TW201228965A - Crystalline glass powder - Google Patents

Abstract

Provided is a crystalline glass powder which is reduced in internal air bubbles, while having low dielectric loss characteristics that are sufficiently suitable for a high performance high frequency circuit. The crystalline glass powder is characterized in that a diopside crystal and a feldspar crystal are deposited as primary crystals by a heat treatment. It is preferable that the crystalline glass powder has a glass composition that contains, in mass%, 20-65% of SiO2, 3-25% of CaO, 7-30% of MgO, 0-20% of Al2O3 and 5-40% of BaO and has a mass ratio satisfying the relation of 1 = SiO2/BaO = 4.

Description

201228965 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a crystalline glass powder used as a glass H dielectric material. [Prior Art] As a high-density MOS (Integrated Circuit), LSI (Large Scale Integration, etc.) multilayer film substrate, thick film circuit parts, semiconductor package The insulating material of the body is known as the glass pottery. In recent years, in the field of communication equipment, the frequency band to be used has gradually become between 1 GHz and above, and a crystalline glass composition which can be used as an insulating material for a multilayer substrate or the like using such a high frequency band is being developed. Further, in the case of a high-performance high-frequency circuit board or a dielectric wave device, for example, a dielectric loss tan5 of 2 〇χ 1 〇·4 is required to be τ >& Loss characteristics (for example, refer to Patent Document 1). CITATION LIST Patent Literature Patent Literature 1: Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 10,120,436, which is a problem to be solved by the invention. However, in recent years, the demand for miniaturization and thinning of electronic components has become more and more high, and Thinner substrates are also required for electronic components. For the soil plate, for example, a glass ceramic dielectric obtained by precipitating diopside crystals obtained by calcining a glass ceramic containing a crystalline glass powder (2si02(10) J60I65.doc 201228965 can be used. In the process of thinning the substrate, if there are minute bubbles (voids) in the glass ceramic dielectric, the problem of disconnection of the wiring becomes remarkable. Further, there is a tendency that dielectric loss increases due to bubbles. The bubbles generated inside the glass ceramic dielectric are caused by the following reasons: in the sintering step of the raw material crystalline glass powder, the formation of the non-flowing portion is faster due to crystallization, thereby hindering the softening deformation of the entire sintered body. In other words, when the crystallized glass powder is not softened and deformed to be crystallized, the volume shrinkage accompanying the crystallization does not extend over the entire sintered body, and bubbles remain in the gaps between the glass powders. Therefore, if the crystallization is reduced during firing, The speed makes the sintered body soften and deform, so that the whole body of the sintered body shrinks uniformly, which also promotes the release of gas or gas to the glass. The dissolution of the phase t effectively suppresses the residual of the bubbles. In order to reduce the crystallization rate, it is considered that the following method is effective: the composition of the crystallized glass is deviated from the theoretical composition of the diopside crystals in such a manner that the glass phase remains after crystallization. When the ratio of the residual glass phase in the glass ceramic dielectric is too large, there is a problem that the dielectric loss increases. 1 When the residual glass phase is composed of a multi-component system, the dielectric loss increases significantly and becomes difficult to use. Therefore, it is an object of the present invention to provide a crystalline glass powder which can reduce internal air bubbles and which has a low dielectric loss characteristic capable of sufficiently coping with two performances of high frequency circuits. As a result of various studies, the inventors have found that the above problem can be solved by precipitating a diopside structure 160165.doc -4- 201228965 曰曰 and a crystallized glass powder having a specific crystal as a main crystal. The invention relates to a crystalline glass powder characterized by treating precipitated diopside crystals and feldspar knots As the main crystal, the inventors have found that 'partially or completely crystallization of the glass phase remaining after the precipitation of diopside crystals is such that the onset temperature is higher than that of diopside crystals and the volume shrinkage is small. The crystallized glass powder of feldspar crystals can suppress the generation of bubbles accompanying crystallization and reduce the residual glass phase, thereby making it possible to produce a glass ceramic crystallized glass having a small cell ratio and a small dielectric loss. It means that the amorphous glass having the property of crystallizing is not only the diopside crystal, but also the one in the present invention, "the heat treatment is to deposit the glass from the glass matrix. Further, the so-called "diaphron crystal", Crystallization of diopside solid solution. For example, crystal and feldspar crystals refer to 800~l〇〇〇°c. The term "heat treatment" means that the crystallization is fully performed at the temperature above the crystallization peak of the diopside, for example, 20 Heat treatment of more than a minute. The crystallized glass of the present invention is characterized in that the feldspar crystal is a lock feldspar crystal (BaAl2Si208). The second 'crystalline glass sphere of the present invention is characterized by containing Si〇2 20 to 65% by mass%, CaO 3 to w 八 25/0, and Mg 〇 7 to 3 〇〇/ 0, Al2〇3 〇~20%, BaO 5~40% as a glass 、, „ 芍 璃 璃 , , , , , , 满足 组成 组成 组成 组成 组成 组成 组成 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足 满足The crystalline glass of the present invention has the above-mentioned composition I60165.doc 201228965, and the diopside crystal and the feldspar crystal are easily precipitated as the main crystal. Furthermore, although the devitrification tendency of the Si〇2_CaO-MgO-based glass is strong, it can be Join

