisfying 0 ≦ m) In the present invention, in order to exert high hydrothermal stability on the substrate material for electronic circuits, space is required. It is more desirable to use crystalline antimonic acid having the crystal structure of group Fd3m.

Compounding ratio of bismuth oxyhydroxy oxyacid compound and antimonic acid In the present invention, the compounding ratio of the bismuth oxyhydroxy oxyacid compound [1] and antimonic acid [2] is [1] and [2]. [1] is 65-80 based on the total weight
%, [2] should be 35 to 20%, preferably [1] should be 68 to 75%, and [2] should be 32 to 25%. When [2] is more than 35% ([1] is less than 65%), since antimonic acid is a solid electrolyte having ion conductivity, the volume resistivity of itself is very low.
It impairs electrical properties such as electrical insulation of the electronic circuit board. In addition, since antimonic acid has a strong action as an acid, it also has an adverse effect of impairing the curability of the thermosetting resin used in the electronic circuit board material.

On the other hand, [2] is less than 20% ([1]
Is more than 80%), there is a problem that the ability to capture the ionized substance of the conductor metal is lowered, and a sufficient effect of preventing electromigration cannot be exhibited.

Electronic Circuit Board Material In the present invention, the electronic circuit board to which the bismuth oxyhydroxyoxyacid oxy compound and antimonic acid are contained is a board for a printed wiring board or a hybrid IC.
The substrate for use may be an ordinary one used in the field of electronic materials, for example, a thermosetting resin laminated substrate (paper-epoxy resin, paper-phenol resin, glass-epoxy resin,
Non-woven fabric-phenolic resin, non-woven fabric-epoxy resin, etc.),
Ceramic substrates (alumina, silicon carbide, etc.), thermoplastic resin substrates (polyester resin, polyphenylene sulfide resin, polyether sulfone resin, etc.), other polyolefin resin substrates, fluororesin substrates and heat resistance that require high frequency characteristics Polyimide resin substrate,
Examples include modified polyimide resin laminated boards, triazine resin boards, metal core printed boards requiring heat dissipation, and multilayer boards of these. The method of adding the inorganic ion exchanger in the present invention may be a general method, for example, dispersion in the resin constituting the substrate, impregnation of paper as a substrate constituting the substrate,
Examples thereof include coating on a glass cloth or the like, dispersion in a copper-clad adhesive, and coating on a substrate surface.

Method of Incorporating Inorganic Ion Exchanger in Electronic Circuit Substrate If the bismuth oxyhydroxyoxyoxy compound and antimonic acid are blended in the above specific ratios, these inorganic ion exchangers for electronic circuits can be used. The amount contained in the substrate is not particularly limited, but is 0.
1 to 25% by weight (hereinafter simply referred to as%) is preferable,
More preferably, it is 0.1 to 10%. When the adhesive for adhering the electronic circuit substrate and the metal thin film to be the electrode is contained, the content of the adhesive is preferably 0.1 to 15%, more preferably 0.1 to 10%. is there.

It is desirable that the particle size of the inorganic ion exchanger is small in order to increase the ion trapping speed and the probability of contact with the target trapped ions, and the preferable average particle diameter is 10
It is at most 5 μm, more preferably at most 5 μm.

[0020]

The functions of the bismuth oxyhydroxy oxyacid compound and antimonic acid contained in the electronic circuit substrate of the present invention as described above have the following effects without impairing the electrical characteristics such as the insulation resistance of the substrate material. It is to express. An action that captures and fixes the ionized metal ion to prevent migration. The function of capturing and fixing impurity ions such as halogen atoms that promote ionization and deactivating them. In the development of the electronic circuit substrate proposed in Japanese Patent Laid-Open No. 63-45703, the present inventors have proposed an electromigration phenomenon when an inorganic cation exchanger for trapping and fixing an ionized metal is used as a main component. It was thought that good results could be obtained, but as described above, antimonic acid was used as the inorganic cation exchanger that plays a role of capturing and fixing the metal ionized product, and impurity ions such as halogen atoms When a bismuth oxyhydroxyoxyoxy compound is used as the inorganic anion exchanger to be trapped and fixed, the inorganic cation exchanger is as small as 35 to 20%, and the inorganic anion exchanger is as much as 65 to 80%. It is truly surprising that the body-containing electronic circuit substrate can exert a sufficient migration preventing effect.

