Extrusion molding body

Abstract

To provide a tubular extrusion molding body which avoids environmental problems due to an inclusion of halogen elements, has excellent physical properties such as low water vapor permeability, low chemical permeability, abrasion resistance, and mechanical properties, and is suitable as a material for chemicals used in manufacture of semiconductors, liquid crystals, etc., and for piping for ultrapure water.SOLUTION: An extrusion molding body is a tubular extrusion molding body made of a resin that does not contain halogen elements, has an ether bond or an ethylene structure, and has a melting point of 200°C or higher, and has an electrical conductivity of 0.5 mS / m or less at 25°C, an amount of ion elution into water of 7500 μg / m2 or less, and an arithmetic mean roughness (Ra) of an inner surface of 0.25 μm or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an extruded product.

Background Art

[0002] Conventionally, in the manufacture of precision devices such as semiconductor devices or liquid crystal display devices, ultrapure water that has been purified to extremely high purity is used in wet processes such as cleaning. Also, special chemical solutions and chemicals are used in the development process of semiconductor manufacturing.

[0003] For the piping that constitutes the transport lines of chemical solutions and chemicals used in the manufacture of precision devices such as semiconductor devices or liquid crystal display devices, and for precision devices and ultrapure water in other applications as well, it is required that the elution of metal ions is extremely low, and that the inner surface smoothness is high for the purpose of preventing the propagation of bacteria and preventing the bubbling of the entrapped air.

[0004] As the material for the piping used in these applications, a fluororesin that is chemically inert, has gas barrier properties, has extremely low elution properties into chemical solutions and chemicals, and has a high inner surface smoothness is used. For example, Patent Document 1 discloses a fluororesin double tube in which a fluororesin is laminated in two layers as the piping used in semiconductor manufacturing equipment, liquid crystal manufacturing equipment, etc. The inner layer tube is made of a fluororesin (for example, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), or tetrafluoroethylene-ethylene copolymer (ETFE)) that is excellent in corrosion resistance and chemical resistance, and the outer layer tube is made of a fluororesin (for example, polyvinylidene fluoride (PVDF)) that can suppress gas permeation.

[0005] Further, Patent Document 2 discloses a multilayer pipe for ultra-pure water piping, which is made of a fluororesin and includes a first resin layer that comes into contact with ultra-pure water and a second resin layer that is made of a gas-impermeable resin and is provided on the outer peripheral surface of the first resin layer. Further, a third resin layer for protecting the second resin layer is provided on the outer peripheral surface of the second resin layer, and it is disclosed that polyethylene is used as the third resin layer.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] Recently, with the improvement of the integration degree of semiconductor chips, circuit patterns have become increasingly finer, and the required characteristics for ultra-pure water piping have been continuously tightened. However, in recent years, the PFAS problem has been raised, and regulations are being imposed on the use of fluorine-related chemical solutions and agents and fluororesins. PFAS is a general term for perfluoroalkyl compounds and polyfluoroalkyl compounds among organic fluorine compounds, and there are more than 10,000 kinds of substances.

[0008] According to the PFAS restriction proposal published by the European Chemicals Agency (ECHA) in March 2023, (1) PFAS and PFAS degradation products may remain in the environment longer than any other artificial chemical substances, and (2) there are concerns about bioaccumulation, mobility, potential for long-distance transport, and ecotoxicity. These two are cited as the reasons for the restriction. The persistence of the former (1) is due to the chemical structure of PFAS, so it applies to all PFAS subject to the restriction, but persistence itself is not a harmful characteristic. Regarding the latter (2), the scientific data available is limited to some PFAS. However, based on the precautionary principle of "when there is uncertainty, taking protective measures without waiting until the existence and degree of risk are fully clarified", the restricted scope is widely set.

[0009] Even materials that are widely used in the world and indispensable for our lives will be subject to restrictions. Since PFAS has superior properties to other materials, there are many applications for which there are no alternatives. Regarding such applications, in addition to an 18-month transition period, an additional grace period of 5 years or 12 years is set, but they will be regulated. Also, as is well known, there are environmental problems in the treatment of waste containing halogen elements, and it is effective not to use them.

