WO2018237297A1 - Article moulé en une résine fluorée pouvant être mis en œuvre à l'état fondu - Google Patents

Article moulé en une résine fluorée pouvant être mis en œuvre à l'état fondu Download PDF

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Publication number
WO2018237297A1
WO2018237297A1 PCT/US2018/039055 US2018039055W WO2018237297A1 WO 2018237297 A1 WO2018237297 A1 WO 2018237297A1 US 2018039055 W US2018039055 W US 2018039055W WO 2018237297 A1 WO2018237297 A1 WO 2018237297A1
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WIPO (PCT)
Prior art keywords
molded article
melt processible
processible fluororesin
fluororesin molded
eluted
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PCT/US2018/039055
Other languages
English (en)
Inventor
Hiromasa Yabe
Takahiro Nishimura
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Dupont-Mitsui Fluorochemicals Co. Ltd
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Publication date
Priority claimed from JP2018107956A external-priority patent/JP7202082B2/ja
Application filed by Dupont-Mitsui Fluorochemicals Co. Ltd filed Critical Dupont-Mitsui Fluorochemicals Co. Ltd
Priority to KR1020197036949A priority Critical patent/KR102611852B1/ko
Priority to EP23210148.5A priority patent/EP4299638A3/fr
Priority to CN201880041602.8A priority patent/CN110785446A/zh
Priority to US16/623,973 priority patent/US11964417B2/en
Priority to EP18743900.5A priority patent/EP3642251A1/fr
Publication of WO2018237297A1 publication Critical patent/WO2018237297A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—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
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—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
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene

Definitions

  • the present invention relates to a melt processible fluororesin molded article with reduced metal ions (eluted metal ions) and fine particles. More specifically, the present invention relates to a melt processible fluororesin molded article with reduced metal ions (eluted metal ions) and submicron size fine particles, used in molded articles for liquid transfer and/or molded articles for liquid contact, that are used in semiconductor manufacturing equipment.
  • Fluororesins exhibit excellent properties such as heat resistance, chemical resistance, high frequency electrical properties, nonadherent properties, flame resistance, and the like, and therefore are widely used in transportation piping for chemicals such as acids, alkali, or the like, solvents, paint, and the like, chemical industrial manufacturing articles such as chemical storing containers, tanks, or the like, and electric industrial articles such as tubes, rollers, electric wires, and the like.
  • chemicals such as acids, alkali, or the like, solvents, paint, and the like
  • chemical industrial manufacturing articles such as chemical storing containers, tanks, or the like
  • electric industrial articles such as tubes, rollers, electric wires, and the like.
  • melt processible fluororesin molded articles are frequently used in semiconductor manufacturing equipment due to these properties.
  • compositions containing unsaturated fluorocarbon ethers for members are provided.
  • Molding methods such as extrusion molding methods, injection molding methods, transfer molding methods, rotational molding methods, blow molding methods, and compression molding methods performed using general
  • thermoplastic resins can be applied when melt molding molded articles using melt processible fluororesin.
  • molding machines that come in contact with melted fluororesin are made of alloys such as Hastelloy and Inconel, which are so- called Ni (nickel) based heat and corrosion resistant alloys, because compared to general thermoplastic resin, molten fluororesin can easily corrode metals and alloys that configure molding machines (non-patent literature 2).
  • Ni as a main component, which is corrosion resistant, and also have a composition containing Cr (Chromium) and Mo (Molybdenum) for preserving and maintaining the corrosion resistant properties (non-patent literature 3).
  • the Ni based heat and corrosion resistant alloys themselves do not have phase transformation temperatures in a range between room temperature to 450 ⁇ , and display high corrosion resistance in a thin, uniform passivation state with high Cr density formed on a surface of the Ni based heat and corrosion resistant alloy, and the Mo in the alloy has a function for repairing the passivation state (non-patent literature 4).
