Ultrapure water (UPW) transport system

Abstract

The present invention relates to a UPW transport system comprising at least one component, wherein the at least one component has a surface intended to come into contact with the UPW, and this surface is made from or comprises a polymer composition (PC), the polymer composition (PC) comprising: at least 50.0% by weight (≧50.0% by weight) of at least one semicrystalline polymer (P) (this percentage is relative to the total weight of the polymer composition (PC)); and at least one optional additional polymer, selected from the group consisting of polyaryl ether ketones (PAEK), polysulfones (PSU), polyphenylsulfones (PPSU), and combinations thereof, which is blended with the polymer (P); the semicrystalline polymer (P) comprises the following repeating units in the following proportions: unit (R PEEK The formula is 65.0-95.0 mol%, and the unit is (R PEDEK ), unit (R PEoEK ), and units selected from the group consisting of combinations thereof (R P ) comprises 5.0 to 35.0 mol% and ; these proportions are relative to the total amount of repeating units of polymer (P); UPW represents water exhibiting an electrical resistivity of at least 18.0 MΩ·cm and a total organic carbon (TOC) of up to 10.0 μg / L at 25°C; relating to the system. [Formula 1] TIFF2026526106000028.tif47170

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims priority to U.S. Provisional Patent Application No. 63 / 515732, filed on 26 July 2023, and European Patent Application No. 23207794.1, filed on 3 November 2023, the entire contents of each of these applications being incorporated herein by reference for all purposes. [Background technology]

[0002] This invention relates to the transport of ultrapure water (UPW).

[0003] Ultrapure water (UPW) is used in many processes in semiconductor manufacturing. Water is used for cleaning and rinsing semiconductor components during manufacturing. It is also used for cleaning and etching, generating vapor for silicon surface oxidation, fabricating photomasks, and depositing light-emitting materials. As semiconductor integration progresses, higher quality water is also required.

[0004] Other high-tech applications requiring UPW include the development and manufacture of solid-state devices, thin-film devices, communication lasers, light-emitting diodes, photodetectors, printed circuits, memory devices, vacuum tube devices, or electrolytic devices.

[0005] Because contamination can lead to unacceptably low yields of electronic devices, UPWs are required to prevent contamination of products during manufacturing, as defined in ASTM D5127-07. Therefore, UPWs are required to keep inorganic cations and anions, organic contaminants, and / or biological contaminants at very low levels.

[0006] The preparation of UPW involves the removal of ions, organic and biological contaminants, and particles. UPW typically exhibits an electrical resistivity of 18.1 MΩ.cm or more at 25°C and a total organic carbon concentration (TOC) of up to 10.0 μg / L. Bacterial contamination can also be suppressed to 10.0 CFU / ml (CFU: colony forming unit).

[0007] U.S. Patent No. 5,106,503 and U.S. Patent No. 5,160,429 disclose an ultrapure water piping system for transporting ultrapure water using pipes made of PVC, PVDF, or PEEK.

[0008] U.S. Patent No. 4,784,772 discloses a PEEK pipe for transporting ultrapure water.

[0009] Japanese Patent Laid-Open No. 4-34282 discloses a pipe material for pure water or ultrapure water manufactured from a blend of PEEK and polyetherimide or polysulfone.

[0010] U.S. Patent No. 1,1673,380 discloses a multilayer pipe for transporting UPW including a layer made of polyolefin. Japanese Patent Laid-Open No. 2022 / 159129 also discloses a polyolefin pipe for transporting UPW.

[0011] International Publication No. 2022 / 013520 pamphlet discloses a copolymer having units of formula -O-Ph-O-Ph-CO-Ph-(I) and units (R PEDEK ) wherein the units (I) are 50 to 90 mol% of the units (R PEEK ) and 10 to 50 mol% of the formula

Chemical formula

[0012] International Publication No. 2021 / 204718 discloses PEDEK-PEoEK copolymers that can be used to manufacture articles for automotive, aerospace, or electronic applications.

[0013] U.S. Patent Application Publication No. 2021 / 0384045 discloses a washing water supply device. [Overview of the Initiative] [Problems that the invention aims to solve]

[0014] Therefore, materials used for transporting water must be of high purity and must not leach high levels of impurities into the transported water. PVDF and other fluoropolymers are widely used in piping systems (e.g., pipes and connectors) used for transporting UPW in the semiconductor industry (see, for example, "High quality PFA for semiconductors", Valqua Review, March 1991, Vol.35, N°3, pp.1-6, issn:0385-6925).

[0015] With the development of smaller chips, the required purity levels for UPW (Uploaded Water) are becoming so high that PVDF is no longer suitable for the entire transport system. This is because organic impurities and fluoride anions leach out, especially in environments where high temperatures (80-120°C) are used. In fact, the current trend is to manufacture electronic circuits with finer linewidths. Currently, some electronics manufacturers are commercializing chips with linewidths of approximately 400 nm. However, several research projects have reported linewidths as narrowed as 10 nm, and even as narrow as 5 nm.

[0016] Polyether ether ketone (PEEK) has been considered particularly suitable as a substitute for PVDF in UPW transport at high temperatures (typically 80-120°C) due to its lower leaching level compared to PVDF. However, one drawback of homopolymer PEEK is its high melting point (340-345°C), which requires high processing temperatures (360-420°C). Processing PEEK at high temperatures generates off-gassing of some organic impurities during the extrusion process (accompanied by associated die deposition).

[0017] Therefore, polymer-based components that can be extruded and welded at lower temperatures than PEEK are needed to avoid the release of organic impurities. Nevertheless, the components and polymers must maintain their mechanical properties, especially when the water temperature exceeds 70°C, and must not contaminate the UPW (Ultraviolet Water).

[0018] The present invention disclosed herein aims to solve this technical problem. [Means for solving the problem]

[0019] The present invention is described in the attached series of claims.

[0020] Therefore, the present invention relates to a UPW transport system according to any one of claims 1 to 10.

[0021] The present invention also relates to the piping described in claim 11.

[0022] The present invention also relates to the pipe connector or fitting described in claim 12.

[0023] The present invention also relates to the UPW transport method described in claim 13.

[0024] The present invention also relates to the use described in any one of claims 14 to 20.

[0025] These topics will be defined in more detail later.