The alkaline earth oxide such as Ah〇3 or BaO stabilizes the glass, and a glass excellent in mass productivity can be obtained. Fourthly, the present invention relates to a glass ceramic material characterized by containing ~% by mass of the crystalline glass powder of any of the above and 0 to 40 mass 〇/0 of Tao Jing powder. Fifth, the glass ceramic material of the present invention is characterized in that the ceramic powder contains the A1 component. When the ceramic powder contains the component A1, the alkaline earth metal such as Si or Ba in the residual glass phase after the precipitation of the diopside crystal reacts with the erbium component in the ceramic powder to cause the feldspar crystal to be easily precipitated. The sixth invention relates to a glass ceramic dielectric obtained by calcining a glass ceramic material according to any one of the above. The seventh 'glass ceramic dielectric of the present invention is characterized by containing feldspar crystals of 20 to 65 mass. /. . Eighth, the glass ceramic dielectric of the present invention is characterized in that the bubble ratio is 3% by volume or less. The ninth 'glass ceramic dielectric of the present invention is characterized in that the dielectric constant ε is 6 to 11 ' and (the dielectric loss 匕 at a frequency higher than U GHz is "2 〇χ 10 _ 4 or less." The glass ceramic dielectric is characterized in that it is used for a circuit component material for microwaves. [Embodiment] 160165.doc -6 · 201228965 The crystalline glass powder of the present invention is characterized in that pyroxene crystals and feldspar crystals are used as main crystals. As a feldspar crystal, it is preferably a celsian crystal. The precipitated crystal can effectively reduce the residual glass phase after the heat treatment, thereby becoming a glass ceramic dielectric with a small bubble rate and dielectric loss. In addition, in addition to the search, about 2 crystals (CaA 2Si2 〇 8) and the like may be precipitated in a range in which the dielectric loss or the bubble rate does not rise. Phenite The crystallized glass powder of the present invention is preferably contained in mass%. Si〇20~65%, Ca〇3~25%, Mg〇7~3〇%, a丨2〇3 〇~fiber, post 5~40%, and the relationship is satisfied by the mass ratio. The reason for limiting the composition of the glass as described above is stated. In addition, in the description of the content of the following components, "%" means "% by mass" unless otherwise specified.

Si〇2 is a network former of glass and is a constituent of diopside crystals and feldspar crystals. The content of Si〇2 is preferably from 20 to 65%, from 30 to 65%, especially from 4 to 55%. When the content of si〇2 is 2% by weight or more, it becomes easier to vitrify, and if it is 65% or less, it tends to be easier to form a low-temperature satin (for example, 1000 ° C or lower).

Ca〇 is a constituent component of diopside crystals, and its content is preferably 3 to 25%, 3 to 2% by weight, particularly 7 to 15%. . When the content of CaO is 3% or more, the diopside crystals are easily precipitated, and the dielectric loss of the glass ceramic dielectric tends to be low. When the content of CaO is 25% or less, the fluidity of the glass tends to be further improved.

MgO is also a constituent component of diopside crystals, and its content is preferably 160I65.doc 201228965 7~30%, 8~30%, 11~30. /. In particular, when the content of 12 to 2% by weight of e gMg is 7 or more, crystals are more likely to be precipitated, and if it is 3 % by weight or less, it becomes easier to vitrify.

AhO3 is a component for stabilizing the glass, and its content is preferably 0 to 20%, 0.5 to 20%, especially 1 to 1% by weight. If the content of gossip 2〇3 is 2〇%, there is a tendency for the diopside crystals to be precipitated in the lower shell, and the dielectric loss of the glass ceramic dielectric tends to be low.

BaO is a constituent component of celsian feldspar crystals, and its content is preferably 5 to 4% by weight, particularly preferably 10 to 35%. When the content of BaO is 5% or more, the surface of the feldspar stone is precipitated, and if the content of the secret is less than Na, the amount of precipitation of diopside crystals tends to increase, and as a result, dielectric n dielectric is dielectric. The loss is difficult to grow. Further, by limiting the ratio (mass ratio) of Si 〇 2 to Ba 限制 to a specific range, feldspar crystals can be efficiently precipitated from the residual glass phase after calcination. Specifically, it preferably satisfies the relationship of asi02/Ba0g4, especially 1.05^Si〇2/BaO^3 95 ^ M ^ ^ c. ^ . When the ratio of 81〇2 to Ba0 is in this range, it becomes more accommodating and it is easier for Ge Fuwen to precipitate feldspar crystals or become more glazed. In addition, the following can also be added to the powder of the present and the Japanese ingredients.

Zn 〇 is a component which makes vitrification easy, and its content is preferably 〇 20%, and particularly preferably (U 〜 15%. If the content of Zn 为 is below hop, crystallinity becomes stronger, diopside crystal The tendency for the amount of precipitation to increase is large... As a result, the dielectric loss of the glass ceramic dielectric is difficult to increase. 160165.doc 201228965

The CuO system has a component for suppressing the coloring effect of the glass ceramic dielectric caused by Ag used as a wiring in the insulating material substrate. The content of Cu 较佳 is preferably 〇 1%, more preferably 0.01 to 0.2%. When the content of CuO is 1% or less, the dielectric loss of the glass ceramic dielectric tends to be small. Further, in the same manner as CuO, Ce02, MnO, Sb2〇3, and SnO are components having an effect of suppressing the f color of the glass ceramic dielectric caused by Ag used as wiring in the insulating material substrate. The content of Ce02, MnO, Sb203, and SnO is preferably 0 to 1 °/, respectively. 'Youjia is 0.01~〇 8%. If Ce〇2, Mn〇,

When the content of Sb>2〇3 and SnO is the following, the dielectric loss of the glass ceramic dielectric material tends to be small.

Ti〇2 and Zr〇2 have components which improve the chemical resistance (acid resistance and alkali resistance) of the glass ceramic dielectric.

The content of Ti02 is preferably 〇 15%, and particularly preferably 〇 1 to 13%. If Ti02 contains 1 for 15❶/. In the following, there is a tendency that the dielectric loss of the glass ceramic dielectric material becomes small.

The content of ZrCh is preferably 〇~15%, and particularly preferably 〇b^%. If the Zr〇2 is 15% or less, the dielectric loss of the glass ceramic dielectric tends to be small. Further, in addition to the above components, a total amount of up to 3% by weight of Sr〇, Nb2〇5, La2〇3, Y2〇3, p2〇 may be added within a range of characteristics such as loss of dielectric loss of the glass ceramic dielectric. 5, b2〇3, Bi2〇3 and other ingredients. Further, alkali metal oxides such as LuO, Na2〇, and K:2〇 have a tendency to cut the glass network and increase the dielectric loss. Further, there is a tendency to lower the insulating properties of the glass ceramic dielectric. Therefore, the total amount of the alkali metal oxide is preferably I60165.doc 201228965 5% or less 'preferably lower chest' is optimally not actually containing an alkali metal oxide (specifically, less than 0.1%). The average particle diameter Dw of the crystalline glass powder of the present invention is preferably l〇 pm#, more preferably 5 μηι or less. When the average particle diameter 〇5 <) is 1 〇 μ〇 or less, it is difficult to generate bubbles in the glass ceramic dielectric. On the other hand, although the lower limit is not particularly limited, it is preferably 0.1 μηι or more from the viewpoint of ease of handling or processing cost. The particle size of the crystalline glass powder was measured by a laser diffraction type scattering method. In the crystallized glass of the present invention, it is also possible to mix the above-mentioned or two or more kinds of alumina powder, cordierite powder, mullite powder for the purpose of the characteristics such as the thermal expansion coefficient, the stagnation property, and the dielectric coefficient. , quartz powder, zircon powder 'titanium oxide powder, oxidized powder, such as ceramic powder or quartz glass powder, etc., and thus used as glass (four) material. The glass ceramic material of the present invention contains 60 to 1% by mass of the crystalline glass powder and 陶4% by mass of the ceramic powder, preferably containing, crystalline glass powder of 65 to 99% by mass and Taojing powder 05. 35 quality /. Further, it is preferable to contain the crystalline glass powder to the mass% and the ceramic powder M0% by mass. If the content of the powder of the ceramics exceeds 4% by mass, the glass ceramics tend to be more difficult to be refined. The average particle size of the Brahma is preferably from 0. 01 to 100 μιη, and particularly preferably from ο. 1 to 50. If the average particle diameter D50 of the ceramic powder is 0.01 (four) or more, it is insoluble in the crystalline powder towel, and the effect of improving the swelling coefficient, the property, the dielectric constant, and the chemical resistance is obtained. On the other hand, if the average particle diameter D50 of the ceramic powder is less than or equal to μιη, the flow of the crystalline glassy soil powder during calcination is not hindered, and it is produced in the glass pottery medium Zheng 160165.doc 201228965 to generate bubbles. Further, by using the ceramic powder containing the component A1 as the ceramic powder, it is easy to react the components of Si, 0, and the components in the remaining glass phase after the precipitation of the diopside crystals with the A1 component in the ceramic powder. Crystallization of feldspar crystals. As the powder containing the exhaustion, a oxidized powder can be mentioned. Cordierite powder, mullite powder, anorthite, albite, barium aluminate, titanic acid, spinel, Shaoshen, Shaoshen, Yanshun and so on. Further, the crystallinity can be improved by mixing crystals of diopside or lock feldspar of about 0.1 to 1% by mass as a crystal nucleus. By heat-treating the surface (4) of the crystallized glass containing the present invention at a crystallization start temperature or higher of the crystallized glass, a glass ceramic dielectric in which a diopside crystal and a feldspar crystal are precipitated as a main crystal can be obtained. The content of the diopside crystal in the glass ceramic dielectric is preferably 35 mass% = upper, and more preferably 40 mass% or more. If the content of the diopside crystals is 35 or more, the dielectric loss tends to be small. Further, the diopside crystal: the upper limit of the content is preferably 80% by mass or less, and more preferably 7% by mass or less. The content of the right diopside crystal is 8 变, and the bubbles in the electricity are less. / Next, then the glass Tao Jingjie. The content of feldspar crystals in the glass Tao Jing dielectric is preferably 2 〇 to 65 mass: f 4 %, especially 3 〇 5 5 5 %. If the feldspar crystal contains two or more Å, the bubble ratio in the dielectric of the glass ceramic enamel will become smaller, and the dielectric loss will become smaller. If the content of feldspar crystals is (4): "Bottom: there is a relatively large amount of diopside crystals", so the dielectric loss becomes smaller, or the mechanical strength tends to increase. I60I65.doc 201228965 In the glass pottery 兖雷曾 φ 1 In the case where the residual glass phase is preferably 5% by mass or more, it is preferably more than 5% by weight. If the remaining glass phase is 〇5 mass (10), it is difficult to generate bubbles in the glass ceramic dielectric. Further, the residual glass The upper limit of the content of the phase is preferably 2% by weight or less, more preferably (four) by mass. 4: If the content of the remaining glass phase is 2% by weight or less, the diopside crystal or the feldspar crystal is not relatively small, and the dielectric loss is The bubble ratio of the glass-ceramic dielectric material of the present invention is preferably 3% by volume or less, and particularly preferably 2% by volume or less. If the bubble ratio is 3% by volume or less, it is used as a substrate for an insulating material. It is difficult to cause disconnection of the wiring, or the tendency of the dielectric loss to become small. The glassy ceramic dielectric of the present invention is characterized by a low dielectric constant and a low dielectric loss in a high frequency region. In terms of the sun and moon glass ceramics The electric quantity is preferably 25t:T·, the dielectric constant is 6~u, especially 6~10' and (the dielectric loss in the high frequency region above U GHz is less than or equal to 4, less than 18X10·4, In particular, 16X10·4 or less. Next, a method for producing the crystalline glass powder and the glass ceramic dielectric of the present invention will be described. The crystalline glass powder of the present invention is prepared by preparing a raw material powder in a specific composition. After the lion U is melted at a temperature, it is formed, cooled, and then pulverized. The glass ceramic dielectric of the present invention is produced, for example, in the following manner. First, the ceramic powder is mixed as needed in the crystalline glass powder obtained as described above. And adding a specific amount of a bonding agent, a plasticizer, and a solvent to prepare a slurry. As the bonding agent, for example, a polyvinyl butyl resin, a methacrylic acid tree 160165.doc 201228965, a plasticizer can be used, for example, For the use of Weitian coffee, as a solvent, for example, toluene, mercaptoethyl ketone or the like can be used. The obtained (4) is formed into a green sheet by a doctor blade forming method. dry Cut into a specific size. If necessary, machined to form a through hole, and a low-resistance metal (4) which becomes a conductor or an electrode is printed on the surface of the through hole and the green sheet. Then, the green sheets of the plurality of sheets are laminated by thermocompression bonding. Further, the laminated green sheets are calcined at 800 to 100 ° C, 800 to 95 ° C, especially 850 to 900 ° C, whereby the diopside crystals and the feldspar crystals are precipitated from the crystalline glass powder. Thus, a multilayer substrate including a glass ceramic insulating layer, that is, a glass ceramic dielectric can be obtained. Further, an example in which the glass ceramic dielectric of the present invention is applied to a multilayer substrate is described herein, but is not limited thereto. For example, it can also be applied to electronic component materials such as thick film circuit parts or semiconductor packages. EXAMPLES Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the examples. Tables 1 to 3 show examples of the present invention (sample Nos. 1 to 15). Table 4 shows comparative examples (sample Nos. 16 to 20). 160165.doc 13 201228965 [Table l] Table 1

No.1 No.2 No.3 No.4 No.5 Si02 54.3 47.0 55.5 45.0 42.1 Crystallization*1 Raw CaO 11.0 13.4 8.7 9.6 12.3 Glass powder MgO 13.3 13.1 12.4 14.5 12.2 12.2 AI2O3 2.4 4.4 1.1 3.8 2.1 End (mass BaO 19.0 22.0 22.3 27.0 31.2 %) CuO 0.1 0.1 0.1 Si02/BaO 2.9 2.1 2.5 1.7 1.3 Ceramic powder Alumina oxide Fused andalusite alumina cordierite glass powder (mass ratio): Ceramic powder 80:20 75:5 75:5 70:0 65:5 Precipitated crystal ※() is the content (mass diopside (55) Ba feldspar diopside (63) Ba feldspar diopside (65) Ba feldspar (31) diopside (59) Ba feldspar diopside ( 53) Ba feldspar (42) (34) (36) (43) Ratio of residual glass phase (% by mass) 3 3 4 5 4 Calcination temperature (°c) 870 950 920 900 880 Bubble ratio (% by volume) <1 1 1 <1 2 Dielectric coefficient 8 8 9 8 8 Dielectric loss (Χίο·4) 14 13 13 12 15 160165.doc •14- 201228965 [Table 2] Table 2 No.6 No.7 No.8 No .9 No. 10 Crystalline glass powder (% by mass) Si02 CaO MgO Al2〇3 BaO Ti02 Zr02 Ce〇2 CuO 43.0 8.7 13.0 4.2 31.0 0.1 46.0 10.3 12.8 3.3 27.5 0.1 44.7 9.2 11.5 4.2 2 6.8 3.5 0.1 44.2 8.9 9.5 3.8 30.7 2.8 0.1 48.6 8.2 14.3 2.2 25.3 1.2 0.2 SiCVBaO 1.4 1.7 1.7 1.4 1.9 Ceramic powder 1 Ceramic powder 2 Alumina oxide TiO2 Alumina zirconia Alumina oxide Alumina nitride Glass powder: Ceramic powder 1 : Ceramic powder 2 (mass ratio) 70:9:1 70:28:2 75:25:0 68:32:0 75:25:0 Precipitated crystals ※() content (% by mass) Diopside (55) Ba feldspar (40) Diopside (62) Ba feldspar (33) Diopside (60) Ba feldspar (37) Diopside (59) Ba feldspar (37) Diopside (45) Ba feldspar (52) Residual glass phase ratio (% by mass) 5 5 3 4 3 Calcination temperature (°C) 890 910 900 920 910 Bubble ratio (% by volume) <1 <1 <1 <1 <1 Dielectric coefficient dielectric loss (xHT4) 8 11 8 12 9 14 8 13 8 11 I60165.doc •15- 201228965 [Table 3]

No. 11 No. 12 No. 14 No. 14 No. 14 No. 14 No. 14 No. 14 No. 14 No. 14 No. 14 No. 14 No. 14 No. 15 No. 15 No. 15 No. 15 No. 15 No. 15 No. 15 No. 14 No. 14 No. 14 No. 14 No. 14 No. 15 No. 15 No. 15 No. 15 No. 15 No. 15 No. 15 No. 15 No. 14 No. 15 No. 7.8 21.8 2.8 0.1 40.5 11.0 17.8 4.0 26.6 0.1 54.1 8.9 15.0 22.0 Si〇2/BaO 1.3 2.2 2.1 1.5 2.5 Ceramic powder 1 Ceramic powder 2 Alumina oxide alumina Alumina quartz glass powder. Ceramic powder 1: Ceramic powder 2 (mass ratio) 65:5 68:32 100:0 65:30:5 75:25 Precipitated crystals ※() content (% by mass) Diopside (45) Ba feldspar h (50) Diopside (54) Ba Feldspar (42) Diopside (53) Ba feldspar (44) Diopside (50) Ba feldspar (46) Diopside (43) Ba feldspar (53) Residual glass phase ratio (% by mass) 5 4 3 4 4 Calcination temperature (°C) 920 920 880 930 900 Bubble rate (% by volume) <1 <1 2 <1 <1 Dielectric coefficient dielectric loss (χιό4) 9 13 8 15 7 14 7 13 8 12 160165.doc -16- 201228965 [Table 4] Table 4

No. 16 Νο·17* No. 18 No. 19 No.20 Si02 46.3 33 58.3 43.3 54.1 CaO 22.5 7.3 9.4 5.2 21.4 Crystalline glass MgO 21.3 10.8 10.3 6.3 9.3 AI2O3 5.4 4.7 3.6 13.2 Powder (mass °/〇) BaO 4.5 44 18.4 32.0 15.2 CuO 0.2 Si02/BaO 10.3 0.8 3.2 1.4 3.6 Ceramic powder Alumina cordierite Alumina bismuth glass powder: ceramic powder 70 : 30 / 65 : 35 60 : 40 75 : 25 (mass weight ratio) / Crystalline diopside ί Ba feldspar diopside *0 content (% by mass) (98) / (92) (88) Residual glass phase ratio (mass 2 / 100 8 12 %) / calcination temperature (°c) 920 / 900 880 850 Bubble rate (% by volume) 5 / 1 10 7 Dielectric coefficient 8 / 8 8 8 Dielectric loss (X10·4) 13 / 40 25 25 * No.l7 is not vitrified. Each sample was prepared in the following manner. First, a raw material powder was prepared in the form shown in the table, and after melting at 1,550 ° C, it was molded and cooled to prepare a crystallized glass. The obtained crystalline glass was pulverized to prepare a crystalline glass powder having an average particle diameter D5Q of 2 μm. The ceramic powder shown in the above table was mixed in a specific ratio for each of the crystalline glass powders, and the crystals were precipitated at the calcination temperature shown in the table for 20 minutes to obtain a glass ceramic dielectric. For the glass ceramic dielectric, precipitation crystals were identified, and the ratio of the precipitated crystal and the glass phase, the bubble ratio, the dielectric constant at 25 ° C, and the dielectric loss were measured. The results are shown in Tables 1 to 4. The precipitated crystals in the glass ceramic dielectric were identified by a powder X-ray diffraction apparatus (Rigaku Co., Ltd., RINT 2100). Precipitating crystals and 160165.doc -17- 201228965 The ratio of residual glass phase is calculated from the enthalpy ray diffraction pattern by multiple peak separation method. The bubble ratio was determined by image analysis of a SEM (Scanning Electron Microscope) image of a glass ceramic dielectric cross section. WINROOF of Mitani Corporation was used for image analysis. The steps of image analysis are shown below. In the SEM image, the contour of the bubble portion is more clearly reflected by the edge effect than the portion of the glass substrate. Therefore, the SEM image is binarized using WINR〇〇F to distinguish the outline of the bubble portion from the glass base portion by color. Further, the inside of the bubble is also coated in the same color as the outline of the bubble portion, whereby the bubble portion and the glass substrate portion are color-coded. Thereafter, the bubble ratio was calculated according to the following formula. Furthermore, it is generally known that the area ratio of the bubbles in the dielectric cross section of the glass ceramic is equal to the volume fraction of the bubbles in the glass ceramic dielectric (for example, refer to Qing Gongyibo, "The volume fraction and area ratio of the particles in the composite material. The relationship, Star University University of Science and Technology Research No. 42, issued in 2006, ρ·21~24). Bubble ratio (% by volume) = (total area of the bubble portion / total area of the processed image) X100 The dielectric constant and the dielectric loss were determined by the Hakki-coleman method (measurement frequency 10 GHz). It is clear from Tables 1 to 3 that in the examples of Ν〇·ΐ~15, since the diopside crystal and the celsian crystal are precipitated as the main crystal, the residual glass phase is less than 3 to 5 mass%, so the bubble ratio is low. It is 2% by volume or less. Further, the dielectric constant is 7 to 9 at a frequency of 1 GHz, and the dielectric loss is 160165.doc 18 201228965 11 〜15χΐ〇-4 0 on the one hand in the comparative example N. -16. Since only the diopside crystals are precipitated, the bubble ratio is increased to 5% by volume or more. In N〇i8~2〇, the residual glass phase is increased to 8 masses, and the riding loss is increased to 25Χ1〇·4 or more. Furthermore, in Νο·17, 'Si 2 is less than 〇8, and it is vitrified. I. Industrial Applicability] The crystallized glass of the present invention is suitable as a small or thin multilayer substrate, a microwave circuit component, and a package because there are few internal bubbles and a small dielectric loss in a high frequency band. The present invention has been described with reference to the specific embodiments of the present invention, and it is to be understood that various changes and modifications may be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on November 17, 2010 (Japanese Patent Application No. 2010-256463), and a patent application filed on December 24, 2010 (Japanese Patent Special Purpose 2〇1〇_ 287〇〇4) and May 2, 2011 曰 申请 曰 曰 专利 专利 专利 专利 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 160165.doc -19·

Claims (1)

201228965 VII. Patent application scope: 1. A crystalline glass powder characterized in that diopside crystals and feldspar crystals are precipitated as main crystals by heat treatment. 2. The crystalline glass powder of claim 1, wherein the feldspar crystal is celsian crystal. 3. The crystalline glass powder according to claim 1 or 2, which contains, by mass%, Si〇2 20 to 65%, CaO 3 to 25%, MgO 7 to 301⁄4, Al2〇3 0 to 20%, Ba0 5 ～4〇% is used as the glass composition, and the relationship of 1 guest Si02/Ba0$4 is satisfied in terms of mass ratio. A glass-ceramic material characterized by containing 60 to 1% by mass of the crystalline glass powder according to any one of claims 1 to 3 and a ceramic powder of 〇4% by mass. 5. The glass-ceramic material of claim 4, wherein the ceramic powder contains an Al component. 6. A type of glass pottery dielectric ‘the system will be calcined as in the glass or ceramic material of claim 4 or 5. 7. The glass Tao Tao Jing dielectric of claim 6 contains feldspar crystals 2〇~65 mass%. The heart is as in the glass (iv) dielectric of claim 6 or 7 wherein the bubble ratio is 3% by volume or less. 9. 10. The glass ceramic dielectric ε of any one of claims 6 to 8 is 6 to 11, and is less than or equal to 2 〇 xl 〇 _4 at frequencies above 1 GHz. The material of the circuit material for the glass ray ceramic dielectric wave according to any one of claims 6 to 9. 'The dielectric charge loss tan5 is 'the system is used for micro 160165.doc 201228965 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the representative figure is simple: If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: (none) 160165.doc