JPH03265543A - Production of glass powder and slurry for glass-ceramics substrate and production of glass-ceramics substrate - Google Patents

Abstract

PURPOSE:To improve diffusivity by surface treating a glass powder with >=1 kind between a coupling agent and a water-soluble or water-insoluble dispersant to improve its diffusivity in a slurry, wet-crushing the product and drying the obtained glass powder. CONSTITUTION:A glass block is added with water and wet-crushed in a ball mill, etc. At least one kind among a titanium-based coupling agent, a silane- based coupling agent, a water-soluble dispersant such as ammonium polycarboxylate and a water-insoluble dispersant based on sorbitan, etc., is added by 0.13 pts.wt. based on the solid matter to 100 pts.wt. of a glass powder and mixed, and the mixture is dried. Subsequently, 5-25 pts.wt. of a binder such as polyvinyl butyral, 1-10 pts.wt. of a plasticizer such as dibutyl phthalate and 50-150 pts.wt. of a solvent such as toluene are added to 100 pts.wt. of the obtained glass powder to obtain a glass powder-contg. slurry. The slurry is applied on a carrier film, dried and released to obtain a green sheet, and the sheet is fired at <=1000 deg.C to obtain a glass-ceramic substrate.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a method for producing glass powder used in producing a glass-ceramic substrate, a method for producing a slurry containing the glass powder, and a method for producing a slurry containing the glass powder. Glass used
The present invention relates to a method for manufacturing a ceramic substrate.

[Conventional technology]

In recent years, there has been a strong demand for higher speed ratios in signal processing, as exemplified by the demand for faster calculations in the computer field. In view of this requirement, when looking at insulating substrates for signal processing circuits, conventional alumina substrates have too high a dielectric constant. Therefore, a glass-ceramic substrate using a glass-based material instead of alumina has been proposed. The dielectric constant of this glass-ceramic substrate is about 1/2 to 2/3 of that of the alumina substrate. In addition, since the sintering temperature is below 1000°C, low resistance materials such as Au (gold), Ag (silver), and Cu (fl) can be used as conductor materials for wiring, allowing for finer wiring. There is also an advantage.

[Problem to be solved by the invention]

However, conventionally, the above-mentioned glass-ceramic substrates have problems in that they have poor dimensional accuracy and are easily warped. This is due to the following reasons.

Glass-ceramic substrates are manufactured by a method commonly called the so-called doctor blade method (for example, G, N, How
att, R, G, Breckenridge and
J., M., Brownl.

w Journal of American Cer
amics 5ocietyvol 30 (1947
) Obtain a green sheet with P2S5). That is,
A slurry containing glass powder is applied onto a carrier film, dried, and then peeled off to obtain a green sheet, which is then fired. The green sheet may be printed with a wiring pattern using conductive paste, or subjected to processing such as lamination, and then fired. In the above manufacturing process, the shrinkage rate during firing of the green sheet is very large, so it is difficult to achieve dimensional accuracy and the green sheet is easily warped. The reason why the green sheet shrinks so much upon firing is that the proportion of the organic binder and solvent in the glass powder-containing slurry must be increased.

In view of the above circumstances, it is an object of the present invention to provide a method in which the ratio of organic binder and solvent in the slurry can be reduced and the shrinkage rate during green sheet firing can be reduced.

[Means to solve the problem]

The inventors focused on surface-treating glass powder to improve its dispersibility within a slurry and mixing it with an organic binder and a solvent, but initially the results were not good. Therefore, as a result of further investigation, we found that after wet pulverization, there is a step of drying the glass powder, and we obtained wet pulverized glass powder that had been surface-treated to improve its dispersibility in the slurry. If you dry it after (during the grinding process or after applying this surface treatment after grinding and before drying),
We were able to obtain the knowledge that the dispersibility of the glass powder in the slurry was improved, and the proportion of organic binder, solvent, etc. could be reduced. By obtaining this knowledge, we were able to complete this invention.

Therefore, in the method for producing glass powder for a glass-ceramic substrate according to claim 1, when a glass lump is pulverized by wet grinding to obtain a glass powder, a surface treatment is performed to improve dispersibility in the slurry. After obtaining wet-milled glass powder, it is dried. For example, the surface treatment for improving dispersibility is performed using at least one of a titanium coupling agent, a silane coupling agent, a water-soluble dispersant, and a water-insoluble dispersant, as in claim 2. When wet pulverization is performed with water and the water-insoluble dispersant is used, the amount of water used for wet pulverization is reduced before surface treatment is performed.