[0026] [Definition] wt% and mol% represent weight percent and mole percent, respectively.

[0027] "Poly(aryl ether ketone) (PAEK)" refers to a polymer whose repeating units are of the formula -Ar-Q- (where Ar is an arylene group and Q is -O- or -C(=O)-), and in which these repeating units are linked to each other by -O- or -C(=O)-. The arylene group is usually selected from the group consisting of phenylene groups and biphenylene groups. [Brief explanation of the drawing]

[0028] [Figure 1] This figure shows embodiment (E2), disclosing a pipe (1) having a layer (L) (2) and one outer layer (3). [Modes for carrying out the invention]

[0029] In a first aspect, the present invention relates to a UPW transport system comprising at least one component, wherein the at least one component has a surface intended to come into contact with the UPW, and the surface is manufactured from or comprises a polymer composition (PC) as defined herein. The component is in particular a pipe or a pipe connector.

[0030] The system also typically includes at least one means (e.g., a pump) for creating a pressure difference to transport water.

[0031] Pipe connectors are components that can be mechanically attached to one end of a pipe. Pipe connectors are intended to (i) mechanically connect two pipe ends, or (ii) mechanically connect one pipe end to another component of a system. These include elbows and T-fittings in particular.

[0032] The components are manufactured by techniques known to those skilled in the art, such as (co)extrusion and injection molding. Piping is generally manufactured by (co)extrusion. Piping connectors or fittings are generally manufactured by injection molding. The use of the polymer composition (P) or polymer (P) disclosed herein is advantageous because the temperature required to melt the composition and mold it into a component is low.

[0033] In a second aspect, the present invention also relates to the piping described in claim 24.

[0034] The piping comprises one or more layers, the inner layer (L) intended to come into contact with water, which is manufactured from or comprises a polymer composition (PC) as defined herein, particularly in the claims. The piping contains UPW and / or is characterized by the amount of eluting impurities shown below.

[0035] According to one embodiment (E1), the piping of the present invention is a single-layer piping. In this case, the single layer consists of an inner layer (L). This includes only layer (L). The single-layer piping can be manufactured by extrusion.

[0036] According to another embodiment (E2), the piping of the present invention comprises two or more layers, where layer (L) is an inner layer (L). For example, the piping may include layer (L) and one outer layer. See Figure 1. According to embodiment (E2), since the layers other than layer (L) are not intended to come into contact with water, there is a low risk of water contamination by molecules leaching from these layers. Therefore, these layers other than layer (L) may contain at least one filler and / or at least a plastic additive.

[0037] Multilayer piping can be manufactured by co-extrusion or by overmolding other layers around a layer (L).

[0038] Therefore, these layers other than layer (L) may include at least one thermoplastic polymer, at least one filler, and / or at least plastic additives, particularly colorants (e.g., dyes and / or pigments), impact modifiers, UV stabilizers, heat stabilizers, antioxidants, internal lubricants and / or external lubricants, flame retardants, antistatic agents, antiblocking agents, and combinations thereof, selected from the group consisting of these plastic additives.

[0039] More specifically, according to embodiment (E2), the piping of the present invention includes the following: An inner layer (L) intended to come into contact with water, which is made from or contains a polymer composition (PC) as defined herein, particularly a polymer composition (PC) as defined in the claims; A polymer composition comprising, or comprising, at least one other layer, made from, a polymer composition comprising (i) at least one filler and / or (ii) at least one plastic additive, particularly a plastic additive selected from the group consisting of colorants (e.g., dyes and / or pigments), impact modifiers, ultraviolet stabilizers, heat stabilizers, antioxidants, internal lubricants and / or external lubricants, flame retardants, antistatic agents, antiblocking agents, and combinations thereof.

[0040] The piping of the present invention can be used for transporting UPW because the layer (L) intended to come into contact with water is made from or contains a polymer composition (PC).

[0041] Piping can be characterized by the amount of eluted impurities as specified herein. SEMI F40 and SEMI F57 are standards compiled by the SEMI® Association (673S. Milpitas Blvd., Milpitas, CA95035 (USA)), and are often used to test polymer materials and components used in UPW systems to evaluate whether the material can be used properly without contaminating the UPW. Based on these standards, the following protocol (p1) can be used to measure the amount of eluted impurities.

[0042] [Table 1]

[0043] The piping of the present invention is such that, in accordance with this protocol, the amount of impurities (Imp) released from layer (L) after contacting layer (L) with UPW at 85°C for 7 days is less than the values ​​shown in the table below.

[0044] [Table 2]

[0045] The amount of leached impurities is measured on the surface of the layer (L) that came into contact with water (1 m). 2 It is expressed in μg per unit.

[0046] The diameter of the pipe is typically 1 to 200 mm. More specifically, the diameter may be 20 to 150 mm.

[0047] The length of the piping is typically a maximum of 100m. More specifically, the length may be a maximum of 50m.

[0048] In a third aspect, the present invention also relates to a pipe connector or fitting having a surface intended to come into contact with a UPW, which is manufactured from or contains a polymer composition (PC) as defined herein, particularly a polymer composition (PC) as defined in the claims.

[0049] The piping connector or fitting of the present invention can be used for transporting UPW because the surface intended to come into contact with water is manufactured from or contains a polymer composition (PC). Similar to piping, SEMI F40 and SEMI F57 are standards that can be used to characterize the piping connector or fitting. Based on these standards, the following protocol (p2) can be used to measure the amount of eluted impurities.

[0050] [Table 3]

[0051] Amount of impurities (Imp) released from the surface in contact with UPW (surface 1 m of the leaching area) 2 The value (expressed in μg per unit) is less than the value of eluted impurities shown in the table below.

[0052] [Table 4]

[0053] About UPW Ultrapure water (UPW) generally refers to water exhibiting an electrical resistivity of at least 18.0 MΩ·cm and a total organic carbon (TOC) of up to 10.0 μg / L at 25°C. Both properties are typically measured using available instruments. TOC is preferably measured according to ASTM D5997-15.

[0054] More specifically, UPW can be any water that meets any of the recommendations in Table 1 of ASTM D5127-13 (re-approved in 2018).

