JP2019104682A - Method for manufacturing quartz glass filament - Google Patents

Abstract

To provide: a method for manufacturing a quartz glass filament used for a semiconductor package substrate, excellent in surface smoothness, having very small variation in mass and thickness and excellent in dimensional stability; a quartz a glass strand; and a method for manufacturing quartz glass yarn.SOLUTION: The method for manufacturing a quartz glass filament comprises heating and drawing a quartz glass ingot to manufacture a quartz glass thick fiber and heating and drawing the quartz glass thick fiber to manufacture a quartz glass filament. When manufacturing the quartz glass thick fiber, the initial response amount proportional to a deviation size between the target diameter value of the thick fiber after the heating and drawing and a measured value and a control operation amount corresponding to the cumulative value of a deviation between the target diameter value and the measured value are reflected on a thick fiber drawing speed, and the control operation amount corresponding to the cumulative value of a deviation between the target speed of the thick fiber drawing speed and an actual speed is reflected on a speed sending the ingot into the furnace.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a quartz glass cloth particularly suitable for use as a substrate of a semiconductor package, a prepreg and a semiconductor package substrate using the same, and a method for producing a quartz glass filament, a quartz glass strand and a quartz glass yarn used for a quartz glass cloth. It is a thing.

  In recent years, with the reduction in thickness and high functionality of electronic devices, the mounting density has been increased. Recently, along with the miniaturization of semiconductor packages, a microminiature package system having almost the same size as a semiconductor chip such as a CSP (Chip Size Package) system has been adopted.

  The semiconductor package is a substrate on which a semiconductor element such as an IC chip is mounted, and the substrate for a semiconductor package is, for example, a base in which a conductor layer such as copper foil is provided on an insulating layer obtained by applying a matrix resin to glass cloth. It is comprised by laminating | stacking two or more materials.

  Each conductor layer is electrically connected in the vertical direction via conduction holes called through holes, inner via holes, and brand via holes.

  As a method of electrically connecting a semiconductor chip and a semiconductor package substrate, a structure in which they are directly connected through bumps is used, and an FC (Flip Chip) method capable of high frequency response and high speed operation is adopted. .

  As a substrate material of the FC-CSP package system, a copper clad laminate (CCL) substrate in which a plastic material and a glass cloth are combined is used. As a method of suppressing the warp of the CCL substrate at the time of heat generation, adoption of a low thermal expansion glass cloth is in progress, and adoption of a quartz glass cloth is also studied.

  In the quartz glass cloth, a yarn obtained by twisting a bundle (strand) of monofilament fibers obtained by stretching the quartz glass is woven by an air jet loom. A semiconductor package substrate material is manufactured by combining such a quartz glass cloth and a resin.

  The substrate for the semiconductor package is a composite material consisting of a matrix resin which is an organic material, a glass cloth which is an inorganic material, and a filler, and the organic material and the inorganic material are nonuniformly present. The laser light absorptivity, decomposition temperature, thermal diffusivity, etc. are different, so the processing condition of each material part is different, roughness of the inner surface of the hole occurs, and defects such as loss of insulation reliability in the plating process On the other hand, a proposal has been made to improve the laser hole processability, and the gap surrounded by the warp yarn and the weft yarn constituting the glass cloth is opened substantially without a gap, and The filling rate is made uniform (Patent Documents 1 to 3).

  The sol-gel method, the heating drawing method, etc. are known about the preparation method of quartz glass fiber, and a slight difference is recognized in the characteristic obtained (patent documents 4-5 and patent documents 9).

  In addition, with regard to the processability improvement of quartz glass fiber, by setting the fictive temperature of synthetic quartz glass fiber to 1200 ° C or more and 1600 ° C or less, an unstable structure is contained, and the processability is improved compared to conventional quartz glass fiber. Good quartz glass fibers have been obtained (Patent Document 6).

  Examples of glass cloths other than quartz glass used as a substrate include E glass, S glass, T glass, L glass, NE glass, D glass and the like, but most of these glass fibers are manufactured by melt spinning method (Patent Document 10).

  On the other hand, in recent years, with the advancement of performance and miniaturization of electronic devices, it has become necessary for semiconductor package substrates to meet the demands for high density and thickness reduction, and the thickness of the insulating layer of the substrate is 60 μm or less It is getting thinner.

  With the thinning of the insulating layer, the thickness of the copper foil is also reduced, which makes more stringent demands also on the surface smoothness of the insulating layer and the cross quality such as fluff.

  As a method of improving the surface smoothness of the insulating layer, although the number of twists of the glass yarn is 40 times / m in the past, weaving with a further reduced twist or no twist has been studied and advanced.

  Conventionally, drilling of conductive holes has been carried out using a drill, but it is difficult to control the depth of the holes with the accuracy of the laminated thickness, and laser drilling has been proposed and put to practical use.

  However, in order to meet the demand for higher density and thinner semiconductor package substrates in recent years, laser processing has become increasingly finer, and the substrates are required to have severe dimensional stability.

  In order to meet the demand for higher density and thinner semiconductor package substrates in recent years, the CCL (Copper Clad Laminate) substrate for the FC-CSP package system has also been made ultra thin.

  With the ultra-thin CCL substrate, the thickness of the prepreg as the insulating layer and the copper foil as the conductor layer are becoming thinner. As the thickness of the prepreg is reduced, the thickness of the glass cloth is also extremely reduced, and the thickness is 10 to 20 μm. In order to ensure the flatness of the prepreg, the requirements for the quality of the ultra-thin glass cloth are becoming strict.

  However, a quartz glass rod having a diameter of 2 to 100 mm is heated and drawn by the method described in the conventional Patent Document 9 to produce a quartz glass fiber having a diameter of 100 to 400 μm and a standard deviation of 10 or less in diameter. In the method of producing the ultrafine quartz glass fiber having a filament diameter of 3 to 5 μm by the method described in, a distribution of filament diameters having a standard deviation of the diameter of 1 or more occurs.

