JPH05330958A - Glass composition for forming metallizing primer layer - Google Patents

Abstract

PURPOSE:To enable firm bonding of a ceramic plate to an electrically conductive layer. CONSTITUTION:The glass composition for forming a metallizing primer layer is composed of (A) 4-80wt.% of SiO2, (B) 1-40wt.% of B2O3 and (C) 1-80wt.% of at least one kind of and Mn; R<4> is Al and/or Bi). A glass layer is formed on the surface of a ceramic plate by the use of the glass composition and the surface of the layer is metallized to form an electrically conductive layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass composition useful for forming an underlayer when metallizing ceramics.

[0002]

2. Description of the Related Art A ceramic substrate has a conductor layer formed on a ceramic plate and has excellent heat resistance and discharge properties and low thermal expansion properties.

As a method for producing a ceramic substrate, the following method is used. (1) A method of plating a ceramic plate after etching it with hydrofluoric acid, nitric acid or the like. (2) A powder of refractory metal such as Mo and W is applied onto a ceramic plate and subjected to a high temperature treatment in a nitrogen atmosphere (1500 to 18).
00 ° C) method.

(3) A so-called thick film in which a noble metal powder such as Au, Ag and Pt or a highly conductive base metal powder such as Cu, Ni and Al and a binder component such as a low melting point glass frit are mixed and dispersed in an organic vehicle. A method in which a conductive paste is applied on ceramics and heated and baked.

(4) A method in which a copper plate having a predetermined shape is placed on ceramics and thermocompression bonded at 1100 to 1500 ° C. in a nitrogen atmosphere.

However, each of these methods has the following problems, and none of them can be said to be mature techniques when considering industrial implementation.

In the method (1), the bonding strength is not constant depending on the quality of the ceramic plate, and in the case of ceramics having high chemical resistance, effective etching is difficult and high bonding strength cannot be obtained. ..

The method (2) has a high bonding strength of the conductor layer, but has a drawback of low productivity because it requires high temperature and atmosphere control. Further, there is a drawback that a plating process is required because soldering cannot be performed directly, and the electrical conductor has high resistance.

In the method (3), the cost is high when a noble metal is used, and there is a problem of migration when it is used as an electric conductor. Further, when a base metal is used, it is necessary to adjust the atmosphere during heating, and the treatment is complicated.

In the method (4), the operation is complicated because it is necessary to adjust the atmosphere at the time of heating, and the copper plate needs to have a thickness of about 0.2 to 0.3 mm or more. However, the patterning accuracy is poor.

As one of the effective means for solving such a problem, the inventor of the present invention forms a glass layer having relatively good adhesiveness to a conductor on the surface of a ceramic plate to be metallized to form a ceramic. We have been investigating according to the prediction that a method of improving the bonding strength between the plate and the conductor layer would be effective. So far, we have found what is superior as a glass for treating the surface of the ceramic plate. Had not reached.

[0012]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a glass suitable as a raw material for a glass for forming a metallized underlayer for improving the bonding strength between a ceramics plate and a conductor layer when producing a ceramics substrate. To provide a composition.

[0013]

Means for Solving the Problems As a result of earnest research to solve the above problems, the present inventor has found that SiO ₂
When a specific metal oxide powder is further added to the glass composition of the powder and the B ₂ O ₃ powder, the property of improving the bonding strength between the ceramic and the conductor layer (metal) (hereinafter,
It is called the bond strength property. ), The present invention was completed.

That is, according to the present invention, (a) SiO ₂ content is 4 to 80% by weight, (b) B ₂ O ₃ content is 1 to 40% by weight, (c) (R ¹ ) ₂ O content, (R ² ) O minutes, (R ³ ) O ₂
And at least one content of (R ⁴ ) ₂ O ₃ of 1 to 8
0% by weight (provided that R ¹ is at least ^one of Li, Na and K, and R ² is Mg, Ca, Ba, Zn, Cd
And Pb, and R ³ is Ti or Zr.
And Mn, and R ⁴ is Al and / or Bi. ) Is a glass composition for forming a metallized underlayer.

The present invention will be described in detail below.

