JP6864513B2 - Composite sintered body - Google Patents

Description

The present invention relates to a composite sintered body capable of high-precision and fine machining, which is obtained by sintering boron nitride, sialon, and a sintering aid. The present invention also relates to a method for producing the composite sintered body.

Boron nitride sintered body is a machinable ceramic having excellent machinability in addition to excellent heat resistance, heat impact resistance, corrosion resistance, and electrical insulation. However, boron nitride itself is a typical difficult-to-sinter property, and it is difficult to obtain a high-density sintered body, and it is also a slidable material that delaminates in the C-axis direction, so its strength is low. There was a drawback. In order to solve this drawback, many technologies for use in combination with other ceramics have been provided, and composite materials with various ceramics such as silicon nitride, aluminum nitride, and zirconia have been developed, and the fields of steel, semiconductor manufacturing equipment, etc. In addition to having a proven track record in semiconductors, such as a probe guide (also called a probe guide) member (that is, a probe guide member) for fixing the stylus (also called a probe) of a probe card used in the inspection process of a semiconductor wafer process. It is also used in fields where high-precision and fine machining is required.

The probe card is a unit for connecting a semiconductor inspection device and a fine electrode on a semiconductor chip such as an IC or LSI, which is a subject thereof, for energization inspection. The probe has a structure in which the tip of the probe is arranged and fixed in a sword-shaped shape so as to match the position of the electrode of the semiconductor chip in a small hole formed in the probe guide member. This probe guide member has a coefficient of thermal expansion close to that of silicon, which is the material of semiconductor chips, has good workability, and has less wear and damage to machining tools such as drill blades, but has high strength. For example, it is required that the hole made in the probe guide member and the wall between the holes are not damaged. If the coefficient of thermal expansion of the probe guide member is far from that of silicon, heat generation during energization inspection and dimensional differences during measurement under heating make it difficult to align the probe tip with the electrodes of the semiconductor chip. Semiconductor inspection becomes impossible.

In recent years, the degree of integration of semiconductors has increased dramatically, and circuit patterns and terminals have become smaller and narrower in pitch, and devices for inspecting these have also been required to support them. It is required to have more pins and more pins. For this reason, a probe guide member capable of performing fine machining with high accuracy is increasingly required, that is, the workability is better than before, and there is less wear and damage to a machining tool represented by a drill blade, for example. A member for probe guidance capable of accurate and fine machining is desired. As a probe guide member, for example, a material in which boron nitride is combined with zirconia or silicon nitride is known, but none of them can be used for high-precision fine hole drilling. (Patent Document 1, Patent Document 2)

Japanese Unexamined Patent Publication No. 2001-354480 Japanese Unexamined Patent Publication No. 2003-286076

An object of the present invention is that it is possible to perform fine machining with high accuracy, and there is little wear or damage to the machining tool, and it is suitable as a probe guide member for a probe card used in, for example, an inspection process of a semiconductor element. It is an object of the present invention to provide a composite sintered body containing boron nitride, sialon, and a sintering aid, and a method for producing the same.