In the method for producing a slurry for a glass-ceramic substrate according to claim 3, the glass powder according to claim 1 or 2 is mixed with a solvent and a binder material to form a slurry. In the method for manufacturing a glass-ceramic substrate according to claim 4, a glass-ceramic substrate is obtained by firing a green sheet obtained by applying the slurry according to claim 3 onto a carrier film and drying it.

This invention will be explained in more detail below.

First, a glass lump to be wet-milled is produced, for example, as follows.

SiOl 48-63wt%Affi
tOs 10~25wt%Mg0
10-25-1% BmOs
4 to 10-t%, of which 3 to 20-t% of MgO is replaced with at least one of CaO, BaO1SrO, and as a nucleating agent, Ti0z, Zr0t, Moot
, P! Os-, As2 Os, Sno! ,Tax
At least one of Os and NbxOs is 0 to 5w
The raw materials are blended so as to have a composition with t% added,
A glass lump is obtained by melting at about 1500° C. and dropping the melt into water.

Then, this glass lump is wet-pulverized by adding water using a ball mill or the like. The particle size of this glass powder is, for example, 1 to
It is about Ion. Although it is not necessary to add water during wet grinding, water is safe and inexpensive. In this invention, a titanium-based coupling agent, a silane-based coupling agent, a water-soluble dispersant, a titanium-based coupling agent, a silane-based coupling agent, a water-soluble dispersant, etc. Add and mix at least one of the water-insoluble dispersants (mixing time is about 1 to 20 hours)
After that, the amount of the surface treatment agent for improving dispersibility, which is dried, is about 0.1 to 3 parts by weight based on solid content per 10 parts of glass powder. In addition, when wet pulverization is performed with water and the water-insoluble dispersant is used, the surface treatment is usually performed after reducing the amount of water for wet pulverization. Examples of coupling agents include silane-based coupling agents and titanium-based coupling agents. Examples of water-soluble dispersants include polycarboxylic acid ammonium salts. Examples of water-insoluble dispersants include sorbitan-based ( For example, sorbitan triolate, sorbitan monooleate)
etc. The coupling agent forms a bond with the 10H group on the surface of the glass powder, improving wettability with the organic binder.

The dispersant is adsorbed by the electric charge on the surface of the glass powder and improves dispersibility.

Next, a slurry is obtained in the following manner using the surface-treated and dried glass powder.

5 parts by weight of a binder material was added to 100 parts by weight of the obtained glass powder.
~25 parts by weight, 1 to 10 ffi parts of plasticizer, 5 parts of solvent
Add 0 to 150 parts by weight and thoroughly knead in a ball mill to obtain a glass powder-containing slurry.

Examples of the binder material include organic binders such as polyvinyl butyral (PVB) and acrylic resin, and examples of the plasticizer include dibutyl phthalate (DBP).
, dioctyl phthalate (DOP), polyethylene glycol (PEG), etc., and solvents include toluene, xylene, isopropyl alcohol (IPA),
Examples include ethanol, butanol, tricrene, methyl ethyl ketone (MEK), and these can be used alone or in combination.

A green sheet is obtained using the slurry thus produced. That is, a slurry containing glass powder is applied onto a carrier film, dried, and then peeled off to obtain a green sheet. Then, cut the green sheet to the specified size,
If necessary, a through hole is provided, a wiring pattern is printed with conductive paste, or a plurality of sheets are laminated, and then fired to obtain a sintered body. The obtained sintered body is a glass-ceramics substrate (glass powder sintered body). Firing can be performed at a temperature as low as 1000°C or less, for example 950°C.

[For production]

The glass powder according to the invention described in claim 1.2 has excellent dispersibility within a slurry. This is because, before drying the glass powder after wet pulverization, surface treatment is performed to improve dispersibility within the slurry. When performing surface treatment after drying,
The glass powder aggregates to form secondary particles, and the surface treatment agent does not sufficiently reach the surface of each glass powder. If the surface is treated before drying as in this invention, each glass powder will not aggregate and the surface treatment agent will be sufficiently spread over the surface of each glass powder.

In the third aspect of the present invention, since the glass powder with such good dispersibility is used, an appropriate slurry can be obtained even if the amount of binder material and solvent is less (for example, about 2/3) than in the past.

In the fourth aspect of the present invention, since the green sheet is produced using a glass powder-containing slurry containing less binder material and solvent than conventional ones, the shrinkage rate during firing is reduced.

〔Example〕

Next, examples and comparative examples of the present invention will be described. It goes without saying that this invention is not limited to the following examples.