The glass composition of the present invention contains, as an essential component,
SiO₂Minutes, B₂O₃Minutes and (R¹) ₂O minutes, (R²) O
Minutes, (R³) O₂Minutes and (R^Four)_FourO₃From the group of minutes
One or more selected ingredients (hereinafter R¹, R², R³and
R^FourIngredients containing are collectively referred to as R ingredient. However, R¹Is
At least one of Li, Na and K, and R²Is M
at least one of g, Ca, Ba, Zn, Cd and Pb
Seed and R³Is at least 1 of Ti, Zr and Mn
Seed and R^FourIs Al and / or Bi. ) Included
It is a waste.

The content of each component is such that the SiO ₂ content is 4 to 80.
% By weight, preferably 20 to 80% by weight, B ₂ O ₃ content is 1 to 40% by weight, preferably 5 to 20% by weight, and R component is 1 to 80% by weight, preferably 10 to 70% by weight. ..

The R component is effective even if used alone, but it is preferable to use two or more kinds in combination. Specifically, (R ²⁾ O minutes (R ⁴⁾ ₂ obtained by combination of two kinds of the O ₃ minutes, (R ¹⁾ ₂ O fraction, (R ²⁾ O content and (R ³⁾ O
_A combination of three types of _two minutes has excellent properties. Also, for each of (R ¹ ) ₂ O, (R ² ) O, (R ³ ) O ₂ and (R ⁴ ) ₂ O ₃ minutes, one kind may be used alone, or 2 You may use together 1 or more types.

It should be noted that, if the content of the R component is too large or too small, the bonding strength characteristics are deteriorated, and if the balance between the content of SiO _{2 and} the content of other components is poor, it is applied to a ceramic plate. When heated later, it becomes difficult to vitrify and the use characteristics deteriorate. Also, 30% by weight or less, preferably 1
If it is 0% by weight or less, components other than the essential components can be contained, but from the viewpoint of bonding strength characteristics, it is preferable that the content of the components other than the essential components is small, and each of the essential components is as pure as possible. Is better to use.

The glass composition of the present invention is applied to the surface of ceramics and is usually used in the form of powder. When using the glass composition of the present invention as a powder,
The particle size is not particularly limited, but a small particle size is preferable from the viewpoint of bonding strength characteristics, and specifically, a particle size in the range of 0.1 to 100 μm, preferably 0.1 to 50 μm. Are suitable.

The method for producing the glass composition of the present invention in a powder form is not particularly limited, but for example, a method of mixing powders obtained by pulverizing each of the components individually and mixing them at an appropriate ratio, two components Examples include a method of mixing and pulverizing the above and blending powders of the remaining components as needed, a method of blending two or more components and heating and melting, and then pulverizing and blending powders of the remaining components as necessary. You can

However, in view of forming a uniform glass layer, a glass composition produced by a method of blending several components, heating and melting, pulverizing, and blending the powder of the remaining components is excellent. ing. Further, in the case of using the product manufactured in this way, the heating temperature when forming the glass layer by heating and melting after coating on the ceramics can be lowered.

Various commonly used mills, for example, ball mills can be used to grind each component, and a generally used mixer, liquor machine or the like can be appropriately selected in addition to the mill for blending each component. Can be used. In addition, in order to adjust the particle size of each component, it is effective to classify by crushing and then sorting.

There are no particular restrictions on the ceramics for which it is effective to form a metallization base layer with the glass composition of the present invention. For example, ceramic materials having a heat-resistant temperature of 500 ° C. or higher are used, and the dielectric constant, insulating property, and dielectric loss tangent are selected. It can be appropriately selected according to the purpose of use in consideration of the characteristics required for a ceramic substrate such as. Specifically, alumina, zirconia, beryllia, mullite, forsterite, cordierite, lead titanate, barium titanate,
Examples thereof include oxide-based ceramics such as lead zirconate titanate and non-oxide-based ceramics such as silicon nitride and aluminum nitride.

A method for producing a ceramic substrate and a method for forming a circuit pattern will be described below as specific examples of the method of using the glass composition of the present invention.

First, the glass composition of the present invention is applied to a ceramic plate to be metallized. The coating method is not particularly limited, but representative examples include (1) a method of directly coating a powdery glass composition, (2) a method of spraying a powdery glass composition, and (3) a powdery glass. Examples thereof include a method in which the composition is dispersed in a solvent and spray coating, and (4) a method in which the powdery glass composition is dispersed in an organic vehicle and applied.

