JP3863308B2 - Method for producing glassy carbon pipe - Google Patents

Description

【００４５】
Ｎｏ．１〜４は本発明に係る樹脂を用いた実施例であり、いずれの場合にも、内径の変動が１．０％以内であり、亀裂のないガラス状炭素製パイプを得ることができた。
【００４６】
Ｎｏ．５〜７は本発明に係る条件を満足しない樹脂を用いた比較例であり、Ｎｏ．５の樹脂は、Ｔ１０が４分で硬化速度が大き過ぎるため、円筒形状に変形する前に硬化が完了し、均一な肉厚のパイプを得ることはできなかった。また、樹脂からのガス抜きも不十分であり、炭素化後のパイプにも割れが発生しており、パイプ内径も不均一であった。
【００４７】
Ｎｏ．６の樹脂はＴ１０は１３分で本発明の範囲内にあるが、円板式流れ試験値が５８ｍｍで本発明の範囲よりも小さい比較例であり、原料樹脂の流動性が小さいため、硬化完了時点においても、円筒形状に成形されておらず、均一な肉厚のパイプを得ることはできなかった。また、樹脂からのガス抜きも不十分であり、樹脂成形体には多くの気泡が含まれていた。炭素化処理後のパイプにも割れが発生した。
【００４８】
Ｎｏ．７の樹脂は、Ｔ１０が６２分と、硬化時間が長過ぎる場合の比較例であり、成形時に発生したガスにより成形体内部に大量の発泡が生じ、パイプ内径にも著しく大きな不均一が生じた。また、キュアリングと炭素化時に亀裂と発泡が生じたため、ガラス状炭素製パイプを得ることはできなかった。
【００４９】
実施例４
Ｔ１０への到達時間が１１５℃において２４分であり、１００℃におけるＪＩＳ−Ｋ６９１１の円板式流れ試験値が１０４ｍｍである粉末状フェノール樹脂を原料として用いたこと以外は、実施例１と同様にして熱硬化性樹脂成形体を製造した。
【００５０】
このパイプを２３０℃で４８時間のキュアリングをおこなったが、キュアによる黒化以外に割れや空隙などの外観の変化は認められなかった。さらに、１５００℃で炭素化処理をおこなったところ、キュアリング時の形状を保ったガラス状炭素製パイプを得ることができた。
【００５１】
ところで、樹脂原料が内包するガス成分及び成形中に発生するガス成分が完全に除かれて緻密な樹脂パイプが成形された場合、成形されたパイプの嵩密度と樹脂の真密度は一致すると考えられる。従って、樹脂パイプの嵩密度の樹脂の真密度に対する比（比密度）は、成形性の指標となる。本実施例で得られた熱硬化性樹脂成形体の比密度は０．９９を超えていた。よって本実施例で得られた樹脂パイプは、樹脂原料が内包するガス成分及び成形中に発生するガス成分がほぼ完全に除去されたものと考えられる。
また、この実施例で得られた炭素パイプの内径の変動は０．１％であった。
【００５２】
実施例５
直径３５０ｍｍ，長さ１０００ｍｍの２分割金型を用いたこと以外は実施例４と同じ樹脂原料と装置を用いてフェノール樹脂パイプを成形した。このパイプは、形状を保ったままで硬化することができ、１５００℃で炭素化すると、収縮による寸法の変化以外は、外観上の変化なく、均一な肉厚の欠縮のないガラス状炭素製パイプとすることができた。
【００５３】
本実施例で得られた熱硬化性樹脂成形体の比密度は０．９９を超えており、実施例４の炭素パイプと同様、成形後のパイプの外観は良好であった。またこのパイプの内径の変動は０．４％であった。
【００５４】
実施例６
触媒濃度あるいは重合時間を変えて、硬化反応性と流動性の異なるフェノール樹脂を調製し、実施例１と同じ装置を用いて樹脂パイプを成形し、空気中２３０℃で４８時間のキュアリングを行い、さらに１５００℃で炭素化した。
樹脂の性状とガラス状炭素製パイプの製造の結果を表２に示す。
【００５５】
【表２】

【００５６】
Ｎｏ．１〜５は本発明に係る樹脂を用いた実施例であり、いずれの場合にも、内径の変動が１％以内であり、且つ亀裂のないガラス状炭素製パイプを得ることができた。
【００５７】
Ｎｏ．６〜９は本発明に係る条件を満足しない樹脂を用いた比較例であり、Ｎｏ．６とＮｏ．８の樹脂は、Ｔ１０が４分で硬化速度が大き過ぎるため、円筒形状に変形する前に硬化が完了し、均一な肉厚のパイプを得ることはできなかった。また、樹脂からのガス抜きも不十分であり、炭素化後のパイプにも割れが発生しており、パイプ内径も不均一であった。
【００５８】
Ｎｏ．７の樹脂は、Ｔ１０が６３分と、硬化時間が長過ぎる場合の比較例であり、成形時に発生したガスにより成形体内部に大量の発泡が生じ、パイプ内径にも著しく大きな不均一が生じた。また、キュアリングと炭素化時に亀裂と発泡が生じたため、ガラス状炭素製パイプを得ることはできなかった。
【００５９】
Ｎｏ．９の樹脂はＴ１０は８分で本発明の範囲内にあるが、円板式流れ試験値が５８ｍｍで本発明の範囲よりも小さい比較例であり、原料樹脂の流動性が小さいため、硬化完了時点においても、円筒形状に成形されておらず、均一な肉厚のパイプを得ることはできなかった。また、樹脂からのガス抜きも不十分であり、樹脂成形体には多くの気泡が含まれていた。炭素化処理後のパイプにも割れが発生した。
【００６０】
【発明の効果】
本発明は以上のように構成されているので、半導体製造用ＣＶＤ装置のインナーチューブをはじめとするガラス状炭素製パイプであって、ＣＶＤ装置の汚染の原因となる充填材を含まないことと高い耐熱・耐食性が要求される大口径部材として好適なガラス状炭素製パイプの製造方法が提供できることとなった。
【図面の簡単な説明】