  For example, 30 to 100 filaments having a diameter of 3 to 5 μm and a standard deviation of 1 or more are produced, and they are collected to produce a quartz glass strand. And when a quartz glass yarn having a size of 0.5 to 10 tex is manufactured by twisting 0.1 to 5 times per 25 mm of a quartz glass strand, the standard deviation of the number is from 0.05 It gets bigger. With such quartz glass yarn, it is difficult to obtain a high quality quartz glass cloth which is very large in mass and thickness variation, excellent in surface smoothness, and excellent in dimensional stability even when woven. It is difficult to secure the flatness of a 10 to 20 μm thick prepreg.

Japanese Patent Application Laid-Open No. 2002-242047 JP 2003-347743 Patent document 1: JP-A-2004-179171 JP-A-62-297236 British Patent No. 507951 Japanese Patent Application Publication No. 2004-99377 Japanese Patent Application Laid-Open No. 2006-027960 Japanese Patent Application Publication No. 2006-282401 Japanese Patent Application Publication No. 2006-182610 Japanese Patent Application Laid-Open No. 57-149839

  The present invention has been made in view of the above-described problems of the prior art, and is used for a semiconductor package substrate, and has excellent surface smoothness, very little variation in mass and thickness, and excellent dimensional stability. It is an object of the present invention to provide a prepreg and a semiconductor package substrate using the same, and a method of manufacturing a quartz glass filament, a quartz glass strand and a quartz glass yarn.

  In order to solve the above problems, the quartz glass cloth of the present invention is a quartz glass cloth used for a semiconductor package substrate, and is a quartz glass filament having an average filament diameter of 3 μm or more and 20 μm or less. It manufactures using the quartz glass strand or quartz glass yarn which used the quartz glass filament whose deviation is 0.15 or less 20 or more and 400 or less.

  0.10 or less is preferable and, as for the standard deviation of the said quartz glass filament diameter, 0.01 or less is more preferable.

  In the present specification, quartz glass fiber refers to a thin thread-like fiber obtained by stretching quartz glass, and quartz glass fiber, quartz glass filament, quartz glass yarn, quartz glass wool and the like can be obtained from quartz glass fiber. Further, in the present specification, a single fiber is defined as a quartz glass filament, a bundle of quartz glass filaments is defined as a quartz glass strand, and a bundle of quartz glass filaments and twisting is defined as a quartz glass yarn.

  It is preferable that the number of twists of the quartz glass yarn is 40 times / m or less. The number of twists of the quartz glass yarn is preferably 0.1 or more and 5 or less per 25 mm. Moreover, the thing whose number of twists is 0 times / m is a quartz glass strand.

  The thickness of the quartz glass cloth is preferably 50 μm or less.

  The prepreg of the present invention is produced using the quartz glass cloth.

  The semiconductor package substrate of the present invention is manufactured using a quartz glass cloth.

  The method for producing a quartz glass filament according to the present invention is a method for producing the quartz glass filament used for the quartz glass cloth, wherein a quartz glass ingot is heated and drawn to produce a thick fiber made of quartz glass, and then the quartz glass is produced A thick fiber is heated and drawn to produce a quartz glass filament, and in producing the thick fiber made of quartz glass, the target fiber diameter value of the thick fiber after the heat drawing is proportional to the size of the deviation of the measured value The initial response amount and the control operation amount according to the cumulative value of the target wire diameter value and the deviation of the measured value are reflected in the drawing speed of the thick fiber, and the accumulated drawing of the deviation of the target speed of the thick fiber and the actual speed A quartz glass with a diameter of 100 to 300 μm and a standard deviation of the diameter of 0.5 or less by reflecting the control operation amount according to the value in the feed speed of the ingot into the furnace Formed by producing a thick fibers.

  As used herein, quartz glass thick fibers refer to those with a diameter of 100 to 300 μm.

  It is preferable to manufacture a quartz glass filament by heating and drawing the quartz glass thick fiber with a burner flame of a mixed gas of oxygen and hydrogen or in an electric furnace.

  The method for producing the quartz glass strand of the present invention is a quartz glass filament having an average filament diameter of 3 μm or more and 20 μm or less using the method for producing the quartz glass filament, and the standard deviation of the diameter of the quartz glass filament is 0.15 or less 20 or more and 400 or less of the quartz glass filaments, and focusing them to produce a quartz glass strand.

  In the method of producing the quartz glass yarn of the present invention, the quartz glass strand is twisted by 0.1 times or more and 5 times or less per 25 mm, and the size of the count is 0.5 to 10 tex, It is a method of producing a quartz glass yarn having a standard deviation of 0.05 or less.

  According to the present invention, it is used for a semiconductor package substrate, quartz glass cloth excellent in surface smoothness, very small in mass and thickness variation, excellent in dimensional stability, prepreg using the same, semiconductor package substrate and quartz A significant effect of providing a method of manufacturing glass filaments, quartz glass strands and quartz glass yarns is exhibited.

FIG. 2 is a schematic explanatory view of a method of producing a quartz glass filament of Example 1. FIG. 6 is a schematic explanatory view of a method of producing a quartz glass filament of Example 2. FIG. 14 is a schematic explanatory view of a method of producing a quartz glass filament of Example 3. It is typical explanatory drawing of the method of manufacturing the quartz glass thick fiber of Example 4 and Example 5. FIG. It is typical explanatory drawing of the method of manufacturing the quartz glass filament of Example 4 and Example 6. FIG. It is typical explanatory drawing of the method of manufacturing the quartz glass filament of Example 5 and Example 7. FIG. It is typical explanatory drawing of the method of manufacturing the quartz glass thick fiber of Examples 6-7. It is the figure which showed distribution of the quartz glass thick fiber diameter of Examples 4-7. It is the figure which showed distribution of the glass filament diameter of Example 4, Example 6, and the comparative example 4. FIG.

