JP2566183B2 - Glass powder capable of producing a sintered glass ceramic containing hexagonal cordierite as the main crystal phase by crystallization - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to glass powders which can be crystallized to give sintered glass ceramics containing hexagonal cordierite as the predominant crystalline phase.

[0002]

BACKGROUND OF THE INVENTION Cordierite, as a result of its good mechanical and electrical properties, is very well suited as a substrate for electronic components, especially multilayer circuit boards. Since pure cordierite has a very high sintering temperature, at which temperature the applied conductive paths are destroyed before sintering, the starting point is to sinter at a relatively low temperature and at the same time It is a glass powder that can be converted into a crystalline phase.

It is known that only glass powders whose composition corresponds to stoichiometrically pure cordierite have a given sintering capacity. Pressing and heat treatment at temperatures up to 1200 ° C. give rise to porous glass ceramics with low mechanical strength. Poor sinterability is due to premature surface crystallization of the glass particles, which results in a dramatic increase in viscosity, on the order of many times, which prevents further sintering of the glass phase. A further disadvantage is that a high-quartz mixed crystalline phase containing MgO is initially formed. Typical examples of mixed crystals in this series are
2: 2: 5 MgO: Al2 O3 : SiO2 Μ-cordierite with an oxide ratio and magnesium aluminosilicate (MAS) with a ratio of 1: 1: 4. The presence of these metastable crystal phases further delays the crystallization that results in hexagonal cordierite.

Glass powders with modified composition and improved sinterability have therefore already been disclosed. For example, in U.S. Pat. No. 3,926,648, 0.5-2
Wt% K2 O and / or Cs2 It is described that the addition of O improves the sinterability. However, the sintered materials produced from these glass powders have inferior electrical and dielectric properties and are therefore generally unsuitable for electrical engineering and electronic components, especially when their demands are high. Is inappropriate. German Patent No. 26 02429
No. 3, the modification oxides BaO, PbO, SrO and Ca
The above correction is performed by adding 0.7 to 5.6 mol% of one or more kinds of O. These oxides can form mixed crystals in the cordierite structure. However, since the low residual glass phase content limits the sinterability of the powder, it is mainly used as a coating for ceramics, glass or glass-ceramic products. German Patent 29 01 172 describes two different sintered glass-ceramics, the first one being a glass ceramic based on β-spodumene as the most important crystalline phase and the second one. It is a sintered glass-ceramic based on cordierite as the most important crystal phase. The structure of the latter sintered glass-ceramic is
It also contains clinoenstatite and in some cases μ-cordierite in addition to hexagonal cordierite. Due to this complex structure, all process parameters such as chemical composition, powder properties and sintering programs are monitored with narrow tolerances in order to achieve uniform structure formation and thus reproducible properties. Will be required. Therefore, the production of these sintered glass-ceramics is complicated and difficult to match different process conditions of different users. U.S. Pat. No. 4,540,671 describes a glass powder that can be sintered to give a sintered glass-ceramic, containing cordierite in the sintered state and a high-quartz mixed crystalline phase in solid solution. There is. However, the advent of metastable high quartz mixed crystal phases results in the disadvantages already mentioned above.

Therefore, it is an object of the present invention to produce a sintered glass-ceramic containing hexagonal cordierite as the predominant crystalline phase by crystallization, which can be sintered in an air-impermeable state at temperatures below 970 ° C. To find a glass powder having a composition that has good electrical and mechanical properties, and that gives the user considerable freedom in selecting the sintering conditions in terms of heating rate, sintering temperature, and sintering time. It is in.

[0006]

According to the present invention, in order to achieve the above-mentioned object, the following composition based on oxide: SiO2 48-61 mol%, ZnO 0-3 mol%, Al2 O3 10 to 16 mol%, CaO 0 to 3 mol%, MgO 23 to 35 mol%, BaO 0 to 1.5 mol%, B2 O3 0 to 4 mol%, F as an O substitute, 0.5 to 12 mol%, P2 O5 0 to 2.5 mol%, ΣB2 O3 + P2 O5 Provided is a glass powder whose crystallization can result in a sintered glass ceramic containing hexagonal cordierite as the predominant crystalline phase, characterized in that it has 0.5 to 5 mol%.