However, the method in which the glass composition is dispersed in an organic vehicle and applied is excellent in that the thickness of the coating film can be easily adjusted. Examples of the organic vehicle used at this time include those obtained by dissolving an organic polymer compound such as ethyl cellulose resin and acrylic resin in an organic solvent such as isopropyl alcohol, pine oil and butyl carbitol acetate. As a method of applying a dispersion liquid in which a glass composition is dispersed in an organic vehicle,
For example, brush painting, screen printing and spray painting can be mentioned.

The coating amount of the glass composition is usually 0.0
It is preferably about 05 to ² g / cm ² .

Next, the glass composition applied on the ceramic plate is heated and melted to form a glass layer. The heating temperature at this time is preferably about 500 to 1500 ° C., and the heating time is preferably about 3 to 60 minutes. The atmosphere during heating is not particularly limited, and may be, for example, an atmosphere of air, nitrogen gas, hydrogen gas, argon gas, or the like.

Then, the ceramic plate having the glass layer formed on the surface is cooled to room temperature, and then metallized on the glass layer to form a metal film. As a method for forming a metal film, (1) plating method, (2) vapor deposition method,
(3) There may be mentioned ordinary methods such as sputtering method,
Any of these may be performed according to a conventional method.

Examples of the method (1) include a method of depositing a catalyst substance and then performing electroless nickel plating or electroless copper plating. At this time, the catalyst deposition method may be a conventional method, for example, a two-step method of imparting sensitivity and catalyst, or a method of printing and firing a catalyst paste. The type of plating film to be formed may be the same as that of a ceramic substrate produced by a conventional plating method. For example, in addition to a single film of electroless nickel plating film or electroless copper plating film, The thing which formed the thick metal layer by performing electrolytic copper plating on the above can be mentioned.

(2) The vapor deposition method may be an ordinary vacuum vapor deposition method, for example, a method of forming a metal film on the glass layer by heating and evaporating a metal such as copper in a high vacuum. .. At this time, the metal to be deposited is not particularly limited as long as it can be deposited, and for example, gold, silver,
Copper, nickel, etc. can be mentioned.

(3) As the sputtering method, for example, 10
There may be mentioned a method of causing a glow discharge in a vacuum of about ⁻¹ to 10 ⁻³ Torr and accelerating impact of cations on the cathode by cathode fall to form a metal film on the glass layer. At this time, as the metal to be sputtered, for example,
Examples thereof include gold, copper, nickel, platinum, molybdenum and the like.

The method of forming the circuit pattern on the ceramics substrate may be the same as that of the conventional ceramics substrate prepared by metallizing by a plating method. For example, a so-called subtractive method may be adopted in which a ceramic substrate is once manufactured, and then an etching resist is printed on the metal film to form a circuit pattern by etching. When the metal film is formed by the plating method, Alternatively, a so-called additive method may be employed in which a required circuit pattern is formed by a plating resist after applying a catalyst for electroless plating on the glass layer and then directly formed by electrolytic plating.

[0035]

The glass composition of the present invention forms a glass layer as a base of metallization by heating while being applied on a ceramic plate. According to the knowledge of the present inventor, the glass layer of the present invention is formed. 0.1 to 1 on the surface of
There is unevenness of about 00 μm, and due to the effect of this unevenness,
It is considered that the bonding strength between the metallized metal and the ceramic plate is significantly improved.

[0036]

【Example】

Example 1 139 g of SiO ₂ powder having a particle size of about 30 μm and a particle size of about 2
28 g of 0 μm B ₂ O ₃ powder, CaO with a particle size of about 10 μm
14 g of powder, 8 g of TiO ₂ powder having a particle size of about 20 μm and 28 g of Al ₂ O ₃ powder having a particle size of about 10 μm were mixed and heated in a platinum crucible at a temperature of 1450 ° C. for 60 minutes to be melted. After cooling this melt, it was pulverized with a ball mill to recover powder having a particle size of 1 to 10 μm, and 100 g of SiO ₂ powder having a particle size of 1 to 10 μm was added to the recovered powder to obtain a powdery glass composition. I got a thing.

Next, the obtained powdery glass composition 10
15% by weight of ethyl cellulose and 85 pine oil in 0 g
Add 19 g of an organic vehicle consisting of wt% and mix,
A three-roll mill was passed three times to obtain a coating composition. This coating composition was screen-printed on a 5 × 5 × 0.1 cm alumina plate using a 200 mesh screen so that the coating amount of the glass composition would be 0.008 g / cm ^2, and then 10 ° C. at 150 ° C. 2 minutes at 870 ℃ after preheating for 2 minutes
Heat for 0 minutes.