  The inventors of the present invention conducted intensive studies for the purpose of obtaining uniform quartz glass filaments, glass yarns, glass cloths and laminates, and as a result, optimized the production conditions of the glass filaments to obtain extremely uniform quality. I was able to get it. In addition, since quartz glass is used, the coefficient of linear expansion is low, and the dimensional stability when performing laser processing on a semiconductor package substrate is also excellent.

The outline will be described below.
In order to meet the demand for higher density and thinner semiconductor package substrates, the thicknesses of the prepreg as the insulating layer and the copper foil as the conductive layer are reduced, and in particular, the smoothness and the surface roughness of the surface of the insulating layer, etc. Demand for cross quality is becoming stricter. As the absolute thickness of the insulating layer is becoming thinner, the smoothness of the surface is required to be more smooth than ever.

  In order to improve the smoothness of the insulating layer, it is necessary to make the quartz glass cloth constituting the insulating layer smooth, and in order to make the quartz glass cloth smooth, opening is performed.

  In order to make the quartz glass cloth smooth, more smoothness can be obtained by reducing the number of twists of the yarn constituting the cloth or making it a non-twisted yarn. Furthermore, by making the counts of the yarns constituting the cloth uniform, even more smoothness can be obtained.

  In order to make the quartz glass yarn uniform, it is necessary to make the diameter of the filaments constituting the yarn uniform, but according to the present invention, the range of variation is very narrow, and the distribution of the filament diameter is very narrow. You can get

  The quartz glass can be spun by a known method. However, in the sol-gel method, control of the discharge amount is required, and in the heating and melting method, stabilization of the melting volume is required. More specifically, in the sol-gel method, in order to make the discharge amount constant at all discharge nozzles, the nozzle diameter should be ± 2% or less in accuracy, and the viscosity fluctuation of the molten mother liquid will not occur, and the mother liquid is cooled and hydrolyzed. Stop disassembly.

  Further, in the heating and melting method, the desired diameter is obtained by controlling the outer diameter of the base material or the feeding speed of the base material in order to set the glass input amount to the heating melting portion within ± 0.1 wt%. The diameter is obtained.

  And about the manufacturing method of a uniform quartz glass yarn, as shown in FIG. 4, the quartz glass ingot 41 of diameter 50mm-200mm is heated and drawn in the resistance heating-type electric furnace 42, 100 micrometers-300 micrometers in diameter The thick fiber 43 made of quartz glass is manufactured. At that time, the outer diameter of the quartz glass thick fiber is measured by the laser type outer diameter measuring device 44, and the initial response is proportional to the deviation of the target wire diameter value of the quartz glass thick fiber 43 after drawing and the measured value. The control operation amount I1 according to the amount P1 and the accumulated value of the target wire diameter value and the deviation of the measured value is reflected in the drawing speed V1 of the thick fiber 43 made of quartz glass, and the target of the drawing speed of the thick fiber 43 made of quartz glass The standard deviation of the diameter of the thick fiber 43 made of quartz glass is made 0.1 or less by reflecting the control operation amount I1 according to the accumulated value of the deviation of the speed and the actual speed V1 into the feed speed V2 into the electric furnace 42. It is possible to In addition, the code | symbol M of FIG. 5 shows the high-precision winding machine for winding up the quartz glass thick fiber 43. As shown in FIG. Further, reference numeral 61 denotes a winding speed control unit for controlling the winding speed of the thick fiber 43 made of quartz glass, and reference numeral 62 denotes an ingot feeding speed control unit for controlling the feeding speed of the quartz glass ingot 41.

y : 操作量
e : 偏差 (=目標値−実際値)
K_p : 比例ゲイン
T_I : 積分時間
よって本発明における目標線径値と測定値の偏差の大きさに比例した初期応答量Ｐ１はＰＩ制御の比例動作にあたり、目標線径値と測定値の偏差の累積値に応じた制御操作量Ｉ１と石英ガラス製太繊維の線引き速度の目標速度と実速度Ｖ１の偏差の累積値に応じた制御操作量Ｉ２はＰＩ制御の積分動作にあたる。 The above control method is a so-called PI control, where P is proportional, I means integral, and it consists of two compensation operations. PI control is expressed as the following equation (1) or (2), and is proportional to a proportional action (Proportional Action: P action) that produces a correction amount proportional to the current deviation e and to the accumulated value of the past deviation It is a combination of the two with the integration operation (Integral Action: I operation) which gives a correction amount.

y: operation amount
e: Deviation (= Target value-Actual value)
K _p : proportional gain
T _I : Integration time Therefore, the initial response amount P1 proportional to the magnitude of deviation between the target wire diameter value and the measured value in the present invention corresponds to the cumulative value of deviation between the target wire diameter value and the measured value in proportional operation of PI control. The control operation amount I2 and the control operation amount I2 corresponding to the accumulated value of the target velocity of the draw speed of the thick fiber made of silica glass and the deviation of the actual velocity V1 correspond to the integral operation of PI control.

  In order to produce a quartz glass strand, as shown in FIG. 5, a plurality of quartz glass thick fibers 43 with a diameter of 100 μm to 300 μm are heated and drawn by a burner flame F1 from a wide oxyhydrogen flame burner B1 After making 100 quartz glass filaments 46 and applying them with a sizing applicator 50, they are focused by a concentrator 47 to produce a quartz glass strand 48. The manufactured quartz glass strand 48 is then wound up by a winder 49. In this method, a quartz glass filament 46 with a diameter of 3 to 5 μm can be obtained.

  Alternatively, as shown in FIG. 6, a plurality of thick fibers 51 made of quartz glass with a diameter of 100 to 300 μm are simultaneously set in a jig, and the inside of a vertical tubular electric furnace 52 with a maximum temperature of 2000 ° C. equipped with a heater means Slowly lower and pull the melted end from the lower part of the electric furnace at high speed to make 30 to 100 quartz glass filaments 53 with an average diameter of 3 to 5 μm, and apply the sizing agent with the sizing applicator 54, Focused by a focuser 55, a quartz glass strand 56 is manufactured. The manufactured quartz glass strand 56 is then wound by a winder 57. In this method, a quartz glass filament 46 with a diameter of 3 to 5 μm can be obtained.