【図１】本発明方法に用いることのできる遠心成形装置を示す説明図である。
【図２】本発明方法に用いることのできる成形用金型（ａ）と、上記金型により得られるガラス状炭素製パイプ（ｂ）を示す説明図である。
【符号の説明】
１ 金型
２ ヒータ
３ 熱硬化性樹脂
４ フランジ付き樹脂パイプの成形用金型
５ フランジ付き樹脂パイプ[0001]
BACKGROUND OF THE INVENTION
The present inventionMethod for producing glassy carbon pipeIn detail, it is a glassy carbon pipe excellent in heat resistance, gas impermeability and corrosion resistance, and is suitable as an inner tube of a semiconductor manufacturing CVD apparatus.Method for producing glassy carbon pipeIt is about.
[0002]
[Prior art]
Quartz glass is generally used for members that are required to have heat resistance, gas impermeability and corrosion resistance, such as an inner tube of a CVD apparatus for semiconductor manufacturing.
However, quartz glass has a problem that it is easily corroded by a fluorine-based gas or a mixed solution of nitric acid and hydrofluoric acid for cleaning, and has a very short life.
[0003]
Thus, vitreous carbon is expected as a material to replace quartz glass. Glassy carbon is a carbon material obtained by carbonizing a thermosetting resin such as phenol resin or furan resin or cellulose at a high temperature around 1000 ° C. or higher, and has a heat resistance higher than that of quartz glass. In addition, it has the characteristics that mechanical strength and hardness are equivalent to quartz glass, gas permeability is extremely small, and corrosion resistance against chemicals as described above is extremely excellent.
[0004]
Therefore, materials containing glassy carbon as a main constituent have been used in various fields as structural members having high heat resistance. However, in order to obtain a glassy carbon pipe, it is necessary to manufacture a thermosetting resin pipe as a precursor thereof, and unlike a thermoplastic resin, a thermosetting resin has a low viscosity in a molten state. It is difficult to obtain a pipe-shaped molded article by using a method such as extrusion molding, compression molding or injection molding, which is a molding method in which a thermoplastic resin is usually used, with a single resin. In particular, the inner tube used in the CVD apparatus has a pipe shape with both ends open, for example, having a diameter of approximately 400 mm, a length of 1000 mm, and a thickness of 3 to 5 mm, and is formed into such a shape using only a thermosetting resin. It was extremely difficult to do.