After the alumina plate was cooled to room temperature, it was immersed in a catalyst applying liquid for electroless plating (trademark "CCP-4230", manufactured by Okuno Chemical Industries Co., Ltd.) at 25 ° C. for 5 minutes to form a copper plating film. After that, electrolytic copper plating was further performed to produce a ceramic substrate having a copper plating thickness of 40 μm.

Then, a masking ink (trademark "top resist G", manufactured by Okuno Chemical Industries Co., Ltd.) was screen-printed on the copper-plated surface in a square shape of 2 × 2 mm at 5 positions, and then UV irradiation was performed to perform masking ink. Was cured. After dipping this sample in a ferric chloride aqueous solution at 50 ° C. to dissolve the copper-plated portion other than the masking portion,
The masking ink was peeled off by immersing in a methylene chloride solution.

When the bonding strength was measured as described below, it had a very high bonding strength of 5.5 kg / mm ² . The sheet resistance of the plating film is 0.
It was 1 mΩ / mouth and had very high conductivity.

(Measurement of Bonding Strength) First, a copper wire having a diameter of 1.0 mm was formed on the copper plating film at a lead: tin mixing ratio of 37: 6.
Solder at 260 ° C. using the solder of No. 3. next,
At 25 ° C, pull this copper wire in the direction perpendicular to the alumina plate and measure the tensile strength when the plating film peels off.
This value is the bonding strength.

Example 2 75 g of SiO ₂ powder having a particle size of about 1 μm and a particle size of about 0.5
20 g of B ₂ O ₃ powder of μm, Li _{2 with} a particle size of about 0.5 μm
O powder 17.5 g, MgO powder 7.5 with a particle size of about 1 μm
g, 12.5 g of PbO powder having a particle size of about 1 μm, and 10 g of ZrO 2 powder having a particle size of about 3 μm were mixed and heated in a platinum crucible at a temperature of 1300 ° C. for 30 minutes to melt. After the melt is cooled, it is crushed with a ball mill to a particle size of 5 to 5.
The powder of 30 μm was collected, and the collected powder had a particle size of about 10 μm.
100 g of Al ₂ O ₃ powder of μm was blended to obtain a powdery glass composition.

Next, a mixed solvent of 10 g of methanol and 10 g of isopropyl alcohol was added to 80 g of the obtained glass composition, and this was applied to a 5 × 5 × 0.1 cm aluminum nitride sintered body. Amount 0.00
It was spray-coated so as to have a weight of 8 g / cm ² , preheated at 150 ° C. for 10 minutes, and then heated at 1000 ° C. for 10 minutes.

After cooling the aluminum nitride sintered body to room temperature, electroless copper plating was performed according to the following methods (1) to (3) to prepare a ceramic substrate.

(1) Degreasing: Immerse in alcohol solution for 5 minutes.

(2) Addition of catalyst: 25 in sensitizer liquid
After soaking at ℃ for 3 minutes, wash with water. As the sensitizer solution, a 100 ml / l aqueous solution of sensitizer (trademark “TMP sensitizer”, manufactured by Okuno Chemical Industries Co., Ltd.) was used, and as the activator liquid, activator (trademark “TMP Activator”, Okuno Chemical Industries Co., Ltd.) was used. Made)
A 100 ml / l aqueous solution is used.

(3) Electroless copper plating: Electroless copper plating solution (trademark "OPC Copper", manufactured by Okuno Chemical Industry Co., Ltd.)
Immerse in it at 55 ° C. for 210 minutes.

The ceramic substrate manufactured as described above had a conductor layer made of a copper plating film having a thickness of 15 μm.

When the bonding strength was measured in the same manner as in Example 1, it had a high bonding strength of 4.0 kg / cm ² . The sheet resistance of the copper film is 0.5 mΩ.
It was / mouth and had sufficient conductivity.

Example 3 In the same manner as in Example 1, the composition obtained by mixing the organic vehicle and the glass composition was placed on a 5 × 5 × 0.06 cm alumina plate through a 200 mesh screen so that the amount of the glass composition was After coating at a rate of 0.008 g / cm2, 9
Heated at 50 ° C. for 5 minutes.