(1) That is, in the present invention, 40 parts by mass or more and 60 parts by mass or less of boron nitride and 25 parts by mass or more of sialon represented by the following formula 1 (however, in formula 1, Z is 0.2 or more and 1.5 or less). A composite sintered body having a relative density of 90% or more and containing 58 parts by mass or less and 2 parts by mass or more and 15 parts by mass or less of a sintering aid, and the fluorescent X-ray of the composite sintered body. In the intensity measurement, the fluctuation coefficient of the fluorescent X-ray intensity of boron (B) is 3.0 or less as related to boron nitride, and the fluctuation coefficient of the fluorescent X-ray intensity of silicon (Si) is 0 as related to sialon. It is a composite sintered body having a three-point bending strength of 250 MPa or more measured in accordance with JIS R1601: 2008, which is 0.8 or less.
Si _6-Z Al _Z O _Z N _8-Z (Equation 1)
^{(2) The composite sintered body of the present invention has a coefficient of thermal expansion of 1 × 10 -6} / ° C. or more and 3 × 10 ^-6 / in a temperature range of 25 ° C. or more and 600 ° C. or less measured in accordance with JIS R1618: 2002. The composite sintered body according to (1) above, which is below ° C. and has a shore hardness of 55 or more and 75 or less measured in accordance with JIS Z2246: 2000, is preferable.
(3) The composite sintered body according to the above (1) or (2) of the present invention can be preferably used as a material for a probe guide member.
(4) The present invention includes a surface area of ^{20 m} 2 / g or more and GI value is 8 or more hexagonal boron nitride powder ratio specific surface area of ^{6 m} 2 / g or more sialon powder, and / or a specific surface area of ^{6 m} 2 / g or more At least two or more kinds of powders selected from the group consisting of silicon nitride powder, aluminum nitride powder, aluminum oxide powder, and silicon oxide powder, and a sintering aid powder are mixed to form a raw material mixed powder of a composite sintered body. (1) to the above, which comprises a step of obtaining the raw material mixed powder under the conditions of a holding temperature of 1510 ° C. or higher and 1780 ° C. or lower, a holding pressure of 10 MPaG or higher and 50 MPaG or lower, and a holding time of 1 hour or more and 5 hours or less. (3) The method for producing a composite sintered body according to any one of the above.

By implementing the present invention, it is possible to perform fine machining with high precision, there is little damage and wear to the machining tool, and boron nitride and sialon are suitable for use as probe guide members used in the inspection process of semiconductor elements. , A composite sintered body containing a sintering aid can be obtained by sintering.

The composite sintered body of the present invention has 40 parts by mass or more and 60 parts by mass or less of boron nitride and 25 parts by mass of sialon represented by the following formula 1 (however, in formula 1, Z is 0.2 or more and 1.5 or less). A composite sintered body having a relative density of 90% or more and containing 58 parts by mass or more and 2 parts by mass or more and 15 parts by mass or less of a sintering aid, and fluorescent X-rays of the composite sintered body. In the intensity measurement of, the fluctuation coefficient of the fluorescence X-ray intensity of boron (B) as related to boron nitride is 3.0 or less, and the fluctuation coefficient of the fluorescence X-ray intensity of silicon (Si) as related to Sialon. Is 0.8 or less, and the three-point bending strength measured in accordance with JIS R1601: 2008 is 250 MPa or more.

The boron nitride is also one of the raw materials of the composite sintered body of the present invention, but the boron nitride as a raw material is in the form of powder, and its specific surface area measured by the BET method according to JIS R1626: 1996 is a mixture of powders. It is a low-crystalline hexagonal boron nitride having a GI value of 8 or more, which is an index showing crystallinity, and ^{20 m 2} / g or more from the viewpoint of properties. From the viewpoint of handleability, the specific surface area is ^{preferably 200 m 2} / g or less. The GI value (GI: Glycemic Index) is also referred to as a graphitization index, and the area ratio of the peaks of the (100), (101), and (102) planes of boron nitride obtained by X-ray diffraction measurement, GI = It can be obtained by the formula of [Area {(100) + (101)}] / [Area (102)] (J. Thomas. Et. Al, J. Am. Che. Soc. 84, 4619 (1962)). ). In order to realize high-precision and fine machinability, it is necessary that boron nitride and sialon in the composite sintered body are finely and uniformly highly dispersed. If the boron nitride in the composite sintered body is large, cracks and chips are likely to occur during machining. When a highly crystalline powder is used as the raw material hexagonal boron nitride, plate-shaped coarse boron nitride particles remain in the sintered body, and the voids between the particles tend to increase. Therefore, it is necessary to use a low crystalline powder having a GI value of 8 or more as the raw material hexagonal boron nitride.

Boron nitride accounts for 40 parts by mass or more and 60 parts by mass or less, preferably 41 parts by mass or more and 59 parts by mass or less, and more preferably 42 parts by mass or more and 58 parts by mass or less in 100 parts by mass of the composite sintered body of the present invention. Is. If the proportion of boron nitride is less than 40 parts by mass, the hardness of the composite sintered body becomes too high, and for example, the life of the processing tool tends to be significantly shortened. On the other hand, if the proportion of boron nitride exceeds 60 parts by mass, the mechanical strength is insufficient, so that the member cannot withstand machining and the member using the composite sintered body of the present invention is cracked or chipped. It is known that boron nitride forms and volatilizes boron oxide during storage or by heating, but the difference in the composition of the composite sintered body due to the volatile content does not pose a practical problem (usually about about). About 1%). Therefore, in the technical fields including the present application, the mass ratio of boron nitride, sialon, and the sintering aid in the composite sintered body is represented by the blending ratio of the raw materials.