  • the melt processible fluororesin itself or an unstable end group of the fluororesin can be thermally decomposed, and will generate fluororesin decomposition matter in the form of a gas containing fluorine (nonpatent literature 2).
  • a molding machine is made from a Ni based heat and corrosion resistant alloy, elements contained in the alloy (e.g., Ni, Cr, Mo) will be mixed with the melted melt processible fluororesin in the form of metal ions as a result of this gas containing fluororesin decomposition matter, thereby destroying the passivation state formed on the surface in the molding machine, or on the surfaces of the cylinder and screw in the melt molding machine, corroding up to the corrosion resistant alloy internal part.
  • elements contained in the alloy e.g., Ni, Cr, Mo
  • the metal ions will remain in the melt processible fluororesin in the form of the final molded article.
  • These metal ions are eluted from the melt processible fluororesin molded article as metal ions during the semiconductor manufacturing process, and since these metal ions provide a corroding and/or etching effect on the semiconductor device during manufacturing and are the cause of device breakdowns, reduction of metal ions in melt processible fluororesin molded articles is strongly desired.
  • fine particles derived from cooled and solidified gaseous fluororesin decomposition matter may adhere to the surface of the melt processible fluororesin molded article. These fine particles accompany chemical solutions that wet the fluororesin molded article, and may be the cause of defects that lead to defective products when adhering to a wafer surface, but efficiently removing submicron size fine particles is not easy.
  • cleaning methods for melt processible fluororesin used during semiconductor manufacturing are performed using a diluted aqueous solution of a surfactant, strong acid, alkali, organic solvent, ultrapure water, or the like, but not only do these methods require a long period of time for cleaning, but reaching a level of cleanliness that satisfies the demand required for melt processible fluororesin molded articles used in semiconductor manufacturing devices is difficult.
  • Patent Document 1 Japanese PCT Patent Application No. 2012-518010
  • Patent Document 2 US Patent No. 4,743,658
  • Non-patent Literature 1 Latest Trends for Semiconductor Cleaning Technology, Semiconductor FPD World 2009.9, HATTORI, Takashi
  • Non-patent Literature 2 Fluororesin Hand Book, Revised 13th Edition,
  • Non-patent Literature 3 Metal Data Book, edited by Japan Metal Society, revised 4th edition, page 150
  • Non-patent Literature 4 Kitchen and Bath Industry Association Report No. 55 (April 1999 issue)
  • the present inventors focused on the point that even though it is important to determine whether or not the elements that comprise a passivation state in alloys that are used in molding machines for melt molding the aforementioned melt processible fluororesins are present in the fluororesin molded article, and in particular whether or not the molding process of the fluororesin molded article is sound, and even though Cr and Ni are included in the requirements for metal contamination specified in SEMI F57, there is no requirement for Mo.
  • the present inventors discovered a melt processible fluororesin molded article with reduced metal ions and fine particles, and thus achieved the present invention.
  • an object of the present invention is to provide a melt processible fluororesin molded article with reduced metal ions after molding and submicron size fine particles.
  • Another object of the present invention is to provide a melt processible fluororesin molded article with reduced metal ions and submicron size fine particles, without a long cleaning process using a dilute solution of a surfactant, strong acid, alkali, organic solvent, ultrapure water, and the like.