[0010] In the present invention, an environmental problem caused by containing halogen elements is avoided, and it has excellent physical properties such as low water vapor permeability, low chemical liquid permeability, abrasion resistance, and mechanical properties, and is suitable for materials such as chemical liquids and drugs used in the manufacture of semiconductors, liquid crystals, etc., and pipes for ultrapure water, etc. A tubular extruded body is provided.

Means for Solving the Problems

[0011] As a result of intensive studies, the inventors of the present invention have found that the above problems can be solved by the extruded product of the present invention. The inventors have found that a tubular extruded product made of a resin that does not contain a halogen element and has an ether bond or an ethylene structure and a melting point of 200°C or higher, and has a MFR of about 7-18 g / 10 min (295°C), has a tendency to be inferior in water vapor low permeability and chemical liquid low permeability to a tubular extruded product made of a copolymer having a MFR of 7 g / 10 min (295°C) or less. Then, as a result of a major review of the extrusion conditions in addition to the composition of the copolymer used for extrusion molding, even when a copolymer having a relatively high MFR of about 7-18 g / 10 min is used, if the amount of ion elution from the tubular extruded product into water with an electrical conductivity of 0.5 mS / m or less at 25°C is small, it has been found that the water vapor low permeability and chemical liquid low permeability of the tubular extruded product are greatly improved, and the tubular extruded product of the present invention has been completed.

[0012] That is, the extruded product of the present invention is a tubular extruded product formed of a resin that does not contain a halogen element and has an ether bond or an ethylene structure and a melting point of 200°C or higher, and the amount of ion elution into water with an electrical conductivity of 0.5 mS / m or less at 25°C is 7500 μg / m 2 or less, and the arithmetic mean roughness (Ra) of the inner surface is 0.25 μm or less.

Advantages of the Invention

[0013] According to the present invention, it is possible to avoid environmental problems caused by the inclusion of halogen elements, and to provide a tubular extruded product that is excellent in physical properties such as low water vapor permeability, low chemical liquid permeability, abrasion resistance, and mechanical properties, and is suitable as a material for chemical solutions and drugs used in the manufacture of semiconductors, liquid crystals, etc., and piping for ultrapure water.

Embodiments for Carrying Out the Invention

[0014] Hereinafter, a preferred embodiment of the extruded article of the present invention will be described in detail. In this embodiment, a tubular extruded article formed of a resin that does not contain a halogen element and has an ether bond or an ethylene structure and a melting point of 200 ° C or higher is exemplified. The ion elution amount of the extruded article into water having an electric conductivity of 0.5 mS / m or less at 25 ° C is 7500 μg / m 2 or less. Further, the arithmetic mean roughness (Ra) of the inner surface of the extruded article is 0.25 μm or less. Since the extruded article of the present embodiment has such a configuration, it is excellent in physical properties such as low water vapor permeability, low chemical liquid permeability, abrasion resistance, mechanical properties, and rigidity at high temperatures.

[0015] The ion elution amount of the extruded article into water having an electric conductivity of 0.5 mS / m or less at 25 ° C is 7500 μg / m 2 or less, preferably 5500 μg / m 2 or less, more preferably 5000 μg / m 2 or less, and particularly preferably 4500 μg / m 2 or less. The lower limit of the ion elution amount is not particularly limited, and the lower the better.

[0016] The ion elution amount of the extruded article into water having an electric conductivity of 0.5 mS / m or less at 25 ° C was measured by elemental absorption analysis (ICP) after immersing the tubular extruded article in water having an electric conductivity of 0.5 mS / m or less at 95 ° C for 1 hour, and the ion elution amount per inner surface area of the tubular extruded article was calculated.

[0017] When the extruded article of the present embodiment is used in the semiconductor industry, for the metal elution suppression performance, based on SEMI F57-0314, the total amount of elution of the main 16 metals (referring to aluminum, barium, boron, calcium, chromium, copper, iron, lead, lithium, magnesium, manganese, nickel, potassium, sodium, strontium, and zinc) is 14 μg / m 2 or less, preferably 12 μg / m 2 or less, more preferably 10 μg / m 2 or less, and even more preferably 9 μg / m2 Preferably, it is 8.5 μg / m or less hereinafter. 2 However, the above concentration standard is not required in all industries using the extruded product of the present embodiment.