Example 1 - A glass-ceramic substrate was obtained according to the process diagram shown in FIG.

First, the glass lump obtained as described above was wet-pulverized using water in a ball mill, and approximately one hour before the end of the pulverization, a silane coupling agent, N-β (aminoethyl) γ-
Aminopropyltrimethoxysilane (100% solids)
Dissolve in water and add 0.5 parts per 100 parts by weight of glass powder.
It was added to a ball mill so that the weight would be the same, and after surface treatment, it was dried.

Then, an organic binder plasticizer and a solvent were mixed in the formulation shown in Table 1 to prepare a slurry.

Next, this slurry was applied onto a carrier film, sufficiently dried and then peeled off to obtain a green sheet, and this green sheet was fired at 950° C. for 3 hours to obtain a glass-ceramic Nox substrate.

Example 2 In Example 1, a titanium-based coupling agent, isopropyltri(N), was used instead of a silane-based coupling agent.
-aminoethyl-aminoethyl) titanate (solid content 1
00%), an organic binder with the formulation shown in Table 1,
A glass ceramic substrate was obtained in the same manner except that a plasticizer and a solvent were mixed to prepare a slurry.

Example 3 In Example 1, γ-(methacryloxypropyl)trimethoxysilane (solid content 100%), which is a silane coupling agent, was used instead of the silane coupling agent.
．． Melt it in 1 svt% acetic acid water, add it to a ball mill so that the amount becomes 1.0 weight per 100 parts by weight of glass powder, and mix the organic binder, plasticizer, and solvent according to the formulation shown in Table 1. A glass ceramic substrate was obtained in the same manner except that the slurry was prepared.

Example 4 In Example 1, instead of the silane coupling agent, isopropyl triisostearoyl titanate (solid content 100%), which is a titanium coupling agent, was emulsified with water and added to 100 parts by weight of glass powder. A glass-ceramic substrate was obtained in the same manner, except that a slurry was prepared by adding the organic binder, plasticizer, and solvent according to the proportions shown in Table 1. Ta.

Example 5 - In Example 1, a water-soluble dispersant, polycarboxylic acid ammonium salt (
D-305 manufactured by Middle East Yushi (solid content 40 wt%) was dissolved in water and added to a ball mill so that the amount was 1.0 weight per 100 parts by weight of glass powder, and an organic binder, A glass-ceramic substrate was obtained in the same manner except that a plasticizer and a solvent were mixed to prepare a slurry.

Example 6 - A glass-ceramic substrate was obtained according to the process diagram shown in FIG.

First, the glass lump obtained as described above was wet-pulverized using water in a ball mill, and after the pulverization was completed, the water in the slurry of glass powder and water was reduced to about half by vacuum filtration, etc. After that, sorbitan monooleate (solid content 100 wt%), which is a water-insoluble dispersant, was dissolved in ethanol and added to a ball mill so that the amount was 1.5 weight per 100 parts by weight of glass powder. After 1 hour of mixing and surface treatment, it was dried.

Then, an organic binder plasticizer and a solvent were mixed in the formulation shown in Table 1 to prepare a slurry.

Next, this slurry was applied onto a carrier film, sufficiently dried and peeled off to obtain a green sheet, and this green sheet was fired at 950° C. for 3 hours to obtain a glass-ceramic substrate.

I got it.

Example 7 - In Example 6, sorbitan triolate (solid content 100 wt%) was used instead of sorbitan monooleate, and an organic binder, plasticizer, and solvent were mixed in the formulation shown in Table 1 to prepare a slurry. A glass-ceramic substrate was obtained in the same manner except for the above steps.

Comparative Examples 1 to 3 - Glass-ceramic substrates were obtained according to the process diagram shown in FIG.

First, the glass lump obtained as described above was wet-pulverized using water in a ball mill, and then dried (without surface treatment).
.

Then, an organic binder plasticizer and a solvent were mixed in the formulation shown in Table 1 to prepare a slurry.

Next, this slurry was applied onto a carrier film, dried sufficiently, and then peeled off to obtain a green sheet.The green sheet was then fired at 950°C for 3 hours. A glass-ceramic substrate was obtained according to the process diagram shown in the figure.

First, the glass lump obtained as described above was wet-pulverized using water in a ball mill, and after the pulverization was completed, it was dried, and the silane coupling agent r-(methacryloxypropyl)trimethoxysilane ( solid content 100wt%)
Dissolve in toluene and add 1 part to 100M parts of glass powder.
．． The mixture was added to a ball mill to give a weight of 0, mixed for 1 hour, and subjected to surface treatment. Then, in this ball mill, an organic binder and a plasticizer were mixed in the formulation shown in Table 1 to prepare a slurry.