[0021]

EXAMPLES AND COMPARATIVE EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. First, various bismuth oxyhydroxyoxyoxy compounds were obtained as follows. [Reference Example 1] Bismuth nitrate pentahydrate [Bi (NO ₃ ) ₃
.5H ₂ O] aqueous solution [Bi (NO ₃ ) 3 .5H ₂ O conversion 51.1%, containing 5.2% free nitric acid] 285 g
Then, 33.3 g of 15% NaOH solution was added at a rate of 15 ml / min using a metering pump while maintaining the reaction temperature at 25 ° C. The slurry generated is divided into three equal parts (A, B, C
15% Na ₂ SiO ₃ · 9 for A
377.3 g of H ₂ O aqueous solution, 566 g of the same aqueous solution for B and 754 g of the same aqueous solution for C were added at a rate of 10 ml / min using a metering pump. After the addition was completed, each was stirred for 30 minutes, and then No. 2 Filtered with filter paper and washed with distilled water. This was placed in a box dryer and dried at 110 ° C. for 15 hours. Then, it was crushed with a table crusher to obtain the following bismuth compounds A to C. Bismuth compounds _{A:... Bi 6 O} 6 (OH) 3 9 (NO 3) 0 89 (HSiO 3) 1 21
· 0.98H ₂ O bismuth compound _{B:... Bi 6 O} 6 (OH) 4 9 (NO 3) 0 38 (HSiO 3) 0 72
· 0.97H ₂ O bismuth compound _{C:... Bi 6 O} 6 (OH) 5 2 (NO 3) 0 23 (HSiO 3) 0 53
・ 0.98H ₂ O

[Reference Example 2] 15% Na was added to 760 g of the same aqueous solution of bismuth nitrate pentahydrate as used in Reference Example 1.
204.4 ml of 814.4 g of OH solution was measured using a metering pump.
It was added at a rate of min while maintaining the reaction temperature at 25 ° C. The produced slurry is divided into four equal parts (referred to as D, E, F, G), and for D and E, distilled water is added to the slurry,
Decantation was performed 3 times. After decantation, for D, 1N-NaHCO ₃ aqueous solution 41.0
Similarly, for g and E, 52.8 g was added and the mixture was stirred overnight at room temperature. For F and G, decantation was not performed, and after the addition of the NaOH aqueous solution was completed, 1N-Na was continuously added.
Was stirred overnight at HCO ₃ solution was added 41.0g and 52.8g, respectively cold. After completion of stirring for each, No. 2 Filtered with filter paper and washed with distilled water. This was placed in a box dryer and dried at 110 ° C. for 15 hours. Then, it was crushed with a table crusher to obtain the following bismuth compounds D to G. Bismuth compounds _{D:... Bi 6 O} 6 (OH) 3 10 (NO 3) 0 25 (HCO 3) 2 65
· 0.68H ₂ O bismuth compound _{E:. Bi 6 O 6 (} OH) 3 00 (HCO 3) 3 00 · 0.76H 2 O bismuth compound _{F:.. Bi 6 O 6} (OH) 3 62 (NO 3) 0 _{. 68 (HCO 3) 1.} 70
· 0.74H ₂ O bismuth compound _{G:... Bi 6 O} 6 (OH) 3 13 (NO 3) 0 52 (HCO 3) 2 35
・ 0.62H ₂ O

Reference Example 3 In Reference Example 2, NaHC
O ₃ in place of the aqueous solution, except for using 1N-NaBO ₂ · 4H ₂ O aqueous solution 52.8 g, to obtain a bismuth compound H having the following composition in the same manner as G in Reference Example 2. Bismuth compounds _{H:.. Bi 6 O 6} (OH) 5 3 (H 2 BO 3) 0 7 · 0.9H 2 O

[Examples 1 to 5 and Comparative Examples 1 to 7] Bismuth oxyhydroxy oxyacid compounds obtained in Reference Examples 1 to 3 [component (a) in Tables 1 and 2 below] and antimonic acid [ The composition formula is Sb ₂ O ₅ .2H ₂ O, and Table 1 below.
And the component (ii) in Table 2] were mixed at the weight ratios shown in Tables 1 and 2 below, and various measurements shown below in the evaluation methods were performed. The result is
The results are shown in Tables 1 and 2 below.・ Hot water extraction test: powder 1.
0 g and 100 ml of pure water were put in a 250 ml polyethylene bottle, left at 95 ° C. for 15 hours and then filtered, and the electric conductivity (unit: μS / cm) of the filtrate was measured.・ Volume resistivity: Pellets (13
mmφ × 2 mm ^t ) (1 at 400 kg / cm ²
After pressurizing for a minute), a silver paste was applied, an electrode was formed, and then measured with a high insulation resistance measuring device. The bismuth oxyhydroxy oxyacid compounds used in the test are as follows. : Bismuth compound of Reference Example 1 C: bismuth compound of Reference Example 2 D: bismuth compound of Reference Example _{3 H:.. Bi 6 O} 6 (OH) 4 2 (NO 3) 1 8 · 0.9H 2 O