[0018] In addition, the roughness of the inner surface of the extruded product of the present embodiment is preferably 0.25 μm or less as the arithmetic mean roughness (Ra) measured based on SEMI F57-0301. If the roughness of the inner surface is large, substances contained in the fluid will get caught, resulting in residues. When another fluid flows through after cleaning, it will contaminate the fluid. In addition, the friction with the fluid increases, causing wear on the inner surface of the extruded product and generating contamination from the extruded product in the fluid. This is particularly undesirable when used in industries such as the semiconductor industry and the pharmaceutical industry as it can cause contamination.

[0019] The metal elution amount is measured based on SEMI F57-0314. As a more specific example of the metal elution amount, as the elution amount of calcium, for example, it is 7 μg / m or less, preferably 6 μg / m or less, more preferably 5.5 μg / m or less. As the elution amount of copper, for example, it is 0.5 μg / m or less, preferably 0.45 μg / m or less, more preferably 0.4 μg / m or less. As the elution amount of sodium, for example, it is 1.5 μg / m or less, preferably 1.1 μg / m or less, more preferably 0.7 μg / m or less. As the elution amount of zinc, for example, it is 0.5 μg / m or less, preferably 0.3 μg / m or less, more preferably 0.2 μg / m or less. 2 Preferably, it is 6 μg / m or less hereinafter. 2 Preferably, it is 5.5 μg / m or less hereinafter, more preferably. 2 As the elution amount of copper, for example, it is 0.5 μg / m or less. 2 Preferably, it is 0.45 μg / m or less. 2 Preferably, it is 0.4 μg / m or less, more preferably. 2 As the elution amount of sodium, for example, it is 1.5 μg / m or less. 2 Preferably, it is 1.1 μg / m or less. 2 Preferably, it is 0.7 μg / m or less, more preferably. 2 As the elution amount of zinc, for example, it is 0.5 μg / m or less. 2 Preferably, it is 0.3 μg / m or less. 2 Preferably, it is 0.2 μg / m or less, more preferably. 2 As follows.

[0020] Regarding the anion elution amount, as the elution amount of bromide ions, for example, it is less than 10 μg / m. As the elution amount of fluoride ions, for example, it is 1000 μg / m or less. 2 As follows. 2Less than, preferably 800 μg / m 2 Less than, more preferably 700 μg / m 2 Less than, even more preferably 600 μg / m 2 Less than may be mentioned. As nitrite ions, for example, 10 μg / m 2 Less than may be mentioned; as sulfate ions, for example, 10 μg / m 2 Less than may be mentioned.

[0021] The elution amount of organic components is measured based on SEMI F57-0314. As the elution amount of total organic components (TOC), for example, 10000 μg / m 2 Or less, preferably 9000 μg / m 2 Or less, more preferably 8500 μg / m 2 Or less, even more preferably 8000 μg / m 2 Or less may be mentioned.

[0022] A resin that does not contain halogen elements and has an ether bond or an ethylene structure and a melting point of 200 °C or higher has a melt flow rate (MFR) at 295 °C of 7.0 to 18.0 g / 10 min, preferably 10.0 - 15.0 g / 10 min or more, and more preferably 11.0 - 13.0 g / 10 min. Since the tubular extruded body in this embodiment contains a resin having a relatively high MFR, it can be easily manufactured by extrusion molding. Moreover, despite having such a resin with a relatively high MFR, it is excellent in low water vapor permeability and low chemical liquid permeability. If the MFR of the resin is too high, the extruded body will be inferior in abrasion resistance and mechanical properties. If the MFR of the resin is too low, the molding of the resin will not be easy. Also, if the MFR of the resin is too low, the extruded body will be inferior in rigidity at high temperatures.

[0023] The MFR disclosed in this specification is a value obtained as the mass (g / 10 min) of the resin flowing out per 10 minutes from a nozzle with an inner diameter of 2.1 mm and a length of 8 mm under a load of 6.6 kg at 295 °C using a melt indexer in accordance with ASTM D1238.