  • the present invention provides a melt processible fluororesin molded article, wherein the amount of eluted Ni ions (pg/cm 2 ), the amount of eluted Cr ions (pg/cm 2 ) and the amount of eluted Mo ions (pg/cm 2 ) in a test solution after eluting for 20 hours at 60°C using 12% nitric acid, quantitatively analyzed by the ICP (induced coupled plasma) mass analysis method, satisfy the following formula (1):
  • the amount of eluted Mo ions in the test solution after eluting for 20 hours at 60°C using 12% nitric acid, and quantitatively analyzed by ICP (induced coupled plasma) mass analysis method is 250 pg/cm 2 or less;
  • anions and cations are not detected by any of ion chromatography, ICP mass analysis methods, and TOF-SIMS methods;
  • fine particles measured in accordance with the fine particles in a liquid measurement method are contained at an amount of from 0 to 5000 particles/mL, as the sum of measurements for 1 hour;
  • the zeta potential of the surface of the melt processible fluororesin molded article measured by the flow potential method is - 50 mV or lower;
  • the zeta potential measured by the flow potential method of the melt processible fluororesin is -50 mV or lower;
  • the melt processible fluororesin is a melt processible fluororesin having a melt flow rate (MFR) of 1 to 100 g/10 minutes when measured with a load of 5 kg at a measurement temperature of 372 ⁇ 0.1°C, in accordance with ASTM D 1238;
  • MFR melt flow rate
  • the melt processible fluororesin is at least one type selected from copolymers of tetrafluoroethylene (TFE) and at least one monomer selected from hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), perfluoro(alkylvinyl ether) (PAVE), vinylidene fluoride (VDF), and vinyl fluoride (VF);
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • CTFE chlorotrifluoroethylene
  • PAVE perfluoro(alkylvinyl ether)
  • VDF vinylidene fluoride
  • VF vinyl fluoride
  • the melt processible fluororesin is a copolymer (PFA) of tetrafluoroethylene (TFE) and perfluoro(alkylvinyl ether) (PAVE), and is a copolymer where the amount of PAVE is 1 to 10 mol%;
  • the melt processible fluororesin is a copolymer of tetrafluoroethylene (TFE) and hexafluoropropylene (FIFP), and is a copolymer (FEP) where the amount of FIFP is 1 to 10 mol%;
  • the melt processible fluororesin molded article is a melt processible fluororesin molded article having transmittance of 50% T or more at a wavelength of 240-800 nm;
  • the melt processible fluororesin molded article is a melt processible fluororesin molded article having transmittance of 60% T or more at a wavelength of 240-800 nm;
  • the melt processible fluororesin molded article is a melt processible fluororesin molded article having transmittance of 75% T or more at a wavelength of 240-800 nm;
  • the melt processible fluororesin molded article is a molded article selected from tubes, pipes, bottles, fittings, gaskets, O-rings, valves, filter housings, regulators, wafer carriers, and sheet molded articles.
  • Thhe present invention provides a melt processible fluororesin molded article with reduced metal ions and submicron size fine particles.
  • FIG. 1 shows the zeta potential of the inner surface of tube (A) obtained in Example 4 and of the tube (B) obtained in Example 5.
  • FIG. 2 shows a photograph of the tube (A) obtained by Example 4 , the tube (B) obtained by Comparative Example 1, and the tube (C) obtained by Reference
  • FIG. 3 shows an image diagram of the number of fine particles that adhere to the melt processible fluororesin molded article.
  • An important characteristic of the melt processible fluororesin molded article of the present invention is that the amount of eluted Ni ions (in pg/cm 2 ), the amount of eluted Cr ions (in pg/cm 2 ), and the amount of eluted Mo ions (in pg/cm 2 ) in a test solution after eluting for 20 hours at 60°C using 12% nitric acid, quantitatively analyzed by the ICP (induced coupled plasma) mass analysis method satisfy the following formula (1):
  • Mi indicates the eluted Cr ion amount (in pg/cm 2 )
  • M 2 refers to the eluted Mo ion amount (in pg/cm 2 )
  • M 3 refers to the eluted Ni ion amount (in pg/cm 2 ).
  • Ni, Cr, and Mo ions are not detected at or below the lower limit of detection, the calculation is performed using the lower limit of detection.
  • the amount of metal ions and submicron size particles is reduced without performing special cleaning.
  • molding machines made of Ni based heat resistant and corrosion resistant alloys containing Ni as a main component and also containing Cr and Mo are generally used for melt molding melt processible fluororesin, and a thin uniform passivation state with high Cr density is formed on the surface that contacts the melt processible fluororesin (surface of the Ni based heat resistant and corrosion resistant alloy).
  • the passivation state is destroyed by halogen ions such as chlorine ions, fluorine ions, and the like, the Cr ions will elute, but Mo has a function of restoring the passivation state. Mo in the parent material diffuses to the surface at the same time that the passivation state is destroyed. Thus, the Cr defect parts of the passivation state are replaced and the passivation state is restored. But if corrosion continues to proceed, the restoration by Mo will not keep up, and the Mo will also elute in addition to the Cr.
  • the degree of breakdown of the passivation state (passivation state section rate) of the molding machine can be determined by the value calculated in the aforementioned formula (1).
  • the amount of eluted Cr ions, the amount of eluted Mo ions, and the amount of eluted Ni ions that elute from the melt processible fluororesin molded article are measured, and if the amounts satisfy the aforementioned formula (1), or in other words, if the value calculated by the aforementioned formula (1) is 0.5 or higher and less than 1, the condition where the passivation state can easily be restored if destroyed is indicated (i.e., high passivation state protection rate). It is understood that in this condition, the corrosion resistance of the Ni based heat resistant and corrosion resistant alloy that is used in the molding machine is sound, and the result is that a melt processible fluororesin molded article with reduced eluted metal ions can be obtained.
  • a value of 1 in the aforementioned formula (1) indicates that the passivation state is not destroyed at all.
  • the value calculated by the aforementioned formula (1) is less than 0.5, breakdown of the passivation state will proceed, and the corrosion resistance of the Ni based heat resistant and corrosion resistant alloy that forms the molding machine will be significantly lost.
  • corrosion of the corrosion resistant alloy that forms the molding machine will proceed, the concentration of Cr, Mo, and Ni, which is the main component, will increase in the melt processible fluororesin molded article, and in addition, the concentration of other additive elements that are included as additive elements in the corrosion resistant alloy, such as W (tungsten), Nb (niobium), Fe (iron), and the like, will also increase, which is not preferable.
  • the amount of eluted Mo ions in the present invention is preferably 250 pg/cm 2 or less, and particularly preferably 200 pg/cm 2 or less when quantitatively analyzed by ICP mass analysis methods. If the amount of eluted Mo ions of the Mo that has a passivation state restoring function exceeds 250 pg/cm 2 , destruction of the passivation state will clearly proceed, which is not preferable.
  • Anions and cations are preferably not detected by any one of ion chromatography, ICP mass analysis methods, and TOF-SIMS (time of flight- secondary ion mass spectrometry) methods, and if anions or cations are detected by any of these methods, this is an indication that the melt processible fluororesin molded article was washed using a cleaning medium containing any of acid, alkali, surfactant, or organic solvent, and the degree to which anions and cations are detected by the aforementioned analysis methods indicates a condition where the cleaning medium remains in the melt processible fluororesin molded article, which is not preferable.
  • Na indicates evidence of washing with sodium hydroxide
  • P indicates washing with phosphoric acid
  • K indicates washing with potassium hydroxide
  • S indicates washing with an acid such as sulfuric acid, or washing with an alkali.
  • B represents boron, which is an element from the molding environment that adheres to the fluororesin molded article.
  • the fine particles that are to be reduced are fine particles where gaseous decomposition products of fluororesin that have adhered to the wetted part surface of the melt processible fluororesin molded article are solidified after cooling.
  • these are submicron size fine particles that have adhered to the melt processible fluororesin molded article wetted part side surface, and are fine particles that can cause defects that lead to defective products by collecting on the wafer during the aforementioned semiconductor cleaning process.
  • the number of fine particles measured by the method described below using ultrapure water as the solution that wets the wetted part side surface after treatment with an alkaline aqueous solution (dilute ammonia aqueous solution) for the melt processible fluororesin molded article of the present invention is 0 to
  • a number of ultrafine particles that exceeds 5000 particles/mL indicates that there are a larger number of ultrafine particles that have adhered to the wetted part side surface, and a large number of ultrafine particles have adhered to the wafer surface and are a cause of defects that lead to defective products, which is not preferable.
  • the adhesion and adsorption of ultrafine particles on the surface of the melt processible fluororesin molded article are evaluated by measuring the zeta potential that is measured by the flow potential method on the surface of the melt processible fluororesin molded article.
  • the ultrafine particles and ions in the solution are positively or negatively charged.
  • the ultrafine particles that remain on the wafer during the cleaning process of a semiconductor have a negative charge.
  • the ultrafine particles derived from the melt processible fluororesin molded article also have a negative charge unless the molecular structure is greatly changed.
  • melt processible fluororesin molded article and the melt processible fluororesin also have a negative charge.
  • the charge status of the surface of melt processible fluororesin molded article can be empirically known as a quantitative value by measuring the zeta potential (if necessary, refer to Koberunikusu, Vol. 10. 2001, pages 6 to 8).
  • melt processible fluororesin molded article with ultrafine particles having a negative zeta potential and the surface of melt processible fluororesin molded article with a negative zeta potential the signs for the charge of the zeta potential are the same, so the product of the zeta potentials of both will be large, indicating an increase in the reactive force of static electricity, and thus the ultrafine particles will not readily adhere to the melt processible fluororesin molded article surface.
  • a smaller zeta potential of the melt processible fluororesin molded article means that the product of both zeta potentials will be large, so the fine particles formed by cooling and solidifying the gaseous melt processible fluororesin decomposition products (which have a negative zeta potential) generated during heat melting will not readily adsorb, and these fine particles will not adhere to the wetted part of the melt processible fluororesin molded article.
  • a zeta potential of the melt processible fluororesin is determined by its molecular structure. Therefore, there is a correlation between a zeta potential of the melt processible fluororesin and a zeta potential of the surface of the melt processible fluororesin molded article.
  • the zeta potential of the surface of the melt processible fluororesin molded article of the present invention is a value that is calculated after measuring the flow current by the flow potential method.
  • the shape of the molded article that is measured must be flat, but methods for flattening are not limited, and can include cleaving, pressing, melt pressing, melt film forming, and other methods.
  • the value of the zeta potential indicates the same zeta potential for the melt processible fluororesin raw material (pellet) or for the molded article made from the raw material, so long as there is not a change to the molecular structure or reactions and mixing of other substances.
  • a larger pH indicates a more negative zeta potential (refer to FIG. 1).
  • the melt processible fluororesin that is used with the present invention is a copolymer of tetrafluoroethylene (TFE) and at least one type of fluorine monomer (comonomer) that can copolymerize with TFE and is present in the polymer at a sufficient rate even below the melting point such as 315°C or lower, where the melting point of the copolymer is essentially lower than the melting point of the TFE homopolymer (polytetrafluoroethylene (PTFE)), and is a copolymer with a melt flow rate (MFR) at 372°C of approximately 1 to 100 g/10 minutes, in accordance with ASTM D-1238.
  • TFE tetrafluoroethylene
  • PTFE polytetrafluoroethylene
  • the melt flow rate (MFR) can be selected based on the molding method, and for example, for the case of melt molding such as melt extrusion molding, injection molding, and the like, the melt flow rate is 1 to 100 g/10 minutes, preferably 1 to 50 g/10 minutes, and more preferably 1 to 20 g/10 minutes.
  • the copolymer includes copolymers containing at least approximately 40 to 98 mol % of tetrafluoroethylene monomer and approximately 2 to 60 mol % of at least one type of comonomer; and examples of the comonomer include hexafluoropropylene(HFP), perfluoro (alkylvinyl ether) (PAVE) (where the alkyl group is a straight chain or branched alkyl group with 1 to 5 carbon atoms), vinylidene fluoride, vinyl fluoride, or the like.
  • the PAVE can have an alkyl group with 1, 2, 3, or 4 carbon atoms.
  • a copolymer containing a plurality of types of PAVE as the comonomer is also acceptable.
  • preferable copolymers include FEP (TFE/HFP copolymer), PFA (TFE/PAVE copolymer), copolymers of TFE/HFP/P AVE where the PAVE is perfluoro (ethylvinyl ether) (PPVE) and/or perfluoro (propylvinyl ether) (PMVE), MFA (copolymers of TFE/perfluoro (methylvinyl ether) (PMVE)/ PAVE, where the alkyl group of the PAVE has two or more carbon atoms), and the like.
  • the hexafluoropropylene (HFP) units in the FEP copolymer are preferably 1 to 10 mol%, more preferably 2 to 8 mol%.
  • the perfluoro (alkylvinyl ether) (PAVE) units in the PFA copolymer are preferably 1 to 10 mol%, more preferably 2 to 8 mol%. Furthermore, these copolymers can be used together as mixtures.
  • melt processible fluororesin where an unstable end group such as - CF2CH2OH, -CO H2, -COF, and the like can be replaced with a thermally stable -CF3 terminal group is preferable because the melt processible fluororesin will have fewer thermal decomposition products.
  • the transmittance of the melt processible fluororesin molded article can be determined by measuring the transmittance at a wavelength of 240 to 800 nm using a UV-Vis-NTR spectrophotometer with a detector of integrating
  • the transmittance (T) is 50% T or more, preferably 60% T or more, and more preferably 75% T or more. In addition to these transmittances, when the transmittance is 50% T or more even in the short wavelength ultraviolet region (wavelength 240 to 340 nm), the transmittance is more improved, which is preferable.
  • the form of the melt processible fluororesin that is used in the present invention can be any form that is suitable for use in melt molding, such as powder, granular products of powder, particles, flakes, pellets, cubes, beads, and the like.
  • the melt processible fluororesin molded article of the present invention is a molded article containing 50 weight % or more, preferably 75 weight % or more, and more preferably 90 weight % or more of the melt processible fluororesin, and the remaining components can be, for example, non-melt processible fluororesin, conductive materials (carbon, graphite), and the like.
  • the method of producing the melt processible fluororesin molded article of the present invention is not particularly limited, and molding can be performed by using a conventionally known molding method using the aforementioned melt processible fluororesin.
  • molding methods include melt extrusion molding, injection molding, melt compression molding, transfer molding, blow molding, injection molding, rotational molding, lining molding, film molding and the like, and of these, melt extrusion molding and injection molding are preferable.
  • Examples of the molded article obtained by melt molding include bottles, films, tubes, sheets, pipes, fittings, gaskets, O-rings, valves, filter housings, regulators, wafer carriers, and sheet molded articles.
  • the ultrapure water that is used in the following methods is ultrapure water where the specific resistivity is controlled to 18 ⁇ cm or more and the TOC (total organic carbon) is controlled to 5 ppb or less.
  • a 12% nitric acid aqueous solution is sealed in a melt processible fluororesin tube with an outer diameter of 6.35 mm, a thickness of 1.00 mm, and a length of 1 m, and after eluting for 20 hours at 60°C, the test solution is quantitatively analyzed by an ICP mass analysis method, and it is confirmed that the amount of eluted Ni ions (pg/cm 2 ), the amount of eluted Cr ions (pg/cm 2 ), and the amount of eluted Mo ions (pg/cm 2 ) satisfy the aforementioned formula (1).
  • Fine particles are measured by passing ultrapure water through an automatic measurement type fine particle meter specified in JIS K 0554.
  • a fluororesin molded article is filled with 1% ammonia water, allowed to sit for 20 hours at room temperature, water rinsed until the pH of the water discharged from the molded article is neutral using ultrapure water with a flow rate of 1 L/minute at room temperature, and then ammonia processing is performed by drying until the water droplets on the molded article disappeared at room temperature using nitrogen gas where fine particles were removed by a 10 nm hollow thread filter.
  • the number of fine particles in the fluororesin molded article after ammonia treatment is determined by measuring the amount of 40 to 125 nm size fine particles using UltraChem 40, manufactured by PMS, at a flow rate of 1 L/minute using ultrapure water by the method according to the measurement method (automatic measurement) of ultrafine particles in a liquid, specified in JIS K 0554.
  • the measurement data of the in-liquid fine particle meter is obtained by continuously measuring for 1 hour at 1 minute intervals, and determining the number of fine particles in a milliliter per hour (sum of 60 measurements). The results are shown in Table 2.
  • the zeta potentials of the surface of the melt processible fluororesin molded article and of the melt processible fluororesin are calculated after measuring the flow current using a flow potential method using a SurPASS manufactured by Anton-Parr.
  • An aqueous solution of 0.001 mol/L of KC1 is used as the electrolyte solution.
  • a cylinder held at 372°C is filled with 5 g of test material and maintained for 5 minutes using a melt indexer provided with a corrosion resistant cylinder, die, and piston (manufactured by Toyo Seiki Co., Ltd.) in accordance with ASTM D-1238-95, and then the test material is extruded through a die orifice under a load of 5 kg (piston and weight), and the extrusion rate at this time (g/10 minutes) is taken as the MFR.
  • An input compensation type differential scanning calorimeter (DSC, manufactured by Perkin Elmer) is used for measuring the melting point of the melt processible fluororesin. Approximately 10 mg of the sample is weighed and placed in an aluminum pan prepared for this device, crimped with a crimper prepared for this device, then stored in a DSC main body and heated from 150 °C to 360 °C at a rate of 10 °C/minute. The melting peak temperature (Tm) is determined from the melting curve obtained at this time.
  • DSC differential scanning calorimeter
  • the transmittance of the a melt processible fluororesin molded article is measured using a UV-Vis-N R spectrophotometer (U-4100, manufactured by Hitachi, Ltd.) with a detector of integrating sphere/photomultiplier tube, at a scan speed of 300 nm/min and a slit width of 6.00 nm, and then the average value was calculated to obtain the transmittance (in terms of device specification, wavelength The light source was switched at 340 nm).
  • An undrawn tube having an outer diameter of 6.35 ⁇ 0.2 mm and a thickness of 1.00 ⁇ 0.1 mm is obtained by molding PFA (1) and (2) at the molding temperatures shown in Table 1 using an extrusion molding machine with a diameter of 30 mm.
  • the amount of eluted Cr ions, the amount of eluted ions, the amount of eluted Ni ions, and the zeta potential are measured for the melt processible fluororesin tubes. The results are shown in Table 1.
  • the transparency is also measured for the National (registered trademark) PTFE tube manufactured by Nichias Corporation. Furthermore, a graph showing the relationship between pH and the zeta potential of the inner surface of the tube (A) obtained in Example 4 the tube (B) obtained in Example 5 is shown in FIG. 1, and a photograph of the tube (A) obtained in Example 4, the tube (B) obtained in Comparative Example 1, and the tube (C) obtained in Reference 4 is shown in FIG. 2.
  • Example 4 did not increase even when the melt processible fluororesin molded article is treated with ammonia.
  • Example 5 most of the fine particles are detected from the melt processible fluororesin molded article that is treated with ammonia, and therefore it is clear that fine particles that could not be measured by the fine particle measurement using ultrapure water remained in the melt processible fluororesin molded article, based on accelerated testing using ammonia.
  • Comparative Example 1 most of the fine particles are measured in the ultrapure water, but this indicates that the molding temperature was not appropriate.
  • PFA (1) is found to maintain transparency regardless of the molding temperature.