  In order to produce a quartz glass yarn, the produced quartz glass strand is preferably twisted not more than 40 times / m, more preferably not less than 0.1 times and not more than 5 times per 25 mm. The quartz glass yarn count obtained in this manner is 0.5 to 10 tex, and the standard deviation of the count is 0.05 or less.

  EXAMPLES The present invention will be more specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto.

Example 1
A quartz glass filament was manufactured using the sol-gel method as described in Patent Document 4. As shown in FIG. 1, a solution consisting of ethyl silicate, ethyl alcohol, water and hydrochloric acid is hydrolyzed to obtain a spinning mother liquor, which is extruded from the 200 nozzles 10 into the atmosphere and 70 m by the winding drum 12 installed below. The continuous gel fiber 14 could be obtained when wound up at a speed of 1 / minute. In FIG. 1, reference numerals 16 and 18 denote sizing means, which are composed of a sizing roller 16 and a concentrator 18. At this time, the tolerance of the diameter of each nozzle is within ± 1%, and further, the hydrolysis of the mother liquor proceeds in the middle of spinning and cooling is sufficiently performed so that the viscosity does not change. The obtained gel fiber 14 was fired at 900 ° C. to obtain a quartz glass filament of 7.3 μm in average. The resulting 200 quartz glass filaments were twisted at 40 times / m with a twisting machine to obtain yarns, and a quartz glass cloth having a weave density of 60 × 58/25 mm was produced using this.

  Moreover, thermosetting resin was apply | coated to the obtained quartz glass cloth, and the prepreg was created. Then, a substrate for a semiconductor package is prepared from this prepreg, and the cut and polished cross section of the prepreg is observed with an SEM (scanning electron microscope, JSM-6490LA manufactured by JEOL), and ten filaments of randomly selected ten from the cross section The variation was measured. The variation measurement was performed by measuring the dimensions of the diameter of the cross section of the selected filament using the dimension measurement function of the SEM, and calculating the average and the standard deviation. The thickness of the quartz glass cloth was also measured from the cross section using the dimension measurement function of the SEM. Table 1 shows the measurement results of the obtained prepreg.

(Example 2)
A quartz glass filament was manufactured using a method using an electric furnace in the same manner as shown in Patent Document 7. As shown in FIG. 2, 50 quartz glass rods 20 each having a diameter of 20 mm and an outer diameter tolerance of ± 0.1 mm are simultaneously set in a jig, and slowly heated in a vertical tubular electric furnace having a maximum temperature of 2000 ° C. It was lowered, the melted end was drawn out from the lower part of the electric furnace at a high speed, and a quartz glass filament 24 of an average of 5.3 μm was wound by a winder 26. In FIG. 2, reference numerals 16 and 18 denote sizing means, which are composed of a sizing roller 16 and a concentrator 18. One hundred of the obtained quartz glass filaments 24 were twisted 20 times / m with a twisting machine to obtain yarns, and a quartz glass cloth having a weave density of 75 × 75/25 mm was produced using this. The obtained glass cloth was observed and measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Example 3)
A quartz glass filament was produced using a burner method similar to that shown in US Pat. As shown in FIG. 3, 50 continuous quartz glass continuous fibers 30 with a diameter of 0.3 mm and an outer diameter tolerance of ± 0.002 mm are simultaneously introduced into the flame of a burner 32 arranged in parallel 50 and heated and drawn. A 4.0 μm quartz glass filament 34 was wound by a winder 36. In FIG. 3, reference numerals 16 and 18 denote sizing means, which are composed of a sizing roller 16 and a concentrator 18. Using 50 obtained quartz glass filaments, the yarn is twisted 5 times / m with a twisting machine to form yarns, and a quartz glass cloth having a weave density of 95 × 95/25 mm is produced using this. The obtained quartz glass cloth was observed and measured in the same manner as in Example 1. The measurement results are shown in Table 1.

(Comparative example 1)
A quartz glass cloth was manufactured and observed in the same manner as in Example 1 except that the tolerance of each nozzle diameter was ± 10%. The measurement results are shown in Table 1.

(Comparative example 2)
A quartz glass cloth was manufactured and observed in the same manner as in Example 2 except that the outer diameter tolerance of the quartz glass rod was 0.5 mm. The measurement results are shown in Table 1.

(Comparative example 3)
A quartz glass cloth was manufactured and observed in the same manner as in Example 3 except that the outer diameter tolerance of the quartz glass continuous fiber was 0.01 mm. The measurement results are shown in Table 1.

In Table 1, the standard deviation of the filament diameter is 0.01 or less, the standard deviation of the filament diameter is 0.10 or less, and the standard deviation of the filament diameter is 0.1. The following items were evaluated as acceptable. Moreover, about the thing of the value of the standard deviation of a filament diameter exceeds 0.15, it was evaluated as unacceptable.
In Examples 1 to 3, the filament diameter and the standard deviation of the yarn count were small, and were more uniform than Comparative Examples 1 to 3. Thereby, in Examples 1-3, the silica glass cloth which was excellent in surface smoothness, had very few variations in mass and thickness, and was excellent in dimensional stability was obtained.

(Example 4)
As shown in FIG. 4, a quartz glass ingot having a diameter of 120 mm was heated and drawn in a resistance heating electric furnace to produce a thick fiber of quartz glass having a diameter of 230 μm. At that time, the outer diameter of the silica glass thick fiber was measured by a laser type outer diameter measuring device, and the feed rate of the quartz glass ingot into the resistance furnace and the winding speed of the silica glass thick fiber were feedback controlled. Feedback control was performed by PI control mentioned above.
The outer diameter and the standard deviation of the silica glass thick fiber measured by the laser type outer diameter measuring device are shown in Table 2.
Subsequently, 50 quartz glass thick fibers with a diameter of 230 μm and a standard deviation of 0.27 prepared by a resistance heating type electric furnace are heated and drawn by a burner flame from a wide burner to a quartz glass filament with a diameter of 4.1 μm. Fifty were simultaneously made and focused by a concentrator to produce a quartz glass strand. The obtained quartz glass strand was twisted 40 times / m with a twisting machine to obtain a quartz glass yarn. The count of the quartz glass yarn was calculated from the weight measured in 1 km units. The measurement results of the counts of the quartz glass yarn and the standard deviation thereof are shown in Table 2.