The sialon is also one of the component elements and one of the raw materials constituting the composite sintered body of the present invention represented by (Formula 1), but in obtaining the composite sintered body of the present invention, the sialon is used as the raw material. _{Silicon Nitride (Si 3} N ₄ ), Aluminum Nitride (Al _{N), Aluminum Oxide (Al 2} ), which may produce the sialon having the chemical composition of (Equation 1) as a result of sintering. O ₃ ), a combination of at least two or more types of silicon oxide (SiO ₂ ) in advance (collectively referred to as a sialon raw material group), or a mixture of sialon as the raw material and the sialon raw material group may be used. The specific surface areas of these raw materials for producing sialon (sialon as a raw material and the sialon raw material group) measured by the BET method according to JIS R1626: 1996 are also 6.0 m ² / g or more and 200 m from the viewpoint of powder mixability. ^{It is preferably 2} / g or less.

The proportion of sialon in 100 parts by mass of the composite sintered body of the present invention is 25 parts by mass or more and 58 parts by mass or less, preferably 26 parts by mass or more and 57 parts by mass or less, and more preferably 27 parts by mass or more and 56 parts by mass or less. .. If the proportion of sialon is less than 25 parts by mass, the bending strength specified in the present invention is insufficient, that is, the mechanical strength is insufficient. Cracks and chips occur. On the other hand, if the proportion of sialon exceeds 60 parts by mass, the shore hardness of the composite sintered body becomes too high, and for example, the life of the processing tool tends to be significantly shortened.

In the composite sintered body of the present invention, the Z value of (Formula 1) relating to the composition of the sialon is 0.2 or more and 1.5 or less, preferably 0.2 or more and 1.0 or less, more preferably. Is 0.3 or more and 0.9 or less. If the value of Z is less than 0.2, in the machining of the composite sintered body of the present invention, for example, the hardness increases as the machining tool becomes more easily worn, which impairs practicality. Further, when the value of Z exceeds 1.5, the bending strength of the composite sintered body falls below 250 MPa specified in the present invention because the sialon particles grow large and the partial strength decreases. Presumed, for example, it becomes impossible to perform high-precision and fine machining such as drilling a large number of round holes having a diameter of 40 μm at intervals of 60 μm pitch in a plate-shaped composite sintered body having a thickness of 1 mm. .. The Z value of (Equation 1) related to the composition of Sialon can be obtained from the correspondence between the lattice constant of Sialon and the Z value based on the data obtained by the X-ray diffraction measurement.

Although there is no particular limitation on the kind of sintering aid can be used in the composite sintered body of the present invention, rare earth oxides or aluminum oxide (alumina, Al 2 O _3), magnesium oxide (magnesia, MgO) and these combined Oxides and the like can be preferably used. Since aluminum oxide is also a raw material preferably used as a component of the Sialon raw material group, aluminum oxide added separately to have an effect as a sintering aid is referred to as alumina in the present invention. The sintering aid chemical, from the viewpoint of physical properties to obtain a stable sintered body can preferably be used a rare earth oxide, more particularly yttrium oxide (yttria, Y 2 _{O 3)} the effect Can be used as a target.

In 100 parts by mass of the composite sintered body of the present invention, the ratio of the sintering aid is 2 parts by mass or more and 15 parts by mass or less, and a more preferable range is 3 parts by mass or more and 14 parts by mass or less, more preferably 3 parts by mass or more and 12 parts by mass. It is less than a part by mass. When the ratio of the sintering aid is less than 2 parts by mass, it is difficult to obtain a high-density and high-strength composite sintered body, and cracks and chips occur due to machining. When the ratio of the sintering aid exceeds 15 parts by mass, the crystal grain size in the sintered body becomes large, and similarly, the strength is lowered and the high precision and fine machinability is inferior.