  • the present invention provides a melt processible fluororesin molded article with reduced metal ions (eluted metal ions) and submicron size fine particles after molding, while maintaining the excellent heat resistance, chemical resistance, mechanical properties, and the like of the melt processible fluororesin
  • the present invention can provide a melt processible fluororesin molded article with reduced metal ions (eluted metal ions) and submicron size fine particles, without requiring a long cleaning process using a dilute solution of a surfactant, strong acid, alkali, organic solvent, ultrapure water, and the like.
  • the melt processible fluororesin molded article with reduced elutable metal ions (eluted metal ions) and submicron size fine particles provided by the present invention can be suitably used in the semiconductor and semiconductor chemical fields. Furthermore, the transparency is maintained regardless of the molding temperature, so visibility of the chemical solution in the melt processible fluororesin molded article that is used in the semiconductor cleaning process or the like can be maintained.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un article moulé en une résine fluorée pouvant être mis en œuvre à l'état fondu, comportant moins d'ions métalliques après moulage (ions métalliques élués) et moins de particules fines submicroniques. L'article moulé en résine fluorée pouvant être mis en œuvre à l'état fondu présente une quantité d'ions Ni élués (en pg/cm2) et une quantité d'ions Cr élués (en pg/cm2) et une quantité d'ions Mo élués (en pg/cm2) dans une solution d'essai après élution pendant 20 heures à 60 °C par utilisation d'acide nitrique à 12 %, soumises à une analyse quantitative par une méthode d'analyse des masses ICP (plasma à couplage inductif), satisfaisant à la formule suivante : 0,5 ≤ 1- [(M1+ M2) / (M1 + M2 + M3)] < 1, dans laquelle M1 désigne la quantité d'ions Cr élués (en pg/cm2), M2 désigne la quantité d'ions Mo élués (en pg/cm2), et M3 désigne la quantité d'ions Ni élués (en pg/cm2).
PCT/US2018/039055 2017-06-23 2018-06-22 Article moulé en une résine fluorée pouvant être mis en œuvre à l'état fondu WO2018237297A1 (fr)

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KR1020197036949A KR102611852B1 (ko) 2017-06-23 2018-06-22 용융 가공성 플루오로수지 성형품
EP23210148.5A EP4299638A3 (fr) 2017-06-23 2018-06-22 Article moulé en une résine fluorée pouvant être mis en uvre à l'état fondu
CN201880041602.8A CN110785446A (zh) 2017-06-23 2018-06-22 可熔融加工的氟树脂模塑制品
US16/623,973 US11964417B2 (en) 2017-06-23 2018-06-22 Melt processible fluororesin molded article
EP18743900.5A EP3642251A1 (fr) 2017-06-23 2018-06-22 Article moulé en une résine fluorée pouvant être mis en uvre à l'état fondu

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JP2018107956A JP7202082B2 (ja) 2017-06-23 2018-06-05 熱溶融性フッ素樹脂成形品
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Cited By (1)

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WO2020180968A1 (fr) 2019-03-05 2020-09-10 Chemours-Mitsui Fluoroproducts Co. Ltd Solvant pour spectrométrie de masse par chromatographie en phase gazeuse, et procédé de détermination de substances contenant du fluor sur la surface de produits moulés par fusion de résine fluorée

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020180968A1 (fr) 2019-03-05 2020-09-10 Chemours-Mitsui Fluoroproducts Co. Ltd Solvant pour spectrométrie de masse par chromatographie en phase gazeuse, et procédé de détermination de substances contenant du fluor sur la surface de produits moulés par fusion de résine fluorée
EP3935379A1 (fr) 2019-03-05 2022-01-12 Chemours-Mitsui Fluoroproducts Co., Ltd. Solvant pour spectrométrie de masse par chromatographie en phase gazeuse, et procédé de détermination de substances contenant du fluor sur la surface de produits moulés par fusion de résine fluorée

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