[0055] More specifically, UPW can be any of the four types of water defined in Table 1 of ASTM D5127-13 (re-approved in 2018): Type E-1, Type E-1.1, Type E-1.2, or Type E-1.3. Note that ASTM Type E-1.3 is the same as that of SEMI (Semiconductor Equipment and Materials International) Guide for Ultrapure Water Used in Semiconductor Processing (F063), 2010 version.

[0056] In a fourth aspect, the present invention relates to a method for transporting UPW, wherein at least one pipe, as defined herein, is used to transport water.

[0057] The temperature of the water inside the pipe can be at least 50°C, preferably at least 70°C.

[0058] In a fifth aspect, the present invention relates to the use of a polymer composition (PC) as defined herein for forming at least one surface of a pipe or pipe connector intended to come into contact with a UPW. The pipe may be a pipe as disclosed herein. The pipe connector may be a pipe connector as disclosed herein.

[0059] More detailed information regarding the polymer composition (PC) and polymer (P) is provided below.

[0060] Polymer composition (PC) Details of the polymer compositions disclosed in this invention are described below.

[0061] The polymer composition (PC) is • At least 50.0% by weight (≧50.0% by weight) of at least one semicrystalline polymer (P) as disclosed herein (this percentage is relative to the total weight of the polymer composition (PC)), • A polymer (P) is blended with at least one optional additional polymer selected from the group consisting of polyaryl ether ketones (PAEK), polysulfones (PSU), polyphenylsulfones (PPSU), and combinations thereof, which are different from the semicrystalline polymer (P). It contains.

[0062] The proportion of semicrystalline polymer (P) in the polymer composition (PC) disclosed in the present invention is at least 50.0% by weight (≥50.0% by weight), and this proportion is relative to the total weight of the polymer composition (PC). This proportion is preferably at least 60.0% by weight, preferably at least 65.0% by weight, preferably at least 70.0% by weight, preferably at least 75.0% by weight, preferably at least 80.0% by weight, preferably at least 85.0% by weight, preferably at least 90.0% by weight, preferably at least 95.0% by weight, and preferably at least 99.0% by weight.

[0063] Polymer (P) is an essential or main component of polymer composition (PC).

[0064] The polymer compositions (PCs) disclosed herein preferably do not contain fillers or plastic additives, particularly selected from the group consisting of colorants (e.g., dyes and / or pigments), impact modifiers, UV stabilizers, heat stabilizers, antioxidants, internal lubricants and / or external lubricants, flame retardants, antistatic agents, antiblocking agents, and combinations thereof.

[0065] To avoid contamination, the polymer composition (PC) is preferably, • At least 50.0% by weight (≧50.0% by weight) of at least one semicrystalline polymer (P) as disclosed herein (this percentage is relative to the total weight of the polymer composition (PC)), • A polymer (P) is blended with at least one optional additional polymer selected from the group consisting of polyaryl ether ketones (PAEK), polysulfones (PSU), polyphenylsulfones (PPSU), and combinations thereof, which are different from the semicrystalline polymer (P). It essentially consists of these.

[0066] The polymer composition (PC) preferably consists essentially of or is derived from at least one semicrystalline polymer (P) as disclosed herein.

[0067] Additional polymers: The polymer composition (PC) may include at least one additional polymer selected from the group consisting of polyaryl ether ketones (PAEK), polysulfones (PSU), polyphenylsulfones (PPSU), and combinations thereof, which are different from the semicrystalline polymer (P), and which are blended with the polymer (P).

[0068] The semicrystalline polymer (P) and the additional polymer preferably form a homogeneous blend. This blend is prepared by techniques well known to those skilled in the art.

[0069] According to one embodiment, the additional polymer in the polymer composition (PC) is PAEK.

[0070] More specifically, PAEK can be selected from the group consisting of polyether ketone (PEK), polyether ether ketone (PEEK), polyether-ether-ketone-ketone (PEEKK), polyether-ether-ketone (PEKK), polyether-ketone-ether-ketone-ketone (PEKEKK), polyether-ether-ketone-ether-ketone (PEEKEK), polyether-ether-ether-ketone (PEEEK), polyether-diphenyl-ether-ketone (PEDEK), and combinations thereof.

[0071] PAEK is generally semi-crystalline.

[0072] PAEK may more specifically be at least one PEEK. In this case, the polymer composition may more specifically be · at least 50.0 wt% (≥ 50.0 wt%) of at least one semi-crystalline polymer (P) disclosed herein, this proportion being relative to the total weight of the polymer composition (PC), and · an optional at least one PEEK, and a polymer composition (PC*) comprising, consisting essentially of, or consisting of these.

[0073] All embodiments and details disclosed herein for the polymer composition (PC) and / or the polymer (P) are also applicable to the polymer composition (PC*).

[0074] In the context of the present invention, PEEK refers to a polymer containing at least 96.0 mol% of repeating units (R PEEK ). Preferably, the repeating units of PEEK consist of repeating units (R PEEK ).

[0075] According to one embodiment, the additional polymer in the polymer composition (PC) is polysulfone (PSU). Polysulfone (PSU) means a polymer containing at least 50.0 mol% of the repeating units (R

Chemical formula

[0076] The repeating unit (R PSU ) preferably has the following formula:

Chemical formula

[0077] The repeating unit (R PSUThe proportion of ) is preferably at least 90.0 mol%, preferably at least 95.0 mol%, and preferably at least 99.0 mol%.

[0078] PSU may be a homopolymer or a copolymer.

[0079] PSU is usually amorphous.

[0080] According to one embodiment, the additional polymer in the polymer composition (PC) is polyphenylsulfone (PPSU). Polyphenylsulfone (PPSU) is defined by the following formula: [ka] Repeating unit (R PPSU This refers to a polymer containing at least 50.0 mol% of ).

[0081] Repeating unit (R PPSU ) is preferably the following formula: [ka] It is a repeating unit.

[0082] Repeating unit (R PPSU The proportion of ) is preferably at least 90.0 mol%, preferably at least 95.0 mol%, and preferably at least 99.0 mol%.

[0083] PPSU may be a homopolymer or a copolymer.

[0084] PPSU is usually amorphous.

[0085] Polymer (P) The polymer (P) disclosed in this invention will be described in detail below.