[0005]
Since thermosetting resins have poor moldability, they are usually molded after being mixed with various fillers. For example, if an inorganic filler such as magnesia, talc, or mica is added to a thermosetting resin at a high concentration and mixed, a high-strength pipe suitable for an electric pipe can be formed by extrusion molding. Further, when a liquid resin is impregnated in a carbon fiber non-woven cloth and compression molded, a carbon fiber / thermosetting resin composite having high strength and elastic modulus can be obtained. That is, when used as a thermosetting resin molding without being carbonized, the use of the filler is preferable because it improves the mechanical properties of the resin material and saves the amount of expensive resin used. Met.
[0006]
However, in order to obtain glassy carbon, it is necessary to carbonize these thermosetting resin molded bodies in a high-temperature inert atmosphere. In this case, if a filler is contained, the following problems are caused. Will cause. In other words, since liquid resin generally shrinks by more than 10% during carbonization, cracking occurs at the interface between the glassy carbon part and the filler part with little dimensional change when the resin composite pipe containing the filler is carbonized. As a result, there has been a problem that the gas impermeability and corrosion resistance, which are characteristic of glassy carbon, are significantly hindered. For example, in the case of the above-described carbon fiber-thermosetting resin composite (so-called carbon / carbon composite precursor), the member obtained by carbonizing the carbon fiber contains many cracks and voids. And carbonization had to be repeated several times.
[0007]
In addition, the filler component is less corrosive than glassy carbon, and impurities due to the filler itself may be scattered in the CVD apparatus to contaminate the CVD film. It is not suitable for use.
[0008]
Therefore, there is a strong demand for the development of a glassy carbon pipe that does not contain a filler, and the glassy carbon content is 95% or more, more preferably a pipe made of substantially glassy carbon. There has been a demand for the development of a glassy carbon pipe that can be suitably used in a CVD apparatus and a method for producing the same.
[0009]
Therefore, the present inventors diligently studied a method for molding a thermosetting resin not containing a filler based on the prior art. As a result, it has been found that it is possible to obtain a pipe-shaped thermosetting resin molding by injection molding or compression molding that is often used conventionally. However, in order to facilitate removal of the resin member from the mold, it is necessary to taper the inner surface of the pipe at an angle of at least 0.5 degrees, preferably 1 degree, and further, dimensions and shapes in the carbonization process after molding. Therefore, the inner diameter of the glass-like carbon pipe, which is the final product, is not uniform, and it has been found that the variation of the inner diameter exceeds 1% of the length when compared with the inner diameters at both ends. This is not preferable in that an industrially useful cylinder, that is, a cylindrical member having the same inner diameter cannot be formed. In addition, injection molding and compression molding are methods that are originally unsuitable for pipe molding, resulting in poor productivity, and molding resin pipes that serve as precursors for large-diameter glassy carbon pipes as described above. To achieve this, an extremely large mold is required, and it has been practically difficult to manufacture at an industrial scale at low cost.
[0010]
Due to the above circumstances, with regard to glassy carbon pipes that do not contain a filler, when trying to obtain a small-diameter pipe having a constant inner diameter using compression molding or injection molding, a taper process for die cutting is performed. The production technology is limited to a pipe that is short and thin, specifically, having a length of 60 mm or less and a diameter of less than 15 mm. For pipes with diameters and lengths exceeding this, it is necessary to taper the mold, which inevitably results in pipe inner diameter differences that exceed 1% of the length. It has been difficult to form a thermosetting resin containing no filler into a pipe shape by extrusion molding.
[0011]
In addition to the molding methods listed above, centrifugal molding methods are disclosed in Japanese Patent Application Laid-Open Nos. 6-247770 and 4-149067 as methods suitable for pipe forming. However, the methods disclosed in these publications are methods that use a filler, and there is no description that suggests a method that does not use a filler or that method. In fact, the present inventors have attempted to form a glassy carbon pipe by simply removing the filler from the methods disclosed in these publications, but the molded body tends to foam, and in order to prevent this, the molding takes a very long time. Therefore, it is difficult to obtain a molded product without voids with good productivity and reproducibility. Even when a good molded body is obtained, a lot of voids are generated in the molded body due to the vapor of the solvent remaining in the subsequent curing or carbonization process and the generated gas, and gas impermeability and corrosion resistance are generated. It was difficult to obtain excellent glassy carbon.