The composite sintered body of the present invention may contain trace impurity elements that are inevitably mixed as long as the machinability and the intended use of the intended use are not hindered. However, the composite sintered body of the present invention is preferably used as a material for a probe guide member that requires high precision and fine processing, and is also required to have electrical characteristics (for example, electrical insulation). It is preferable that metal impurities are not contained as much as possible.

In the method for producing a composite sintered body of the present invention, a hexagonal boron nitride powder as a raw material, sialon and / or a sialon raw material group as a raw material, and a sintering aid are mixed to form a composite sintered body. The production includes a step of obtaining the raw material mixed powder, and a step of pressure sintering the raw material mixed powder under the conditions of a holding temperature of 1510 ° C. or higher and 1780 ° C. or lower, a holding pressure of 10 MPaG or higher and 50 MPaG or lower, and a holding time of 1 hour or more and 5 hours or less. The method.

The mixing method in the step of obtaining the raw material mixed powder is not particularly limited, and there is no particular limitation on whether it is a dry method in which only the raw materials are mixed as they are or a wet method in which a liquid component is added to the raw materials and mixed. Absent. In the case of the wet method, for example, ethanol is preferably used as the solvent. Further, a known device can be used as the mixing device, and for example, a ball mill is preferably used.

In the method for producing a composite sintered body of the present invention, it is necessary to perform pressure sintering, but the method and type of the sintering apparatus itself are not particularly limited, and an apparatus generally used in the field of ceramics production is adopted. can do. Examples of the pressure sintering method include hot press sintering, discharge plasma sintering, ultra-high pressure sintering, and hot isotropic pressure sintering by gas compression.

Regarding the material and shape of the container and mold used for pressure sintering, the composition of the composite sintered body of the present invention obtained in particular is affected, and the container and the container and the shape are subjected to sintering. There is no particular limitation as long as the mold does not deteriorate, deform or break. Considering this point, a graphite container or mold is preferably used.

The sintering temperature at the time of performing pressure sintering is 1510 ° C. or higher and 1780 ° C. or lower, preferably 1520 ° C. or higher and 1760 ° C. or lower, and even more preferably 1540 ° C. or higher and 1740 ° C. or lower. If the sintering temperature is less than 1510 ° C., a sintered body that has been sufficiently sintered cannot be obtained, the relative density of the sintered body is less than 90%, and the three-point bending strength is also low, less than 250 MPa specified in the present invention. It becomes a thing. On the other hand, even when the temperature exceeds 1780 ° C., the three-point bending strength specified in the present invention is as low as less than 250 MPa, which is a result of the progress of growth of the boron nitride and sialon crystal phases in the composite sintered body. It is presumed that, as a result, there is an increased tendency for cracks and chips to occur during machining and for the drill bit to be damaged.

The pressure applied during pressure firing is in the range of 10 MPa or more and 50 MPa or less, preferably 11 MPa or more and 45 MPa or less, and even more preferably 13 MPa or more and 40 MPa or less. If the pressure is less than 10 MPa, a sintered body having a sufficiently sintered density cannot be obtained, the relative density of the composite sintered body is less than 90%, and the three-point bending strength is also as low as less than 250 MPa. On the other hand, a device to which a pressure exceeding 50 MPa is applied has a large equipment, which is disadvantageous in terms of cost.

The sintering time (including the pressurization holding time) of the pressure firing is 1 hour or more and 5 hours or less, preferably 1.5 hours or more and 4.5 hours or less, and even more preferably 1.5 hours or more and 4 hours or less. The range. If the holding time is less than 1 hour, there is a problem that the distribution of the characteristics in the sintered body tends to be large, the overall strength is lowered, and the three-point bending strength specified in the present invention is as low as less than 250 MPa. However, if the holding time exceeds 5 hours, the growth of the boron nitride and sialon crystal phases will proceed excessively in the composite sintered body, and as a result, the composite sintered body will be cracked or chipped, and wear on the processing tool will occur. Damage tends to increase.