[0025]

[Table 1]

[0026]

[Table 2]

From the results of Examples 1 to 5, when the bismuth oxyhydroxy oxyacid compound and antimonic acid were blended in a specific ratio in the present invention, the hot water extraction water conductivity was low and the volume resistance of the powder was low. Since the rate is high, it has been suggested that inclusion of this in an electronic circuit board or the like does not impair electrical properties such as electrical insulation. On the other hand, in Comparative Examples 1 to 8, the electric conductivity of hot water extraction is high and the volume resistivity of the powder is small, so that the electronic circuit board materials containing these powders have poor electrical characteristics, particularly electrical insulation. Is suggested.

[Examples 6 to 9 and Comparative Example 9] The inorganic ion exchanger (hereinafter, simply referred to as inorganic ion exchanger) composed of the bismuth oxyhydroxyoxyacid compound and antimonic acid used in Example 1 was used as a phenol resin 100. 0, 1, 5, 10 or 20 with respect to parts by weight (hereinafter simply referred to as parts)
Partial mixing was performed to obtain 5 kinds of resin liquid. These resin solutions were individually impregnated into kraft paper (NKP-150 manufactured by Tomoegawa Paper Co., Ltd.) which had been dried in a desiccator in advance. By stacking 6 sheets impregnated with a resin liquid having the same content ratio of the inorganic ion exchanger and pressurizing at 120 ° C., the volume percentage of paper and resin is 6%.
At 0:40, five types of paper-phenol resin laminated substrates having a thickness of about 1.66 mm were obtained. Separately, silver powder 100
Part, 43 parts of a resole type phenolic resin and 40 parts of a solvent (butyl carbitol) are added together, and 3 rolls make 10
After kneading for a minute, a silver paste was prepared. This paste was applied by screen printing to the previously prepared five types of laminated substrates and heat-cured at 180 ° C. for 1 hour to form two facing comb-shaped printed wirings as shown in FIG. A conductor (electrode) was formed. As shown in FIG. 1, the shortest distance between the electrodes is 1 mm and the thickness is about 20 μm. In order to evaluate the effect of preventing the occurrence of the electromigration phenomenon, a DC voltage of 100 V was applied between the two comb-shaped electrodes shown in FIG. 1, and the insulation resistance value between the electrodes was maintained at 40 ° C. and 95% RH. There was measured as the time which led to short-circuit the l0 ⁶ Ω or less and the summer was time. The results are shown in Table 3.

[0029]

[Table 3]

[Examples 10 to 14 and Comparative Example 10] The inorganic ion exchanger used in Example 1 was JIS K6915-PM.
-For 100 parts of phenol resin corresponding to EG material,
Six kinds of resin liquids were obtained by mixing 0, 0.5, 1, 5, 10, or 25 parts. Each of these individually 20mm × 20mm ×
165 ℃, 300kg / cm ² , 120 for 2mm contour
Transfer molding was performed under the condition of seconds to obtain 6 types of substrates.
The same silver paste as in Example 6 was used for these six types of substrates, and conductors (electrodes) printed with the same conditions as in Example 6 were prepared. A DC voltage of 100 V was applied between the electrodes, the temperature was kept at 85 ° C. and 95% RH, and the time to the short circuit was measured in the same manner as in Example 6. The results are shown in Table 4.

[0031]

[Table 4]

[Examples 15-18, Comparative Examples 11-12]
43 parts of a resol-type phenol resin, 100 parts of copper powder and 40 parts of a solvent (butyl carbitol) were added and kneaded with a three-roll for 10 minutes to prepare a copper paste. This copper paste was used in Examples 6, 7, 11, and 12 and Comparative Example 9,
Substrate used in No. 10 (In Table 5, the type of substrate is shown by Example No. or Comparative Example No. in parentheses)
Then, screen printing was performed under the same conditions as in Example 6 to prepare a printed wiring conductor (electrode). A DC voltage of 500 V is applied between these electrodes, and at 95 ° C, 90%
The time at which a short circuit was reached was measured in the same manner as in Example 6 while maintaining RH. The results are shown in Table 5.