[0012]
Furthermore, in the literature (“Carbon”, 1996, vol. 34, No. 6, p. 789-796), removal of the solvent while continuously applying a liquid phenolic resin on the outer surface of the rotating metal cylinder in the form of a spray. And a method of obtaining a glassy carbon precursor resin pipe by performing a resin curing reaction. However, the glassy carbon pipe exemplified in the above technical document has an inner diameter of 12.7 mm, and the manufacturing method of a pipe having a larger diameter is not clarified. When the present inventors tried this method, the resin supply speed, the rotation speed of the cylindrical shape, the temperature for controlling the resin curing reaction and the amount of evaporation of the solvent, etc. were precisely controlled. However, a uniform thickness resin pipe could not be obtained.
[0013]
As described above, various methods for producing glassy carbon pipes have been studied. However, a pipe production method that can be molded even with a small amount of filler and that can handle a large diameter is not sufficient. An inner tube of a CVD apparatus that has both properties, gas impermeability, corrosion resistance, durability and little contamination has not been provided.
[0014]
[Problems to be solved by the invention]
The present invention has been made paying attention to the above circumstances, and is intended to provide a glass-like carbon pipe with less contamination that is optimal as an inner tube of a semiconductor manufacturing CVD apparatus. Furthermore, in the conventional method, Large diameter and uniform thickness that could not be manufacturedMethod for producing glassy carbon pipeIs to provide.
[0015]
[Means for Solving the Problems]
The production method of the present invention that has solved the above problems is a thermosetting resin.PowderA pipe raw material is made into a thermosetting resin molded body by a centrifugal molding method, and a glassy carbon pipe is produced by subjecting the thermosetting resin molded body to carbonization treatment, and the thermosetting property of the pipe raw material As a resin, it has a curability with a cure time of 10% (T10) at 115 ° C. of 5 to 60 minutes, and has a fluidity of 60 mm or more at 100 ° C. in a disk flow test of JIS-K6911. Use a functional resinProduction of glassy carbon pipes substantially free of filler. This method can also be applied to a method for manufacturing a glassy carbon pipe having an inner diameter of 15 mm or more.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
In order to solve the above-mentioned problems, the present inventors have made extensive studies and, as a result, if the thermosetting resin has specific curability and fluidity, the pipe can be formed by centrifugal molding without mixing the filler. As a result, the inventors have found that a molded article can be obtained.
[0018]
The thermosetting resin used as a pipe raw material in the present invention has a curability such that an arrival time of a resin curing degree of 10% (T10) is 5 minutes or more and 60 minutes or less at 115 ° C. Is a thermosetting resin having fluidity of 60 mm or more at 100 ° C.
[0019]
The curability of the thermosetting resin should be 5 minutes or more at T10 at 115 ° C. because the pipe raw material needs to be plastically deformed into a cylindrical shape along the mold before completing the curing reaction. is necessary. When the T10 is less than 5 minutes, the resin is completely cured before the pipe raw material is deformed into a cylindrical shape along the mold, or is generated during the gas component contained in the raw material or during molding. Since the curing of the resin is completed before the gas component is dissipated, it is impossible to obtain a resin molded body having a desired shape and free from bubbles and cracks. T10 is desirably 10 minutes or longer. If the time until the curing is completed is increased, molding can be performed with a smaller centrifugal force (a smaller number of rotations). However, a resin having a too long curing time is not preferable because a large amount of gas is generated during the curing reaction in the rotary mold, and the molded body easily foams and contains bubbles, and T10 needs to be within 60 minutes. Yes, more preferably within 40 minutes.
[0020]
In the method of the present invention, centrifugal molding is performed while heating the molding raw material to a temperature higher than the temperature at which the resin curing reaction occurs. Therefore, the thermosetting resin used for the raw material needs to have appropriate fluidity at the molding temperature. is there. In the present invention, one having a fluidity value of 60 mm or more when a disc type flow test of JIS-K6911 is conducted at 100 ° C. is used. Here, the flow test is performed at 100 ° C. for the following reason. Usually, the curing reaction of the thermosetting resin starts around 100 ° C., and the fluidity of the resin gradually decreases as the reaction proceeds. Therefore, in order to shape the resin into a cylindrical shape, it is essential that the resin can cause a certain flow deformation at this temperature. In order to evaluate this property, the disk type flow test of JIS-K6911 is 100. Perform at ℃.
[0021]
When the fluidity value of the forming raw material is less than 60 mm, it is extremely difficult to form a desired cylindrical shape even if a large centrifugal force is applied while heating. If the fluidity of the molding raw material is 60 mm or more, it can be molded into a cylindrical shape by centrifugal molding. However, if the fluidity value is 100 mm or more, molding can be performed at a lower rotational speed and in a short time. Therefore, it is preferable.
[0022]
There is no particular upper limit to the fluidity value of the forming raw material. However, resins with extremely high fluidity generally contain a relatively large amount of low molecular weight oligomer components, so that a large amount of gas is generated during the curing reaction in the rotary mold, and the molded product is likely to foam, and the curing reaction takes a long time. Therefore, the fluidity value is desirably 150 mm or less.
[0023]
As described above, by setting the curing reactivity and fluidity of the pipe raw material within a specific range, the pipe material does not include a filler, which has been impossible with conventional centrifugal molding, and is essentially made of glassy carbon. Even if it was, it became possible to manufacture.
[0024]
  The pipe raw material used in the present invention is preferably a powdered pipe raw material having fluidity and curing degree in the above ranges. The reason for this is that when a liquid pipe raw material or a solution pipe raw material dissolved in a solvent is used, even if the fluidity and the degree of hardening are within the above ranges, the gas or solvent vapor generated in the centrifugal molding process is used. This is because the molded body is easily foamed, and voids are likely to occur in the glassy carbon pipe as the final product.
[0025]
In addition, when a glassy carbon pipe optimal for the inner tube of a CVD apparatus is obtained by the method of the present invention, a pipe raw material containing 95% or more of a thermosetting resin having the above fluidity and curing degree is used. Further, it is more preferable to use a pipe raw material in which 99% or more of the thermosetting resin is composed of inevitable impurities, since the contamination during use can be reduced.
[0026]
As the thermosetting resin contained in the pipe raw material, generally known thermosetting resins such as phenol resin and furan resin can be used, and are not particularly limited, but the phenol resin is described below. More preferred for reasons. That is, the phenol resin has a higher material yield after carbonization than other resins, and therefore has little dimensional change. Therefore, it is suitable for obtaining a glassy carbon pipe having a desired shape and size. The fluidity and degree of cure of the pipe material can be controlled by adjusting the amount of thermosetting resin, amount of catalyst, and polymerization reaction time, and can also be adjusted by the type and amount of filler and solvent. Is possible.
[0027]
In producing a thermosetting resin molding by centrifugal molding, a pipe material containing a thermosetting resin is loaded into a substantially cylindrical mold that can be rotated in the circumferential direction, and the substantially cylindrical mold is formed. What is necessary is just to manufacture the substantially cylindrical thermosetting resin molding by heating to the curing temperature of resin, rotating.
[0028]
In producing the pipe made of thermosetting resin, it is recommended to use a centrifugal molding apparatus as shown in FIG. In FIG. 1, reference numeral 1 denotes a cylindrical mold, and at least one end portion needs to have an opening so that gas generated during the resin curing reaction can escape to the outside. This mold 1 can be rotated at high speed by a motor or a pulley. In addition, it is desirable that the structure be separable from the viewpoint of facilitating removal of the resin pipe. As the mold material, metal, ceramic, resin, or the like can be used, but metal is preferable in terms of strength and ease of processing.
[0029]
In FIG. 2, 4 is a schematic explanatory view of a mold for obtaining a pipe having flanges at both ends. If the mold 4 is molded, a resin pipe 5 having flanges at both ends can be obtained. By carbonizing the resin pipe 5, a glassy carbon pipe having flanges at both ends can be obtained at a low cost. be able to. According to the method of the present invention, since the outer diameter and length of the glassy carbon pipe are defined only by the inner diameter and length of the cylindrical mold, a long pipe having a large outer diameter can be easily manufactured. The wall thickness of the pipe can be easily controlled by changing the amount of resin loaded in the mold.