Next, after applying the catalyst according to (1) and (2) shown in Example 2, it was immersed in the same electroless plating solution as used in Example 2 at 55 ° C. for 30 minutes to obtain a thickness. Is 2 μm
Copper film was formed. Then, a masking ink for plating (trade name "Photomar MT" made by Okuno Chemical Industries Co., Ltd.) was applied on the copper-plated surface in a 2 × 2 mm square shape.
After the screen printing was performed leaving the spots, UV irradiation was performed for 10 seconds to cure the masking ink, and then electrolytic copper plating was performed to make the thickness of the copper plating 30 μm. After that, the masking ink was peeled and removed by immersing it in a methylene chloride solution, and then immersing it in an aqueous solution of ammonium persulfate at 20 ° C. to dissolve only the electroless plating part.

The bonding strength of the remaining copper plating film was measured in Example 1
When measured in the same manner as above, it had a high bonding strength of 5.0 kg / cm ² . Further, the sheet resistance of the copper film was 0.2 mΩ / mouth, and had high conductivity.

Example 4 A composition obtained by mixing an organic vehicle and a glass composition in the same manner as in Example 1 was put on a 5 × 5 × 0.06 cm alumina plate with a glass composition amount of 0 by a 200 mesh screen. 95 after application at a rate of 0.008 g / cm ^2.
Heated at 0 ° C. for 5 minutes.

After cooling the alumina plate to room temperature, it was placed in a vacuum vapor deposition apparatus, and metallic copper was heated and vapor deposited at a vacuum degree of 10 ^-6 Torr to form a copper film. Next, after acid activation, it was immersed in the same electroless plating solution as that used in Example 2 at 55 ° C. for 30 minutes to form a copper film having a thickness of 2 μm. Then, electrolytic copper plating was further performed to produce a ceramics substrate having a copper plating thickness of 20 μm.

After performing masking and etching in the same manner as in Example 1, the bonding strength of the copper plating film was measured and found to have a high bonding strength of 4.6 kg / mm ² . Further, the sheet resistance of the copper film was 0.2 mΩ / mouth, and had high conductivity.

Example 5 80 g of SiO ₂ powder having a particle size of about 5 μm and a particle size of about 10 μm
20g of B ₂ O ₃ powder and Li ₂ O having a particle size of about 10 μm
20 g of the powder was blended and heated in a platinum crucible at a temperature of 1400 ° C. for 60 minutes to melt. After the melt was cooled, it was pulverized with a ball mill to obtain a powdery glass composition having a particle size of 1 to 10 μm.

Next, the obtained powdery glass composition 10
15% by weight of ethyl cellulose and 85 pine oil in 0 g
Add 25 g of an organic vehicle consisting of wt% and mix,
A three-roll mill was passed three times to obtain a coating composition. This coating composition was screen-printed on a 5 × 5 × 0.1 cm alumina plate using a 200 mesh screen so that the coating amount of the glass composition would be 0.008 g / cm ^2, and then 10 ° C. at 150 ° C. Heated for minutes.

After cooling the alumina plate to room temperature, honing was performed to roughen the glass surface. The roughened alumina plate was thoroughly washed with water, dried, and then placed in a vacuum vapor deposition apparatus, and metallic copper was thermally vapor deposited at a vacuum degree of 10 ⁻⁶ Torr to form a copper film. Next, after acid activation, it was immersed in the same electroless plating solution as that used in Example 2 at 55 ° C. for 30 minutes to form a copper film having a thickness of 2 μm. Then, electrolytic copper plating was further performed to produce a ceramics substrate having a copper plating thickness of 20 μm.

After carrying out masking and etching in the same manner as in Example 1, the bonding strength of the copper plating film was measured and found to have a bonding strength of 1.5 kg / mm ² . Further, the sheet resistance of the copper film was 0.2 mΩ / mouth, and had high conductivity.

Example 6 80 g of SiO ₂ powder having a particle size of about 5 μm and a particle size of about 10 μm
20 g of B ₂ O ₃ powder and 33 g of PbO powder having a particle size of about 20 μm were mixed, and the mixture was mixed in a platinum crucible at a temperature of 1300 ° C. for 6 hours.
Heated for 0 minutes to melt. After the melt was cooled, it was pulverized with a ball mill to obtain a powdery glass composition having a particle size of 1 to 10 μm.