[0033]

[Table 5]

[Examples 19 and 20, Comparative Example 13] The inorganic ion exchanger used in Example 1 was prepared with epoxy equivalent of 450-
To 100 parts of 500 bisphenol A type epoxy resin, 0, 1 or 5 parts was added, and further 4 parts of dicyandiamide as an epoxy curing agent, 0.4 parts of benzyldimethylamine as a reaction accelerator, and a solvent (methyl ethyl ketone) 6
Three parts of resin varnish for impregnation were prepared by adding 0 parts of each and stirring and mixing. Next, a 0.2 mm-thick low-alkali glass cloth for electrical use was impregnated with the resin varnish prepared above.
Then, it was dried at 160 ° C. for 5 minutes to prepare a prepreg. These prepregs were cut into a size of 50 mm x 50 mm, and six sheets having the same content ratio of the inorganic ion exchangers were stacked, and the initial condition was 30 kg / cm ² , 16
0 ℃, 15 minutes, then 70kg / cm ² , 165 ℃
By hot pressing for 1 hour, three kinds of laminated plates having a volume fraction of the resin and the glass cloth substrate of 50:50 and a thickness of about 1.6 mm were obtained. Silver paste (Dotite XA208 manufactured by Fujikura Kasei Co., Ltd.) was used for these three types of laminated plates,
Screen printing was carried out in the same manner as in Example 6, and the temperature was 130 ° C.
And was cured by heating for 1 hour to form a printed wiring conductor (electrode) having the same pattern as in FIG. As shown in FIG. 1, the shortest distance between the electrodes is 1 mm and the thickness is about 20 mm.
is μ. A DC voltage of 100 V was applied between the electrodes, the temperature was kept at 40 ° C. and 95% RH, and the time to reach a short circuit was measured in the same manner as in Example 6. The results are shown in Table 6.

[0035]

[Table 6]

[Examples 21 to 22 and Comparative Example 14] The inorganic ion exchanger used in Example 1 was prepared by using 1.5 parts of Coronate AP Stable (manufactured by Nippon Polyurethane Co., Ltd.) and Curesol 2PZCM (manufactured by Shikoku Kasei Co., Ltd.). ) 1.5 parts, 62 parts of polyvinyl formal resin (residual hydroxyl group 17%, polymerization degree of 1200) 62 parts, bisphenol A type epoxy resin (epoxy equivalent 450-500) 35 parts and solvent (methyl ethyl ketone) 500 parts copper clad laminate An adhesive containing an inorganic ion exchanger was prepared by adding it to the copper clad adhesive for plates. Apply these adhesives to 0.035mm copper foil,
I did a dry operation. JISK6912-PL-PEM-P paper-based phenol resin laminate (thickness: 1.6 mm) and the above-mentioned copper foil were adhered by a hot press method to obtain three types of copper-clad laminate. A commercially available etching resist was coated on the copper surface of this laminate and etched with an iron chloride solution to form a printed wiring conductor (electrode) having the same pattern as in FIG.
Applying a DC voltage of 500 V between these electrodes,
The time to reach a short circuit was measured in the same manner as in Example 6 while maintaining the temperature at 5 ° C. and 90% RH. The results are shown in Table 7.

[0037]

[Table 7]

[0038]

When the electronic circuit board substrate of the present invention is used,
It is possible to prevent a short circuit of the electronic circuit board and an electromigration phenomenon which is a problem as a cause of failure of electronic components and electronic elements mounted on the board without impairing the electrical characteristics of the electronic circuit board.

[Brief description of drawings]

FIG. 1 is a pattern of printed wiring conductors (electrodes) used in an embodiment of the present invention. Here, the shortest distance between the electrodes is 1 mm in each case. A, B ...... Terminal parts (A, B) for connecting to an external power supply
Is + for one and-for the other. )

Claims (1)

[Claims] 1. A bismuth oxyhydroxy oxyacid compound represented by the following formula [1] and an antimonic acid represented by the following formula [2] are used, the former of which is 65 to 80 based on the total weight of both.
%, The latter is contained in a proportion of 35 to 20%. Bix Oy (OH) p (Y) q (NO ₃ ) r · nH ₂ O [1] (wherein Y represents an oxyacid residue having an ionic valency a other than the nitrate group. Also, x, y , P, q, r and n are values satisfying the following formulas: 1 ≦ x, 1 ≦ y, 0 ≦ n, 0.
08x ≦ p ≦ 0.92x, 0.02x ≦ aq ≦ 0.92
x, 0 ≦ r ≦ 0.2x, 3x = 2y + p + aq + r) Sb ₂ O ₅ · mH ₂ O [2] (where m is a number satisfying 0 ≦ m).