[0030]
The pipe raw material 3 is loaded into the cylindrical mold 1 as shown in FIG. The resin may be loaded while the mold is stationary or while rotating. The rotational speed of the mold varies depending on the diameter of the mold and the properties / reactivity of the resin, but it is desirable to set the gravity so as to generate a gravity more than twice, preferably 10G or more.
[0031]
In the present invention, a pipe raw material is loaded into a centrifugal mold, and the resin is heated to a temperature higher than the temperature at which the curing reaction proceeds while rotating the mold. When the pipe raw material has the above properties, the resin is melted by heating, and a compressive force is exerted by the centrifugal force generated by the rotation of the mold, so that the pipe material is formed into a uniform wall shape having a substantially constant inner diameter. Volatile components contained in the resin and gaseous components generated in the molding process can be dissipated from the resin surface not in contact with the mold. Further, since the resin on the outside of the pipe is in direct contact with the inner surface of the rotating mold, the outer surface of the pipe can be shaped to be approximately the same as the inner surface of the mold.
[0032]
In the molding method of the present invention, the mold is heated to a temperature higher than the temperature at which the resin curing reaction starts while rotating the mold loaded with the resin, and a heater (heating furnace) disposed on the outer periphery of the cylindrical mold 1 is used. ) 2 may be used.
[0033]
In addition, since various gases including water vapor are generated during the curing reaction of the thermosetting resin, it is important to vent the gas during molding. Degassing is virtually impossible when a large diameter tube such as an inner tube is formed by a general method such as compression molding. Further, when the molded body is taken out of the mold at a stage where the curing reaction is insufficient to suppress the generation of gas, the shape cannot be maintained because it is deformed in the curing process.
[0034]
On the other hand, in the method of the present invention, a compressive force acts on the resin due to the centrifugal force caused by the rotation of the mold, so that a pipe having a uniform thickness can be formed, and the resin pipe is in contact with the mold. Since the surface to be removed is open to the atmosphere, the generated gas can be easily dissipated to the outside of the molded body. Further, since the resin is heated to a temperature at which a curing reaction occurs while being rotationally molded, it can be fired while maintaining the pipe shape without being deformed even after being taken out of the mold. The molding temperature varies depending on the properties and reactivity of the resin, but is 100 ° C. or higher, preferably 120 ° C. or higher.
[0035]
Moreover, there is no restriction | limiting in particular in the method of the carbonization process performed following pipe molding of a thermosetting resin, A non-oxidizing atmosphere WHEREIN: The resin molded object is 800 degreeC or more, Preferably it is the temperature of 1000 degreeC or more. This can be done by heat treatment. If necessary, a post-curing treatment may be performed by heating the resin molded body at 100 ° C. to 300 ° C. in air or a non-oxidizing atmosphere before the carbonization treatment.
[0036]
According to such a method of the present invention, a glassy carbon pipe having a large diameter of 15 mm or more (more preferably 60 mm or more) and containing substantially no filler is manufactured. Is possible.
[0037]
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are not of a nature that limits the present invention, and any design changes may be made in accordance with the gist of the present invention. It is included in the range.
[0038]
【Example】
Example 1
A powdery phenol resin having a curing degree of 10% (T10) reaching time of 25 ° C. at 115 ° C. and a disc type flow test value of JIS-K6911 at 100 ° C. of 140 mm was used as a raw material.
[0039]
The mold used has a cylindrical shape with an inner diameter of 80 mm, a length of 300 mm, and a thickness of 15 mm with both ends open, and can be divided into two on a plane including the center line. 300 g of resin is charged inside the mold and rotated at a speed of 2500 revolutions per minute while being heated from room temperature to 120 ° C. in 30 minutes by a heater installed outside the mold and then held at this temperature for 10 minutes. Further, the temperature was raised to 160 ° C. in 60 minutes, and a curing reaction was performed at 160 ° C. for 30 minutes. Then, it stood to cool, stopped rotation at 80 degreeC, and demolded. As a result, a substantially uniform crack-free pipe having a thickness of about 2 mm could be obtained.
[0040]
This pipe was cured at 230 ° C. for 48 hours, but no changes in appearance such as cracks and voids other than blackening due to curing were observed. Furthermore, when the carbonization process was performed at 1500 degreeC, the glass-like carbon pipe which maintained the shape at the time of curing was able to be obtained.
[0041]
Furthermore, in order to evaluate the uniformity of the pipe, the fluctuation of the inner diameter was measured by the following method. That is, the pipe was divided into four equal parts in the length direction, the difference between the maximum value and the minimum value of the inner diameter of each part was obtained, and the value (percentage) divided by the total length of the pipe was taken as the fluctuation of the inner diameter. The variation of the inner diameter of the pipe of this example was 0.4%.
[0042]
Example 2
A phenol resin pipe was molded using the same resin raw material and apparatus as in Example 1 except that a two-part mold having a diameter of 350 mm and a length of 1000 mm was used. The obtained pipe can be cured while maintaining its shape, and when carbonized at 1500 ° C., there is no change in the appearance other than a change in dimensions due to shrinkage, and there is no glassy carbon with uniform thickness. It was possible to make a pipe. Further, the fluctuation of the inner diameter of this pipe was 0.8%.
[0043]
Example 3
A phenol resin having different curing reactivity and fluidity is prepared by changing the catalyst concentration or polymerization time, and a resin pipe is molded using the same apparatus as in Example 1, followed by curing at 230 ° C. in air for 48 hours. Further, carbonization was performed at 1500 ° C.
Table 1 shows the characteristics of the raw material resin [curability (T10) and fluidity] and the characteristics of the obtained glassy carbon pipe.
[0044]
[Table 1]

[0045]
No. Examples 1 to 4 are examples using the resin according to the present invention, and in any case, the fluctuation of the inner diameter was within 1.0%, and a glassy carbon pipe without cracks could be obtained.
[0046]
No. Nos. 5 to 7 are comparative examples using a resin that does not satisfy the conditions according to the present invention. Since the resin No. 5 had a T10 of 4 minutes and the curing speed was too high, the curing was completed before it was deformed into a cylindrical shape, and a pipe having a uniform thickness could not be obtained. In addition, degassing from the resin was insufficient, cracks occurred in the pipe after carbonization, and the inner diameter of the pipe was also uneven.
[0047]
No. The resin No. 6 is within the range of the present invention at T10 of 13 minutes, but the disk type flow test value is 58 mm, which is a comparative example smaller than the range of the present invention. However, it was not formed into a cylindrical shape, and a pipe having a uniform thickness could not be obtained. In addition, degassing from the resin was insufficient, and the resin molded body contained many bubbles. Cracks also occurred in the pipe after carbonization.
[0048]
No. The resin No. 7 is a comparative example in which the curing time is too long as T10 is 62 minutes. A large amount of foaming is generated inside the molded body due to the gas generated during molding, and a remarkably large non-uniformity is also generated in the inner diameter of the pipe. . Moreover, since cracking and foaming occurred during curing and carbonization, it was not possible to obtain a glassy carbon pipe.
[0049]
Example 4
The time to reach T10 was 24 minutes at 115 ° C, and the same procedure as in Example 1 was used except that a powdered phenol resin having a disc-type flow test value of JIS-K6911 at 100 ° C of 104 mm was used as a raw material. A thermosetting resin molding was produced.
[0050]
This pipe was cured at 230 ° C. for 48 hours, but no changes in appearance such as cracks and voids other than blackening due to curing were observed. Furthermore, when the carbonization process was performed at 1500 degreeC, the glass-like carbon pipe which maintained the shape at the time of curing was able to be obtained.
[0051]
By the way, when the dense resin pipe is molded by completely removing the gas component contained in the resin raw material and the gas component generated during molding, it is considered that the bulk density of the molded pipe matches the true density of the resin. . Therefore, the ratio (specific density) of the bulk density of the resin pipe to the true density of the resin is an index of moldability. The specific density of the thermosetting resin molding obtained in this example was over 0.99. Therefore, the resin pipe obtained in the present example is considered to be obtained by almost completely removing the gas component contained in the resin raw material and the gas component generated during molding.
Further, the variation of the inner diameter of the carbon pipe obtained in this example was 0.1%.
[0052]
Example 5
A phenol resin pipe was molded using the same resin raw material and apparatus as in Example 4 except that a two-part mold having a diameter of 350 mm and a length of 1000 mm was used. This pipe can be cured while maintaining its shape, and when it is carbonized at 1500 ° C., there is no change in appearance except for the change in dimensions due to shrinkage, and the glass-like carbon pipe has no uniform thickness. And was able to.
[0053]
The specific density of the thermosetting resin molded product obtained in this example exceeded 0.99, and the appearance of the molded pipe was good, similar to the carbon pipe of Example 4. The variation in the inner diameter of this pipe was 0.4%.
[0054]
Example 6
A phenol resin having different curing reactivity and fluidity is prepared by changing the catalyst concentration or polymerization time, and a resin pipe is formed using the same apparatus as in Example 1, and then cured at 230 ° C. in air for 48 hours. Further, carbonization was performed at 1500 ° C.
Table 2 shows the properties of the resin and the results of the production of the glassy carbon pipe.
[0055]
[Table 2]

[0056]
No. Examples 1 to 5 are examples using the resin according to the present invention. In any case, a glass-like carbon pipe having an inner diameter variation of 1% or less and having no cracks could be obtained.
[0057]
No. Nos. 6 to 9 are comparative examples using resins that do not satisfy the conditions according to the present invention. 6 and no. Since the resin No. 8 had a T10 of 4 minutes and the curing speed was too high, the curing was completed before it was deformed into a cylindrical shape, and a pipe having a uniform thickness could not be obtained. In addition, degassing from the resin was insufficient, cracks occurred in the pipe after carbonization, and the inner diameter of the pipe was also uneven.
[0058]
No. The resin of No. 7 is a comparative example in which the curing time is too long as T10 is 63 minutes, and a large amount of foaming is generated inside the molded body due to the gas generated during molding, and a remarkably large non-uniformity is also generated in the pipe inner diameter. . Moreover, since cracking and foaming occurred during curing and carbonization, it was not possible to obtain a glassy carbon pipe.
[0059]
No. The resin No. 9 is within the range of the present invention at T10 of 8 minutes, but the disk type flow test value is 58 mm, which is a comparative example smaller than the range of the present invention. However, it was not formed into a cylindrical shape, and a pipe having a uniform thickness could not be obtained. In addition, degassing from the resin was insufficient, and the resin molded body contained many bubbles. Cracks also occurred in the pipe after carbonization.
[0060]
【The invention's effect】
Since this invention is comprised as mentioned above, it is a glass-like carbon pipe including the inner tube of the CVD apparatus for semiconductor manufacture, Comprising: It does not contain the filler which causes the contamination of a CVD apparatus, and is high Suitable as a large-diameter member that requires heat and corrosion resistanceMethod for producing glassy carbon pipeCan be provided.
[Brief description of the drawings]
FIG. 1 is an explanatory view showing a centrifugal molding apparatus that can be used in the method of the present invention.
FIG. 2 is an explanatory view showing a molding die (a) that can be used in the method of the present invention and a glassy carbon pipe (b) obtained by the die.
[Explanation of symbols]
1 Mold
2 Heater
3 Thermosetting resin
4 Mold for plastic pipe with flange
5 Flange plastic pipe

Claims (2)

A method for producing a glassy carbon pipe by making a thermosetting resin powder pipe raw material into a thermosetting resin molded body by centrifugal molding, and subjecting the thermosetting resin molded body to carbonization treatment, As a raw material thermosetting resin, it has a curability with a cure time of 10% (T10) at 115 ° C. of 5 to 60 minutes, and a flow of 60 mm or more at 100 ° C. in a disc type flow test of JIS-K6911. For producing a glassy carbon pipe containing substantially no filler , using a thermosetting resin having a property. It is a manufacturing method of Claim 1, Comprising: The manufacturing method of the glass-like carbon pipe whose internal diameter is 15 mm or more.

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