Next, the obtained powdery glass composition 10
15% by weight of ethyl cellulose and 85 pine oil in 0 g
Add 25 g of an organic vehicle consisting of wt% and mix,
A three-roll mill was passed three times to obtain a coating composition. This coating composition was screen-printed on a 5 × 5 × 0.1 cm alumina plate using a 200 mesh screen so that the coating amount of the glass composition would be 0.008 g / cm ^2, and then 10 ° C. at 150 ° C. Preheat for 1 minute and then at 850 ° C for 1
Heat for 0 minutes.

After cooling the alumina plate to room temperature, honing was performed to roughen the glass surface. The roughened alumina plate was thoroughly washed with water, dried, and then placed in a vacuum vapor deposition apparatus, and metallic copper was thermally vapor deposited at a vacuum degree of 10 ⁻⁶ Torr to form a copper film. Next, after acid activation, it was immersed in the same electroless plating solution as that used in Example 2 at 55 ° C. for 30 minutes to form a copper film having a thickness of 2 μm. Then, electrolytic copper plating was further performed to produce a ceramics substrate having a copper plating thickness of 20 μm.

After performing masking and etching in the same manner as in Example 1, the bonding strength of the copper plating film was measured and found to be 1.0 kg / mm ² . Further, the sheet resistance of the copper film was 0.2 mΩ / mouth, and had high conductivity.

Example 7 80 g of SiO ₂ powder having a particle size of about 5 μm and a particle size of about 10 μm
20g of B ₂ O ₃ powder and Bi ₂ O _{3 having} a particle size of about 20 μm
25 g of the powder was blended and heated in a platinum crucible at a temperature of 1350 ° C. for 60 minutes to melt. After the melt was cooled, it was pulverized with a ball mill to obtain a powdery glass composition having a particle size of 1 to 10 μm.

Next, the obtained powdery glass composition 10
15% by weight of ethyl cellulose and 85 pine oil in 0 g
Add 25 g of an organic vehicle consisting of wt% and mix,
A three-roll mill was passed three times to obtain a coating composition. This coating composition was screen-printed on a 5 × 5 × 0.1 cm alumina plate using a 200 mesh screen so that the coating amount of the glass composition would be 0.008 g / cm ^2, and then 10 ° C. at 150 ° C. Preheat for 1 minute and then at 850 ° C for 1
Heat for 0 minutes.

After cooling the alumina plate to room temperature, honing was performed to roughen the glass surface. The roughened alumina plate was thoroughly washed with water, dried, and then placed in a vacuum vapor deposition apparatus, and metallic copper was thermally vapor deposited at a vacuum degree of 10 ⁻⁶ Torr to form a copper film. Next, after acid activation, it was immersed in the same electroless plating solution as that used in Example 2 at 55 ° C. for 30 minutes to form a copper film having a thickness of 2 μm. Then, electrolytic copper plating was further performed to produce a ceramics substrate having a copper plating thickness of 20 μm.

After performing masking and etching in the same manner as in Example 1, the bonding strength of the copper plating film was measured and found to be 1.2 kg / mm ² . Further, the sheet resistance of the copper film was 0.2 mΩ / mouth, and had high conductivity.

Example 8 130 g of SiO ₂ powder having a particle size of about 5 μm and a particle size of about 10
36 g of B ₂ O ₃ powder of μm and CaO with a particle size of about 20 μm
30 g of the powder was blended and heated in a platinum crucible at a temperature of 1500 ° C. for 60 minutes to melt. After the melt was cooled, it was pulverized with a ball mill to obtain a powdery glass composition having a particle size of 1 to 10 μm.

Next, the obtained powdery glass composition 10
15% by weight of ethyl cellulose and 85 pine oil in 0 g
Add 25 g of an organic vehicle consisting of wt% and mix,
A three-roll mill was passed three times to obtain a coating composition. This coating composition was screen-printed on a 5 × 5 × 0.1 cm alumina plate using a 200 mesh screen so that the coating amount of the glass composition would be 0.008 g / cm ^2, and then 10 ° C. at 150 ° C. It was preheated for 1 minute and then heated at 1200 ° C. for 10 minutes.

Then, a catalyst was added in the same manner as in Example 3,
Only electroless plating, plating masking, electrolytic copper plating and electroless copper plating were dissolved.