Next, this slurry was applied onto a carrier film, sufficiently dried and peeled off to obtain a green sheet, and this green sheet was fired at 950° C. for 3 hours to obtain a glass-ceramic substrate.

- Comparative Example 5 - In Comparative Example 4, instead of the silane coupling agent,
Same procedure except that sorbitan monooleate (solid content 100%), which is a water-insoluble dispersant, was dissolved in isopropyl alcohol and added to the ball mill in an amount of 1.5 parts by weight per 100 parts by weight of glass powder. A glass-ceramic substrate was obtained.

Comparative Example 6 - A glass-ceraminx substrate was obtained according to the process diagram shown in FIG.

First, the glass lump obtained as described above was wet-pulverized using water in a ball mill, and after the pulverization was sufficiently dried, Dissolve silane in 0.1 wt% acetic acid water and add 1.0 parts by weight to 100 parts by weight of glass powder.
The mixture was added to a ball mill, mixed for 1 hour, surface treated, and dried again.

Next, an organic binder plasticizer and a solvent were mixed according to the formulation shown in Table 1 to prepare a slurry, and this slurry was applied onto a carrier film and, after sufficiently drying, was peeled off to obtain a green sheet.

A glass-ceramic substrate was obtained by firing the obtained green sheet at 950 tons for 3 hours.

Approximately 10 cm obtained in each of the above Examples and Comparative Examples
Regarding the corner glass-ceramic substrates (30 pieces each),
The shrinkage rate and warpage were examined.

Table 1 shows the average shrinkage percentage and the number of samples rejected due to large warpage. As for warpage, as shown in FIG. 6, those with X/A≧0.05% were considered defective (for a 10 ae square substrate, if X was 50 tns or more, it was considered defective). The results are shown in Table 2.

As shown in Table 2, in the case of the example, the shrinkage rate is smaller than in the case of the comparative example, and the number of defects due to warpage is very small. This is because the amount of binder material and solvent can be reduced.

〔Effect of the invention〕

As described above, in the method for producing glass powder according to claim 1.2, the surface treatment for improving dispersibility in the slurry has already been completed before drying the glass powder after wet pulverization. Glass powder with sufficient surface treatment and excellent dispersibility in slurry can be obtained.

In the slurry manufacturing method according to the third aspect, since glass powder having better dispersibility than before is used, less binder material and solvent are required.

In the method for manufacturing a glass-ceramic substrate according to claim 4, since the shrinkage rate during firing is small, dimensional accuracy is good;
A substrate with less warpage can be obtained.

[Brief explanation of drawings]

Fig. 1 is a process diagram showing the manufacturing process of Examples 1 to 5, Fig. 2 is a process diagram showing the manufacturing process of Examples 6 and 7, and Fig. 3 is a process diagram showing the manufacturing process of Comparative Examples 1 to 3. Fig. 4 is a process diagram showing the manufacturing process of Comparative Example 4.5, Fig. 5 is a process diagram showing the manufacturing process of Comparative Example 6, and Fig. 6 is a process diagram showing the manufacturing process of Comparative Example 6. FIG. 3 is a side view showing the state of warpage in the substrate. 1...Glass-ceramics substrate

Claims (1)

[Claims] 1. A method for obtaining glass powder used in a slurry for a glass-ceramic substrate by pulverizing a glass lump by wet pulverization, wherein a wet pulverized glass lump is surface-treated to improve dispersibility in the slurry. 1. A method for producing glass powder for a glass-ceramic substrate, which comprises drying the glass powder after obtaining the glass powder. 2 Surface treatment to improve dispersibility is performed using at least one of a titanium-based coupling agent, a silane-based coupling agent, a water-soluble dispersant, and a water-insoluble dispersant, and wet grinding is performed using water. 2. The method for producing glass powder for a glass-ceramic substrate according to claim 1, wherein when the water-insoluble dispersant is used, water for wet grinding is reduced before the surface treatment is carried out. 3. A glass in which the glass powder according to claim 1 or 2 is mixed with a solvent and a binder material to form a slurry.
A method for producing slurry for ceramic substrates. 4. A method for producing a glass-ceramic substrate, which comprises baking a green sheet obtained by applying the slurry according to claim 3 onto a carrier film and drying it to obtain a glass-ceramic substrate.