[0007]

The process of sintering and crystallization is important in order to obtain a sintered glass-ceramic with a high crystalline phase content, which is dense or has no open pores. In contrast to the compression glass powder resulting volume nucleation inside as a result of the addition of nucleating agents such as titanium dioxide emissions <br/> or zirconium dioxide, crystallization in the preparation of a sintered glass ceramic from glass powder It proceeds from the original surface of the glass powder particles. Dense sintering must still be substantially completed in the glassy state. If premature surface crystallization occurs, the viscosity of the surface layer of glass particles increases so much that further dense sintering is significantly hindered if not interrupted. On the other hand, if the crystallization capacity of the glass is suppressed, for example by adding a relatively large amount of modifying oxide, a homogeneous and fine crystal structure with the desired high crystalline phase content can no longer be produced. Can not. A low-strength, coarse-grained sintered glass-ceramic is then produced which is unsuitable for most applications.

SiO2 in glass powder Content is 48-61
Should be mol%. If SiO2 If the content drops below 48 mol%, proper sinter with crystallization of the hexagonal cordierite phase is not possible below 970 ° C. If SiO2 When the content exceeds 61 mol%, metastable magnesium aluminosilicate crystals are preferentially crystallized, and the above-mentioned disadvantages are involved. Particularly suitable SiO2
The content is 51 to 57 mol%. Al2 O3 Content is 10
Is about 16 mol%. If the upper limit of 16 mol% is exceeded, the temperature required for the production of dense sintered glass-ceramics increases, while Al2 O3 When the content is reduced to less than 10 mol%, the desired hexagonal cordierite phase has a reduced crystal phase content, and MgO and SiO which increase the dielectric constant.
2 The contained crystalline phase is formed in a considerable quantitative proportion. Suitable Al2 O3 The content is 12.5-15.5 mol%. M
The gO content should be 23-35 mol%. If it exceeds this range, the content of hexagonal cordierite decreases, while if the content of MgO is less than this range, the sintering characteristics of the glass powder deteriorate. Suitable MgO content is 26-31
Mol%.

In order to lower the sintering temperature, the glass powder contains B2 of 4 mol% or less. O3 And P2 of 2.5 mol% or less
O5 And the total content of these two compounds is 0.5
Should be ˜5 mol%. The upper limit of these ranges should not be exceeded, otherwise the residual glass phase will become abundant and the properties will deteriorate. However, B
2 O3 And / or P2 O5 Since the addition of Al contributes to a decrease in sintering temperature, the total amount should not be less than 0.5 mol%.

The addition of zinc oxide promotes the crystallization of hexagonal cordierite at low temperatures. However, the zinc oxide content should not exceed 3 mol%, as sintering which results in a dense body as a result of premature surface crystallization is more difficult. The preferred zinc oxide content is 0.
It is 3 to 2.5 mol%. Similarly, the CaO content promotes crystallization at low temperatures, but its content should not exceed 3 mol%, otherwise anortite (anorthite) as an additional undesired crystalline phase is such low. Because even the content occurs. The addition of BaO improves the homogeneity and stability of the glass melt, but the BaO content is 1.5.
It should not exceed mol%, otherwise crystallization of the glass powder is suppressed at such a high content and shifts to unacceptably high temperatures.

The essential component of the present invention is 0.5 to 12 mol%,
The fluorine content is preferably 0.5 to 11 mol%, and the fluorine ion replaces a corresponding amount of oxygen ion in the crystal lattice. Surprisingly, the addition of fluorine raises the crystallization temperature of the glass powder to 9 without adversely affecting the sintering operation.
It was found to shift to low temperatures below 00 ° C. This behavior is in contrast to crystallization-promoting additives such as zinc oxide and barium oxide, where a compromise must always be made between dense sintering and low crystallization temperatures. Addition of fluorine promotes crystallization of the hexagonal cordierite phase and suppresses the undesirable precursor phases μ-cordierite and magnesium aluminosilicate. The structure remains stable to sintering and crystallization over a wide temperature range. This is because the fluorine content should not exceed 12 mol%, otherwise new fluorine-containing crystalline phases will be formed, which will adversely affect the stability of the structure and cause changes in the sintering temperature. Moreover, the homogeneity of the glass melt and the hydrolytic stability of the sintered glass-ceramic are also reduced. Even the addition of a small amount of fluorine causes a significant decrease in the crystallization temperature, which in turn reduces the sintering temperature or the sintering time, but the fluorine content should not drop below 0.5 mol%. Otherwise, the effect of fluorine addition is not always sufficient below this level.