The bonding strength of the remaining copper plating film was measured in Example 1
When measured in the same manner as above, it had a bonding strength of 3.0 kg / cm ² . Further, the sheet resistance of the copper film was 0.1 mΩ / mouth, and the copper film had high conductivity.

Example 9 115 g of SiO ₂ powder having a particle size of about 5 μm and a particle size of about 10
30 g of B ₂ O ₃ powder having a particle size of 25 μm and 25 g of ZnO powder having a particle size of about 5 μm were mixed, and the mixture was mixed in a platinum crucible at 1450 ° C.
Heated for 0 minutes to melt. After the melt was cooled, it was pulverized with a ball mill to obtain a powdery glass composition having a particle size of 1 to 10 μm.

Next, the obtained powdery glass composition 10
15% by weight of ethyl cellulose and 85 pine oil in 0 g
Add 25 g of an organic vehicle consisting of wt% and mix,
A three-roll mill was passed three times to obtain a coating composition. This coating composition was screen-printed on a 5 × 5 × 0.1 cm alumina plate using a 200 mesh screen so that the coating amount of the glass composition would be 0.008 g / cm ^2, and then 10 ° C. at 150 ° C. It was preheated for 1 minute and then heated at 1050 ° C. for 10 minutes.

Next, a catalyst was added in the same manner as in Example 3,
Only electroless plating, plating masking, electrolytic copper plating and electroless copper plating were dissolved.

The bonding strength of the remaining copper plating film was measured in Example 1
When measured in the same manner as above, it had a bonding strength of 2.5 kg / cm ² . Further, the sheet resistance of the copper film was 0.1 mΩ / mouth, and the copper film had high conductivity.

Example 10 110 g of SiO ₂ powder having a particle size of about 5 μm, having a particle size of about 10
30 g of B ₂ O ₃ powder of μm and TiO _{2 with a} particle size of about 30 μm
15 g of the powder was blended and heated in a platinum crucible at a temperature of 1450 ° C. for 60 minutes to melt. After the melt was cooled, it was pulverized with a ball mill to obtain a powdery glass composition having a particle size of 1 to 10 μm.

Next, the obtained powdery glass composition 10
15% by weight of ethyl cellulose and 85 pine oil in 0 g
Add 25 g of an organic vehicle consisting of wt% and mix,
A three-roll mill was passed three times to obtain a coating composition. This coating composition was screen-printed on a 5 × 5 × 0.1 cm alumina plate using a 200 mesh screen so that the coating amount of the glass composition would be 0.008 g / cm ^2, and then 10 ° C. at 150 ° C. It was preheated for 1 minute and then heated at 1100 ° C. for 10 minutes.

Then, a catalyst was added in the same manner as in Example 3,
Only electroless plating, plating masking, electrolytic copper plating and electroless copper plating were dissolved.

The bonding strength of the remaining copper plating film was measured in Example 1
When measured in the same manner as above, it had a bonding strength of 3.5 kg / cm ² . Further, the sheet resistance of the copper film was 0.1 mΩ / mouth, and the copper film had high conductivity.

Example 11 110 g of SiO ₂ powder having a particle size of about 5 μm and a particle size of about 10
25 g of B ₂ O ₃ powder of μm and MnO having a particle size of about 10 μm
₂ powder 10g is blended, and temperature is 1500 ℃ in platinum crucible.
It was heated for 60 minutes to melt. After the melt was cooled, it was pulverized with a ball mill to obtain a powdery glass composition having a particle size of 1 to 10 μm.

Next, the obtained powdery glass composition 10 was used.
15% by weight of ethyl cellulose and 85 pine oil in 0 g
Add 25 g of an organic vehicle consisting of wt% and mix,
A three-roll mill was passed three times to obtain a coating composition. This coating composition was screen-printed on a 5 × 5 × 0.1 cm alumina plate using a 200 mesh screen so that the coating amount of the glass composition would be 0.008 g / cm ^2, and then 10 ° C. at 150 ° C. It was preheated for 1 minute and then heated at 1200 ° C. for 10 minutes.

Then, a catalyst was added in the same manner as in Example 3,
Only electroless plating, plating masking, electrolytic copper plating and electroless copper plating were dissolved.

The bonding strength of the remaining copper plating film was measured in Example 1
When measured in the same manner as above, it had a bonding strength of 2.5 kg / cm ² . Further, the sheet resistance of the copper film was 0.1 mΩ / mouth, and the copper film had high conductivity.