  In addition, the filament diameter randomly selected from the obtained quartz glass yarn is observed with a SEM (scanning electron microscope, JSM-6490LA manufactured by JEOL), and the dimension of the selected filament diameter is determined using the dimension measurement function of the SEM. It measured and calculated the mean value and the standard deviation. The measurement results of the filament diameter obtained in Table 2 show the standard deviation.

  Using this, a quartz glass cloth having a weave density of 95 × 95/25 mm was produced with a width of 1.1 and 500 m. Table 2 shows measured values of the thickness of the quartz glass cloth.

(Example 5)
In the same manner as in Example 4, a thick fiber made of quartz glass with a diameter of 230 μm was produced. The outer diameter of the quartz glass thick fiber of Example 4 and the standard deviation thereof are shown in Table 2.
Subsequently, a quartz glass filament was manufactured using a method using an electric furnace. As shown in FIG. 6, 50 quartz glass thick fibers having a diameter of 200 μm manufactured by the same method as in Example 4 are simultaneously set in a jig and the inside of a vertical tubular electric furnace having a maximum temperature of 2000 ° C. It was slowly lowered, the melted end was drawn out from the lower part of the electric furnace at high speed, and a quartz glass filament having an average outer diameter of 4.1 μm was wounded by a winder.
50 quartz glass strands 16 obtained were twisted 40 times / m with a twisting machine to form yarns. The filament diameter and count of the obtained quartz glass yarn, and the thickness of the quartz glass cloth were measured in the same manner as in Example 4. The measurement results are shown in Table 2.
A quartz glass cloth was produced in the same manner as in Example 4 using the obtained quartz glass yarn.

(Example 6)
As shown in Patent Document 9, as shown in FIG. 7, a thick silica glass fiber 17 having a diameter of 230 μm was produced from a quartz glass rod 15 having a diameter of 4 mm using a method using an oxyhydrogen flame burner. The outer diameter of the quartz glass thick fiber 17 was measured by a two-dimensional high-speed size measuring machine (TM-006 made by Keyence).
Next, a quartz glass yarn was produced in the same manner as in Example 4 for a quartz glass fiber 17 having a diameter of 230 μm, and the diameter of the quartz glass filament was measured. In the same manner as in Example 4, a quartz glass cloth was produced.
The filament diameter and yarn count of the obtained quartz glass yarn, and the thickness of the quartz glass cloth were measured in the same manner as in Example 4. The measurement results are shown in Table 2.

(Example 7)
In the same manner as shown in Patent Document 9, as shown in FIG. 7, a thick fiber 59 made of quartz glass having a diameter of 230 μm is produced from a quartz glass rod 58 having a diameter of 4 mm using a method using an oxyhydrogen flame burner. The film was taken up by a take-up machine 60. The outer diameter of the quartz glass thick fiber 59 was measured by a two-dimensional high-speed size measuring machine (TM-006 made by Keyence).
Next, a quartz glass yarn was produced from a quartz glass fiber 59 having a diameter of 230 μm in the same manner as in Example 5, and the diameter of the quartz glass filament was measured. In the same manner as in Example 4, a quartz glass cloth was produced.
The filament diameter and yarn count of the obtained quartz glass yarn, and the thickness of the quartz glass cloth were measured in the same manner as in Example 4. The measurement results are shown in Table 2.

(Comparative example 4)
An E-glass cloth was produced in the same manner as in Example 4 using a yarn consisting of 50 E-glass filaments having a diameter of 4.1 μm and produced in the same manner as described in Patent Document 10.
The filament diameter and yarn count of the obtained E glass yarn, and the thickness of the E glass cloth were measured in the same manner as in Example 4. The measurement results are shown in Table 2.

In Table 2, the standard deviation value of the filament diameter is 0.01 or less, the standard deviation value of the filament diameter is 0.10 or less is good, and the standard deviation value of the filament diameter is 0. The following items were evaluated as acceptable. Moreover, about the thing of the value of the standard deviation of a filament diameter exceeds 0.15, it was evaluated as unacceptable.
In Examples 4 to 7, the large fiber diameter, the filament diameter and the standard deviation of the yarn count were small, and were more uniform than Comparative Example 4. The comparison of distribution of the diameter of the quartz glass thick fiber of Examples 4-7 was shown in FIG. In FIG. 9, distribution of the filament diameter of Example 4, Example 6, and Comparative Example 4 is shown. Thereby, it turns out that especially in Examples 4-5, thickness variation was very small and the silica glass cloth excellent in dimensional stability was obtained.

  10: nozzle, 12: take-up drum, 14: gel fiber, 16: sizing roller, 18: focusing device, 20: quartz glass rod, 22: heater means, 24: quartz glass filament, 26, 36: winder, 30: Quartz glass continuous fiber, 32: burner, 34: quartz glass filament, 41: quartz glass ingot, 42: resistance heating electric furnace, 43: quartz glass thick fiber, 44: laser type outer diameter measuring tree, 45: quartz glass Thick fiber, 46: quartz glass filament, 47: collector, 48: quartz glass strand, 49: winder, 50: sizing applicator, 51: quartz glass thick fiber, 52: vertical tubular electric furnace, 53: quartz Glass filament, 54: Sizing applicator, 55: Focuser, 56: Quartz glass ingot 57: winding machine, 58: quartz glass rod, 59: thick fiber made of quartz glass, 60: winding machine, 61: winding speed control section, 62: ingot feeding speed control section, V1: ingot feeding speed, V2 : Take-up speed of thick fiber, M: High-precision winder, F1: Burner flame, B1: Wide oxyhydrogen flame burner, B2: Oxyhydrogen flame burner, P1: Deviation of target wire diameter value and measurement of thick fiber Initial response amount of winding speed V1 of thick yarn in proportion to the size of I, I: control operation amount to winding speed V1 of thick yarn proportional to the size of deviation of target wire diameter value and measured value of thick fiber , I2: A control operation amount to a feeding speed V2 of the ingot according to an accumulated value of a target speed of drawing speed of a thick fiber and a deviation of an actual speed V1.

Each conductor layers through holes in the vertical direction, the inner via hole are electrically connected through a conductive hole called bra India via hole.

However, a quartz glass rod having a diameter of 2 to 100 mm is heated and drawn by the method described in the conventional patent document 9 to produce a quartz glass fiber having a diameter of 100 to 400 μm and a standard deviation of the diameter of 10 μm or less. In the method of producing the ultrafine quartz glass fiber having a filament diameter of 3 to 5 μm by the method described in 8, a distribution of filament diameters with a standard deviation of the diameter of 1 μm or more occurs.

For example, 30 to 100 filaments having a diameter of 3 to 5 .mu.m and a standard deviation of 1 .mu.m or more are produced, and they are collected to produce a quartz glass strand. And when a quartz glass yarn having a size of 0.5 to 10 tex is manufactured by twisting 0.1 to 5 times per 25 mm of the quartz glass strand, the standard deviation of the number is 0.05 tex. It gets bigger. With such quartz glass yarn, it is difficult to obtain a high quality quartz glass cloth which is very large in mass and thickness variation, excellent in surface smoothness, and excellent in dimensional stability even when woven. It is difficult to secure the flatness of a 10 to 20 μm thick prepreg.

In order to solve the above problems, the present quartz glass cloth is a quartz glass cloth used for a semiconductor package substrate, is a quartz glass filament having an average filament diameter of 3 μm to 20 μm, and the standard deviation of the diameter of the quartz glass filament is A quartz glass strand or quartz glass yarn using 20 or more and 400 or less of quartz glass filaments of 0.15 μm or less is produced.

The standard deviation of the diameter of the quartz glass filament is preferably 0.10 μm or less, and more preferably 0.01 μm or less.

The method for producing a quartz glass filament according to the present invention is a method for producing a quartz glass filament used for a quartz glass cloth used for a semiconductor package substrate , wherein a quartz glass ingot is heated and drawn to produce a thick fiber made of quartz glass. A quartz glass filament is produced by heating and stretching the thick fiber made of quartz glass, and when manufacturing the thick fiber made of quartz glass, the deviation of the target wire diameter value of the thick fiber after the heat drawing and the measurement value The initial response amount proportional to the size and the control operation amount according to the cumulative value of the target wire diameter value and the deviation of the measured value are reflected on the draw speed of the thick fiber, and the target speed and actual speed of the draw speed of the thick fiber The standard deviation of the diameter is 100 to 300 μm by reflecting the control operation amount according to the accumulated value of the deviation of 0.5 [mu] m obtained by preparing the following quartz glass SeiFutoshi fibers.

  The method for producing a quartz glass strand of the present invention is a method for producing a quartz glass strand by producing 20 to 400 quartz glass filaments using the method for producing a quartz glass filament and focusing them.

In the method of producing the quartz glass yarn of the present invention, the quartz glass strand is twisted by 0.1 times or more and 5 times or less per 25 mm, and the size of the count is 0.5 to 10 tex, It is a method of producing a quartz glass yarn having a standard deviation of 0.05 tex or less.

FIG. 6 is a schematic explanatory view of a method of producing a quartz glass filament of Experimental Example 1. FIG. 6 is a schematic explanatory view of a method of producing a quartz glass filament of Experimental Example 2. FIG. 14 is a schematic explanatory view of a method of producing a quartz glass filament of Experimental Example 3. FIG. 6 is a schematic explanatory view of a method for producing thick silica glass fibers of Example 1 and Example 2 . FIG. 6 is a schematic explanatory view of a method of producing the quartz glass filament of Example 1 and Experimental Example 4 . It is typical explanatory drawing of the method of manufacturing the quartz glass filament of Example 2 and Experimental example 5. FIG. It is typical explanatory drawing of the method of manufacturing the quartz glass thick fiber of Experimental example 4-5 . It is the figure which showed distribution of the quartz glass thick fiber diameter of Example 1-2 and Experimental example 4-5 . It is the figure which showed distribution of the glass filament diameter of Example 1 , Experimental example 4 and Comparative Example 4. FIG.

And about the manufacturing method of a uniform quartz glass yarn, as shown in FIG. 4, the quartz glass ingot 41 of diameter 50mm-200mm is heated and drawn in the resistance heating-type electric furnace 42, 100 micrometers-300 micrometers in diameter The thick fiber 43 made of quartz glass is manufactured. At that time, the outer diameter of the quartz glass thick fiber is measured by the laser type outer diameter measuring device 44, and the initial response is proportional to the deviation of the target wire diameter value of the quartz glass thick fiber 43 after drawing and the measured value. The control operation amount I1 according to the amount P1 and the accumulated value of the target wire diameter value and the deviation of the measured value is reflected in the drawing speed V1 of the thick fiber 43 made of quartz glass, and the target of the drawing speed of the thick fiber 43 made of quartz glass The standard deviation of the diameter of the thick fiber 43 made of quartz glass is 0.1 μm or less by reflecting the control operation amount I1 according to the accumulated value of the deviation of the speed and the actual speed V1 into the feed speed V2 into the electric furnace 42 It is possible to In addition, the code | symbol M of FIG. 5 shows the high-precision winding machine for winding up the quartz glass thick fiber 43. As shown in FIG. Further, reference numeral 61 denotes a winding speed control unit for controlling the winding speed of the thick fiber 43 made of quartz glass, and reference numeral 62 denotes an ingot feeding speed control unit for controlling the feeding speed of the quartz glass ingot 41.

In order to produce a quartz glass yarn, the produced quartz glass strand is preferably twisted not more than 40 times / m, more preferably not less than 0.1 times and not more than 5 times per 25 mm. The quartz glass yarn count obtained in this manner is 0.5 to 10 tex, and the standard deviation of the count is 0.05 tex or less.

( Experimental example 1)
A quartz glass filament was manufactured using the sol-gel method as described in Patent Document 4. As shown in FIG. 1, a solution consisting of ethyl silicate, ethyl alcohol, water and hydrochloric acid is hydrolyzed to obtain a spinning mother liquor, which is extruded from the 200 nozzles 10 into the atmosphere and 70 m by the winding drum 12 installed below. The continuous gel fiber 14 could be obtained when wound up at a speed of 1 / minute. In FIG. 1, reference numerals 16 and 18 denote sizing means, which are composed of a sizing roller 16 and a concentrator 18. At this time, the tolerance of the diameter of each nozzle is within ± 1%, and further, the hydrolysis of the mother liquor proceeds in the middle of spinning and cooling is sufficiently performed so that the viscosity does not change. The obtained gel fiber 14 was fired at 900 ° C. to obtain a quartz glass filament of 7.3 μm in average. The resulting 200 quartz glass filaments were twisted at 40 times / m with a twisting machine to obtain yarns, and a quartz glass cloth having a weave density of 60 × 58/25 mm was produced using this.

( Experimental example 2)
A quartz glass filament was manufactured using a method using an electric furnace in the same manner as shown in Patent Document 7. As shown in FIG. 2, 50 quartz glass rods 20 each having a diameter of 20 mm and an outer diameter tolerance of ± 0.1 mm are simultaneously set in a jig, and slowly heated in a vertical tubular electric furnace having a maximum temperature of 2000 ° C. It was lowered, the melted end was drawn out from the lower part of the electric furnace at a high speed, and a quartz glass filament 24 of an average of 5.3 μm was wound by a winder 26. In FIG. 2, reference numerals 16 and 18 denote sizing means, which are composed of a sizing roller 16 and a concentrator 18. One hundred of the obtained quartz glass filaments 24 were twisted 20 times / m with a twisting machine to obtain yarns, and a quartz glass cloth having a weave density of 75 × 75/25 mm was produced using this. The obtained glass cloth was observed and measured in the same manner as in Experimental Example 1. The measurement results are shown in Table 1.

( Experimental example 3)
A quartz glass filament was produced using a burner method similar to that shown in US Pat. As shown in FIG. 3, 50 continuous quartz glass continuous fibers 30 with a diameter of 0.3 mm and an outer diameter tolerance of ± 0.002 mm are simultaneously introduced into the flame of a burner 32 arranged in parallel 50 and heated and drawn. A 4.0 μm quartz glass filament 34 was wound by a winder 36. In FIG. 3, reference numerals 16 and 18 denote sizing means, which are composed of a sizing roller 16 and a concentrator 18. Using 50 obtained quartz glass filaments, the yarn is twisted 5 times / m with a twisting machine to form yarns, and a quartz glass cloth having a weave density of 95 × 95/25 mm is produced using this. The obtained quartz glass cloth was observed and measured in the same manner as in Experimental Example 1. The measurement results are shown in Table 1.

(Comparative example 1)
A quartz glass cloth was manufactured and observed in the same manner as in Experimental Example 1 except that the tolerance of each nozzle diameter was ± 10%. The measurement results are shown in Table 1.

(Comparative example 2)
A quartz glass cloth was manufactured and observed in the same manner as in Experimental Example 2 except that the outer diameter tolerance of the quartz glass rod was 0.5 mm. The measurement results are shown in Table 1.

(Comparative example 3)
A quartz glass cloth was manufactured and observed in the same manner as in Experimental Example 3 except that the outer diameter tolerance of the quartz glass continuous fiber was 0.01 mm. The measurement results are shown in Table 1.

In Table 1, the standard deviation value of the filament diameter is 0.01 μm or less, the standard deviation value of the filament diameter is 0.10 μm or less, and the standard deviation value of the filament diameter is Those having a size of 0.15 μm or less were evaluated as acceptable. In addition, those having a filament diameter standard deviation of more than 0.15 μm were evaluated as unacceptable.
In Experimental Examples 1 to 3, the filament diameter and the standard deviation of the yarn count were small, and were more uniform than Comparative Examples 1 to 3. As a result, in Experimental Examples 1 to 3, a silica glass cloth excellent in surface smoothness, very small in mass and thickness variation, and excellent in dimensional stability was obtained.

(Example 1 )
As shown in FIG. 4, a quartz glass ingot having a diameter of 120 mm was heated and drawn in a resistance heating electric furnace to produce a thick fiber of quartz glass having a diameter of 230 μm. At that time, the outer diameter of the silica glass thick fiber was measured by a laser type outer diameter measuring device, and the feed rate of the quartz glass ingot into the resistance furnace and the winding speed of the silica glass thick fiber were feedback controlled. Feedback control was performed by PI control mentioned above.
The outer diameter and the standard deviation of the silica glass thick fiber measured by the laser type outer diameter measuring device are shown in Table 2.
Subsequently, 50 thick quartz glass thick fibers having a diameter of 230 μm and a standard deviation of 0.27 μm prepared by a resistance heating type electric furnace are heated and drawn by a burner flame from a wide burner to form quartz glass having a diameter of 4.1 μm. Fifty filaments were simultaneously produced and focused by a concentrator to produce a quartz glass strand. The obtained quartz glass strand was twisted 40 times / m with a twisting machine to obtain a quartz glass yarn. The count of the quartz glass yarn was calculated from the weight measured in 1 km units. The measurement results of the counts of the quartz glass yarn and the standard deviation thereof are shown in Table 2.