The relative density of the composite sintered body of the present invention with respect to the theoretical density is 90%. When the relative density is 90% or more, there are almost no pores communicating with the composite sintered body, and even if high-precision and fine machining is performed, large defects are unlikely to occur. The relative density is a value obtained by dividing the apparent density of the composite sintered body by its theoretical density (however, it is expressed as a percentage multiplied by 100). The theoretical density of the composite sintered body is a value obtained by proportionally dividing the true density of each component (that is, of each component) based on the mass ratio of boron nitride, sialon, and the sintering aid in the composite sintered body. The weighted average value of the true density). The apparent density of the composite sintered body can be obtained in accordance with JIS R 1634: 1998 using a measuring device to which the Archimedes method is applied.

In the composite sintered body of the present invention, the coefficient of variation of the fluorescent X-ray intensity of boron (B) is 3.0 or less as related to boron nitride, and the fluorescent X-ray of silicon (Si) is related to Sialon. The coefficient of variation of intensity is 0.8 or less. When the coefficient of variation of boron (B) related to boron nitride exceeds 3.0 or the coefficient of variation of silicon (Si) related to sialon exceeds 0.8, each crystal of boron nitride or sialon in the composite sintered body. Since the uneven distribution of phases becomes large, it becomes difficult to perform high-precision and fine machining. In the present invention, the coefficient of variation of the intensity of the fluorescent X-ray is a fluorescent X-ray (Kα ray) peculiar to boron (B) and silicon (Si) at 10 locations on the surface of the composite sintered body by a fluorescent X-ray analyzer. ) Is measured, and is a value obtained from their average value and standard deviation.

Since the composite sintered body of the present invention is premised on being subjected to high-precision and fine machining, it is necessary that the three-point bending strength measured in accordance with JIS R1601: 2008 is 250 MPa or more. Is. If the three-point bending strength is not at least 250 MPa or more, cracks and chips will occur when the composite sintered body is machined.

In the composite sintered body of the present invention, it is necessary that the three-point bending strength is 250 MPa or more as described above, but the shore hardness measured in accordance with JIS Z2246: 2000 is 55 or more and 75. preferable. The hardness is not in an appropriate range as specified in the present invention, that is, even if it has sufficient bending strength, it tends to be too hard and damage to the machining tool increases.

The composite sintered body of the present invention is, for example, a material for a probe card used in an inspection device for a semiconductor element formed on a silicon wafer, that is, a substrate for press-welding the probe tip according to the interval of a fine electric circuit. It is a preferable material for a probe guide member. Therefore, the coefficient of thermal expansion of the composite sintered body is preferably close to the coefficient of thermal expansion of high-purity silicon, and specifically, the coefficient of thermal expansion in the temperature range of 25 ° C. or higher and 600 ° C. or lower is 1 × ^10-6 / ° C. or higher. It is preferably 3 × 10 ^-6 / ° C or lower. The coefficient of thermal expansion is a value measured according to the method shown in JIS R1618: 2002.

The composite sintered body of the present invention is finely machined, for example, a large number of round holes having a diameter of 40 μm are perforated at intervals of 60 μm pitch between centers in a plate-shaped composite sintered body having a thickness of 1 mm. It is intended to be preferably used for applications subject to machining, but if the mechanical strength during or after machining is insufficient, defects such as cracks and chips occur. Therefore, in the composite sintered body of the present invention, it is preferable that the three-point bending strength is 250 MPa or more and the shore hardness is 55 or more and 75 or less. The three-point bending strength is a value measured according to the method shown in JIS R1601: 2008, and the shore hardness is measured according to the method shown in JIS Z2246: 2000. The value.

As a method of confirming whether or not the composite sintered body of the present invention solves the problem of the present invention, for example, a large number of holes are actually made in the composite sintered body in the form of a thin plate, and the processing accuracy and the composite firing thereof are obtained. The method of observing and evaluating the occurrence of cracks and chips in the body is suitable, and the evaluation is close to practical use.

For example, the small hole of the probe guide member often has a diameter of 40 to 100 μm, but there are also smaller holes. One part is machined with 500 to 20,000 holes. In this case, in order to determine whether or not high-precision and fine machining accuracy has been achieved, the shape of the hole itself that was actually machined, that is, the deviation from the set hole diameter, the roundness, and the hole position The accuracy of the above is a guide, and the presence or absence of damage such as cracks or chips in the wall between the holes is a criterion.