Example 12 120 g of SiO ₂ powder having a particle size of about 5 μm and a particle size of about 10
μm of B ₂ O ₃ powder 30g and particle size of about 3 [mu] m Al ₂ O ₃
50 g of the powder was blended and heated in a platinum crucible at a temperature of 1600 ° C. for 60 minutes to melt it. After the melt was cooled, it was pulverized with a ball mill to obtain a powdery glass composition having a particle size of 1 to 10 μm.

Next, the obtained powdery glass composition 10 was used.
15% by weight of ethyl cellulose and 85 pine oil in 0 g
Add 25 g of an organic vehicle consisting of wt% and mix,
A three-roll mill was passed three times to obtain a coating composition. This coating composition was screen-printed on a 5 × 5 × 0.1 cm alumina plate using a 200 mesh screen so that the coating amount of the glass composition would be 0.008 g / cm ^2, and then 10 ° C. at 150 ° C. It was preheated for 1 minute and then heated at 1200 ° C. for 10 minutes.

Then, a catalyst was added in the same manner as in Example 3,
Only electroless plating, plating masking, electrolytic copper plating and electroless copper plating were dissolved.

The bonding strength of the remaining copper plating film was measured in Example 1
When measured in the same manner as above, it had a bonding strength of 4.0 kg / cm ² . Further, the sheet resistance of the copper film was 0.1 mΩ / mouth, and the copper film had high conductivity.

Comparative Example 1 120 g of SiO ₂ powder having a particle size of about 5 μm and a particle size of about 1
60 g of 0 μm B ₂ O ₃ powder was blended and heated in a platinum crucible at a temperature of 1450 ° C. for 60 minutes to melt. After the melt is cooled, it is crushed by a ball mill to have a particle size of 1 to 1
A 0 μm powdery glass composition was obtained.

Next, the obtained powdery glass composition 10 was used.
15% by weight of ethyl cellulose and 85 pine oil in 0 g
Add 25 g of an organic vehicle consisting of wt% and mix,
A three-roll mill was passed three times to obtain a coating composition. This coating composition was screen-printed on a 5 × 5 × 0.1 cm alumina plate using a 200 mesh screen so that the coating amount of the glass composition would be 0.008 g / cm ^2, and then 10 ° C. at 150 ° C. It was preheated for 1 minute and then heated at 1100 ° C. for 10 minutes.

Then, a catalyst was added in the same manner as in Example 3,
Only electroless plating, plating masking, electrolytic copper plating and electroless copper plating were dissolved.

The bonding strength of the remaining copper plating film was measured in Example 1
When measured in the same manner as above, the bonding strength was extremely low at 0.1 kg / cm ² , which was not suitable for practical use.

Comparative Example 2 110 g of SiO ₂ powder having a particle size of about 10 μm and 30 g of Al ₂ O ₃ powder having a particle size of about 20 μm were mixed and heated in a platinum crucible at 1600 ° C. for 60 minutes to melt them. , Did not become a uniform glass. Melting glass at a temperature above this is extremely inconvenient in practice and is not suitable for use in the present invention.

[0093]

EFFECTS OF THE INVENTION By using the glass composition of the present invention to form an underlayer for metallizing ceramics, it is possible to improve the bonding strength between the metal film and the ceramics due to metallization and to obtain sufficient conductivity of the metal film. And good soldering characteristics can be secured.

In addition, when the glass composition of the present invention is used, no special process or conditions are required to form the metallization base layer on the ceramics, so that the production efficiency of the ceramics substrate is improved.

Further, since the glass composition of the present invention can be applied to various metal coatings depending on the purpose, there is an advantage that the application range is wide.

Claims (1)

[Claims] (A) SiO ₂ content of 4 to 80% by weight,
(B) B ₂ O ₃ content of 1 to 40% by weight, (c) (R ¹ ) ₂
O content, (R ² ) O content, (R ³ ) O ₂ content and (R ⁴ ) ₂ O ₃ content of at least one content of 1 to 80% by weight (provided that R ¹
Is at least one of Li, Na and K, R ² is at least one of Mg, Ca, Ba, Zn, Cd and Pb, R ³ is at least one of Ti, Zr and Mn, R ⁴ is Al and / or Bi. A glass composition for forming a metallized underlayer, comprising: