WO2004052987A1 - フッ素樹脂組成物、フッ素樹脂組成物製造方法、半導体製造装置及び被覆電線 - Google Patents
フッ素樹脂組成物、フッ素樹脂組成物製造方法、半導体製造装置及び被覆電線 Download PDFInfo
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- WO2004052987A1 WO2004052987A1 PCT/JP2003/015761 JP0315761W WO2004052987A1 WO 2004052987 A1 WO2004052987 A1 WO 2004052987A1 JP 0315761 W JP0315761 W JP 0315761W WO 2004052987 A1 WO2004052987 A1 WO 2004052987A1
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- tetrafluoroethylene
- fluororesin composition
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- fluorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- Fluororesin composition Fluororesin composition, fluororesin composition production method, semiconductor production equipment and coated electric wire
- the present invention relates to a fluororesin composition, a method for producing a fluororesin composition, a semiconductor manufacturing apparatus, and a covered electric wire.
- Tetrafluoroethylene // fluoroalkoxytrifluoroethylene copolymer (PFA) is a fluororesin with excellent chemical resistance, heat resistance, and moldability. Used for tubes and bottles for transport lines that come into contact with (gas, liquid), and as members of semiconductor manufacturing equipment, tubes for flowing ozone-containing media, tubes for sending slurry containing abrasives, etc. It is used for
- the surface of the tube obtained from PFA does not have sufficient smoothness, especially when slurry containing an abrasive is sent, polishing mixes the tube material into the feed line and lowers the polishing efficiency. In addition, it causes polishing abnormalities and lowers the electrical characteristics of the obtained semiconductor, which greatly reduces the product yield. In addition, when the ozone-containing medium is distributed, the deposition of pollutants easily proceeds, and there is a problem in terms of maintainability. A tube used as a member of a semiconductor manufacturing apparatus is required to be hardly deteriorated and to have a smooth inner surface.
- PFA is used not only as a tube material but also as a wire coating material.However, due to its high melting point, it is difficult to increase the line speed during molding.If it is raised, cracks will occur on the outer surface of the coating material. There was a major problem in moldability.
- One object of the present invention is to provide, in view of the above situation, excellent ozone resistance and surface smoothness.
- a second object of the present invention is to provide a member relating to a semiconductor manufacturing apparatus, and a fluororesin composition comprising a tetrafluoroethylene fluoroalkoxytrifluoroethylene copolymer excellent in moldability. Is to provide.
- the present invention is a fluororesin composition
- a fluororesin composition comprising a tetrafluoroethylene z fluoroalkoxytrifluoroethylene copolymer and a tetrafluoroethylenenohexafluoropropylene copolymer
- the tetrafluoroethylenenohexafluoro mouth propylene copolymer includes the above tetrafluoroethylenenohexafluoropropylene copolymer and the above tetrafluoroethylenefluoroalkoxytrifluoroethylene copolymer
- melt-kneading of a mixed composition consisting of a tetrafluoroethylene Z fluoroalkoxy trifluoroethylene copolymer and a tetrafluoroethylene / hexafluoropropylene copolymer is performed.
- a method for producing a fluororesin composition for producing the above fluororesin composition comprising a melt kneading step and a purification step of performing a purification treatment using a fluorine-containing gas in this order, wherein the melt kneading is performed by a cylinder
- the process is performed until the viscosity of the mixed composition no longer changes using an extruder in which the temperature of the mixed composition is controlled at 350 to 3995 ° C.
- the refining treatment comprises exposing the extrudate obtained by the melt-kneading step to the fluorine-containing gas to decompose and remove low molecular weight substances.
- the fluororesin composition of the present invention is a molded tube for measurement comprising a tetrafluoroethylene / fluoroalkoxy trifluoroethylene copolymer and a tetrafluoroethylene // hexafluoropropylene copolymer.
- the inner surface has an average roughness [Ra] of not more than 0.035 ⁇ .
- the average roughness of the inner surface [Ra] is If a fluid containing abrasives is allowed to flow through a tube exceeding 0.035 ⁇ m for a long period of time, it will be easily worn, and if it comes into contact with a fluid that has a strong chemical deterioration for a long time, contaminants and the like will be exposed inside the tube. Almost accumulates on the deteriorated part of A preferred upper limit of the average roughness [R a] is 0.03 ⁇ . If the average roughness [R a] is within the above range, the lower limit can be set to 0.005 ⁇ due to the restrictions on the production method of the tube-formed body for measurement.
- the fluororesin composition of the present invention is a molded tube for measurement comprising a tetrafluoroethylene / fluoroalkoxy trifluoroethylene copolymer and a tetrafluoroethylene / hexafluoropropylene copolymer,
- the average roughness [R a] is within the above range, and the maximum roughness [R t] is less than 0. If it is 0.3 / zm or more, it does not satisfy the standard level required for various products, which is not preferable.
- a preferred upper limit is 0.25 zm. If the maximum roughness [R a] is within the above range, the lower limit can be set to 0.1 ⁇ due to restrictions on the production method of the molded tube for measurement.
- the average roughness [R a] and the maximum roughness [R t] are values obtained by measuring according to JIS SB 06,01.
- the average roughness [R a] and the maximum roughness [R t] of the inner surface of the molded tube for measurement usually increase in the presence of a low molecular weight substance described later.
- the above-mentioned molded tube for measurement is obtained by molding and cooling by extruding the outer surface while contacting the outer surface with an external object such as a mold, similarly to a normal tube.
- the surface irregularities are relatively smooth, governed by the smoothness of the surface of the mold, etc., Force The inner surface does not keep contact with the jigs etc. during cooling, but the surface irregularities are reduced by the external objects such as molds.
- the spherulites are easily formed and the surface is liable to be rough.
- the molded tube for measurement obtained by using the fluororesin composition of the present invention has surface smoothness even on the inner surface thereof, and has an average roughness [Ra] and a maximum roughness.
- the roughness [R t] satisfies the above range.
- the fluororesin composition of the present invention is sufficient for other general molded bodies. It can have excellent smoothness.
- the other general molded body is not particularly limited.
- a conventional one whose surface is easily roughened for example, a covering material of an electric wire obtained using a cone, a cast product A film or the like obtained by a film may be used.
- the fluororesin composition of the present invention comprises a tetrafluoroethylene / fluoroalkoxy trifluoroethylene copolymer CT FEZFTE copolymer].
- the TFEZFTE copolymer is a copolymer in which fluoroalkoxytrifluoroethylene [FTE] is a comonomer of tetrafluoroethylene [TFE].
- FTE fluoroalkoxytrifluoroethylene
- TFE comonomer of tetrafluoroethylene
- E means 1 to 15% by mass of the total mass of TFE and FTE.
- the amount represented by mass% of the total amount of the comonomer is such that the comonomer unit derived from the comonomer is “monomer” in the molecular structure of the copolymer.
- the “comonomer unit” described above is, for example, represented by one CF 2 —CF (CF 3 ) when derived from HFP described below.
- the fluoroalkoxyl group in the above fluoroalkoxy trifluoroethylene may be a perfluoroalkoxyl group in which all carbon-hydrogen bonds of the alkoxyl group are carbon-fluorine bonds, An alkoxyl group in which hydrogen of a hydrogen bond is partially substituted by fluorine may be used.
- the TFE / FTE copolymer preferably has a melt flow rate [MFR] of 9 (g / l 0 min) or less.
- the amount exceeds 9 ( g / lO content), the molecular weight is too low, and the ozone resistance and heat resistance of the obtained molded article are liable to decrease.
- a more preferred upper limit is 4 (g / 10 minutes), and a still more preferred upper limit is 3.5 (gZlO content). If the MFR is within the above range, the lower limit can be set to, for example, 0.5 (g / 10 minutes) in terms of moldability.
- the MFR is a value obtained by measuring under a load of 5 kg at 372 ° C. in accordance with ASTM D 3307 (1998).
- the fluororesin composition of the present invention comprises the above TFE / FTE copolymer and a tetrafluoroethylene / hexafluoropropylene copolymer [TFE / HFP copolymer].
- TFE / HFP copolymer a tetrafluoroethylene / hexafluoropropylene copolymer
- the ozone resistance can be enhanced by adding the TFEZHFP copolymer.
- the TFE / HFP copolymer is a copolymer having hexafluoropropylene (HFP) as a comonomer of TFE, and the HFP includes TFE and HFP.
- HFP hexafluoropropylene
- the TFEZHFP copolymer may be a tertiary or higher copolymer obtained by using HFP as a comonomer of TFE and, if desired, butyl ether.
- the T FE / HF P copolymer is a ternary or more copolymer above
- the Bulle ether is usually a 1 mass 0/0 hereinafter the total mass of TFE and HFP and Bulle ether
- the total weight of TFE, HFP and butyl ether may exceed 1% by mass, and if it exceeds 1% by mass, a preferable upper limit is, for example, 2.5% by mass. / 0 , a more preferable upper limit can be set to 2% by mass.
- Y 1 and Y 2 are the same or different and each represent a hydrogen atom or a fluorine atom.
- R is an ether in which a part or all of the hydrogen atoms bonded to the carbon atoms may be substituted with a fluorine atom.
- the TFE / HFP copolymer preferably has a melt flow rate [MFR] of 9 (g / l 0 min) or less. If the amount exceeds 9 (g / 10 minutes), the molecular weight is too low, and the ozone resistance and heat resistance of the obtained molded article are likely to be reduced. A more preferred upper limit is 4 (gZlO content), and a still more preferred upper limit is 3 (g / 10 minutes). If the MFR is within the above range, the lower limit can be set to, for example, 0.5 (g / l 0 minutes) in terms of moldability.
- the average roughness (Ra) and the maximum roughness (Rt) of the inner surface of the molded tube for measurement can be adjusted as described above. Range.
- the average roughness [Ra] and the maximum roughness [Rt] of the inner surface of the molded tube for measurement can be further reduced by performing a purification treatment using a fluorine-containing gas described later.
- the TFEZFTE having an MFR of 1.0 to 3.5 (gZ10 minutes) is used.
- the average roughness [Ra] and the maximum roughness of the inner surface of the molded tube for measurement are obtained.
- the [R t] can be in the above-mentioned range.
- the TFEZHFP copolymer accounts for 0.5 to 60% by mass of the total solid content of the TFEZHFP copolymer and the TFE / FTE copolymer.
- the molded product obtained using the fluororesin composition of the present invention may have poor surface smoothness. May have poor mechanical properties at high temperatures.
- the preferable upper limit is 50% by mass, and the dimensional stability is not impaired even when used at a practical washing temperature without lowering the heat resistance of the obtained molded body.
- a more preferable upper limit is 30% by mass.
- the upper limit is more preferably 10% by mass from the viewpoint of exhibiting a high melting point as described later, but the optimum composition should be set for each application in view of the balance between moldability and developed performance.
- the TFEZFTE copolymer is It is preferable to carry out melt-kneading with the TFE / HFP copolymer.
- a mixture of the above TFE / FTE copolymer and the above TFE / HFP copolymer, which is before and during the above-mentioned melt-kneading, is referred to as a ⁇ mixture composition ''. There is.
- melt kneading is carried out using an extruder as described below.
- what is melt-kneaded with the above mixed composition and extruded from the extruder may be referred to as an “extrudate”.
- the proportion of the TFEZH FP copolymer in the total solid mass of the mixed composition is 0. 5% to about 10% is most preferred.
- the extrudate has a melting point higher or equal to the melting point of the TFE ZFTE copolymer alone before melt kneading according to the differential scanning calorimeter analysis, so that the heat resistance is high. Can be improved.
- the TFE_HFP copolymer when the TFE_HFP copolymer is in a range of more than 10% by mass and not more than approximately 35% by mass of the total solid content of the mixed composition, the TFE before melt-kneading is used. It shows a higher heat of fusion than the FEZHF P copolymer, and shows a lower heat of fusion than the TFE / HFP copolymer before melt kneading in the region exceeding about 35% by mass.
- the fluororesin composition of the present invention can exhibit such specific thermal characteristics by being melt-kneaded.
- the amount of heat of fusion can be adjusted as described above, and the average molecular weight and the melt viscosity can be controlled.
- the melt kneading will be described later.
- the fluororesin composition of the present invention can also adjust the heat of fusion, the average molecular weight, and the melt viscosity as described above by performing a treatment of pressurizing and pulverizing the mixed composition. It is conceivable that.
- a screw having a high kneading effect of a screw mounted on a molding apparatus is used.
- Fluororesin composition of the present invention, a TFE / / FTE copolymer and TFE / HFP copolymer polymer may be made from a tetrafluoropropoxy O b ethylene polymer.
- the tetrochloroethylene polymer when added, has the effect of improving the moldability during molding as described below, and thus has the significance of being used as a molding aid.
- the ⁇ tetrafluoroethylene polymer '' is a homopolymer of tetrafluoroethylene, and Z or a copolymer of the tetrafluoroethylene and another comonomer
- the above-mentioned other comonomer means one which is less than 1% by mass of the total mass of tetrafluoroethylene and the above-mentioned other comonomer.
- the tetrafluoroethylene polymer is different from the TFEZFTE copolymer and the TFEZHF P copolymer in that the content of the copolymer component other than tetrafluoroethylene is limited to less than 1% by mass. It is a distinct concept.
- the other comonomer is not particularly limited, and examples thereof include trifluoroethylene [CTFE], HFP, and perfluoro (alkyl vinyl ether) [p AVE].
- the above tetrafluoroethylene polymer preferably has a heat of fusion of 60 J / g or more.
- a fluororesin composition having excellent bending resistance and crack resistance as described above and having good moldability when melt-molded to obtain a molded article can be obtained.
- the above-mentioned tetrafluoroethylene polymer may have a heat of fusion of less than 6 jJg.For example, even if a polymer having a heat of fusion of 35 to 48 j / g is used, there is a slight Improvement in bending resistance and crack resistance.
- the fluororesin composition of the present invention is composed of the tetrafluoroethylene polymer
- the tetrafluoroethylene polymer is 0.2 to 5% by mass of the solid content of the fluororesin composition. %. If the amount is less than 0.2% by mass, the improvement in moldability due to the use of the above-mentioned tetrafluoroethylene polymer may not be remarkably exhibited. If the amount exceeds 5% by mass, the surface of the obtained molded body becomes smooth. May deteriorate. A more preferred lower limit is 0.5% by mass, and a more preferred upper limit is 3% by mass.
- the fluororesin composition of the present invention in addition to the TFE / FTE copolymer, the TFE / HFP copolymer and the tetrafluoroethylene polymer used as desired, It may contain additives.
- the additives are not particularly limited, and include, for example, fillers, lubricants, molding aids, pigments, and the like.
- fillers for example, fillers, lubricants, molding aids, pigments, and the like.
- the TFEZFTE copolymer and the TFEZHFP copolymer are preferably prepared by adjusting the number of terminal functional groups.
- the number of the terminal functional groups is adjusted prior to the melt-kneading. Adjustment of the number of terminal functional groups will be described later.
- the fluororesin composition is preferably one that has been treated with a fluorine-containing gas.
- treatment using a fluorine-containing gas refers to not only adjusting the number of terminal functional groups before melt-kneading, suppressing foaming during molding, but also extrudate obtained after melt-kneading.
- the purpose is to decompose and remove the low molecular weight substances contained in.
- the treatment using the fluorine-containing gas is a purification treatment using a fluorine-containing gas.
- exposing to a fluorine-containing gas it is possible to decompose and remove low-molecular-weight substances contained in the extrudate obtained after the above-mentioned melt-kneading.
- the fluororesin composition of the present invention preferably has a molecular weight distribution of from 1.0 to 2.2.
- the value in monodispersion is immediately set to 1.0, and is a value indicating the degree of variation therefrom.
- the molecular weight distribution exceeds 2.2, the molecular weight varies greatly and low molecular weight substances may be present, and when molding a molded article whose surface irregularities such as the inner surface of the tube are not restricted by a mold, etc. Low molecular weight compounds bleed out on the surface and surface smoothness tends to decrease.
- a more preferred upper limit is 1.6.
- the molecular weight distribution is a value for the fluororesin composition of the present invention as described above, and when the fluororesin composition of the present invention is obtained by performing a purification treatment using a fluorine-containing gas, This is the value after performing the purification treatment using the contained gas.
- By performing the purification treatment using the above-mentioned fluorine-containing gas low molecular weight substances can be removed, and the molecular weight distribution within the above range can be suppressed.
- Fluorine-containing gas In the case where the purification treatment is carried out using the above, the value of the molecular weight distribution before performing the above-mentioned purification treatment may exceed the above range.
- the removal of the low molecular weight substance can be determined by the fact that the value of the above molecular weight distribution has decreased and the MFR has decreased through the purification treatment using a fluorine-containing gas.
- the reason that the low molecular weight substance cannot be determined based on only the decrease in the molecular weight distribution described above is that the result of the melt viscoelasticity measurement is fitted to a normal distribution curve to make it closer to the ideal curve, so that the spread of the distribution is expanded. This is because even if it is an indicator, it cannot evaluate the uneven distribution.
- the method for measuring the MFR of the fluororesin composition after melt-kneading is the same as described above.
- At least one terminal functional group selected from the group consisting of one CF 2 —CH 2 OH, one CONH 2 , —COOH, and one COF has less than 10 per 10 6 carbon atoms. Preferably, there is. If it is 10 or more, foaming is likely to occur during melt molding.
- the fluororesin composition of the present invention may have no terminal functional group.
- the number of the terminal functional groups is a value obtained by measurement by infrared spectroscopy.
- the number of the terminal functional groups is a value in the fluororesin composition of the present invention, and is obtained by performing the purification treatment using the above-described fluorine-containing gas on the fluororesin composition of the present invention. In some cases, it is the value after this purification process.
- the carbon number is the sum of the carbon number of the TFE / FTE copolymer and the carbon number of the TFEZHFP copolymer.
- the number of carbon atoms and the number of the terminal functional groups are, when the fluororesin composition of the present invention is composed of the above-mentioned tetrafluoroethylene polymer, the number of carbon atoms and the terminal functional groups of the tetrafluoroethylene polymer Including the number of
- the above-mentioned terminal functional group is the same as the above-mentioned TF EZF den E copolymer and / or TF EZHF P It exists at the molecular chain terminal of the polymer.
- the molecular chain terminal may be a main chain terminal or a side chain terminal.
- the terminal functional group is formed by using a monohydric lower alcohol or the like as a chain transfer agent at the time of polymerization of the TFEZFTE copolymer or TFE / HFP copolymer, thereby forming the main chain terminal and / or the side chain terminal. Can be introduced.
- the method for producing a fluororesin composition of the present invention is for producing the above fluororesin composition.
- the method for producing a fluororesin composition of the present invention includes a melt-kneading step of melt-kneading a mixed composition comprising a TFE / FTE copolymer and a TFE / HFP copolymer, and a purification treatment using a fluorine-containing gas. And a purification step for performing the above steps in this order.
- the terminal functional groups of the molecular chains of the TFE / FTE copolymer, the TFE / HFP copolymer and the optional tetrafluoroethylene polymer in the mixed composition are bonded to each other. (Hereinafter referred to as a coupling reaction).
- the melt-kneading step is a step for generating a coupling body by a coupling reaction of the terminal functional groups, thereby enabling to obtain a molded article having excellent ozone resistance.
- the shearing force applied to the mixed composition temporarily increases, and the molecular chains are locally cut. , Avoids lowering of melt viscosity and formation of low molecular weight Was not.
- the melt kneading step is performed by adjusting parameters such as the time required for melt kneading, the temperature at which the melt kneading is performed, the shear rate, and the number of terminal functional groups. Since the progress of the coupling reaction can be controlled, even a molecular chain whose molecular weight has been reduced by shearing once due to shearing is bonded to another molecular chain by the coupling reaction, and the same molecular level as before the molecular chain was cut. Therefore, it is possible to suppress the abundance of the low-molecular-weight product and obtain a molded product having excellent ozone resistance.
- the melt-kneading step controls the coupling reaction so that the melt reaction does not excessively increase due to the progress of the coupling reaction proceeding at a rate exceeding the breaking of molecular chains by shearing. It is thought that deterioration of sex can be prevented.
- the melt-kneading step the melt-kneading is performed until the viscosity of the mixed composition no longer changes. The change in viscosity during melt-kneading of the above mixed composition is observed through the change over time of the rotational torque by a torque meter via a screw.
- the expression “until the viscosity change of the mixed composition disappears” means that the process is performed until the viscosity of the mixed composition does not change.
- the above-mentioned “state in which the viscosity of the mixed composition does not change” means a state in which the fluctuation of the value of the rotational torque is within 5% of the center value for a certain period of time or more.
- the “constant time” is, for example, 10 minutes.
- the time required for the melt-kneading may vary depending on the temperature at which the melt-kneading described below is performed, the mixing ratio of the mixed composition, the screw shape, and the like, but is generally 2 minutes or more.
- the upper limit of the time required for the melt kneading can be set to, for example, 10 minutes in terms of economy and productivity.
- the TF EZF TE copolymer having 17 terminal functional groups When the active group TFE ZH FP copolymer is kneaded at a mass ratio of 90: 1.0, the mixing time is about 4 to 9 minutes at 390 ° C.
- this corresponds to a transit time of about 2.5 to 5 minutes.
- the passage time is set based on data of the time-dependent change of the viscosity measured beforehand using a batch-type kneader.
- the melt-kneading is performed by setting the temperature of the mixed composition of the TFE / FTE copolymer and the TFE / HFP copolymer in the cylinder to 350 to 3995 ° C. It is controlled using an extruder.
- the kneading temperature is within the above range, it is possible to obtain a fluororesin composition in which the surface of the molded article can be easily smoothed during molding.
- a preferred lower limit of the above kneading temperature is 360 ° C.
- the temperature in the cylinder of the extruder is kept constant after inputting the control conditions in a state where the above-mentioned mixed composition is not put into the cylinder.
- the measurement can be performed by using a plurality of thermocouples over a period of time, and it can be controlled by confirming that the temperature is the target.
- a single-screw extruder equipped with a screw having a high kneading effect may be used, but it is more preferable to use a twin-screw extruder.
- the shear rate is preferably set in the above-mentioned temperature range according to the composition ratio of the above-mentioned mixed composition.
- the TFE / FTE copolymer and the TFE / HFP copolymer used are preferably powders after polymerization, and the powders preferably have a small particle diameter. This is because, when the number of terminal functional groups is adjusted with a fluorine-containing gas prior to melt-kneading, as described later, not only the treatment is facilitated but also a uniform melt-kneaded state is obtained.
- the above-mentioned powder after polymerization is a powder obtained by drying after completion of the polymerization reaction.
- the powder of the TFE-no-FTE copolymer and the powder of the TFE-HFP copolymer are mixed without heating.
- the mixing of the powder can be performed using a conventionally known device.
- the TF EZF TE copolymer and the TFE / HFP copolymer are preferably prepared by adjusting the number of terminal functional groups. Adjustment of the number of terminal functional groups is achieved by mixing in melt-kneading while maintaining the number of terminal functional groups to such an extent that a force-pulling body capable of obtaining a molded article having excellent ozone resistance is formed in melt-kneading. This is for suppressing the number of terminal functional groups to such an extent that the excessive increase in the shearing force applied to the composition and the accompanying generation of low molecular weight substances are suppressed.
- the number of the terminal functional groups is adjusted such that the number of the terminal functional groups is 4 to 100 per 10 6 in total of the carbon number of the TFE / FTE copolymer and the carbon number of the TFE / HFP copolymer. It is preferable that the process be performed as follows. A more preferred upper limit is 70, and a still more preferred lower limit is 50. In the case where a tetrafluoroethylene polymer is used, the number of the terminal functional groups is preferably adjusted prior to the melt-kneading step also in the case of using the tetrafluoroethylene polymer.
- the number and the number of terminal functional groups are values of a combination of the above-mentioned TFEZFTE copolymer, the above-mentioned TFE-no-HFP copolymer and the above-mentioned tetrafluoroethylene polymer.
- the number of the terminal functional groups is adjusted as follows: (A) in which the number of the terminal functional groups is originally 0 in the polymerization stage or 0 due to the inactivation of the terminal functional groups described later; By mixing with (B) which has not been completely deactivated in the terminal functional group, it is possible to apparently adjust the number, but this is not preferred. This is because the above (B) can cause an increase in the molecular weight due to the coupling reaction when performing the melt kneading, whereas the above (A) causes only the degradation due to the main chain fragmentation. This is because the generation amount of the dimer cannot be avoided.
- the number of the terminal functional groups is adjusted so that the mixture of the TFE / FTE copolymer, the TFE / HFP copolymer, and the tetrafluoroethylene polymer is adjusted so as to be uniform between molecules. It is preferable to perform it uniformly on the object.
- the refining step in the method for producing a fluororesin composition of the present invention is performed so that the fluororesin composition of the present invention has a uniform composition by removing low molecular weight substances generated by the melt-kneading step. You.
- the fluorine-containing gas contains fluorine in an amount of 5% by mass or more.
- a preferred lower limit is 10% by mass, and a more preferred lower limit is 20% by mass.
- the fluorine-containing gas may contain 100% by mass or less of fluorine as long as it is within the above range, or may be fluorine gas itself.
- the refining treatment in the refining step comprises exposing the extrudate obtained in the melt-kneading step to the fluorine-containing gas to remove low molecular weight substances.
- the above-mentioned purification treatment involves removing low-molecular-weight substances as described above, and In some cases, the terminal functional group may be inactivated.
- the fluororesin composition of the present invention obtained through the above-described melt-kneading step and the above-described purification step is subjected to melt molding.
- foaming due to the remaining terminal functional groups may occur. May occur. Therefore, in order to suppress the foaming during melt molding, it is preferable to inactivate the remaining terminal functional groups after the above-described melt-kneading step.
- the method of inactivating the terminal functional group is not particularly limited.For example, a method of changing the terminal to a trifluoromethyl group by exposure to the above-mentioned fluorine-containing gas, immersion in a methanol solution of aniline, There is a method of substituting a phenyl group by treating at high temperature and high pressure in an autoclave. However, the method is not limited as long as it is changed to a terminal that does not decompose during molding at high temperature. Since the fluororesin composition of the present invention has the above-described composition and is produced by the above-described production method, a molded article having excellent ozone resistance and surface smoothness can be obtained. It is possible to get.
- the fluororesin composition of the present invention can remove low-molecular-weight substances by performing a purification treatment using a fluorine-containing gas. Even when a molded article having a surface such as a surface is obtained, it is considered that a low molecular weight substance hardly bleeds out on the surface of the molded article, and the surface smoothness of the obtained molded article is improved.
- the fluororesin composition of the present invention is further characterized in that a low-molecular-weight substance is hardly generated by controlling the force coupling reaction between the terminal functional groups in the melt-kneading as described above.
- the fluororesin composition of the present invention is composed of a TFE / HFP copolymer component which is hardly susceptible to ozonolysis, it suppresses a decrease in the crack resistance and the like of the molded article after exposure to ozone, and causes slight deterioration.
- the fluororesin composition of the present invention may also be one in which the remaining terminal functional groups have been inactivated after purification treatment using a fluorine-containing gas.
- inactivating the terminal functional groups it is possible to suppress the decomposition of the terminal functional groups and the foaming accompanying the coupling reaction of the terminal functional groups when performing melt molding in order to obtain a molded product, which is obtained. It is thought to contribute to the improvement of the surface smoothness of the molded body.
- a molded article characterized by being obtained from the above-mentioned fluororesin composition is also one of the present invention.
- a semiconductor manufacturing apparatus comprising the above-mentioned molded article, wherein an ozone-containing medium containing 10% by volume or more of ozone is used at 60 ° C. or more. This is one of the inventions.
- the ozone-containing medium is not particularly limited, and may be a liquid such as ozone water or a gas such as an ozone-containing gas.
- the molded body used in the semiconductor manufacturing apparatus is not particularly limited, and examples thereof include tubes and the like.
- Tubes obtained from the above-mentioned fluororesin composition have high ozone resistance, and therefore, when used in a semiconductor manufacturing apparatus using an ozone-containing medium such as ozone-containing water or ozone gas, compared to existing fluororesin tubes. Because of its high durability, it can reduce the frequency of equipment maintenance, increase the equipment operation rate, and reduce maintenance costs, contributing to the manufacture of less expensive semiconductors.
- the tube obtained from the fluororesin composition of the present invention has a low average roughness [R a] and a maximum roughness [R t] of the inner surface, and therefore has excellent surface smoothness and abrasion resistance. Even when used in a polishing line in the semiconductor manufacturing process, it has high durability and can contribute to the manufacture of less expensive semiconductors.
- a semiconductor manufacturing apparatus comprising the above-mentioned molded body, wherein the particle-containing slurry is used at 15 ° C or more, and the particle-containing slurry contains particles made of alumina and / or silica.
- the above-mentioned joint for a cylindrical molded product is a member for joining cylindrical molded products or for joining a cylindrical molded product to other members.
- the cylindrical molded product to be joined by the cylindrical molded product joint is preferably made of a fluororesin composition similarly to the cylindrical molded product joint, and has a seamless cylindrical shape. Therefore, there is no dimensional restriction such as thickness, thickness, length, cross-sectional shape, etc., provided that the use of the above fluororesin composition can show superiority in physical properties.
- the use is not particularly limited.
- Examples of the cylindrical molded article include various shapes such as a heat-shrinkable tube and a thick-walled tube, and are preferably used in a semiconductor manufacturing apparatus.
- the cylindrical molded product exhibits excellent surface smoothness, crack resistance, and ozone resistance as compared with the cylindrical molded product obtained using only the TFEZF TE copolymer.
- a covered electric wire wherein the electric wire is covered with a covering material obtained from the fluororesin composition, is also one of the present invention.
- the fluororesin-coated electric wire can be manufactured at a high speed.
- the fluororesin composition also has a lower melt viscosity, and therefore has better moldability than a covered electric wire obtained using only the TFE / HFP copolymer. Also, since it contains a TFE / FTE copolymer component, it exhibits higher volume resistivity at high temperatures than a covered wire obtained using only the TFE / HFP copolymer.
- the molded product obtained from the fluororesin composition of the present invention generally has smaller spherulites formed on the surface of the molded product than the molded product obtained using only the TF EZ FTE copolymer. It will be.
- a smaller spherulite means a smaller grain boundary area, and a smaller grain boundary reduces the local concentration of stress, resulting in durability against fatigue rupture ⁇ bending resistance. It is considered to be improved, and is suitable for use in the above-mentioned covered electric wires and the like.
- FIG. 1 is an electron microscope image of the surface of the inside of the measurement tube molded body after the slurry liquid transfer test in Example 1.
- FIG. 2 is an electron microscope image of the surface of the inside of the molded tube for measurement after the slurry transfer test in Comparative Example 1.
- FIG. 3 is a cross-sectional view in the thickness direction of a joint in which cracks occurred after an ozone exposure test in Comparative Example 5. Explanation of reference numerals
- Example 1
- the number of terminal functional groups in the above-mentioned mixed composition was determined based on TF EZF TE copolymer and T FE / HFP Copolymer totaled 17 Number 10 6 per carbon in.
- the molecular weight distribution (CMWD) of the obtained fluororesin composition was 1.45, which was reduced from 1.63, which was the value before the purification treatment, and the MFR was the value before the purification treatment. From 2.1 (gZlO content), it decreased to 1.7 (gZlO content) after purification. It was determined that low molecular weight substances were removed from the extrudate based on the decrease in the MWD and the decrease in the MFR. The number of terminal functional groups contained in the fluororesin composition was confirmed by this time infrared spectroscopy, was between 4-10 several 10 6 per carbon.
- the MFR was measured at 372 ° C. under a load of 5 kg according to ASTM D 3307 (1998).
- melt compression molding was performed at a hot plate temperature of 360 ° C to obtain a 2 mm thick sheet, and the obtained sheet was preheated to 370 ° C. The presence or absence of foaming when left in the oven for 2 hours was visually checked, but no foaming was observed.
- the average roughness [Ra] and the maximum roughness [Rt] of the inner surface of the molded tube for measurement molded by the above-described method using the fluororesin composition were measured in accordance with JIS B0601.
- a slurry (particles: alumina, concentration: 50 gZL) was passed through the above molded tube for measurement at a flow rate of 10 L / min and a temperature of 25 ° C for 800 hours.
- the inner surface of the molded tube for measurement before and after sending the slurry was observed using an electron microscope. The results are shown in Figure 1. There were few particles adhered to the inner surface, and no scratches were seen.
- Example 2
- Example 3 0.8 parts by mass of tetrafluoroethylene polymer (comonomer: HFP, 0.08% by mass, heat of fusion 45 j / g, molecular weight of about 180 with respect to 100 parts by mass of the raw material of Example 1)
- HFP tetrafluoroethylene polymer
- Example 3 A fluororesin composition was obtained in the same manner as in Example 1 except that (10,000) was added, and evaluations other than the slurry feeding test were performed.
- a fluororesin composition was obtained in the same manner as in Example 1 except that the obtained extrudate was not exposed to a fluorine-containing gas, and evaluations other than the slurry liquid sending test were performed. Comparative Example 1
- Example 2 A fluororesin composition was obtained in the same manner as in Example 1 except that only the TFE / FTE copolymer resin was used as the raw material, and the same evaluation was performed.
- Fig. 2 shows electron microscope images of the inner surface of the molded tube for measurement before and after the slurry feeding test. A more remarkable streak-like wear mark was observed as compared with the tube obtained in Example 1. Comparative Example 2
- a fluororesin composition was obtained in the same manner as in Example 1 except that the temperature of the mixed composition was set to 405 ° C. in the melt kneading, and evaluations other than the slurry feeding test were performed.
- Example 3 90 10 Not performed 2.1 0.031 0.256 Comparative example 1 100 Before 2
- Comparative Example 2 90 10 0.101 0.637
- Table 2.8 shows that Examples 1 to 3 have smaller average roughness and maximum roughness of the inner surface of the molded tube for measurement than Comparative Examples 1 and 2.
- Example 4
- Example 2 Melt kneading was performed in the same manner as in Example 1 except that the TFE / HFP copolymer component ratio in the mixed composition was set to 50% by mass, followed by treatment using a fluorine-containing gas to obtain a fluororesin composition.
- the calorie of fusion was measured from the endothermic peak area near 292 ° C. using DSC.
- the above fluororesin composition was prepared using a cylinder with a diameter of ⁇ 3 Omm, a screw.
- the molding speed of the wire coating was about 1.2 times that of Comparative Example 3 below, confirming an improvement in productivity.
- the volume resistivity of the obtained wire coating at 120 ° C. is 1 ⁇ 10 18 ⁇ ⁇ cm or more, and the volume resistivity of ordinary TFEZHF P copolymer (10 17 ⁇ ⁇ cm). cm or less). Comparative Example 3
- an electric wire covering was manufactured to have the same coating thickness as that manufactured in Example 4, and was evaluated by the same evaluation method as in Example 4.
- Example 5 From Table 2, it was found that, in Example 4 in which the TFE / HFP copolymer was added, a fluororesin composition having a low heat of fusion was obtained while having the same electrical properties as Comparative Example 3 in which no TFE / HFP copolymer was added. .
- Example 5 From Table 2, it was found that, in Example 4 in which the TFE / HFP copolymer was added, a fluororesin composition having a low heat of fusion was obtained while having the same electrical properties as Comparative Example 3 in which no TFE / HFP copolymer was added. .
- Example 5 Example 5
- a fluororesin composition obtained by the same method as in Example 1 except that the raw material was used as a raw material a joint capable of connecting the two molded tube articles for measurement obtained in Example 1 was obtained by injection molding. .
- a set obtained by connecting the above two molded tube for measurement to the above-mentioned joint was assembled into a chemical circulation line, and a slurry liquid sending test was performed under the same conditions as in Example 1.
- Comparative Example 4 The set obtained by connecting the joint obtained from the composition of Comparative Example 1 to the two molded tube articles for measurement obtained in Example 1 was incorporated into the same chemical circulation line as in Example 5, and The same slurry feeding test as in 5 was performed. An electron microscope was used to observe the inner surface of the joint after the slurry feeding test. As a result, deposition of alumina was observed on the inner surface of the joint, and streak-like wear marks were observed around the alumina deposition portion.
- Example 5 The joint obtained in Example 5 was subjected to an ozone 1-dew test. No crack as shown in Fig. 3 was observed on the cross section of the joint after the ozone exposure test.
- the fluororesin composition of the present invention has the above-mentioned constitution, it has excellent ozone resistance and surface smoothness while maintaining excellent heat resistance and electric characteristics inherently possessed by the TFE / FTE copolymer. A molded article can be obtained.
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Abstract
Description
Claims
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JP2004558450A JP4876395B2 (ja) | 2002-12-11 | 2003-12-10 | フッ素樹脂組成物、フッ素樹脂組成物製造方法、半導体製造装置及び被覆電線 |
AU2003288997A AU2003288997A1 (en) | 2002-12-11 | 2003-12-10 | Fluororesin composition, process for producing the same, semiconductor producing apparatus and coated wire |
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JP2002359737 | 2002-12-11 | ||
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AU (1) | AU2003288997A1 (ja) |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007137994A (ja) * | 2005-11-17 | 2007-06-07 | Yunimatekku Kk | 含フッ素アロイ化共重合体 |
WO2009044753A1 (en) | 2007-10-03 | 2009-04-09 | Daikin Industries, Ltd. | Fluororesin composition and covered electric wire |
JP2013514435A (ja) * | 2009-12-18 | 2013-04-25 | ウィットフォード コーポレーション | 複数の溶融加工可能なフルオロポリマーを含有するブレンドフルオロポリマー組成物 |
WO2022181845A1 (ja) * | 2021-02-26 | 2022-09-01 | ダイキン工業株式会社 | 含フッ素共重合体 |
JP2022132101A (ja) * | 2021-02-26 | 2022-09-07 | ダイキン工業株式会社 | 共重合体、成形体、射出成形体および被覆電線 |
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- 2003-12-10 AU AU2003288997A patent/AU2003288997A1/en not_active Abandoned
- 2003-12-10 JP JP2004558450A patent/JP4876395B2/ja not_active Expired - Fee Related
- 2003-12-10 WO PCT/JP2003/015761 patent/WO2004052987A1/ja active Application Filing
- 2003-12-11 TW TW92135062A patent/TWI256955B/zh not_active IP Right Cessation
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JP2007137994A (ja) * | 2005-11-17 | 2007-06-07 | Yunimatekku Kk | 含フッ素アロイ化共重合体 |
WO2009044753A1 (en) | 2007-10-03 | 2009-04-09 | Daikin Industries, Ltd. | Fluororesin composition and covered electric wire |
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JP2013514435A (ja) * | 2009-12-18 | 2013-04-25 | ウィットフォード コーポレーション | 複数の溶融加工可能なフルオロポリマーを含有するブレンドフルオロポリマー組成物 |
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JP2022132101A (ja) * | 2021-02-26 | 2022-09-07 | ダイキン工業株式会社 | 共重合体、成形体、射出成形体および被覆電線 |
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Also Published As
Publication number | Publication date |
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JP4876395B2 (ja) | 2012-02-15 |
TWI256955B (en) | 2006-06-21 |
JPWO2004052987A1 (ja) | 2006-04-13 |
TW200416231A (en) | 2004-09-01 |
AU2003288997A1 (en) | 2004-06-30 |
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