Further, PbO, S as a crystallization promoting additive is used.
rO or SnO2 Can also be added. These pieces
The maximum amount of each oxide should not exceed 3 mol%.
If one or more of these three oxides are used together
The total content used should also exceed 3 mol%.
I'm not. Addition of a large amount exceeding 3 mol% will result in premature
Crystallization occurs and thus prevents good sintering. If Pb
Higher in reducing sintering atmosphere when O is used
Lead oxide can be reduced to metallic lead at the sintering temperature, which
The result is an unacceptable reduction in volume resistance and
It should be further noted that

In the production of glass for producing the glass powder of the present invention, for example, Sb2 O3 , As2 O3 Alternatively, conventional fining agents such as cerium compounds can be added to the glass in conventional amounts up to about 1% by weight without adversely affecting its properties. However, these are not absolutely necessary.

The particle size of sinterable glass powders plays an important part in the optimization of sintering and subsequent surface crystallization. In general, good results are obtained with glass powders having an average particle size of 1-12 μm. If the particle size is too small, the glass powder tends to premature surface crystallization due to the large surface / volume ratio,
Prevent good sintering. On the other hand, excessively large grain size results in more difficult late crystallization, resulting in a relatively rough crystal structure with low mechanical strength, and a sintered product with increased surface roughness. Particularly preferable results are obtained when the average particle size of the glass powder is 1.5 to 7 μm.

The glass powder is a conventional glass raw material at about 1450 to 1650 ° C. so as to give a glass having the above-mentioned composition.
And then the molten glass is quenched by pouring it into cold water or onto a chilled metal roller to form a glass cullet, which is converted by known frit or grinding methods into a powder having the particle size described above. Manufactured by a method known per se.

The glass powder thus obtained is then processed in a manner known per se, for example by dry pressing, extrusion,
It can be converted into a molded product by using a usual molding method in the ceramics industry such as injection molding and calendering. This conversion is carried out by adding commercially available organic auxiliaries and / or suitable suspending agents. Thus, for example, the extrusion is performed from a plasticized composition having plasticity. Dry press
It is carried out by adding a pressing aid and proceeds until a free-flowing pressed granule is produced. Calendering from ceramic slurries has proven successful for the production of flexible untreated films, from which electronic substrates will later be produced. If a suspending agent is added, a drying step is also required before sintering.
Any organic auxiliaries present are burnt out during the heating stage by suitable temperature control in the sintering program before significant sintering of the glass takes place. Sintering and crystallization of the glass powder occurs at temperatures of about 850-970 ° C, depending on the composition of the glass powder. The required sintering time depends on the sintering temperature used and is between about 15 minutes and several hours. Longer sintering times are required at lower sintering temperatures. For a given glass composition, if desired, structures similar to those obtained at high sintering temperatures and short sintering times can be obtained at the desired low sintering temperatures and long sintering times. Therefore, a pore-free sintered glass ceramic produces a glass having the above composition, pulverizes this glass to a particle size of 1 to 12 μm, forms the glass particles into a desired shape, Continuously heated to a temperature below 970 ° C at
It is produced by holding this temperature until the particles are sintered together, devitrifying the glass and then cooling the sintered product. Prior to heating and sintering, the molded product or its precursors can be patterned with conductive paths, for example by screen printing.