[0086] The semicrystalline polymer (P) disclosed in this invention comprises the following repeating units in the following proportions: • For 65.0 to 95.0 mol%, the following formula: [ka] The unit (R PEEK ) • 5.0 to 35.0 mol%, using the following formula: [ka] The unit (R PEDEK ), unit (R PEoEK ), and a unit (RP) selected from the group consisting of combinations thereof. These proportions are relative to the total amount of repeating units of the polymer.

[0087] According to one embodiment, the unit (R P ) is (R PEDEK )

[0088] According to another embodiment, (R P ) is (R PEoEK )

[0089] According to another embodiment, (R P ) is (R PEDEK ) and (R PEoEK This is a combination with ).

[0090] The repeating units of the polymer (P) are preferably units (R PEEK ) and units (R P ) consists of.

[0091] The polymer (P) is preferably (R PEmEK (Units not included.)

[0092] Unit (R PEEK The proportion of ) is 65.0 to 95.0 mol%. More specifically, this proportion may be 65.0 to 85.0 mol%.

[0093] Unit (R PThe proportion of ) is 5.0 to 35.0 mol%. More specifically, this proportion may be 15.0 to 35.0 mol%.

[0094] The terminal group of polymer (P) is preferably a group following the formula -Ar-F or -Ar-H (where Ar represents an arylene group).

[0095] Polymer (P) is prepared by nucleophilic polycondensation. More specifically, polymer (P) is prepared by heating a reaction mixture (RM) containing at least one solvent (S), a monomer mixture (MM), and at least one base selected from the group consisting of Na2CO3, K2CO3, and mixtures thereof. The monomer mixture (MM) contains or consists of the following monomers: 4,4'-difluorobenzophenone + hydroquinone + 4,4'-biphenol and / or pyrocatechol.

[0096] The solvent (S) is usually diphenylsulfone.

[0097] The temperature at which the reaction mixture (RM) is heated is typically at least 250°C, preferably at least 270°C. The nucleophilic polycondensation may involve stopping the polycondensation reaction by reaction with at least one termination agent selected from the group consisting of end-capping agents, termination agents, and combinations thereof.

[0098] Endocapping agents are molecules that terminate nucleophilic polycondensation and are incorporated into the polymer backbone through condensation reactions. Terminating agents are molecules that terminate nucleophilic polycondensation and are incorporated into the polymer backbone through condensation reactions.

[0099] The end-capping agent is selected from the group consisting of molecules of formula (A): R 1 -Ph-R 2 (A) (In the formula, R 1 is F, Cl, or OH, and R 2 is -C(O)-Ar-R 3 , -O-Ar-R3 , -SO2-Ar-R 3 -Ar-R 3 , alkyl (for example, C1~C 10 Alkyl (preferably C1-C5 alkyl), or -H, where Ar is an arylene group containing at least one benzene ring (i.e., one or more benzene rings), R 3 (These are F, Cl, or H).

[0100] R 3 It is preferably F.

[0101] R 1 is preferably F or OH. More preferably R 1 It is F.

[0102] R 2 If it is different from -H, R 1 and R 2 It may be located at the ortho, meta, or para position on the phenylene ring.

[0103] The end capping agent is more specifically selected from the group consisting of 4,4'-difluorobenzophenone, phenol, 4-phenoxyphenol, 4-phenylphenol, 4-fluorobenzophenone, 3-fluorobenzophenone, 2-fluorobenzophenone, 4,4'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone, and mixtures thereof.

[0104] The end capping agent is more specifically selected from the group consisting of 4,4'-difluorobenzophenone, 4-fluorobenzophenone, phenol, 4-phenoxyphenol, 4-phenylphenol, and mixtures thereof.

[0105] The inhibitor is preferably lithium chloride.

[0106] The nucleophilic polycondensation may involve terminating the polycondensation reaction by reacting lithium chloride with at least one of the end-capping agents disclosed above, particularly 4,4'-difluorobenzophenone.

[0107] Since 4,4'-difluorobenzophenone is a monomer used in the preparation of polymer (P), it is added to the reaction mixture (RM) at the start of polycondensation. In this case, the reaction mixture (RM) contains this monomer and an excess amount of 4,4'-difluorobenzophenone relative to the monomer having an OH group. In this case, the molar ratio r at the start of polycondensation is ≥1.000, preferably ≥1.003, more preferably ≥1.006, and even more preferably ≥1.010, where r is defined as 4,4'-difluorobenzophenone / [hydroquinone + 4,4'-biphenol and / or pyrocatechol].

[0108] The preparation conditions for the polymer of the present invention, as shown in the experimental section, can also be applied to the preparation of polymer (P).

[0109] After polycondensation, polymer (P) is treated to obtain a polymer suitable for transport in UPW. The treatment of polymer (P) is as follows: (i) A step of washing the polymer (P) with an organic solvent, and then washing it with demineralized water. (ii) The polymer (P) is then heated to a temperature of at least 100°C. Includes. These processes are preferably carried out using a polymer (P) in powder form.

[0110] The organic solvent used in step (i) is usually selected from the group consisting of C1-C6 alcohols, C3-C6 ketones, and combinations thereof. The C1-C6 alcohols can be methanol, ethanol, propanol, or butanol. The C3-C6 ketones can be acetone, butanone, or methyl isobutyl ketone. The organic solvent is preferably acetone or ethanol.

[0111] The amount of organic solvent used to treat the polymer (P) is preferably at least 20 kg per 1 kg of polymer. This thorough treatment makes it possible to remove most of the solvent and other organic impurities.

[0112] The amount of desalinated water used to treat the polymer (P) is preferably at least 20 kg / k of polymer. This thorough treatment makes it possible to remove most of the salt.

[0113] To obtain polymer (P) of sufficient purity, the processing conditions shown in the experimental section can be followed.

[0114] The polymer (P) preferably contains a residual solvent such as diphenylsulfone, up to a maximum of 2000 mg / kg. polymer(P) more preferably up to 1000 mg / kg polymer(P) include.

[0115] The polymer (P) preferably contains the residual monomer 4,4'-difluorobenzophenone at a maximum concentration of 200 mg / kg. polymer(P) Preferably a maximum of 100 mg / kg polymer(P) , more preferably up to 80 mg / kg polymer(P) include.

[0116] The proportions of residual solvent and residual monomer, 4,4'-difluorobenzophenone, are expressed in mg per kg of polymer (P).