[0024] The resin that does not contain a halogen element and has an ether bond or an ethylene structure has a melting point of 200 °C or higher, preferably 200 to 250 °C, and more preferably 200 to 220 °C. When the melting point of the above resin is within the above range, the physical properties such as the mechanical properties and the rigidity at high temperature of the tubular extruded body become more excellent.

[0025] Examples of the resin that does not contain a halogen element and has an ether bond or an ethylene structure include polyetherimide resin (such as "ULTEM (registered trademark)" manufactured by SABIC), modified polyetherimide resin (such as "SILTEM (registered trademark)" manufactured by SABIC), a mixture of polyetherimide resin or modified polyetherimide resin and other resins, rubbers, elastomers that do not contain a halogen element, long-chain alkyl resin, α-olefin resin, ethylene-α-olefin resin, cycloolefin resin, polymethylpentene resin (such as "TPX (registered trademark)" manufactured by Mitsui Chemicals), polysulfone resin (such as "Udel (registered trademark)" manufactured by Solvay), polyethersulfone resin (such as "Veradel (registered trademark)" manufactured by Solvay, "Ultrason (registered trademark)" manufactured by BASF), etc., but are not limited thereto.

[0026] The tubular extruded body according to the present embodiment may contain other components such as a filler, a pigment, a flame retardant, a lubricant, a light stabilizer, a weather stabilizer, a conductive agent, and an antistatic agent.

[0027] In this embodiment, a known extrusion molding machine can be used. Specifically, an extrusion molding machine including a cylinder and a screw accommodated in the cylinder can be used. In the manufacturing process of the tubular extruded body according to the present embodiment, it is preferable to adjust the temperature of the copolymer in the cylinder in the extrusion molding to 250 °C to 395 °C.

[0028] The tubular extrusion molded body according to the present embodiment described above is excellent in physical properties such as low water vapor permeability, low chemical liquid permeability, abrasion resistance, mechanical properties, and rigidity at high temperatures. Therefore, for example, it can be suitably used as a piping member used for transferring chemical liquids.

[0029] As described above, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist thereof.

Example

[0030] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the described scope of the present invention is not limited thereto. In this example, resin-made tubular extrusion molded bodies and sheet-like extrusion molded bodies of Examples 1 to 6 and Comparative Examples 1 to 3 were produced, and various measurements were performed on each of the produced extrusion molded bodies. Hereinafter, Examples 1 to 6 and Comparative Examples 1 to 3 will be described.

[0031] Table 2 below shows each resin constituting the extrusion molded bodies of Examples 1 to 6 and Comparative Examples 1 to 3. Further, Table 1 below shows the resin physical properties (presence or absence of halogen elements, differences in ether structure or ethylene structure, melting point, melt flow rate) of the resins constituting the extrusion molded bodies of Examples 1 to 6 and Comparative Examples 1 to 3.

[0032] (Melting point) Using a differential scanning calorimeter (trade name: X-DSC7000, manufactured by Hitachi High-Tech Science Corporation), the first temperature increase from 200°C to 350°C was performed at a temperature increase rate of 10°C / min, and then, cooling was performed from 350°C to 200°C at a cooling rate of 10°C / min. Again, the second temperature increase from 200°C to 350°C was performed at a temperature increase rate of 10°C / min, and the melting point was determined from the melting curve peak generated during the second temperature increase process. In Table 1, those with a melting point of 200 to 220°C are indicated as "〇", those with a melting point of 220 to 250°C are indicated as "+", those with a melting point higher than 250°C are indicated as "++", and those with a melting point less than 200°C are indicated as "-".

[0033] (Melt Flow Rate (MFR)) In accordance with ASTM D1238, using a melt indexer G-01 (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the mass (g / 10 min) of the polymer flowing out per 10 minutes from a nozzle with an inner diameter of 2.1 mm and a length of 8 mm under a load of 6.6 kg at 295°C was determined. In Table 1, those with an MFR less than 7.0 are indicated as "-", those from 7.0 to 18.0 as "〇", those from 18.0 to 29.0 as "+", and those greater than 29.0 as "++".