Examples and comparative examples of the composite sintered body of the present invention are shown below, that is, the manufacturing method of the composite sintered body is specifically shown, and the evaluation results when actually processed as a probe guide member are shown. However, the present invention is not limited to this description.

(Composite sintered body of Example 1)
As the raw material powder of the composite sintered body of the present invention, as shown in Table 1, ^{48 parts by mass of hexagonal boron nitride powder (GI value: 15, specific surface area: 41 m 2} / g) and sialon powder ((Formula 1). ) Is 0.5, specific surface area: 15 m ² / g,) and 46 parts by mass of) and alumina powder (specific surface area: 14 m ² / g, purity: 99.99% by mass or more) as a sintering aid. 1.5 parts by mass and 4.5 parts by mass of Itria powder (purity: 99% by mass, average particle size: 0.4 μm) are sufficiently wet-mixed with a ball mill using etanol as a solvent. Then, this was vacuum-dried to obtain a raw material mixed powder of the composite sintered body. The raw material mixed powder is filled in a graphite die having an inner diameter of 80 mmφ, hot-pressed under the conditions of a sintering temperature of 1710 ° C., a sintering pressure of 30 MPa, and a sintering time of 3 hours, and then taken out from the die to be taken out from the die. A composite sintered body was obtained.

(Measurement of relative density)
The outer shape of the composite sintered body of Example 1 was ground by about 1 mm, and its apparent density was measured by the Archimedes method. Further, the relative density was calculated by dividing the apparent density by the theoretical density of the composite sintered body obtained according to the mass ratio of each component of the composite sintered body shown in Table 1 (notation is expressed in%). .. The results are shown in Table 3.

(Measurement of coefficient of variation)
A test piece cut out to a width of 40 mm, a thickness of 3 mm, and a length of 40 mm was prepared from the composite sintered body, and the surface 10 of the test piece was prepared by a fluorescent X-ray analyzer (ZSX-PrimusII, manufactured by RIGAKU). The intensity (unit: kcps) of fluorescent X-rays (Kα rays) at one location was measured, and the coefficient of variation was calculated from the average value and standard deviation. The results are shown in Table 3.

(Measurement of 3-point bending strength)
The three-point bending strength was measured according to JIS R1601: 2008 using a test piece cut out from the composite sintered body to a width of 4 mm, a thickness of 3 mm, and a length of 40 mm. The results are shown in Table 3.

(Measurement of coefficient of thermal expansion)
A test piece having a width of 4 mm, a thickness of 4 mm, and a length of 20 mm is cut out from the composite sintered body, and a coefficient of thermal expansion of 25 ° C. to 600 ° C. is used using a thermal expansion measuring device (TMA8301, manufactured by RIGAKU). Was measured. The results are shown in Table 3.

(Evaluation by machining)
A test piece cut out from the composite sintered body to a width of 40 mm, a thickness of 1 mm, and a length of 40 mm was prepared, and a machining center equipped with a cemented carbide microdrill blade (hereinafter referred to as a drill blade) having a diameter of 40 μm was used. Drilling was performed dry at a rotation speed of 15,000 rpm. A total of 400 holes with a pitch of 60 μm (hole-hole partition wall set value 20 μm, depth 200 μm) were drilled in the test piece, and the hole diameter and hole position were measured using a CNC optical measuring instrument. Those whose hole diameter and position were within the standard of ± 4 μm were regarded as acceptable (○ indication), and those outside the standard were rejected (× indication). In addition, those with no cracks or chips on the wall between holes were accepted (marked with ○), and those with cracks or chips were judged to be rejected (displayed with ×). In addition, those that could process all 400 holes with one drill blade were evaluated as acceptable (indicated by ○), and those that could not be processed due to damage to the drill blade were evaluated as rejected (indicated by ×). These results are shown in Table 3. The accuracy of the hole diameter and hole position was not evaluated when the wall was cracked or chipped or the drill blade was damaged.