[0117] These proportions can be easily measured by extracting the polymer (P) powder with a solvent such as acetone and analyzing the acetone extract by gas chromatography or liquid chromatography. It is advantageous to measure these proportions according to the conditions shown in Table B in the experimental section.

[0118] These proportions can be measured according to the conditions shown in the experimental section.

[0119] These levels of residual solvent and 4,4'-difluorobenzophenone also apply to polymer compositions (PCs).

[0120] The melt viscosity (MV) of the polymer composition (PC), measured at 410°C and 46.3 s⁻¹ according to ASTM D3885, is preferably at least 0.20 kN-s / m². 2 Preferably at least 0.30 kN-s / m 2 , more preferably at least 0.40 kN-s / m 2 This viscosity is preferably a maximum of 1.50 kN-s / m. 2 Preferably a maximum of 1.00 kN-s / m 2 That is the case.

[0121] MV can be measured according to the conditions shown in the experimental section.

[0122] The glass transition temperature (Tg) of the polymer (P) is measured by a second heating scan using DSC after heating and cooling at a rate of 20°C / min, and is preferably at least 135°C. The Tg is preferably at least 138°C, more preferably at least 140°C. The Tg is typically up to 160°C.

[0123] The melting point (Tm) of the polymer (P) is measured by a second heating scan using DSC after heating and cooling at a rate of 20°C / min, and is preferably up to 325°C, more preferably up to 320°C. Tm is typically at least 270°C.

[0124] Similarly, the melting point (Tm*) of the polymer composition (PC) measured under the same conditions is preferably up to 325°C, more preferably up to 320°C. Tm* is typically at least 270°C.

[0125] The crystallization temperature (Tc) of the polymer (P) is measured by the first cooling scan using DSC after heating and cooling at a rate of 20°C / min, and is preferably up to 270°C. Tc is typically at least 180°C.

[0126] The polymer (P) is semicrystalline. The heat of fusion (Hm) of polymer (P) is measured by a second heating scan using DSC after heating and cooling at a rate of 20°C / min and is at least 5.0 J / g. More specifically, Hm may be between 5.0 and 45.0 J / g.

[0127] The heat of fusion (Hm*) of the polymer composition (PC) is measured by a second heating scan using DSC after heating and cooling at a rate of 20°C / min and is at least 2.0 J per gram of polymer. More specifically, Hm* may be between 2.0 and 45.0 J per gram of polymer.

[0128] Tm, Tg, Tc, and Hm can be measured by DSC according to ASTM D3418, and more specifically, according to the conditions in Table A shown in the experimental section.

[0129] Tm, Tg, Tc, and Hm can be measured according to the conditions shown in the experimental section.

[0130] The polymer composition (PC) preferably exhibits a tensile modulus (ASTM D638) of at least 400 ksi.

[0131] The polymer composition (PC) preferably exhibits a low-speed elongation at break of at least 5.0% (ASTM D638). [Examples]

[0132] [Experimental item] raw materials Photo-grade hydroquinone was sourced from Eastman, USA. This hydroquinone contains 0.38% by weight of water, which was used to adjust the load. All weights shown include water.

[0133] We procured ACS reagent-grade resorcinol from Aldrich, USA.

[0134] Polymer-grade 4,4'-biphenol was sourced from SI, USA.

[0135] Flake pyrocatechol was sourced from Solvay USA. Its purity was 99.85% according to GC. It contained 680 ppm of moisture, which was used to adjust the load. All weights shown include moisture.

[0136] Polymer-grade (99.8%+) 4,4'-difluorobenzophenone was sourced from Malwa, India.

[0137] Diphenyl sulfone (polymer grade) was sourced from Proviron (99.8% purity).

[0138] We sourced the light soda ash, sodium carbonate, from Solvay SA, France.

[0139] Potassium carbonate with a d90 < 45 μm was sourced from Armand Products.

[0140] The lithium chloride (anhydrous grade) was sourced from Acros.

[0141] Thermal properties: Determination of melting point (Tm), crystallization temperature (Tc), and heat of fusion. Tm, Tc, and Hm are measured according to the following conditions.

[0142] [Table 5]

[0143] Further details of the procedure are also provided: A TA Instruments DSC Q20 was used with nitrogen (99.998% purity, 50 mL / min) as the carrier gas. Temperature and heat flow calibration were performed using indium. Sample size was 5–7 mg. Weight was recorded to the nearest ±0.01 mg.

[0144] Determination of melt viscosity (MV) The melt viscosity was measured using a capillary rheometer according to ASTM D3835. The following characteristics were observed: a die with a diameter of 1.016 mm, a length of 20.32 mm, and a cone angle of 120° was used, at 410°C, 46.3 seconds. -1 Readings were taken after residence times of 10 minutes and 40 minutes at the specified shear rate.

[0145] Determination of residual solvent and monomer concentrations

[0146] [Table 6]

[0147] Further details of the procedure are also provided: The supernatant was collected and analyzed using a capillary GC (Shimadzu 2010) equipped with a flame ionization detector (FID), with known concentrations of diphenylsulfone and 4,4'-difluorobenzophenone used as external standards. The GC conditions were as follows: - Column: DB-5 - Length: 15 meters - Inner diameter: 0.25mm - Film thickness: 0.25 μm - Carrier gas: Nitrogen - Column flow rate: 0.56 mL / min - Split: 80 mL / min - Septum purge: 3.0 mL / min - Column temperature: Hold at 100°C for 1 minute, then increase temperature at 20°C / min to 300°C, hold at 300°C for 1 minute. - Injection temperature: 300℃ - Detector temperature: 300℃ - Injection volume: 1.0μL.

[0148] Determination of tensile properties by compression molding Plaques measuring 762mm × 762mm × 3.2mm were fabricated from polymer by compression molding 30g of polymer under the following conditions: Preheat T1, ·T1 / 20min, 2000kg-f ·T1 / 2 min, 2700kg-f • Cool to 30°C over 40 minutes, 2000 kg-f

[0149] The T1 values ​​used for the polymers are shown in the results table. The plaques were then annealed at 200°C for 3 hours.

[0150] Compression-molded plaques measuring 762 mm × 762 mm × 3.2 mm were machined into V-type ASTM tensile test specimens. These specimens, representing various polymer compositions, were subjected to tensile testing according to ASTM method D638 at room temperature (i.e., 23°C) at 0.05 inches / min for three specimens. The arithmetic mean of the three specimens is shown.

[0151] Determination of impurities that can be extracted from the surface Test plaques were obtained by pelletizing polymer powder and injection molding. The pellets required for injection molding were prepared by melt-mixing using a 26 mm diameter Coperion® co-rotating partial-meshing twin-screw extruder with an L / D ratio of 48:1. The extruder had 12 barrel sections, with barrel sections 2-12 being temperature-controlled. The extruder was fitted with a 3 mm diameter single-hole die. A resin feeder supplied resin to the feed hopper (barrel section 1). During mixing, vacuum venting was performed in barrel section 10 at a vacuum level of >25 in Hg to strip off moisture and any potentially residual volatile substances from the compound. Extruded materials from each composition were formed into strands, cooled in a demineralizing water bath, and then pelletized using a Maag Primo 60E pelletizer.

[0152] [Table 7]

[0153] [Table 8]

[0154] Each sample container, containing one plaque, was filled with ultrapure water (milliQ) for two minutes. The water was then drained. This was repeated 10 times. In the actual leaching test, on the 11th time, the container was filled with just enough water to cover the plaque. The test was performed three times for each plaque type.

[0155] In parallel, the exact same procedure was performed on five "blank" glass containers and five "blank" HDPE containers containing the same amount of ultrapure water but without plaque, as was done with the bottle containing plaque. These were "procedure blanks."

[0156] Subsequently, the containers containing the plaque and the blank procedure containers were placed in an 85°C oven for 7 days. They were stirred once a day.

[0157] After 7 days of leaching, the sample solution was transferred to a clean receiver for TOC, metal, and anion analysis. The solution for metal quantification was slightly acidified with concentrated HNO3 immediately after transfer to stabilize the metal.

[0158] Metals extractable from the surface (SEMI F57 list) were measured by high-resolution ICP-MS using a Thermo Element 2 instrument.

[0159] Anions extractable from the surface (SEMI F57 list) were measured by ion chromatography (IC) using a Dionex ICS-5000 instrument.

[0160] TOC (Total Organic Carbon) was measured using the Shimadzu TOC-L instrument as the difference between TC (Total Carbon) and TIC (Total Inorganic Carbon).

[0161] Polymer preparation Comparative Example 2: Preparation of PEEK-PEmEK copolymer 75 / 25 A 1000 mL four-neck reaction flask, equipped with a stirrer, an N2 injection tube, a Claisen-type connector with a thermocouple inserted into the reaction medium, and a Dean-Stark trap with a condenser and dry eye trap, was introduced with 338.33 g of diphenylsulfone, 41.665 g of hydroquinone, 13.863 g of resorcinol, and 112.593 g of 4,4'-difluorobenzophenone. The flask contents were evacuated and then filled with high-purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then subjected to continuous nitrogen purging (60 mL / min).

[0162] The reaction mixture was slowly heated to 150°C. At 150°C, a mixture of 55.482 g of Na2CO3 and 0.174 g of K2CO3 was added to the reaction mixture over 30 minutes using a powder dispenser. At the end of the addition, the reaction mixture was heated to 300°C at a rate of 1°C / min. After 36 minutes at 300°C, 13.169 g of 4,4'-difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 2.132 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 4.390 g of 4,4'-difluorobenzophenone was added to the reactor, and the temperature of the reaction mixture was maintained for 15 minutes.

[0163] Subsequently, the contents of the reactor were poured from the reactor into a stainless steel receiving dish and cooled. The solid was crushed and ground in an attrition mill through a 2 mm sieve. Diphenyl sulfone and salts were extracted from the solid with 6 × 1.2 L of acetone and 7 × 1.2 L of water at a pH of 1 to 12. The powder was then removed from the reactor and dried under vacuum at 100°C for 12 hours to obtain 165 g of light brown powder. The final polymer contained less than 500 mg / kg of diphenyl sulfone and less than 100 mg / kg of 4,4'-difluorobenzophenone. Other monomers were completely consumed during polymerization and were present in the final polymer at less than 3 mg / kg.

[0164] Example 3: Preparation of PEEK-PEDEK copolymer 75 / 25 A 500 mL four-neck reaction flask equipped with a stirrer, an N2 injection tube, a Claisen-type connector with a thermocouple inserted into the reaction medium, and a Dean-Stark trap with a condenser and dry eye trap was introduced with 128.21 g of diphenylsulfone, 20.297 g of hydroquinone, 11.411 g of 4,4'-biphenol, and 54.377 g of 4,4'-difluorobenzophenone. The contents of the flask were evacuated under vacuum and then filled with high-purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then subjected to continuous nitrogen purging (60 mL / min).

[0165] The reaction mixture was slowly heated to 150°C. At 150°C, a mixture of 26.955 g of Na2CO3 and 0.169 g of K2CO3 was added to the reaction mixture over 30 minutes using a powder dispenser. After the addition was complete, the reaction mixture was heated to 320°C at a rate of 1°C / min. After 13 minutes at 320°C, 3.742 g of 4,4'-difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 1.039 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 2.138 g of 4,4'-difluorobenzophenone was added to the reactor, and the temperature of the reaction mixture was maintained for 15 minutes.

[0166] Subsequently, the contents of the reactor were poured from the reactor into a stainless steel receiving dish and cooled. The solid was crushed and ground in an attrition mill through a 2 mm sieve. Diphenyl sulfone and salts were extracted from the mixture with 6 × 1.2 L of acetone and 7 × 1.2 L of water at a pH of 1 to 12. The powder was then removed from the reactor and dried under vacuum at 120°C for 12 hours to obtain 74 g of white powder. The final polymer contained less than 1000 mg / kg of diphenyl sulfone and less than 100 mg / kg of 4,4'-difluorobenzophenone. Other monomers were completely consumed during polymerization and were present in the final polymer at less than 3 mg / kg.

[0167] Example 4: Preparation of PEEK-PEoEK copolymer 70 / 30 343.63 g of diphenylsulfone, 54.121 g of hydroquinone, 23.139 g of pyrocatechol, and 153.351 g of 4,4'-difluorobenzophenone were introduced into a 1000 mL four-neck reaction flask equipped with a stirrer, an N2 injection tube, a Claisen-type connector with a thermocouple inserted into the reaction medium, and a Dean-Stark trap with a condenser and a dry eye trap. The flask contents were evacuated and then filled with high-purity nitrogen (containing less than 10 ppm of O2). The reaction mixture was then subjected to continuous nitrogen purging (60 mL / min).