[0034] In the production of the extruded molded body, a known extrusion molding machine was used. The maximum temperature of the cylinder in extrusion molding was set at 350°C, and the mold temperature was set at 300°C. A tubular extruded molded body with an inner diameter of 4 mm and a wall thickness of 1 mm was produced. A sheet-like extruded molded body with a thickness of 0.5 mm was produced.

[0035] For each of the produced tubular extruded molded bodies, specified physical properties, specifically, inner surface roughness, ion elution amount, metal ion elution amount, and specific metal ion elution amount, were measured. For each of the produced sheet-like extruded molded bodies, performance tests, specifically, measurement of water vapor permeability, measurement of MEK permeability, abrasion test, and measurement of the load deflection rate at 95°C, were conducted.

[0036] (Inner surface roughness (Ra)) The tubular extruded molded body was split longitudinally, and its inner surface was measured according to the method described in JIS standard (B0601). In Table 1, those with an inner surface roughness (Ra) of 0.25 μm or less are indicated as "〇", and those greater than 0.25 μm as "×".

[0037] (Measurement of ion elution amount, metal ion elution amount, and specific metal elution amount) After enclosing the tubular extruded molded body in water with an electrical conductivity of 0.5 mS / m or less at 25°C for 1 hour at 95°C, the concentration was measured by elemental absorption analysis (ICP), and the ion elution amount per inner surface area of the tubular extruded molded body was calculated. In Table 1, those with an ion elution amount greater than 7500 μg / m 2 are indicated as "×", those from 7500 μg / m 2 to 5500 μg / m 2 are indicated as "△", and those from 5500 μg / m 2 to 4500 μg / m 2is marked as "〇" for 4500 μg / m 2 and those less than that are marked as "◎".

[0038] Also, in Table 1, those with a metal ion elution amount of more than 5500 μg / m 2 are marked as "×", those with 5500 μg / m 2 ~5000 μg / m 2 are marked as "△", those with 5000 μg / m 2 ~4500 μg / m 2 are marked as "〇", and those 4500 μg / m 2 and below are marked as "◎".

[0039] Furthermore, the total amount of the elution amounts of the 16 main metals based on SEMI F57 - 0314 was calculated as the specific metal elution amount. In Table 1, those with a specific metal elution amount of more than 14 μg / m 2 are marked as "×", and those 14 μg / m 2 and below are marked as "〇".

[0040] (Water vapor permeability) After leaving the sheet - shaped extruded body at 60 °C for 24 hours, test pieces were prepared from the extruded body. 10 g of water was put into a test cup (permeation area 7.065 cm 2 ), covered with a sheet - shaped test piece, clamped with a PTFE gasket and tightened to be sealed. Keeping it at 95 °C for 60 days with the sheet - shaped test piece in contact with water, then taken out, left at room temperature for 2 hours, and the mass reduction amount was measured. The water vapor permeability (g / m 2 ) was measured by the following formula. Water vapor permeability (g / m 2 ) = mass reduction amount (g) / permeation area (m 2 ) In Table 1, those with a water vapor permeability of more than 600 g / m 2 are marked as "×", those with 600 g / m 2 ~500 g / m 2 are marked as "△", those with 500 g / m 2 ~400 g / m 2 are marked as "〇", and those 400 g / m 2 and below are marked as "◎".

[0041] (Methyl ethyl ketone (MEK) permeability) After leaving the sheet-like extruded body at 60 °C for 24 hours, a sheet-like test piece was prepared from the extruded body. 10 g of MEK was placed in a test cup (transmission area 12.56 cm 2 ), covered with the sheet-like test piece, clamped with a PTFE gasket, and tightened to seal. After keeping it at 60 °C for 60 days with the sheet-like test piece in contact with MEK, it was taken out, left at room temperature for 1 hour, and then the mass reduction amount was measured.

[0042] The MEK permeability (g / m 2 ) was calculated by the following formula. MEK permeability (g / m 2 ) = mass reduction amount (g) / transmission area (m 2 ) In Table 1, those with an MEK permeability of more than 85 g / m 2 are indicated as "×", those from 85 g / m 2 to 80 g / m 2 are indicated as "△", those from 80 g / m 2 to 75 g / m 2 are indicated as "〇", and those of 75 g / m 2 or less are indicated as "◎".