(Examples 2 to 16, Comparative Examples 1 to 14)
The compounding of the raw material mixed powder of the composite sintered body, the sintering temperature, the sintering pressure, and the sintering time are changed to the compounding and sintering conditions shown in Tables 1 to 4, and the mixing conditions of the other raw material mixed powders and baking are changed. The apparatus and the like used for the conclusion were the same as in Example 1, and the composite sintered bodies of Examples 2 to 16 and Comparative Examples 1 to 14 were prepared. Further, these various evaluations were carried out in the same manner as in Example 1, and are shown in Tables 3 and 4 together with the results of Example 1.

(Comparative Example 15)
The blending of the raw material mixed powder of the composite sintered body, the sintering temperature, the sintering pressure, and the sintering conditions were changed to the blending and the sintering conditions shown in Table 2, and the raw material mixed powder was mixed by a dry vibration mill. A ceramic sintered body was prepared and evaluated in the same manner as in Example 1 except for the points. The evaluation results of each of the obtained sintered bodies are shown in Table 4.

The composite sintered body of Examples 1 to 15 showing the provisions of the present invention shown in Tables 1 and 3, that is, 40 parts by mass or more and 60 parts by mass or less of boron nitride, and the following formula 1 (however, in formula 1, Z Is 0.2 or more and 1.5 or less), and a total of 100 parts by mass including 25 parts by mass or more and 58 parts by mass or less of Sialon and 2 parts by mass or more and 15 parts by mass or less of the sintering aid is relative. In the measurement of the intensity of the fluorescent X-ray of the composite sintered body having a density of 90% or more, the fluctuation coefficient of the intensity of the fluorescent X-ray of boron (B) is 3. Composite sintering with 0 or less, a fluctuation coefficient of fluorescent X-ray intensity of silicon (Si) of 0.8 or less as related to Sialon, and a 3-point bending intensity of 250 MPa or more measured in accordance with JIS R1601: 2008. All of the bodies obtained good evaluation results, indicating that the object of the present invention was achieved.
Si _6-Z Al _Z O _Z N _8-Z (Equation 1)

Claims (4)

Sintered with 40 parts by mass or more and 60 parts by mass or less of boron nitride and 25 parts by mass or more and 58 parts by mass or less of Sialon represented by the following formula 1 (however, in formula 1, Z is 0.2 or more and 1.5 or less). A composite sintered body containing 2 parts by mass or more and 15 parts by mass or less of an auxiliary agent and having a relative density of 90% or more. The fluctuation coefficient of the fluorescent X-ray intensity of boron (B) is 3.0 or less, and the fluctuation coefficient of the fluorescent X-ray intensity of silicon (Si) related to Sialon is 0.8 or less, JIS R1601: 2008. A composite sintered body having a three-point bending strength of 250 MPa or more measured in accordance with the above.
Si _6-Z Al _Z O _Z N _8-Z (Equation 1) The coefficient of thermal expansion in the temperature range of 25 ° C or higher and 600 ° C or lower measured according to JIS R1618: 2002 is 1 × ^10-6 / ° C or higher and 3 × ^10-6 / ° C or lower, and conforms to JIS Z2246: 2000. The composite sintered body according to claim 1, wherein the shore hardness measured as described above is 55 or more and 75 or less. The composite sintered body according to claim 1 or 2, which is a material for a probe guide member. Hexagonal boron nitride powder with a specific surface area of 20 m ² / g or more and a GI value of 8 or ^{more, Sialon powder with a specific surface area of 6 m 2} / g or more, and / or silicon nitride powder or aluminum nitride with a ^{specific surface area of 6 m 2 / g or more.} A step of mixing at least two or more kinds of powders selected from the group consisting of powders, aluminum oxide powders, and silicon oxide powders with a sintering aid powder to obtain a raw material mixed powder of a composite sintered body, the raw material mixed powder. The composite baking according to any one of claims 1 to 3, which includes a step of pressure sintering under the conditions of a holding temperature of 1510 ° C. or higher and 1780 ° C. or lower, a holding pressure of 10 MPaG or higher and 50 MPaG or lower, and a holding time of 1 hour or more and 5 hours or less. How to make a body.