[0168] The reaction mixture was slowly heated to 150°C. At 150°C, a mixture of 76.938 g of Na2CO3 and 0.484 g of K2CO3 was added to the reaction mixture over 30 minutes using a powder dispenser. At the end of the addition, the reaction mixture was heated to 320°C at a rate of 1°C / min. After 73 minutes at 320°C, the reaction was completed in three steps: 18.329 g of 4,4'-difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 2.388 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 6.110 g of 4,4'-difluorobenzophenone was added to the reactor, and the temperature of the reaction mixture was maintained for 15 minutes.

[0169] Subsequently, the contents of the reactor were poured from the reactor into a stainless steel receiving pan and cooled. The solid was crushed and ground in an attrition mill through a 2 mm sieve. Diphenyl sulfone and the salt were extracted from the mixture by sequential extraction with 6 × 1.2 L of acetone and 7 × 1.2 L of water at room temperature. The powder was then dried under vacuum at 120°C for 12 hours to obtain 188 g of white powder. The final polymer contained less than 1000 mg / kg of diphenyl sulfone and less than 100 mg / kg of 4,4'-difluorobenzophenone. The other monomers were completely consumed during polymerization and were present in the final polymer at less than 3 mg / kg.

[0170] Example 5: Preparation of PEEK-PEoEK copolymer 80 / 20 The same procedure as in Example 4 was performed using the following reagent amounts.

[0171] [Table 9]

[0172] The properties of the polymers in Comparative Examples 1 and 2 and Examples 3 to 5 are shown in detail in Table 4 below.

[0173] [Table 10]

[0174] The data shown in Table 4 indicates that PEEK-PEDEK and PEEK-PEoEK exhibit the following combination of characteristics suitable for the manufacture of piping or pipe connectors: • A lower Tm than PEEK; • Tg is higher than or the same as that of PEEK; • Improved ductility (elongation at break) compared to PEEK-PEmEK. As a result, it is shown that the presence of PEmEK repeating units adversely affects the properties of the polymer.

[0175] Surface-extractable impurities were measured for the low-Tm PAEK=PEEK-PEoEK copolymer of Example 5. These are listed in Table 5. The detected levels are consistent with the requirements expected for ultrapure water transport, suggesting that the low-melting-point PEEK-PEoEK copolymer meets the purity requirements for this application.

[0176] [Table 11]

Claims

1. An ultrapure water (UPW) transport system comprising at least one component, wherein the at least one component has a surface intended to come into contact with the UPW, and the surface is manufactured from or comprises a polymer composition (PC), and the polymer composition (PC) is - At least 50.0% by weight (≥50.0% by weight) of at least one semicrystalline polymer (P) (this percentage is relative to the total weight of the polymer composition (PC)), - A polymer (P) blended with at least one additional polymer, which is selected from the group consisting of polyaryl ether ketones (PAEK), polysulfones (PSU), polyphenylsulfones (PPSU), and combinations thereof, which is different from the semicrystalline polymer (P). Including, essentially being derived from, or consisting of; The semicrystalline polymer (P) consists of the following repeating units in the following proportions: • For 65.0 to 95.0 mol%, the following formula: 【Chemistry 1】 The unit (R ＰＥＥＫ ) • For concentrations between 5.0 and 35.0 mol%, the following formula: 【Chemistry 2】 The unit (R ＰＥＤＥＫ ), unit (R ＰＥｏＥＫ ), and a unit selected from the group consisting of combinations thereof (R Ｐ ) This includes, and these proportions are relative to the total amount of repeating units of the polymer (P); UPW represents water exhibiting an electrical resistivity of at least 18.0 MΩ·cm and a total organic carbon (TOC) of up to 10.0 μg / L at 25°C; system.

2. The system according to claim 1, wherein the aforementioned component is a pipe or a pipe connector.

3. The system according to claim 1 or 2, wherein the proportion of semicrystalline polymer (P) in the polymer composition (PC) is at least 60.0% by weight, preferably at least 65.0% by weight, preferably at least 70.0% by weight, preferably at least 75.0% by weight, preferably at least 80.0% by weight, preferably at least 85.0% by weight, preferably at least 90.0% by weight, preferably at least 95.0% by weight, and preferably at least 99.0% by weight, and this proportion is the proportion of the total weight of the polymer composition (PC).

4. The system according to claim 1 or 2, wherein UPW is one of the seven types of water listed in Table 1 of ASTM D5127-13 (re-approved in 2018).

5. The system according to any one of claims 1 to 4, wherein UPW is one of four types of water as defined in Table 1 of ASTM D5127-13 (re-approved in 2018): type E-1, type E-1.1, type E-1.2, or type E-1.

3.

6. (R Ｐ )but, ・(R ＰＥＤＥＫ ); or ・(R ＰＥｏＥＫ ); or ・ (R ＰＥＤＥＫ ) and (R ＰＥｏＥＫ ) combination The system according to any one of claims 1 to 5.

7. The repeating unit of the polymer (P) is the unit (R ＰＥＥＫ ) and units (R Ｐ The system according to any one of claims 1 to 6, comprising the above.

8. ・(R ＰＥＥＫ The proportion of ) is 65.0 to 85.0 mol%; and / or ・(R Ｐ The proportion of ) is 15.0 to 35.0 mol%, The system according to any one of claims 1 to 7.

9. Polymer (P) absorbs residual solvents such as diphenyl sulfone up to a maximum of 2000 mg / kg ｐｏｌｙｍｅｒ（Ｐ） Preferably, up to 1000 mg / kg ｐｏｌｙｍｅｒ（Ｐ） Contains and / or residual monomer 4,4'-difluorobenzophenone, up to a maximum of 200 mg / kg ｐｏｌｙｍｅｒ（Ｐ） Preferably a maximum of 100 mg / kg ｐｏｌｙｍｅｒ（Ｐ） More preferably, up to 80 mg / kg ｐｏｌｙｍｅｒ（Ｐ） The system includes the system according to any one of claims 1 to 8.