[0043] (Wear test) The sheet-like extruded body was left at 60 °C for 24 hours and then used as a test piece. The test piece was fixed to the test bench of a Taber abrasion tester (No. 101 special type Taber abrasion tester, manufactured by Yasuda Seiki Seisakusho Co., Ltd.), and a wear test was conducted using the Taber abrasion tester under the conditions of a load of 500 g, a wear wheel CS-10 (polished 20 times with abrasive paper #240), and a rotation speed of 60 rpm. The weight of the test piece after 1000 rotations was measured, and the weight of the test piece was measured again after a further 10000 rotations with the same test piece.

[0044] The wear amount was calculated by the following formula. Wear amount (mg) = M1 - M2 M1: Weight of the test piece after 1000 rotations (mg) M2: Weight of the test piece after 10000 rotations (mg) In Table 1, those with a wear amount greater than 17 mg are indicated as "×", those between 17 and 15 mg as "△", those between 15 and 13 mg as "〇", and those 13 mg or less as "◎".

[0045] (Deflection rate under load at 95 °C) After leaving the sheet-like extruded body at 60 °C for 24 hours, a test piece of 80 mm × 10 mm was cut out from the extruded body and heated in an electric furnace at 100 °C for 20 hours. Except for using the obtained test piece, in accordance with the method described in JIS K-K 7191-1, a heat distortion tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) was used to conduct a test under the conditions of a test temperature of 30 to 150 °C, a heating rate of 120 °C / hour, a bending stress of 1.8 MPa, and the flatwise method.

[0046] The deflection rate under load was calculated by the following formula. A sheet with a small deflection rate under load at 95 °C has excellent high-temperature rigidity. Deflection rate under load (%) = a2 / a1 × 100 a1: Thickness of the test piece before the test (mm) a2: Deflection amount at 95 °C (mm) In Table 1, those with a deflection rate under load greater than 70% are indicated as "×", those between 70 and 60% as "△", those between 60 and 50% as "〇", and those 50% or less as "◎".

[0047]

Table 1

[0048]

Table 2

[0049] As is clear from Table 1, the extruded body of each example is a tubular body formed of a resin that does not contain a halogen element, has an ether bond or an ethylene structure, and has a melting point of 200 °C or higher, and the amount of ion elution into water with an electrical conductivity of 0.5 mS / m or less at 25 °C is 7500 μg / m 2The following was found: a tubular extruded body with an inner surface roughness (Ra) of 0.25 μm or less is non-halogen-based, avoiding environmental problems, and has excellent physical properties such as low water vapor permeability, low chemical solution permeability, abrasion resistance, and rigidity at high temperatures. Furthermore, since the extruded bodies of Examples 1 to 3 have a small elution amount of specific metals and all physical properties are evaluated as "〇" or higher, it was confirmed that they can be suitably used particularly for chemical solutions and drugs used in the manufacture of semiconductors, liquid crystals, etc., and piping for ultrapure water.

Claims

1. A tubular extruded body formed of a resin that does not contain a halogen element, has an ether bond or an ethylene structure, and has a melting point of 200 °C or higher, wherein the amount of ion elution into water with an electrical conductivity of 0.5 mS / m or less at 25 °C is 7500 μg / m ２ or less, and the arithmetic mean roughness (Ra) of the inner surface is 0.25 μm or less. Extruded body.

2. The amount of ion elution into water with an electrical conductivity of 0.5 mS / m or less at 25 °C is 5500 μg / m ２ or less. The extruded body according to claim 1.

3. Based on SEMI F57-0314, the total amount of elution of aluminum, barium, boron, calcium, chromium, copper, iron, lead, lithium, magnesium, manganese, nickel, potassium, sodium, strontium, and zinc is 14 μg / m 2 or less. The extruded body according to claim 1 or 2.

4. The melt flow rate of the resin at 295 °C is 7.0 to 18.0 g / 10 min. The extruded body according to any one of claims 1 to 3.

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