(Example 2 )
In the same manner as in Example 1 , a thick fiber made of quartz glass with a diameter of 230 μm was produced. The outer diameter of the quartz glass thick fiber of Example 1 and its standard deviation are shown in Table 2.
Subsequently, a quartz glass filament was manufactured using a method using an electric furnace. As shown in FIG. 6, 50 quartz glass thick fibers having a diameter of 200 μm manufactured by the same method as in Example 1 are simultaneously set in a jig and the inside of a vertical tubular electric furnace having a maximum temperature of 2000 ° C. It was slowly lowered, the melted end was drawn out from the lower part of the electric furnace at high speed, and a quartz glass filament having an average outer diameter of 4.1 μm was wounded by a winder.
50 quartz glass strands 16 obtained were twisted 40 times / m with a twisting machine to form yarns. The filament diameter and count of the obtained quartz glass yarn, and the thickness of the quartz glass cloth were measured in the same manner as in Example 1 . The measurement results are shown in Table 2.
A quartz glass cloth was produced in the same manner as in Example 1 using the obtained quartz glass yarn.

( Experimental example 4 )
As shown in Patent Document 9, as shown in FIG. 7, a thick silica glass fiber 17 having a diameter of 230 μm was produced from a quartz glass rod 15 having a diameter of 4 mm using a method using an oxyhydrogen flame burner. The outer diameter of the quartz glass thick fiber 17 was measured by a two-dimensional high-speed size measuring machine (TM-006 made by Keyence).
Next, a quartz glass yarn was produced in the same manner as in Example 1 for a quartz glass fiber 17 having a diameter of 230 μm, and the diameter of the quartz glass filament was measured. Further, in the same manner as in Example 1 , a quartz glass cloth was produced.
The filament diameter and yarn count of the obtained quartz glass yarn, and the thickness of the quartz glass cloth were measured in the same manner as in Example 1 . The measurement results are shown in Table 2.

( Experimental example 5 )
In the same manner as shown in Patent Document 9, as shown in FIG. 7, a thick fiber 59 made of quartz glass having a diameter of 230 μm is produced from a quartz glass rod 58 having a diameter of 4 mm using a method using an oxyhydrogen flame burner. The film was taken up by a take-up machine 60. The outer diameter of the quartz glass thick fiber 59 was measured by a two-dimensional high-speed size measuring machine (TM-006 made by Keyence).
Next, a quartz glass yarn was produced from a quartz glass fiber 59 having a diameter of 230 μm in the same manner as in Example 2, and the diameter of the quartz glass filament was measured. Further, in the same manner as in Example 1 , a quartz glass cloth was produced.
The filament diameter and yarn count of the obtained quartz glass yarn, and the thickness of the quartz glass cloth were measured in the same manner as in Example 1 . The measurement results are shown in Table 2.

(Comparative example 4)
An E-glass cloth was produced in the same manner as in Example 1 using a yarn consisting of 50 E-glass filaments having a diameter of 4.1 μm and produced in the same manner as shown in Patent Document 10.
The filament diameter and yarn count of the obtained E glass yarn, and the thickness of the E glass cloth were measured in the same manner as in Example 1 . The measurement results are shown in Table 2.

In Table 2, the standard deviation value of the filament diameter is 0.01 μm or less, the standard deviation value of the filament diameter is 0.10 μm or less, and the standard deviation value of the filament diameter is Those having a size of 0.15 μm or less were evaluated as acceptable. In addition, those having a filament diameter standard deviation of more than 0.15 μm were evaluated as unacceptable.
In Examples 1 to 2 and Experimental Examples 4 to 5 , the large fiber diameter, the filament diameter, and the standard deviation of the yarn count were small, and were more uniform than Comparative Example 4. FIG. 8 shows a comparison of the distribution of the diameter of thick silica glass fibers of Examples 1 and 2 and Experimental Examples 4 and 5 . FIG. 9 shows the distribution of filament diameters of Example 1 , Experimental Example 4 and Comparative Example 4. From this, it can be seen that particularly in Examples 1 to 2 , a quartz glass cloth having very small thickness variation and excellent dimensional stability was obtained.

Claims (7)

A method of manufacturing a quartz glass filament used for a quartz glass cloth used for a semiconductor package substrate, comprising:
A quartz glass ingot is heated and drawn to produce a thick fiber made of quartz glass, and then the thick fiber made of quartz glass is heated and stretched to produce a quartz glass filament,
In producing the quartz glass thick fiber,
The initial response amount proportional to the target wire diameter value of the thick fiber after the heating and drawing and the deviation of the measured value, and the control operation amount according to the cumulative value of the deviation of the target wire diameter value and the measured value The diameter is 100 to 300 μm by reflecting the control operation amount according to the accumulated value of the target speed of the drawing speed of the thick fiber and the deviation of the actual speed, reflecting the drawing speed, and reflecting the feed speed of the ingot into the furnace. A method for producing a quartz glass filament, comprising producing a thick fiber made of quartz glass having a standard deviation of its diameter of 0.5 μm or less.   The method for producing a quartz glass filament according to claim 1, wherein the quartz glass filament is produced by heating drawing with a burner flame of a mixed gas of oxygen and hydrogen or heating drawing in an electric furnace.   The method for producing a quartz glass filament according to claim 1, wherein an average filament diameter of the quartz glass filament is 3 μm or more and 20 μm or less.   The manufacturing method of the quartz glass filament of any one of Claims 1-3 whose standard deviation of the diameter of the said quartz glass filament is 0.15 micrometer or less.   The method of manufacturing the quartz glass strand which manufactures the said quartz glass filament 20-400 using the manufacturing method of the quartz glass filament of any one of Claims 1-4, and which integrates them.   A quartz glass strand according to claim 5 is twisted by 0.1 times or more and 5 times or less per 25 mm, and the size of a count is 0.5 to 10 tex, and the standard deviation of the count is 0.05 tex or less Method of producing quartz glass yarn.   A method for producing a quartz glass cloth, wherein a quartz glass cloth is produced using the quartz glass strand produced by the method according to claim 5 or the quartz glass yarn produced according to the method according to claim 6.

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