10. According to ASTM D3885, 410°C, 46.3 s －１ The melt viscosity (MV) of the polymer composition (PC) measured is at least 0.20 kN-s / m ２ Preferably at least 0.30 kN-s / m ２ , more preferably at least 0.40 kN-s / m ２ The system according to any one of claims 1 to 9.

11. A piping comprising one or more layers, wherein an inner layer (L) intended to be in contact with the UPW is made from or comprises a polymer composition (PC), and the polymer composition (PC) is - At least 50.0% by weight (≥50.0% by weight) of at least one semicrystalline polymer (P) (this percentage is relative to the total weight of the polymer composition (PC)), - A polymer (P) blended with at least one additional polymer, which is selected from the group consisting of polyaryl ether ketones (PAEK), polysulfones (PSU), polyphenylsulfones (PPSU), and combinations thereof, which is different from the semicrystalline polymer (P). Including, essentially being derived from, or consisting of; UPW represents water exhibiting an electrical resistivity of at least 18.0 MΩ·cm and a total organic carbon (TOC) of up to 10.0 μg / L at 25°C; The semicrystalline polymer (P) consists of the following repeating units in the following proportions: • For 65.0 to 95.0 mol%, the following formula: 【Transformation 3】 The unit (R ＰＥＥＫ ) • For concentrations between 5.0 and 35.0 mol%, the following formula: 【Chemistry 4】 The unit (R ＰＥＤＥＫ ), unit (R ＰＥｏＥＫ ), and a unit selected from the group consisting of combinations thereof (R Ｐ ) This includes, and these proportions are relative to the total amount of repeating units of the polymer (P); - The aforementioned piping includes UPW: and / or - Amount of impurities (Imp) released from layer (L) after contacting layer (L) with UPW according to the protocol (p1) described in the specification (surface 1 m of the leaching area) ２ (expressed as μg per unit) is shown in the following table: Table 1 Piping that is below the value of eluted impurities indicated by [the specified symbol].

12. A piping connector having a surface intended to come into contact with ultrapure water (UPW) and manufactured from or comprising a polymer composition (PC) according to any one of claims 1 to 11, wherein the UPW represents water exhibiting an electrical resistivity of at least 18.0 MΩ·cm at 25°C and a maximum total organic carbon (TOC) of 10.0 μg / L, and the amount of impurities (Imp) released from the surface in contact with the UPW according to the protocol (p2) described in the specification (surface 1 m of the leaching area) ２ (expressed as μg per unit) is shown in the following table: Table 2 A piping connector whose eluted impurities are less than the value indicated by [the specified symbol].

13. A method for transporting ultrapure water (UPW), comprising transporting ultrapure water using at least one pipe according to claim 11 or at least one pipe connector according to claim 12, wherein the UPW represents water exhibiting an electrical resistivity of at least 18.0 MΩ·cm and a total organic carbon (TOC) of up to 10.0 μg / L at 25°C.

14. The use of a polymer composition (PC) for forming at least one surface of a pipe or pipe connector intended to come into contact with ultrapure water (UPW), wherein the polymer composition (PC) is - At least 50.0% by weight (≥50.0% by weight) of at least one semicrystalline polymer (P) (this percentage is relative to the total weight of the polymer composition (PC)), - A polymer (P) blended with at least one additional polymer, which is selected from the group consisting of polyaryl ether ketones (PAEK), polysulfones (PSU), polyphenylsulfones (PPSU), and combinations thereof, which is different from the semicrystalline polymer (P). Including, essentially being derived from, or consisting of; The semicrystalline polymer (P) consists of the following repeating units in the following proportions: • For 65.0 to 95.0 mol%, the following formula: 【Transformation 5】 The unit (R ＰＥＥＫ ) • For concentrations between 5.0 and 35.0 mol%, the following formula: 【Transformation 6】 The unit (R ＰＥＤＥＫ ), unit (R ＰＥｏＥＫ ), and a unit selected from the group consisting of combinations thereof (R Ｐ ) This includes, and these proportions are relative to the total amount of repeating units of the polymer; UPW represents water exhibiting an electrical resistivity of at least 18.0 MΩ·cm and a total organic carbon (TOC) of up to 10.0 μg / L at 25°C.

15. The use according to claim 14, wherein the proportion of semicrystalline polymer (P) in the polymer composition (PC) is at least 60.0% by weight, preferably at least 65.0% by weight, preferably at least 70.0% by weight, preferably at least 75.0% by weight, preferably at least 80.0% by weight, preferably at least 85.0% by weight, preferably at least 90.0% by weight, preferably at least 95.0% by weight, and preferably at least 99.0% by weight, and this proportion is the proportion of the total weight of the polymer composition (PC).

16. (R Ｐ )but, ・(R ＰＥＤＥＫ ); or ・(R ＰＥｏＥＫ ); or ・(R ＰＥＤＥＫ ) and (R ＰＥｏＥＫ ) combination The use according to claim 14 or 15.

17. The repeating unit of the polymer (P) is the unit (R ＰＥＥＫ ) and units (R Ｐ The use according to any one of claims 14 to 16, comprising the above.

18. ・(R ＰＥＥＫ The proportion of ) is 65.0 to 85.0 mol%; and / or ・(R Ｐ The proportion of ) is 15.0 to 35.0 mol%, The use according to any one of claims 14 to 17.

19. Polymer (P) absorbs residual solvents such as diphenyl sulfone up to a maximum of 2000 mg / kg ｐｏｌｙｍｅｒ（Ｐ） Preferably, up to 1000 mg / kg ｐｏｌｙｍｅｒ（Ｐ） Contains and / or residual monomer 4,4'-difluorobenzophenone, up to a maximum of 200 mg / kg ｐｏｌｙｍｅｒ（Ｐ） Preferably a maximum of 100 mg / kg ｐｏｌｙｍｅｒ（Ｐ） More preferably, up to 80 mg / kg ｐｏｌｙｍｅｒ（Ｐ） The use described in any one of claims 14 to 18, including.

20. According to ASTM D3885, 410°C, 46.3 s －１ The melt viscosity (MV) of the polymer composition (PC) measured is at least 0.20 kN-s / m ２ Preferably at least 0.30 kN-s / m ２ , more preferably at least 0.40 kN-s / m ２ The use according to any one of claims 14 to 19.

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