[0017]

The composition of the glass powder according to the present invention is different from the stoichiometric composition of cordierite, but nevertheless a high crystal phase component having a hexagonal cordierite structure is produced by mixed crystal formation. The cordierite-free crystalline phase or residual glass phase is kept relatively low. Due to the formation of this mixed crystal, Al2 O3 Over stoichiometric amount of MgO and SiO2 at the sacrifice of Can be added. However, the sinterability of the glass powder is improved and the amount of modifying oxide required is reduced.

The sintered glass-ceramics produced from the glass powder according to the invention are air-impermeable and therefore allow the encapsulation of sensitive electronic components. Due to its low dielectric constant, metallized electronic substrates produced therefrom have almost no delay in signal propagation time. The low sintering temperature of up to 970 ° C. makes it possible to employ metallization with highly conductive metals such as copper, silver, silver / palladium and gold. The coefficient of thermal expansion of the sintered glass-ceramic can be matched to that of silicon, thereby minimizing the mechanical stress due to the different coefficient of thermal expansion between the substrate material and the silicon semiconductor wafer. In addition to compression-sintered glass-ceramic substrates, multilayer wiring boards with internal conductive paths can also be manufactured. Sintered glass ceramic components produced from the glass powder according to the invention are distinguished by low thermal conductivity, high heat resistance and good thermal shock behavior. High volume resistance and high dielectric strength allow it to be used for insulation. Glass powder is also suitable for grouting between coatings and ceramics and is stable even at high temperatures.

[0019]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples.
This will be described in detail. The results are summarized in Tables 1-4. table
1 and Table 3 show the chemical composition, and Tables 2 and 4 show each Example.
Shows the physical data of. Of the physical data,
Average particle size (d50 ) Is measured by a laser granulometer
Was. Sintering is performed at the indicated temperature and a uniform heating rate of 3 ° C / min.
The degree was used. The following X-ray reflection was used to determine the crystal phase component.
T: 102 reflections, M for hexagonal cordierite
011 reflection for AS, forsterite
120 reflections, 6 for magnesium aluminosilicate
10 reflections (JCPDS 35-310). Some cases
Sintered glass ceramic is still small
It contained the modified enstatite. Many possible changes
Due to the nature and low content, a qualitative estimate may be made here.
Was needed. Hexagonal Cordierite (JCPDS
File No. 13-293), μ-cordierai
To (JCPDS File No. 14-249) and
Forsterite (JCPDS File No. 34)
-189) was determined against a fully crystallized standard.
Comparison for MAS phase (JCPDS 27-716)
Since the standard also contained other crystalline phases, here
Quantitative data with a somewhat large error (on the order of about 20%
-). Dielectric constant ε and loss angle tan
 δ was measured at 25 ° C. and a frequency of 1 MHz. Gigaher
In the high frequency range, the dielectric constant and loss angle are remarkable.
descend. Differential thermal analysis method for estimating crystallization temperature
It was adopted. This method has a high heating rate (here 5 ° C
/ Min) is required, so it is true for a standard sintering program.
The crystallization temperature of fruit is systematically low. However, crystallization
It is possible to give an indication of the effect of chemical composition on temperature
Is. The table shows the start of the crystallization peak in each case and
It shows the maximum crystallization. From these values, various sintering
The crystallization temperatures of glass ceramics are compared with each other and estimated.
It becomes possible to set.

Examples 1 to 4 (Tables 1 and 2) show the effect of the fluorine content on the sintering temperature and the crystallization behavior for compositions containing no fluorine. Example 1 is used for comparison. Glass powder having the composition shown in Table 1 was prepared by melting a suitable glass batch at 1600 ° C., quenching the melt between two metal rollers and grinding to the particle size shown in Table 2. Prepared. This powder was coarsely crushed with an aqueous solution of polyethylene glycol in an intensive mixer by a method known per se to obtain free-flowing pressed granules from glass powder. Molded products for the sintering test were produced by dry pressing under a pressure of 800 bar. The sintering time is 1 hour at the indicated sintering temperature,
The heating rate was 3 ° C / min. The temperature was maintained at 310 ° C. for 1 hour to remove polyethylene glycol from the sintered product.

Examples 2 to 4 very clearly show the very clear effect exhibited by the fluorine content compared to Example 1. From Table 2, it can be seen that fluorine shifts the crystallization temperature to the lower temperature side. Crystallization of hexagonal cordierite is promoted and other crystal phases are suppressed. The structure is stabilized and the crystalline phase content changes only slightly over a wide temperature range. Therefore, the hexagonal cordierite content in Example 3 is substantially constant at the sintering temperature of 910-970 ° C. Structural stabilization with fluorine content also means that for the composition according to the invention the coefficient of thermal expansion changes little at sintering temperatures of 910-970 ° C. On the other hand, in Example 1 which was carried out for the composition containing no fluorine, the crystal phase content was greatly changed, and the thermal expansion coefficient was also changed. All the sintered products according to the invention are air-impermeable,
Sintered at the indicated sintering temperature.

Further, Examples 5 to 13 using the glass powder composition according to the present invention are summarized in Tables 3 and 4.
Examples 11 to 13 are crystallization promoting additives SrO, PbO and SnO2. Shows the effect of.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

[0026]

[Table 4]

Example 14 A flexible untreated film having a thickness of 200 μm was prepared from the glass powder of Example 8 above. A mixture of organic auxiliaries and organic solvents was added to the glass powder in a ball mill and the mixture was homogenized to prepare a pourable slurry. This batch consists of 53% by weight glass powder, 37% by weight azeotropic solvent mixture of trichlorethylene and ethanol, 5% by weight polyvinyl butyral as binder, 4% by weight dioctyl phthalate as plasticizer, and 1% by weight menhaden fish oil as thinner. Was made. The slurry was degassed and poured onto an endless moving belt. The casting shoe and the belt are separated by a narrow adjustable gap through which the film thickness is adjusted. After passing through the drying zone, the flexible film can be removed from the casting belt.

Several layers of these untreated films are stacked and laminated press at a temperature of 90 ° C. to 0.5-3 kN.
/ Cm2 It was pressed under the pressure of 1 to form a uniform laminated material. The laminate thus obtained was sintered on a flat combustion support plate at a temperature of 930 ° C. for a sintering time of 1 hour.
Due to the relatively high organic auxiliary content, a heating rate of 2 ° C./min was generally used. The heating rate was reduced to 1 ° C./min in the region of the burning temperature of the organic auxiliary agent, that is, in the temperature region of 220 ° C. to 330 ° C. The laminate was then treated at 330 ° C. for 2 hours in order to complete the removal of organic auxiliaries. The heating was then continued at 2 ° C / min until the desired sintering temperature was reached. The structure and properties of the sintered glass-ceramic substrate thus obtained were in agreement with the values obtained with sintered compacts, which also used the same temperature program.

In all the examples, the volume resistivity at room temperature was 10 13 Greater than Ω-cm, i.e. the material was a very good electrical insulator.

Claims (4)

(57) [Claims] 1. The following composition based on oxide: SiO2 48-61 mol%, ZnO 0-3 mol%, Al2 O3 10 to 16 mol%, CaO 0 to 3 mol%, MgO 23 to 35 mol%, BaO 0 to 1.5 mol%, B2 O3 0 to 4 mol%, F as an O substitute, 0.5 to 12 mol%, P2 O5 0 to 2.5 mol%, ΣB2 O3 + P2 O5 Glass powder capable of yielding a sintered glass-ceramic containing hexagonal cordierite as the predominant crystal phase by crystallization, characterized in that it has 0.5 to 5 mol%. 2. The following composition based on oxide: SiO2 51-57 mol% Al2 O3 12.5-15.5 mol% MgO 26-31 mol% P2 O5 0.5-2.5 mol% B2 O3 0.3-2.0 mol% ΣP2 O5 + B2 O3 1.0-3.0 mol% ZnO 0.3-2.5 mol% O Glassy powder according to claim 1, having F 0.5-11.0 mol% as a substitute. 3. Oxides PbO, SrO and SnO2 The glass powder according to claim 1 or 2, containing at least 3 mol% of one or more of the above. 4. The glass powder according to claim 1, which has an average particle size of 1 to 12 μm.